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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Multiscale CO₂ Electrocatalysis to C₂₊ Products: Reaction Mechanisms, Catalyst Design, and Device Fabrication

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10530 - 10583

Published: Aug. 17, 2023

Electrosynthesis of value-added chemicals, directly from CO2, could foster achievement carbon neutral through an alternative electrical approach to the energy-intensive thermochemical industry for utilization. Progress in this area, based on electrogeneration multicarbon products CO2 electroreduction, however, lags far behind that C1 products. Reaction routes are complicated and kinetics slow with scale up high levels required commercialization, posing significant problems. In review, we identify summarize state-of-art progress synthesis a multiscale perspective discuss current hurdles be resolved generation reduction including atomistic mechanisms, nanoscale electrocatalysts, microscale electrodes, macroscale electrolyzers guidelines future research. The review ends cross-scale links discrepancies between different approaches extensions performance stability issues arise industrial environment.

Language: Английский

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Halide-guided active site exposure in bismuth electrocatalysts for selective CO2 conversion into formic acid

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(9), P. 796 - 806

Published: Aug. 17, 2023

Abstract It remains a challenge to identify the active sites of bismuth catalysts in electrochemical CO 2 reduction reaction. Here we show through situ characterization that activation oxyhalide electrocatalysts metallic is guided by halides. In X-ray diffraction results bromide promotes selective exposure planar surfaces, whereas chloride and iodide result more disordered sites. Furthermore, find bromide-activated outperform counterparts, achieving high current density (>100 mA cm –2 ) formic acid selectivity (>90%), suggesting surfaces are for addition, absorption spectroscopy measurements reveal reconstruction proceeds rapidly chloride-activated gradually when present, facilitating formation ordered surfaces. These findings pivotal role halogens on facet activated bismuth-based during

Language: Английский

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Tafel Slope Plot as a Tool to Analyze Electrocatalytic Reactions

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(4), P. 1871 - 1879

Published: April 1, 2024

Kinetic and nonkinetic contributions to the Tafel slope value can be separated using a plot, where constant region indicates kinetic meaningfulness. Here, we compare values obtained from linear sweep voltammetry chronoamperometry impedance spectroscopy, apply plot various electrocatalytic reactions. We show that similar are observed different techniques under high-mass-transport conditions for oxygen evolution reaction on NiFeOOH in 0.2 M KOH. However, alkaline hydrogen CO2 reduction reaction, no horizontal regions were observed. In contrast, expected of 30 mV/dec HER Pt 1 HClO4. argue widespread application or numerical differentiation techniques, would result an improved comparison data many reactions when traditional analysis is ambiguous.

Language: Английский

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Understanding Cation Effects on the Hydrogen Evolution Reaction

ACS Energy Letters, Journal Year: 2022, Volume and Issue: 8(1), P. 657 - 665

Published: Dec. 21, 2022

The hydrogen evolution reaction (HER) is known to be influenced by the identity of alkali metal cations in electrolyte. But a clear understanding this behavior has not been developed. Here, we present results experimental and theoretical studies that describe how influence HER acidic basic electrolytes. Alkali are shown have no systematic effect on rates acid. In alkaline media, decrease with increasing cation size over Ir, Pd, Pt (Li+ > Na+ K+ Cs+) increase Cu, Ag, Au < Cs+). We argue interfacial lower activation barrier for water dissociation, an elementary step unique media. limited but Pt, explaining inverted activity trend. Based ab initio molecular dynamics simulations, suggest trends attributable greater willingness large, weakly solvated approach electrode surface.

Language: Английский

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Polyoxometalate-based nanostructures for electrocatalytic and photocatalytic CO ₂ reduction

Polyoxometalates, Journal Year: 2022, Volume and Issue: 1(1), P. 9140006 - 9140006

Published: Sept. 1, 2022

Electro/photocatalytic carbon dioxide (CO₂) reduction to value-added chemicals and fuels is being actively studied as a promising pathway for renewable energy storage climate change mitigation. Because of inert molecular properties competing hydrogen generation reactions, high-performance electrocatalysts with high Faradaic efficiency product selectivity but low overpotential are urgently needed. Polyoxometalates (POMs) class polynuclear metal oxide clusters precise atomic structure, providing an ideal research platform reveal the relationship between macroscopic microstructures. Moreover, their highly tunable redox abundant transition atom composition ensure thriving POM-based nanostructures toward CO₂ reduction. In this review, we first introduce specific roles POMs in electro/photocatalytic Recent advances ranging from single clusters, assemblies, organic–inorganic hybrids derivatives systematically summarized. particular, structure–performance discussed at levels. Finally, challenges opportunities design high-efficiency promote

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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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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Regulating reconstruction of oxide-derived Cu for electrochemical CO ₂ reduction toward n-propanol

Science Advances, Journal Year: 2023, Volume and Issue: 9(43)

Published: Oct. 27, 2023

Oxide-derived copper (OD-Cu) is the most efficient and likely practical electrocatalyst for CO 2 reduction toward multicarbon products. However, inevitable but poorly understood reconstruction from pristine state to working of OD-Cu under strong conditions largely hinders rational construction catalysts products, especially C 3 products like n-propanol. Here, we simulate CuO Cu O into their derived by molecular dynamics, revealing that CuO-derived (CuOD-Cu) intrinsically has a richer population undercoordinated sites higher surficial atom density than counterpart O-derived (Cu OD-Cu) because vigorous oxygen removal. In situ spectroscopes disclose coordination number CuOD-Cu considerably lower OD-Cu, enabling fast kinetics reaction strengthened binding *C intermediate(s). Benefiting rich sites, achieves remarkable n-propanol faradaic efficiency up ~17.9%, whereas dominantly generates formate.

Language: Английский

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Deciphering Electrolyte Selection for Electrochemical Reduction of Carbon Dioxide and Nitrogen to High‐Value‐Added Chemicals

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(11)

Published: Jan. 4, 2023

Abstract Electrochemical reduction of CO 2 (CO RR) and nitrogen (NRR) constitute alternatives to fossil fuel‐based technologies for the production high‐value‐added chemicals. Yet their practical application is still hampered by low energy Faradaic efficiencies although numerous efforts have been paid overcome fatal shortcomings. To date, most studies focused on designing developing advanced electrocatalysts, while understanding electrolyte, which would significantly influence reaction microenvironment, are not enough provide insight construct highly active selective electrochemical systems. Here, a comprehensive review different electrolytes participating in RR NRR provided, including acidic, neutral, alkaline, water‐in‐salt electrolyte as aqueous electrolytes, well organic ionic‐liquids mixture two non‐aqueous electrolytes. Through discussion roles these various it aimed grasp essential function during process how functions can be used design parameters improving electrocatalytic performance. Finally, priorities future suggested support in‐depth effects thus guide efficient selection next‐generation gas‐involving reactions.

Language: Английский

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