ORCID Profile
0000-0003-1329-4290
Current Organisation
University of Adelaide
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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.
Nanomaterials | Functional Materials | Theory and Design of Materials | Nanotechnology | Nanoscale characterisation | Nanotechnology | Materials Engineering | Carbon sequestration science | Nanomaterials | Functional materials | Photonics optoelectronics and optical communications | Electrochemical energy storage and conversion
Renewable Energy not elsewhere classified | Expanding Knowledge in the Chemical Sciences | Expanding Knowledge in Engineering |
Publisher: Wiley
Date: 18-08-2023
Abstract: As a burgeoning electrolyte system, eutectic electrolytes based on ZnCl 2 /Zn(CF 3 SO 3 ) 2 /Zn(TFSI) 2 have been widely proposed in advanced Zn‐I 2 batteries however, safety and cost concerns significantly limit their applications. Here, we report new‐type ZnSO 4 ‐based eutectic electrolytes that are both safe and cost‐effective. Their universality is evident in various solvents of polyhydric alcohols, in which multiple −OH groups not only involve in Zn 2+ solvation but also interact with water, resulting in the high stability of electrolytes. Taking propylene glycol‐based hydrated eutectic electrolyte as an ex le, it features significant advantages in non‐flammability and low price that is /200 cost of Zn(CF 3 SO 3 ) 2 /Zn(TFSI) 2 ‐based eutectic electrolytes. Moreover, its effectiveness in confining the shuttle effects of I 2 cathode and side reactions of Zn anodes is evidenced, resulting in Zn‐I 2 cells with high reversibility at 1 C and 91.4 % capacity remaining under 20 C. After scaling up to the pouch cell with a record mass loading of 33.3 mg cm −2 , super‐high‐capacity retention of 96.7 % is achieved after 500 cycles, which exceeds other aqueous counterparts. This work significantly broadens the eutectic electrolyte family for advanced Zn battery design.
Publisher: Wiley
Date: 02-2014
Abstract: Carbon nanotubes with specific nitrogen doping are proposed for controllable, highly selective, and reversible CO2 capture. Using density functional theory incorporating long-range dispersion corrections, we investigated the adsorption behavior of CO2 on (7,7) single-walled carbon nanotubes (CNTs) with several nitrogen doping configurations and varying charge states. Pyridinic-nitrogen incorporation in CNTs is found to induce an increasing CO2 adsorption strength with electron injecting, leading to a highly selective CO2 adsorption in comparison with N2 . This functionality could induce intrinsically reversible CO2 adsorption as capture/release can be controlled by switching the charge carrying state of the system on/off. This phenomenon is verified for a number of different models and theoretical methods, with clear ramifications for the possibility of implementation with a broader class of graphene-based materials. A scheme for the implementation of this remarkable reversible electrocatalytic CO2 -capture phenomenon is considered.
Publisher: Wiley
Date: 02-08-2021
Abstract: The shuttling of soluble lithium polysulfides between the electrodes leads to serious capacity fading and excess use of electrolyte, which severely bottlenecks practical use of Li‐S batteries. Here, selective catalysis is proposed as a fundamental remedy for the consecutive solid‐liquid‐solid sulfur redox reactions. The proof‐of‐concept Indium (In)‐based catalyst targetedly decelerates the solid‐liquid conversion, dissolution of elemental sulfur to polysulfides, while accelerates the liquid‐solid conversion, deposition of polysulfides into insoluble Li 2 S, which basically reduces accumulation of polysulfides in electrolyte, finally inhibiting the shuttle effect. The selective catalysis is revealed, experimentally and theoretically, by changes of activation energies and kinetic currents, modified reaction pathway together with the probed dynamically changing catalyst (LiInS 2 catalyst), and gradual deactivation of the In‐based catalyst. The In‐based battery works steadily over 1000 cycles at 4.0 C and yields an initial areal capacity up to 9.4 mAh cm −2 with a sulfur loading of ≈9.0 mg cm −2 .
Publisher: Springer Science and Business Media LLC
Date: 12-09-2016
Publisher: American Chemical Society (ACS)
Date: 12-2017
DOI: 10.1021/JACS.7B10817
Abstract: A major impediment to the electrocatalytic CO
Publisher: Wiley
Date: 14-09-2018
Publisher: American Chemical Society (ACS)
Date: 04-08-2022
DOI: 10.1021/JACS.2C06820
Abstract: An ere-level current density of CO
Publisher: American Chemical Society (ACS)
Date: 28-01-2022
DOI: 10.1021/JACS.1C12212
Abstract: Copper is the only metal catalyst that can perform the electrocatalytic CO
Publisher: Elsevier BV
Date: 08-2022
Publisher: Wiley
Date: 07-04-2020
Abstract: Single‐atom catalysts (SACs) have great potential in electrocatalysis. Their performance can be rationally optimized by tailoring the metal atoms, adjacent coordinative dopants, and metal loading. However, doing so is still a great challenge because of the limited synthesis approach and insufficient understanding of the structure–property relationships. Herein, we report a new kind of Mo SAC with a unique O,S coordination and a high metal loading over 10 wt %. The isolation and local environment was identified by high‐angle annular dark‐field scanning transmission electron microscopy and extended X‐ray absorption fine structure. The SACs catalyze the oxygen reduction reaction (ORR) via a 2 e − pathway with a high H 2 O 2 selectivity of over 95 % in 0.10 m KOH. The critical role of the Mo single atoms and the coordination structure was revealed by both electrochemical tests and theoretical calculations.
Publisher: Elsevier BV
Date: 10-2023
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8TA05245J
Abstract: This review highlights the intriguing physicochemical and structural versatility of PDA-based nanomaterials and their energy conversion and storage applications.
Publisher: Springer Science and Business Media LLC
Date: 27-03-2023
Publisher: American Chemical Society (ACS)
Date: 23-04-2021
DOI: 10.1021/JACS.1C02379
Publisher: Wiley
Date: 11-07-2023
Abstract: In the past, the design of efficient electrocatalyst materials for alkaline hydrogen evolution reaction (HER) was mostly focused on tuning the adsorption properties of reaction intermediates. A recent breakthrough shows that the performance can be improved by manipulating water structure at the electrode‐electrolyte interface using atomically localized electric fields. The new approach was realized by using IrRu dizygotic single‐atom sites and led to a significantly accelerated water dissociation and an overall improved alkaline HER performance. Supported by extensive data from advanced modeling, characterization, and electrochemical measurements, the work delivers an intricate examination of the interaction between water molecules and the catalyst surface, thereby enriching our understanding of water dissociation kinetics and offering new insights to boost overall alkaline HER efficiency.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CC04231H
Abstract: Simultaneous oxidation state engineering of Co, N and S for cobalt nitride and sulfide electrocatalysts is demonstrated to facilitate intermediate desorption for OER and HER, leading to efficient overall water electrolysis in a neutral buffer electrolyte.
Publisher: Wiley
Date: 24-11-2020
Publisher: American Chemical Society (ACS)
Date: 05-2014
DOI: 10.1021/NN501434A
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0TA00967A
Abstract: Dual-shell structured sodium titanate cubes with oxygen vacancies are rationally designed and synthesized. Various state-of-the-art approaches offer understandings of its enhanced ion kinetics as an anode for sodium-ion battery..
Publisher: Elsevier BV
Date: 11-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0TA03991H
Abstract: Designed metal-free electrocatalysts combined with compressive strain can efficiently convert CO to valuable chemicals and fuels.
