ORCID Profile
0000-0003-3063-6539
Current Organisation
Monash University
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Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Catalysis and Mechanisms of Reactions | Physical Chemistry (Incl. Structural) | Electrochemistry | Physical Chemistry of Materials | Catalytic Process Engineering | Reaction kinetics and dynamics | Electrochemistry | Synthesis of Materials | Photodetectors, Optical Sensors and Solar Cells | Non-automotive Combustion and Fuel Engineering (incl. Alternative/Renewable Fuels) | Chemical Engineering | Reaction Kinetics and Dynamics | Physical chemistry | Nanomaterials | Functional Materials | Nanotechnology | Materials Engineering | Composite and Hybrid Materials
ANZSRC Socio-Economic Objective (SEO)
Chemical Fertilisers | Hydrogen Production from Renewable Energy | Energy Storage (excl. Hydrogen) | Expanding Knowledge in Engineering | Hydrogen Storage | Hydrogen Distribution | Solar-Photovoltaic Energy | Environmentally Sustainable Energy Activities not elsewhere classified | Expanding Knowledge in the Chemical Sciences | Industrial Chemicals and Related Products not elsewhere classified |
Related Links
Publications
Analysis of HypD Disulfide Redox Chemistry via Optimization of Fourier Transformed ac Voltammetric Data
Publisher: American Chemical Society (ACS)
Date: 19-01-2017
DOI: 10.1021/ACS.ANALCHEM.6B03589
Abstract: Rapid disulfide bond formation and cleavage is an essential mechanism of life. Using large litude Fourier transformed alternating current voltammetry (FTacV) we have measured previously uncharacterized disulfide bond redox chemistry in Escherichia coli HypD. This protein is representative of a class of assembly proteins that play an essential role in the biosynthesis of the active site of [NiFe]-hydrogenases, a family of H
Vertically Aligned Interlayer Expanded MoS2 Nanosheets on a Carbon Support for Hydrogen Evolution Electrocatalysis
Publisher: American Chemical Society (ACS)
Date: 17-03-2017
Expanded ring N-heterocyclic carbene adducts of group 15 element trichlorides: synthesis and reduction studies
Publisher: Royal Society of Chemistry (RSC)
Date: 22-08-2014
DOI: 10.1039/C4DT02074J
Abstract: Reactions of the expanded ring N-heterocyclic carbene, 6-Dip (:C{N(Dip)CH2}2CH2, Dip = 2,6-diisopropylphenyl), with group 15 element trichlorides have yielded the monomeric complexes, [(6-Dip)ECl3] (E = P, As or Sb), two ex les of which (E = P and Sb) have been crystallographically characterised. Reduction of [(6-Dip)PCl3] with KC8 yielded the unusual tetraphosphorus dicationic complex, [(6-Dip)2(μ-P4)]Cl2, the X-ray crystal structure of which shows it to be an ion-separate salt. The compound can also be prepared from the direct reaction of excess 6-Dip with PCl3. Treatment of the cyclic amidinium salt, [6-MesH]Br (6-MesH = [HC{N(Mes)CH2}2CH2](+), Mes = mesityl) with KC8, leads to reductive coupling of the heterocycle and formation of the hindered bis(hexahydropyrimidine), (6-MesH)2. An X-ray crystallographic analysis of (6-MesH)2 shows the compound to have a long central C-C bond, while an electrochemical analysis reveals it to undergo an irreversible two-electron oxidation in dichloromethane solutions.
High performance acidic water electrooxidation catalysed by manganese–antimony oxides promoted by secondary metals
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3EY00046J
Abstract: Modification of the manganese–antimony oxide nanocomposites with lead produces an active and highly robust electrocatalyst for anodes of hydrogen-generating water electrolysers with proton conducting electrolytes.
Liquefied Sunshine: Transforming Renewables into Fertilizers and Energy Carriers with Electromaterials
Publisher: Wiley
Date: 25-11-2020
Abstract: It has become apparent that renewable energy sources are plentiful in many, often remote, parts of the world, such that storing and transporting that energy has become the key challenge. For long-distance transportation by pipeline and bulk tanker, a liquid form of energy carrier is ideal, focusing attention on liquid hydrogen and ammonia. Development of high-activity and selectivity electrocatalyst materials to produce these energy carriers by reductive electrochemistry has therefore become an important area of research. Here, recent developments and challenges in the field of electrocatalytic materials for these processes are discussed, including the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the nitrogen reduction reaction (NRR). Some of the mis-steps currently plaguing the nitrogen reduction to ammonia field are highlighted. The rapidly growing roles that in situ/operando and quantum chemical studies can play in new electromaterials discovery are also surveyed.
Possible prebiotic synthesis of monosaccharides from formaldehyde in presence of phosphates
Publisher: Elsevier BV
Date: 2007
Aggregation of a Dibenzo[b,def]chrysene Based Organic Photovoltaic Material in Solution
Publisher: American Chemical Society (ACS)
Date: 04-06-2014
DOI: 10.1021/JP501220V
Abstract: Detailed electrochemical studies have been undertaken on molecular aggregation of the organic semiconductor 7,14-bis((triisopropylsilyl)-ethynyl)dibenzo[b,def]chrysene (TIPS-DBC), which is used as an electron donor material in organic solar cells. Intermolecular association of neutral TIPS-DBC molecules was established by using (1)H NMR spectroscopy as well as by the pronounced dependence of the color of TIPS-DBC solutions on concentration. Diffusion limited current data provided by near steady-state voltammetry also reveal aggregation. Furthermore, variation of concentration produces large changes in shapes of transient DC and Fourier transformed AC (FTAC) voltammograms for oxidation of TIPS-DBC in dichloromethane. Subtle effects of molecular aggregation on the reduction of TIPS-DBC are also revealed by the highly sensitive FTAC voltammetric method. Simulations of FTAC voltammetric data provide estimates of the kinetic and thermodynamic parameters associated with oxidation and reduction of TIPS-DBC. Significantly, aggregation of TIPS-DBC facilitates both one-electron oxidation and reduction by shifting the reversible potentials to less and more positive values, respectively. EPR spectroscopy is used to establish the identity of one-electron oxidized and reduced forms of TIPS-DBC. Implications of molecular aggregation on the HOMO energy level in solution are considered with respect to efficiency of organic photovoltaic devices utilizing TIPS-DBC as an electron donor material.
The impact of electrode conductivity on electrolyte interfacial structuring and its implications on the Na0/+ electrochemical performance
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3EE00864A
Abstract: Is solid-electrolyte interphase formation affected by electrode conductivity?
Photon-Induced, Timescale, and Electrode Effects Critical for the in Situ X-ray Spectroscopic Analysis of Electrocatalysts: The Water Oxidation Case
Publisher: American Chemical Society (ACS)
Date: 25-10-2019
Prospects of Z-Scheme Photocatalytic Systems Based on Metal Halide Perovskites
Publisher: American Chemical Society (ACS)
Date: 23-04-2021
Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X‐Ray Spectroscopy
Publisher: Wiley
Date: 06-02-2019
Abstract: Manganese oxide (MnO
Silver Bismuth Sulfoiodide Solar Cells: Tuning Optoelectronic Properties by Sulfide Modification for Enhanced Photovoltaic Performance
Publisher: Wiley
Date: 14-12-2018
Tuning Catalyst Selectivity for Ammonia vs Hydrogen: An Investigation into the Coprecipitation of Mo and Fe Sulfides
Publisher: American Chemical Society (ACS)
Date: 06-06-2023
Isopolytungstate Adsorption on Platinum: Manifestations of Underpotential Deposition
Publisher: Springer Science and Business Media LLC
Date: 06-10-2012
Transesterification of rapeseed oil under flow conditions catalyzed by basic solids: MAl(La)O (M=Sr, Ba), MMgO (M=Y, La)
Publisher: Elsevier BV
Date: 03-2012
The aperiodic current, and its semiintegral, in reversible a.c. voltammetry: Theory and experiment
Publisher: Elsevier BV
Date: 04-2014
The nature of autocatalysis in the Butlerov reaction
Publisher: Pleiades Publishing Ltd
Date: 03-2007
Nitrogen reduction to ammonia at high efficiency and rates based on a phosphonium proton shuttle
Publisher: American Association for the Advancement of Science (AAAS)
Date: 11-06-2021
Abstract: An electrochemical route to ammonia could substantially lower the greenhouse gas emissions associated with the current thermal Haber-Bosch process. One relatively promising option under study involves reductive formation of lithium nitride, which can be protonated to ammonia. However, the ethanol used to date as a local proton source in these studies may degrade under the reaction conditions. Suryanto et al. report the use of a tetraalkyl phosphonium salt in place of ethanol (see the Perspective by Westhead et al. ). This cation can stably undergo deprotonation–reprotonation cycles and, as an added benefit, it enhances the ionic conductivity of the medium. Science , abg2371, this issue p. 1187 see also abi8329, p. 1149
Intrinsically stable in situ generated electrocatalyst for long-term oxidation of acidic water at up to 80 °C
Publisher: Springer Science and Business Media LLC
Date: 13-05-2019
Putative mechanism of the sugar formation on prebiotic Earth initiated by UV-radiation
Publisher: Elsevier BV
Date: 2005
Solar Water Oxidation by Multicomponent TaON Photoanodes Functionalized with Nickel Oxide
Publisher: Wiley
Date: 10-2016
Abstract: Efficient solar-powered water oxidation over the TaON-based anodes requires coupling this photoactive n-type semiconductor to an electrooxidation catalyst to improve the otherwise unsatisfactory activity and stability. Herein, we examine how functionalization with electrodeposited nickel oxide, NiO
Selective synthesis of erythrulose and 3-pentulose from formaldehyde and dihydroxyacetone catalyzed by phosphates in a neutral aqueous medium
Publisher: Pleiades Publishing Ltd
Date: 07-2007
Study of the photoinduced formose reaction by flash and stationary photolysis
Publisher: Elsevier BV
Date: 2006
Perovskite solar cells with a hybrid electrode structure
Publisher: AIP Publishing
Date: 12-2019
DOI: 10.1063/1.5127275
Abstract: Perovskite solar cells (PSCs) with a novel hybrid electrode structure, in which a single device can operate with either a vertical (sandwich) or lateral (back-contact) configuration of contacts, are demonstrated in this work. The hybrid structure was achieved by depositing an additional anode on top of a prefabricated back-contact PSC device, giving a final device with three electrodes—one shared cathode and two anodes. Device performances are tested and evaluated for both operation modes, and a semianalytical model along with coupled optoelectronic simulations is used to rationalize the experimental results. It is determined that due to the intrinsically narrow depletion region near the contact interfaces, the charge collection efficiency in the back-contact device structure appears to be significantly lower compared to the sandwich device structure. This finding provides an insight into the cause of the performance disparity between these two architectures.
