Zn-induced In-S bond modulation in In2S3 enables selective CO2-to-formate conversion at industrial current densities

doi:10.1016/S1872-2067(26)65009-7

Abstract

Abstract:

Electrochemical CO₂ reduction to formate presents a promising route toward carbon neutrality. Nevertheless, achieving superior selectivity at current densities comparable to industrial standards constitutes a core bottleneck to the scalable development of this route. Herein, we report a Zn-doped In₂S₃ catalyst (Zn-In₂S₃) that delivers nearly complete CO₂-to-formate conversion with exceptional stability and efficiency at current densities up to 300 mA cm^-2 at -1.0 V. The incorporation of Zn precisely shortens the In-S bond length from 2.61  to 2.44  Å, leading to increased covalency, strengthened binding of the OCHO* intermediate, and efficient suppression of the side hydrogen evolution reaction. Spectroscopic and theoretical studies reveal that Zn modulates the local coordination environment and the electronic properties of the catalyst, optimizing the reaction pathway toward formate formation. The catalyst achieves a Faradaic efficiency of 98% and stable performance for over 100 h. This work highlights a powerful strategy of coordination tuning for advancing scalable CO₂ electroreduction technologies.

Key words: Carbon neutrality, CO₂ reduction reaction, Formate, Zn-doped In₂S₃, Industrial current densities

Ben Li, Lihua Wang, De Xia, Yong Wang, Huajie Liu, Shanjun Mao. Zn-induced In-S bond modulation in In₂S₃ enables selective CO₂-to-formate conversion at industrial current densities[J]. Chinese Journal of Catalysis, 2026, 85: 106-116.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65009-7

https://www.cjcatal.com/EN/Y2026/V85/I6/106

Figures/Tables 5

Fig. 1. Structural Characterization. (a) Schematic diagram for the synthesis of Zn-In2S3. (b) XRD patterns of the Zn-In2S3 and In2S3. SEM images of Zn-In2S3 at different resolutions: 20 μm (c) and 1 μm (d). (e) AFM images and corresponding height profiles of Zn-In2S3. HRTEM (f) and EDS images (g-j) of Zn-In2S3. (k) UV-vis-NIR diffuse reflectance spectra for In2S3 and Zn-In2S3 nanosheets. (l,m) Atomic-resolution HAADF-STEM images corresponding to Zn-In2S3.

Fig. 2. Fine structure characterizations. XANES spectra at the In K-edge (a) and FT-EXAFS (b) spectra of Zn-In2S3, In2S3, and relevant references. (c) High-resolution XPS In spectra of Zn-In2S3 and In2S3. EXAFS fitting profiles at the R space (d), EXAFS k-space fitting curves (e), and Wavelet-transformed EXAFS (f) for Zn-In2S3. EXAFS fitting profiles at the R space, (g) EXAFS k-space fitting curves (h) and Wavelet-transformed EXAFS (i) for In2S3.

Fig. 3. CO2RR performance. LSV curves in Ar or CO2-saturated 0.5 mol L-1 KHCO3 in an H-type cell (a), FEs of formate (b), partial current density for formate (c), and Tafel slope (d) under di?erent working potentials. (e) Single oxidative scans by using OH- as surrogate ion on Zn-In2S3 and In2S3. (f) Long-term stability test of Zn-In2S3 in H-type cell. (g) Schematic diagram of the flow cell. (h) LSV curve in CO2-saturated 1 mol L-1 KOH. (i) Formate FE under di?erent working potentials of Zn-In2S3. (j) Comparison of performances of some typical electrocatalysts reported in the literature for the CO2RR to formate. (k) Stability test of Zn-In2S3 at 300?mA?cm-2.

Fig. 4. Structural characterizations after CO2RR. (a) XRD patterns of Zn-In2S3 and In2S3 after CO2RR. (b) In-situ Raman setup. (c) In-situ FTIR setup. In-situ electrochemical Raman spectra at various applied potentials on Zn-In2S3 (d) and In2S3 (g) and after CO2 electrolysis for various times on Zn-In2S3 (e) and In2S3 (h). In-situ ATR-FTIR spectra at various applied potentials on Zn-In2S3 (f) and In2S3 (i).

