Tailoring CO₂ Adsorption Configuration with Spatial Confinement Switches Electroreduction Product from Formate to Acetate

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Multi-proton-coupled electron transfer, multitudinous intermediates, and unavoidable competing hydrogen evolution reaction during CO2 electroreduction make it tricky to control high selectivity for specific products. Here, we present spatial confinement of Fe single atoms (FeN2S2) by adjacent FeS clusters (Fe4S4) orientate the transition adsorption configuration from C,O-side O-end, which triggers a shift activated first-step protonation C–C coupling, thus switching target product HCOOH in Faraday efficiency (FE: 90.6%) on FeN2S2 CH3COOH 82.3%) Fe4S4/FeN2S2. The strength *OCHO upon solitary site is linearly related coordination number Fe–S, with predominantly produced over single-atom (ortho-substituted S atoms). Fe4S4 cluster functions as switch reduction product, can not only optimize electronic structure neighboring but also impel complete hydrocarbon intermediate *CH3, followed coupling CO2* *CH3 via synergistic catalysis This strategy provides new avenue modulate reactant model desirable pathways, potential applications diverse multistep electrochemical processes controlled selectivity.

Language: Английский

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Vanadium Oxide Clusters Mediated Bismuth‐Tin Alloy for Accelerated Dynamics of Electrocatalytic CO₂ Conversion

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 16, 2024

Abstract The electrocatalytic conversion of carbon dioxide (CO 2 ) to formate is significant for neutrality. How improve the reaction kinetics electrocatalysts one important challenges. An innovative electrodeposition strategy presented herein rationally synthesize vanadium oxide (VO x clusters decorated Bi‐Sn alloy (BiSn(VO )) catalyst. Theoretical and in situ spectral studies confirm simultaneously improved CO activation subsequent protonation via VO mediated water dissociation process, thereby optimizing activity selectivity formate. Remarkably, this BiSn(VO catalyst achieves high Faradic efficiency (FE) over 90% within wide potential window 800 mV excellent stability 100 h at −0.6 V versus RHE. Moreover, cathode integrated rechargeable Zn‐CO battery realizes largest power density 3.8 mW cm −2 , while assembled co‐electrolysis electrolyzer delivers a total FE 182% cell voltage 0.6 V, outperforming highest value so far. work provides promising way develop advanced electrolysis.

Language: Английский

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Engineering S-Scheme Heterojunction via MOF-on-MOF for Photocatalytic Nitroarene Hydrogenation

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

Photocatalytic nitroarene reduction provides a promising strategy for the sustainable production of aniline. The construction S-scheme heterostructures with clear interfacial charge transfer mechanism is considered as an effective to improve photocatalytic performance photocatalysts. assembly MOF-on-MOF might be used construct heterojunctions due rich structures, transport channels, and fast mass MOFs. Herein, 2D Pd-PPF-1 was coated on 3D Pd-PCN-222 through presurface modification strategy, prepared Pd-PPF-1/Pd-PCN-222 heterojunction displayed morphology nanoflower winding around rod. As hydrogenation, as-obtained catalyst exhibited much higher than Pd-PPF-1, Pd-PCN-222, or physical mixture Pd-PCN-222. high catalytic attributed formation heterojunction, which not only retained redox capability parent MOFs but also separated photogenerated carriers. This work presents constructive route designing 2D-on-3D MOF controllable ability.

Language: Английский

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Covalently Modified Electrode with Bismuth Nanoparticles Encapsulated in Ultrathin Porous Organic Polymer Linked by Amine Bonding for Efficient CO₂ Electroreduction

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: April 23, 2025

Bismuth-based materials in electrocatalytic CO2 reduction (CO2RR) usually face the problem of high overpotential. We first show a covalently modified electrode with Bi nanoparticles encapsulated ultrathin porous organic polymer nanosheets (POPs) amine linkages to effectively reduce overpotential for CO2-to-formate conversion, which exhibits formate Faradaic efficiency (FEHCOO-) 98.5% and partial current density up 148.7 mA cm-2 at -0.85 V comparison that bare bismuth FEHCOO- 85% -1.15 (versus reversible hydrogen electrode). Different from reaction mechanism *CO2•- radicals as intermediate over sites, situ spectroscopic studies functional theory calculations reveal abundant POPs backbone provide chemisorption sites interact enriched molecules form carbamates (*[-NCOO-]) intermediates low barrier 0.064 eV, significantly reduces free energy conversion process formate. Moreover, promote water dissociation subsequent protonation on surface reduced -0.31 eV than 0.11 eV. This work not only delivers new but also offers clean platform investigate influence modification.

Language: Английский

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Mg-Doped Cu Catalyst for Electroreduction of CO₂ to Multicarbon Products: Lewis Acid Sites Simultaneously Promote *CO Adsorption and Water Dissociation

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 21, 2024

The electroreduction of CO

Language: Английский

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