Electrocatalysis for CO₂conversion: from fundamentals to value-added products

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(8), P. 4993 - 5061

Published: Jan. 1, 2021

This timely and comprehensive review mainly summarizes advances in heterogeneous electroreduction of CO₂: from fundamentals to value-added products.

Language: Английский

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Electrochemical CO2 reduction (CO2RR) to multi-carbon products over copper-based catalysts

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 454, P. 214340 - 214340

Published: Dec. 13, 2021

Language: Английский

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Cu-Ag Tandem Catalysts for High-Rate CO2 Electrolysis toward Multicarbons

Joule, Journal Year: 2020, Volume and Issue: 4(8), P. 1688 - 1699

Published: Aug. 1, 2020

Language: Английский

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Photocatalytic C–C Coupling from Carbon Dioxide Reduction on Copper Oxide with Mixed-Valence Copper(I)/Copper(II)

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(7), P. 2984 - 2993

Published: Feb. 11, 2021

To realize the evolution of C2+ hydrocarbons like C2H4 from CO2 reduction in photocatalytic systems remains a great challenge, owing to gap between relatively lower efficiency multielectron transfer photocatalysis and sluggish kinetics C–C coupling. Herein, with Cu-doped zeolitic imidazolate framework-8 (ZIF-8) as precursor, hybrid photocatalyst (CuOX@p-ZnO) CuOX uniformly dispersed among polycrystalline ZnO was synthesized. Upon illumination, catalyst exhibited ability reduce 32.9% selectivity, rate 2.7 μmol·g–1·h–1 water hole scavenger high 22.3 presence triethylamine sacrificial agent, all which have rarely been achieved systems. The X-ray absorption fine structure spectra coupled situ FT-IR studies reveal that, original catalyst, Cu mainly existed form CuO, while unique Cu+ surface layer upon CuO matrix formed during reaction, this site is active anchor generated CO further perform coupling C2H4. intermediate *OC–COH experimentally identified by for first time reduction. Moreover, theoretical calculations showed critical role such sites strengthening binding *CO stabilizing intermediate. This work uncovers new paradigm achieve system.

Language: Английский

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Boosting electrocatalytic CO2–to–ethanol production via asymmetric C–C coupling

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 29, 2022

Abstract Electroreduction of carbon dioxide (CO 2 ) into multicarbon products provides possibility large-scale chemicals production and is therefore significant research commercial interest. However, the efficiency for ethanol (EtOH), a chemical feedstock, impractically low because limited selectivity, especially under high current operation. Here we report new silver–modified copper–oxide catalyst (dCu O/Ag 2.3% that exhibits Faradaic 40.8% energy 22.3% boosted EtOH production. Importantly, it achieves CO –to–ethanol conversion operation with partial density 326.4 mA cm −2 at −0.87 V vs reversible hydrogen electrode to rank highly significantly amongst reported Cu–based catalysts. Based on in situ spectra studies show results from tailored introduction Ag optimize coordinated number oxide state surface Cu sites, which * adsorption steered as both atop bridge configuration trigger asymmetric C–C coupling stablization intermediates.

Language: Английский

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Stabilizing Cu²⁺ Ions by Solid Solutions to Promote CO₂ Electroreduction to Methane

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2079 - 2084

Published: Jan. 28, 2022

Copper is the only metal catalyst that can perform electrocatalytic CO2 reduction reaction (CRR) to produce hydrocarbons and oxygenates. Its surface oxidation state determines pathway various products. However, under cathodic potential of CRR conditions, chemical composition most Cu-based catalysts inevitably undergoes electroreduction from Cu2+ Cu0 or Cu1+ species, which generally coupled with phase reconstruction formation new active sites. Since initial sites are hard retain, there have been few studies about for CRR. Herein we propose a solid-solution strategy stabilize ions by incorporating them into CeO2 matrix, works as self-sacrificing ingredient protect species. In situ spectroscopic characterization density functional theory calculations reveal compared conventionally derived Cu sites, species in solid solution (Cu-Ce-Ox) significantly strengthen adsorption *CO intermediate, facilitating its further hydrogenation CH4 instead dimerization give C2 As result, different other catalysts, Cu-Ce-Ox delivered high Faradaic efficiency 67.8% low value 3.6% C2H4.

Language: Английский

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Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO₂ Electroreduction

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(1), P. 259 - 269

Published: Dec. 28, 2021

The electrosynthesis of valuable multicarbon chemicals using carbon dioxide (CO2) as a feedstock has substantially progressed recently but still faces considerable challenges. A major difficulty lines in the sluggish kinetics forming carbon-carbon (C-C) bonds, especially neutral media. We report here that oxide-derived copper crystals enclosed by six {100} and eight {111} facets can reduce CO2 to products with high Faradaic efficiency 74.9 ± 1.7% at commercially relevant current density 300 mA cm-2 1 M KHCO3 (pH ∼ 8.4). By combining experimental computational studies, we uncovered Cu(100)/Cu(111) interfaces offer favorable local electronic structure enhances *CO adsorption lowers C-C coupling activation energy barriers, performing superior Cu(100) Cu(111) surfaces, respectively. On this catalyst, no obvious degradation was observed over 50 h continuous operation.

Language: Английский

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Efficient Electrocatalytic CO2 Reduction to C2+ Alcohols at Defect-Site-Rich Cu Surface

Joule, Journal Year: 2021, Volume and Issue: 5(2), P. 429 - 440

Published: Jan. 12, 2021

Language: Английский

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Steering the structure and selectivity of CO2 electroreduction catalysts by potential pulses

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(4), P. 259 - 267

Published: April 21, 2022

Abstract Convoluted selectivity trends and a missing link between reaction product distribution catalyst properties hinder practical applications of the electrochemical CO 2 reduction (CO RR) for multicarbon generation. Here we employ operando X-ray absorption diffraction methods with subsecond time resolution to unveil surprising complexity catalysts exposed dynamic conditions. We show that by using pulsed protocol consisting alternating working oxidizing potential periods dynamically perturb derived from Cu O nanocubes, one can decouple effect ensemble coexisting copper species on distribution. In particular, an optimized balance oxidized reduced surface achieved within narrow range cathodic anodic pulse durations resulted in twofold increase ethanol production compared static RR This work thus prepares ground steering through controlled structural chemical transformations.

Language: Английский

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Double sulfur vacancies by lithium tuning enhance CO2 electroreduction to n-propanol

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: March 11, 2021

Abstract Electrochemical CO 2 reduction can produce valuable products with high energy densities but the process is plagued by poor selectivities and low yields. Propanol represents a challenging product to obtain due complicated C 3 forming mechanism that requires both stabilization of *C intermediates subsequent 1 –C coupling. Herein, density function theory calculations revealed double sulfur vacancies formed on hexagonal copper sulfide feature as efficient electrocatalytic centers for stabilizing CO* OCCO* dimer, further CO–OCCO coupling form species, which cannot be realized CuS single or no vacancies. The were then experimentally synthesized an electrochemical lithium tuning strategy, during was well-tuned charge/discharge cycle number. vacancy-rich catalyst exhibited Faradaic efficiency toward n-propanol 15.4 ± 1% at −1.05 V versus reversible hydrogen electrode in H-cells, partial current 9.9 mA cm −2 −0.85 flow-cells, comparable best reported n-propanol. Our work suggests attractive approach create anion vacancy pairs catalytic multi-carbon-products.

Language: Английский

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