Cu clusters immobilized on Cd-defective cadmium sulfide nano-rods towards photocatalytic CO2 reduction

doi:10.1016/j.jmst.2021.11.055

Abstract

Abstract:

Single-site metal atoms or clusters (SMCs) present high potential to enable the exploration of energetics and kinetics in heterogeneous photocatalysis owing to their unique properties. Here, we report the first work for highly no ligands-protected atomic-level Cu clusters by mediating them in Cd vacancies at the edge of CdS nanorods (CuCR SCC) towards photocatalytic CO₂ conversion. X-ray absorption spectrometric analysis and photoelectric dynamic characterizations demonstrate that the well-defined Cu clusters across the Cd vacancies induce a synergistic effect on CO₂ reduction through the interfacial conjunction, accelerating charge carrier mobility and facilitating atom utilization. In situ diffuse reflectance infrared Fourier transform spectroscopy, low-coverage calculated isosteric heat, and theoretical studies unveil that the direct cluster/substrate conjunction provides a driving force for interfacial electronic modification and dynamic cooperation. Besides, Cu acts as the active site in the process of CO₂ photoreduction, which enhances the adsorption and activation of CO₂. Consequently, this leads to outstanding CO₂-to-CO conversion with a turnover number of more than 90 without the addition of any sacrificial agent. Particularly, the Cu clusters-mediated CdS nanorods are able to serve as carrier provider, allowing the photogenerated electrons transfer from CdS to Cu clusters. These electrons received from CdS can further enhance the charge carrier separation and thus achieve high photostability during longtime light irradiation.

Key words: Single-site Cu, Cd-vacancies, Interfacial conjunction, CdS nano-rods, Photocatalytic CO₂ reduction

Lei Cheng, Baihai Li, Hui Yin, Jiajie Fan, Quanjun Xiang. Cu clusters immobilized on Cd-defective cadmium sulfide nano-rods towards photocatalytic CO₂ reduction[J]. J. Mater. Sci. Technol., 2022, 118: 54-63.

Figures/Tables 6

Fig. 1. Structural characterizations. (a) SEM image of CR. (b) HRTEM and (c, d) AC HAADF-STEM images of CuCR SCC. (e) Partially zoomed-in image of the selected region 1 in (d). (f) Corresponding fast Fourier transform pattern of the selected region 2 in (d). Scale bars, 2 1/nm. (g) EDS mapping of CuCR SCC. (h) Corresponding intensity profiles along lines 1 and 2 in (e). (i) XRD patterns of CR, CR-H, and CuCR SCC.

Fig. 2. Atomic structure and coordination state analysis. (a) Normalized Cu K-edge XANES and (b) Fourier-transformed EXAFS spectra of CuCR SCC with Cu foil, Cu2O and CuO as references. Wavelet transform contour plots of (c) CuCR SCC and (d) Cu foil. (e) Schematic illustration for the Cd vacancies formed by annealing treatment on protonated CdS nanorods (left), and the Cu clusters anchored on Cd vacancies at the edge of CdS nanorods (right). (f) Low temperature X-band EPR spectra of CuCR SCC before and after photoactivation.

Fig. 3. Photocatalytic performance of CO2 reduction. Photocatalytic performance for (a) CO and (b) CH4 generation of CuCR SCC, CR and CR-H during the reaction proceeds upon illumination for 5 h. (c) The average rate of CO and CH4 generation of as-synthesized samples with reaction proceeds for 5 h. (d) Calculated TON and (e) selectivity for CO of CuCR SCC, CR and CR-H. (f) Photocatalytic stability for CO production of CuCR SCC, CR and CR-H.

Fig. 4. In situ DRIFTS analysis. (a-c) The in situ DRIFTS spectra of CuCR SCC. The characteristic infrared peaks are highlighted after the introduction of mixed gas (CO2 + H2O) under dark and Xenon lamp irradiation in the wavenumber ranges of 700-3900 cm-1. (d) Three-dimensional visualization for the dynamically adsorbed surface species and CO2 conversion intermediates during the photocatalytic period. (e) Schematic illustration of the possible conversion of reactive intermediates for CO and CH4 generation on CuCR SCC.

Fig. 5. Charge carrier dynamics analysis. High resolution XPS spectra for (a) Cd 3d and (b) S 2p of CuCR SCC and CR. (c) High resolution XPS spectra for Cu 2p of CuCR SCC and CuCR-L SCC. (d-f) Time-resolved transient PL decay curves (the fitted curves indicated as black lines) of (d) CuCR SCC, (e) CR-H and (f) CR (Excitation wavelength of 370 nm). (g) Schematic illustration of internal charge carrier field formation in CuCR SCC and CR, respectively. (h) The calculated isosteric heat (Qst) for CO2 adsorption of CuCR SCC and CR.

Fig. 6. CO2 adsorption and DFT analysis. (a) The calculated absorption energies and Qst for CO2 over CuCR SCC and CR. (b) Projected density of states (PDOS) of 3d-orbitals of Cu clusters for CuCR SCC, 2p-orbitals of free CO2, and their p-d hybridization after CO2 adsorption (the enlarged image of CO2 on CuCR SCC as shown in the right). (c) DOS of CuCR SCC and CR before and after CO2 adsorption, respectively (the dotted line represents Fermi level). (d) Charge density differences of CuCR SCC by Cu clusters occupying in Cd vacancies of CdS nano-rods (cyan represents for holes and yellow for electrons).

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Cu clusters immobilized on Cd-defective cadmium sulfide nano-rods towards photocatalytic CO₂ reduction

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