Publisher: Elsevier BV
Date: 03-2022
Publisher: Wiley
Date: 16-10-2021
Publisher: Elsevier BV
Date: 09-2019
Publisher: American Chemical Society (ACS)
Date: 07-04-2021
Abstract: Human ferritin is regarded as an attractive and promising vaccine platform because of its uniform structure, good plasticity, and desirable thermal and chemical stabilities. Besides, it is biocompatible and presumed safe when used as a vaccine carrier. However, there is a lack of knowledge of how different antigen insertion sites on the ferritin nanocage impact the resulting protein stability and performance. To address this question, we selected Epstein-Barr nuclear antigen 1 as a model epitope and fused it at the DNA level with different insertion sites, namely, the N- and C-termini of ferritin, to engineer proteins E1F1 and F1E1, respectively. Protein properties including hydrophobicity and thermal, pH, and chemical stability were investigated both by molecular dynamics (MD) simulation and by experiments. Both methods demonstrate that the insertion site plays an important role in protein properties. The C-terminus insertion (F1E1) leads to a less hydrophobic surface and more tolerance to the external influence of high temperature, pH, and high concentration of chemical denaturants compared to N-terminus insertion (E1F1). Simulated protein hydrophobicity and thermal stability by MD were in high accordance with experimental results. Thus, MD simulation can be used as a valuable tool to engineer nanovaccine candidates, cutting down costs by reducing the experimental effort and accelerating vaccine design.
Publisher: Wiley
Date: 14-07-2015
Abstract: Over the past decade, developing advanced catalysts for clean and sustainable energy conversion has been subject to extensive study. Driven by great advances achieved in computational quantum chemistry, synthetic chemistry, and material characterization techniques, the preferential design of a most-appropriate catalyst for a specific electrochemical reaction is possible. Here a universal process for the design of high-performance carbon-based electrocatalysts, by engineering their intrinsic electronic structures and physical structures to promote their extrinsic activities for different energy conversion reactions, is presented and summarized. How such a powerful strategy may aid the discovery of more electrocatalysts for a sustainable and clean energy infrastructure is discussed.
Publisher: American Chemical Society (ACS)
Date: 27-06-2022
Publisher: Wiley
Date: 30-09-2019
Publisher: Springer Science and Business Media LLC
Date: 30-10-2022
DOI: 10.1038/S41467-022-34303-8
Abstract: Rechargeable aqueous metal||I 2 electrochemical energy storage systems are a cost-effective alternative to conventional transition-metal-based batteries for grid energy storage. However, the growth of unfavorable metallic deposition and the irreversible formation of electrochemically inactive by-products at the negative electrode during cycling hinder their development. To circumvent these drawbacks, herein we propose 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) as negative electrode active material and a saturated mixed KCl/I 2 aqueous electrolyte solution. The use of these components allows for exploiting two sequential reversible electrochemical reactions in a single cell. Indeed, when they are tested in combination with an active carbon-enveloped I 2 electrode in a glass cell configuration, we report an initial specific discharge capacity of 900 mAh g −1 (electrode mass of iodine only) and an average cell discharge voltage of 1.25 V at 40 A g −1 and 25 $$\pm$$ ± 1 °C. Finally, we also report the assembly and testing of a PTCDI|KCl-I 2 |carbon paper multilayer pouch cell prototype with a discharge capacity retention of about 70% after 900 cycles at 80 mA and 25 $$\pm$$ ± 1 °C.
Publisher: Wiley
Date: 15-08-2012
Abstract: Replacing precious and nondurable Pt catalysts with cheap and commercially available materials to facilitate sluggish cathodic oxygen reduction reaction (ORR) is a key issue in the development of fuel cell technology. The recently developed cost effective and highly stable metal-free catalysts reveal comparable catalytic activity and significantly better fuel tolerance than that of current Pt-based catalysts therefore, they can serve as feasible Pt alternatives for the next generation of ORR electrocatalysts. Their promising electrocatalytic properties and acceptable costs greatly promote the R&D of fuel cell technology. This review provides an overview of recent advances in state-of-the-art nanostructured metal-free electrocatalysts including nitrogen-doped carbons, graphitic-carbon nitride (g-C(3) N(4) )-based hybrids, and 2D graphene-based materials. A special emphasis is placed on the molecular design of these electrocatalysts, origin of their electrochemical reactivity, and ORR pathways. Finally, some perspectives are highlighted on the development of more efficient ORR electrocatalysts featuring high stability, low cost, and enhanced performance, which are the key factors to accelerate the commercialization of fuel cell technology.
Publisher: Springer Science and Business Media LLC
Date: 10-12-2021
DOI: 10.1038/S41467-021-27551-7
Abstract: Metal sulfides electrodeposition in sulfur cathodes mitigates the shuttle effect of polysulfides to achieve high Coulombic efficiency in secondary metal-sulfur batteries. However, fundamental understanding of metal sulfides electrodeposition and kinetics mechanism remains limited. Here using room-temperature sodium-sulfur cells as a model system, we report a Mo 5 N 6 cathode material that enables efficient Na 2 S electrodeposition to achieve an initial discharge capacity of 512 mAh g −1 at a specific current of 1 675 mA g −1 , and a final discharge capacity of 186 mAh g −1 after 10,000 cycles. Combined analyses from synchrotron-based spectroscopic characterizations, electrochemical kinetics measurements and density functional theory computations confirm that the high d -band position results in a low Na 2 S 2 dissociation free energy for Mo 5 N 6 . This promotes Na 2 S electrodeposition, and thereby favours long-term cell cycling performance.
Publisher: American Chemical Society (ACS)
Date: 03-01-2020
DOI: 10.1021/JACS.9B11774
Abstract: Lean-electrolyte conditions are highly pursued for practical lithium (Li) metal batteries. The previous studies on the Li metal anodes, in general, exhibited good stability with a large excess of electrolyte. However, the targeted design of Li hosts under relatively low electrolyte conditions has been rarely studied so far. Herein, we have shown that electrolyte consumption severely affects the cycling stability of Li metal anode. Considering carbon hosts as typical ex les, we innovatively employed in situ synchrotron X-ray diffraction, in situ Raman spectroscopy, and theoretical computations to obtain a better understanding of the Li nucleation/deposition processes. We also showed the usefulness of in situ electrochemical impedance spectra to analyze interfacial fluctuation at the Li/electrolyte interface, together with nuclear magnetic resonance data to quantify electrolyte consumption. We have found that uneven Li nucleation/deposition and the crack of surface-area-derived solid-electrolyte interface (SEI) layer both lead to a great consumption of electrolyte. Then, we suggested a design principle for Li host to overcome the electrolyte loss, that is, uneven growth of the Li structure and the crack of the SEI layer must be simultaneously controlled. As a proof of concept, we demonstrated the usefulness of a 3D low-surface-area defective graphene host (L-DG) to control Li nucleation/deposition and stabilize the SEI layer, contributing to a highly reversible Li plating/stripping. As a result, such a Li host can achieve stable cycles (e.g., 1.0 mAh cm
Publisher: American Chemical Society (ACS)
Date: 02-01-2020
Publisher: American Chemical Society (ACS)
Date: 27-02-2012
DOI: 10.1021/JA211637P
Abstract: Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long-range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C(3)N(4)) and electronically active graphene. We find an inhomogeneous planar substrate (g-C(3)N(4)) promotes electron-rich and hole-rich regions, i.e., forming a well-defined electron-hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C(3)N(4) substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C(3)N(4) interface opens a 70 meV gap in g-C(3)N(4)-supported graphene, a feature that can potentially allow overcoming the graphene's band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C(3)N(4) is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C(3)N(4) monolayer, the hybrid graphene/g-C(3)N(4) complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.
