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.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

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

https://www.cjcatal.com/EN/Y2026/V85/I6/153

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.

References

[1]	R. Schäppi, D. Rutz, F. Dähler, A. Muroyama, P. Haueter, J. Lilliestam, A. Patt, P. Furler, A. Steinfeld, Nature, 2022, 601, 63-68.
[2]	X. Jiao, X. Li, X. Jin, Y. Sun, J. Xu, L. Liang, H. Ju, J. Zhu, Y. Pan, W. Yan, Y. Lin, Y. Xie, J. Am. Chem. Soc., 2017, 139, 18044-18051.
[3]	Z. Dai K,. Lai X,. Li L,. Ge L,. Li Z,. Liu N. Li, Adv. Funct. Mater., 2025, https://doi.org/10.1002/adfm.202514227.
[4]	Y. Huo P,. Zhang J,. Chi F,. Fang Y,. Song D. Sun, Adv. Energy Mater., 2024, 14, 2304282.
[5]	H. Wu L,. Huang J,. Timoshenko K,. Qi W,. Wang J,. Liu Y,. Zhang S,. Yang E,. Petit V,. Flaud J,. Li C,. Salameh P,. Miele L,. Lajaunie B,. Roldán Cuenya D,. Rao D. Voiry, Nat. Energy, 2024, 9, 422-433.
[6]	A. H. Nyhus, M. Yliruka N,. Shah B. Chachuat, Energy Environ. Sci., 2024, 17, 1931-1949.
[7]	M. Monai, M. Gambino, S. Wannakao, B. M. Weckhuysen, Chem. Soc. Rev., 2021, 50, 11503-11529.
[8]	Y. Gao L,. Neal D,. Ding W,. Wu C,. Baroi A. M., Gaffney F. Li, ACS Catal., 2019, 9, 8592-8621.
[9]	H. Zhang, A. Yohannes, H. Zhao, Z. Li, Y. Xiao, X. Cheng, H. Wang, Z. Li, S. Siahrostami, M. G. Kibria, J. Hu, Nat. Commun., 2025, 16, 534.
[10]	E. Cui Y,. Lu X.-L., Yang G,. Dong Y,. Zhang Y. Bi, Energy Environ. Sci., 2025, 18, 613-619.
[11]	C. Ren Q,. Li C,. Ling J. Wang, J. Am. Chem. Soc., 2023, 145, 28276-28283.
[12]	Y. Xu M,. Zhang J,. Long W,. Dai P,. Wang L,. Yang J,. Zou X. Luo, Appl. Catal. B, 2024, 340, 123230.
[13]	C. Chen, M. Wu, Y. Xu, C. Ma, M. Song, G. Jiang, J. Am. Chem. Soc., 2024, 146, 9163-9171.
[14]	H. Huang, J. Zhao, B. Weng, F. Lai, M. Zhang, J. Hofkens, M. B. J. Roeffaers, J. A. Steele, J. Long, Angew. Chem. Int. Ed., 2022, 61, e202204563.
[15]	S. Liu Z,. Guo Z,. Li S,. Yang D,. Wang H. Li, Angew. Chem. Int. Ed., 2025, 64, e202506608.
[16]	L. Y. Peng, G. N. Pan, W. K. Chen, X. Y. Liu, W. H. Fang, G. Cui, Angew. Chem. Int. Ed., 2024, 63, e202315300.
[17]	J. Zhou, J. Li, L. Kan, L. Zhang, Q. Huang, Y. Yan, Y. Chen, J. Liu, S.-L. Li, Y.-Q. Lan, Nat. Commun., 2022, 13, 4681.
[18]	Y. Sun K,. Lai X,. Shi N,. Li Y,. Gao L. Ge, Appl. Catal. B, 2025, 365, 124907.
[19]	Y. Sun K,. Lai N,. Li Y,. Gao L. Ge, Appl. Catal. B, 2024, 357, 124302.
[20]	K. Lai Y,. Sun N,. Li Y,. Gao H,. Li L,. Ge T. Ma, Adv. Funct. Mater., 2024, 34, 2409031.
[21]	D. Zhong, Q. Fang, R. Du, Y. Jin, C. Peng, D. Cheng, T. Li, T. Zhao, S. Zhang, Y. Zheng, Q. Zhao, Y. Sun, J. Li, Angew. Chem. Int. Ed., 2025, 64, e202501773.