Probing Electron Transfer in the Manganese-Oxide-Forming MnxEFG Protein Complex using Fourier Transformed AC Voltammetry: Understanding the Oxidative Priming Effect
Publisher: Wiley
Date: 10-08-2018
Solvent Engineering of a Dopant-Free Spiro-OMeTAD Hole-Transport Layer for Centimeter-Scale Perovskite Solar Cells with High Efficiency and Thermal Stability
Publisher: American Chemical Society (ACS)
Date: 29-01-2020
Abstract: High efficiency and environmental stability are mandatory performance requirements for commercialization of perovskite solar cells (PSCs). Herein, efficient centimeter-scale PSCs with improved stability were achieved by incorporating an additive-free 2,2',7,7'-tetrakis[
Leone Spiccia Memorial Issue
Publisher: Wiley
Date: 25-06-2018
Abstract: Leone Spiccia will be remembered as an outstanding scientist with a warm and generous personality. At the time of his death he was at the pinnacle of his scientific career with much more yet to be achieved. However, his legacy will continue to inspire new exciting science. Leone's scientific research was truly multidisciplinary and his friends and colleagues honour his memory with this special issue.
Electrolysis of Natural Waters Contaminated with Transition‐Metal Ions: Identification of A Metastable FePb‐Based Oxygen‐Evolution Catalyst Operating in Weakly Acidic Solutions
Publisher: Wiley
Date: 25-04-2018
Abstract: The possibility of efficient water electrooxidation sustained by continuous (re)generation of catalysts derived from the oxidative electrodeposition of transition-metal contaminants is examined herein for three natural water s les from Australia and China. The metal composition of the solutions has been determined by inductively coupled plasma optical emission spectrometry, and a range of strategies to produce water-splitting catalysts by means of in situ electrodeposition have been applied. The performance of the resulting electrocatalysts is below the state-of-the-art level owing to large amounts of impurities in the solutions and non-optimal concentrations of naturally available catalyst precursors. Nevertheless, these studies have identified the FePb-based system as a rare ex le of an electrocatalyst for water oxidation that forms in situ and maintains reasonable activity (≥4.5 mA cm
Interfacial benzenethiol modification facilitates charge transfer and improves stability of cm-sized metal halide perovskite solar cells with up to 20% efficiency
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8EE00754C
Abstract: A facile method to produce metal halide perovskite solar cells with improved stability and efficiency.
Molecular Engineering of Zinc‐Porphyrin Sensitisers for p‐Type Dye‐Sensitised Solar Cells
Publisher: Wiley
Date: 19-06-2018
Abstract: Invited for this month's cover are the groups of Prof. Dr. Udo Bach, Prof. Dr. Yi-Bing Cheng, and Prof. Dr. Leone Spiccia (Monash University, Australia), and Dr. Mingkui Wang (Huazhong University of Science and Technology, China). The cover picture shows the charge-transfer processes between a novel porphyrin dye adsorbed on nickel oxide and tris(acetylacetonato) iron(III/II) redox mediator after excitation by sunlight. Read the full text of the article at 10.1002/cplu.201800104.
Microstructure effects on the electrochemical corrosion of carbon materials and carbon-supported Pt catalysts
Publisher: Elsevier BV
Date: 12-2010
Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia
Publisher: Springer Science and Business Media LLC
Date: 18-03-2019
Electrochemistry of cytochrome P450 17 alpha-hydroxylase/17,20-lyase (P450c17)
Publisher: Elsevier BV
Date: 02-2017
DOI: 10.1016/J.MCE.2016.09.034
Abstract: Within the superfamily of cytochrome P450 enzymes (P450s), there is a small class which is functionally employed for steroid biosynthesis. The enzymes in this class appear to have a small active site to accommodate the steroid substrates specifically and snuggly, prior to the redox transformation or hydroxylation to form a product. Cytochrome P450c17 is one of these and is also a multi-functional P450, with two activities, the first 17α-hydroxylation of pregnenolone is followed by a subsequent 17,20-lyase transformation to dehydroepiandrosterone (DHEA) as the dominant pathways to cortisol precursors or androgens in humans, respectively. How P450c17 regulates these two redox reactions is of special interest. There is a paucity of direct electrochemical studies on steroidogenic P450s, and in this mini-review we provide an overview of these studies with P450c17. Historical consideration as to the difficulties in obtaining reliable electrochemistry due to issues of handling proteins on an electrode, together with advances in the electrochemical techniques are addressed. Recent work using Fourier transformed alternating current voltammetry is highlighted as this technique can provide both catalytic information simultaneously with the underlying redox transfer with the P450 haem.
Identification and elimination of false positives in electrochemical nitrogen reduction studies
Publisher: Springer Science and Business Media LLC
Date: 03-11-2020
DOI: 10.1038/S41467-020-19130-Z
Abstract: Ammonia is of emerging interest as a liquefied, renewable-energy-sourced energy carrier for global use in the future. Electrochemical reduction of N 2 (NRR) is widely recognised as an alternative to the traditional Haber–Bosch production process for ammonia. However, though the challenges of NRR experiments have become better understood, the reported rates are often too low to be convincing that reduction of the highly unreactive N 2 molecule has actually been achieved. This perspective critically reassesses a wide range of the NRR reports, describes experimental case studies of potential origins of false-positives, and presents an updated, simplified experimental protocol dealing with the recently emerging issues.
Vacuum compatible flow‐cell for high‐quality in situ and operando soft X‐ray photon‐in–photon‐out spectroelectrochemical studies of energy materials
Publisher: Wiley
Date: 19-12-2021
Abstract: Soft X‐ray spectroscopy is a powerful method to investigate materials on an element selective level with respect to their atomic and electronic structure. However, its application is technically challenging for in situ or operando investigations of materials for electrochemical applications. Herein, we present a spectroelectrochemical flow‐cell designed to enable state‐of‐the‐art electrochemical characterization while being installed in a vacuum chamber for the direct accessibility of the electroactive s le to soft X‐rays. An overview of the application of soft X‐ray photon‐in–photon‐out spectroscopic studies to electromaterials is provided, along with discussions of experimental and technical considerations specific to this highly sensitive mode of analysis. Application of the cell for the in situ spectroelectrochemical characterization of an electrodeposited nickel oxide water electrooxidation catalyst is demonstrated.
Mixed Silver–Bismuth Oxides: A Robust Oxygen Evolution Catalyst Operating at Low pH and Elevated Temperatures
Publisher: American Chemical Society (ACS)
Date: 11-10-2202
New insights into the analysis of the electrode kinetics of flavin adenine dinucleotide redox center of glucose oxidase immobilized on carbon electrodes
Publisher: American Chemical Society (ACS)
Date: 13-03-2014
DOI: 10.1021/LA404872P
Abstract: New insights into electrochemical kinetics of the flavin adenine dinucleotide (FAD) redox center of glucose-oxidase (GlcOx) immobilized on reduced graphene oxide (rGO), single- and multiwalled carbon nanotubes (SW and MWCNT), and combinations of rGO and CNTs have been gained by application of Fourier transformed AC voltammetry (FTACV) and simulations based on a range of models. A satisfactory level of agreement between experiment and theory, and hence establishment of the best model to describe the redox chemistry of FAD, was achieved with the aid of automated e-science tools. Although still not perfect, use of Marcus theory with a very low reorganization energy (≤0.3 eV) best mimics the experimental FTACV data, which suggests that the process is gated as also deduced from analysis of FTACV data obtained at different frequencies. Failure of the simplest models to fully describe the electrode kinetics of the redox center of GlcOx, including those based on the widely employed Laviron theory is demonstrated, as is substantial kinetic heterogeneity of FAD species. Use of a SWCNT support lifies the kinetic heterogeneity, while a combination of rGO and MWCNT provides a more favorable environment for fast communication between FAD and the electrode.
Polypyridyl Iron Complex as a Hole-Transporting Material for Formamidinium Lead Bromide Perovskite Solar Cells
Publisher: American Chemical Society (ACS)
Date: 27-07-2017
Polar Organic Cations at Electrified Metal with Superconcentrated Ionic Liquid Electrolyte and Implications for Sodium Metal Batteries
Publisher: American Chemical Society (ACS)
Date: 09-09-2022
Engineering high-energy-density sodium battery anodes for improved cycling with superconcentrated ionic-liquid electrolytes
Publisher: Springer Science and Business Media LLC
Date: 04-05-2020
Optimisation of windowing for harmonic recovery in large-amplitude Fourier transformed a.c. voltammetry
Publisher: Elsevier BV
Date: 10-2014
Understanding the Factors Determining the Faradaic Efficiency and Rate of the Lithium Redox-Mediated N2 Reduction to Ammonia
Publisher: American Chemical Society (ACS)
Date: 24-05-2021
Mixed metal–antimony oxide nanocomposites: low pH water oxidation electrocatalysts with outstanding durability at ambient and elevated temperatures
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1TA07293E
Abstract: Stability of the anode catalysts for PEM water electrolysers can be substantially improved by combining the catalytic component with antimony oxides. However, the mechanisms of the catalyst stabilisation differ depending on the active element used.