Publisher: Wiley
Date: 09-01-2023
Abstract: The design of heterogeneous catalysts is necessarily surface‐focused, generally achieved via optimization of adsorption energy and microkinetic modelling. A prerequisite is to ensure the adsorption energy is physically meaningful is the stable existence of the conceived active‐site structure on the surface. The development of improved understanding of the catalyst surface, however, is challenging practically because of the complex nature of dynamic surface formation and evolution under in‐situ reactions. We propose therefore data‐driven machine‐learning (ML) approaches as a solution. In this Minireview we summarize recent progress in using machine‐learning to search and predict (meta)stable structures, assist operando simulation under reaction conditions and micro‐environments, and critically analyze experimental characterization data. We conclude that ML will become the new norm to lower costs associated with discovery and design of optimal heterogeneous catalysts.
Publisher: Elsevier BV
Date: 09-2022
Publisher: Wiley
Date: 30-04-2021
Abstract: A constant energy supply is crucial for the exploration of deep‐sea extreme environments, and a self‐powered energy conversion device is ideal for this situation. Dissolved‐oxygen seawater batteries (SWBs) that generate electricity by reducing the dissolved oxygen are promising candidates but the ultralow oxygen concentration in deep sea limits the reaction kinetics. As a result, oxygenophilic electrocatalysts for lean‐oxygen conditions are urgently needed. A microwave heating method is reported that achieves the ultrafast synthesis of atomic dispersed FeNC catalyst (FeNgraphene (G)/carbon nanotube (CNT)), which possesses high activity and strong oxygenophilic interface between graphene and CNTs. DFT calculations and experimental results both show that the high oxygenophilicity is due to the double‐adsorption sites on the G/CNT interface, and the high activity FeN 4 active sites is caused by the charge separation. FeNG/CNT catalysts have an outstanding oxygen reduction reaction (ORR) performance in both O 2 ‐saturated alkaline medium and neutral seawater with half‐wave potentials ( E 1/2 ) of 0.929 and 0.704 V, respectively, far better than commercial Pt/C. A SWB shows excellent performance in lean‐oxygen seawater (≈0.4 mg L −1 ), with a discharge voltage of 1.18 V at 10 mA cm −2 . These results suggest a critical role for oxygenophilic catalyst specifically for SWBs under lean‐oxygen conditions.
Publisher: Wiley
Date: 04-02-2019
Abstract: Effective electrocatalysts are required for the CO
Publisher: American Chemical Society (ACS)
Date: 09-03-2012
DOI: 10.1021/JP211930A
Publisher: Elsevier BV
Date: 02-2020
Publisher: Wiley
Date: 18-11-2020
Abstract: The oule method provides a promising pathway towards the controllable synthesis of novel electrocatalysts for water electrolysis due to its straightforward manipulation of reaction conditions, accessible experimental design, and controlled environment. This Concept introduces the development of the oule method and anticipates its application in electrocatalyst synthesis for water electrolysis. First, the history, device configuration, and merits of the oule method are briefly introduced. Afterwards, typical materials synthesized by the oule method are discussed. Then, recent process in applying the oule method to synthesize electrocatalysts for water electrolysis is highlighted. Finally, opportunities and potentials of this method in facilitating electrocatalyst synthesis for water electrolysis are discussed.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8TA11626A
Abstract: The dissociative chemisorption energy of water was proposed to address both thermodynamics and kinetics of alkaline hydrogen evolution.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1SC01694F
Abstract: Densely-arrayed Cu nanopyramids have spatial confinement induced by the additional Cu–O bond. This promotes C–C coupling, regulates post-C–C coupling, and retains both oxygen atoms in an alternative pathway toward ethylene glycol formation from CO.
Publisher: Wiley
Date: 16-12-2022
Abstract: We demonstrate a widely applicable method to alter the adsorption configuration of multi‐carbon containing reactants by no catalyst engineering but simply adjusting the local reaction environment of the catalyst surface. Using electrocatalytic acetone to propane hydrogenation (APH) as a model reaction and common commercial Pt/Pt‐based materials as catalysts, we found local H + concentration can significantly influence the adsorption mode of acetone reactant, for ex le, in vertical or flat mode, and target product selectivity. Electrocatalytic measurement combined with in situ spectroscopic characterizations reveals that the vertically adsorbed acetone is favorable for propane production while the flatly adsorbed mode suppresses the reaction. DFT calculations indicate that the H coverage on catalyst surface plays a decisive role in the adsorption configuration of acetone. The increased local acidity can facilitate the adsorption configuration of acetone from flat to vertical mode and suppress the competing hydrogen evaluation reaction, which consequently enhances the APH selectivity.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1EE00740H
Abstract: The review presents the important role of oxygen-bound intermediates in directing the selectivity of electrochemical CO 2 reduction by considering available theoretical calculations, electrochemical measurements and operando spectroscopy observations.
Publisher: Springer Science and Business Media LLC
Date: 28-04-2014
DOI: 10.1038/NCOMMS4783
Publisher: American Chemical Society (ACS)
Date: 26-02-2019
Publisher: American Chemical Society (ACS)
Date: 21-06-2023
DOI: 10.1021/JACS.3C03022
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5CP05512A
Abstract: Density functional theory calculations reveal that hybrid carbon nanodots and graphitic carbon nitride can form a type-II van der Waals heterojunction, leading to significant reduction of band gap and enhanced visible light response.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2NR02568J
Abstract: The introduction of iron and molybdenum in catalytic systems has been employed to optimize the nanostructure and improve its catalytic performance toward OER.
Publisher: Springer Science and Business Media LLC
Date: 29-09-2021
DOI: 10.1038/S41467-021-26056-7
Abstract: Sulfur is an important electrode material in metal−sulfur batteries. It is usually coupled with metal anodes and undergoes electrochemical reduction to form metal sulfides. Herein, we demonstrate, for the first time, the reversible sulfur oxidation process in AlCl 3 /carbamide ionic liquid, where sulfur is electrochemically oxidized by AlCl 4 − to form AlSCl 7 . The sulfur oxidation is: 1) highly reversible with an efficiency of ~94% and 2) workable within a wide range of high potentials. As a result, the Al−S battery based on sulfur oxidation can be cycled steadily around ~1.8 V, which is the highest operation voltage in Al−S batteries. The study of sulfur oxidation process benefits the understanding of sulfur chemistry and provides a valuable inspiration for the design of other high-voltage metal−sulfur batteries, not limited to Al−S configurations.
Publisher: American Chemical Society (ACS)
Date: 05-09-2019
Publisher: Elsevier BV
Date: 08-2018
Publisher: American Chemical Society (ACS)
Date: 27-04-2018
Publisher: American Chemical Society (ACS)
Date: 27-02-2017
DOI: 10.1021/JACS.6B13100
Abstract: Organometallic complexes with metal-nitrogen/carbon (M-N/C) coordination are the most important alternatives to precious metal catalysts for oxygen reduction and evolution reactions (ORR and OER) in energy conversion devices. Here, we designed and developed a range of molecule-level graphitic carbon nitride (g-C
Publisher: American Chemical Society (ACS)
Date: 02-06-2015
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3TA01926H
Abstract: Ordered macroporous carbon nitride supported single-atom Co catalysts with Co–N 1+3 /Co–N 2+2 geometric structures are developed using a spatial confinement strategy for (photo-)Fenton-like catalytic reactions.
