Synergetic photocatalytic H2 evolution and H2S conversion over S-scheme Co3(PO4)2/CoSx/twinned-Cd0.5Zn0.5S

doi:10.1016/S1872-2067(25)64857-1

Abstract

Abstract:

Developing sustainable, low-cost H₂S conversion technologies holds significant importance for the coal chemical and petrochemical industries. Herein, twinned Cd_0.5Zn_0.5S (T-CZS) homojunctions serve as model photocatalysts, with a Na₂S/NaH₂PO₂ solution simulating H₂S absorption to regulate S²⁻/HS⁻ transformation pathways for concurrent efficient H₂ evolution and desulfurization. Notably, at 3 mol∙L⁻¹ NaH₂PO₂ concentration, the H₂ evolution rate (r_H2) over T-CZS reaches 233.9 mmol∙g⁻¹∙h⁻¹—representing a 5.5-fold enhancement versus 0.1 mol∙L⁻¹ Na₂S alone. Mechanistic studies reveal that the two-step oxidation of H₂PO₂⁻ delivers four electrons for H⁺ reduction while simultaneously scavenging deleterious S₂²⁻ species. This dual function mitigates light-absorption competition, enhances interfacial electron density, and accelerates H₂-evolution kinetics. Further, Co₃(PO₄)₂/CoS_x loading boosts H₂ production to 292.1 mmol∙g⁻¹∙h⁻¹, primarily ascribed to suppressed bulk/interface charge recombination. Crucially, acidification of post-reaction solutions yields pure elemental sulfur (S) as a yellow solid. Practical viability was validated using H₂S preparation and absorption system, confirming robust catalyst performance and system efficacy for integrated high-efficiency H₂ production and S recovery. The critical role and significant potential of H₂PO₂⁻ in enhancing H₂ evolution in S²⁻/HS⁻ solutions were emphasized, offering potential strategies for efficient photocatalytic conversion of S²⁻/HS⁻. This work establishes a new paradigm for green, economical H₂S valorization.

Key words: Photocatalyst, Desulfurization, Conversion of S^2?/HS^?, Twinned-Cd_0.5Zn_0.5S, Homo-heterojunction

Xinyi Ma, Ziyi Xiao, Xueqing Hu, Haobin Hu, Wenhua Xue, Enzhou Liu. Synergetic photocatalytic H₂ evolution and H₂S conversion over S-scheme Co₃(PO₄)₂/CoS_x/twinned-Cd_0.5Zn_0.5S[J]. Chinese Journal of Catalysis, 2026, 80: 146-158.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64857-1

https://www.cjcatal.com/EN/Y2026/V80/I1/146

Figures/Tables 6

Fig. 1. (a) Schematic illustration of Co3(PO4)2/CoSx/T-CZS formation processes. (b) XRD patterns of the samples. (c-g) SEM images of the samples. (h) Element mapping of 4 wt% Co3(PO4)2/CoSx/T-CZS. TEM and HRTEM images of T-CZS (i,j) and 4 wt% Co3(PO4)2/CoSx/T-CZS (k-m).

Fig. 2. High resolution XPS of S 2p (a), Zn 2p (b), Cd 3d (c) P 2p, (d), O 1s (e), and Co 2p (f) of the samples.

Fig. 3. (a) UV-Vis DRS of the samples. (b) K-M curves of the samples. (c) Linear fitting of the current density versus scan rate curves. MS curves of T-CZS (d) and Co3(PO4)2 (e). LSV curves (f), I-t curves (g), EIS spectra (h) and Bode curves (i) of samples in different electrolyte.

Fig. 4. H2 evolution yield (a) and rates (b) of the T-CZS in various environment. (c) H2 evolution activity of tha samples in 0.1 mol·L?1 Na2S/3 mol·L?1 NaH2PO2 solution. (d) H2 evolution of composite in different environment (inset: the H2S preparation and absorption equipment). (e) The photos in which FTO glass coated with composite irradiates with 300 W Xe lamp in 0.1 mol·L?1 Na2S/3 mol·L?1 NaH2PO2 solution. (f) UV-Vis DRS and AQY of 4 wt% Co3(PO4)2/CoSx/T-CZS. (g) The figure depicting the photocatalytic H2 evolution of reported materials from H2S-absorbed solution and Na2S/NaH2PO2 solution [11,13,47-62].

Fig. 5. (a) UV-vis spectra of 500 times diluted solution at 0.1 mol·L?1 Na2S and different environment which after 3 h reaction. (b) UV-vis spectra of 20 times diluted solution at various environment which after 3 h reaction. (c) XRD pattern of the final product after acidification (inset: image of the collected S product). (d) FTIR spectra in different environment which after 3 h reaction with T-CZS catalyst. (e) Illustration of S2?/HS?/H2PO2? system reaction routes.