[22]	D. Wen N,. Wang J,. Peng T,. Majima J. Jiang, Chin. J. Catal., 2025, 69, 58-74.
[23]	C. Ning, J. Yang, S. Bai, G. Chen, G. Liu, T. Shen, L. Zheng, S.-M. Xu, X. Kong, B. Liu, Y. Zhao, Y.-F. Song, Adv. Funct. Mater., 2023, 33, 2300365.
[24]	H.-X. Liu, Z.-J. Zhou, L. Xie, C. Liu, L. Cai, X.-P. Wu, T.-F. Liu, Angew. Chem. Int. Ed., 2024, 63, e202411508.
[25]	Q. Zhou, Y. Guo, Y. Zhu, Nat. Catal., 2025, 8, 728-739.
[26]	J. Li Y,. Chen B,. Yao W,. Yang X,. Cui H,. Liu S,. Dai S,. Xi Z,. Sun W,. Chen Y,. Qin J,. Wang Q,. He C,. Ling D,. Wang Z. Zhang, J. Am. Chem. Soc., 2024, 146, 5693-5701.
[27]	H. Wang, L. Qian, Y. Zheng, S. Duan, B. Qin, Z. Liu, Z. Li, Q. Ma, Y. Jiang, W. Yan, J. Zhang, Adv. Mater., 2025, 37, e10197.
[28]	Y. Xu P,. Wang M,. Zhang W,. Dai Y,. Xu J.-P., Zou X. Luo, Energy Environ. Sci., 2024, 17, 5060-5069.
[29]	Y. Wu Q,. Chen J,. Zhu K,. Zheng M,. Wu M,. Fan W,. Yan J,. Hu J,. Zhu Y,. Pan X,. Jiao Y,. Sun Y. Xie, Angew. Chem. Int. Ed., 2023, 62, e202301075.
[30]	H. Shi H,. Wang Y,. Zhou J,. Li P,. Zhai X,. Li G. G., Gurzadyan J,. Hou H,. Yang X. Guo, Angew. Chem. Int. Ed., 2022, 61, e202208904.
[31]	Q. Hu Z,. Zhang Y,. Yu W,. Liu J,. Xu W,. Yan J,. Hu J,. Zhu Y,. Pan J,. Zeng X,. Li X,. Jiao Y. Xie, Nano Lett., 2025, 25, 9032-9039.
[32]	A. Rahman, J. R. Jennings, M. M. Khan, Mater. Sci. Semicond. Process., 2024, 169, 107930.
[33]	Y. Xu X,. He X,. Liang H,. Huang J,. Wu D,. Ju J,. Guo S,. Dong Z,. Hu M. Liu, Energy Environ. Sci., 2025, 18, 8339-8351.
[34]	L. Zhang, L. Chen, X. Zhou, Z. Liu, Sci. Rep., 2015, 5, 18263.
[35]	S. Zhang, Z. Zhang, Y. Si, B. Li, F. Deng, L. Yang, X. Liu, W. Dai, S. Luo, ACS Nano, 2021, 15, 15238-15248.
[36]	G. Zhou, Y. Chen, G. Chen, H. Xu, W. Yin, B. Wang, X. Zhu, X. Ning, P. K. Chu, X. Wang, H. Xu, Appl. Catal. B, 2025, 361, 124617.
[37]	Y. Z. Shi, S. Xiong, Y. Zhang, L. K. Chin, Y.-Y. Chen, J. B. Zhang, T. H. Zhang, W. Ser, A. Larrson, S. H. Lim, J. H. Wu, T. N. Chen, Z. C. Yang, Y. L. Hao, B. Liedberg, P. H. Yap, K. Wang, D. P. Tsai, C.-W. Qiu, A. Q. Liu, Nat. Commun., 2018, 9, 815.
[38]	B. Zhao, X. Qiu, Y. Song, S. Li, K. Zhang, Z. Mou, Q. Wang, B. Zhang, Z. Wang, Small, 2025, 21, 2500877.
[39]	F. Zhou, Y. Zhang, J. Wu, W. Yang, X. Fang, T. Jia, Y. Ling, P. He, Q. Liu, J. Lin, Appl. Catal. B, 2024, 341, 123347.
[40]	X. Yang, L. Ren, Z. Chen, H. Li, Y. Yuan, Adv. Mater., 2025, 37, 2412299.
[41]	J. P. Perdew, K. Burke M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[42]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[43]	M. Xu Q,. Zhang S,. Wei S,. Liu M,. Zhou Y,. Zhao B,. Li Y. Xie, Angew. Chem. Int. Ed., 2025, 64, e202506072.
