CO2 electroreduction to multicarbon products in strongly acidic electrolyte via synergistically modulating the local microenvironment

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

Published: Dec. 9, 2022

Electrochemical CO2 reduction to multicarbon products faces challenges of unsatisfactory selectivity, productivity, and long-term stability. Herein, we demonstrate electroreduction in strongly acidic electrolyte (pH ≤ 1) on electrochemically reduced porous Cu nanosheets by combining the confinement effect cation synergistically modulate local microenvironment. A Faradaic efficiency 83.7 ± 1.4% partial current density 0.56 0.02 cm-2, single-pass carbon 54.4%, stable electrolysis 30 h a flow cell are demonstrated for aqueous consisting sulfuric acid KCl with pH 1. Mechanistically, accumulated species (e.g., K+ OH-) Helmholtz plane account selectivity activity toward kinetically reducing proton coverage thermodynamically favoring conversion. We find that cations facilitate C-C coupling through interaction between key intermediate *OCCO.

Language: Английский

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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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Recent advances on electrocatalytic CO2 reduction to resources: Target products, reaction pathways and typical catalysts

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 453, P. 139663 - 139663

Published: Oct. 8, 2022

Language: Английский

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Turning Waste into Wealth: Sustainable Production of High-Value-Added Chemicals from Catalytic Coupling of Carbon Dioxide and Nitrogenous Small Molecules

ACS Nano, Journal Year: 2022, Volume and Issue: 16(11), P. 17911 - 17930

Published: Oct. 31, 2022

Carbon neutrality is one of the central topics not only scientific community but also majority human society. The development highly efficient carbon dioxide (CO2) capture and utilization (CCU) techniques expected to stimulate routes concepts go beyond fossil fuels provide more economic benefits for a carbon-neutral economy. While various single-carbon (C1) multi-carbon (C2+) products have been selectively produced date, scope CCU can be further expanded valuable chemicals simple species by integration nitrogenous reactants into CO2 reduction. In this Review, research progress toward sustainable production high-value-added (urea, methylamine, ethylamine, formamide, acetamide, glycine) from catalytic coupling small molecules (NH3, N2, NO3–, NO2–) highlighted. C–N bond formation key mechanistic step in N-integrated reduction, so we focus on possible pathways starting reduction processes as well attributes that enable coupling. We propose directions prospects field, aiming inspire future investigations achieve comprehensive improvement performance product systems.

Language: Английский

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Understanding and leveraging the effect of cations in the electrical double layer for electrochemical CO2 reduction

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(6), P. 1267 - 1276

Published: April 18, 2022

Language: Английский

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Rare‐Earth Single‐Atom Catalysts: A New Frontier in Photo/Electrocatalysis

Small Methods, Journal Year: 2022, Volume and Issue: 6(8)

Published: June 25, 2022

Abstract Single‐atom catalysts (SACs) provide well‐defined active sites with 100% atom utilization, and can be prepared using a wide range of support materials. Therefore, they are attracting global attention, especially in the fields energy conversion storage. To date, research has focused on transition‐metal precious‐metal‐based SACs. More recently, rare‐earth (RE)‐based SACs have emerged as new frontier photo/electrocatalysis owing to their unique electronic structure arising from spin‐orbit coupling 4f valence orbitals, unsaturated coordination environment, behavior charge‐transport bridges. However, systematic review role RE sites, catalytic mechanisms, synthetic methods for is lacking. this review, latest developments having applications summarized discussed. First, theoretical advantages briefly introduced, focusing roles orbitals coupled levels. In addition, most recent progress several important photo/electrocatalytic reactions corresponding mechanisms Further, strategies production reported. Finally, challenges development highlighted, along future directions perspectives.

Language: Английский

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In-situ/operando Raman techniques for in-depth understanding on electrocatalysis

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 461, P. 141939 - 141939

Published: Feb. 16, 2023

Language: Английский

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Stability Issues in Electrochemical CO₂ Reduction: Recent Advances in Fundamental Understanding and Design Strategies

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(51)

Published: Aug. 11, 2023

Electrochemical CO2 reduction reaction (CO2 RR) offers a promising approach to close the anthropogenic carbon cycle and store intermittent renewable energy in fuels or chemicals. On path commercializing this technology, achieving long-term operation stability is central requirement but still confronts challenges. This motivates organize present review systematically discuss issue of RR. starts from fundamental understanding on destabilization mechanisms RR, with focus degradation electrocatalyst change microenvironment during continuous electrolysis. Subsequently, recent efforts catalyst design stabilize active sites are summarized, where increasing atomic binding strength resist surface reconstruction highlighted. Next, optimization electrolysis system enhance by maintaining especially mitigating flooding carbonate problems demonstrated. The manipulation conditions also enables prolong RR lifespan through recovering catalytically mass transport process. finally ends up indicating challenges future opportunities.

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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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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