Review on strategies for improving the added value and expanding the scope of CO₂ electroreduction products

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 5149 - 5189

Published: Jan. 1, 2024

This review summarizes promising strategies including the design of catalysts and construction coupled electrocatalytic reaction systems, aimed at achieving selective production various products from CO 2 electroreduction.

Language: Английский

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Coordination Environment Engineering of Metal Centers in Coordination Polymers for Selective Carbon Dioxide Electroreduction toward Multicarbon Products

ACS Nano, Journal Year: 2024, Volume and Issue: 18(9), P. 7192 - 7203

Published: Feb. 22, 2024

Electrocatalytic carbon dioxide reduction reaction (CO2RR) toward value-added chemicals/fuels has offered a sustainable strategy to achieve carbon-neutral energy cycle. However, it remains great challenge controllably and precisely regulate the coordination environment of active sites in catalysts for efficient generation targeted products, especially multicarbon (C2+) products. Herein we report engineering metal centers polymers electroreduction CO2 C2+ products under neutral conditions. Significantly, Cu polymer with Cu–N2S2 configuration (Cu–N–S) demonstrates superior Faradaic efficiencies 61.2% 82.2% ethylene respectively, compared selective formic acid on an analogous Cu–I2S2 mode (Cu–I–S). In situ studies reveal balanced formation atop bridge *CO intermediates Cu–N–S, promoting C–C coupling production. Theoretical calculations suggest that can induce electronic modulations sites, where d-band center is upshifted Cu–N–S stronger selectivity Consequently, displays trend while Cu–I–S favors due suppression couplings pathways large barriers.

Language: Английский

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Regulating the Electronic Configuration of Ni Sites by Breaking Symmetry of Ni‐Porphyrin to Facilitate CO₂ Photocatalytic Reduction

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(25)

Published: Feb. 10, 2024

Abstract Adapting the coordination environment to influence electronic configuration of active sites represents an efficient approach for improving photocatalytic performance CO 2 reduction reaction (CO RR) but how execute it precisely remains challenging. Herein, heteroatom‐substitution in Ni‐porphyrin break symmetry Ni center is proposed be effective solution. Based on this, two symmetry‐breaking Ni‐porphyrins, namely Ni(Cl)ON 3 Por and Ni(Cl)SN , are designed successfully prepared. By theoretical calculation, found that efficiently regulates d orbital energy levels center. Furthermore, experimental findings jointly revealed Ni‐porphyrins facilitates generation highly reactive I species during catalytic process, effectively stabilizing reducing barrier formation key * COOH intermediate. As a result, gave production rates 24.7 38.8 mmol g −1 h as well selectivity toward 94.0% 96.4%, respectively, outperforming symmetric NiN 4 rate 6.6 82.8%). These offer microscopic insights into modulate activity by tuning rational design competent catalyst RR photocatalysis.

Language: Английский

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Steering the Site Distance of Atomic Cu‐Cu Pairs by First‐Shell Halogen Coordination Boosts CO2‐to‐C2 Selectivity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 6, 2024

Electrocatalytic reduction of CO

Language: Английский

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A Comprehensive Analysis of Luminescent Crystallized Cu Nanoclusters

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(4), P. 947 - 958

Published: Jan. 22, 2024

Photoluminescence (PL) emission is an intriguing characteristic displayed by atomically precise d10 metal nanoclusters (NCs), renowned for their meticulous atomic arrangements, which have captivated the scientific community. Cu(I) NCs are a focal point in extensive research due to abundance, cost-effectiveness, and unique luminescent attributes. Despite similar core sizes, characteristics vary, influenced multiple factors. Progress hinges on synthesizing new modifying existing ones, with postsynthetic alterations impacting properties. The rapid advancements this field pose challenges discerning essential points excelling amidst competition other NCs. This Perspective explores intricate origins of PL NCs, providing comprehensive review correlated structural architectures. Understanding mechanistic origin each cluster crucial correlating diverse characteristics, contributing deeper comprehension from both fundamental applied perspectives.

Language: Английский

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Promoting Water Activation via Molecular Engineering Enables Efficient Asymmetric C–C Coupling during CO₂ Electroreduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32870 - 32879

Published: Nov. 13, 2024

Water activation plays a crucial role in CO

Language: Английский

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NIR-II emissive anionic copper nanoclusters with intrinsic photoredox activity in single-electron transfer

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

Published: June 1, 2024

Abstract Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of transformations that can catalyze remain limited date. Herein, we report a structurally well-defined anionic Cu 40 nanocluster emits second near-infrared region (NIR-II, 1000−1700 nm) after photoexcitation conduct single-electron transfer fluoroalkyl iodides without need external ligand activation. This photoredox-active efficiently catalyzes three-component radical couplings alkenes, iodides, trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety fluorine-containing electrophiles nucleophile be added onto an array including styrenes aliphatic olefins. Our current work demonstrates viability using readily accessible metal establish photocatalytic systems high degree practicality reaction complexity.

Language: Английский

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Eight‐Electron Copper Nanoclusters for Photothermal Conversion

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(28)

Published: March 12, 2024

Owing to distinct physicochemical properties in comparison gold and silver counterparts, atomically precise copper nanoclusters are attracting embryonic interest material science. The introduction of cluster nanomaterials more interesting fields is currently urgent desired. Reported this work novel [XCu

Language: Английский

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Promoting CO2 Electroreduction to Hydrocarbon Products via Sulfur‐Enhanced Proton Feeding in Atomically Precise Thiolate‐Protected Cu Clusters

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 22, 2024

Abstract Thiolate‐protected Cu clusters with well‐defined structures and stable low‐coordinated + species exhibit remarkable potential for the CO 2 RR are ideal model catalysts establishing structure‐electrocatalytic property relationships at atomic level. However, extant employed in predominantly yield 2e − products. Herein, two 4 (MMI) 8 ( t BuS) (MMI=2‐mercapto‐1‐methylimidazole) prepared to investigate synergistic effect of adjacent S sites on RR. can reduce deep‐reduced products a 91.0 % Faradaic efficiency (including 53.7 CH ) while maintaining stability. Conversely, shows preference C 2+ products, achieving maximum FE 58.5 current density 152.1 mA⋅cm −2 . In situ XAS ex XPS spectra reveal preservation during RR, extensively enhancing adsorption capacity *CO intermediate. Moreover, kinetic analysis theoretical calculations confirm that facilitate H O dissociation into *H species, which directly participate protonation process *CHO. This study highlights important role Cu−S dual provides mechanistic insights pathway

Language: Английский

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Luminescent Hydride-Free [Cu₇(SC₅H₉)₇(PPh₃)₃] Nanocluster: Facilitating Highly Selective C–C Bond Formation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 20937 - 20944

Published: July 9, 2024

Amidst burgeoning interest, atomically precise copper nanoclusters (Cu NCs) have emerged as a remarkable class of nanomaterials distinguished by their unparalleled reactivity. Nonetheless, the synthesis hydride-free Cu NCs and role stable catalysts remain infrequently explored. Here, we introduce facile synthetic approach to fabricate [Cu

Language: Английский

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