On the mechanism of H2 activation over single-atom catalyst: An understanding of Pt1/WOx in the hydrogenolysis reaction

doi:10.1016/S1872-2067(19)63517-5

Abstract

Abstract: Owing to the atomic dispersion of active sites via electronic interaction with supports, single-atom catalysts (SACs) grant maximum utilization of metals with unique activity and/or selectivity in various catalytic processes. However, the stability of single atoms under oxygen-poor conditions, and the mechanism of hydrogen activation on SACs remain elusive. Here, through a combination of theoretical calculation and experiments, the stabilization of metal single atoms on tungsten oxide and its catalytic properties in H₂ activation are investigated. Our calculation results indicate that the oxygen defects on the WO₃(001) surface play a vital role in the stabilization of single metal atoms through electron transfer from the oxygen vacancies to the metal atoms. In comparison with Pd and Au, Pt single atoms possess greatly enhanced stability on the WO_x(001) surface and carry negative charge, facilitating the dissociation of H₂ to metal-H species (H^δ-) via homolytic cleavage of H₂ similar to that occurring in metal ensembles. More importantly, the facile diffusion of Pt-H to the WO_x support results in the formation of Brønsted acid sites (H^δ+), imparting bifunctionality to Pt₁/WO_x. The dynamic formation of Brønsted acid sites in hydrogen atmosphere proved to be the key to chemoselective hydrogenolysis of glycerol into 1,3-propanediol, which was experimentally demonstrated on the Pt₁/WO_x catalyst.

Key words: Single-atom catalyst, Pt, Density function theory, Hydrogen dissociation, Tungsten oxide

CLC Number:

Maoxiang Zhou, Man Yang, Xiaofeng Yang, Xiaochen Zhao, Lei Sun, Weiqiao Deng, Aiqin Wang, Jun Li, Tao Zhang. On the mechanism of H₂ activation over single-atom catalyst: An understanding of Pt₁/WO_x in the hydrogenolysis reaction[J]. Chinese Journal of Catalysis, 2020, 41(3): 524-532.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(19)63517-5

https://www.cjcatal.com/EN/Y2020/V41/I3/524

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On the mechanism of H₂ activation over single-atom catalyst: An understanding of Pt₁/WO_x in the hydrogenolysis reaction

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