简易合成中熵金属硫化物作为高效助催化剂用于光催化制氢

doi:10.1016/S1872-2067(25)64823-6

摘要/Abstract

摘要：

面对日益严峻的能源与环境挑战, 开发高效、稳定的光催化制氢技术对于实现太阳能向化学能的转化具有重要意义. 石墨相氮化碳(g-C₃N₄)因其成本低、稳定性好而备受关注, 但其光吸收能力有限、载流子易复合及表面活性位点不足等问题严重制约了其催化性能. 贵金属助催化剂虽能有效改善上述问题, 但其高昂的成本限制了大规模应用. 因此, 开发基于非贵金属的高性能助催化剂, 并通过多组分协同策略提升g-C₃N₄的光催化产氢活性, 已成为该领域的研究热点. 本研究成功构建了一种基于中熵金属硫化物(FeCoNi)S₂和质子化g-C₃N₄纳米片(HCN)的复合光催化剂, 为实现高效、低成本光催化制氢提供了新思路.

本研究通过溶剂热法将中熵(FeCoNi)S₂助催化剂均匀负载于具有大比表面积和卷曲层状结构的质子化g-C₃N₄纳米片(HCN)上, 成功制备出(FeCoNi)S₂-HCN复合材料. 该设计充分利用HCN纳米片的结构优势及其对金属硫化物的锚定作用, 实现了助催化剂的高分散负载. 系统表征(包括X射线衍射、透射电镜、X射线光电子能谱和紫外-可见光漫反射光谱等)结果表明, HCN的独特形貌不仅增强了光吸收和电子传输能力, 还为助催化剂提供了高分散锚定位点; (FeCoNi)S₂的引入进一步拓宽了复合材料在可见光区的吸收范围, 显著促进了光生电子-空穴对的分离与迁移, 并提供了丰富的表面活性位点. 光催化产氢性能测试结果表明, 该复合材料在模拟太阳光下的产氢速率高达2996 μmol·h^-1·g^-1, 分别是纯HCN (36 μmol·h^-1·g^-1), FeS₂-HCN (327 μmol·h^-1·g^-1)和(FeCo)S₂-HCN (2240 μmol·h^-1·g^-1)的83.22倍、9.16倍和1.34倍, 且在370 nm波长单色光下的表观量子效率(AQE)达到12.29%, 显示出优异的光子利用效率. 通过电化学阻抗谱、瞬态光电流响应和莫特-肖特基测试等光电化学表征, 进一步证实该复合材料具有更低的电荷传输阻力和更高的载流子分离效率. 对比不同金属组合的硫化物助催化剂FeS₂, (FeCo)S₂和(FeCoNi)S₂, 发现Fe, Co, Ni三种金属元素之间存在显著协同效应: 它们共同调控材料的电子结构, 提高载流子浓度, 降低电荷传输电阻, 从而显著提升光催化析氢性能. 机理研究进一步揭示, (FeCoNi)S₂与HCN之间形成了高效的载流子转移通道, 助催化剂作为电子捕获中心有效促进光生电子由HCN向(FeCoNi)S₂转移并用于表面还原反应, 有效抑制了电子-空穴对的复合.

综上, 本工作不仅证实了中熵金属硫化物作为高效非贵金属助催化剂在光催化制氢中的巨大潜力, 而且为通过多金属协同和界面工程设计开发高性能、低成本的复合光催化剂提供了重要借鉴, 对推动太阳能光催化技术的实际应用具有积极意义.