[44]	R. J. Reeder, G. M. Lamble, P. A. Northrup, Am. Mineral., 1999, 84, 1049-1060.
[45]	A. Kocak, M. A. Ashraf, R. B. Metz, J. Phys. Chem. A, 2015, 119, 9653-9665.
[46]	L. S. Sapochak, A. Ranasinghe H,. Kohlmann K. F., Ferris P. E. Burrows, Chem. Mater., 2004, 16, 401-406.
[47]	J. Wang, T. Bo, B. Shao, Y. Zhang, L. Jia, X. Tan, W. Zhou, T. Yu, Appl. Catal. B, 2021, 297, 120498.
[48]	C. Liao, Z. He, F. Wang, Y. Liu, L. Guo, ACS Nano, 2024, 18, 35480-35489.
[49]	F. Qiao, W. Liu, J. Yang, Y. Liu, J. Yuan, Int. J. Hydrogen Energy, 2024, 53, 840-847.
[50]	R. Chen, F. Fan, T. Dittrich, C. Li, Chem. Soc. Rev., 2018, 47, 8238-8262.
[51]	Z. Meng, J. Zhang, H. Long, H. García, L. Zhang, B. Zhu, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202505456.
[52]	K. Liu H,. Zhang Y,. Muhammad T,. Fu R,. Tang Z,. Tong Y. Wang, Sep. Purif. Technol., 2021, 274, 118992.
[53]	J. Song, J. Li, Y. Zhuang, D. Guo, S. Meng, D. Zhang, X. Yang, Y. Li, G. Sui, Sep. Purif. Technol., 2025, 367, 132889.
[54]	N. Li Y,. Qiu L,. Li J,. Zhang Y,. Gao L. Ge, Small, 2025, 21, 2408057.
[55]	F. Xing, Q. Li, J. Li, Z. Xiong, C. Wang, N. Li, H. Jin, Y. Su, C. Feng, J. Li, J. Colloid Interface Sci., 2025, 691, 137388.
[56]	K. Yan D,. Wu T,. Wang C,. Chen S,. Liu Y,. Hu C,. Gao H,. Chen B. Li, ACS Catal., 2023, 13, 2302-2312.
[57]	J. Wang, C. Yang, L. Mao, X. Cai, Z. Geng, H. Zhang, J. Zhang, X. Tan, J. Ye, T. Yu, Adv. Funct. Mater., 2023, 33, 2213901.
[58]	W. Zheng, J. Zhou, F. Chen, S. Tu, X. Xu, H. Huang, Surf. Interfaces, 2025, 62, 106137.
[59]	H. Li Y,. Zhang J,. Li Q,. Liu X,. Zhang Y,. Zhang H. Huang,. Chin. J. Catal., 2025, 69, 111-122.
[60]	H. Cai F,. Chen C,. Hu W,. Ge T,. Li X,. Zhang H. Huang, Chin. J. Catal., 2024, 57, 123-132.
[61]	H. Liang, X. Liu, B. Li, Y. Liang, J. Li, Y. Wang, Z. Zhang, G. Wang, Z. Zheng, Z. Wang, B. Li, Z. Lou, Appl. Catal. B, 2025, 379, 125683.
[62]	J. Zhu W,. Shao X,. Li X,. Jiao J,. Zhu Y,. Sun Y. Xie, J. Am. Chem. Soc., 2021, 143, 18233-18241.
[63]	W. Xie K,. Li X. H., Liu X,. Zhang H. Huang,. Adv. Mater., 2023, 35, 2208132.
[64]	J. Yin D,. Li C,. Sun Y,. Jiang Y,. Li H. Fei, Adv. Mater., 2024, 36, 2403651.
[65]	J. Ding, P. Du, P. Li, W. Liu, J. Xu, W. Yan, Y. Pan, J. Hu, J. Zhu, Q. Chen, X. Jiao, Y. Xie, Angew. Chem. Int. Ed., 2025, 64, e202414453.
[66]	D. Liu L,. Jiang D,. Chen Z,. Hao B,. Deng Y,. Sun X,. Liu B,. Jia L,. Chen H. Liu, ACS Catal., 2024, 14, 5326-5343.
[67]	X.-F. Qiu, H.-L. Zhu, J.-R. Huang, P.-Q. Liao, X.-M. Chen, J. Am. Chem. Soc., 2021, 143, 7242-7246.
[68]	F. Xie Z,. Wang C.-W., Kao J,. Lan Y.-R., Lu Y. Tan, Angew. Chem. Int. Ed., 2024, 63, e202407661.

