Why do Single‐Atom Alloys Catalysts Outperform both Single‐Atom Catalysts and Nanocatalysts on MXene?

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(4)

Опубликована: Дек. 1, 2023

Abstract Single‐atom alloys (SAAs), combining the advantages of single‐atom and nanoparticles (NPs), play an extremely significant role in field heterogeneous catalysis. Nevertheless, understanding catalytic mechanism SAAs catalysis reactions remains a challenge compared with single atoms NPs. Herein, ruthenium‐nickel (RuNi ) synthesized by embedding atomically dispersed Ru Ni NPs are anchored on two‐dimensional Ti 3 C 2 T x MXene. The RuNi SAA‐3 −Ti catalysts exhibit unprecedented activity for hydrogen evolution from ammonia borane (AB, NH BH hydrolysis mass‐specific (r mass value 333 L min −1 g . Theoretical calculations reveal that anchoring optimizes dissociation AB H O as well binding ability H* intermediates during due to d‐band structural modulation caused alloying effect metal‐supports interactions (MSI) This work provides useful design principles developing optimizing efficient hydrogen‐related demonstrates over energy

Язык: Английский

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Modulation of Phase Transition in Cobalt Selenide with Simultaneous Construction of Heterojunctions for Highly‐Efficient Oxygen Electrocatalysis in Zinc–Air Battery

Advanced Materials, Год журнала: 2023, Номер unknown

Опубликована: Окт. 9, 2023

Abstract Phase transformation of cobalt selenide (CoSe 2 ) can effectively modulate its intrinsic electrocatalytic activity. However, enhancing electroconductivity and catalytic activity/stability CoSe still remains challenging. Heterostructure engineering may be feasible to optimize interfacial properties promote the kinetics oxygen electrocatalysis on a ‐based catalyst. Herein, heterostructure consisting nitride (CoN) embedded in hollow carbon cage is designed via simultaneous phase/interface strategy. Notably, phase transition orthorhombic‐CoSe cubic‐CoSe (c‐CoSe accompanied by situ CoN formation realized build c‐CoSe /CoN heterointerface, which exhibits excellent/highly stable activities for reduction/evolution reactions (ORR/OER). local coordination environment increase Co‐Se/N bond lengths. Theoretical calculations show that Co‐site with an electronic state near Fermi energy level main active site ORR/OER.Energetical tailoring d‐orbital structure Co atom incorporation lowers thermodynamic barriers ORR/OER. Attractively, zinc‐air battery ‐CoN cathode displays excellent cycling stability (250 h) charge/discharge voltage loss (0.953/0.96 V). It highlights heterointerface provides option modulating bifunctional activity metal selenides controlled transformation.

Язык: Английский

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Tandem Catalysts Enabling Efficient C−N Coupling toward the Electrosynthesis of Urea

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 6, 2024

Abstract The development of a methodology for synthesizing value‐added urea (CO(NH 2 ) via renewable electricity‐driven C−N coupling reaction under mild conditions is highly anticipated. However, the complex catalytic active sites that act on carbon and nitrogen species make mechanism unclear, resulting in low efficiency from co‐reduction dioxide (CO nitrate (NO 3 − ). Herein, we propose novel tandem catalyst Mo‐PCN‐222(Co), which Mo serve to facilitate reduction *NH intermediate, while Co enhance CO carbonic oxide (CO), thus synergistically promoting coupling. synthesized Mo‐PCN‐222(Co) exhibited noteworthy yield rate 844.11 mg h −1 g , alongside corresponding Faradaic 33.90 % at −0.4 V vs. reversible hydrogen electrode (RHE). By combining situ spectroscopic techniques with density functional theory calculations, demonstrate efficient attributed system *CO intermediates produced by stabilize formation *CONH intermediate. This study provides an effective avenue design synthesis catalysts electrocatalytic synthesis.

