Defect-mediated dual-site synergy in Zn-CuInS2 enables orbital-tailored high performance photocatalytic CO2-to-ethylene conversion

doi:10.1016/S1872-2067(26)65022-X

Abstract

Abstract:

The photocatalytic conversion of CO₂ into high-value fuels represents a promising strategy for achieving carbon neutrality by utilizing solar energy. Overcoming kinetic barriers in multi-electron transfer and C-C coupling is critical for photocatalytic CO₂-to-C₂H₄ conversion. Herein, Zn-doped CuInS₂ (Zn-CIS) with spontaneously generated sulfur vacancies (S_v) was designed and constructed for highly selective photocatalytic CO₂ reduction. Experimental and density functional theory studies reveal that Zn²⁺ preferentially substitutes In³⁺ sites, inducing S_v formation via charge compensation. S_v acts as an electron reservoir, elevating the Fermi level (E_f) by 0.375 eV and prolonging lifetime of photogenerated charge carriers. Moreover, Zn²⁺ substitution creates adjacent Cu-Zn dual sites with a 2.60 Å spacing, enabling an asymmetric coordination where CO₂ bonds via Cu-C and Zn-O interactions. Furthermore, S_v-mediated charge redistribution activates the Zn 3d orbitals, driving their coupling with the CO₂ bonding orbitals (4σ/1π), which synergizes with Cu 3d-CO₂ 2π* antibonding hybridization and promotes the adsorption and activation of CO₂molecules. This dual-site synergy reduces the energy barrier of the rate-determining step by 0.41 eV and drives efficient *CO → *CHO → *COCHO dimerization, resulting in a 15.9 μmol g^-1 h^-1 C₂H₄ yield, 5.9-fold enhancement with 77.5% electron selectivity. This work highlights the effectiveness of defect-mediated dual-site engineering, coupled with orbital-level insights, facilitating efficient C2 product formation and provides a new paradigm for solar-driven carbon resource conversion.

Key words: Photocatalytic CO₂ reduction, Zn-doped CuInS₂, Sulfur vacancies, C-C coupling

Kezhen Lai, Yuxin Sun, Linping Li, Xiaoqing Shi, Xiaosong Zhou, Ning Li, Yangqin Gao, Lei Ge. Defect-mediated dual-site synergy in Zn-CuInS₂ enables orbital-tailored high performance photocatalytic CO₂-to-ethylene conversion[J]. Chinese Journal of Catalysis, 2026, 85: 153-167.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65022-X

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Figures/Tables 6

Fig. 1. (a) Schematic diagram of the synthesis route of Zn-CuInS2. XRD patterns (b), enlarged XRD patterns (c), and ESR spectra (d) of the as-prepared catalysts. (e) The interplanar spacing of CuInS2 and 3Zn-CIS. TEM images of CuInS2 (f) and 3Zn-CIS (h). HRTEM images of CuInS2 (g) and 3Zn-CIS (i). (j) Element mapping of 3Zn-CIS.

Fig. 2. (a) The formation energy of Sv at different sites in the Zn-CIS model. (b) The Wf of CuInS2, Zn-CIS without Sv and Zn-CIS with Sv. (c) Bader charge visualization model of Zn-CIS without Sv and Zn-CIS with Sv. Surface potential under dark and light irradiation and corresponding KPFM images of CuInS2 (d-f) and 3Zn-CIS (g-i).

Fig. 3. XPS spectra of Cu 2p (a), In 3d (b), S 2p (c) and Zn 2p (d). (e) Normalized XANES spectra at the Zn K-edge of the Zn foil, ZnS and 3Zn-CIS. (f) Magnitude of Fourier transforms of the k2-weighted Zn K-edge EXAFS spectra. k2-weighted Zn K-edge EXAFS spectra (g), the wavelet-transformed EXAFS data of Zn foil (h), ZnS (i), and 3Zn-CIS (j).

Fig. 4. Gas generation rate (a) and electron selectivity (b) of CuInS2 and Zn-CIS. (c) Cyclic stability tests of 3Zn-CIS. (d) Electron selectivity using recycled 3Zn-CIS. (e) Control experiments for photocatalytic CO2 reduction over 3Zn-CIS. (f) mass spectrometry spectrum of 13CO2 isotope experiments on 3Zn-CIS (the insert picture is the zoomed-in part with a pink dashed frame). (g) EIS of CuInS2 and Zn-CIS. Transient photocurrent (h) and TRPL spectra (i) of CuInS2 and 3Zn-CIS.

Fig. 5. (a) In-situ DRIFTS spectra of 3Zn-CIS. CO2 adsorption model, differential charge and bader charge of CuInS2 (b) and Zn-CIS (c) (the electron-density isosurface was plotted at 0.0004 e Å-3 for CuInS2 and 0.004 e Å-3 for Zn-CIS, the pink and green zones indicate electron accumulation and depletion, respectively). CO adsorption model of CuInS2 on In atom (d) and Cu atom (e). CO adsorption model of Zn-CIS on Zn atom (f) and Cu atom (g). (h) ∆G plot of *CO conversion. (i) Proposed reaction pathway for photocatalytic CO2RR to C2H4 in Zn-CIS. (j) ΔG plot of CuInS2 and Zn-CIS.

Fig. 6. (a) COHP and ICOHP of Cu-C in CuInS2, Zn-CIS without Sv and Zn-CIS with Sv. (b) COHP and ICOHP of In-O in CuInS2, Zn-O in Zn-CIS without Sv and Zn-CIS with Sv. (c) DOS of free CO2 molecule, CO2 absorbed on CuInS2 and Zn-CIS. (d) d-band center of Zn-CIS without Sv and Zn-CIS with Sv.

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Defect-mediated dual-site synergy in Zn-CuInS₂ enables orbital-tailored high performance photocatalytic CO₂-to-ethylene conversion

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