Fig. 5. DFT analysis. COHP for In-S bonding of Zn-In2S3 (a) and In2S3 (b). (c) PDOS of Zn-In2S3 and In2S3 slab. (d) Gibbs free energy of CO2-to-HCOOH conversion of Zn-In2S3. (e) Plane averaged charge density difference in the z-axis direction for OCHO* adsorbed on Zn-In2S3. (f) COHP of active In atom of Zn-In2S3 and O atom of adsorbed OCHO*. (g) Gibbs free energy of CO2-to-HCOOH conversion of In2S3. (h) Plane averaged charge density difference in the z-axis direction for OCHO* adsorbed on In2S3. (i) COHP of active In atom of In2S3 and O atom of adsorbed OCHO*.

References

[1]	O. S. Bushuyev, P. De Luna C. T., Dinh L,. Tao G,. Saur J,. van de Lagemaat S. O., Kelley E. H. Sargent, Joule, 2018, 2, 825-832.
[2]	L. Fan C,. Xia P,. Zhu Y,. Lu H. Wang, Nat. Commun., 2020, 11, 3633.
[3]	Y. Zhang, H. Jang, X. Ge, W. Zhang, Z. Li, L. Hou, L. Zhai, X. Wei, Z. Wang, M. G. Kim, S. Liu, Q. Qin, X. Liu, J. Cho, Adv. Energy Mater., 2022, 12, 2202695.
[4]	H. Shang, T. Wang, J. Pei, Z. Jiang, D. Zhou, Y. Wang, H. Li, J. Dong, Z. Zhuang, W. Chen, D. Wang, J. Zhang, Y. Li, Angew. Chem. Int. Ed., 2020, 59, 22465-22469.
[5]	S. Yang, H. An, S. Arnouts, H. Wang, X. Yu, J. de Ruiter, S. Bals, T. Altantzis, B. M. Weckhuysen, W. van der Stam, Nat. Catal., 2023, 6, 796-806.
[6]	M. Jouny, W. Luc, F. Jiao, Ind. Eng. Chem. Res., 2020, 59, 8121-8123.
[7]	Y. Jiang, J. Shan, P. Wang, L. Huang, Y. Zheng, S.-Z. Qiao, ACS Catal., 2023, 13, 3101-3108.
[8]	Q. Cheng, M. Huang, L. Xiao, S. Mou, X. Zhao, Y. Xie, G. Jiang, X. Jiang, F. Dong, ACS Catal., 2023, 13, 4021-4029.
[9]	Z. Niu X,. Gao S,. Lou N,. Wen J,. Zhao Z,. Zhang Z,. Ding R,. Yuan W,. Dai J. Long, ACS Catal., 2023, 13, 2998-3006.
[10]	Y.-J. Ko, J.-Y. Kim, W. H. Lee, M. G. Kim, T.-Y. Seong, J. Park, Y. Jeong, B. K. Min, W.-S. Lee, D. K. Lee, H.-S. Oh, Nat. Commun., 2022, 13, 2205.
[11]	J. Zhang, C. Guo, S. Fang, X. Zhao, L. Li, H. Jiang, Z. Liu, Z. Fan, W. Xu, J. Xiao, M. Zhong, Nat. Commun., 2023, 14, 1298.
[12]	R. Chen, J. Zhao, X. Zhang, Q. Zhao, Y. Li, Y. Cui, M. Zhong, J. Wang, X. Li, Y. Huang, B. Liu, J. Am. Chem. Soc., 2024, 146, 24368-24376.
[13]	Z. Li Y,. Yang H,. Ding Z,. Li L,. Wang X,. Zhang J,. Li W,. Xie X,. Hu B,. Wang M. Wei, Chem Catal., 2023, 3, 100767.
[14]	X. Zhao, M. Huang, B. Deng, K. Li, F. Li, F. Dong, Chem. Eng. J., 2022, 437, 135114.
[15]	C. Li Z,. Liu X,. Zhou L,. Zhang Z,. Fu Y,. Wu X,. Lv G,. Zheng H. Chen, Energy Environ. Sci., 2023, 16, 3885-3898.
[16]	X. Wei Z,. Li H,. Jang M,. Gyu Kim S,. Liu J,. Cho X,. Liu Q. Qin, Angew. Chem. Int. Ed., 2024, 63, e202409206.
[17]	Y. Li N. M., Adli W,. Shan M,. Wang M. J., Zachman S,. Hwang H,. Tabassum S,. Karakalos Z,. Feng G,. Wang Y. C., Li G. Wu, Energy Environ. Sci., 2022, 15, 2108-2119.