Hydrogen electrooxidation on PdAu supported nanoparticles: An experimental RDE and kinetic modeling study
Publisher: Elsevier BV
Date: 03-2013
Critical Assessment of the Electrocatalytic Activity of Vanadium and Niobium Nitrides toward Dinitrogen Reduction to Ammonia
Publisher: American Chemical Society (ACS)
Date: 05-02-2019
Transparent Quasi-Interdigitated Electrodes for Semitransparent Perovskite Back-Contact Solar Cells
Publisher: American Chemical Society (ACS)
Date: 20-08-2018
Solution Processable Direct Bandgap Copper‐Silver‐Bismuth Iodide Photovoltaics: Compositional Control of Dimensionality and Optoelectronic Properties
Publisher: Wiley
Date: 17-07-2022
Abstract: The search for lead‐free alternatives to lead‐halide perovskite photovoltaic materials resulted in the discovery of copper(I)‐silver(I)‐bismuth(III) halides exhibiting promising properties for optoelectronic applications. The present work demonstrates a solution‐based synthesis of uniform Cu x AgBiI 4+ x thin films and scrutinizes the effects of x on the phase composition, dimensionality, optoelectronic properties, and photovoltaic performance. Formation of pure 3D CuAgBiI 5 at x = 1, 2D Cu 2 AgBiI 6 at x = 2, and a mix of the two at 1 x 2 is demonstrated. Despite lower structural dimensionality, Cu 2 AgBiI 6 has broader optical absorption with a direct bandgap of 1.89 ± 0.05 eV, a valence band level at ‐5.25 eV, improved carrier lifetime, and higher recombination resistance as compared to CuAgBiI 5 . These differences are mirrored in the power conversion efficiencies of the CuAgBiI 5 and Cu 2 AgBiI 6 solar cells under 1 sun of 1.01 ± 0.06% and 2.39 ± 0.05%, respectively. The latter value is the highest reported for this class of materials owing to the favorable film morphology provided by the hot‐casting method. Future performance improvements might emerge from the optimization of the Cu 2 AgBiI 6 layer thickness to match the carrier diffusion length of ≈40–50 nm. Nonencapsulated Cu 2 AgBiI 6 solar cells display storage stability over 240 days.
Selective Oxidation of Glucose Over Carbon-supported Pd and Pt Catalysts
Publisher: Springer Science and Business Media LLC
Date: 21-08-2010
Cooperative silanetriolate-carboxylate sensitiser anchoring for outstanding stability and improved performance of dye-sensitised photoelectrodes
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8SE00056E
Abstract: New dye anchoring system that sustains intimate electronic coupling while addressing the notorious instability of dye-sensitised electrodes in aqueous media is introduced.
Modelling ac voltammetry with MECSim: facilitating simulation-experiment comparisons
Publisher: Elsevier BV
Date: 02-2017
Electroreduction of nitrogen with almost 100% current-to-ammonia efficiency
Publisher: Springer Science and Business Media LLC
Date: 22-07-2022
DOI: 10.1038/S41586-022-05108-Y
Abstract: In addition to its use in the fertilizer and chemical industries
Mechanistic Scrutiny Identifies a Kinetic Role for Cytochrome b5 Regulation of Human Cytochrome P450c17 (CYP17A1, P450 17A1)
Publisher: Public Library of Science (PLoS)
Date: 20-11-2015
(Digital Presentation) Towards Li-Mediated Nitrogen Reduction Reaction at High Current-to-Ammonia Efficiency
Publisher: The Electrochemical Society
Date: 07-07-2022
DOI: 10.1149/MA2022-01391788MTGABS
Abstract: Apart from its role as a main precursor of the synthetic fertiliser production, ammonia is likely to become an even more important chemical in the future due to its prospects as an energy carrier. (1) To meet the associated growing demand while meeting the CO 2 emission reductions targets, recent efforts have aimed to translate the conventional polluting NH 3 synthesis to low CO 2 emissions technology by supplying the Haber-Bosch reactors with H 2 derived from renewable-powered water electrolysis rather than steam methane reforming. (2) This solution will likely to be implemented in many NH 3 synthesis plants soon, but the most preferred future technology for green ammonia synthesis is through a 100% renewable-powered, one step electrochemical process involving nitrogen reduction at the cathode and water oxidation at the anode. However, the possibility of direct dinitrogen reduction with traditional heterogeneous catalysts in both aqueous and aprotic electrolyte solutions at practical rates and faradaic efficiencies is yet to be proven, (3, 4) which calls for investigations of alternative pathways. One prominent possibility, with clear practical prospects, is the indirect lithium redox mediated process in organic electrolytes, which has been evidenced as genuine and by far the most efficient process to electrochemically convert N 2 to NH 3 . (5) However, several key challenges, including insufficiently high yield rate and faradaic efficiency as well as instability of the system, are yet to be resolved before the lithium-mediated nitrogen reduction reaction (Li-NRR) can be considered a process of applied significance. Our first step towards this aim was to introduce a stable phosphonium cation/ylide proton shuttle that delivers protons to the cathode to support rapid and controllable conversion of lithium nitride into ammonia. (6) It was demonstrated that phosphonium cation provides favourable proton activity in the system, which enables high Li-NRR faradaic efficiency of 69 ± 1 %. Moreover, the phosphonium shuttle exhibits high stability under the reaction conditions, i.e. was genuinely able to cycle between anode and cathode without being consumed. Our further efforts have focussed on understanding the effects of the electrolyte-electrode environment on the Li-NRR kinetics. As a result of this investigation, a system configuration that enables the electroreduction of N 2 to ammonia at a faradaic efficiency closely approaching 100% was discovered. Moreover, the synthesis can run in both uninterrupted and interrupted regimes on a timescale of days. The rate of ammonia electrosynthesis in the Li-NRR with the optimised electrode-electrolyte interface can achieve as high as ca 500 nmol s -1 cm -2 (per geometric electrode surface area) with electrodes of cm 2 scale. Finally, we examined the degradation of the electrolyte solution components during the high-performance Li-NRR. It was found that the major source of these undesired processes are the anode processes rather than the cathode. This highlights the urgent need for the development of effective H 2 - or H 2 O-feed anodes that can be integrated with the lithium mediated process. This and other future challenges on our way towards achieving sustainable and stabile NH 3 electrosynthesis system to support the development of the Ammonia Economy will be highlighted. D. R. MacFarlane, J. Choi, B. H. R. Suryanto, R. Jalili, M. Chatti, L. M. Azofra and A. N. Simonov, Adv. Mater. , 32 , 1904804 (2020). D. R. MacFarlane, P. V. Cherepanov, J. Choi, B. H. R. Suryanto, R. Y. Hodgetts, J. M. Bakker, F. M. Ferrero Vallana and A. N. Simonov, Joule , 4 , 1186 (2020). H.-L. Du, T. R. Gengenbach, R. Hodgetts, D. R. MacFarlane and A. N. Simonov, ACS Sustainable Chem. Eng. , 7 , 6839 (2019). H.-L. Du, R. Y. Hodgetts, M. Chatti, C. K. Nguyen, D. R. Macfarlane and A. N. Simonov, J. Electrochem. Soc. , 167 , 146507 (2020). B. H. R. Suryanto, H.-L. Du, D. Wang, J. Chen, A. N. Simonov and D. R. MacFarlane, Nat. Catal. , 2 , 290 (2019). B. H. Suryanto, K. Matuszek, J. Choi, R. Y. Hodgetts, H.-L. Du, J. M. Bakker, C. S. Kang, P. V. Cherepanov, A. N. Simonov and D. R. MacFarlane, Science , 372 , 1187 (2021).
Electro-synthesis of ammonia from nitrogen at ambient temperature and pressure in ionic liquids
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7EE02716H
Abstract: High faradaic efficiency reduction of N 2 to NH 3 is achieved in ionic liquid media under ambient conditions.
Separating the Effects of Experimental Noise from Inherent System Variability in Voltammetry: The [Fe(CN)6]3–/4– Process
Publisher: American Chemical Society (ACS)
Date: 19-12-2019
DOI: 10.1021/ACS.ANALCHEM.8B04238
Abstract: Recently, we introduced the use of techniques drawn from Bayesian statistics to recover kinetic and thermodynamic parameters from voltammetric data and were able to show that the technique of large litude ac voltammetry yielded significantly more accurate parameter values than the equivalent dc approach. In this paper, we build on this work to show that this approach allows us, for the first time, to separate the effects of random experimental noise and inherent system variability in voltammetric experiments. We analyze ten repeated experimental data sets for the [Fe(CN)
The chemistry of proton carriers in high-performance lithium-mediated ammonia electrosynthesis
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2EE03901J
Abstract: Proton transfer is a key step of the lithium-mediated electrochemical reduction of nitrogen to ammonia. Herein, we investigate the impact of the chemical nature of the proton carrier on the performance and highlight shuttles that enable effective ammonia synthesis.
Spray deposition of AgBiS2 and Cu3BiS3 thin films for photovoltaic applications
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7TC05711C
Abstract: Spray-deposited AgBiS 2 films are introduced as light-harvesters in planar solar cells that demonstrate up to 18 mA cm −2 short-circuit current density under 1 sun irradiation.
Promoting Nitrogen Electroreduction to Ammonia with Bismuth Nanocrystals and Potassium Cations in Water
Publisher: American Chemical Society (ACS)
Date: 31-01-2020
DOI: 10.26434/CHEMRXIV.11768814.V1
Abstract: We demonstrate that bismuth exhibits no measurable electrocatalytic activity for the nitrogen reduction reaction to ammonia in aqueous electrolyte solutions, contrary to several recent reports on the highly impressive rates of Bi-catalysed electrosynthesis of NH 3 from N 2 .
