Engineering Spatially Adjacent Redox Sites with Synergistic Spin Polarization Effect to Boost Photocatalytic CO₂ Methanation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15538 - 15548

Published: May 20, 2024

The integration of oxidation and reduction half-reactions to amplify their synergy presents a considerable challenge in CO2 photoconversion. Addressing this requires the construction spatially adjacent redox sites while suppressing charge recombination at these sites. This study introduces an innovative approach that utilizes spatial enable synergistic reactions within atomic proximity employs spin polarization inhibit recombination. We incorporate Mn into Co3O4 as catalyst, which tend enrich holes water activation sites, Co preferentially capture electrons activate CO2, forming synergy. direct H transfer from H2O facilitates formation *COOH on with remarkably favorable thermodynamic energy. Notably, incorporation induces system, significantly photogenerated charges effect is further enhanced by applying external magnetic field. By synergizing polarization, Mn/Co3O4 exhibits CH4 production rate 23.4 μmol g–1 h–1 photoreduction, showcasing 28.8 times enhancement over Co3O4. first address issues offering novel insights for photocatalytic systems.

Language: Английский

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Not One, Not Two, But at Least Three: Activity Origin of Copper Single-Atom Catalysts toward CO₂/CO Electroreduction to C₂₊ Products

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 14954 - 14958

Published: May 28, 2024

Copper (Cu) single-atom catalysts (SACs) exhibit great potential for generating multicarbon (C2+) products, but the intrinsic activity of Cu (Cu1) under realistic conditions remains controversial. Herein, we perform extensive calculations with explicit solvation to investigate underlying mechanism SACs, disclosing absence C2+ in Cu1 sites regardless different substrates. The original (first taking stably anchored on carbon nitride as an example) cannot facilitate *CO hydrogenation and CO–CO coupling due lack active nearby, they are unstable operation, causing leaching aggregation form small clusters. derived clusters composed at least three atoms can efficiently promote coupling, revealed by kinetic analyses. We extend modeling other typical SACs reveal that all inactive, while performance Cu-cluster is substrate-dependent. This study offers mechanistic insights into provides practical guidance their rational optimization.

Language: Английский

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Atomically Dispersed Cu Active Centers: Local Structure and Mechanism Modulation for Carbon Dioxide Reduction

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract Reducing carbon dioxide （CO 2 ）to high‐value products using green renewable energy is a promising approach for addressing and greenhouse effect issues. Consequently, electrocatalytic CO reduction reaction (CO RR) technology has become current research hotspot. Since the discovery of high activity selectivity copper in RR, atomically dispersed Cu catalysts have garnered widespread attention due to their efficient atom utilization, unique electronic structure, outstanding catalytic performance. However, great challenge remains providing rational catalyst design principles achieve regulation product distribution. A clear understanding materials an in‐depth interpretation mechanism as well elucidation strategy progress toward different are keys building solving above problem. Therefore, this review starts with introduction advanced characterization techniques reveal structure mechanisms. Then, various optimization strategies applications producing targeted summarized discussed. Finally, perspectives on RR field future development offered.

Language: Английский

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Understanding the chemistry of mesostructured porous nanoreactors

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 23, 2024

Language: Английский

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Alloying and confinement effects on hierarchically nanoporous CuAu for efficient electrocatalytic semi-hydrogenation of terminal alkynes

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

Published: July 17, 2024

Abstract Electrocatalytic alkynes semi-hydrogenation to produce alkenes with high yield and Faradaic efficiency remains technically challenging because of kinetically favorable hydrogen evolution reaction over-hydrogenation. Here, we propose a hierarchically nanoporous Cu 50 Au alloy improve electrocatalytic performance toward alkynes. Using Operando X-ray absorption spectroscopy density functional theory calculations, find that modulate the electronic structure Cu, which could intrinsically inhibit combination H* form H 2 weaken alkene adsorption, thus promoting alkyne hampering Finite element method simulations experimental results unveil catalysts induce local microenvironment abundant K + cations by enhancing electric field within nanopore, accelerating water electrolysis more H*, thereby conversion As result, electrocatalyst achieves highly efficient 94% conversion, 100% selectivity, 92% over wide potential window. This work provides general guidance rational design for high-performance transfer catalysts.