Publisher: Wiley
Date: 07-07-2021
Abstract: Monitoring and controlling the reconstruction of materials under working conditions is crucial for the precise identification of active sites, elucidation of reaction mechanisms, and rational design of advanced catalysts. Herein, a Bi‐based metal–organic framework (Bi‐MOF) for electrochemical CO 2 reduction is selected as a case study. In situ Raman spectra combined with ex situ electron microscopy reveal that the intricate reconstruction of the Bi‐MOF can be controlled using two steps: 1) electrolyte‐mediated dissociation and conversion of Bi‐MOF to Bi 2 O 2 CO 3 , and 2) potential‐mediated reduction of Bi 2 O 2 CO 3 to Bi. The intentionally reconstructed Bi catalyst exhibits excellent activity, selectivity, and durability for formate production, and the unsaturated surface Bi atoms formed during reconstruction become the active sites. This work emphasizes the significant impact of pre‐catalyst reconstruction under working conditions and provides insight into the design of highly active and stable electrocatalysts through the regulation of these processes.
Publisher: American Chemical Society (ACS)
Date: 15-04-2019
DOI: 10.1021/JACS.9B02124
Abstract: Electrochemical reduction of CO
Publisher: American Chemical Society (ACS)
Date: 06-07-2023
DOI: 10.1021/JACS.3C05171
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1NR06066J
Abstract: An effective strategy ( i.e. , single-atom Cu doping) to improve the performance of a phosphorene-based CO 2 RR catalyst is investigated.
Publisher: Wiley
Date: 12-07-2019
Abstract: Heterogeneous electrocatalysis typically involves charge transfer between surface active sites and adsorbed species. Therefore, modulating the surface charge state of an electrocatalyst can be used to enhance performance. A series of negatively charged transition‐metal (Fe, Co, Ni, Cu,and NiCo) phosphides were fabricated by designing strong electronic coupling with hydr(oxy)oxides formed in situ. Physicochemical characterizations, together with DFT computations, demonstrate that strong electronic coupling renders transition‐metal phosphides negatively charged. This facilitates destabilization of alkaline water adsorption and dissociation to result in significantly improved H 2 evolution. Negatively charged Ni 2 P/nickel hydr(oxy)oxide for ex le exhibits a significantly low overpotential of 138 mV at 100 mA cm −2 , superior to that without strong electronic coupling and also commercial Pt/C.
Publisher: Springer Science and Business Media LLC
Date: 17-09-2022
DOI: 10.1038/S41467-022-33258-0
Abstract: Electrosynthesis of urea from CO 2 and NO X provides an exceptional opportunity for human society, given the increasingly available renewable energy. Urea electrosynthesis is challenging. In order to raise the overall electrosynthesis efficiency, the most critical reaction step for such electrosynthesis, C-N coupling, needs to be significantly improved. The C-N coupling can only happen at a narrow potential window, generally in the low overpotential region, and a fundamental understanding of the C-N coupling is needed for further development of this strategy. In this regard, we perform ab initio Molecular Dynamics simulations to reveal the origin of C-N coupling under a small electrode potential window with both the dynamic nature of water as a solvent, and the electrode potentials considered. We explore the key reaction networks for urea formation on Cu(100) surface in neutral electrolytes. Our work shows excellent agreement with experimentally observed selectivity under different potentials on the Cu electrode. We discover that the * NH and * CO are the key precursors for C-N bonds formation at low overpotential, while at high overpotential the C-N coupling occurs between adsorbed * NH and solvated CO. These insights provide vital information for future spectroscopic measurements and enable us to design new electrochemical systems for more value-added chemicals.
Publisher: American Chemical Society (ACS)
Date: 05-05-2016
DOI: 10.1021/JACS.6B02692
Abstract: Reducing carbon dioxide to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single atoms of palladium and platinum supported on graphitic carbon nitride (g-C3N4), i.e., Pd/g-C3N4 and Pt/g-C3N4, respectively, acting as photocatalysts for CO2 reduction were investigated by density functional theory calculations for the first time. During CO2 reduction, the in idual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from the hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, deposition of atom catalysts on g-C3N4 significantly enhances the visible-light absorption, rendering them ideal for visible-light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2TA01024K
Abstract: Ag cathodes with highly self-crosslinked networks are prepared by one-pot multi-directional growth of AgNWs. The constructed Zn–Ag battery exhibits super-stretchability, a high energy density of 3.15 mW h cm −2 and a power density of 6.84 mW cm −2 .
Publisher: Wiley
Date: 20-10-2021
Abstract: Aqueous Zn‐ion batteries (ZIBs) are regarded as alternatives to Li‐ion batteries benefiting from both improved safety and environmental impact. The widespread application of ZIBs, however, is compromised by the lack of high‐performance cathodes. Currently, only the intercalation mechanism is widely reported in aqueous ZIBs, which significantly limits cathode options. Beyond Zn‐ion intercalation, we comprehensively study the conversion mechanism for Zn 2+ storage and its diffusion pathway in a CuI cathode, indicating that CuI occurs a direct conversion reaction without Zn 2+ intercalation due to the high energy barrier for Zn 2+ intercalation and migration. Importantly, this direct conversion reaction mechanism can be readily generalized to other high‐capacity cathodes, such as Cu 2 S (336.7 mA h g −1 ) and Cu 2 O (374.5 mA h g −1 ), indicating its practical universality. Our work enriches the Zn‐ion storage mechanism and significantly broadens the cathode horizons towards next‐generation ZIBs.
Publisher: American Chemical Society (ACS)
Date: 11-03-2014
DOI: 10.1021/JA500432H
Publisher: Elsevier BV
Date: 10-2015
Publisher: Beilstein Institut
Date: 23-12-2015
DOI: 10.3762/BJNANO.6.256
Abstract: The development of low energy cost membranes to separate He from noble gas mixtures is highly desired. In this work, we studied He purification using recently experimentally realized, two-dimensional stanene (2D Sn) and decorated 2D Sn (SnH and SnF) honeycomb lattices by density functional theory calculations. To increase the permeability of noble gases through pristine 2D Sn at room temperature (298 K), two practical strategies (i.e., the application of strain and functionalization) are proposed. With their high concentration of large pores, 2D Sn-based membrane materials demonstrate excellent helium purification and can serve as a superior membrane over traditionally used, porous materials. In addition, the separation performance of these 2D Sn-based membrane materials can be significantly tuned by application of strain to optimize the He purification properties by taking both diffusion and selectivity into account. Our results are the first calculations of He separation in a defect-free honeycomb lattice, highlighting new interesting materials for helium separation for future experimental validation.
Publisher: Wiley
Date: 09-08-2013
Publisher: American Chemical Society (ACS)
Date: 29-11-2011
DOI: 10.1021/JA209206C
Abstract: Based on theoretical prediction, a g-C(3)N(4)@carbon metal-free oxygen reduction reaction (ORR) electrocatalyst was designed and synthesized by uniform incorporation of g-C(3)N(4) into a mesoporous carbon to enhance the electron transfer efficiency of g-C(3)N(4). The resulting g-C(3)N(4)@carbon composite exhibited competitive catalytic activity (11.3 mA cm(-2) kinetic-limiting current density at -0.6 V) and superior methanol tolerance compared to a commercial Pt/C catalyst. Furthermore, it demonstrated significantly higher catalytic efficiency (nearly 100% of four-electron ORR process selectivity) than a Pt/C catalyst. The proposed synthesis route is facile and low-cost, providing a feasible method for the development of highly efficient electrocatalysts.