Fig. 6. DMPO-·O2? signals (a,b), work function (c,d), band structure (e, f) and PDOS (g,h) of the samples. (i) Photocatalytic mechanism of charge transfer in Co3(PO4)2/CoSx/T-CZS homo-heterojunctions in S2?/HS?/H2PO2? system.

References

[1]	J. Chen, W. Xu, J. Zhu, X. Wang, J. Zhou, Appl. Catal. B, 2020, 268, 118454.
[2]	X. Zheng, G. Lei, S. Wang, L. Shen, Y. Zhan, L. Jiang, ACS Catal., 2023, 13, 11723-11752.
[3]	B. Hao, Y. Ahmadi, J. Szulejko, T. Zhang, Z. Lu, K.-H. Kim, Chin. J. Catal., 2025, 68, 282-299.
[4]	M. Dan, S. Yu, Y. Li, S. Wei, J. Xiang, Y. Zhou, J. Photochem. Photobiol. C, 2020, 42, 100339.
[5]	M. Ren, T. Liu, Y. Dong, Z. Li, J. Yang, Z. Diao, H. Lv, G.-Y. Yang, Chin. J. Catal., 2024, 61, 312-321.
[6]	X. Wu, G. Chen, L. Li, J. Wang, G. Wang, J. Mater. Sci. Technol., 2023, 167, 184-204.
[7]	J. Yu, P. Su, D. Zhang, H. Zhao, N. Yang, T. Liang, D. Zhang, X. Pu, Sep. Purif. Technol., 2025, 354, 128694.
[8]	Y. Chan, A. Loy, K. Cheah, S. Chai, L. Ngu, B. How, C. Li, S. Lock, M. Wong, C. Yiin, B. Chin, Z. Chan, S. Lam, Chem. Eng. J., 2023, 458, 141398.
[9]	Y. Li, D. Bahamon, M. Sinnokrot, K. Al-Ali, G. Palmisano, L. F. Vega, J. Photochem. Photobiol. C, 2021, 49, 100456.
[10]	Y. H. Chan, S. S. M. Lock, M. K. Wong, C. L. Yiin, A. C. M. Loy, K. W. Cheah, S. Y. W. Chai, C. Li, B. S. How, B. L. F. Chin, Z. P. Chan, S. S. Lam, Environ. Pollut., 2022, 314, 120219.
[11]	J. S. Jang, H. Gyu Kim, P. H. Borse, J. S. Lee, Int. J. Hydrogen Energy, 2007, 32, 4786-4791.
[12]	H. Oladipo, A. Yusuf, S. Al Jitan, G. Palmisano, Catal. Today, 2021, 380, 125-137.
[13]	J. Liu, C. Wang, W. Yu, H. Zhao, Z.-Y. Hu, F. Liu, T. Hasan, Y. Li, G. Van Tendeloo, C. Li, B.-L. Su, CCS Chem., 2023, 5, 1470-1482.
[14]	J. Reber, K. Meier, J. Phys. Chem., 1984, 88, 5903-5913.
[15]	D. Liu, B. Sun, S. Bai, T. Gao, G. Zhou, Chin. J. Catal., 2023, 50, 273-283.
[16]	Q. Yao, P. Liu, F. Yang, Y. Zhu, Y. Pan, H. Xue, W. Mao, L. Chu, Sci. China Mater., 2024, 67, 3160-3167.
[17]	J. Tian, C. Guan, H. Hu, E. Liu, D. Yang, Acta Phys.-Chim. Sin., 2025, 41, 100068.
[18]	F. Wang, J. Li, X. Yu, H. Tang, J. Xu, L. Sun, Q. Liu, J. Mater. Sci. Technol., 2023, 146, 49-60.
[19]	M. Dan, S. Yu, W. Lin, M. Abdellah, Z. Guo, Z.-Q. Liu, T. Pullerits, K. Zheng, Y. Zhou, Adv. Mater., 2025, 37, 2415138.
[20]	F. Liu, Y. Fu, K. Lu, S. Wang, B. Wang, J. Huang, X. Yan, Y. Zheng, L. Guo, M. Liu, ACS Catal., 2023, 13, 15591-15602.
[21]	K. Huang, D. Chen, X. Zhang, R. Shen, P. Zhang, D. Xu, X. Li, Acta Phys. Chim. Sin., 2024, 40, 2407020.
[22]	Y. Xiao, Y. Jiang, E. Zhou, W. Zhang, Y. Liu, J. Zhang, X. Wu, Q. Qi, Z. Liu, J. Mater. Sci. Technol., 2023, 153, 205-218.
[23]	L. Sun, X. Yu, L. Tang, W. Wang, Q. Liu, Chin. J. Catal., 2023, 52, 164-175.