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

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 6

References

Related Articles 15

Recommended Articles

Metrics

[1]	Yanglin Chen, Ruiming Fang, Huibo Zhao, Minjun Feng, Weidong Hou, Tze Chien Sum, Wen Liu, Liang Wang, Lydia Helena Wong, Can Xue. Bipolar photocatalysis for CO generation via biopolyol oxidation and CO₂ reduction over brown polymeric carbon nitride nanowires [J]. Chinese Journal of Catalysis, 2026, 84(5): 214-225.
[2]	Fuhao Yin, Qianyu Zhang, Mao Xu, Shupeng Wei, Yi Li, Pengzuo Chen, Yanying Zhao, Benxia Li. Synergistic Pd species anchored in ordered macroporous In₂O₃ boosting solar-driven CO₂ and H₂O conversion [J]. Chinese Journal of Catalysis, 2026, 82(3): 238-250.
[3]	Haopeng Jiang, Jinhe Li, Xiaohui Yu, Huilong Dong, Weikang Wang, Qinqin Liu. Interface engineering of covalent β-ketoenamine-bridged S-scheme heterojunction for synergistic solar-powered CO₂-to-CO conversion paired with selective alcohol oxidation [J]. Chinese Journal of Catalysis, 2026, 80(1): 113-122.
[4]	Xianlong Lu, Lili Wang, Xueyang Zhao, Binbin Pan, Zhendong Li, Xiangfei Du, Shihan Zhang, Fan Dong, Bangwei Deng. Unlocking asymmetric C-C coupling pathways on commercial Cu catalysts via Cu (100) grain boundaries for efficient and durable CO electroreduction [J]. Chinese Journal of Catalysis, 2025, 76(9): 198-209.
[5]	Chen Hongjing, Li Yueying, Chen Min, Xie Zhongkai, Shi Weidong. Sulfur electron bridge mediating CuInS₂/CuS heterostructure for highly selective CO₂ photoreduction to C₂H₄ [J]. Chinese Journal of Catalysis, 2025, 75(8): 180-191.
[6]	Lin Zhang, Hui Zhang, Jinghong Fang, Jialin Cui, Jie Liu, Hui Liu, Lishui Sun, Qiong Sun, Lifeng Dong, Yingjie Zhao. Highly conjugated and chemically stable three-dimensional covalent organic frameworks for efficient photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 144-154.
[7]	Ya-Hui Li, Yu Chen, Jin-Yu Guo, Rui Wang, Shu-Na Zhao, Gang Li, Shuang-Quan Zang. Engineering coordination microenvironments of polypyridine Ni catalysts embedded in covalent organic frameworks for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 155-166.
[8]	Rui Li, Pengfei Feng, Bonan Li, Jiayu Zhu, Yali Zhang, Ze Zhang, Jiangwei Zhang, Yong Ding. Photocatalytic reduction of CO₂ over porous ultrathin NiO nanosheets with oxygen vacancies [J]. Chinese Journal of Catalysis, 2025, 73(6): 242-251.
[9]	Dongxiao Wen, Nan Wang, Jiahe Peng, Tetsuro Majima, Jizhou Jiang. Collaborative photocatalytic C-C coupling with Cu and P dual sites to produce C₂H₄ over Cu_xP/g-C₃N₄ heterojunction [J]. Chinese Journal of Catalysis, 2025, 69(2): 58-74.
[10]	Zhe Chen, Tao Wang. Understanding the C−C coupling mechanism in electrochemical CO reduction at low CO coverage: Dynamic change in site preference matters [J]. Chinese Journal of Catalysis, 2025, 69(2): 193-202.
[11]	Lingkun Yang, Zongjun Li, Xin Wang, Lingling Li, Zhe Chen. Facile electrospinning synthesis of S-scheme heterojunction CoTiO₃/g-C₃N₄ nanofiber with enhanced visible light photocatalytic activity [J]. Chinese Journal of Catalysis, 2024, 59(4): 237-249.
[12]	Xiaotian Wang, Bo Hu, Yuan Li, Zhixiong Yang, Gaoke Zhang. Dipole moment regulation by Ni doping ultrathin Bi₄O₅Br₂ for enhancing internal electric field toward efficient photocatalytic conversion of CO₂ to CO [J]. Chinese Journal of Catalysis, 2024, 66(11): 257-267.
[13]	Bai-Chuan Zhou, Wen-Cui Li, Jia Wang, Dan-Hui Sun, Shi-Yu Xiang, Xin-Qian Gao, An-Hui Lu. PO₄^3- coordinated Co²⁺ species on yttrium phosphate boosting the valorization of ethanol to butadiene [J]. Chinese Journal of Catalysis, 2024, 56(1): 166-175.
[14]	Mingming Song, Xianghai Song, Xin Liu, Weiqiang Zhou, Pengwei Huo. Enhancing photocatalytic CO₂ reduction activity of ZnIn₂S₄/MOF-808 microsphere with S-scheme heterojunction by in situ synthesis method [J]. Chinese Journal of Catalysis, 2023, 51(8): 180-192.
[15]	Zizi Li, Jia-Wei Wang, Yanjun Huang, Gangfeng Ouyang. Enhancing CO₂ photoreduction via the perfluorination of Co(II) phthalocyanine catalysts in a noble-metal-free system [J]. Chinese Journal of Catalysis, 2023, 49(6): 160-167.