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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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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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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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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Catalyst design for the electrochemical reduction of carbon dioxide: from copper nanoparticles to copper single atoms

Microstructures, Journal Year: 2025, Volume and Issue: 5(1)

Published: Jan. 17, 2025

Carbon dioxide reduction reaction (CO2RR) is an efficacious method to mitigate carbon emissions and simultaneously convert CO2 into high-value products. The efficiency of CO2RR depends on the development highly active selective catalysts. Copper (Cu)-based catalysts can effectively reduce hydrocarbons oxygen-containing compounds because their unique geometric electronic structures. Most importantly, Cu multiple products (C2+). Therefore, this review aims outline recent research progress in Cu-based for CO2RR. After introducing mechanism electroreduction reaction, we summarize influence size, morphology, coordination environment single component performance, especially performance control that contain nano or single-atom sites. Then, synergistic regulation strategies doping other metals are summarized. Finally, supports used reviewed. prospects challenges discussed.

Language: Английский

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Establishment of Gas–Liquid–Solid Interface on Multilevel Porous Cu₂O for Potential-Driven Selective CO₂ Electroreduction toward C₁ or C₂ Products

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

Published: Jan. 20, 2025

Copper-based catalysts demonstrate distinctive multicarbon product activity in the CO2 electroreduction reaction (CO2RR); however, their low selectivity presents significant challenges for practical applications. Herein, we have developed a multilevel porous spherical Cu2O structure, wherein mesopores are enriched with catalytic active sites and effectively stabilize Cu+, while macropores facilitate formation of "gas–liquid–solid" three-phase interface, thereby creating microenvironment an increasing water concentration gradient from interior to exterior. Potential-driven phase engineering protonation synergistically optimize pathway, facilitating switch between CO C2H4. At current density 100 mA cm–2, faradaic efficiency (FE) reaches impressive 96.97%. When increases 1000 FEC2H4 attains 53.05%. Experiments theoretical calculations indicate that at lower potentials, pure diminishes adsorption *CO intermediates, weak inhibits hydrogen evolution reactions, promoting production. Conversely, more negative Cu0/Cu+ interface strong generate locally elevated concentrations *COOH which enhance C–C coupling deep hydrogenation, ultimately improving toward C2+ products. This study provides novel insights into rational design copper-based customizable

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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Ethylene Electrosynthesis via Selective CO₂ Reduction: Fundamental Considerations, Strategies, and Challenges

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

Published: June 11, 2024

Abstract The electrochemical carbon dioxide reduction reaction (CO 2 RR) is a promising approach for reducing atmospheric ) emissions, allowing harmful CO to be converted into more valuable carbon‐based products. On one hand, single (C 1 products have been obtained with high efficiency and show great promise industrial capture. However, multi‐carbon 2+ possess market value demonstrated significant as potential RR. Due RR's multiple pathways similar equilibrium potentials, the extended mechanisms necessary form C continue reduce overall selectivity of ‐to‐C electroconversion. Meanwhile, RR whole faces many challenges relating system optimization, owing an intolerance low surface pH, systemic stability utilization issues, competing side in H evolution (HER). Ethylene 4 remains incredibly within chemical industry; however, current established method producing ethylene (steam cracking) contributes emission atmosphere. Thus, strategies significantly increase this technology are essential. This review will discuss vital factors influencing forming summarize recent advancements electrosynthesis.

Language: Английский

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