Recent advances of single-atom catalysts in CO₂conversion

Energy & Environmental Science, Год журнала: 2023, Номер 16(7), С. 2759 - 2803

Опубликована: Янв. 1, 2023

The catalytic transformation of CO 2 into valuable fuels/chemicals is a promising and economically profitable process because it offers an alternative toward fossil feedstocks the benefit transforming cycling on scale-up.

Язык: Английский

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Review of Carbon Support Coordination Environments for Single Metal Atom Electrocatalysts (SACS)

Advanced Materials, Год журнала: 2023, Номер 36(1)

Опубликована: Апрель 20, 2023

This topical review focuses on the distinct role of carbon support coordination environment single-atom catalysts (SACs) for electrocatalysis. The article begins with an overview atomic configurations in SACs, including a discussion advanced characterization techniques and simulation used understanding active sites. A summary key electrocatalysis applications is then provided. These processes are oxygen reduction reaction (ORR), evolution (OER), hydrogen (HER), nitrogen (NRR), dioxide (CO

Язык: Английский

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Unraveling the Influence of Oxygen Vacancy Concentration on Electrocatalytic CO₂ Reduction to Formate over Indium Oxide Catalysts

ACS Catalysis, Год журнала: 2023, Номер 13(6), С. 4021 - 4029

Опубликована: Март 8, 2023

Rational engineering of oxygen vacancies in a metal oxide-based catalyst represents an effective strategy to regulate catalytic performances by influencing both their electrochemical active surface areas and the microelectronic structure. However, precise control modulation concentration uniformity on still remains inadequately explored poorly elucidated. Herein, we develop facile method prepare series In2O3 nanorods with varying vacancy concentrations for efficient electrolytic CO2 reduction formate. Experimental results theoretical calculations reveal that abundant significantly improve activation promote production *HCOO intermediates, achieving maximum formate Faradaic efficiency 91.2% at −1.27 V vs reversible hydrogen electrode (RHE) high partial current density and, meanwhile, superior stability. The underlying relationship between reaction (CO2RR) performance was further established. This work offers feasible finely tune p-block catalysts highly CO2RR.

Язык: Английский

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Continuous electroproduction of formate via CO2 reduction on local symmetry-broken single-atom catalysts

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 27, 2023

Abstract Atomic-level coordination engineering is an efficient strategy for tuning the catalytic performance of single-atom catalysts (SACs). However, their rational design has so far been plagued by lack a universal correlation between symmetry and properties. Herein, we synthesised planar-symmetry-broken CuN 3 (PSB-CuN ) SACs through microwave heating electrocatalytic CO 2 reduction. Remarkably, as-prepared exhibited selectivity 94.3% towards formate at −0.73 V vs. RHE, surpassing symmetrical 4 catalyst (72.4% −0.93 RHE). In flow cell equipped with PSB-CuN electrode, over 90% was maintained average current density 94.4 mA cm −2 during 100 h operation. By combining definitive structural identification operando X-ray spectroscopy theoretical calculations, revealed that intrinsic local breaking from planar D configuration induces unconventional dsp hybridisation, thus strong activity microenvironment metal centre (i.e., number distortion), high preference production in moiety. The finding opens avenue designing specific symmetries selective electrocatalysis.

Язык: Английский

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Axial coordination regulation of MOF-based single-atom Ni catalysts by halogen atoms for enhanced CO2 electroreduction

Nano Research, Год журнала: 2022, Номер 15(12), С. 10063 - 10069

Опубликована: Июнь 21, 2022

Язык: Английский

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Single‐Product Faradaic Efficiency for Electrocatalytic of CO₂ to CO at Current Density Larger than 1.2 A cm⁻² in Neutral Aqueous Solution by a Single‐Atom Nanozyme

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(44)