Язык: Английский

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Introducing Hydrogen-Bonding Microenvironment in Close Proximity to Single-Atom Sites for Boosting Photocatalytic Hydrogen Production

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 20391 - 20400

Опубликована: Июль 10, 2024

Inspired by enzymatic catalysis, it is crucial to construct hydrogen-bonding-rich microenvironment around catalytic sites; unfortunately, its precise construction and understanding how the distance between such sites affects catalysis remain significantly challenging. In this work, a series of metal-organic framework (MOF)-based single-atom Ru

Язык: Английский

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Water-assisted catalytic transfer hydrogenation of guaiacol to cyclohexanol over Ru/NiAl2O4

Chemical Engineering Journal, Год журнала: 2024, Номер 485, С. 149934 - 149934

Опубликована: Фев. 29, 2024

Язык: Английский

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Microenvironment Modulation for Electronic Structure of Atomically Dispersed Ir Species in Metal–Organic Frameworks Toward Boosting Catalytic DCPD Hydrogenation Performance

Carbon Neutralization, Год журнала: 2025, Номер 4(2)

Опубликована: Март 1, 2025

ABSTRACT The fine‐tuning of the electronic structure and local environment surrounding atomically dispersed metal centers is crucial in catalysis but remains a grand challenge that requires in‐depth exploration. In this study, Ir species were incorporated into series UiO‐type metal−organic frameworks via strong metal–support interactions (SMSI), their state was precisely modulated by regulating metal‐oxo clusters (Ce, Zr, Hf) organic ligands (BDC‐X, where X = ‐H, ‐NH 2 , ‐Me, or ‐NO ) for enhancing catalytic performance dicyclopentadiene (DCPD) hydrogenation. optimized Ir@Ce‐UiO‐66‐NO effectively transforms DCPD tetrahydrodicyclopentadiene (THDCPD), giving 100% conversion over 99% THDCPD selectivity, far superior to corresponding counterparts. Experimental theoretical results jointly demonstrated Ce‐oxo with unique Ce III /Ce IV redox pairs can facilitate electron transfer species. Furthermore, electron‐withdrawing groups play role increasing ratio, promoting efficient uptake MOF support leading low density around species, which enhances stronger between substrate molecules active sites contributes excellent activity. findings presented work provide valuable insights rational design advanced heterogeneous catalysts leveraging properties modulation capabilities supports.

Язык: Английский

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Promoted hydrogenation of CO2 to methanol over single-atom Cu sites with Na+-decorated microenvironment

National Science Review, Год журнала: 2024, Номер 11(6)

Опубликована: Март 21, 2024

ABSTRACT Although single-atom Cu sites exhibit high efficiency in CO2 hydrogenation to methanol, they are prone forming nanoparticles due reduction and aggregation under reaction conditions, especially at temperatures. Herein, stabilized by adjacent Na+ ions have been successfully constructed within a metal–organic framework (MOF)-based catalyst, namely MOF-808-NaCu. It is found that the electrostatic interaction between Hδ− species plays pivotal role upholding atomic dispersion of MOF-808-NaCu during hydrogenation, even temperatures up 275°C. This exceptional stabilization effect endows catalyst with excellent activity (306 g·kgcat−1·h−1), selectivity methanol (93%) long-term stability elevated temperatures, far surpassing counterpart absence (denoted as MOF-808-Cu). work develops an effective strategy for fabrication stable advanced catalysis creating alkali-decorated microenvironment close proximity.

Язык: Английский

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Atomic Single-Layer Ir Clusters Enabling 100% Selective Chlorine Evolution Reaction

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1962 - 1969

Опубликована: Янв. 22, 2024

The exclusive selectivity of the chlorine evolution reaction (CER) is crucial for chlor-alkali industry to obtain pure gas and avoid cost separating byproduct oxygen. However, 100% CER remains a challenge currently known catalysts. Here, we report catalyst atomic single-layer Ir clusters on CeO2 nanorods (IrSL/CeO2). Under strong metal/support interaction, IrSL has adsorption oxygen, thereby suppressing oxygen reaction. Coupled with uniform active sites clusters, IrSL/CeO2 achieves almost in acidic NaCl solution ranging from open circuit potential practical current density levels. In addition, exhibits 1.7 times higher catalytic activity than its single-atom counterparts, noble metal efficiency 84 that commercial anodes (DSAs). Our finding provides selective catalysis electrolysis.

Язык: Английский

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In situ Construction of Single‐Atom Electronic Bridge on COF to Enhance Photocatalytic H2 Production

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Авг. 13, 2024

Photocatalytic hydrogen production is one of the most valuable technologies in future energy system. Here, we designed a metal-covalent organic frameworks (MCOFs) with both small-sized metal clusters and nitrogen-rich ligands, named COF-Cu

Язык: Английский

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Competition and synergistic effects of Ru-based single-atom and cluster catalysts in electrocatalytic reactions

Science China Materials, Год журнала: 2024, Номер 67(6), С. 1706 - 1720

Опубликована: Апрель 8, 2024

Язык: Английский

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