Structural optimization of carbon-based diatomic catalysts towards advanced electrocatalysis

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 492, P. 215288 - 215288

Published: June 12, 2023

Language: Английский

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Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO₂ Electroreduction to Ethylene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5693 - 5701

Published: Feb. 9, 2024

Rationally modulating the binding strength of reaction intermediates on surface sites copper-based catalysts could facilitate C–C coupling to generate multicarbon products in an electrochemical CO2 reduction reaction. Herein, theoretical calculations reveal that cascade Ag–Cu dual synergistically increase local CO coverage and lower kinetic barrier for protonation, leading enhanced asymmetric C2H4. As a proof concept, Cu3N-Ag nanocubes (NCs) with Ag located partial Cu Cu3N unit center are successfully synthesized. The Faraday efficiency current density C2H4 over NCs 7.8 9.0 times those NCs, respectively. In situ spectroscopies combined confirm produce promote *COCHO, significantly enhancing generation Our work provides new insights into catalysis strategy at atomic scale boosting products.

Language: Английский

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Ag Single Atoms Anchored on CeO₂ with Interfacial Oxygen Vacancies for Efficient CO₂ Electroreduction

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(25), P. 30262 - 30271

Published: June 20, 2023

Ag single-atom catalysts (SACs) have great potential in selective electrocatalysis of the CO2 reduction reaction (CO2RR) to CO, while it is still a challenge achieve high current density and atom efficiency simultaneously. Here, we present new simple situ adsorption-reduction method prepare SACs supported on CeO2 (Ag1/CeO2). It found that single atoms are anchored through strong metal-support interaction (SMSI), each accompanied with three interfacial oxygen vacancies. This Ag1/CeO2 exhibits performance electrocatalytic CO2RR CO faradaic (FE) >95% under wide range. The turnover frequency (TOF) value can reach 50,310 h-1 at FECO = 99.5% H-cells. Notably, achieves an industrial-grade 403 mA cm-2 97.2% flow cells. Experimental results combined functional theory calculation revealed this superior was mainly ascribed existence vacancies, which lead formation Ag-O-Ce3+ atomic interfaces, activates Ce3+-O structures as synergistic active center Ag, thus promoting adsorption activation reducing barrier *COOH-to-*CO.

Language: Английский

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Emerging materials for electrochemical CO₂reduction: progress and optimization strategies of carbon-based single-atom catalysts

Nanoscale, Journal Year: 2023, Volume and Issue: 15(8), P. 3666 - 3692

Published: Jan. 1, 2023

This review highlights the synthesis, characterization and optimization strategies for improving performance of SACs CO 2 RR.

Language: Английский

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Silver Single Atoms Combined with Clusters on Carbon Nanotubes Mediates Exclusive Electrochemical CO₂‐to‐CO Conversion

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(33)

Published: May 29, 2024

Abstract The electrochemical reduction of CO 2 (eCO RR) that exclusively produces one product at industrial current density is crucial for the substantial storage renewable energy. Modulating electronic structure atomically dispersed catalysts can effectively regulate adsorption rate‐determining‐step intermediates to achieve desired products. Here, study constructs a hybrid catalyst consisting single Ag atoms and atomic clusters supported on nitrogen‐doped multi‐walled carbon nanotubes important intermediate *COOH. X‐ray photoelectron absorption near‐edge spectroscopies demonstrate turning into weaken electron transfer between Ag–N present relatively rich state. Thus, rate‐determining step *COOH massive formation significantly accelerated, as proven by in situ synchrotron infrared spectroscopy functional theory calculations. Using this strategy, Faradaic efficiency outperforming 99% from −0.3 −0.8 V (vs reversible hydrogen electrode) with densities above 200 mA cm −2 half‐cell energetic 86% achieved. This work highlights promising approach advancing synergistic achieving more controllable efficient eCO RR.