Publisher: Elsevier BV
Date: 11-2018
Publisher: American Chemical Society (ACS)
Date: 07-12-2022
DOI: 10.1021/JACS.2C11374
Publisher: Wiley
Date: 09-07-2021
Abstract: Monitoring and controlling the reconstruction of materials under working conditions is crucial for the precise identification of active sites, elucidation of reaction mechanisms, and rational design of advanced catalysts. Herein, a Bi‐based metal–organic framework (Bi‐MOF) for electrochemical CO 2 reduction is selected as a case study. In situ Raman spectra combined with ex situ electron microscopy reveal that the intricate reconstruction of the Bi‐MOF can be controlled using two steps: 1) electrolyte‐mediated dissociation and conversion of Bi‐MOF to Bi 2 O 2 CO 3 , and 2) potential‐mediated reduction of Bi 2 O 2 CO 3 to Bi. The intentionally reconstructed Bi catalyst exhibits excellent activity, selectivity, and durability for formate production, and the unsaturated surface Bi atoms formed during reconstruction become the active sites. This work emphasizes the significant impact of pre‐catalyst reconstruction under working conditions and provides insight into the design of highly active and stable electrocatalysts through the regulation of these processes.
Publisher: Research Square Platform LLC
Date: 30-03-2022
DOI: 10.21203/RS.3.RS-1441754/V1
Abstract: Metal//iodine (I 2 ) batteries have sparked enormous interest as particularly promising energy storage devices. Still, the inherent dendrite growth and electrochemically inactive complexes formed with iodine anionic species at their metal anode make it challenging to substantially improve their performance. Herein, we report the first orgainc anode//I 2 battery. The battery delivers ultra-long lifespan (92000 cycles at 40 A g − 1 ), high rate tolerance (104 mAh g − 1 at 160 A g − 1 ), energy density (434 Wh kg − 1 at 50420 W kg − 1 ) and power density (155072 W kg − 1 at 86 Wh kg − 1 ), far exceeding all the reported aqueous I 2 -batteries. Moreover, the cascade form of this battery enables a voltage of 2.5 V without employing highly concentrated salts or polymer additives. This work addresses the major challenge of I 2 -batteries and enriches the family of aqueous halogen-batteries with high performance and unlimited possibilities, and provides a new sight for the construction of high-performance battery systems based on sulfur electrodes.
Publisher: Wiley
Date: 10-2019
Abstract: Since first being reported as possible electrocatalysts to substitute platinum for the oxygen reduction reaction (ORR), carbon-based metal-free nanomaterials have been considered a class of promising low-cost materials for clean and sustainable energy-conversion reactions. However, beyond the ORR, the development of carbon-based catalysts for other electrocatalytic reactions is still limited. More importantly, the intrinsic activity of most carbon-based metal-free catalysts is inadequate compared to their metal-based counterparts. To address this challenge, more design strategies are needed in order to improve the overall performance of carbon-based materials. Herein, using water splitting as an ex le, some state-of-the-art strategies in promoting carbon-based nanomaterials are summarized, including graphene, carbon nanotubes, and graphitic-carbon nitride, as highly active electrocatalysts for hydrogen evolution and oxygen evolution reactions. It is shown that by rationally tuning the electronic and/or physical structure of the carbon nanomaterials, adsorption of reaction intermediates is optimized, consequently improving the apparent electrocatalytic performance. These strategies may facilitate the development in this area and lead to the discovery of advanced carbon-based nanomaterials for various applications in energy-conversion processes.
Publisher: Wiley
Date: 10-10-2012
Publisher: Springer Science and Business Media LLC
Date: 21-09-2016
DOI: 10.1038/NCOMMS12876
Abstract: Engineering the surface structure at the atomic level can be used to precisely and effectively manipulate the reactivity and durability of catalysts. Here we report tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets. These CoO nanorods exhibit superior catalytic activity and durability towards oxygen reduction/evolution reactions. The combined experimental studies, microscopic and spectroscopic characterization, and density functional theory calculations reveal that the origins of the electrochemical activity of single-crystal CoO nanorods are in the oxygen vacancies that can be readily created on the oxygen-terminated {111} nanofacets, which favourably affect the electronic structure of CoO, assuring a rapid charge transfer and optimal adsorption energies for intermediates of oxygen reduction/evolution reactions. These results show that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts.
Publisher: Springer Science and Business Media LLC
Date: 31-08-2022
DOI: 10.1038/S41467-022-32740-Z
Abstract: Electrocatalytic reduction of CO 2 into alcohols of high economic value offers a promising route to realize resourceful CO 2 utilization. In this study, we choose three model bicentric copper complexes based on the expanded and fluorinated porphyrin structure, but different spatial and coordination geometry, to unravel their structure-property-performance correlation in catalyzing electrochemical CO 2 reduction reactions. We show that the complexes with higher intramolecular tension and coordination asymmetry manifests a lower electrochemical stability and thus more active Cu centers, which can be reduced during electrolysis to form Cu clusters accompanied by partially-reduced or fragmented ligands. We demonstrate the hybrid structure of Cu cluster and partially reduced O-containing hexaphyrin ligand is highly potent in converting CO 2 into alcohols, up to 32.5% ethanol and 18.3% n- propanol in Faradaic efficiencies that have been rarely reported. More importantly, we uncover an interplay between the inorganic and organic phases to synergistically produce alcohols, of which the intermediates are stabilized by a confined space to afford extra O-Cu bonding. This study underlines the exploitation of structure-dependent electrochemical property to steer the CO 2 reduction pathway, as well as a potential generic tactic to target alcohol synthesis by constructing organic/inorganic Cu hybrids.
Publisher: Elsevier BV
Date: 02-2016
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CC03796J
Abstract: The OC–COH coupling is kinetically facilitated compared to OC–CHO coupling, which is induced by the optimized composition and electronic structures of copper alloys.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9TA01932D
Abstract: The direct conversion of CO 2 to syngas with controllable composition remains an intense interest for the production of renewable fuels.
Publisher: American Chemical Society (ACS)
Date: 09-04-2010
DOI: 10.1021/JP911419K
Publisher: Wiley
Date: 24-07-2019
Abstract: Common-metal-based single-atom catalysts (SACs) are quite difficult to design due to the complex synthesis processes required. Herein, we report a single-atom nickel iodide (SANi-I) electrocatalyst with atomically dispersed non-metal iodine atoms. The SANi-I is prepared via a simple calcination step in a vacuum-sealed oule and subsequent cyclic voltammetry activation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and synchrotron-based X-ray absorption spectroscopy are applied to confirm the atomic-level dispersion of iodine atoms and detailed structure of SANi-I. Single iodine atoms are found to be isolated by oxygen atoms. The SANi-I is structural stable and shows exceptional electrocatalytic activity for the hydrogen evolution reaction (HER). In situ Raman spectroscopy reveals that the hydrogen adatom (H
Publisher: Elsevier BV
Date: 05-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CC05635A
Abstract: Herein, we review the recent research progress of heteroatom-doped 2D materials, including carbon, molybdenum disulfide and metal carbides, for the electrocatalytic N 2 reduction reaction.
Publisher: Wiley
Date: 14-02-2020
Publisher: Wiley
Date: 16-03-2023
Abstract: The electrochemical urea oxidation reaction (UOR) is an alternative to electrooxidation of water for energy–saving hydrogen (H 2 ) production. To maximize this purpose, design of catalysts for selective urea‐to‐nitrite (NO 2 – ) electrooxidation with increased electron transfer and high current is practically important. Herein, a cobalt, germanium (Co, Ge) co‐doped nickel (Ni) oxyhydroxide catalyst is reported first time that directs urea‐to‐NO 2 – conversion with a significant Faradaic efficiency of 84.9% at 1.4 V versus reversible hydrogen electrode and significantly boosts UOR activity to 448.0 mA cm −2 . Importantly, this performance is greater than for most reported Ni‐based catalysts. Based on judiciously combined synchrotron‐based measurement, in situ spectroscopy and density functional theoretical computation, significantly boosted urea‐to‐NO 2 – production results from Co, Ge co‐doping is demonstrated that optimizes electronic structure of Ni sites in which urea adsorption is altered as NO‐terminal configuration to facilitate CN cleavage for *NH formation, and thereby expedites pathway for urea to NO 2 – conversion. Findings highlight the importance of tuning intermediate adsorption behavior for design of high‐performance UOR electrocatalysts, and will be of practical benefit to a range of researchers and manufacturers in replacing conventional water electrooxidation with UOR for energy‐saving H 2 production.
