Stabilizing Oxidation State of SnO₂ for Highly Selective CO₂ Electroreduction to Formate at Large Current Densities

ACS Catalysis, Год журнала: 2023, Номер 13(5), С. 3101 - 3108

Опубликована: Фев. 16, 2023

Even though electrocatalytic CO2 reduction reaction (CO2RR) to formate has made significant advances, achieving a high cell energy efficiency at industrial-level current densities is still bottleneck for the large-scale application of this technology. SnO2 promising electrocatalyst production but restricted by unstable oxidation state under potentials, causing catalyst reconstruction and inactivation. Herein, we present an atomic doping strategy (by Cu, Bi, or Pt) trigger emergence oxygen vacancy in lattice stabilize during CO2RR. As result, optimal Cu-incorporated can keep Faradic >80% about 50–60% wide range up 500 mA cm–2 commercial flow cell, surpassing most reported works. A set situ spectroscopy measurements controlled electrochemical tests suggest that vacancy, induced participation Cu/Bi/Pt single atoms, holds key stabilizing as well promoting adsorption formate-related *OCHO intermediate. qualitative relationship between concentration CO2-to-formate conversion constructed on series doped catalysts.

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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A Nanocomposite of Bismuth Clusters and Bi₂O₂CO₃ Sheets for Highly Efficient Electrocatalytic Reduction of CO₂ to Formate

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Окт. 29, 2022

The renewable-electricity-driven CO2 reduction to formic acid would contribute establishing a carbon-neutral society. current catalyst suffers from limited activity and stability under high selectivity the ambiguous nature of active sites. Herein, we report powerful Bi2 S3 -derived that demonstrates density 2.0 A cm-2 with formate Faradaic efficiency 93 % at -0.95 V versus reversible hydrogen electrode. energy conversion single-pass yield reach 80 67 %, respectively, durability reaches 100 h an industrial-relevant density. Pure concentration 3.5 mol L-1 has been produced continuously. Our operando spectroscopic theoretical studies reveal dynamic evolution into nanocomposite composed Bi0 clusters O2 CO3 nanosheets pivotal role -Bi2 interface in activation conversion.

Язык: Английский

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Selective CO2 electrolysis to CO using isolated antimony alloyed copper

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

Опубликована: Янв. 20, 2023

Abstract Renewable electricity-powered CO evolution from 2 emissions is a promising first step in the sustainable production of commodity chemicals, but performing electrochemical reduction economically at scale challenging since only noble metals, for example, gold and silver, have shown high performance -to-CO. Cu potential catalyst to achieve industrial scale, C-C coupling process on significantly depletes CO* intermediates, thus limiting rate producing many hydrocarbon oxygenate mixtures. Herein, we tune selectivity by alloying second metal Sb into Cu, report an antimony-copper single-atom alloy (Sb 1 Cu) isolated Sb-Cu interfaces that catalyzes efficient conversion -to-CO with Faradaic efficiency over 95%. The partial current density reaches 452 mA cm −2 approximately 91% efficiency, negligible C 2+ products are observed. In situ spectroscopic measurements theoretical simulations reason atomic interface promotes adsorption/activation weakens binding strength CO*, which ends up enhanced rates.

Язык: Английский

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Embedding oxophilic rare-earth single atom in platinum nanoclusters for efficient hydrogen electro-oxidation

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

Опубликована: Июнь 24, 2023

Designing Pt-based electrocatalysts with high catalytic activity and CO tolerance is challenging but extremely desirable for alkaline hydrogen oxidation reaction. Herein we report the design of a series single-atom lanthanide (La, Ce, Pr, Nd, Lu)-embedded ultrasmall Pt nanoclusters efficient electro-oxidation catalysis based on vapor filling spatially confined reduction/growth metal species. Mechanism studies reveal that oxophilic species in can serve as Lewis acid site selective OH- adsorption regulate binding strength intermediates sites, which promotes kinetics by accelerating combination *H/*CO thermodynamics, endowing electrocatalyst up to 14.3-times higher mass than commercial Pt/C enhanced tolerance. This work may shed light nanocluster-based energy conversion.

Язык: Английский

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