Tuning the morphology and structure of disordered hematite photoanodes for improved water oxidation: A physical and chemical synergistic approach
Publisher: Elsevier BV
Date: 11-2018
On choosing a reference redox system for electrochemical measurements: a cautionary tale
Publisher: Springer Science and Business Media LLC
Date: 24-07-2013
Potentiostatic electrodeposition of Pt on GC and on HOPG at low loadings: Analysis of the deposition transients and the structure of Pt deposits
Publisher: Elsevier BV
Date: 12-2014
Copper‐Catalyzed Electrosynthesis of Nitrite and Nitrate from Ammonia: Tuning the Selectivity via an Interplay Between Homogeneous and Heterogeneous Catalysis
Publisher: Wiley
Date: 29-09-2021
Abstract: Electrocatalytic oxidation of ammonia is an appealing, low‐temperature process for the sustainable production of nitrites and nitrates that avoids the formation of pernicious N 2 O and can be fully powered by renewable electricity. Currently, however, the number of known efficient catalysts for such a reaction is limited. The present work demonstrates that copper‐based electrodes exhibit high electrocatalytic activity and selectivity for the NH 3 oxidation to NO 2 − and NO 3 − in alkaline solutions. Systematic investigation of the effects of pH and potential on the kinetics of the reaction using voltammetric analysis andin situ Raman spectroscopy suggest that ammonia electrooxidation on copper occurrs via two primary catalytic mechanisms. In the first pathway, NH 3 is converted to NO 2 − via a homogeneous electrocatalytic process mediated by redox transformations of aqueous [Cu(OH) 4 ] −/2− species, which dissolve from the electrode. The second pathway is the heterogeneous catalytic oxidation of NH 3 on the electrode surface favoring the formation of NO 3 − . By virtue of its nature, the homogeneous‐mediated pathway enables higher selectivity and was less affected by electrode poisoning with the strongly adsorbed “N” intermediates that have plagued the electrocatalytic ammonia oxidation field. Thus, the selectivity of the Cu‐catalyzed NH 3 oxidation towards either nitrite or nitrate can be achieved through balancing the kinetics of the two mechanisms by adjusting the pH of the electrolyte medium and potential.
Can laminated carbon challenge gold? Towards universal, scalable and low-cost carbon electrodes for perovskite solar cells
Publisher: Wiley
Date: 05-11-2021
Abstract: While perovskite solar cell (PSC) efficiencies are soaring at a laboratory scale, these are most commonly achieved with evaporated gold electrodes, which would present a significant expense in large‐scale production. This can be remedied through the use of significantly cheaper carbon electrodes that, in contrast to metals, also do not migrate through the device. To this end, the present work investigates simple‐to‐prepare aluminum‐supported carbon electrodes derived from commercially available, inexpensive materials that can be applied onto various hole‐transporting materials and enable photovoltaic performances on par with those provided by gold electrodes. Successful integration of the new carbon‐based electrode into flexible devices produced by a roll‐to‐roll printing technology by both pressing and lamination is demonstrated. However, temperature cycling durability tests reveal that the use of carbon electrodes based on commercial pastes is hindered by incompatibility of adhesive additives with the key components of the PSCs under heating. Resolving this issue, tailor‐made graphite electrodes devoid of damaging additives are introduced, which improve the PSC stability under temperature cycling test protocol to the level provided by benchmark gold electrodes. The study highlights current challenges in developing laminated carbon electrodes in PSCs and proposes strategies toward the resolution thereof.
Binder-Free Electrodes Derived from Interlayer-Expanded MoS2 Nanosheets on Carbon Cloth with a 3D Porous Structure for Lithium Storage
Publisher: Wiley
Date: 15-04-2019
Robust Sub‐Monolayers of Co3O4Nano‐Islands: A Highly Transparent Morphology for Efficient Water Oxidation Catalysis
Publisher: Wiley
Date: 31-05-2016
Kinetics of rapeseed oil transesterification over a heterogeneous barium-aluminum oxide catalyst with the methanol pressure taken into account
Publisher: Pleiades Publishing Ltd
Date: 10-2013
A Roadmap to the Ammonia Economy
Publisher: Elsevier BV
Date: 06-2020
Catalytic Activity and Impedance Behavior of Screen-Printed Nickel Oxide as Efficient Water Oxidation Catalysts
Publisher: Wiley
Date: 30-11-2015
Abstract: We report that films screen printed from nickel oxide (NiO) nanoparticles and microballs are efficient electrocatalysts for water oxidation under near-neutral and alkaline conditions. Investigations of the composition and structure of the screen-printed films by X-ray diffraction, X-ray absorption spectroscopy, and scanning electron microscopy confirmed that the material was present as the cubic NiO phase. Comparison of the catalytic activity of the microball films to that of films fabricated by using NiO nanoparticles, under similar experimental conditions, revealed that the microball films outperform nanoparticle films of similar thickness owing to a more porous structure and higher surface area. A thinner, less-resistive NiO nanoparticle film, however, was found to have higher activity per Ni atom. Anodization in borate buffer significantly improved the activity of all three films. X-ray photoelectron spectroscopy showed that during anodization, a mixed nickel oxyhydroxide phase formed on the surface of all films, which could account for the improved activity. Impedance spectroscopy revealed that surface traps contribute significantly to the resistance of the NiO films. On anodization, the trap state resistance of all films was reduced, which led to significant improvements in activity. In 1.00 m NaOH, both the microball and nanoparticle films exhibit high long-term stability and produce a stable current density of approximately 30 mA cm(-2) at 600 mV overpotential.
Is Molybdenum Disulfide Modified with Molybdenum Metal Catalytically Active for the Nitrogen Reduction Reaction?
Publisher: The Electrochemical Society
Date: 27-10-2020
Abstract: Inspired by the previously published theoretical findings, the present work aims to assess the electrocatalytic activity of molybdenum(IV) sulfide modified with metallic molybdenum for the nitrogen reduction reaction in aqueous electrolyte solution (0.1 M Li 2 SO 4 pH 3) and in aprotic [C 4 mpyr][eFAP] ionic liquid electrolyte at ambient temperature. The material of interest was synthesized via a high-temperature partial reduction of MoS 2 , while electrocatalytic tests followed a previously established robust protocol, which in particular involves strict control over any NH 3 and NO 3 − /NO 2 − contamination at every key step. As expected, no activity was found in aqueous solutions. In aprotic medium, the formation of small amounts of ammonia at low rates was observed and was found to strongly depend on the water concentration and applied potential. However, the amount of electrochemically generated NH 3 always reached a particular limit and did not increase further, even when the N 2 pressure was increased from 1 to 16 bar. The results suggest rapid blockage of the surface of the investigated electromaterial with NH 3 , which prevents its operation as a catalyst for the ammonia electrosynthesis.
Tunable Biogenic Manganese Oxides
Publisher: Wiley
Date: 28-08-2017
Abstract: Influence of the conditions for aerobic oxidation of Mn2+(aq) catalysed by the MnxEFG protein complex on the morphology, structure and reactivity of the resulting biogenic manganese oxides (MnO
Determination of diffusion coefficients from semiintegrated d.c. and a.c. voltammetric data: Overcoming the edge effect at macrodisc electrodes
Publisher: Elsevier BV
Date: 05-2015
Slot-die coated scalable hole transporting layers for efficient perovskite solar modules
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2TA07989E
Abstract: We demonstrate herein the fabrication of large-area (up to 30 cm 2 ) organic-semiconductor-based films using slot-die coating – an established and highly scalable printing technology that enables deposition of uniform thin films on various substrates.
Redox levels of a closo-osmaborane: a density functional theory, electron paramagnetic resonance and electrochemical study
Publisher: American Chemical Society (ACS)
Date: 21-04-2015
DOI: 10.1021/IC503027G
Abstract: A closo-type 11-vertex osmaborane [1-(η(6)-pcym)-1-OsB10H10] (pcym = para-cymene) has been synthesized and characterized by single-crystal X-ray diffraction and elemental analysis, as well as by (11)B and (1)H NMR, UV-visible, and mass spectrometry. The redox chemistry has been probed by dc and Fourier transformed ac voltammetry and bulk reductive electrolysis in CH3CN (0.10 M (n-Bu)4NPF6) and by voltammetry in the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (Pyrr1,4-NTf2), which allows the oxidative chemistry of the osmaborane to be studied. A single-crystal X-ray diffraction analysis has shown that [1-(η(6)-pcym)-1-OsB10H10] is isostructural with other metallaborane compounds of this type. In CH3CN (0.10 M (n-Bu)4NPF6), [1-(η(6)-pcym)-1-OsB10H10] undergoes two well-resolved one-electron reduction processes with reversible potentials separated by ca. 0.63-0.64 V. Analysis based on a comparison of experimental and simulated ac voltammetric data shows that the heterogeneous electron transfer rate constant (k(0)) for the first reduction process is larger than that for the second step at GC, Pt, and Au electrodes. k(0) values for both processes are also larger at GC than metal electrodes and depend on the electrode pretreatment, implying that reductions involve specific interaction with the electrode surface. EPR spectra derived from the product formed by one-electron reduction of [1-(η(6)-pcym)-1-OsB10H10] in CH3CN (0.10 M (n-Bu)4NPF6) and electron orbital data derived from the DFT calculations are used to establish that the formal oxidation state of the metal center of the original unreduced compound is Os(II). On this basis it is concluded that the metal atom in [1-(η(6)-pcym)-1-OsB10H10] and related metallaboranes makes a 3-orbital 2-electron contribution to the borane cluster. Oxidation of [1-(η(6)-pcym)-1-OsB10H10] coupled to fast chemical transformation was observed at 1.6 V vs ferrocene(0/+) in Pyrr1,4-NTf2. A reaction scheme for the oxidation involving formation of [1-(η(6)-pcym)-1-OsB10H10](+), which rearranges to an unknown electroactive derivative, is proposed, and simulations of the voltammograms are provided.
