Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO2 reduction and aryl alcohol oxidation

doi:10.1016/S1872-2067(24)60109-9

Abstract

Abstract:

Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity, abundant surface active sites, and efficient charge separation. Nevertheless, the roles of different forms of atomically-dispersed metals (i.e., single-atoms and atomic clusters) in photocatalytic reactions remain ambiguous. Herein, we developed an ethylenediamine (EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms (Au_SA), Au clusters (Au_C), and a mixed-phase of Au_SA and Au_C (Au_SA+C) on CdS. In addition, we elucidate the synergistic effect of Au_SA and Au_C in enhancing the photocatalytic performance of CdS substrates for simultaneous CO₂ reduction and aryl alcohol oxidation. Specifically, Au_SA can effectively lower the energy barrier for the CO₂→*COOH conversion, while Au_C can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation. As a result, the Au_SA and Au_C co-loaded CdS show impressive overall photocatalytic CO₂ conversion performance, achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g⁻¹ h⁻¹, with the selectivities of 93% and 99%, respectively. More importantly, the solar-to-chemical conversion efficiency of Au_SA+C/CdS reaches 0.57%, which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature (ca. 0.1%). This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions, which is anticipated to pave a new avenue in energy and environmental applications.

Key words: Photocatalysis, Atomically-dispersed metal, Single-atom, CO₂ reduction, Aryl alcohol oxidation

Jian Lei, Nan Zhou, Shuaikang Sang, Sugang Meng, Jingxiang Low, Yue Li. Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO₂ reduction and aryl alcohol oxidation[J]. Chinese Journal of Catalysis, 2024, 65: 163-173.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60109-9

https://www.cjcatal.com/EN/Y2024/V65/I10/163

Figures/Tables 6

Fig. 1. (a) Schematic illustration of the preparation procedure of CdS, AuSA/CdS, AuC/CdS and AuSA+C/CdS. (b) XRD patterns of the prepared samples. TEM (c) and HRTEM (d) images of pristine CdS. HAADF-STEM images of AuSA/CdS (e), AuSA+C/CdS (f) and AuC/CdS (g). CO adsorption DRIFTS spectra of AuSA/CdS (h), AuSA+C/CdS (i) and AuC/CdS (j).

Fig. 2. Normalized Au K L3-edge XANES (a) spectra and Fourier transformed magnitudes of the experimental Au K L3-edge (b) for Au foil, AuC/CdS, AuSA+C/CdS and AuSA/CdS. (c) Au K L3-edge WT-EXAFS for AuC/CdS, AuSA+C/CdS and AuSA/CdS.

Fig. 3. Photocatalytic CO2 reduction (a) and BA oxidation (b) performance of the CdS, AuSA/CdS, AuSA+C/CdS and AuC/CdS. (c) Recycling photocatalytic test AuSA+C/CdS. (d) Photocatalytic performance of Au anchored on different metal sulfides. (e) Comparison of photocatalytic performance of Au/CdS prepared by different methods. (f) Controlled experiments for photocatalytic CO2 reduction and BA oxidation over AuSA+C/CdS. (g) GC-MS spectra of 13CO generated over AuSA+C/CdS in the photocatalytic 13CO2 conversion.

Fig. 4. Transient photocurrent responses (a) and EIS Nyquist plots (b) of the prepared samples. (c) PL spectra of CdS, AuSA/CdS, AuSA+C/CdS and AuC/CdS. Pseudocolor plots of the initial fs‐TAS for CdS (d) and AuSA+C/CdS (e). Normalized fs‐TAS decay kinetic curves at 490 nm in CdS (f) and AuSA+C/CdS (g). In situ EPR spectra of photogenerated electrons (h) and holes (i) using TEMPO spin-label with BA over CdS, AuSA/CdS, AuSA+C/CdS and AuC/CdS under light irradiation.

Fig. 5. In situ DRIFTS spectra for photocatalytic CO2 reduction over AuSA /CdS (a), AuSA+C /CdS (b), and AuC/CdS (c). In situ EPR spectra for AuSA/CdS (d), AuSA+C/CdS (e), and AuC/CdS (f) in the presence of DMPO with or without light irradiation.

Fig. 6. Free energy diagrams of H adsorption (a) and photocatalytic CO2 methanation (b) over CdS, AuSA/CdS and AuC/CdS. (c) Free energy profiles for BA conversion on CdS, AuSA/CdS and AuC/CdS. Side view of the charge density difference of CdS (d), AuSA/CdS (e) and AuC/CdS (f) adsorbed with BA, where their corresponding isosurface values are set to 1.1 × 10-3, 2.1 × 10-4, and 4.2 × 10-4 e ??3, respectively. The charge accumulation is shown as the yellow region, and the charge depletion is shown as the cyan region.

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Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO₂ reduction and aryl alcohol oxidation

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