Ordered Mesopore Confined Pt Nanoclusters Enable Unusual Self-Enhancing Catalysis

Meiqi Gao; Zhirong Yang; Haijiao Zhang; Junhao Ma; Yidong Zou; Xiaowei Cheng; Limin Wu; Dongyuan Zhao; Yonghui Deng

doi:10.1021/acscentsci.2c01290

Ordered Mesopore Confined Pt Nanoclusters Enable Unusual Self-Enhancing Catalysis

ACS Cent Sci. 2022 Dec 28;8(12):1633-1645. doi: 10.1021/acscentsci.2c01290. Epub 2022 Dec 16.

Authors

Meiqi Gao¹, Zhirong Yang², Haijiao Zhang³, Junhao Ma¹, Yidong Zou¹, Xiaowei Cheng¹, Limin Wu⁴, Dongyuan Zhao¹, Yonghui Deng¹

Affiliations

¹ Department of Chemistry, Department of Gastroenterology and Hepatology, Zhongshan Hospital, State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai200433, China.
² State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai200237, China.
³ Institute of Nanochemistry and Nanobiology, School of Environmental and Chemical Engineering, Shanghai University, Shanghai200444, People's Republic of China.
⁴ Institute of Energy and Materials Chemistry, Inner Mongolia University, Hohhot010021, China.

Abstract

As an important kind of emerging heterogeneous catalyst for sustainable chemical processes, supported metal cluster (SMC) catalysts have received great attention for their outstanding activity; however, the easy aggregation of metal clusters due to their migration along the substrate's surface usually deteriorates their activity and even causes catalyst failure during cycling. Herein, stable Pt nanoclusters (NCs, ∼1.06 nm) are homogeneously confined in the uniform spherical mesopores of mesoporous titania (mpTiO₂) by the interaction between Pt NCs and metal oxide pore walls made of polycrystalline anatase TiO₂. The obtained Pt-mpTiO₂ exhibits excellent stability with well-retained CO conversion (∼95.0%) and Pt NCs (∼1.20 nm) in the long term water-gas shift (WGS) reaction. More importantly, the Pt-mpTiO₂ displays an unusual increasing activity during the cyclic catalyzing WGS reaction, which was found to stem from the in situ generation of interfacial active sites (Ti³⁺-O_v-Pt^δ+) by the reduction effect of spillover hydrogen generated at the stably supported Pt NCs. The Pt-mpTiO₂ catalysts also show superior performance toward the selective hydrogenation of furfural to 2-methylfuran. This work discloses an efficient and robust Pt-mpTiO₂ catalyst and systematically elucidates the mechanism underlying its unique catalytic activity, which helps to design stable SMC catalysts with self-enhancing interfacial activity in sustainable heterogeneous catalysis.