Sabatier Phenomenon in Hydrogenation Reactions Induced by Single-Atom Density

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12023 - 12032

Published: May 26, 2023

The Sabatier principle is a fundamental concept in heterogeneous catalysis that provides guidance for designing optimal catalysts with the highest activities. For first time, we here report new phenomenon hydrogenation reactions induced by single-atom density at atomic scale. We produce series of Ir (SACs) predominantly Ir1-P4 coordination structure densities ranging from 0.1 to 1.7 atoms/nm2 through P-coordination strategy. When used as hydrogenation, volcano-type relationship between and activity emerges, summit moderate 0.7 atoms/nm2. Mechanistic studies show balance adsorption desorption strength activated H* on single atoms found be key factor phenomenon. transferred Bader charge these SACs proposed descriptor interpret structure-activity relationship. In addition, maximum selectivity can simultaneously achieved chemoselective optimized catalyst due uniform geometric electronic structures sites SACs. present study reveals an insightful rational design more efficient practicable reactions.

Language: Английский

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Unraveling Synergistic Effect of Defects and Piezoelectric Field in Breakthrough Piezo‐Photocatalytic N₂ Reduction

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(5)

Published: Aug. 28, 2023

Piezo-photocatalysis is a frontier technology for converting mechanical and solar energies into crucial chemical substances has emerged as promising sustainable strategy N

Language: Английский

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Simultaneous CO₂and H₂O Activation via Integrated Cu Single Atom and N Vacancy Dual‐Site for Enhanced CO Photo‐Production

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(28)

Published: April 23, 2023

Abstract Photocatalytic conversion of CO 2 into fuels using pure water as the proton source is immense potential in simultaneously addressing climate‐change crisis and realizing a carbon‐neutral economy. Single‐atom photocatalysts with tunable local atomic configurations unique electronic properties have exhibited outstanding catalytic performance past decade. However, given their single‐site features they are usually only amenable to activations involving single molecules. For photoreduction entailing complex activation dissociation process, designing multiple active sites on photocatalyst for both reduction H O still daunting challenge. Herein, it precisely construct Cu single‐atom centers two‐coordinated N vacancies dual CN (Cu 1 /N 2C V‐CN). Experimental theoretical results show that promote chemisorption via accumulating photogenerated electrons, V enhance O, thereby facilitating from COO* COOH*. Benefiting dual‐functional sites, V‐CN exhibits high selectivity (98.50%) decent production rate 11.12 µmol g −1 h . An ingenious atomic‐level design provides platform integrating modified catalyst deterministic identification property during process.

Language: Английский

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Optimizing Electrocatalytic Nitrogen Reduction via Interfacial Electric Field Modulation: Elevating d‐Band Center in WS₂‐WO₃ for Enhanced Intermediate Adsorption

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 25, 2023

Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, protonation intermediates rate-determining step (RDS). Enhancing adsorption crucial increase intermediates, which can lead improved catalytic performance. Herein, we constructed strong interfacial electric field in WS2 -WO3 elevate d-band center W, thereby strengthening intermediates. Experimental results demonstrated that led significantly Specifically, exhibited high NH3 yield 62.38 μg h-1 mgcat-1 and promoted faraday efficiency (FE) 24.24 %. Furthermore, situ characterizations theoretical calculations showed upshifted W towards Fermi level, leading enhanced -NH2 -NH on catalyst surface. This resulted rate RDS. Overall, our study offers new insights into relationship between provides strategy enhance during process.

Language: Английский

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Atomic Cobalt–Silver Dual-Metal Sites Confined on Carbon Nitride with Synergistic Ag Nanoparticles for Enhanced CO₂ Photoreduction