Impact of the electrode conductivity on the electrolyte interfacial structuring and its implications to the Na0/+ electrochemical performance
Publisher: Research Square Platform LLC
Date: 23-02-2023
DOI: 10.21203/RS.3.RS-2618698/V1
Abstract: The molecular and ionic assemblies at an electrode/liquid electrolyte interface, i.e., electric double layer (EDL), define battery performance by directing the formation of stable interphases. An unstable interphase can h er metal-cation diffusion, lead to continuous electrolyte consumption, and also promote non-uniform electrochemical processes, like dendrite formation. The co-selection of electrolyte chemistry and initial cycling conditions together are generally considered for the design of desirable interphases. At the same time, the dielectric nature of the electrode material is largely ignored, notwithstanding high unreliability of the assumption that the nature of the EDL and the mechanism of the interphase formation at metallic and semiconductive electrodes are identical. Here we show that the dielectric nature of the charged electrode greatly affects the interfacial metal-anion-solvent composition therefore, different interphase chemistry will be formed, suggesting different initial cycling conditions on a case-by-case basis to form the desired interphase. This phenomenon correlates with the metal ion solvation chemistry and the adsorption of species at the electrified electrode due to competition of van der Waals and Coulombic interactions.
High-Performance Magnesium Electrochemical Cycling with Hybrid Mg–Li Electrolytes
Publisher: American Chemical Society (ACS)
Date: 25-07-2022
Impurity Tolerance of Unsaturated Ni-N-C Active Sites for Practical Electrochemical CO2 Reduction
Publisher: American Chemical Society (ACS)
Date: 09-02-2022
Intrinsic Catalytic Activity for the Alkaline Hydrogen Evolution of Layer-Expanded MoS2 Functionalized with Nanoscale Ni and Co Sulfides
Publisher: American Chemical Society (ACS)
Date: 19-05-2022
(Keynote) Towards Robust Li-Mediated Electrosynthesis of Ammonia at High Rate and Faradaic Efficiency
Publisher: The Electrochemical Society
Date: 19-10-2021
Use of Bayesian Inference for Parameter Recovery in DC and AC Voltammetry
Publisher: Wiley
Date: 19-10-2017
Reassessment of the catalytic activity of bismuth for aqueous nitrogen electroreduction
Publisher: Springer Science and Business Media LLC
Date: 25-05-2022
Separating the Effects of Experimental Noise from Inherent System Variability in Voltammetry: The [Fe(CN)_6]^3−/4− Process
Publisher: American Chemical Society (ACS)
Date: 10-2018
DOI: 10.26434/CHEMRXIV.7149281.V1
Abstract: Recently, we have introduced the use of techniques drawn from Bayesian statistics to recover kinetic and thermodynamic parameters from voltammetric data, and were able to show that the technique of large litude ac voltammetry yielded significantly more accurate parameter values than the equivalent dc approach. In this paper we build on this work to show that this approach allows us, for the first time, to separate the effects of random experimental noise and inherent system variability in voltammetricexperiments. We analyse ten repeated experimental data sets for the [Fe(CN) 6 ] 3−/4− process, again using large- litude ac cyclic voltammetry. In each of the ten caseswe are able to obtain an extremely good fit to the experimental data and obtain very narrow distributions of the recovered parameters governing both the faradaic (the reversible formal faradaic potential, E_0, the standard heterogeneous charge transfer rate constant k_0, and the charge transfer coefficient α) and non-faradaic terms (uncompensated resistance, R_u , and double layer capacitance, C_dl). We then employ hierarchicalBayesian methods to recover the underlying “hyperdistribution” of the faradaic and non-faradaic parameters, showing that in general the variation between the experimental data sets is significantly greater than suggested by in idual experiments, except for α where the inter-experiment variation was relatively minor. Correlations between pairs of parameters are provided, and for ex le, reveal a weak link between k_0 and C_dl (surface activity of a glassy carbon electrode surface). Finally, we discuss theimplications of our findings for voltammetric experiments more generally.
Prebiotic Carbohydrates and Their Derivates
Publisher: Springer US
Date: 2008
Transient photoresponse of nitrogen-doped ultrananocrystalline diamond electrodes in saline solution
Publisher: AIP Publishing
Date: 07-03-2016
DOI: 10.1063/1.4942976
Abstract: Beyond conventional electrically-driven neuronal stimulation methods, there is a growing interest in optically-driven approaches. In recent years, nitrogen-doped ultrananocrystalline diamond (N-UNCD) has emerged as a strong material candidate for use in electrically-driven stimulation electrodes. This work investigates the electrochemical activity of N-UNCD in response to pulsed illumination, to assess its potential for use as an optically-driven stimulation electrode. Whilst N-UNCD in the as-grown state exhibits a weak photoresponse, the oxygen plasma treated film exhibits two orders of magnitude enhancement in its sub-bandgap open circuit photovoltage response. The enhancement is attributed to the formation of a dense network of oxygen-terminated diamond nanocrystals at the N-UNCD surface. Electrically connected to the N-UNCD bulk via sub-surface graphitic grain boundaries, these diamond nanocrystals introduce a semiconducting barrier between the sub-surface graphitic semimetal and the electrolyte solution, leading to a photovoltage under irradiation with wavelengths of λ = 450 nm and shorter. Within the safe optical exposure limit of 2 mW mm−2, charge injection capacity of 0.01 mC cm−2 is achieved using a 15 × 15 μm electrode, meeting the requirements for extracellular and intercellular stimulation. The nanoscale nature of processes presented here along with the diamond's biocompatibility and biostability open an avenue for the use of oxygen treated N-UNCD as optically driven stimulating electrodes.
Biogenic Manganese-Oxide Mineralization is Enhanced by an Oxidative Priming Mechanism for the Multi-Copper Oxidase, MnxEFG
Publisher: Wiley
Date: 21-12-2017
Abstract: In a natural geochemical cycle, manganese-oxide minerals (MnO
Interrelation between catalytic activity for oxygen electroreduction and structure of supported platinum
Publisher: Elsevier BV
Date: 09-2014
Refining Universal Procedures for Ammonium Quantification via Rapid 1H NMR Analysis for Dinitrogen Reduction Studies
Publisher: American Chemical Society (ACS)
Date: 04-02-2020
13C NMR studies of isomerization of D-glucose in an aqueous solution of Ca(OH)2. The effect of molecular oxygen
Publisher: Springer Science and Business Media LLC
Date: 08-2005
Water Oxidation in Acidic Solutions: Beyond Noble Metals
Publisher: The Electrochemical Society
Date: 05-2020
DOI: 10.1149/MA2020-01371539MTGABS
Abstract: Water oxidation, a kinetically demanding half-reaction, plays a vital role in hydrogen production through electrochemical water-splitting. Thus, the development of efficient and stable oxygen evolution reaction electrocatalysts has become a central theme for basic research in the field of renewable energy. Substantial progress has been made in developing robust and inexpensive noble metal-free heterogeneous electrocatalysts for water oxidation operating under alkaline and neutral pH conditions. There is, however, a scarcity of active and stable electrocatalysts for acidic water oxidation, which is an ideal pH condition for high purity hydrogen production and offers several other technological advantages. Low performance and poor stability of existing water oxidation electrocatalysts based on non-noble metals are mainly attributed to the dissolution of respective elements in acidic solution. Considering these challenging aspects, we constructed the water oxidations catalysts based on thermodynamically and acid-stable oxides, which are incorporated with catalytically active species (transition metal-based water oxidation catalysts). Specifically, the highly-disordered mixed metal oxide, based on cobalt, iron, and lead, produced in situ exhibits excellent OER performance with unprecedented stability, through self-healing mechanism, under harsh operating conditions of pH 0 and temperature 80 °C. Importantly, the Cobalt-iron-lead oxide demonstrates the capability of operating at industrially relevant rates of 0.5 A cm -2 at low OER overpotentials of 0.7 V. These findings highlight the new strategy to design highly active and acid-stable, noble metal-free, OER electrocatalysts that can essentially operate indefinitely. Our most recent developments focused on replacement of lead with alternative, less toxic components. The presentation will also highlight these new systems, some of which demonstrate outstanding stability even without a self-healing mechanism.
A Survey of Catalytic Materials for Ammonia Electrooxidation to Nitrite and Nitrate
Publisher: Wiley
Date: 29-09-2022
Abstract: Studies of the ammonia oxidation reaction (AOR) for the synthesis of nitrite and nitrate (NO 2/3 − ) have been limited to a small number of catalytic materials, majorly Pt based. As the demand for nitrate‐based products such as fertilisers continues to grow, exploration of alternative catalysts is needed. Herein, 19 metals immobilised as particles on carbon fibre electrodes were tested for their catalytic activity for the ammonia electrooxidation to NO 2/3 − under alkaline conditions (0.1 m KOH). Nickel‐based electrodes showed the highest overall NO 2/3 − yield with a rate of 5.0±1.0 nmol s −1 cm −2 , to which nitrate contributed 62±8 %. Cu was the only catalyst that enabled formation of nitrate, at a rate of 1.0±0.4 nmol s −1 cm −2 , with undetectable amounts of nitrite produced. Previously unexplored in this context, Fe and Ag also showed promise and provided new insights into the mechanisms of the process. Ag‐based electrodes showed strong indications of activity towards NH 3 oxidation in electrochemical measurements but produced relatively low NO 2/3 − yields, suggesting the formation of alternate oxidation products. NO 2/3 − production over Fe‐based electrodes required the presence of dissolved O 2 and was more efficient than with Ni on longer timescales. These results highlight the complexity of the AOR mechanism and provide a broad set of catalytic activity and nitrate versus nitrite yield data, which might guide future development of a practical process for the distributed sustainable production of nitrates and nitrites at low and medium scales.
