Ligand-shell engineering of a Au25 nanocluster boosting CO2 electroreduction to syngas with tunable range proportion

doi:10.1016/S1872-2067(26)65113-3

Abstract

Abstract:

Au nanoclusters (NCs) with atomic-level precision represent an ideal model catalyst enabling efficient CO₂-to-chemical conversion, yet the catalytic performance of distinct active sites in Au NCs remains poorly understood. In this work, ligand-shell engineering has been successfully carried out through a "ligand-stripping pyrolysis" strategy to obtain modified Au₂₅ NCs for electrocatalytic CO₂ reduction reaction (eCO₂RR). Significantly, in situ pyrolysis techniques and structural characterization identify that the exposure of S/Au active sites has been precisely controlled during the adjusted thermal decomposition of the Au NCs, which establishs a clear site-product relationship. The CO/H₂ molar ratio can be precisely adjusted across an exceptionally wide range (0.26-25.47) - a span that encompasses key industrially relevant ratios, such as the 1:2 ratio optimal for Fischer-Tropsch synthesis. Molecular dynamics (MD) simulations quantitatively disclose the interaction trend between exposed S/Au sites and CO₂. S sites exhibit a superior CO₂ affinity, with the local CO₂ concentration increasing as S-site density increases, thereby kinetically promoting eCO₂RR. Theoretical calculations also reveal that S sites facilitate the stabilization of *CO₂ and *CO intermediates and promote electron transfer. In contrast, Au sites are energetically more favorable for the hydrogen evolution reaction. This study establishes an ideal platform for investigating structure-performance relationships of atomically precise NCs and provides guidance for designing metal NCs-based catalysts.

Key words: Au nanoclusters, Ligand engineering, Active sites, Electrochemical CO₂ reduction reaction, Syngas

Bowen Li, Changlin Lin, Qi Wang, Yongfeng Lun, Jun Fang, Shuqin Song, Yi Wang. Ligand-shell engineering of a Au₂₅ nanocluster boosting CO₂ electroreduction to syngas with tunable range proportion[J]. Chinese Journal of Catalysis, 2026, 87: 396-409.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65113-3

https://www.cjcatal.com/EN/Y2026/V87/I8/396

Figures/Tables 8

Fig. 1. In-situ TG-FTIR 2D (a) and 3D (b) top view spectra recorded at 150, 200, 300, 400, and 500 °C of Au25(DT)18. (c) In-situ TG-MS curves of Au25(DT)18 pyrolysis process. UV-vis spectra of all samples of Au25(DT)18 treated for differnent times at 200 (d), 300 (e), and 400 °C (f).

Fig. 2. Schematic illustration for ligand disintegration process. For clarity, only one ligand is removed.

Fig. 3. High resolution Au 4f (a) and S 2p (b) XPS spectra of Au25(DT)18, Au25/200-3, Au25/300-2.5, and Au25/400-2 samples. (c) Au and S atomic percentage from XPS spectra. (d) 1H NMR spectra of experimental samples.

Fig. 4. HAADF image and element mappings of Au25/200-3 (a), Au25/400-2 (b), and Au25(DT)18 (c). (d) XRD patterns of Au25(DT)18, Au25/200-3, Au25/300-2.5, and Au25/400-2.

Fig. 5. LSV curves (a), Nyquist plot (b), and jH2 (c) of Au25(DT)18, Au25/200-3, Au25/300-2.5, and Au25/400-2 samples. (d) jCO of Au25/200 series of samples. (e) jCO of Au25/300-t series of samples. (f) jH2 of Au25/400-t series of samples.

Fig. 6. FECO (a), FEH2 (b), and molar ratio of CO/H2 (c) from eCO2RR on Au25(DT)18, Au25/200-3, Au25/300-2.5, and Au25/400-2 samples. (d) A comparison of the range of CO/ H2 molar ratio of this work with other reported catalysts. Syngas yield rate (e) and FE (f) of the flow cells with Au25(DT)18, Au25/200-3, Au25/300-2.5, and Au25/400-2 as the eCO2RR electrocatalysts.

Fig. 7. (a) Schematic diagram of Au25(DT)18 NCs removing n-dodecane and 1-dodecanethiol ligands. RDF of CO2 molecules around the S (b) and Au (c) active sites surface. (d) Initial and simulated states of the dynamic process of CO2 adsorption on ligand-removed Au25(DT)18 NCs.

Fig. 8. Free energy diagrams for CO2RR (a) and HER (b) on S and Au sites of Au25(DT)18 NCs. (c) The top and front view of differential charge density of S/Au sites, *CO2 on S/Au sites, *CO on S/Au sites of Au25(DT)18 NCs. The yellow and blue indicate electron accumulation and depletion, respectively. The isosurface level is 0.001 e Å-3. (d) DFT-calculated CO and H2 synthesis cycle on on S and Au sites of Au25(DT)18 NCs. Color code, pink: S, violet: S sites, yellow: Au, brown: Au sites, gray: C, red: O, white: H. All the ligands are replaced with -CH3 for clarity.

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Ligand-shell engineering of a Au₂₅ nanocluster boosting CO₂ electroreduction to syngas with tunable range proportion

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