Tail group structure effect of ligand-protected gold nanocluster catalysts on electrochemical CO2 reduction

doi:10.1016/S1872-2067(25)64908-4

Abstract

Abstract:

The application of thiolate-protected gold nanoclusters (NCs) for the electrochemical CO₂ reduction reaction (CO₂RR) has received widespread attentions. In this work, three types of atomically precise [Au₂₅(SR)₁₈]^‒ NCs protected by 2-phenylethanethiol (PET), 1-hexanethiol (C6T), and 1-dodecanethiol (C12T), respectively, are employed as model catalysts for CO₂RR, where the molecular configuration and length of thiolate ligands are varied. The electrochemical results demonstrate that the [Au₂₅(C12T)₁₈]^‒ NC possesses lower activity and selectivity towards CO formation than [Au₂₅(PET)₁₈]^‒ and [Au₂₅(C6T)₁₈]^‒ NCs. Owing to their identical gold kernels, the differences in electrocatalytic CO₂RR performance of these three Au₂₅ NCs can be fully attributed to their distinctions in tail group structure. Density functional theory (DFT) calculations exclude the possible effects on the electronic structures of the active sites exerted by the distinctions in tail group structure, while molecular dynamics (MD) calculations reveal that different orientation modes of tail groups in aqueous solution affect the diffusion of the reactants to active sites. Overall, this work provides a unique perspective on the structure-property relationships for ligand-protected NCs in electrocatalytic CO₂RR.

Key words: Gold nanoclusters, Electrochemical CO₂ reduction, Precise structure, Ligands effect, Interfacial microenvironment

Liting Huang, Yecheng Zhou, Yongfeng Lun, Qi Wang, Zhaobin Ding, Shuqin Song, Yi Wang. Tail group structure effect of ligand-protected gold nanocluster catalysts on electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2026, 81: 195-205.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64908-4

https://www.cjcatal.com/EN/Y2026/V81/I2/195

Figures/Tables 9

Fig. 1. (a) UV-vis spectra of the three Au25 NCs. (b) Negative-mode EIS-MS profiles of [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs. (c) Comparison of the FT-IR spectra of the three Au25 NCs and their respective thiolate ligands (black).

Fig. 2. (a) XPS spectra of [Au25(PET)18]?, [Au25(C6T)18]?, and [Au25(C12T)18]? NCs. (b) Au 4f XPS profiles of the three Au25 NCs. (c) High resolution S 2p XPS profiles of the three Au25 NCs. The experimental data (dots) are shown with envelopes (cyan and purple lines for Au 4f and S 2p, respectively.) and component fitting of Au(0) 4f (green lines), Au(I) 4f (yellow lines), S 2p3/2 (magenta lines), and S 2p1/2 (lavender lines).

Fig. 3. (a) Total current densities at various applied potentials on the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs in a CO2-saturated 0.1 mol L?1 KHCO3 solution. (b) The H2 partial current densities (jH2). (c)The CO partial current densities (jCO) of the three Au25 NCs. (d) The CO Faradaic efficiencies (CO FE). (e) The CO mass activities (MA). (f) The CO turnover frequencies (TOF).

Fig. 4. (a) Nyquist plots from the electrochemical impedance spectra at the respective open circuit potentials of the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs (Inset: the equivalent electric circuit). (b) The Tafel plots of the three Au25 NCs.

Fig. 5. The DFT-optimized and simplified crystal structures of the dethiolated [Au25(PET)(SCH3)16]? NC (a), [Au25(C6T)(SCH3)16]? NC (b), and [Au25(C12T)(SCH3)16]? NC (c) (color codes: yellow, Au; magenta, dethiolated Au site; green, S; gray, C; white, H). (d) Free energy diagrams for the CO formation in CO2RR. (e) H+ reduction to H2 on the three simplified dethiolated Au25 NCs at the potential of ?1.0 V (vs. computational hydrogen electrode, CHE) (* represents the active site).

Fig. 6. The diagrams of Au25 sphere (a), reactive sphere (b), and statistical region (c).

Fig. 7. The time-dependent surface coverage rates of the thiolate ligands on the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs.

Fig. 8. MD simulation snapshots of [Au25(PET)18]? NC (a), [Au25(C6T)18]? NC (b), and [Au25(C12T)18]? NC (c) in aqueous system (the size of H2O molecule is reduced for clarity). Schematic diagrams of the dispersive (d) and concentrative orientation mode (e) of the thiolate ligands in Au25 NCs (the tail groups are simplified as gray curves).

Fig. 9. (a) MSD curves of H2O molecules in the defined statistical regions, of the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta) and [Au25(C12T)18]? (orange) NCs systems. (b) The H2O exchange frequencies of the three Au25 NCs systems (the number of H2O molecules exchanged between the defined statistical region and the external environment per fs).

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Tail group structure effect of ligand-protected gold nanocluster catalysts on electrochemical CO₂ reduction

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