Front Cover: Molecular Engineering of Zinc‐Porphyrin Sensitisers for p‐Type Dye‐Sensitised Solar Cells (ChemPlusChem 7/2018)
Publisher: Wiley
Date: 14-06-2018
Catalytic condensation of glycolaldehyde and glyceraldehyde with formaldehyde in neutral and weakly alkaline aqueous media: Kinetics and mechanism
Publisher: Pleiades Publishing Ltd
Date: 03-2009
Stable and Efficient Lithium Metal Anode Cycling through Understanding the Effects of Electrolyte Composition and Electrode Preconditioning
Publisher: American Chemical Society (ACS)
Date: 23-12-2021
Metallic Inverse Opal Frameworks as Catalyst Supports for High‐Performance Water Electrooxidation
Publisher: Wiley
Date: 23-09-2022
Abstract: High intrinsic activity of oxygen evolution reaction (OER) catalysts is often limited by their low electrical conductivity. To address this, we introduce copper inverse opal (IO) frameworks offering a well‐developed network of interconnected pores as highly conductive high‐surface‐area supports for thin catalytic coatings, for ex le, the extremely active but poorly conducting nickel‐iron layered double hydroxides (NiFe LDH). Such composites exhibit significantly higher OER activity in 1 m KOH than NiFe LDH supported on a flat substrate or deposited as inverse opals. The NiFe LDH/Cu IO catalyst enables oxygen evolution rates of 100 mA cm −2 (727±4 A g catalyst −1 ) at an overpotential of 0.305±0.003 V with a Tafel slope of 0.044±0.002 V dec −1 . This high performance is achieved with 2.2±0.4 μm catalyst layers, suggesting compatibility of the inverse‐opal‐supported catalysts with membrane electrolyzers, in contrast to similarly performing 10 3 ‐fold thicker electrodes based on foams and other substrates.
Limitations in Electrochemical Determination of Mass-Transport Parameters: Implications for Quantification of Electrode Kinetics Using Data Optimisation Methods
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH17241
Abstract: Voltammetric quantification of the electrode kinetics for the quasi-reversible reaction requires detailed experiment–theory comparisons. Ideally, predicted data derived from the theoretical model are fitted to the experimental data by adjusting the reversible potential (E0), heterogeneous electron transfer rate constant at E0 (k0), and charge transfer coefficient α, with mass-transport and other parameters exactly known. However, parameters relevant to mass transport that include electrode area (A), diffusion coefficient (D), and concentration (c), are usually subject to some uncertainty. Herein, we examine the consequences of having different combinations of errors present in A, D, and c in the estimation of E0, k0, and α on the basis of the a.c. (alternating current) voltammetric experiment–theory comparisons facilitated by the use of a computer-assisted parameter optimisation algorithm. In most cases, experimentally reasonable errors ( %) in the mass-transport parameters do not introduce significant errors in recovered E0, k0, and α values. However, a pernicious situation may emerge when a slight overestimation of A, D or c is included in the model and results in erroneous identification of a reversible redox process as a quasi-reversible one with a report of apparently quantifiable kinetic parameters k0 and α.
Formic acid electrooxidation over carbon-supported nanoparticles of non-stoichiometric palladium carbide
Publisher: Elsevier BV
Date: 11-2012
Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X‐Ray Spectroscopy
Publisher: Wiley
Date: 06-02-2019
Multiple Roles of Cobalt Pyrazol-Pyridine Complexes in High-Performing Perovskite Solar Cells
Publisher: American Chemical Society (ACS)
Date: 21-07-2019
DOI: 10.1021/ACS.JPCLETT.9B01783
Abstract: Chemical doping is a ubiquitously applied strategy to improve the charge-transfer and conductivity characteristics of spiro-OMeTAD, a hole-transporting material (HTM) used widely in solution-processed perovskite solar cells (PSCs). Cobalt(III) complexes are commonly employed HTM dopants, whose major role is to oxidize spiro-OMeTAD to provide
Inside Cover: Optimization of Titania Post‐Necking Treatment of TaON Photoanodes to Enhance Water‐Oxidation Activity under Visible‐Light Irradiation (ChemElectroChem 9/2015)
Publisher: Wiley
Date: 27-08-2015
Stable Acidic Water Oxidation with a Cobalt–Iron–Lead Oxide Catalyst Operating via a Cobalt‐Selective Self‐Healing Mechanism
Publisher: Wiley
Date: 15-06-2021
Abstract: The instability and expense of anodes for water electrolyzers with acidic electrolytes can be overcome through the implementation of a cobalt‐iron‐lead oxide electrocatalyst, [Co–Fe–Pb]O x , that is self‐healing in the presence of dissolved metal precursors. However, the latter requirement is pernicious for the membrane and especially the cathode half‐reaction since Pb 2+ and Fe 3+ precursors poison the state‐of‐the‐art platinum H 2 evolving catalyst. To address this, we demonstrate the invariably stable operation of [Co–Fe–Pb]O x in acidic solutions through a cobalt‐selective self‐healing mechanism without the addition of Pb 2+ and Fe 3+ and investigate the kinetics of the process. Soft X‐ray absorption spectroscopy reveals that low concentrations of Co 2+ in the solution stabilize the catalytically active Co(Fe) sites. The highly promising performance of this system is showcased by steady water electrooxidation at 80±1 °C and 10 mA cm −2 , using a flat electrode, at an overpotential of 0.56±0.01 V on a one‐week timescale.
A CoOxHy/β-NiOOH electrocatalyst for robust ammonia oxidation to nitrite and nitrate
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3GC01835K
Abstract: In this work, we describe a composite electrocatalyst for the electrooxidation of ammonia to nitrite and nitrate under ambient conditions as a step towards stable, practical materials for this process.
Enhancement of the photoelectrochemical water splitting by perovskite BiFeO3 via interfacial engineering
Publisher: Elsevier BV
Date: 05-2020
Hydrogen electrooxidation over palladium–gold alloy: Effect of pretreatment in ethylene on catalytic activity and CO tolerance
Publisher: Elsevier BV
Date: 08-2012
Electrochemically Induced Generation of Extraneous Nitrite and Ammonia in Organic Electrolyte Solutions During Nitrogen Reduction Experiments
Publisher: Wiley
Date: 30-03-2021
Abstract: Oxidised nitrogen species (NO x ) are recognised as a major source of false‐positive nitrogen reduction reaction (NRR) results. Even when addressed, NO x are commonly eradicated at the initial stages of the experiment only. The present work demonstrates the shortcomings of this approach through a scrutiny of the evolution of NH 3 , NO 2 − and NO 3 − during the reduction of N 2 ‐saturated acetonitrile solutions with an Fe‐modified electrode. Notwithstanding, thorough purification of the experimental setup, persistent evolution of NO 2 − during electroreduction was detected in solution and attributed to the pH increase at the electrode surface inducing the release of strongly adsorbed adventitious nitrite. This species could be then reduced to NH 3 , while the rate of the NRR was unmeasurably low, as confirmed by 15 N 2 reduction experiments. This effect of the electrochemically induced changes in pH has not been previously discussed in nonaqueous NRR, which is arguably the only effective means for the N 2 electroreduction to NH 3 . This work also demonstrates that CH 3 CN might present a suitable solvent for the NRR if a genuinely active catalyst that operates at reasonable overpotentials becomes available.
On the Effect of Cu on the Activity of Carbon Supported Ni Nanoparticles for Hydrogen Electrode Reactions in Alkaline Medium
Publisher: Springer Science and Business Media LLC
Date: 21-09-2015
Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme
Publisher: Proceedings of the National Academy of Sciences
Date: 11-11-2015
Abstract: The mononuclear Mo enzymes are ubiquitous throughout life, and the notion that their activity arises from Mo(VI/V/IV) redox cycling is a central dogma of bioinorganic chemistry. We prove that YedY, a structurally simple mononuclear Mo enzyme, operates via a strikingly different mechanism: the catalytically active state is generated from addition of three electrons and three protons to the Mo(V) form of the enzyme, suggesting for the first time (to our knowledge) that organic-ligand–based electron transfer reactions at the pyranopterin play a role in catalysis. We showcase Fourier-transformed alternating-current voltammetry as a technique with powerful utility in metalloenzyme studies, allowing the simultaneous measurement of redox catalysis and the underlying electron transfer reactions.
Electrodeposited Pd Sub-Monolayers on Carbon-Supported Au Particles of Few Nanometers in Size: Electrocatalytic Activity for Hydrogen Oxidation and CO Tolerance Vs. Pd Coverage
Publisher: Springer Science and Business Media LLC
Date: 25-02-2012
Diammonium and Monoammonium Mixed‐Organic‐Cation Perovskites for High Performance Solar Cells with Improved Stability
Publisher: Wiley
Date: 23-05-2017
High‐Temperature One‐Step Synthesis of Efficient Nanostructured Bismuth Vanadate Photoanodes for Water Oxidation
Publisher: Wiley
Date: 24-04-2019
2,6-Diiminopyridine complexes of group 2 metals: synthesis, characterisation and redox behaviour
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0DT01278E
Abstract: Electrochemical studies suggest the redox active complexes may prove useful as soluble reducing agents.
