TY - JOUR
T1 - Coordination-Induced Trigger for Activity
T2 - N-Heterocyclic Carbene-Decorated Ceria Catalysts Incorporating Cr and Rh with Activity Induction by Surface Adsorption Site Control
AU - Ikemoto, Satoru
AU - Muratsugu, Satoshi
AU - Koitaya, Takanori
AU - Tsuji, Yuta
AU - Das, Mowpriya
AU - Yoshizawa, Kazunari
AU - Glorius, Frank
AU - Tada, Mizuki
N1 - Funding Information:
S.I. acknowledges a JSPS fellowship (No. 20J22190). This work was financially supported in part by JSPS KAKENHI (Grant Nos. JP18K05144, JP18H01940, JP20H04808 [hybrid catalysis], JP21K18978, JP21K04996, JP22H05146, and JP22H00335), JST PRESTO program (Nos. JPMJPR15S7 and JPMJPR17S3), JST CREST (No. JPMJCR15P5), the MEXT project Integrated Research on Chemical Synthesis, the Integrated Research Consortium on Chemical Sciences, the World Research Unit (B-1) at Nagoya University “Reaction Infography (R-ing)”, the Iketani Science and Technology Foundation, the Hori Science and Arts Foundation, and the Chubei Itoh Foundation. XAFS measurements were performed with the approval of PF-PAC (Nos. 2019G105, 2021G110, and 2021G113) and the Aichi Synchrotron Radiation Center (Nos. 202102001, 202102055, and 202106019). Part of this work was conducted at the Institute for Molecular Science, supported by the Nanotechnology Platform Program (JPMXP09S19MS1052, JPMXP09S20MS1064, and JPMXP09S21MS1061) and (JPMXP1222MS1011) of MEXT, Japan. The computations in this work were performed using the computer facilities at the Research Institute for Information Technology, Kyushu University, at the Supercomputer Center, the Institute for Solid State Physics, the University of Tokyo, and at Research Center for Computational Science, Okazaki, Japan (Project: 21-IMS-C261). Generous financial support by the Deutsche Forschungsgemeinschaft (SFB 858 and SFB 1459) is gratefully acknowledged.
Publisher Copyright:
© Author(s).
PY - 2022
Y1 - 2022
N2 - A coordination-induced trigger for catalytic activity is proposed on an N-heterocyclic carbene (NHC)-decorated ceria catalyst incorporating Cr and Rh (ICy-r-Cr0.19Rh0.06CeOz). ICy-r-Cr0.19Rh0.06CeOz was prepared by grafting 1,3-dicyclohexylimidazol-2-ylidene (ICy) onto H2-reduced Cr0.19Rh0.06CeOz (r-Cr0.19Rh0.06CeOz) surfaces, which went on to exhibit substantial catalytic activity for the 1,4-arylation of cyclohexenone with phenylboronic acid, whereas r-Cr0.19Rh0.06CeOz without ICy was inactive. FT-IR, Rh K-edge XAFS, XPS, and photoluminescence spectroscopy showed that the ICy carbene-coordinated Rh nanoclusters were the key active species. The coordination-induced trigger for catalytic activity on the ICy-bearing Rh nanoclusters could not be attributed to electronic donation from ICy to the Rh nanoclusters. DFT calculations suggested that ICy controlled the adsorption sites of the phenyl group on the Rh nanocluster to promote the C-C bond formation of the phenyl group and cyclohexenone.
AB - A coordination-induced trigger for catalytic activity is proposed on an N-heterocyclic carbene (NHC)-decorated ceria catalyst incorporating Cr and Rh (ICy-r-Cr0.19Rh0.06CeOz). ICy-r-Cr0.19Rh0.06CeOz was prepared by grafting 1,3-dicyclohexylimidazol-2-ylidene (ICy) onto H2-reduced Cr0.19Rh0.06CeOz (r-Cr0.19Rh0.06CeOz) surfaces, which went on to exhibit substantial catalytic activity for the 1,4-arylation of cyclohexenone with phenylboronic acid, whereas r-Cr0.19Rh0.06CeOz without ICy was inactive. FT-IR, Rh K-edge XAFS, XPS, and photoluminescence spectroscopy showed that the ICy carbene-coordinated Rh nanoclusters were the key active species. The coordination-induced trigger for catalytic activity on the ICy-bearing Rh nanoclusters could not be attributed to electronic donation from ICy to the Rh nanoclusters. DFT calculations suggested that ICy controlled the adsorption sites of the phenyl group on the Rh nanocluster to promote the C-C bond formation of the phenyl group and cyclohexenone.
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U2 - 10.1021/jacs.2c07290
DO - 10.1021/jacs.2c07290
M3 - Article
C2 - 36511728
AN - SCOPUS:85144042451
SN - 0002-7863
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -