Cu-Zn-based alloy/oxide interfaces for enhanced electroreduction of CO2 to C2+ products

Journal of Energy Chemistry, Journal Year: 2023, Volume and Issue: 83, P. 90 - 97

Published: May 11, 2023

Language: Английский

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Hydrophobic, Ultrastable Cu^δ+ for Robust CO₂ Electroreduction to C₂ Products at Ampere-Current Levels

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11323 - 11332

Published: May 11, 2023

Copper (Cu) is the only known material that can efficiently electrocatalyze CO2 to value-added multicarbon products. Owing instability of Cuδ+ state and microscopic structure in reactions, Cu catalysts are still facing big challenges with low selectivity poor durability, particularly at high current densities. Herein, we report a rational one-step surface coordination approach for synthesis dendrites an ultrastable hydrophobicity (Cu CF), even after exposure air over 6 months. As result, CF exhibited C2 FE 90.6% partial density 453.3 mA cm-2 flow cell. A 400 h stable electrolysis 800 ground-breaking operation large industrial 10 were achieved membrane electrode assembly (MEA) form. We further demonstrated continuous production C2H5OH solution 90% relative purity 600 50 solid-electrolyte reactor. Spectroscopy computation results suggested Cu(II) carboxylate species formed on CF, which ensured stability hydrophobicity. rich active sites three-phase interface catalyst achieved, along optimized *CO adsorption strength configuration. The mixed configurations made dimerization process easier, promoted conversion This work provides promising paradigm design development Cu-based ultrahigh under

Language: Английский

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Acidic CO2-to-HCOOH electrolysis with industrial-level current on phase engineered tin sulfide

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 18, 2023

Acidic CO2-to-HCOOH electrolysis represents a sustainable route for value-added CO2 transformations. However, competing hydrogen evolution reaction (HER) in acid remains great challenge selective production, especially industrial-level current densities. Main group metal sulfides derived S-doped metals have demonstrated enhanced selectivity alkaline and neutral media by suppressing HER tuning reduction intermediates. Yet stabilizing these sulfur dopants on surfaces at large reductive potentials HCOOH production is still challenging acidic medium. Herein, we report phase-engineered tin sulfide pre-catalyst (π-SnS) with uniform rhombic dodecahedron structure that can derive metallic Sn catalyst stabilized In situ characterizations theoretical calculations reveal the π-SnS has stronger intrinsic Sn-S binding strength than conventional phase, facilitating stabilization of residual species subsurface. These effectively modulate CO2RR intermediates coverage medium enhancing *OCHO intermediate adsorption weakening *H binding. As result, (Sn(S)-H) demonstrates significantly high Faradaic efficiency (92.15 %) carbon (36.43 to industrial densities (up -1 A cm-2)

Language: Английский

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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 3101 - 3108

Published: Feb. 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.

Language: Английский

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Engineering strategies and active site identification of MXene-based catalysts for electrochemical conversion reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 3215 - 3264

Published: Jan. 1, 2023

This review summarizes engineering strategies to modify MXene-based catalysts and their active site identification for applications in electrochemical conversion reactions.

Language: Английский

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C₂₊ Selectivity for CO₂ Electroreduction on Oxidized Cu-Based Catalysts

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14335 - 14344

Published: June 21, 2023

Design for highly selective catalysts CO2 electroreduction to multicarbon (C2+) fuels is pressing and important. There is, however, presently a poor understanding of selectivity toward C2+ species. Here we report the first time method judiciously combined quantum chemical computations, artificial-intelligence (AI) clustering, experiment development model relationship between product composition oxidized Cu-based catalysts. We 1) evidence that Cu surface more significantly facilitates C-C coupling, 2) confirm critical potential condition(s) this oxidation state under different metal doping components viaab initio thermodynamics computation, 3) establish an inverted-volcano experimental Faradaic efficiency using multidimensional scaling (MDS) results based on physical properties dopant elements, 4) demonstrate design electrocatalysts selectively generate product(s) through co-doping strategy early late transition metals. conclude combination theoretical AI can be used practically relationships descriptors complex reactions. Findings will benefit researchers in designing conversions products.

Language: Английский

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Electrocatalytic CO₂ Reduction to C₂₊ Products in Flow Cells

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(5)

Published: Aug. 31, 2023

Abstract Electrocatalytic CO 2 reduction into value‐added fuels and chemicals by renewable electric energy is one of the important strategies to address global shortage carbon emission. Though classical H‐type electrolytic cell can quickly screen high‐efficiency catalysts, low current density limited mass transfer process essentially impede its industrial applications. The cells based on electrolyte flow system (flow cells) have shown great potential for devices, due higher density, improved local concentration, better efficiency. design optimization are significance further accelerate industrialization electrocatalytic reaction (CO RR). In this review, progress RR C 2+ products concerned. Firstly, main events in development outlined. Second, principles products, architectures, types summarized. Third, optimizing generate reviewed detail, including cathode, anode, ion exchange membrane, electrolyte. Finally, preliminary attempts, challenges, research prospects toward discussed.

Language: Английский

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SiO₂ assisted Cu⁰–Cu⁺–NH₂ composite interfaces for efficient CO₂ electroreduction to C₂₊ products

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 12(2), P. 1218 - 1232

Published: Dec. 13, 2023

SiO 2 assisted abundant Cu 0 –Cu + –NH composite interfaces enhance the adsorption and activation of CO H O, strengthen intermediates, promote C–C coupling to produce C 2+ products.

Language: Английский

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Direct OC-CHO coupling towards highly C2+ products selective electroreduction over stable Cu0/Cu2+ interface

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 24, 2023

Electroreduction of CO2 to valuable multicarbon (C2+) products is a highly attractive way utilize and divert emitted CO2. However, major fraction C2+ selectivity confined less than 90% by the difficulty coupling C-C bonds efficiently. Herein, we identify stable Cu0/Cu2+ interfaces derived from copper phosphate-based (CuPO) electrocatalysts, which can facilitate production with low-energy pathway OC-CHO verified in situ spectra studies theoretical calculations. The CuPO precatalyst shows high Faradaic efficiency (FE) 69.7% towards C2H4 an H-cell, exhibits significant FEC2+ 90.9% under industrially relevant current density (j = -350 mA cm-2) flow cell configuration. interface breaks new ground for structural design electrocatalysts construction synergistic active sites improve activity products.

Language: Английский

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Sn Dopants with Synergistic Oxygen Vacancies Boost CO₂ Electroreduction on CuO Nanosheets to CO at Low Overpotential

ACS Nano, Journal Year: 2022, Volume and Issue: 16(11), P. 19210 - 19219

Published: Oct. 18, 2022

Using the electrochemical CO2 reduction reaction (CO2RR) with Cu-based electrocatalysts to achieve carbon-neutral cycles remains a significant challenge because of its low selectivity and poor stability. Modulating surface electron distribution by defects engineering or doping can effectively improve CO2RR performance. Herein, we synthesize electrocatalyst Vo-CuO(Sn) nanosheets containing oxygen vacancies Sn dopants for application in CO2RR-to-CO. Density functional theory calculations confirm that incorporation atoms substantially reduces energy barrier *COOH *CO intermediate formation, which results high efficiency, overpotential, superior stability CO conversion. This possesses Faraday efficiency (FE) 99.9% at overpotential 420 mV partial current density up 35.22 mA cm-2 -1.03 V versus reversible hydrogen electrode (RHE). The FECO could retain over 95% within wide potential area from -0.48 -0.93 RHE. Moreover, obtain long-term more than 180 h only slight decay activity. Therefore, this work provides an effective route designing environmentally friendly

Language: Английский

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