The Observation of Dianions Generated by Electrochemical Reduction of trans-Stilbenes in Ionic Liquids at Room Temperature
Publisher: American Chemical Society (ACS)
Date: 28-05-2013
DOI: 10.1021/AC400915Z
Abstract: Three highly aprotic bis(trifluoromethylsulfonyl)amide (NTf2(-)) based ionic liquids (ILs) containing the cations trihexyl(tetradecyl)phosphonium (P6,6,6,14(+)), N-butyl-N-methylpyrrolidinium (Pyrr4,1(+)), and (trimethylamine)(dimethylethylammine)dihydroborate ((N111)(N112)BH2(+)) have been examined as media for room temperature voltammetric detection of highly basic stilbene dianions electrochemically generated by the reduction of trans-stilbene (t-Stb) and its derivatives (4-methoxy-, 2-methoxy-, 4,4'-dimethyl-, and 4-chloromethyl-). Transient and steady-state data in the ILs were compared with results obtained in the molecular solvent acetonitrile. In all media examined, the t-Stb(0/•-) process is chemically and electrochemically reversible with a heterogeneous charge transfer rate constant in CH3CN of 1.5 cm s(-1), as determined by Fourier transformed AC voltammetry. However, further reduction to the dianion was always irreversible in this molecular but weakly acidic solvent. On the other hand, a substantial level of chemical reversibility for the reduction of t-Stb(•-) to t-Stb(2-) on the time scale of cyclic voltammetry is achieved when the concentration of trans-stilbene, [t-Stb], appreciably exceeds the concentration of adventitious water or other proton sources. In particular, these conditions are met when [t-Stb] ≥ 0.1 M in thoroughly dehydrated and purified ILs, while in the presence of CH3CN, t-Stb(2-) still suffers fast irreversible protonation under these stilbene concentration conditions. The E0/•-(0) values (vs Fc(0/+)) for substituted trans-stilbenes in acetonitrile and (N111)(N112)BH2-NTf2 do not differ substantially, nor do the E0/•-(0) and E•-/2-(0) differences or other aspects of the voltammetric behavior.
Electroreduction of Nitrates, Nitrites, and Gaseous Nitrogen Oxides: A Potential Source of Ammonia in Dinitrogen Reduction Studies
Publisher: American Chemical Society (ACS)
Date: 22-05-2020
Cover Feature: Probing Electron Transfer in the Manganese‐Oxide‐Forming MnxEFG Protein Complex using Fourier Transformed AC Voltammetry: Understanding the Oxidative Priming Effect (ChemElectroChem 6/2
Publisher: Wiley
Date: 21-02-2018
Nanoscale TiO2 Coatings Improve the Stability of an Earth-Abundant Cobalt Oxide Catalyst during Acidic Water Oxidation
Publisher: American Chemical Society (ACS)
Date: 15-07-2022
Molecular Engineering of Zinc‐Porphyrin Sensitisers for p‐Type Dye‐Sensitised Solar Cells
Publisher: Wiley
Date: 02-05-2017
Abstract: Design of novel efficient light-harvesters for p-type dye-sensitised solar cells (DSSCs) is indispensable for further advances in this photovoltaic technology. Herein, a novel D-π-A (D=donor, π=π-conjugated linker, A=acceptor) sensitiser, ZnP1, featuring an electron acceptor, perylenemonoimide (PMI), connected to an electron donor, di(p-carboxyphenyl)amine (DCPA), through fluorene and a zinc(II) porphyrin with alkyl chains as a π-conjugated bridge is introduced. Spectroscopic and electrochemical characterisation of this dye along with a newly synthesised PMI-free reference dye ZnP0 has been undertaken to demonstrate strong electron coupling between the DCPA donor and PMI acceptor subunits through the porphyrin ring in ZnP1, which redshifts the light absorption onset to the near-IR region. When integrated into p-DSSCs based on a mesoporous nickel(II) oxide semiconductor electrode and a tris(acetylacetonato) iron(III/II) redox mediator, ZnP1 exhibits an onset of the incident photon-to-current conversion efficiency at 800 nm and a power conversion efficiency of up to 0.92 % under simulated 100 mW cm
Concluding remarks: Sustainable nitrogen activation – are we there yet?
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3FD00087G
Abstract: In this paper we set out to provide an overview of different approaches to activation of dinitrogen and their commonalities.
A Critical Review of the Methods Available for Quantitative Evaluation of Electrode Kinetics at Stationary Macrodisk Electrodes
Publisher: Wiley
Date: 24-06-2014
Studies on the Nuances of the Electrochemically Induced Room Temperature Isomerization of cis-Stilbene in Acetonitrile and Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 10-03-2014
DOI: 10.1021/JP500786J
Abstract: Electrochemical reduction of cis-stilbene occurs by two well-resolved one-electron reduction steps in acetonitrile with (n-Bu)4NPF6 as the supporting electrolyte and in N-butyl-N-methylpyrrolidinium (Pyrr1,4(+)) and (trimethylamine)(dimethylethylamine)-dihydroborate bis(trifluoromethylsulfonyl)amide (NTf2(-)) ionic liquids (ILs). Mechanistic details of the electroreduction have been probed by dc and Fourier transformed ac voltammetry, simulation of the voltammetry, bulk electrolysis, and EPR spectroscopy. The first one-electron reduction induces fast cis to trans isomerization in CH3CN and ILs, most likely occurring via disproportionation of cis-stilbene radical anions and fast transformation of the cis-dianion to the trans-configuration. The second reduction process is chemically irreversible in CH3CN due to protonation of the dianion but chemically reversible in highly aprotic ILs under high cis-stilbene concentration conditions. Increase of the (n-Bu)4NPF6 supporting electrolyte concentration (0.01-1.0 M) in CH3CN induces substantial positive shifts in the potentials for reduction of cis-stilbene, consistent with strong ion pairing of the anion radical and dianion with (n-Bu)4N(+). However, protection by ion pairing against protonation of the stilbene dianions or electrochemically induced cis-trans-stilbene isomerization is not achieved. Differences in electrode kinetics and reversible potentials for cis-stilbene(0/•-) and trans-stilbene(0/•-) processes are less pronounced in the Pyrr1,4-NTf2 ionic liquid than in the molecular solvent acetonitrile.
Photo-electrocatalytic hydrogen generation at dye-sensitised electrodes functionalised with a heterogeneous metal catalyst
Publisher: Elsevier BV
Date: 11-2016
Highly Dispersed Cobalt Oxide on TaON as Efficient Photoanodes for Long-Term Solar Water Splitting
Publisher: American Chemical Society (ACS)
Date: 28-04-2016
Fourier transformed alternating current voltammetry in electromaterials research: Direct visualisation of important underlying electron transfer processes
Publisher: Elsevier BV
Date: 08-2018
Electrocorrosion properties of multiwall carbon nanotubes
Publisher: Wiley
Date: 13-09-2010
Abstract: The electrochemical corrosion properties of a set of multiwalled carbon nanotubes (MWCNT) with different average diameters (〈 d 〉 = 7–22 nm) and conventional carbon black Vulcan XC‐72 were studied potentiostatically in 2 M H 2 SO 4 at 80 °C. Effects of grinding and high‐temperature treatment (2800 °C) in inert gas on the corrosion stability of MWCNT were also examined. Excitation of MWCNTs with large 〈 d 〉 in activator mill results in local disruption of the fine structure of the NTs and increase of the corrosion current densities. No rupture and changes of the corrosion behaviour occur for MWCNTs with lower 〈 d 〉 after grinding. High‐temperature treatment of MWCNTs leads to removal of amorphous carbon and defects from the surface of the materials and results in drastic decrease of the reactivity of the surface of the materials towards electrocorrosion. The A BET ‐weighted corrosion current densities of the MWCNTs are significantly lower than that of conventional XC‐72 material evidencing of their higher stability towards electrocorrosion.
Engineering High Energy Density Sodium Battery Anodes for Improved Cycling with Superconcentrated Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 30-01-2020
DOI: 10.26434/CHEMRXIV.11691714.V2
Abstract: Non-uniform metal deposition and dendrite formation in high density energy storage devices reduces the efficiency, safety, and life of batteries with metal anodes. Superconcentrated ionic liquid (IL) electrolytes (e.g. 1:1 IL:alkali ion) coupled with anode preconditioning at more negative potentials can completely mitigate these issues, and therefore revolutionize high density energy storage devices. However, the mechanisms by which very high salt concentration and preconditioning potential enable uniform metal deposition and prevent dendrite formation at the metal anode during cycling are poorly understood, and therefore not optimized. Here, we use atomic-force microscopy and molecular dynamics simulations to unravel the influence of these factors on the interface chemistry in a sodium electrolyte, demonstrating how a molten salt like structure at the electrode surface results in dendrite free metal cycling at higher rates. Such a structure will support the formation of a more favorable solid electrolyte interphase (SEI) accepted as being a critical factor in stable battery cycling. This new understanding will enable engineering of efficient anode electrodes by tuning interfacial nanostructure via salt concentration and high voltage preconditioning.
Photo-assisted electrodeposition of manganese oxide on TaON anodes: effect on water photooxidation capacity under visible light irradiation
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CY01432H
Abstract: Photo-assisted deposition of MnO x on the TaON anodes enhances activity and stability during water photooxidation.
Competition between metal-catalysed electroreduction of dinitrogen, protons, and nitrogen oxides: a DFT perspective
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2CY00389A
Abstract: Metals are common electrocatalysts for N 2 -into-NH 3 reduction. In protic media, H + competes with N 2 to be reduced into H 2 . NO x , common air pollutants, are predicted to be more selectively converted into NH 3 than N 2 , and even more than H + into H 2 .
Stable Acidic Water Oxidation with a Cobalt–Iron–Lead Oxide Catalyst Operating via a Cobalt‐Selective Self‐Healing Mechanism
Publisher: Wiley
Date: 15-06-2021
Abstract: The instability and expense of anodes for water electrolyzers with acidic electrolytes can be overcome through the implementation of a cobalt‐iron‐lead oxide electrocatalyst, [Co–Fe–Pb]O x , that is self‐healing in the presence of dissolved metal precursors. However, the latter requirement is pernicious for the membrane and especially the cathode half‐reaction since Pb 2+ and Fe 3+ precursors poison the state‐of‐the‐art platinum H 2 evolving catalyst. To address this, we demonstrate the invariably stable operation of [Co–Fe–Pb]O x in acidic solutions through a cobalt‐selective self‐healing mechanism without the addition of Pb 2+ and Fe 3+ and investigate the kinetics of the process. Soft X‐ray absorption spectroscopy reveals that low concentrations of Co 2+ in the solution stabilize the catalytically active Co(Fe) sites. The highly promising performance of this system is showcased by steady water electrooxidation at 80±1 °C and 10 mA cm −2 , using a flat electrode, at an overpotential of 0.56±0.01 V on a one‐week timescale.