关键词: 中熵, 金属硫化物, 质子化g-C₃N₄纳米片, 光催化制氢, 助催化剂

Abstract:

Facing the dual challenges of environmental pollution and energy crisis, photocatalytic water splitting for hydrogen (H₂) production has emerged as a promising strategy to convert solar energy into storable chemical energy. In this work, the medium-entropy metal sulfides ((FeCoNi)S₂) as cocatalysts are successfully anchored onto protonated g-C₃N₄ nanosheets (HCN NSs) to fabricated (FeCoNi)S₂-HCN composite via a solvothermal method. The photocatalytic hydrogen production rate of (FeCoNi)S₂-HCN composite reaches 2996 μmol·h^-1·g^-1, representing 83.22, 9.16, and 1.34-fold enhancements compared to HCN (36 μmol·h^-1·g^-1), FeS₂-HCN (327 μmol·h^-1·g^-1) and (FeCo)S₂-HCN (2240 μmol·h^-1·g^-1). The apparent quantum efficiency of (FeCoNi)S₂-HCN composite attains 12.29% at λ = 370 nm. Comprehensive characterizations and experimental analyses reveal that the superior photocatalytic performance stems from three synergistic mechanisms: (1) The curled-edge lamellar morphology of HCN nanosheets provides a large specific surface area, which enhances light absorption, facilitates electron transfer, and promotes cocatalyst loading. (2) (FeCoNi)S₂ as cocatalyst expands the light absorption range and capacity, accelerates the separation and transfer of electron-hole pairs, and creates abundant active sites to trap photogenerated carriers for surface hydrogen evolution reactions. (3) The synergistic interactions among multiple metallic elements (Fe, Co and Ni) further enhance surface activity, increase photogenerated carrier density, and reduce charge transport resistance, ultimately optimizing hydrogen production efficiency.

Key words: Medium-entropy, Metal sulfides, Protonated g-C₃N₄ nanosheets, Photocatalytic hydrogen production, Cocatalysts

臧云珠, 任佳丽, 安杉娜, 田健. 简易合成中熵金属硫化物作为高效助催化剂用于光催化制氢[J]. 催化学报, 2025, 78: 242-251.

Yunzhu Zang, Jiali Ren, Shanna An, Jian Tian. Facile synthesis of medium-entropy metal sulfides as high-efficiency cocatalysts toward photocatalytic hydrogen production[J]. Chinese Journal of Catalysis, 2025, 78: 242-251.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64823-6

https://www.cjcatal.com/CN/Y2025/V78/I11/242

图/表 8

Scheme 1. The synthesis process of HCN (a) and (FeCoNi)S2-HCN composites (b) materials.

Fig. 1. (a) XRD patterns of HCN, FeS2-HCN, (FeCo)S2-HCN and (FeCoNi)S2-HCN composites. Survey (b), C 1s (c), N 1s (d), Fe 2p (e), Co 2p (f), Ni 2p (g), S 2p (h), and O 1s (i) XPS spectra of (FeCoNi)S2-HCN composites.

Fig. 2. SEM images of HCN (a), FeS2-HCN (b), (FeCo)S2-HCN (c), and (FeCoNi)S2-HCN (d). TEM (e-h) and EDS elemental mapping (i) images of the (FeCoNi)S2-HCN composite.

Fig. 3. (a) UV-vis absorption spectra of HCN, FeS2-HCN, (FeCo)S2-HCN, and (FeCoNi)S2-HCN composites. Band gap value (b), Mott-Schottky plot (c), and schematic diagram (d) of the band structure of HCN.

Fig. 4. Steady-state (a) and time-resolved (b) PL spectra of HCN and (FeCoNi)S2-HCN composites. Transient photocurrent responses (c) and EIS spectra (d) of HCN, FeS2-HCN, (FeCo)S2-HCN, and (FeCoNi)S2-HCN composites.

Fig. 5. Photocatalytic hydrogen evolution activity (a) and corresponding rates (b) of HCN, FeS2-HCN, (FeCo)S2-HCN, and (FeCoNi)S2-HCN composites. (c) Hydrogen evolution rates for (FeCoNi)S2-HCN in this work compared with representative reported photocatalysts.

Fig. 6. Structural model (a), differential charge density (b), and Gibbs free energy (c) in HER of (FeCoNi)S2-HCN. (d) Schematic illustration of the photocatalytic hydrogen evolution mechanism for the (FeCoNi)S2-HCN composite.