Опубликована: Сен. 7, 2022

Electroreduction of CO2 to CO is a promising approach for the cycling use , while it still suffers from impractical current density and durability. Here we report single-atom nanozyme (Ni-N5 -C) that achieves industrial-scale performance -to-CO conversion with Faradaic efficiency (FE) exceeded 97 % over -0.8--2.4 V vs. RHE. The at -2.4 RHE reached maximum 1.23 A cm-2 (turnover frequency 69.7 s-1 ) an FE 99.6 %. No obvious degradation was observed 100 hours continuous operation. Compared planar Ni-N4 site, square-pyramidal Ni-N5 site has increase decrease in dz2${{{\rm d}}_{{z}^{2}}}$ dxz/yz orbital energy levels, respectively, as revealed by functional theory calculations. Thus, catalytic more superior activate molecule reduce barriers well promote desorption, thus boosting kinetic activation process activity.

Язык: Английский

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Convergent paired electrosynthesis of dimethyl carbonate from carbon dioxide enabled by designing the superstructure of axial oxygen coordinated nickel single-atom catalysts

Energy & Environmental Science, Год журнала: 2022, Номер 16(2), С. 502 - 512

Опубликована: Дек. 22, 2022

A dual-channel superstructured Ni single-atom catalyst with a unique axial oxygen coordination configuration was controllably constructed and affords preeminent performance for convergent paired electrosynthesis of dimethyl carbonate from CO 2 .

Язык: Английский

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Progress in metal-organic-framework-based single-atom catalysts for environmental remediation

Coordination Chemistry Reviews, Год журнала: 2022, Номер 474, С. 214855 - 214855

Опубликована: Окт. 4, 2022

Язык: Английский

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Asymmetric Coordination Induces Electron Localization at Ca Sites for Robust CO₂ Electroreduction to CO

Advanced Materials, Год журнала: 2023, Номер 35(21)

Опубликована: Март 16, 2023

Main group single atom catalysts (SACs) are promising for CO2 electroreduction to CO by virtue of their ability in preventing the hydrogen evolution reaction and poisoning. Unfortunately, delocalized orbitals reduce activation *COOH. Herein, an O doping strategy localize electrons on p-orbitals through asymmetric coordination Ca SAC sites (Ca-N3 O) is developed, thus enhancing activation. Theoretical calculations indicate that Ca-N3 improves electron-localization around promotes *COOH formation. X-ray absorption fine spectroscopy shows obtained features: one three N coordinated atoms with as a reactive site. In situ attenuated total reflection infrared proves As result, catalyst exhibits state-of-the-art turnover frequency ≈15 000 per hour H-cell large current density -400 mA cm-2 Faradaic efficiency (FE) ≥ 90% flow cell. Moreover, retain FE above even 30% diluted concentration.

Язык: Английский

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Edge-Hosted Mn-N₄-C₁₂ Site Tunes Adsorption Energy for Ultralow-Temperature and High-Capacity Solid-State Zn-Air Battery

ACS Nano, Год журнала: 2023, Номер 17(10), С. 9565 - 9574

Опубликована: Май 9, 2023

Robust operation of Zn-air batteries (ZABs) with high capacity and excellent energy efficiency is desirable for practical harsh applications, whose bottlenecks are mainly originated from the sluggish oxygen catalytic kinetics unstable Zn|electrolyte interface. In this work, we synthesized edge-hosted Mn-N4-C12 coordination supported on N-doped defective carbon (Mn1/NDC) catalyst, exhibiting a good bifunctional performance reduction/evolution reaction (ORR/OER) low potential gap 0.684 V. Theoretical calculation reveals that displayed lowest overpotential ORR/OER owing to decreased adsorption free OH*. The Mn1/NDC-based aqueous ZABs deliver impressive rate performance, ultralong discharging lifespan, stability. Notably, assembled solid-state demonstrate 1.29 Ah, large critical current density 8 mA cm-2, robust cycling stability at -40 °C, which should be attributed Mn1/NDC anti-freezing electrolyte (SSE). Meanwhile, zincophilic nanocomposite SSE polarity accounts stable Zn|SSE interface compatibility. This work not only highlights importance atomic structure design electrocatalysts ultralow-temperature high-capacity but also spurs development sustainable Zn-based conditions.

Язык: Английский

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