[24]	J. Tian, X. Cao, T. Sun, H. Miao, Z. Chen, W. Xue, J. Fan, E. Liu, Compos. Part B Eng., 2024, 277, 111389.
[25]	L. Hu, X. Liu, R. Dai, H. Lai, J. Li, Fuel, 2025, 382, 133737.
[26]	S. Cao, B. Zhong, C. Bie, B. Cheng, F. Xu, Acta Phys. Chim. Sin., 2024, 40, 2307016.
[27]	M. Liu, L. Wang, G. Max Lu, X. Yao, L. Guo, Energy Environ. Sci., 2011, 4, 1372-1378.
[28]	P. Su, H. Liu, Z. Jin, Inorg. Chem., 2021, 60, 19402-19413.
[29]	M. Huang, Z. Kong, Z. Ai, D. Shi, M. Yang, X. Yao, Y. Shao, Y. Wu, X. Hao, Small, 2024, 20, 2304784.
[30]	Y. X. Leiu, G. Z. S. Ling, A. R. Mohamed, S. Wang, W.-J. Ong, Mater. Today Energy, 2023, 34, 101281.
[31]	D. Meng, S. Ran, L. Gao, Y. Zhang, X. San, L. Zhang, R. Li, Q. Jin, Chem. Res. Chin. Univ., 2024, 40, 490-498.
[32]	B. Qi, R. Shen, Z. Ren, Y. Teng, H. Ding, X. Zhang, Y. Zhang, L. Hao, X. Li, J. Mater. Sci. Technol., 2025, 232, 65-73.
[33]	H. Liu, X. Liu, Z. Mao, Z. Zhao, X. Peng, J. Luo, X. Sun, J. Power Sources, 2018, 400, 190-197.
[34]	S. Yu, J. Li, J. Yin, W. Liang, Y. Zhang, T. Liu, M. Hu, Y. Wang, Z. Wu, Y. Zhang, Y. Du, Chin. Chem. Lett., 2024, 35, 110068.
[35]	T. Gao, Y. Li, J. Tian, J. Fan, T. Sun, E. Liu, J. Alloys Compd., 2023, 951, 169939.
[36]	B. Zhang, F. Liu, B. Sun, T. Gao, G. Zhou, Chin. J. Catal., 2024, 59, 334-345.
[37]	J. Tian, C. Guan, Q. Zhang, T. Sun, H. Hu, E. Liu, J. Mater. Sci. Technol., 2025, 231, 308-321.
[38]	X. Ning, A. Hao, X. Qiu, Adv. Funct. Mater., 2025, 35, 2413217.
[39]	Q. Xiao, T. Liu, Q. Zhou, L. Li, C. Chang, D. Gao, D. Li, F. You, Chem. Res. Chin. Univ., 2024, 40, 484-489.
[40]	Z. Ma, S. Zhan, Y. Zhang, A. Kuklin, Y. Chen, Y. Lin, H. Zhang, X. Ren, H. Ågren, Y. Zhang, Adv. Mater., 2025, 37, 2416581.
[41]	K. Huang, B. Feng, X. Wen, L. Hao, D. Xu, G. Liang, R. Shen, X. Li, Chin. J. Struct. Chem., 2023, 42, 100204.
[42]	Z. Liang, D. Shen, Y. Wei, F. Sun, Y. Xie, L. Wang, H. Fu, Adv. Mater., 2024, 36, 2408634.
[43]	Q. Zhang, H. Miao, J. Wang, T. Sun, E. Liu, Chin. J. Catal., 2024, 63, 176-189.
[44]	A. Jiang, H. Guo, S. Yu, F. Zhang, T. Shuai, Y. Ke, P. Yang, Y. Zhou, Appl. Catal. B, 2023, 332, 122747.
[45]	M. Lashgari, M. Ghanimati, J. Hazard. Mater., 2018, 345, 10-17.
[46]	Y. Li, S. Yu, J. Xiang, F. Zhang, A. Jiang, Y. Duan, C. Tang, Y. Cao, H. Guo, Y. Zhou, ACS Catal., 2023, 13, 8281-8292.
[47]	S. S. Patil, D. R. Patil, S. K. Apte, M. V. Kulkarni, J. D. Ambekar, C.-J. Park, S. W. Gosavi, S. S. Kolekar, B. B. Kale, Appl. Catal. B, 2016, 190, 75-84.
[48]	A. P. Bhirud, S. D. Sathaye, R. P. Waichal, J. D. Ambekar, C.-J. Park, B. B. Kale, Nanoscale, 2015, 7, 5023-5034.
[49]	U. V. Kawade,R. P. Panmand, Y. A. Sethi, M. V. Kulkarni, S. K. Apte, S. D. Naik, B. B. Kale, RSC Adv., 2014, 4, 49295-49302.
