Atomically Precise Au24Pt(thiolate)12(dithiolate)3 Nanoclusters with Excellent Electrocatalytic Hydrogen Evolution Reactivity

Miyu Sera; Sakiat Hossain; Sara Yoshikawa; Kana Takemae; Ayaka Ikeda; Tomoya Tanaka; Taiga Kosaka; Yoshiki Niihori; Tokuhisa Kawawaki; Yuichi Negishi

doi:10.1021/jacs.4c10868

Atomically Precise Au₂₄Pt(thiolate)₁₂(dithiolate)₃ Nanoclusters with Excellent Electrocatalytic Hydrogen Evolution Reactivity

J Am Chem Soc. 2024 Oct 30;146(43):29684-29693. doi: 10.1021/jacs.4c10868. Epub 2024 Oct 15.

Authors

Miyu Sera¹, Sakiat Hossain², Sara Yoshikawa¹, Kana Takemae¹, Ayaka Ikeda¹, Tomoya Tanaka¹, Taiga Kosaka¹, Yoshiki Niihori², Tokuhisa Kawawaki^{1

2}, Yuichi Negishi^{2

3}

Affiliations

¹ Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
² Research Institute for Science & Technology, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
³ Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577, Japan.

PMID: 39405364
DOI: 10.1021/jacs.4c10868

Abstract

[Au₂₄Pt(C6)₁₈]⁰ (C6 = 1-hexanethiolate) is twice as active as commercial Pt nanoparticles in promoting the electrocatalytic hydrogen evolution reaction (HER), thereby attracting attention as new HER catalysts with well-controlled geometric structures. In this study, we succeeded in synthesizing two new Au-Pt alloy nanoclusters, namely, [Au₂₄Pt(TBBT)₁₂(TDT)₃]⁰ (TBBT = 4-tert-butylbenzenethiolate; TDT = thiodithiolate) and [Au₂₄Pt(TBBT)₁₂(PDT)₃]⁰ (PDT = 1,3-propanedithiolate), by exchanging all the ligands of [Au₂₄Pt(PET)₁₈]⁰ (PET = 2-phenylethanethiolate) with mono- or dithiolates. Although [Au₂₄Pt(TBBT)₁₂(TDT)₃]⁰ was synthesized serendipitously, a similar cluster, [Au₂₄Pt(TBBT)₁₂(PDT)₃]⁰, was subsequently obtained by selecting the appropriate reaction conditions and optimal combination of thiolate and dithiolate ligands. Single crystal X-ray diffraction analyses revealed that the lengths and orientations of -Au(I)-SR-Au(I)- staples in [Au₂₄Pt(TBBT)₁₂(TDT)₃]⁰ and [Au₂₄Pt(TBBT)₁₂(PDT)₃]⁰ were different from those in [Au₂₄Pt(C6)₁₈]⁰, [Au₂₄Pt(PET)₁₈]⁰, and [Au₂₄Pt(TBBT)₁₈]⁰, and these subtle differences were reflected in the geometric and electronic structures as well as the HER activities of [Au₂₄Pt(TBBT)₁₂(TDT)₃]⁰ and [Au₂₄Pt(TBBT)₁₂(PDT)₃]⁰. Accordingly, the HER activities of products [Au₂₄Pt(TBBT)₁₂(TDT)₃]⁰ and [Au₂₄Pt(TBBT)₁₂(PDT)₃]⁰ were, respectively, 3.5 and 4.9 times higher than those of [Au₂₄Pt(C6)₁₈]⁰ and [Au₂₄Pt(TBBT)₁₈]⁰.