Publisher: American Chemical Society (ACS)
Date: 08-10-2021
DOI: 10.1021/JACS.1C06255
Publisher: Wiley
Date: 07-11-2018
Abstract: Lithium-sulfur batteries hold promise for next-generation batteries. A problem, however, is rapid capacity fading. Moreover, atomic-level understanding of the chemical interaction between sulfur host and polysulfides is poorly elucidated from a theoretical perspective. Here, a two-dimensional (2D) heterostructured MoN-VN is fabricated and investigated as a new model sulfur host. Theoretical calculations indicate that electronic structure of MoN can be tailored by incorporation of V. This leads to enhanced polysulfides adsorption. Additionally, in situ synchrotron X-ray diffraction and electrochemical measurements reveal effective regulation and utilization of the polysulfides in the MoN-VN. The MoN-VN-based lithium-sulfur batteries have a capacity of 708 mA h g
Publisher: American Chemical Society (ACS)
Date: 25-03-2021
DOI: 10.1021/JACS.1C01525
Publisher: Elsevier BV
Date: 10-2022
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CP44414G
Abstract: Molecular modelling has become a useful and widely applied tool to investigate separation and diffusion behavior of gas molecules through nano-porous low dimensional carbon materials, including quasi-1D carbon nanotubes and 2D graphene-like carbon allotropes. These simulations provide detailed, molecular level information about the carbon framework structure as well as dynamics and mechanistic insights, i.e. size sieving, quantum sieving, and chemical affinity sieving. In this perspective, we revisit recent advances in this field and summarize separation mechanisms for multicomponent systems from kinetic and equilibrium molecular simulations, elucidating also anomalous diffusion effects induced by the confining pore structure and outlining perspectives for future directions in this field.
Publisher: IOP Publishing
Date: 06-2022
Abstract: Fe-based metal-organic frameworks (MOFs) are promising drug delivery materials due to their large surface area, high stability, and biocompatibility. However, their drug loading capacity is constrained by their small pore size, and a further improvement in their drug capacity is needed. In this work, we report an effective and green structural modification strategy to improve drug loading capacity for Fe-based MOFs. Our strategy is to grow MIL-100 (Fe) on carboxylate-terminated polystyrene (PS-COOH) via a sustainable route, which creates a large inner cavity as well as exposure to more functional groups that benefit drug loading capacity. We employ the scanning electron microscope and transmission electron microscope to confirm the hollow structure of MIL-100 (Fe). Up to 30% of drug loading capacity has been demonstrated in our study. We also conduct cell viability tests to investigate its therapeutic effects on breast cancer cells (MDA-MB-231). Confocal laser scanning microscopy imaging confirms cellular uptake and mitochondrial targeting function of doxorubicin-loaded H-M (DOX@H-M) nanoparticles. JC-1 staining of cancer cells reveals a significant change in the mitochondrial membrane potential, indicating the mitochondrial dysfunction and apoptosis of tumor cells. Our study paves the way for the facile synthesis of hollow structural MOFs and demonstrates the potential of applying Fe-based MOFs in breast cancer treatment.
Publisher: Wiley
Date: 21-10-2021
Abstract: Aqueous Zn‐ion batteries (ZIBs) are regarded as alternatives to Li‐ion batteries benefiting from both improved safety and environmental impact. The widespread application of ZIBs, however, is compromised by the lack of high‐performance cathodes. Currently, only the intercalation mechanism is widely reported in aqueous ZIBs, which significantly limits cathode options. Beyond Zn‐ion intercalation, we comprehensively study the conversion mechanism for Zn 2+ storage and its diffusion pathway in a CuI cathode, indicating that CuI occurs a direct conversion reaction without Zn 2+ intercalation due to the high energy barrier for Zn 2+ intercalation and migration. Importantly, this direct conversion reaction mechanism can be readily generalized to other high‐capacity cathodes, such as Cu 2 S (336.7 mA h g −1 ) and Cu 2 O (374.5 mA h g −1 ), indicating its practical universality. Our work enriches the Zn‐ion storage mechanism and significantly broadens the cathode horizons towards next‐generation ZIBs.
Publisher: Wiley
Date: 10-11-2014
Abstract: The electrocatalytic hydrogen‐evolution reaction (HER), as the main step of water splitting and the cornerstone of exploring the mechanism of other multi‐electron transfer electrochemical processes, is the subject of extensive studies. A large number of high‐performance electrocatalysts have been developed for HER accompanied by recent significant advances in exploring its electrochemical nature. Herein we present a critical appraisal of both theoretical and experimental studies of HER electrocatalysts with special emphasis on the electronic structure, surface (electro)chemistry, and molecular design. It addresses the importance of correlating theoretical calculations and electrochemical measurements toward better understanding of HER electrocatalysis at the atomic level. Fundamental concepts in the computational quantum chemistry and its relation to experimental electrochemistry are also presented along with some featured ex les.
Publisher: Wiley
Date: 22-01-2013
Publisher: Wiley
Date: 11-07-2023
Abstract: In the past, the design of efficient electrocatalyst materials for alkaline hydrogen evolution reaction (HER) was mostly focused on tuning the adsorption properties of reaction intermediates. A recent breakthrough shows that the performance can be improved by manipulating water structure at the electrode‐electrolyte interface using atomically localized electric fields. The new approach was realized by using IrRu dizygotic single‐atom sites and led to a significantly accelerated water dissociation and an overall improved alkaline HER performance. Supported by extensive data from advanced modeling, characterization, and electrochemical measurements, the work delivers an intricate examination of the interaction between water molecules and the catalyst surface, thereby enriching our understanding of water dissociation kinetics and offering new insights to boost overall alkaline HER efficiency.
Publisher: Wiley
Date: 24-03-2023
Abstract: Solar hydrogen (H 2 ) generation via photocatalytic water splitting is practically promising, environmentally benign, and sustainably carbon neutral. It is important therefore to understand how to controllably engineer photocatalysts at the atomic level. In this work, atomic‐level engineering of defected ReSe 2 nanosheets (NSs) is reported to significantly boost photocatalytic H 2 evolution on various semiconductor photocatalysts including TiO 2 , CdS, ZnIn 2 S 4 , and C 3 N 4 . Advanced characterizations, such as atomic‐resolution aberration‐corrected scanning transmission electron microscopy (AC‐STEM), synchrotron‐based X‐ray absorption near edge structure (XANES), in situ X‐ray photoelectron spectroscopy (XPS), transient‐state surface photovoltage (SPV) spectroscopy, and transient‐state photoluminescence (PL) spectroscopy, together with theoretical computations confirm that the strongly coupled ReSe 2 /TiO 2 interface and substantial atomic‐level active sites of defected ReSe 2 NSs result in the significantly raised activity of ReSe 2 /TiO 2 . This work not only for the first time realizes the atomic‐level engineering of ReSe 2 NSs as a versatile platform to significantly raise the activities on different photocatalysts, but, more importantly, underscores the immense importance of atomic‐level synthesis and exploration on 2D materials for energy conversion and storage.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5TA01062D
Abstract: Nitrogen doping into graphdiyne leads to a reduced H 2 diffusion barrier and hence an enhanced hydrogen purification capability.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9TA01903K
Abstract: Simple methods for fabricating highly active and stable interfacial bifunctional electrocatalysts for water electrolysis are essential for hydrogen production.