ACS Nano, Journal Year: 2023, Volume and Issue: 17(12), P. 11869 - 11881

Published: June 8, 2023

Photocatalytic reduction of CO2 to value-added solar fuels is great significance alleviate the severe environmental and energy crisis. Herein, we report construction a synergistic silver nanoparticle catalyst with adjacent atomic cobalt-silver dual-metal sites on P-doped carbon nitride (Co1Ag(1+n)-PCN) for photocatalytic reduction. The optimized photocatalyst achieves high CO formation rate 46.82 μmol gcat-1 70.1% selectivity in solid-liquid mode without sacrificial agents, which 2.68 2.18-fold compared that exclusive single-atom (Ag1-CN) site (Co1Ag1-PCN) photocatalysts, respectively. closely integrated situ experiments density functional theory calculations unravel electronic metal-support interactions (EMSIs) Ag nanoparticles Ag-N2C2 Co-N6-P promote adsorption CO2* COOH* intermediates form CH4, as well boost enrichment transfer photoexcited electrons. Moreover, atomically dispersed Co-Ag SA serve fast-electron-transfer channel while act electron acceptor enrich separate more photogenerated This work provides general platform delicately design high-performance catalysts highly efficient conversion.

Language: Английский

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Manipulating the d-band center enhances photoreduction of CO2 to CO in Zn2GeO4 nanorods

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 468, P. 143569 - 143569

Published: May 26, 2023

Language: Английский

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Tuning Coordination Structures of Zn Sites Through Symmetry‐Breaking Accelerates Electrocatalysis

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(4)

Published: Aug. 31, 2023

Manipulating the coordination environment of individual active sites in a precise manner remains an important challenge electrocatalytic reactions. Herein, inspired by theoretical predictions, facile procedure to synthesize series symmetry-breaking zinc metal-organic framework (Zn-MOF) catalysts with well-defined structures is presented. Benefiting from optimized microenvironment regulated symmetry-breaking, Zn-N

Language: Английский

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Construction of carbonized polymer dots/potassium doped carbon nitride nanosheets Van der Waals heterojunction by ball milling method for facilitating photocatalytic CO2 reduction performance in pure water

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 351, P. 123993 - 123993

Published: April 24, 2024

Language: Английский

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Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO₂ Reduction

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1468 - 1479

Published: Jan. 13, 2024

Doping engineering has enabled the construction of homogeneous and abundant atomic-level catalytic sites for photocatalytic CO2 reduction with improved selectivity target product. However, little is known about effect spatial position heteroatoms on activity semiconductors toward reduction. Herein, uniform Cu doping into bulk phase hollow CdS cubes (HCC) onto surface HCC, denoted as Cu/HCC HCC@Cu, respectively, are prepared by tuning introduction order sources. Experimental analysis shows that both methods can promote separation migration photoinduced charge carriers in CdS. Notably, HCC@Cu leads to much better proton H2 production performance but lower efficiency compared bare In sharp contrast, enhances CO2-to-CO conversion while mitigating evolution. This should be ascribed smaller overpotential saturated system than Ar system. addition, atoms shifts d band center upward near Fermi energy level, which promotes adsorption activation These results indicate photoelectrons a prolonged lifetime preferably reduce molecules rather protons. The density functional theory (DFT) calculation show desorption CO*, adaptable sulfur vacancies (Vs) produced situ techniques stimulate formation CO* intermediates, resulting high CO. work reveals different heteroatom locations will provide reference design efficient photocatalysts fine structure.

Language: Английский

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Regulating Photocatalytic CO₂ Reduction Kinetics through Modification of Surface Coordination Sphere

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(9)

Published: Oct. 28, 2023

Abstract Solar‐driven reduction of CO 2 to value‐added products represents a sustainable strategy for mitigating the greenhouse effect and addressing related green‐energy crisis. Herein, it is demonstrated that modifying surface coordination sphere can significantly enhance reaction kinetics overall efficiency reduction. More specifically, decoration isolated Mn atoms over multi‐edged TiO nano‐pompons (Mn/TONP) upshifts d‐band center allows favorable adsorption. Ultrafast spectroscopy demonstrates greatly accelerated charge transfer between photoexcited TONP newly implanted reactive centers, supplying long‐lifetime electrons reduce absorbed molecules. By integrating adsorption activation functions into decorated sites, developed photocatalyst demonstrate impressive capacity (80.51 mmol g −1 h ). The modulation at atomic level not only opens new avenues regulating toward photocatalytic reduction, but also paves way rational design highly efficient selective photocatalysts clean energy conversion.

Language: Английский

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