Language: Английский

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Single‐atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

Carbon Energy, Journal Year: 2023, Volume and Issue: 6(3)

Published: Sept. 6, 2023

Abstract The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification decarbonization chemical fuel industries. In this technology, an electrocatalytic material renewable energy‐generated electricity drive conversion into high‐value chemicals carbon‐neutral fuels. Over past few years, single‐atom catalysts have been intensively studied as they could provide near‐unity atom utilization unique catalytic performance. Single‐atom become one state‐of‐the‐art catalyst materials monoxide. However, it remains challenge to facilitate efficient products beyond review, we summarize present important findings critical insights from studies on reaction hydrocarbons oxygenates using catalysts. It is hoped that review gives thorough recapitulation analysis science behind catalysis more reduced through so can be guide future research development with industry‐ready performance

Language: Английский

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Defect engineering of high-loading single-atom catalysts for electrochemical carbon dioxide reduction

Materials Reports Energy, Journal Year: 2023, Volume and Issue: 3(2), P. 100197 - 100197

Published: May 1, 2023

Electrochemical carbon dioxide reduction reaction (CO2RR) provides an attractive approach to capture and utilization for the production high-value-added products. However, CO2RR still suffers from poor selectivity low current density due its sluggish kinetics multitudinous pathways. Single-atom catalysts (SACs) demonstrate outstanding activity, excellent selectivity, remarkable atom efficiency, which give impetus search electrocatalytic processes aiming at high selectivity. There appears significant activity in development of efficient SACs CO2RR, while atomic sites remains a considerable barrier be overcome. To construct high-metal-loading SACs, aggregation must prevented, thus novel strategies are required. The key creating high-density atomically dispersed is designing enough anchoring sites, normally defects, stabilize highly mobile separated metal atoms. In this review, we summarized advances developing high-loading through defect engineering, with focus on synthesis achieve site loading. Finally, future opportunities challenges area single-atom electrocatalysts also discussed.

Language: Английский

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Metal oxide/chalcogenide/hydroxide catalysts for water electrolysis

International Journal of Hydrogen Energy, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

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Synergistic engineering of heteronuclear Ni-Ag dual-atom catalysts for high-efficiency CO2 electroreduction with nearly 100% CO selectivity

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 476, P. 146556 - 146556

Published: Oct. 12, 2023

Single-atom catalysts (SACs) have emerged as attractive materials for the electrocatalytic carbon dioxide reduction (ECO2R). Dual-atom (DACs), an extension of SACs, exhibit more compelling functionalities due to synergistic effects between adjacent metal atoms. However, rational design, clear coordination mode, and in-depth understanding heteronuclear dual-atom mechanisms remain elusive. Herein, a Ni-Ag catalyst loaded on defective nitrogen-rich porous carbon, denoted Ni-Ag/PC-N, was synthesized using cascade pyrolysis. The configuration sites is confirmed N3-Ni-Ag-N3. Ni-Ag/PC-N demonstrates remarkable CO Faradaic efficiency (FECO) exceeding 90% over broad range applied potentials, i.e., from −0.7 −1.3 V versus reversible hydrogen electrode (RHE). peak FECO 99.2% observed at −0.8 (vs. RHE). Tafel analysis reveals that rate-determining step ECO2R-to-CO formation *COOH intermediate, exhibits optimal electrokinetics. In situ FTIR in Raman spectra indicate accelerated production intermediates during process. Density functional theory (DFT) calculations demonstrate coordinated Ni atom lowers energy barrier surface, while Ag mitigates poisoning caused by strong *CO affinity atomic site.

Language: Английский

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Chlorine‐Coordinated Unsaturated Ni–N₂ Sites for Efficient Electrochemical Carbon Dioxide Reduction

Small, Journal Year: 2023, Volume and Issue: 19(52)

Published: Aug. 30, 2023

Abstract Heteroatom‐doping is an effective method for modifying the geometric symmetry of metal–nitrogen–carbon (M–N–C) single‐atom catalysts and thereby tuning electronic structure. Up to now, most current reports have concentrated on introducing heteroatoms into highly symmetrical M–N 4 The coordination‐unsaturated 2 structure more sterically favorable insertion alien atoms optimize Herein, a Ni–N catalyst with out‐of‐plane coordinated chlorine (Cl) (Ni–N Cl/C) successfully constructed chlorine‐functionalized carbon supports (C–Cl) efficient dioxide reduction reaction (CO RR). Density functional theory calculations demonstrate that prepared Cl/C exhibits higher capability in balancing COOH* formation CO* desorption. In addition, situ Raman spectra confirm lower CO binding energy facilitates escape, leading excellent RR performance. A high Faradaic efficiency (FE ) than 80% achieved from −0.6 −1.2 V versus reversible hydrogen electrode it negligible FE declination over 40‐h stability test. Furthermore, turnover frequency (TOF) value 15 808 h −1 obtained, which ten times /C (1476 without Cl atoms.

Language: Английский

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