Publisher: Wiley
Date: 29-12-2017
Publisher: American Chemical Society (ACS)
Date: 06-12-2016
DOI: 10.1021/JACS.6B11291
Abstract: Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.
Publisher: Springer Science and Business Media LLC
Date: 18-05-2023
DOI: 10.1038/S41467-023-38497-3
Abstract: Acidic CO 2 -to-HCOOH electrolysis represents a sustainable route for value-added CO 2 transformations. However, competing hydrogen evolution reaction (HER) in acid remains a great challenge for selective CO 2 -to-HCOOH production, especially in industrial-level current densities. Main group metal sulfides derived S-doped metals have demonstrated enhanced CO 2 -to-HCOOH selectivity in alkaline and neutral media by suppressing HER and tuning CO 2 reduction intermediates. Yet stabilizing these derived sulfur dopants on metal surfaces at large reductive potentials for industrial-level HCOOH production is still challenging in acidic medium. Herein, we report a phase-engineered tin sulfide pre-catalyst (π-SnS) with uniform rhombic dodecahedron structure that can derive metallic Sn catalyst with stabilized sulfur dopants for selective acidic CO 2 -to-HCOOH electrolysis at industrial-level current densities. In situ characterizations and theoretical calculations reveal the π-SnS has stronger intrinsic Sn-S binding strength than the conventional phase, facilitating the stabilization of residual sulfur species in the Sn subsurface. These dopants effectively modulate the CO 2 RR intermediates coverage in acidic medium by enhancing *OCHO intermediate adsorption and weakening *H binding. As a result, the derived catalyst (Sn(S)-H) demonstrates significantly high Faradaic efficiency (92.15 %) and carbon efficiency (36.43 %) to HCOOH at industrial current densities (up to −1 A cm −2 ) in acidic medium.
Publisher: Wiley
Date: 25-09-2023
Publisher: Springer Science and Business Media LLC
Date: 20-09-2023
Publisher: Elsevier BV
Date: 10-2011
Publisher: Elsevier BV
Date: 02-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2MH01218A
Abstract: This review introduces fundamental aspects of the electrocatalytic CO 2 RR process together with a systematic examination of recent developments in Cu-based electrocatalysts for the electroreduction of CO 2 to various high-value multicarbon products.
Publisher: American Chemical Society (ACS)
Date: 29-11-2018
Abstract: Transition metal nitrides (TMNs) have great potential for energy-related electrocatalysis because of their inherent electronic properties. However, incorporating nitrogen into a transition metal lattice is thermodynamically unfavorable, and therefore most of the developed TMNs are deficient in nitrogen. Consequently, these TMNs exhibit poor structural stability and unsatisfactory performance for electrocatalytic applications. In this work, we design and synthesize an atomically thin nitrogen-rich nanosheets, Mo
Publisher: Wiley
Date: 14-05-2018
Abstract: The hydrogen evolution reaction (HER) is a fundamental process in electrocatalysis and plays an important role in energy conversion for the development of hydrogen-based energy sources. However, the considerably slow rate of the HER in alkaline conditions has hindered advances in water splitting techniques for high-purity hydrogen production. Differing from well documented acidic HER, the mechanistic aspects of alkaline HER are yet to be settled. A critical appraisal of alkaline HER electrocatalysis is presented, with a special emphasis on the connection between fundamental surface electrochemistry on single-crystal models and the derived molecular design principle for real-world electrocatalysts. By presenting some typical ex les across theoretical calculations, surface characterization, and electrochemical experiments, we try to address some key ongoing debates to deliver a better understanding of alkaline HER at the atomic level.
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3NR00149K
Abstract: Photoelectrochemical (PEC) water splitting combined with renewable energy is an appealing approach for solar energy conversion and storage.
Publisher: American Chemical Society (ACS)
Date: 28-12-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4CS00470A
Abstract: This review provides insights into theoretical and experimental electrochemistry toward a better understanding of a series of key energy conversion reactions.
Publisher: American Chemical Society (ACS)
Date: 30-05-2019
DOI: 10.1021/JACS.9B03811
Abstract: The lack of chemical understanding and efficient catalysts impedes the development of electrocatalytic nitrogen reduction reaction (eNRR) for ammonia production. In this work, we employed density functional theory calculations to build up a picture (activity trends, electronic origins, and design strategies) of single-atom catalysts (SACs) supported on nitrogen-doped carbons as eNRR electrocatalysts. To construct such a picture, this work presents systematic studies of the eNRR activity of SACs covering 20 different transition metal (TM) centers coordinated by nitrogen atoms contained in three types of nitrogen-doped carbon substrates, which gives 60 SACs. Our study shows that the intrinsic activity trends could be established on the basis of the nitrogen adatom adsorption energy (Δ E
Publisher: Elsevier BV
Date: 03-2022
Publisher: Elsevier BV
Date: 12-2015
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1TA09608G
Abstract: Embedding Ag single atoms onto densely arrayed Cu nanopyramids could optimize the *CO adsorption strength toward direct propanediol production via a one-step concerted *CO trimerization mechanism.
Publisher: American Chemical Society (ACS)
Date: 19-03-2018
DOI: 10.1021/ACS.CHEMREV.7B00689
Abstract: Over the past few decades, the design and development of advanced electrocatalysts for efficient energy conversion technologies have been subjects of extensive study. With the discovery of graphene, two-dimensional (2D) nanomaterials have emerged as some of the most promising candidates for heterogeneous electrocatalysts due to their unique physical, chemical, and electronic properties. Here, we review 2D-nanomaterial-based electrocatalysts for selected electrocatalytic processes. We first discuss the unique advances in 2D electrocatalysts based on different compositions and functions followed by specific design principles. Following this overview, we discuss various 2D electrocatalysts for electrocatalytic processes involved in the water cycle, carbon cycle, and nitrogen cycle from their fundamental conception to their functional application. We place a significant emphasis on different engineering strategies for 2D nanomaterials and the influence these strategies have on intrinsic material performance, such as electronic properties and adsorption energetics. Finally, we feature the opportunities and challenges ahead for 2D nanomaterials as efficient electrocatalysts. By considering theoretical calculations, surface characterization, and electrochemical tests, we describe the fundamental relationships between electronic structure, adsorption energy, and apparent activity for a wide variety of 2D electrocatalysts with the goal of providing a better understanding of these emerging nanomaterials at the atomic level.
Publisher: Wiley
Date: 17-08-2023
Abstract: As a burgeoning electrolyte system, eutectic electrolytes based on ZnCl 2 /Zn(CF 3 SO 3 ) 2 /Zn(TFSI) 2 have been widely proposed in advanced Zn‐I 2 batteries however, safety and cost concerns significantly limit their applications. Here, we report new‐type ZnSO 4 ‐based eutectic electrolytes that are both safe and cost‐effective. Their universality is evident in various solvents of polyhydric alcohols, in which multiple −OH groups not only involve in Zn 2+ solvation but also interact with water, resulting in the high stability of electrolytes. Taking propylene glycol‐based hydrated eutectic electrolyte as an ex le, it features significant advantages in non‐flammability and low price that is /200 cost of Zn(CF 3 SO 3 ) 2 /Zn(TFSI) 2 ‐based eutectic electrolytes. Moreover, its effectiveness in confining the shuttle effects of I 2 cathode and side reactions of Zn anodes is evidenced, resulting in Zn‐I 2 cells with high reversibility at 1 C and 91.4 % capacity remaining under 20 C. After scaling up to the pouch cell with a record mass loading of 33.3 mg cm −2 , super‐high‐capacity retention of 96.7 % is achieved after 500 cycles, which exceeds other aqueous counterparts. This work significantly broadens the eutectic electrolyte family for advanced Zn battery design.