[18]	M. Chen, K. Chang, Y. Zhang, Z. Zhang, Y. Dong, X. Qiu, H. Jiang, Y. Zhu, J. Zhu, Angew. Chem. Int. Ed., 2023, 62, e202305530.
[19]	Z. Li B,. Sun D,. Xiao Z,. Wang Y,. Liu Z,. Zheng P,. Wang Y,. Dai H,. Cheng B. Huang, Angew. Chem. Int. Ed., 2023, 62, e202217569.
[20]	G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[21]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010, 132, 154104.
[22]	A. Zhang, Y. Liang, H. Li, X. Zhao, Y. Chen, B. Zhang, W. Zhu, J. Zeng, Nano Lett., 2019, 19, 6547-6553.
[23]	S. Adhikari, A. V. Charanpahari, G. Madras, ACS Omega, 2017, 2, 6926-6938.
[24]	X. Wang, J. Chen, Q. Li, L. Li, Z. Zhuang, F.-F. Chen, Y. Yu, Chem. Eur. J., 2021, 27, 3786-3792.
[25]	J. Di C,. Chen C,. Zhu X,. Cao J,. Xiong R,. Long S,. Li W,. Jiang Z. Liu, Small, 2024, 2402808.
[26]	J. Zhang, T. Fan, P. Huang, X. Lian, Y. Guo, Z. Chen, X. Yi, Adv. Funct. Mater., 2022, 32, 2113075.
[27]	M. Dunwell, Q. Lu, J. M. Heyes, J. Rosen, J. G. Chen, Y. Yan, F. Jiao, B. Xu, J. Am. Chem. Soc., 2017, 139, 3774-3783.
[28]	J. Chen, M. Qin, S. Ma, R. Fan, X. Zheng, S. Mao, C. Chen, Y. Wang, Appl. Catal. B, 2021, 299, 120640.
[29]	D. Xu S.-N., Zhang J.-S., Chen X.-H. Li, Chem. Rev., 2023, 123, 1-30.
[30]	J. Chen, C. Chen, Y. Chen, H. Wang, S. Mao, Y. Wang, J. Catal., 2020, 392, 313-321.
[31]	Z. Wang, Y. Zhou, D. Liu, R. Qi, C. Xia, M. Li, B. You, B.-Y. Xia, Angew. Chem. Int. Ed., 2022, 61, e202200552.
[32]	R. Vismara, S. Terruzzi, A. Maspero, T. Grell, F. Bossola, A. Sironi, S. Galli, J. A. R. Navarro, V. Colombo, Adv. Mater., 2024, 36, 2209907.
[33]	W. Zhang, S. Ding, W. Zhuang, D. Wu, P. Liu, X. Qu, H. Liu, H. Yang, Z. Wu, K. Wang, X.-W. Sun, Adv. Funct. Mater., 2020, 30, 2005303.
[34]	S.-H. Li, S. Hu, H. Liu, J. Liu, X. Kang, S. Ge, Z. Zhang, Q. Yu, B. Liu, ACS Nano, 2023, 17, 9338-9346.
[35]	D.-H. Guan, X.-X. Wang, M.-L. Li, F. Li, L.-J. Zheng, X.-L. Huang, J.-J. Xu, Angew. Chem. Int. Ed., 2020, 59, 19518-19524.
[36]	J. Poater, M. Duran, M. Solà, B. Silvi, Chem. Rev., 2005, 105, 3911-3947.
[37]	B. Ren G,. Wen R,. Gao D,. Luo Z,. Zhang W,. Qiu Q,. Ma X,. Wang Y,. Cui L,. Ricardez-Sandoval A,. Yu Z. Chen, Nat. Commun., 2022, 13, 2486.
[38]	M. Chen, S. Wan, L. Zhong, D. Liu, H. Yang, C. Li, Z. Huang, C. Liu, J. Chen, H. Pan, D.-S. Li, S. Li, Q. Yan, B. Liu, Angew. Chem. Int. Ed., 2021, 60, 26233-26237.
[39]	J. Wang, W. Tang, Z. Zhu, Y. Lin, L. Zhao, H. Chen, X. Qi, X. Niu, J.-S. Chen, R. Wu, Angew. Chem. Int. Ed., 2025, 64, e202423658.

Zn-induced In-S bond modulation in In₂S₃ enables selective CO₂-to-formate conversion at industrial current densities

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