Catalytic Formation of Monosaccharides: From the Formose Reaction towards Selective Synthesis
Publisher: Wiley
Date: 16-06-2014
Abstract: The formose reaction (FR) has been long the focus of intensive investigations as a simple method for synthesis of complex biologically important monosaccharides and other sugar-like molecules from the simplest organic substrate-formaldehyde. The fundamental importance of the FR is predominantly connected with the ascertainment of plausible scenarios of chemical evolution which could have occurred on the prebiotic Earth to produce the very first molecules of carbohydrates, amino- and nucleic acids, as well as other vitally important substances. The practical importance of studies on the FR is the elaboration of catalytic methods for the synthesis of rare and non-natural monosaccharides and polyols. This Minireview considers the FR from the point of view of chemists working in the field of catalysis with emphasis on the mechanisms of numerous parallel and consequent catalytic transformations that take place during the FR. Based on its kinetics, the FR may be considered as a non-radical chain process with degenerate branching. The Minireview also considers different approaches to the control of selectivity of carbohydrate synthesis from formaldehyde and lower monosaccharides.
Untangling Complex Redox Chemistry in Zeolitic Imidazolate Frameworks Using Fourier Transformed Alternating Current Voltammetry
Publisher: American Chemical Society (ACS)
Date: 18-09-2017
DOI: 10.1021/ACS.ANALCHEM.7B01224
Abstract: Two zeolitic imidazolate frameworks, ZIF-67 and ZIF-8, were interrogated for their redox properties using Fourier transformed alternating current voltammetry, which revealed that the 2-methylimidazolate ligand is responsible for multiple redox transformations. Further insight was gained by employing discrete tetrahedral complexes, [M(DMIM)
Characterization of Energy Materials with X-ray Absorption Spectroscopy─Advantages, Challenges, and Opportunities
Publisher: American Chemical Society (ACS)
Date: 15-02-2022
Electrocatalytic Oxidation of Hydrogen as an Anode Reaction for the Li-Mediated N2 Reduction to Ammonia
Publisher: American Chemical Society (ACS)
Date: 16-04-2022
Photoinduced catalytic synthesis of biologically important metabolites from formaldehyde and ammonia under plausible “prebiotic” conditions
Publisher: Elsevier BV
Date: 08-2011
Radical doped hole transporting material for high-efficiency and thermostable perovskite solar cells
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2TA01096H
Abstract: We report a new p-doping strategy for organic semiconductors with free radicals that enable reproducible enhancement in the conductivity and tuning of the work function. High efficiency and thermo-stability perovskite solar cells were achieved.
(Invited) Critical Assessment of Aqueous Electrochemical Synthesis of NH3: N2 Reduction Versus NOx Reduction
Publisher: The Electrochemical Society
Date: 05-2020
DOI: 10.1149/MA2020-01411820MTGABS
Abstract: As an ideal alternative to the Haber-Bosch process, the renewable energy-powered electrochemical N 2 reduction to NH 3 is a promising approach since the electrochemical reduction can occur under mild conditions only water and N 2 are consumed during overall nitrogen reduction reaction.[1] Recently, there have been many efforts devoted to developing electrocatalysts for energy efficient NH 3 synthesis from N 2 however, it remains very challenging due to the thermodynamic inertness of the dinitrogen triple bond. The electrochemical reduction of N 2 to NH 3 (the nitrogen reduction reaction “NRR”) requires the consecutive six-electron roton transfer reactions to proceed and this leads to the sluggish kinetics. In addition, the competitive hydrogen evolution reaction (HER, Eº = 0 V vs. RHE) can concomitantly occur at similar potentials to the NRR (Eº = 0.092 V vs. RHE), resulting in both low faradaic efficiency ( 10 %) and low yield rates ( 10 -10 mole cm -2 s -1 ) for NH 3 synthesis. Such poor conversion efficiency and yield rates also make it more difficult to confirm the origins of the NH 3 production, ie whether it genuinely comes from electrocatalytic NRR, as opposed to some other readily reducible N-containing contaminants (NO, NO 2 , N 2 O and doped N atoms in the materials) under reducing potentials. Herein, we investigate the catalytic nature of nitrogen reduction reaction on three different types of preeminent electrocatalysts from the literature (bismuth, gold and N-doped carbon)[2, 3] using a rigorous experimental protocol developed by our group.[4] It is demonstrated that all of the catalysts are essentially inactive (below LOD) towards dinitrogen reduction to NH 3 . We also systematically unravel the origins of the reported activity, showing that other N-containing species, particularly ionic/gaseous NO x or doped N atoms in the materials, are strongly active reactants towards NH 3 production. Our presentation will conclude with a summary of the critical contaminants leading to false-positive NRR and also provide further protocol recommendations to avoid this outcome. [1] S.L. Foster, S.I.P. Bakovic, R.D. Duda, S. Maheshwari, R.D. Milton, S.D. Minteer, M.J. Janik, J.N. Renner, L.F. Greenlee, Nature Catalysis, 1 (2018) 490-500. [2] Y.-C. Hao, Y. Guo, L.-W. Chen, M. Shu, X.-Y. Wang, T.-A. Bu, W.-Y. Gao, N. Zhang, X. Su, X. Feng, Nature Catalysis, 2 (2019) 448. [3] Y. Liu, Y. Su, X. Quan, X. Fan, S. Chen, H. Yu, H. Zhao, Y. Zhang, J. Zhao, ACS Catalysis, 8 (2018) 1186-1191. [4] B.H.R. Suryanto, H.-L. Du, D. Wang, J. Chen, A.N. Simonov, D.R. MacFarlane, Nature Catalysis, 2 (2019) 290-296.
Durable Electrooxidation of Acidic Water Catalysed by a Cobalt‐Bismuth‐based Oxide Composite: An Unexpected Role of the F‐doped SnO2 Substrate
Publisher: Wiley
Date: 26-04-2022
Abstract: Aiming to design a catalyst for stable electrooxidation of water at low pH, the present work explores the properties and structural features of electrodeposited composite oxides based on Bi and Co, which were anticipated to provide stability and catalytical activity, respectively. Materials deposited as very thin ( ca 50 nm) films on F‐doped SnO 2 (FTO) substrate do not initially exhibit high activity in 0.1 M H 2 SO 4 , but are activated during operation through the electrooxidatively‐induced enrichment of the catalytic surface with Co and Sn oxides. The latter originate from the FTO support and are identified as an important component of the catalyst through control experiments with a Sn‐free substrate and with Sn 2+ intentionally added at the electrodeposition stage. A distinctive feature of the Co−Bi−Sn‐based electrocatalyst is the slow but persistent improvement in the activity during operation in 0.1 M H 2 SO 4 at both ambient and elevated (60 °C) temperatures, which contrasts with the continuously degrading behaviour of state‐of‐the‐art oxygen evolution catalysts at low pH. This is demonstrated by 9‐day‐long galvanostatic tests at 10 mA cm −2 , during which the Co−Bi−Sn‐based thin film catalyst shows no degradation and sustains stable water oxidation at ca 1.9 V vs . reversible hydrogen electrode. The effects of tin leaching from the support detected herein might have implications to other acidic water oxidation catalysts supported on high‐surface area doped SnO 2 materials.
Enhancement of the intrinsic light harvesting capacity of Cs2AgBiBr6double perovskiteviamodification with sulphide
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9TA10422D
Abstract: Light harvesting capacity of caesium silver bismuth bromide double perovskite need to be enhanced to render this non-toxic and thermodynamically stable material suitable for photovoltaic applications, for ex le as a top layer in tandem solar cells.
An integrated instrumental and theoretical approach to quantitative electrode kinetic studies based on large amplitude Fourier transformed a.c. voltammetry: A mini review
Publisher: Elsevier BV
Date: 08-2015
Highly dispersed and disordered nickel-iron layered hydroxides and sulphides: Robust and high-activity water oxidation catalysts
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8SE00129D
Abstract: A rapid low-temperature microwave-assisted synthesis of nickel(iron) layered hydroxides and sulphides that exhibit robust catalytic activity for electrooxidation of alkaline water is introduced.
Exploring the oxygen evolution electrocatalysis of an amine-based cobalt metal–organic framework
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2ME00259K
Abstract: The interpenetrating 2D-sheet framework of Co-TMBT-MOF cast onto nickel foam is used as a pre-catalyst to generate an efficient OER catalyst with low overpotential.
Performance of Ba-containing catalysts in the transesterification reaction of rapeseed oil with methanol under flow conditions
Publisher: Elsevier BV
Date: 02-2012
Optimization of Titania Post‐Necking Treatment of TaON Photoanodes to Enhance Water‐Oxidation Activity under Visible‐Light Irradiation
Publisher: Wiley
Date: 02-07-2015
Parameterization of Water Electrooxidation Catalyzed by Metal Oxides Using Fourier Transformed Alternating Current Voltammetry
Publisher: American Chemical Society (ACS)
Date: 02-12-2016
DOI: 10.1021/JACS.6B10304
Abstract: Detection and quantification of redox transformations involved in water oxidation electrocatalysis is often not possible using conventional techniques. Herein, use of large litude Fourier transformed ac voltammetry and comprehensive analysis of the higher harmonics has enabled us to access the redox processes responsible for catalysis. An examination of the voltammetric data for water oxidation in borate buffered solutions (pH 9.2) at electrodes functionalized with systematically varied low loadings of cobalt (CoO
Origin of Photoelectrochemical Generation of Dihydrogen by a Dye-Sensitized Photocathode without an Intentionally Introduced Catalyst
Publisher: American Chemical Society (ACS)
Date: 10-11-2017
Enhanced catalytic activity for hydrogen electrooxidation and CO tolerance of carbon-supported non-stoichiometric palladium carbides
Publisher: Elsevier BV
Date: 02-2012
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