Fully Exposed Iridium Clusters Enable Efficient Hydrogenation of N-Heteroarenes

Chen, Weiming1,6; Yao, Zhen2; Chen, Wenxing3; Shen, Qikai1,6; Yuan, Desheng4; Zhang, Chi4; Zhu, Yifeng4; Liang, Hai-Wei5; Wang, Yang-Gang2; Song, Weiguo1,6; Cao, Changyan1,6

2023-08-31

10.1021/acscatal.3c03148

ACS CATALYSIS   影响因子和分区

2155-5435

Fully exposed cluster catalysts (FECCs) can not only provide the catalytic sites with multiple metal atoms as in nanoparticles (NPs) but also maintain a full atomic utilization efficiency as in single-atom catalysts (SACs), making them a bridge linking metal SACs and NPs. Due to these particular characteristics, FECCs have been widely studied and have exhibited enhanced catalytic performance in dehydrogenation and oxidation reactions. However, their application in hydrogenation was rarely reported, and the reaction mechanism has yet to be understood. Herein, we report that fully exposed Ir clusters anchored on the sulfur-doped carbon support (Irn/SC) are an efficient catalyst for hydrogenation of N-heteroarenes and exhibit much higher activity and stability compared to the counterpart Ir SAC (Ir1/SC) and Ir NPs catalysts. Especially, we elucidate the hydrogenation reaction mechanism on Irn/SC and disclose how it differs from that on Ir1/ SC. Both experimental studies and density functional theory calculations reveal that the distinct geometric and electronic structures of Irn/SC enable the preferable dissociation of H2 molecules and improve the hydrogenation of quinoline via the classic Horiuti-Polanyi mechanism. In contrast, the absence of metal-metal bonds and the oxidized state of Ir atoms in Ir1/SC result in the difficulty in hydrogen activation and the hydrogenation of quinoline into dihydroquinoline via the Langmuir-Hinshelwood mechanism. This work demonstrates the particular usefulness of fully exposed metal clusters in hydrogenation and provides an insightful understanding of the reaction mechanism.

fully exposed cluster single-atom catalysis electronic structure hydrogenation N-heteroarenes

SCI ; EI

英语

通讯

National Key R&D Program of China["2018YFA0208504","2018YFA0703503"] ; National Natural Science Foundation of China["NSFC 92161112","21932006","22272181"] ; Youth Innovation Promotion Association of CAS[Y2017049]

Chemistry

Chemistry, Physical

WOS:001061201000001

AMER CHEMICAL SOC

20233914782790

Atoms ; Catalysts ; Catalytic oxidation ; Density functional theory ; Hydrogen bonds ; Hydrogenation ; Metal nanoparticles

Air Pollution Control:451.2 ; Nanotechnology:761 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Chinese Acad Sci, CAS Key Lab Mol Nanostruct & Nanotechnol, CAS Res Educ Ctr Excellence Mol Sci, Beijing Natl Lab Mol Sci BNLMS,Inst Chem, Beijing 100190, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
3.Beijing Inst Technol, Sch Mat Sci & Engn, Beijing Key Lab Construct Tailorable Adv Funct Mat, Beijing, Peoples R China
4.Fudan Univ, Collaborat Innovat Ctr Chem Energy Mat, Shanghai Key Lab Mol Catalysis & Innovat Mat, Dept Chem, Shanghai 200433, Peoples R China
5.Univ Sci & Technol China, Hefei Natl Res Ctr Phys Sci Microscale, Dept Chem, Hefei 230026, Peoples R China
6.Univ Chinese Acad Sci, Beijing 100190, Peoples R China

Chen, Weiming,Yao, Zhen,Chen, Wenxing,et al. Fully Exposed Iridium Clusters Enable Efficient Hydrogenation of N-Heteroarenes[J]. ACS CATALYSIS,2023,13(18):12153-12162.

Chen, Weiming.,Yao, Zhen.,Chen, Wenxing.,Shen, Qikai.,Yuan, Desheng.,...&Cao, Changyan.(2023).Fully Exposed Iridium Clusters Enable Efficient Hydrogenation of N-Heteroarenes.ACS CATALYSIS,13(18),12153-12162.

Chen, Weiming,et al."Fully Exposed Iridium Clusters Enable Efficient Hydrogenation of N-Heteroarenes".ACS CATALYSIS 13.18(2023):12153-12162.