首页|The proximity between hydroxyl and single atom determines the catalytic reactivity of Rh1/CeO2 single-atom catalysts

The proximity between hydroxyl and single atom determines the catalytic reactivity of Rh1/CeO2 single-atom catalysts

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The local structure of the metal single-atom site is closely related to the catalytic activity of metal single-atom catalysts(SACs).However,constructing SACs with homogeneous metal active sites is a challenge due to the surface heterogeneity of the conventional support.Herein,we prepared two Rh1/CeO2 SACs(0.5Rh1/r-CeO2 and 0.5Rh1/c-CeO2,respectively)using two shaped CeO2(rod and cube)exposing different facets,i.e.,CeO2(111)and CeO2(100).In CO oxidation reaction,the T100 of 0.5Rh1/r-CeO2 SACs is 120 ℃,while the T100 of 0.5Rh1/c-CeO2 SACs is as high as 200 ℃.Via in-situ CO diffuse reflectance infrared Fourier transform spectroscopy(CO-DRIFTS),we found that the proximity between OH group and Rh single atom on the plane surface plays an important role in the catalytic activity of Rh1/CeO2 SAC system in CO oxidation.The Rh single atom trapped at the CeO2(111)crystal surface forms the Rh1(OH)adjacent species,which is not found on the CeO2(100)crystal surface at room temperature.Furthermore,during CO oxidation,the OH group far from Rh single atom on the 0.5Rh1/c-CeO2 disappears and forms Rh1(OH)adjacent species when the temperature is above 150 ℃.The formation of Rh1(OH)adjacentCO intermediate in the reaction is pivotal for the excellent catalytic activity,which explains the difference in the catalytic activity of Rh single atoms on two different CeO2 planes.The formed Rh1(OH)adjacent-O-Ce structure exhibits good stability in the reducing atmosphere,maintaining the Rh atomic dispersion after CO oxidation even when pre-reduced at high temperature of 500 ℃.Density functional theory(DFT)calculations validate the unique activity and reaction path of the intermediate Rh1(OH)adjacentCO species formed.This work demonstrates that the proximity between metal single atom and hydroxyl can determine the formation of active intermediates to affect the catalytic performances in catalysis.

crystal planeRh1/CeO2 single-atom catalystproximity of Rh and hydroxylcoordination structureCO oxidation

Danfeng Wu、Shuyun Zhou、Congcong Du、Juan Li、Jianyu Huang、Hong-xia Shen、Abhaya K.Datye、Shan Jiang、Jeffrey T.Miller、Sen Lin、Haifeng Xiong

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State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China

State Key Laboratory of Photocatalysis on Energy and Environment,College of Chemistry,Fuzhou University,Fuzhou 350002,China

Clean Nano Energy Center,State Key Laboratory of Metastable Materials Science and Technology,Yanshan University,Qinhuangdao 066004,China

College of Biology and Chemical Engineering,Jiaxing University,Jiaxing 314000,China

Department of Chemical & Biological Engineering,University of New Mexico,Albuquerque,NM 8731-0001,USA

Davidson School of Chemical Engineering,Purdue University,West Lafayette,IN 47907-2100,USA

Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM),Xiamen 361102,China

Fujian Key Laboratory of Rare-earth Functional Materials,Fujian Shanhai Collaborative Innovation Center of Rare-earth Functional Materials,Longyan 366300,China

State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Che

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National High-Level Talent Fund and the National Natural Science Foundation of ChinaNational High-Level Talent Fund and the National Natural Science Foundation of ChinaNational High-Level Talent Fund and the National Natural Science Foundation of ChinaNational High-Level Talent Fund and the National Natural Science Foundation of ChinaNational High-Level Talent Fund and the National Natural Science Foundation of ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces of Xiamen UniversityScience and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKFundamental Research Funds for the Central Universitiesa U.S.Department of Energy(DOE)Office of Science User Facility operated for the DOE Office of Science by Brookhaven National LabNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNatural Science Foundation of Hebei Province

2207211822372138223881022197301322373017HRTP-[2022]-320720220008DE-SC0012704U20A2033621935009B2020203037

2024

10.1007/s12274-023-6333-3

纳米研究(英文版)

纳米研究(英文版)

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ISSN：
年,卷(期)：2024.17(1)
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