Fig. 7. Structural model of (FeCoNi)S2-HCN (a), (FeCo)S2-HCN (b), FeS2-HCN (c) and HCN (d).

参考文献

[1]	L. Yao, Energy Rep., 2022, 8, 9211-9220.
[2]	H. Huang, L. Jiang, J. Yang, S. Zhou, X. Yuan, J. Liang, H. Wang, H. Wang, Y. Bu, H. Li, Renew. Sustain. Energy Rev., 2023, 173, 113110.
[3]	N. Lu, M. Zhang, X. Jing, P. Zhang, Y. Zhu, Z. Zhang, Energy Environ. Mater., 2023, 6, e12338.
[4]	T. Li, N. Tsubaki, Z. Jin, J. Mater. Sci. Technol., 2024, 169, 82-104.
[5]	P. L. Cruz, J. Dufour, D. Iribarren, Renewable Energy, 2023, 210, 424-430.
[6]	F. Xu, B. Weng, J. Mater. Chem. A, 2023, 11, 4473-4486.
[7]	H. Šalipur, D. Manojlović, K. Milošević, M. Fronczak, A. G. Silva, D. Lončarević, J. Dostanić, J. Environ. Chem. Eng., 2024, 12, 112862.
[8]	K. Liu, F. Jin, J. Du, P. Wang, G. Jiang, Z. Jin, Solar RRL, 2025, 9, 2500038.
[9]	Z. Zhang, Y. Kang, L.-C. Yin, P. Niu, C. Zhen, R. Chen, X. Kang, F. Wu, G. Liu, J. Mater. Sci. Technol., 2021, 95, 167-171.
[10]	C. Feng, Z. Chen, J. Jing, M. Sun, J. Tian, G. Lu, L. Ma, X. Li, J. Hou, J. Mater. Sci. Technol., 2021, 80, 75-83.
[11]	Z. Qin, F. Xue, Y. Chen, S. Shen, L. Guo, Appl. Catal. B, 2017, 217, 551-559.
[12]	Y. Wei, G. Cheng, J. Xiong, J. Zhu, Y. Gan, M. Zhang, Z. Li, S. Dou, J. Energy Chem., 2019, 32, 45-56.
[13]	P. Qiu, J. Xiong, M. Lu, L. Liu, W. Li, Z. Wen, W. Li, R. Chen, G. Cheng, J. Colloid Interface Sci., 2022, 622, 924-937.
[14]	W. Zhang, H. Zhang, J. Xu, H. Zhuang, J. Long, Chin. J. Catal., 2019, 40, 320-325.
[15]	W. Zhang, J. Xiong, S. Li, W. Li, Mol. Catal., 2025, 570, 114701.
[16]	C. Feng, Z. Chen, J. Hou, J. Li, X. Li, L. Xu, M. Sun, R. Zeng, Chem. Eng. J., 2018, 345, 404-413.
[17]	H. Chen, J. Wu, Y. Zhu, J. Yang, B. Tang, T. Zhang, H. Yang, Renewable Energy, 2024, 228, 120672.
[18]	W. Huang, Z. Li, C. Wu, H. Zhang, J. Sun, Q. Li, J. Mater. Sci. Technol., 2022, 120, 89-98.
[19]	Y. Jia, P. Liu, Q. Wang, Y. Wu, D. Cao, Q.-A. Qiao, J. Colloid Interface Sci., 2021, 585, 459-469.
[20]	R. Hou, M. Xu, Z. Fan, R. Zhong, Y. Xie, Y. Ling, Y. Wang, Mater. Today Phys., 2024, 44, 101426.
[21]	C.-J. Chang, Y.-C. Chen, Z.-T. Tsai, Int. J. Hydrogen Energy, 2022, 47, 40777-40786.
[22]	B. Zhang, D. Wang, S. Jiao, Z. Xu, Y. Liu, C. Zhao, J. Pan, D. Liu, G. Liu, B. Jiang, Y. Li, L. Zhao, J. Wang, Chem. Eng. J., 2022, 446, 137138.
