Distribution of Pt single atom coordination environments on anatase TiO2 supports controls reactivity

Wenjie Zang; Jaeha Lee; Peter Tieu; Xingxu Yan; George W Graham; Ich C Tran; Peikui Wang; Phillip Christopher; Xiaoqing Pan

doi:10.1038/s41467-024-45367-z

Distribution of Pt single atom coordination environments on anatase TiO₂ supports controls reactivity

Nat Commun. 2024 Feb 2;15(1):998. doi: 10.1038/s41467-024-45367-z.

Authors

Wenjie Zang^#¹, Jaeha Lee^#², Peter Tieu³, Xingxu Yan¹, George W Graham^{1

4}, Ich C Tran⁵, Peikui Wang⁶, Phillip Christopher⁷, Xiaoqing Pan^{8

9

10}

Affiliations

¹ Department of Materials Science and Engineering, University of California, Irvine, CA, 92697, USA.
² Department of Chemical Engineering, University of California, Santa Barbara, CA, 93106, USA.
³ Department of Chemistry, University of California, Irvine, CA, 92697, USA.
⁴ Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI, 48109, USA.
⁵ Irvine Materials Research Institute, University of California, Irvine, CA, 92697, USA.
⁶ Department of Chemistry, University of Sherbrooke, Sherbrooke, QC, J1K 2R1, Canada.
⁷ Department of Chemical Engineering, University of California, Santa Barbara, CA, 93106, USA. pchristopher@ucsb.edu.
⁸ Department of Materials Science and Engineering, University of California, Irvine, CA, 92697, USA. xiaoqinp@uci.edu.
⁹ Irvine Materials Research Institute, University of California, Irvine, CA, 92697, USA. xiaoqinp@uci.edu.
¹⁰ Department of Physics and Astronomy, University of California, Irvine, CA, 92697, USA. xiaoqinp@uci.edu.

^# Contributed equally.

Abstract

Single-atom catalysts (SACs) offer efficient metal utilization and distinct reactivity compared to supported metal nanoparticles. Structure-function relationships for SACs often assume that active sites have uniform coordination environments at particular binding sites on support surfaces. Here, we investigate the distribution of coordination environments of Pt SAs dispersed on shape-controlled anatase TiO₂ supports specifically exposing (001) and (101) surfaces. Pt SAs on (101) are found on the surface, consistent with existing structural models, whereas those on (001) are beneath the surface after calcination. Pt SAs under (001) surfaces exhibit lower reactivity for CO oxidation than those on (101) surfaces due to their limited accessibility to gas phase species. Pt SAs deposited on commercial-TiO₂ are found both at the surface and in the bulk, posing challenges to structure-function relationship development. This study highlights heterogeneity in SA coordination environments on oxide supports, emphasizing a previously overlooked consideration in the design of SACs.

Abstract

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