Single-Site Heterogeneous Organometallic Ir Catalysts Embedded on Graphdiyne: Structural Manipulation Beyond the Carbon Support

Liu，Hong1,2; Zou，Haiyuan2; Wang，Mei1; Dong，Hongliang3; Wang，Dan2; Li，Fan2; Dai，Hao2; Song，Tao2; Wei，Shuting2; Ji，Yongfei4; Wang，Chenguang5; Duan，Lele2

2022

10.1002/smll.202203442

Small   影响因子和分区

1613-6810

1613-6829

Accurate control over the coordination circumstances of single-atom catalysts (SACs) is decisive to their intrinsic activity. Here, two single-site heterogeneous organometallic catalysts (SHOCs), Cp*Ir‒L/GDY (L = OH and Cl; Cp* = pentamethylcyclopentadienyl), with the fine-tuned local coordination and electronic structure of Ir sites, are constructed by anchoring Cp*Ir complexes on graphdiyne (GDY) matrix via a one-pot procedure. The spectroscopic studies and theoretical calculations indicate that the Ir atoms in Cp*Ir‒Cl/GDY and Cp*Ir‒OH/GDY have a much higher oxidation state than Ir in the SAC Ir/GDY. As a proof-of-principle demonstration, the GDY-supported SHOCs are used for formic acid dehydrogenation, which display a fivefold enhancement of catalytic activity compared with SAC Ir/GDY. The kinetic isotope effect and in situ Fourier-transform infrared studies reveal that the rate-limiting step is the β-hydride elimination process, and Cp* on the Ir site accelerates the β-hydride elimination reaction. The GDY-supported SHOCs integrate the merits of both SACs and molecular catalysts, wherein the isolated Ir anchored on GDY echoes with SACs’ behavior, and the Cp* ligand enables precise structural and electronic regulation like molecular catalysts. The scheme of SHOCs adds a degree of freedom in accurate regulation of the local structure, the electronic property, and therefore the catalytic performance of single-atom catalysts.

catalysis formic acid dehydrogenation graphdiyne single-atom catalysts single-site heterogeneous organometallic catalysts

SCI

英语

通讯

National Natural Science Foundation of China["22179057","5227622","21903016"] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925152742003] ; Educational Commission of Guangdong Province[2020KTSCX121]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Multidisciplinary ; Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied ; Physics, Condensed Matter

WOS:000859138300001

WILEY-V C H VERLAG GMBH

2-s2.0-85138695981

Scopus

1.State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian,116024,China
2.Department of Chemistry,Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen,518055,China
3.Center for High-Pressure Science and Technology Advanced Research,Pudong,Shanghai,201203,China
4.School of Chemistry and Chemical Engineering,Guangzhou University,Guangzhou,Guangdong,510006,China
5.Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences,Guangzhou,510075,China

Liu，Hong,Zou，Haiyuan,Wang，Mei,et al. Single-Site Heterogeneous Organometallic Ir Catalysts Embedded on Graphdiyne: Structural Manipulation Beyond the Carbon Support[J]. Small,2022.

Liu，Hong.,Zou，Haiyuan.,Wang，Mei.,Dong，Hongliang.,Wang，Dan.,...&Duan，Lele.(2022).Single-Site Heterogeneous Organometallic Ir Catalysts Embedded on Graphdiyne: Structural Manipulation Beyond the Carbon Support.Small.

Liu，Hong,et al."Single-Site Heterogeneous Organometallic Ir Catalysts Embedded on Graphdiyne: Structural Manipulation Beyond the Carbon Support".Small (2022).