Single‐Atom Rh on High‐Index CeO2 Facet for Highly Enhanced Catalytic CO Oxidation DOI
Jing Xu, Ying Wang, Ke Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 11, 2023

Reducible oxide-supported noble metal nanoparticles exhibit high activity in catalyzing many important oxidation reactions. However, atom migration under harsh reaction conditions leads to deactivation of the catalyst. Meanwhile, single-atom catalysts demonstrate enhanced stability, but often suffer from poor catalytic owing ionized surface states. In this work, we simultaneously address and stability issues by synthesizing highly active durable rhodium (Rh) through a "wrap-bake-peel" process. The pre-coated SiO2 layer during synthesis catalyst plays crucial role not only protecting CeO2 support against sintering, also donating electron weaken Ce-O bond, producing loaded Rh single atoms on exposed with high-index {210} facets. Benefiting unique electronic structure facets, more oxygen vacancies are generated along deposition electropositive atoms, leading remarkably improved performance CO oxidation.

Language: Английский

Tuning the local coordination environment of single-atom catalysts for enhanced electrocatalytic activity DOI

Wenhao Feng,

Chunli Liu, Guangxun Zhang

et al.

EnergyChem, Journal Year: 2024, Volume and Issue: 6(2), P. 100119 - 100119

Published: Feb. 17, 2024

Language: Английский

Citations

26
Bimetallic Single-Atom Catalysts for Water Splitting DOI Creative Commons
Megha A. Deshmukh, Aristides Bakandritsos, Radek Zbořil

et al.

Nano-Micro Letters, Journal Year: 2024, Volume and Issue: 17(1)

Published: Sept. 25, 2024

Abstract Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead global transition fossil fuel-independent society. The field of catalysis been revolutionized by single-atom catalysts (SACs), which exhibit unique and intricate interactions between atomically dispersed metal atoms their supports. Recently, bimetallic SACs (bimSACs) have garnered significant attention for leveraging synergistic functions two ions coordinated on appropriately designed BimSACs offer an avenue rich metal–metal metal–support cooperativity, potentially addressing current limitations in effectively furnishing transformations involve synchronous proton–electron exchanges, substrate activation reversible redox cycles, simultaneous multi-electron transfer, regulation spin states, tuning electronic properties, cyclic states low energies. This review aims encapsulate growing advancements bimSACs, emphasis pivotal role generation via splitting. We subsequently delve into advanced experimental methodologies elaborate characterization SACs, elucidate discuss local coordination environment. Overall, we present comprehensive discussion deployment bimSACs both evolution reaction oxygen reaction, half-reactions electrolysis process.

Language: Английский

Citations

19
Structure–Reactivity Relationship of Zeolite-Confined Rh Catalysts for Hydroformylation of Linear α-Olefins DOI
Xiaomeng Dou, Tao Yan,

W.Z Li

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Substituting the molecular metal complexes used in industrial olefin hydroformylation process is of great significance fundamental research and practical application. One major difficulties replacing classic catalysts with supported low chemoselectivity regioselectivity because lack a well-defined coordination environment active sites. In this work, we have systematically studied influences key factors (crystallinity, alkali promoters, etc.) Rh-MFI zeolite on their performances for long-chain α-olefins (LAOs). With help comprehensive spectroscopy electron microscopy characterization results, can correlate structural features various catalytic performances. The resultant structure–reactivity relationship guides us to prepare nanosized catalyst, which exhibits about 3-fold improvement specific activity compared catalyst conventional crystallite sizes maintains very high LAOs.

Language: Английский

Citations

3
Exploring the properties, types, and performance of atomic site catalysts in electrochemical hydrogen evolution reactions DOI Creative Commons
M. Nur Hossain, Lei Zhang, Roberto Neagu

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review investigates atomic site catalysts (ASCs) for electrochemical hydrogen evolution reaction (HER), discussing their properties, types, performance, significance, activity, selectivity, stability, challenges, and future research directions.

Language: Английский

Citations

2
Striding the threshold of an atom era of organic synthesis by single-atom catalysis DOI Creative Commons
Wenhao Li, Jiarui Yang, Dingsheng Wang

et al.

