Improving CO₂-to-C₂₊ Product Electroreduction Efficiency via Atomic Lanthanide Dopant-Induced Tensile-Strained CuO_x Catalysts

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(17), P. 9857 - 9866

Published: April 24, 2023

Cu is a promising electrocatalyst in CO2 reduction reaction (CO2RR) to high-value C2+ products. However, as important C-C coupling active sites, the Cu+ species usually unstable under conditions. How atomic dopants affect performance of Cu-based catalysts interesting be studied. Herein, we first calculated difference between thermodynamic limiting potentials CO2RR and hydrogen evolution reaction, well *CO binding energy over Cu2O doped with different metals, results indicated that doping Gd into could improve catalyst effectively. On basis theoretical study, designed Gd1/CuOx catalysts. The distinctive electronic structure large ion radii not only keep stable during but also induce tensile strain Gd1/CuOx, resulting excellent for electroreduction Faradic efficiency products reach 81.4% product partial current density 444.3 mA cm-2 at -0.8 V vs reversible electrode. Detailed experimental studies revealed enhanced activation on catalyst, stabilized key intermediate O*CCO, reduced barrier reaction.

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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Localized Alkaline Environment via In Situ Electrostatic Confinement for Enhanced CO₂-to-Ethylene Conversion in Neutral Medium

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6339 - 6348

Published: March 9, 2023

Electrocatalytic CO2 reduction reaction (CO2RR) is one of the most promising routes to facilitate carbon neutrality. An alkaline electrolyte typically needed promote production valuable multi-carbon molecules (such as ethylene). However, between and OH- consumes a significant quantity CO2/alkali causes rapid decay CO2RR selectivity stability. Here, we design catalyst-electrolyte interface with an effective electrostatic confinement in situ generated improve ethylene electrosynthesis from neutral medium. In Raman measurements indicate direct correlation intensities surface Cu-CO Cu-OH species, suggesting promoted C-C coupling enrichment OH-. Thus, report CO2-to-ethylene Faradaic efficiency (FE) 70% partial current density 350 mA cm-2 at -0.89 V vs reversible hydrogen electrode. Furthermore, system demonstrated 50 h stable operation 300 average FE ∼68%. This study offers universal strategy tune micro-environment, significantly improved 64.5% was obtained even acidic electrolytes (pH = 2).

Language: Английский

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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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High‐Entropy Alloy Aerogels: A New Platform for Carbon Dioxide Reduction

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(2)

Published: Nov. 14, 2022

High-entropy alloy aerogels (HEAAs) combined with the advantages of high-entropy alloys and are prospective new platforms in catalytic reactions. However, due to differences reduction potentials miscibility behavior different metals, realization HEAAs a single phase is still great challenge. Herein, series fabricated via freeze-thaw method as highly active durable electrocatalysts for carbon dioxide reaction (CO2 RR). Especially, PdCuAuAgBiIn can achieve Faradaic efficiency (FE) C1 products almost 100% from -0.7 -1.1 V versus reversible hydrogen electrode (VRHE ), maximum FE formic acid (FEHCOOH ) 98.1% at VRHE , outperforming particles (HEAPs) Pd metallic (MAs). Specifically, current density FEHCOOH 200 mA cm-2 87% flow cell. The impressive CO2 RR performance attributed strong interactions between metals surface unsaturated sites, which regulate electronic structures allow optimal HCOO* intermediate adsorption desorption onto catalysts enhance HCOOH production. work not only provides facile synthetic strategy fabricate HEAAs, but also opens avenue development efficient beyond.

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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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 Copper by a Reconstruction-Resistant Atomic Cu–O–Si Interface for Electrochemical CO₂ Reduction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8656 - 8664

Published: April 8, 2023

Copper (Cu), a promising catalyst for electrochemical CO2 reduction (CO2R) to multi-electron products, suffers from an unavoidable and uncontrollable reconstruction process during the reaction, which not only may lead deactivation but also brings great challenges exploration of structure-performance relationship. Herein, we present efficient strategy stabilizing Cu with silica synthesize reconstruction-resistant CuSiOx amorphous nanotube catalysts abundant atomic Cu-O-Si interfacial sites. The strong interaction between makes sites ultrastable in CO2R reaction without any apparent reconstruction, thus exhibiting high CO2-to-CH4 selectivity (72.5%) stability (FECH4 remains above 60% after 12 h test). A remarkable conversion rate 0.22 μmol cm-2 s-1 was achieved flow cell device. This work provides very route design highly active stable Cu-based catalysts.

Language: Английский

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Oxophilicity-Controlled CO₂ Electroreduction to C₂₊ Alcohols over Lewis Acid Metal-Doped Cu^δ+ Catalysts

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(40), P. 21945 - 21954

Published: Sept. 26, 2023

Cu-based electrocatalysts have great potential for facilitating CO2 reduction to produce energy-intensive fuels and chemicals. However, it remains challenging obtain high product selectivity due the inevitable strong competition among various pathways. Here, we propose a strategy regulate adsorption of oxygen-associated active species on Cu by introducing an oxophilic metal, which can effectively improve C2+ alcohols. Theoretical calculations manifested that doping Lewis acid metal Al into affect C–O bond Cu–C breaking toward selectively determining intermediate (shared ethanol ethylene), thus prioritizing pathway. Experimentally, Al-doped catalyst exhibited outstanding Faradaic efficiency (FE) 84.5% with remarkable stability. In particular, alcohol FE could reach 55.2% partial current density 354.2 mA cm–2 formation rate 1066.8 μmol h–1. A detailed experimental study revealed improved strength oxygen surface stabilized key *OC2H5, leading ethanol. Further investigation showed this also be extended other metals.

Language: Английский

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