Evolution of catalytic activity driven by structural fusion of icosahedral gold cluster cores

doi:10.1016/S1872-2067(20)63659-2

Abstract

Abstract:

Atomically precise gold cluster catalysts have emerged as a new frontier in catalysis science, owing to their unexpected catalytic properties. In this work, we explore the evolution of the catalytic activity of clusters formed by the structural fusion of icosahedral Au₁₃ units, namely Au₂₅(SR)₁₈, Au₃₈(SR)₂₄, and Au₂₅(PPh₃)₁₀(SC₂H₄Ph)₅Cl₂, in the oxidation of pyrrolidine to γ-butyrolactam. We demonstrate that the structural fusion of icosahedral Au₁₃units, forming vertex-fused (vf), face-fused (ff), and body-fused (bf) clusters, can induce a decrease in the catalytic activity in the following order: Au_bf > Au_ff > Au_vf. The structural fusion of icosahedral Au₁₃ units in the clusters does not distinguish the adsorption modes of pyrrolidine over the three clusters from each other, but modulates the chemical adsorption capacity and electronic properties of the three clusters, which is likely to be the key reason for the observed changes in catalytic reactivity. Our results are expected to be extendable to study and design atomically defined catalysts with elaborate structural patterns, in order to produce desired products.

Key words: Gold cluster, Structure fusion, Icosahedral unit, Oxidation of pyrrolidine, Active sites, Catalytic activity

Dan Yang, Yan Zhu. Evolution of catalytic activity driven by structural fusion of icosahedral gold cluster cores[J]. Chinese Journal of Catalysis, 2021, 42(2): 245-250.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63659-2

https://www.cjcatal.com/EN/Y2021/V42/I2/245

Figures/Tables 5

Fig. 1. Structural fusion of icosahedral Au13 units: (a) vertex-fused bi-icosahedral Au25, (b) face-fused bi-icosahedral Au38, and (c) body-fused icosahedral Au25. C and H atoms are omitted for clarity. Color labels: yellow, pink, and magenta: gold; light green: S; dark green: Cl; orange: P. ESI-MS profiles of (d) Auvf, (e) Auff, and (f) Aubf.

Fig. 2. (a) Catalytic oxidation of pyrrolidine over Auvf, Auff, and Aubf catalysts. Reaction conditions: catalyst (100 mg, 2 wt% Au), pyrrolidine (0.44 mmol), O2 (0.4 MPa), n-butanol/H2O (4.5 mL/0.5 mL), 85 °C for different reaction times. (b) Linear dependence of ln(Ct/C0) on reaction time for the oxidation of pyrrolidine over Auvf, Auff, and Aubf catalysts. (c) Arrhenius plot for pyrrolidine oxidation. (d) Conversion of pyrrolidine over Aubf catalysts protected by different thiolate groups (n-butyl mercaptan, 1-octanethiol, and 1-dodecanethiol) (48 h).

Fig. 3. (a) In situ FT-IR spectra of CO adsorbed onto the Auvf, Auff, and Aubf clusters; (b) In situ FT-IR spectra of CO adsorbed onto the Aubf clusters capped by different alkanethiol ligands.

Fig. 4. (a) FT-IR spectra of adsorbed species over the catalysts in the presence of pyrrolidine; (b) XPS profiles of Auvf, Auff, and Aubf clusters.

Scheme 1. Proposed mechanism of pyrrolidine oxidation on gold clusters.

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