Electrochemical reduction of carbon dioxide to multicarbon (C₂₊) products: challenges and perspectives

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(11), P. 4714 - 4758

Published: Jan. 1, 2023

This review analyzes advanced catalysts and C 2+ synthesis mechanisms based on theoretical explorations in situ / operando characterizations. Triphasic interface optimization is discussed for the potential of industry-compatible stability.

Language: Английский

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Atomic-scale surface restructuring of copper electrodes under CO2 electroreduction conditions

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(9), P. 837 - 846

Published: Aug. 17, 2023

Abstract Potentiodynamic methods that induce structural changes in Cu catalysts for the electrochemical reduction of CO 2 (CO RR) have been identified as a promising strategy steering catalyst selectivity towards generation multi-carbon products. In current approaches, active species are created via sequential oxidation–reduction process. Here we show by situ scanning tunnelling microscopy, surface X-ray diffraction and Raman spectroscopy measurements low-coordinated form spontaneously near onset electrocatalytic reduction. This process starts CO-induced nanocluster formation initial stages reaction, leading to irreversible restructuring persists over wide potential range. On subsequent increase, nanoclusters disperse into adatoms, which stabilize reaction intermediates on surface. The observed self-induced undercoordinated sites -converting can account its reactivity may be exploited (re)generate RR potentiodynamic protocols.

Language: Английский

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In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO₂ Reduction and C–C Coupling on Oxide-Derived Copper

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 1935 - 1945

Published: Jan. 8, 2024

The reaction mechanism of CO2 electroreduction on oxide-derived copper has not yet been unraveled even though high C2+ Faradaic efficiencies are commonly observed these surfaces. In this study, we aim to explore the effects anodization adsorption various CO2RR intermediates using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) metallic and mildly anodized thin films. SEIRAS results show that preoxidation process can significantly improve overall reduction activity by (1) enhancing activation, (2) increasing CO uptake, (3) promoting C–C coupling. First, strong *COO– redshift indicates enhances first elementary step activation. rapid uptake adsorbed *COatop also illustrates how a *CO coverage be achieved electrocatalysts. Finally, for time, formation *COCHO dimer film. Using DFT calculations, presence subsurface oxygen within Cu lattice thermodynamics C2 product via coupling *CHO intermediates. This study advances our understanding role surface conditions improving catalytic kinetics selectivity reduction.

Language: Английский

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Local reaction environment in electrocatalysis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(4), P. 2022 - 2055

Published: Jan. 1, 2024

Beyond conventional electrocatalyst engineering, recent studies have unveiled the effectiveness of manipulating local reaction environment in enhancing performance electrocatalytic reactions. The general principles and strategies environmental engineering for different processes been extensively investigated. This review provides a critical appraisal advancements aiming to comprehensively assess this emerging field. It presents interactions among surface structure, ions distribution electric field relation environment. Useful protocols such as interfacial reactant concentration, mass transport rate, adsorption/desorption behaviors, binding energy are in-depth discussed toward modifying Meanwhile, electrode physical structures cell configurations viable optimization methods environments. In combination with

Language: Английский

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Different distributions of multi-carbon products in CO2 and CO electroreduction under practical reaction conditions

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(12), P. 1115 - 1124

Published: Dec. 20, 2023

Language: Английский

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Unintended cation crossover influences CO2 reduction selectivity in Cu-based zero-gap electrolysers

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

Published: April 12, 2023

Membrane electrode assemblies enable CO2 electrolysis at industrially relevant rates, yet their operational stability is often limited by formation of solid precipitates in the cathode pores, triggered cation crossover from anolyte due to imperfect ion exclusion anion exchange membranes. Here we show that concentration affects degree movement through membranes, and this substantially influences behaviors copper catalysts catholyte-free electrolysers. Systematic variation (KOH or KHCO3) ionic strength produced a distinct switch selectivity between either predominantly CO C2+ products (mainly C2H4) which closely correlated with quantity alkali metal (K+) crossover, suggesting cations play key role C-C coupling reaction pathways even cells without discrete liquid catholytes. Operando X-ray absorption quasi situ photoelectron spectroscopy revealed Cu surface speciation showed strong dependence on concentration, wherein dilute anolytes resulted mixture Cu+ Cu0 species, while concentrated led exclusively under similar testing conditions. These results cells, effects (including unintentional ones) significantly influence pathways, important consider future development devices.

Language: Английский

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Molecular tuning for electrochemical CO2 reduction

Joule, Journal Year: 2023, Volume and Issue: 7(8), P. 1700 - 1744

Published: Aug. 1, 2023

Language: Английский

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Circumventing CO₂ Reduction Scaling Relations Over the Heteronuclear Diatomic Catalytic Pair

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11829 - 11836

Published: May 18, 2023

In the electrochemical CO2 reduction reaction (CO2RR), activation is always first step, followed by subsequent hydrogenation. The catalytic performance of CO2RR intrinsically restricted competition between molecular and product release. Here, we design a heteronuclear Fe1-Mo1 dual-metal pair on ordered porous carbon that features high for driving to CO. Combining real-time near-ambient pressure X-ray photoelectron spectroscopy, operando 57Fe Mössbauer in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements with density functional theory calculations, chemical adsorption observed through bridge configuration, which prompts bending molecule then facilitates hydrogeneration reaction. More importantly, dynamic configuration transition from linear CO Fe1 center results breaking scaling relationship CO2RR, simultaneously promoting

Language: Английский

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Understanding the complexity in bridging thermal and electrocatalytic methanation of CO₂

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(11), P. 3627 - 3662

Published: Jan. 1, 2023

The selective methanation of CO2 is an important research area to meet the net-zero emission targets. Furthermore, it crucial develop solutions achieve carbon neutrality, hydrogen utilization, circularity, and chemical-energy storage. This conversion can be realized via thermocatalytic multistep power-to-X route or by direct electro- (or photoelectro)-catalytic technologies. Herein, we discuss need accelerate Improving these technologies requires a better understanding catalytic chemistry complexity aspects consider in bridging electrocatalytic methanation. In this tutorial review, initially analyze fundamental question competitive adsorption key reactants regulation strategies promote overall reaction. Then, approach used guide reader differences between thermocatalysis electrocatalysis. Finally, necessary include modelling designing next-generation electrocatalysts for analyzed.

Language: Английский

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Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(14), P. 9823 - 9851

Published: March 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Language: Английский

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