Asymmetric Coordination Environment Engineering of Atomic Catalysts for CO2 Reduction

Nanomaterials, Journal Year: 2023, Volume and Issue: 13(2), P. 309 - 309

Published: Jan. 11, 2023

Single-atom catalysts (SACs) have emerged as well-known in renewable energy storage and conversion systems. Several supports been developed for stabilizing single-atom catalytic sites, e.g., organic-, metal-, carbonaceous matrices. Noticeably, the metal species their local atomic coordination environments a strong influence on electrocatalytic capabilities of atom active centers. In particular, asymmetric electrocatalysts exhibit unique properties an unexpected carbon dioxide reduction reaction (CO2RR) performance different from those traditional metal-N4 sites. This review summarizes recent development sites CO2RR with emphasis structure regulation strategies effects performance. Ultimately, several scientific possibilities are proffered aim further expanding deepening advancement CO2RR.

Language: Английский

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Ampere-level CO2 electroreduction with single-pass conversion exceeding 85% in acid over silver penetration electrodes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 19, 2024

Abstract Synthesis of valuable chemicals from CO 2 electroreduction in acidic media is highly desirable to overcome carbonation. However, suppressing the hydrogen evolution reaction such proton-rich environments remains a considerable challenge. The current study demonstrates use hollow fiber silver penetration electrode with hierarchical micro/nanostructures enable reduction strong acids via balanced coordination and K + /H supplies. Correspondingly, faradaic efficiency 95% achieved at partial density as high 4.3 A/cm pH = 1 solution H SO 4 KCl, sustaining 200 h continuous electrolysis over 85% single-pass conversion . experimental results functional theory calculations suggest that controllable feeding induced by configuration primarily coordinate balance on Ag active sites acids, favoring activation key intermediate *COOH formation, resulting enhanced formation.

Language: Английский

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Modulating the Coordination Environment of Atomically Dispersed Nickel for Efficient Electrocatalytic CO₂ Reduction at Low Overpotentials and Industrial Current Densities

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Electrocatalytic CO2-to-CO conversion with a high CO Faradaic efficiency (FECO) at low overpotentials and industrial-level current densities is highly desirable but huge challenge over non-noble metal catalysts. Herein, graphitic N-rich porous carbons supporting atomically dispersed nickel (NiN4–O sites an axial oxygen) were synthesized (denoted as O–Ni–Nx–GC) applied the cathode catalyst in CO2RR flow cell. O–Ni–Nx–GC showed excellent selectivity FECO 92% ranging from 17 to 60 mV, 99% 80 mV. The was ∼100% 200 900 mA·cm–2. Impressively, delivered state-of-the-art of >96% 1 A·cm–2 turnover frequency 81.5 s–1 M KOH electrolyte. offered stability during long-term operation for 140 h 100 mA·cm–2, maintaining > 99%. Mechanism studies revealed that oxygen enhanced electron delocalization, carbon support lowering energy barrier inducing negative shift Ni-3d d-band center, effectively promoting formation *COOH intermediate while weakening adsorption *CO intermediate, thus optimizing catalytic activity/selectivity under practical conditions.

Language: Английский

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Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 25, 2025

In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al2O3-CuSAC, CeO2-CuSAC, and TiO2-CuSAC) are used as theoretical models to explore correlations between electronic structures CO2RR performances. For these catalysts, metal-support interaction (EMSI) induced charge transfer sites supports subtly modulates structure form different highest occupied-orbital. The occupied 3dyz orbital of Al2O3-CuSAC enhances adsorption strength CO weakens C-O bonds through 3dyz-π* electron back-donation. This reduces energy barrier for C-C coupling, thereby promoting multicarbon formation on Al2O3-CuSAC. 3dz2 TiO2-CuSAC accelerates H2O activation, lowers reaction forming CH4. over activated H2O, in turn, intensifies competing hydrogen evolution (HER), which hinders high-selectivity production CH4 TiO2-CuSAC. CeO2-CuSAC with 3dx2-y2 promotes CO2 activation its localized state inhibits coupling. moderate water activity facilitates *CO deep hydrogenation without excessively activating HER. Hence, exhibits Faradaic efficiency 70.3% at 400 mA cm−2. Rational regulation control electroreduction pathways is challenging. Here, authors report modulating single-sites via interaction, enabling switchable selectivity multicarbons methane.

Language: Английский

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Boosting electrocatalytic CO₂reduction reaction over viologen-functionalized metal–organic frameworks by enhancement of electron-transfer capacity

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(16), P. 8739 - 8746

Published: Jan. 1, 2023

Viologen-based MOFs were developed to show highly efficient electrocatalytic CO 2 reduction reaction with a high faradaic efficiency of 93.8% at 2.3 V and large partial current density 111.1 mA cm −2 2.9 V.

Language: Английский

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