[23]	W. Zhang, Z. Zhang, S. Kwon, F. Zhang, B. Stephen, K. K. Kim, R. Jung, S. Kwon, K.-B. Chung, W. Yang, Appl. Catal. B, 2017, 206, 271-281.
[24]	Z. Pan, W. Ding, H. Chen, H. Ji, Chin. Chem. Lett., 2024, 35, 108567.
[25]	Q. Zhu, Z. Xu, B. Qiu, M. Xing, J. Zhang, Small, 2021, 17, 2101070.
[26]	D. Ma, Z. Zhang, Y. Zou, J. Chen, J.-W. Shi, Coord. Chem. Rev., 2024, 500, 215489.
[27]	Y. Jiang, F. Qu, L. Tian, X. Yang, Z. Zou, Z. Lin, Appl. Surf. Sci., 2019, 487, 59-67.
[28]	Z. Sun, M. Zhu, M. Fujitsuka, A. Wang, C. Shi, T. Majima, ACS Appl. Mater. Interfaces, 2017, 9, 30583-30590.
[29]	X. Xu, Z. Huang, L. Tan, Z. Zhang, B. Chen, X. Xia, G. Cheng, X. Chen, Appl. Surf. Sci., 2024, 672, 160794.
[30]	H. Ali, Z. Ajmal, I. Boukhris, A. M. Alenad, M. S. Al-Buriahi, A. M. Abu-Dief, N. S. Alsaiari, A. Hayat, H. M. A. Hassan, Y. Liang, D. Yue, Int. J. Hydrogen Energy, 2025, 100, 79-128.
[31]	H. Zhang, X. Bai, J. Colloid Interface Sci., 2022, 627, 541-553.
[32]	D. Wu, S. Hu, H. Xue, X. Hou, H. Du, G. Xu, Y. Yuan, J. Mater. Chem. A, 2019, 7, 20223-20228.
[33]	J. Pan, B. Wang, Z. Dong, C. Zhao, Z. Jiang, C. Song, J. Wang, Y. Zheng, C. Li, Int. J. Hydrogen Energy, 2019, 44, 19942-19952.
[34]	J. Liu, Q. Jia, J. Long, X. Wang, Z. Gao, Q. Gu, Appl. Catal. B, 2018, 222, 35-43.
[35]	G. Zhou, L. Zhang, Y. Xia, W. Yin, X. Zhu, J. Hou, S. Wang, X. Ning, X. Wang, J. Cleaner Prod., 2024, 434, 139950.
[36]	X. Han, T. Si, Q. Liu, F. Zhu, R. Li, X. Chen, J. Liu, H. Sun, J. Zhao, H. Ling, Q. Zhang, H. Wang, Chem. Eng. J., 2021, 426, 130824.
[37]	S. Liang, Y. Xia, S. Zhu, S. Zheng, Y. He, J. Bi, M. Liu, L. Wu, Appl. Surf. Sci., 2015, 358, 304-312.
[38]	B. Lv, X. Feng, X. Xi, X. Feng, Z. Yuan, Y. Yang, F. Zhang, J. Colloid Interface Sci., 2021, 601, 177-185.
[39]	H. Shi, B. Yan, H. Li, D. Liu, G. Yang, J. Colloid Interface Sci., 2024, 672, 126-132.
[40]	F. Li, H. Wu, S. Lv, Y. Ma, B. Wang, Y. Ren, C. Wang, Y. Shi, H. Ji, J. Gu, S. Tang, X. Meng, Small, 2024, 20, 2309025.
[41]	H. Wu, Z. Li, Z. Wang, Y. Ma, S. Huang, F. Ding, F. Li, Q. Zhai, Y. Ren, X. Zheng, Y. Yang, S. Tang, Y. Deng, X. Meng, Appl. Catal. B, 2023, 325, 122356.
[42]	L. Wu, X. Shen, Z. Ji, J. Yuan, S. Yang, G. Zhu, L. Chen, L. Kong, H. Zhou, Adv. Funct. Mater., 2023, 33, 2208170.
