Remote Activation of H-H Bonds by Platinum in Dilute Alloy Catalysts

Tongxin Han; Yuanyuan Li; Tao Wu; Debora Motta Meira; Shuting Xiang; Yueqiang Cao; Ilkeun Lee; Xing-Gui Zhou; De-En Jiang; Anatoly I Frenkel; Francisco Zaera

doi:10.1021/acscatal.4c00886

Remote Activation of H-H Bonds by Platinum in Dilute Alloy Catalysts

ACS Catal. 2024 Apr 23;14(9):7157-7165. doi: 10.1021/acscatal.4c00886. eCollection 2024 May 3.

Authors

Tongxin Han¹, Yuanyuan Li², Tao Wu³, Debora Motta Meira^{4

5}, Shuting Xiang², Yueqiang Cao^{1

6}, Ilkeun Lee¹, Xing-Gui Zhou⁶, De-En Jiang⁷, Anatoly I Frenkel^{2

8}, Francisco Zaera¹

Affiliations

¹ Department of Chemistry and UCR Center for Catalysis, University of California, Riverside, Riverside, California 92521, United States.
² Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, New York 11794, United States.
³ The State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China.
⁴ CLS@APS, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States.
⁵ Canadian Light Source Inc., 44 Innovation Boulevard, Saskatoon, Saskatchewan S7N 2V3, Canada.
⁶ State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
⁷ Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37212, United States.
⁸ Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States.

Abstract

With heterogeneous catalysts, chemical promotion takes place at their surfaces. Even in the case of single-atom alloys, where small quantities of a reactive metal are dispersed within the main host, it is assumed that both elements are exposed and available to bond with the reactants. Here, we show, on the basis of in situ X-ray absorption spectroscopy data, that in alloy catalysts made from Pt highly diluted in Cu the Pt atoms are located at the inner interface between the metal nanoparticles and the silica support instead. Kinetic experiments indicated that these catalysts still display better selectivity for the hydrogenation of unsaturated aldehydes to unsaturated alcohols than the pure metals. Density functional theory calculations corroborated the stability of Pt at the metal-support interface and explained the catalytic performance as being due to a remote lowering of the activation barrier for the dissociation of H₂ at Cu sites by the internal Pt atoms.