Patterning the consecutive Pd3 to Pd1 on Pd2Ga surface via temperature-promoted reactive metal-support interaction

Yiming Niu; Yongzhao Wang; Junnan Chen; Shiyan Li; Xing Huang; Marc-Georg Willinger; Wei Zhang; Yuefeng Liu; Bingsen Zhang

doi:10.1126/sciadv.abq5751

Patterning the consecutive Pd₃ to Pd₁ on Pd₂Ga surface via temperature-promoted reactive metal-support interaction

Sci Adv. 2022 Dec 9;8(49):eabq5751. doi: 10.1126/sciadv.abq5751. Epub 2022 Dec 9.

Authors

Yiming Niu^{1

2}, Yongzhao Wang^{1

2}, Junnan Chen^{1

2}, Shiyan Li³, Xing Huang^{4

5}, Marc-Georg Willinger^{4

6}, Wei Zhang⁷, Yuefeng Liu³, Bingsen Zhang^{1

2

3}

Affiliations

¹ Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China.
² Department of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China.
³ Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
⁴ Scientific Center for Optical and Electron Microscopy, ETH Zurich, Otto-Stern-Weg 3, Zurich 8093, Switzerland.
⁵ College of Chemistry, Fuzhou University, Fuzhou 36108, China.
⁶ School of Natural Science (NAT), Department of Chemistry, Technical University of Munich, Lichtenbergstraße 4, Garching 85747, Germany.
⁷ School of Materials Science and Engineering, Key Laboratory of Automobile Materials MOE, and Electron Microscopy Center, Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials, Jilin University, Changchun 130012, China.

Abstract

Atom-by-atom control of a catalyst surface is a central yet challenging topic in heterogeneous catalysis, which enables precisely confined adsorption and oriented approach of reactant molecules. Here, exposed surfaces with either consecutive Pd trimers (Pd₃) or isolated Pd atoms (Pd₁) are architected for Pd₂Ga intermetallic nanoparticles (NPs) using reactive metal-support interaction (RMSI). At elevated temperatures under hydrogen, in situ atomic-scale transmission electron microscopy directly visualizes the refacetting of Pd₂Ga NPs from energetically favorable (013)/(020) facets to (011)/(002). Infrared spectroscopy and acetylene hydrogenation reaction complementarily confirm the evolution from consecutive Pd₃ to Pd₁ sites of Pd₂Ga catalysts with the concurrent fingerprinting CO adsorption and featured reactivities. Through theoretical calculations and modeling, we reveal that the restructured Pd₂Ga surface results from the preferential arrangement of additionally reduced Ga atoms on the surface. Our work provides previously unidentified mechanistic insight into temperature-promoted RMSI and possible solutions to control and rearrange the surface atoms of supported intermetallic catalyst.