[43]	C.-L. Huang, Z.-F. He, J.-Y. Pai, Y.-H. Yang, W.-Y. Jao, C.-Y. Lai, Y.-T. Lu, H.-Y. Ku, C.-C. Hu, Chem. Eng. J., 2023, 469, 143855.
[44]	H. Wu, F. Li, S. Huang, Z. Wang, Y. Ma, H. Bian, C. Wang, Q. Zhou, S. Jia, G. Xue, Z. Hu, J. Gu, S. Tang, X. Meng, J. Colloid Interface Sci., 2025, 680, 472-483.
[45]	Y. Shang, T. Liu, G. Chen, Y. Wang, Int. J. Hydrogen Energy, 2023, 48, 36377-36388.
[46]	F. Li, R. Zhao, B. Yang, W. Wang, Y. Liu, J. Gao, Y. Gong, Int. J. Hydrogen Energy, 2019, 44, 30185-30195.
[47]	Y. Xiong, T. Liu, W. Liu, X. Wang, Y. Xue, J. Tian, Int. J. Hydrogen Energy, 2023, 48, 7284-7293.
[48]	T. X. Nguyen, Y.-H. Su, C.-C. Lin, J.-M. Ting, Adv. Funct. Mater., 2021, 31, 2106229.
[49]	F. Hasanvandian, D. Fayazi, B. Kakavandi, S. Giannakis, M. Sharghi, N. Han, A. Bahadoran, Chem. Eng. J., 2024, 496, 153771.
[50]	P. Qiu, Y. An, X. Wang, S. An, X. Zhang, J. Tian, W. Zhu, Chin. Chem. Lett., 2023, 34, 108246.
[51]	P. Qiu, R. Hu, X. Wang, Y. Xue, J. Tian, X. Chen, Mater. Chem. Front., 2022, 6, 718-723.
[52]	Z. Tan, L. Sharma, R. Kakkar, T. Meng, Y. Jiang, M. Cao, Inorg. Chem., 2019, 58, 7615-7627.
[53]	W. Zhang, X. Ma, C. Zhong, T. Ma, Y. Deng, W. Hu, X. Han, Front. Chem., 2018, 6, 569.
[54]	H.-Q. Fu, L. Zhang, C.-W. Wang, L.-R. Zheng, P.-F. Liu, H.-G. Yang, ACS Energy Lett., 2018, 3, 2021-2029.
[55]	X. Wang, J. You, J. Ren, Y. Xue, J. Tian, H. Zhang, Appl. Catal. B, 2024, 345, 123722.
[56]	A. Nemati Tamar, T. Hamzehlouyan, M. R. Khani, M. Alihoseini, B. Shokri, Results Eng., 2023, 17, 100997.
[57]	Z. Liang, Y. Xue, X. Wang, Y. Zhou, X. Zhang, H. Cui, G. Cheng, J. Tian, Chem. Eng. J., 2021, 421, 130016.
[58]	D. Liu, J. Yao, S. Chen, J. Zhang, R. Li, T. Peng, Appl. Catal. B, 2022, 318, 121822.
[59]	F. Gao, H. Xiao, J. Yang, X. Luan, D. Fang, L. Yang, J. Zi, Z. Lian, Appl. Catal. B, 2024, 341, 123334.
[60]	L. Mao, B. Zhai, L. Wen, W. Xiao, J. Shi, X. Kang, Y. Liu, C. Cheng, H. Jin, L. Guo, Appl. Catal. B, 2025, 362, 124712.
[61]	G. Liu, P. Niu, C. Sun, S. C. Smith, Z. Chen, G. Q. M. Lu, H.-M. Cheng, J. Am. Chem. Soc., 2010, 132, 11642-11648.
[62]	Z. Yang, J. Ren, J. You, X. Luo, X. Wang, Y. Xue, Y. Qin, J. Tian, H. Zhang, S. Han, J. Colloid Interface Sci., 2025, 680, 124-136.