Regulating Second-Shell Coordination in Cobalt Single-Atom Catalysts toward Highly Selective Hydrogenation

ACS Nano, Journal Year: 2024, Volume and Issue: 18(32), P. 21326 - 21335

Published: July 31, 2024

Manipulating the local coordination environment of central metal atoms in single-atom catalysts (SACs) is a powerful strategy to exploit efficient SACs with optimal electronic structures for various applications. Herein, Co-SACs featured by Co single coordinating S second shell dispersed nitrogen-doped carbon matrix have been developed toward selective hydrogenation halo-nitrobenzene. The location atom model Co-SAC verified through synchrotron-based X-ray absorption spectroscopy and theoretical calculations. resultant containing second-coordination demonstrate excellent activity outstanding durability hydrogenation, superior most precious metal-based catalysts. In situ characterizations results verify that high selectivity are attributed advantageous formation Co–O bond between p-chloronitrobenzene at Co1N4–S moieties lower free energy barriers reaction. Our findings unveil correlation performance second-shell SACs.

Language: Английский

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Size-Dependent Fe-Based Catalysts for the Catalytic Transfer Hydrogenation of α,β-Unsaturated Aldehydes

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

Metal-based catalysts ranging from nanoparticles (NPs) to the atomic level usually exhibit varying catalytic performance. The underlying size effect is both fascinating and evident. This study thoroughly investigates size-dependent effects of Fe-based on transfer hydrogenation (CTH) furfural (FF) at level. Fe was precisely loaded onto N-doped porous carbon in three forms: single atoms (Fe-SAs/NC), clusters (Fe-ACs/NC), (Fe-NPs/NC). achieved through meticulous control iron precursor composition. Remarkably, Fe-SAs/NC exhibited exceptional efficiency, achieving an FF conversion 91.3% a turnover frequency (TOF) 262.3 h-1 110 °C, which 9.2 times higher than Fe-ACs/NC impressive 93.7 Fe-NPs/NC. high selectivity toward furfuryl alcohol further substantiated by theoretical calculations. These calculations indicated benefits η1(O)-aldehyde adsorption configuration, formed vertical molecules Fe-N4 active sites. Geometrical optimization catalyst scale enhances its intrinsic activity selectivity. proposed provides deeper insights into mechanism single-atom contributes exploration high-performance

Language: Английский

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High-Throughput Screening of Selective Bimetallic Atomic Catalysts for Self-Adaptive Matched Electrochemical Reduction

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

Published: Feb. 7, 2025

Due to the impediments of spatial and temporal resolution, comprehension microdynamic processes still remains limited, which seriously hinders advancement catalyst regulating expansion application. Herein, efficient selective bimetallic atomic electrode interface was cultivated via high-throughput screening, achieving self-adaptive parallel electrochemical reduction Cu(II) As(III). Combined in situ X-ray absorption fine structure (XAFS) spectroscopy coordination field theory verified Ni-Cu specific energy level matching promoted by permitted d-d transition also reproduced microscopic dynamic process. Additionally, it discovered that Fe-As bonding barrier smallest potential-determining step (1.40 eV) were derived from linear shift main s p peaks key arsenic intermediates high-energy orbital. This work offers insights into transient reaction dynamics methods theoretical simulations, broadens design multisite catalysts.

Language: Английский

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Transfer hydrogenation of cinnamaldehyde to cinnamyl alcohol over SnO-MgO composite catalysts

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 162483 - 162483

Published: April 1, 2025

Language: Английский

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Theoretical Understandings on Mechanisms of Hydrogenation Activities Using Graphene‐Based Single‐Atom Catalysts

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(21)

Published: July 29, 2024

Abstract Metal single‐atom catalysts (SACs) have emerged as a promising class of in various fields, owing to their well‐defined active centers, tunable coordination environments, and high reaction selectivity. Among the diverse supports, graphene‐based SACs garnered significant attention due exceptional properties hydrogenation reactions. This review elucidates recent advancements theoretical investigations electronic geometric structures metal SACs, with focus on modulation strategies such number adjustment, heteroatom doping, defect site engineering, frustrated Lewis pair construction. emphasizes atomic‐level insights into mechanism thermocatalysis, including activation H‐source molecules, hydrogen diffusion, elementary steps. Strategies for modulating catalytic activity are summarized. Lastly, this offers perspectives design effective from standpoint, paving way future research exciting field.

Language: Английский

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Selective Hydrogenation of α, β-Unsaturated Aldehydes/Ketones via Photocatalytic and Electrocatalytic Techniques: A Review

Applied Catalysis A General, Journal Year: 2024, Volume and Issue: unknown, P. 120063 - 120063

Published: Dec. 1, 2024

Language: Английский

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Tailoring catalysis at the atomic level: trends and breakthroughs in single atom catalysts for organic transformation reactions

Nanoscale Horizons, Journal Year: 2024, Volume and Issue: 10(3), P. 423 - 459

Published: Dec. 5, 2024

This review analyzes the latest advances in field of design single atom catalysts (SACs) for various industrially relevant organic transformation reactions along with challenges and their possible counter measures.

Language: Английский

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Understanding the working principle of sustainable catalytic materials for selective hydrogenation of carbonyls bond in α, β-unsaturated aldehydes

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 525, P. 216295 - 216295

Published: Nov. 20, 2024

Language: Английский

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