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

The Progress and Outlook of Metal Single-Atom-Site Catalysis DOI
Liang Xiao, Ninghua Fu,

Shuangchao Yao

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(40), P. 18155 - 18174

Published: Sept. 29, 2022

Single-atom-site catalysts (SASCs) featuring maximized atom utilization and isolated active sites have progressed tremendously in recent years as a highly prosperous branch of catalysis research. Varieties SASCs been developed that show excellent performance many catalytic applications. The major goal SASC research is to establish feasible synthetic strategies for the preparation high-performance catalysts, achieve an in-depth understanding active-site structures mechanisms, develop practical with industrial value. This Perspective describes up-to-date development related such dual-atom-site (DASCs) nano-single-atom-site (NSASCs), analyzes current challenges encountered by these applications, proposes their possible future path.

Language: Английский

Citations

371
Design of Single-Atom Catalysts and Tracking Their Fate Using Operando and Advanced X-ray Spectroscopic Tools DOI Creative Commons
Bidyut Bikash Sarma, Florian Maurer, Dmitry E. Doronkin

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 123(1), P. 379 - 444

Published: Nov. 23, 2022

The potential of operando X-ray techniques for following the structure, fate, and active site single-atom catalysts (SACs) is highlighted with emphasis on a synergetic approach both topics. absorption spectroscopy (XAS) related have become fascinating tools to characterize solids they can be applied almost all transition metals deriving information about symmetry, oxidation state, local coordination, many more structural electronic properties. SACs, newly coined concept, recently gained much attention in field heterogeneous catalysis. In this way, one achieve minimum use metal, theoretically highest efficiency, design only site-so-called single catalysts. While sites are not easy especially under operating conditions, XAS as probe together complementary methods (infrared spectroscopy, electron microscopy) ideal research area prove structure these dynamic changes during reaction. review, starting from their fundamentals, various conventional photon in/out discussed detailed mechanistic situ/operando studies. We systematically summarize strategies SACs outline exploration supported by density functional theory (DFT) calculations recent machine learning tools.

Language: Английский

Citations

133
Single‐Atom Catalysis in Organic Synthesis DOI Creative Commons
Vitthal B. Saptal, Vincenzo Ruta, Mark A. Bajada

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: March 15, 2023

Single-atom catalysts hold the potential to significantly impact chemical sector, pushing boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist many coordination environments, all which have shown important functions specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging gap between homogeneous heterogeneous catalysis. This Review outlines impressive progress made recent years regarding use single-atom organic synthesis. We illustrate knowledge gaps search more sustainable, earth-abundant synthetic applications.

Language: Английский

Citations

111
Highly efficient CeO2-supported noble-metal catalysts: From single atoms to nanoclusters DOI Creative Commons
Han Yan, Ningqiang Zhang, Dingsheng Wang

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(7), P. 1594 - 1623

Published: May 31, 2022

Language: Английский

Citations

101
Heterogeneous hydroformylation of alkenes by Rh-based catalysts DOI Creative Commons
Boyang Liu, Yu Wang, Ning Huang

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(10), P. 2630 - 2658

Published: Aug. 19, 2022

Language: Английский

Citations

85
Homogeneity of Supported Single‐Atom Active Sites Boosting the Selective Catalytic Transformations DOI Creative Commons
Yujie Shi, Yuwei Zhou, Yang Lou

et al.

Advanced Science, Journal Year: 2022, Volume and Issue: 9(24)

Published: July 9, 2022

Selective conversion of specific functional groups to desired products is highly important but still challenging in industrial catalytic processes. The adsorption state surface species the key factor modulating groups, which correspondingly determined by uniformity active sites. However, non-identical number metal atoms, geometric shape, and morphology conventional nanometer-sized particles/clusters normally lead non-uniform sites with diverse configurations local coordination environments, causes distinct states species. Hence, it modulate homogeneity so that transformations can be better confined direction. In this review, construction strategies characterization techniques uniform are atomically dispersed on various supports examined. particular, their unique behavior boosting performance chemical discussed, including selective hydrogenation, oxidation, Suzuki coupling, other reactions. addition, dynamic evolution under reaction conditions utilization single-atom catalysts highlighted. Finally, current challenges frontiers identified, perspectives flourishing field provided.

Language: Английский

Citations

77
Boosting the Hydroformylation Activity of a Rh/CeO2 Single-Atom Catalyst by Tuning Surface Deficiencies DOI
Ying Zheng, Qiang Wang, Yang Qi

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7243 - 7255

Published: May 15, 2023

Controlling the interactions between atomically dispersed metal atoms and support plays significant roles in determining activity selectivity of single-atom catalysts. In this report, we tuned local coordination environment Rh single on CeO2 via calcination to construct a highly active hydroformylation catalyst. Single-atom Rh/CeO2 calcined at high temperature exhibits more oxygen vacancies, which lead formation large amount low-coordination species that are for hydroformylation. Under optimum conditions, best catalyst achieved TOF approximately 5000 h–1 with 100% aldehyde propylene butanal. situ FTIR spectroscopy XPS characterizations provide strong evidence 800 °C-calcined is easily activated form surface HRh(CO)2 species, favoring adsorption CO insertion. This work highlights significance engineering metal–support tuning performance catalysts contributes mechanistic insights into Rh-catalyzed reactions.

Language: Английский

Citations

50
Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson’s catalyst for hydroformylation of olefins DOI Creative Commons
Yifeng Liu, Zhiqiang Liu, Hui Yu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 3, 2023

Hydroformylation is one of the largest industrially homogeneous processes that strongly relies on catalysts with phosphine ligands such as Wilkinson's catalyst (triphenylphosphine coordinated Rh). Heterogeneous for olefin hydroformylation are highly desired but suffer from poor activity compared catalysts. Herein, we demonstrate rhodium nanoparticles supported siliceous MFI zeolite abundant silanol nests very active hydroformylation, giving a turnover frequency high ~50,000 h-1 even outperforms classical catalyst. Mechanism study reveals could efficiently enrich molecules to adjacent nanoparticles, enhancing reaction.

Language: Английский

Citations

48
Suppressing Metal Leaching and Sintering in Hydroformylation Reaction by Modulating the Coordination of Rh Single Atoms with Reactants DOI
Zhounan Yu,

Shengxin Zhang,

Leilei Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11955 - 11967

Published: April 19, 2024

Hydroformylation reaction is one of the largest homogeneously catalyzed industrial processes yet suffers from difficulty and high cost in catalyst separation recovery. Heterogeneous single-atom catalysts (SACs), on other hand, have emerged as a promising alternative due to their initial activity reasonable regioselectivity. Nevertheless, stability SACs against metal aggregation leaching during has rarely been addressed. Herein, we elucidate mechanism Rh by investigating structural evolution

Language: Английский

Citations

29
Regioselective hydroformylation with subnanometre Rh clusters in MFI zeolite DOI
Xiaomeng Dou, Tao Yan, Lixiang Qian

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(6), P. 666 - 677

Published: May 15, 2024

Language: Английский

Citations

27