Language: Английский

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Asymmetrically Coordinated Cu Dual‐Atom‐Sites Enables Selective CO₂ Electroreduction to Ethanol

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

Published: Oct. 6, 2024

Abstract Electrochemical reduction of CO 2 (CO RR) to value‐added liquid fuels is a highly attractive solution for carbon‐neutral recycling, especially C 2+ products. However, the selectivity control preferable products great challenge due complex multi‐electron proton transfer process. In this work, series Cu atomic dispersed catalysts are synthesized by regulating coordination structures optimize RR selectivity. ‐SNC catalyst with uniquely asymmetrical coordinated CuN ‐CuNS site shows high ethanol selective FE 62.6% at −0.8 V versus RHE and 60.2% 0.9 in H‐Cell Flow‐Cell test, respectively. Besides, nest‐like structure beneficial mass process selection catalytic situ experiments theory calculations reveal reaction mechanisms such ethanol. The S atoms weaken bonding ability adjacent carbon atom, which accelerates from *CHCOH generate *CHCHOH, resulting This work indicates promising strategy rational design asymmetrically single, dual, or tri‐atom provides candidate material produce

Language: Английский

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Experimental and Theoretical Insights into Single Atoms, Dual Atoms, and Sub‐Nanocluster Catalysts for Electrochemical CO₂ Reduction (CO₂RR) to High‐Value Products

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(52)

Published: Nov. 26, 2024

Abstract Electrocatalytic carbon dioxide (CO 2 ) conversion into valuable chemicals paves the way for realization of recycling. Downsizing catalysts to single‐atom (SACs), dual‐atom (DACs), and sub‐nanocluster (SNCCs) has generated highly active selective CO transformation reduced products. This is due introduction numerous sites, unsaturated coordination environments, efficient atom utilization, confinement effect compared their nanoparticle counterparts. Herein, recent Cu‐based SACs are first reviewed newly emerged DACs SNCCs expanding catalysis electrocatalytic reduction RR) high‐value products discussed. Tandem SAC–nanocatalysts (NCs) (SAC–NCs) also discussed RR Then, non‐Cu‐based SACs, DACs, SAC–NCs, theoretical calculations various transition‐metal summarized. Compared previous achievements less‐reduced products, this review focuses on double objective achieving full increasing selectivity formation rate toward C–C coupled with additional emphasis stability catalysts. Finally, through combined experimental research, future outlooks offered further develop over isolated atoms sub‐nanometal clusters.

Language: Английский

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Metal‐Organic Frameworks‐Based Copper Catalysts for CO₂ Electroreduction Toward Multicarbon Products

Exploration, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

ABSTRACT Copper (Cu) is the most promising catalyst for electrochemical CO 2 ‐to‐C 2+ conversion, whereas performance remains below practical thresholds due to high energy barrier of C−C coupling and lack effective approaches steer reaction pathway. Recent advances show that metal‐organic frameworks (MOF) could be a platform as support, pre‐catalyst, co‐catalyst modify electronic structure local environment Cu catalysts promoting reduction by virtue their great tunability over compositions pore architectures. In this review, we discussed general design principles, catalytic mechanisms, achievements MOF‐based catalysts, aiming boost refinement steering pathway C products. The fundamentals challenges are first introduced. Then, summarized conceptions from three aspects: engineering properties Cu, regulating environment, managing site exposure mass transport. Further, latest progress products namely Cu‐based MOF, MOF‐derived Cu@MOF hybrid discussed. Finally, future research opportunities strategies suggested innovate rational advanced electrifying transformation.

Language: Английский

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OH‐Induced Surface Reconstitution in Single Atoms and Clusters Integrated Electrocatalysts for Self‐Adaptive Oxygen Electrocatalysis

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(52)

Published: Aug. 27, 2024

Abstract The integration of atom clusters and single atoms into a unified system represents desirable approach for attaining enhanced catalytic performance. Nonetheless, the controllable synthesis single‐atom nanocluster integrated (SA‐NC) faces considerable challenges, mechanisms underlying activity remain poorly understood. In this research, cobalt‐based catalyst containing both coordinatively unsaturated (CoN 3 ) small nanoclusters (Co@SA‐NC) is synthesized. Co@SA‐NC not only facilitates charge mass transfer due to interconnected long‐range micromorphology, thus endowing efficient oxygen electrocatalytic reaction (ORR/OER), but also undergoes surface reconfiguration upon OH adsorption at high potentials in alkaline ORR/OER conditions. More appealingly, OH‐involved reconfigured adaptive structure promotes optimization energy barriers owing dynamic regulation from bridged between Co cluster whole process. Specific application metrics, zinc–air battery assembled using exhibit targeted power density enhancement with 270 mW cm −2 an medium. This work offers effective insight study SA‐NC pathways catalysis.

Language: Английский

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Ni‐Electrocatalytic CO₂ Reduction Toward Ethanol

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

Published: Sept. 12, 2024

The electroreduction of CO

Language: Английский

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