[50]	V. U. Pandit, S. S. Arbuj, U. P. Mulik, B. B. Kale, Environ. Sci. Technol., 2014, 48, 4178-4183.
[51]	S. K. Apte, S. N. Garaje, S. D. Naik, R. P. Waichal, B. B. Kale, Green Chem., 2013, 15, 3459-3467.
[52]	N. S. Chaudhari, S. S. Warule, S. A. Dhanmane, M. V. Kulkarni, M. Valant, B. B. Kale, Nanoscale, 2013, 5, 9383-9390.
[53]	N. S. Chaudhari, A. P. Bhirud, R. S. Sonawane, L. K. Nikam, S. S. Warule, V. H. Rane, B. B. Kale, Green Chem., 2011, 13, 2500-2506.
[54]	A. Bhirud, N. Chaudhari, L. Nikam, R. Sonawane, K. Patil, J.-O. Baeg, B. Kale, Int. J. Hydrogen Energy, 2011, 36, 11628-11639.
[55]	B. B. Kale, J.-O. Baeg, K.-J. Kong, S.-J. Moon, L. K. Nikam, K. R. Patil, J. Mater. Chem., 2011, 21, 2624-2631.
[56]	B. B. Kale, J.-O. Baeg, S. M. Lee, H. Chang, S.-J. Moon, C. W. Lee, Adv. Funct. Mater., 2006, 16, 1349-1354.
[57]	B. B. Kale, J.-O. Baeg, S. K. Apte, R. S. Sonawane, S. D. Naik, K. R. Patil, J. Mater. Chem., 2007, 17, 4297-4303.
[58]	B. B. Kale, J.-O. Baeg, K.-J. Kong, S.-J. Moon, S.-M. Lee, W.-W. So, Int. J. Energy Res., 2010, 34, 404-411.
[59]	E. Subramanian, J. Baeg, S. Lee, S. Moon, K. Kong, Int. J. Hydrogen Energy, 2008, 33, 6586-6594.
[60]	K. Kanade, J. Baeg, K. Kong, B. Kale, S. Lee, S. Moon, C. Lee, S. Yoon, Int. J. Hydrogen Energy, 2008, 33, 6904-6912.
[61]	B. B. Kale, J.-O. Baeg, J. S. Yoo, S.-M. Lee, C. W. Lee, S.-J. Moon, H. Chang, Can. J. Chem., 2005, 83, 527-532.
[62]	W. Liu, Y. Xiong, Q. Liu, X. Chang, J. Tian, J. Colloid Interface Sci., 2023, 651, 633-644.
[63]	Z. Xiao, C. Lu, J. Wang, Y. Qian, B. Wang, Q. Zhang, A. Tang, H. Yang, Adv. Funct. Mater., 2023, 33, 2212183.
[64]	C. Duan, C. Tang, S. Yu, L. Li, J. Li, Y. Zhou, Appl. Catal. B, 2023, 324, 122255.
[65]	B. Liu, J. Cai, J. Zhang, H. Tan, B. Cheng, J. Xu, Chin. J. Catal., 2023, 51, 204-215.
[66]	C. Cui, X. Xu, X. Zhao, N. Xi, M. Li, X. Wang, Y. Sang, X. Yu, H. Liu, J. Wang, Nano Energy, 2024, 126, 109632.
[67]	A. H. Raza, S. Farhan, Z. Yu, Y. Wu, Acta Phys.-Chim. Sin., 2024, 40, 2406020.
[68]	R. Gao, R. Shen, C. Huang, K. Huang, G. Liang, P. Zhang, X. Li, Angew. Chem. Int. Ed., 2025, 64, e202414229.
[69]	M. Dan, F. Wu, J. Xiang, Y. Cao, Y. Zhong, K. Zheng, Y. Liu, Z.-Q. Liu, S. Yu, Y. Zhou, Chem. Eng. J., 2021, 423, 130201.
[70]	Z. Xie, S. Yu, X.-B. Fan, S. Wei, L. Yu, Y. Zhong, X.-W. Gao, F. Wu, Y. Zhou, J. Energy Chem., 2021, 52, 234-242.
[71]	J. Zhao, Y. Wang, H. Liu, R. Zhang, W. Jia, J. Zhang, Y. Sun, L. Peng, ACS Catal., 2025, 15, 3464-3474.
[72]	K. Wang, T. Yang, G. Dawson, J. Zhang, C. Shao, K. Dai, Chem. Res. Chin. Univ., 2025, 41, 716-725.

Synergetic photocatalytic H₂ evolution and H₂S conversion over S-scheme Co₃(PO₄)₂/CoS_x/twinned-Cd_0.5Zn_0.5S

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