Publisher: Wiley
Date: 13-11-2020
Publisher: Springer Science and Business Media LLC
Date: 24-11-2021
DOI: 10.1038/S41467-021-27169-9
Abstract: Electrochemical CO 2 reduction (CO 2 RR) in a product-orientated and energy-efficient manner relies on rational catalyst design guided by mechanistic understandings. In this study, the effect of conducting support on the CO 2 RR behaviors of semi-conductive metal-organic framework (MOF) — Cu 3 (HITP) 2 are carefully investigated. Compared to the stand-alone MOF, adding Ketjen Black greatly promotes C 2 H 4 production with a stabilized Faradaic efficiency between 60-70% in a wide potential range and prolonged period. Multicrystalline Cu nano-crystallites in the reconstructed MOF are induced and stabilized by the conducting support via current shock and charge delocalization, which is analogous to the mechanism of dendrite prevention through conductive scaffolds in metal ion batteries. Density functional theory calculations elucidate that the contained multi-facets and rich grain boundaries promote C–C coupling while suppressing HER. This study underlines the key role of substrate-catalyst interaction, and the regulation of Cu crystalline states via conditioning the charge transport, in steering the CO 2 RR pathway.
Publisher: Springer Science and Business Media LLC
Date: 15-11-2017
DOI: 10.1038/S41467-017-01872-Y
Abstract: Designing high-performance and cost-effective electrocatalysts toward oxygen evolution and hydrogen evolution reactions in water–alkali electrolyzers is pivotal for large-scale and sustainable hydrogen production. Earth-abundant transition metal oxide-based catalysts are particularly active for oxygen evolution reaction however, they are generally considered inactive toward hydrogen evolution reaction. Here, we show that strain engineering of the outermost surface of cobalt(II) oxide nanorods can turn them into efficient electrocatalysts for the hydrogen evolution reaction. They are competitive with the best electrocatalysts for this reaction in alkaline media so far. Our theoretical and experimental results demonstrate that the tensile strain strongly couples the atomic, electronic structure properties and the activity of the cobalt(II) oxide surface, which results in the creation of a large quantity of oxygen vacancies that facilitate water dissociation, and fine tunes the electronic structure to weaken hydrogen adsorption toward the optimum region.
Publisher: American Chemical Society (ACS)
Date: 13-05-2021
DOI: 10.1021/JACS.1C03135
Publisher: Wiley
Date: 13-01-2023
Abstract: Aqueous zinc‐ion batteries (AZIBs) have attracted wide attention for large‐scale energy storage. However, the practical application of AZIBs is limited by the poor reversibility of Zn anodes. Recently, a strategy of adding low‐cost anti‐solvent to electrolytes is proposed experimentally, which can improve Zn reversibility therefore the AZIBs performance. Nevertheless, the mechanism of the strategy remains elusive, especially how the Zn reversibility is improved and why various anti‐solvents perform differently. Herein, atomic‐level insight into the mechanism, is provided, by modeling ZnSO 4 electrolytes with different anti‐solvents, that is, methanol and ethanol. Through molecular dynamics simulations and density‐functional theory calculations, how anti‐solvents impact Zn 2+ solvation sheath and water activity is explored. It is suggested in the results that methanol promotes Zn reversibility for two reasons. First, methanol can modify the Zn 2+ solvation sheath to reduce the energy barrier for Zn 2+ de‐solvation. Second, methanol can form H‐bond with water molecules to suppress H 2 evolution. Based on the new atomic level insight, herein, the practical universality of the anti‐solvent strategy is confirmed in other aqueous batteries for developing more effective anti‐solvents.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0TA11604A
Abstract: Understanding the late stages of C 2 pathways provides great opportunities for fully achieving a selective CO 2 electroreduction. The C 2 product selectivity can be directed by the active site's oxygen affinity on a range of non-metal doped Cu surfaces.
Publisher: Wiley
Date: 05-07-2021
Abstract: The electroreduction of carbon dioxide (CO 2 RR) to CH 4 stands as one of the promising paths for resourceful CO 2 utilization in meeting the imminent “carbon‐neutral” goal of the near future. Yet, limited success has been witnessed in the development of high‐efficiency catalysts imparting satisfactory methane selectivity at a commercially viable current density. Herein, a unique category of CO 2 RR catalysts is fabricated with the yolk–shell nanocell structure, comprising an Ag core and a Cu 2 O shell that resembles the tandem nanoreactor. By fixing the Ag core and tuning the Cu 2 O envelope size, the CO flux arriving at the oxide‐derived Cu shell can be regulated, which further modulates the *CO coverage and *H adsorption at the Cu surface, consequently steering the CO 2 RR pathway. Density functional theory simulations show that lower CO coverage favors methane formation via stabilizing the intermediate *CHO. As a result, the best catalyst in the flow cell shows a high CH 4 Faraday efficiency of 74 ± 2% and partial current density of 178 ± 5 mA cm − 2 at −1.2 V RHE , ranking above the state‐of‐the‐art catalysts reported today for methane production. These findings mark the significance of precision synthesis in tailoring the catalyst geometry for achieving desired CO 2 RR performance.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1CC15129K
Abstract: We theoretically extend the applications of graphdiyne, an experimentally available one-atom-thin carbon allotrope, to nanoelectronics and superior separation membrane for hydrogen purification on a precise level.
Publisher: Research Square Platform LLC
Date: 12-2020
DOI: 10.21203/RS.3.RS-98178/V1
Abstract: The shuttling of soluble lithium polysulfides between the electrodes leads to serious capacity fading and excess use of electrolyte, which severely bottlenecks practical use of Li-S batteries. Here selective catalysis is proposed as a fundamental remedy for the consecutive solid-liquid-solid sulfur redox reactions. The proof-of-concept In 2 O 3 catalyst targetedly slows down the solid-liquid conversion, dissolution of elemental sulfur to polysulfides, while accelerates the liquid-solid conversion, deposition of polysulfides into insoluble Li 2 S, which basically reduces accumulation of polysulfides in electrolyte, finally inhibiting the shuttle effect. The selective catalysis is revealed, experimentally and theoretically, by changes of activation energies and kinetic currents, modified reaction pathway together with the probed LiInS 2 intermediates, and gradual deactivation of the catalyst. The In 2 O 3 -catalysed Li-S battery works steadily over 1000 cycles at 4.0 C and yields an initial areal capacity up to 9.4 mAh cm −2 with a sulfur loading of ~9.0 mg cm −2 .
Publisher: Wiley
Date: 15-03-2018
Abstract: Conventional development of nanomaterials for efficient electrocatalysis is largely based on performance-oriented trial-and-error/iterative approaches, while a rational design approach at the atomic/molecular level is yet to be found. Here, inspired by a fundamental understanding of the mechanism for both oxygen and hydrogen evolution half reactions (OER/HER), a unique strategy is presented to engineer RuO
Start Date: 2023
End Date: 2023
Funder: Australian Research Council
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Funder: Australian Research Council
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End Date: 2022
Funder: Australian Research Council
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End Date: 2021
Funder: Australian Research Council
View Funded ActivityStart Date: 2019
End Date: 12-2023
Amount: $350,000.00
Funder: Australian Research Council
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End Date: 12-2023
Amount: $970,000.00
Funder: Australian Research Council
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End Date: 12-2023
Amount: $728,014.00
Funder: Australian Research Council
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End Date: 02-2031
Amount: $35,000,000.00
Funder: Australian Research Council
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