Chem, Journal Year: 2021, Volume and Issue: 8(1), P. 119 - 140

Published: Nov. 24, 2021

Language: Английский

Citations

104
Metal-Specific Reactivity in Single-Atom Catalysts: CO Oxidation on 4d and 5d Transition Metals Atomically Dispersed on MgO DOI
Bidyut Bikash Sarma,

Philipp N. Pleßow,

Giovanni Agostini

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(35), P. 14890 - 14902

Published: Aug. 12, 2020

Understanding and tuning the catalytic properties of metals atomically dispersed on oxides are major stepping-stones toward a rational development single-atom catalysts (SACs). Beyond individual showcase studies, design synthesis structurally regular series SACs opens door to systematic experimental investigations performance as function metal identity. Herein, based various 4d (Ru, Rh, Pd) 5d (Ir, Pt) transition has been synthesized common MgO carrier. Complementary (X-ray absorption spectroscopy) theoretical (Density Functional Theory) studies reveal that, regardless identity, cations occupy preferably octahedral coordination lattice positions under step-edges, hence highly confined by oxide support. Upon exposure O2-lean CO oxidation conditions, FTIR spectroscopy indicates partial deconfinement monatomic centers driven at precatalysis temperatures, followed surface carbonate species steady-state conditions. These findings supported DFT calculations, which show driving force final structure for protrusion be metal-dependent, but point an equivalent octahedral-coordinated M4+ resting state in all cases. Experimentally, apparent reaction activation energies range 96 ± 19 kJ/mol determined, with Pt leading lowest energy barrier. The results indicate sites SACs, differences reactivity enforceable via selection lower magnitude than those evidenced previously through mechanistic involvement adjacent redox carrier, suggesting that chemistry is relevant metal.

Language: Английский

Citations

102
Economizing on Precious Metals in Three‐Way Catalysts: Thermally Stable and Highly Active Single‐Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions** DOI
Konstantin Khivantsev, Carlos Garcia Vargas, Jinshu Tian

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(1), P. 391 - 398

Published: Sept. 3, 2020

Abstract We show for the first time that atomically dispersed Rh cations on ceria, prepared by a high‐temperature atom‐trapping synthesis, are active species (CO+NO) reaction. This provides direct link with organometallic homogeneous I complexes capable of catalyzing dry The thermally stable in 0.1 wt % 1 /CeO 2 achieve full NO conversion turn‐over‐frequency (TOF) around 330 h −1 per atom at 120 °C. Under conditions, main product above 100 °C is N O being minor product. presence water promotes low‐temperature activity . In wet stream, ammonia and nitrogen products uniformity ions support, allows us to detect intermediates reaction via IR measurements zeolite ceria. also NH 3 formation correlates gas shift (WGS) material hydride spectroscopically.

Language: Английский

Citations

78
Promotion of Inorganic Phosphorus on Rh Catalysts in Styrene Hydroformylation: Geometric and Electronic Effects DOI
Boyang Liu, Ning Huang, Yu Wang

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(3), P. 1787 - 1796

Published: Jan. 22, 2021

Rh-based homogeneous catalysts with phosphine ligands are highly active in hydroformylation reactions. Using DFT calculations, we found a similar electronic effect of inorganic phosphorus the Rh2P structure. The energy profiles demonstrated that would significantly enhance styrene activity comparison Rh, which was further confirmed by experiments. Triphenylphosphine (PPh3) used as source, and supported on silica prepared impregnation at relatively low temperature (550 °C). turnover frequency (TOF) increased to 1496 h–1, comparable some single atom (SACs). Recycling tests showed good stability five runs. Furthermore, HAADF-STEM, XPS, other characterizations synthesis promotion P bifunctional. On one hand, doped separated surface Rh atoms, eliminated hollow sites prevented excessively strong adsorption reactants. electrons transferred from P, causing atoms be positively charged, favorable for geometric effects improved dispersion changed rate-determining step CO insertion phenylpropionyl hydrogenation, both leading higher activity.

Language: Английский

Citations

68
Progress in batch preparation of single-atom catalysts and application in sustainable synthesis of fine chemicals DOI

Yifan Hu,

Hongxuan Li, Zesheng Li

et al.

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(22), P. 8754 - 8794

Published: Jan. 1, 2021

The batch preparation technology and the thermo-catalysis application of SACs in fine chemical industries are highlighted.

Language: Английский

Citations

68
Single‐Atom Catalysis: From Simple Reactions to the Synthesis of Complex Molecules DOI
Zhongxin Chen, Jia Liu, Ming Joo Koh

et al.

Advanced Materials, Journal Year: 2021, Volume and Issue: 34(25)

Published: Sept. 12, 2021

Abstract To date, the scope of single‐atom catalysts (SAC) in liquid‐phase transformations is rather limited owing to stability issues and inability activate complex substances. This calls for a better design catalyst support that can provide dynamic coordination environment needed catalytic action, yet retain robustness against leaching or aggregation. In addition, chemical orthogonality SAC useful designing tandem multicomponent reactions, which side reactions common metal nanoparticles are suppressed. this review, intrinsic mechanism will be highlighted controls reaction efficiency selectivity SAC‐catalyzed pathways, as well structural dynamism under conditions. These mechanistic insights helpful development next‐generation systems synthesis high‐value pharmaceuticals through late‐stage functionalization, sequential strategies.

Language: Английский

Citations

66