Tailoring the d-band center of CoSe2 cocatalyst via Ni-doping-induced p-d hybridization perturbation for enhanced photocatalytic H2 production

doi:10.1016/S1872-2067(26)65236-9

Abstract

Abstract:

Loading cocatalysts plays a crucial role in enhancing the photocatalytic H₂ evolution performance of semiconductors. However, due to the undesirable electronic configuration of active sites, the H₂ evolution activity of intrinsic cocatalysts remains significantly limited. Herein, we propose a novel strategy for modulating the d-band center (ε_d) of transition metal active sites by transition metal heteroatom doping. The introduced heteroatoms perturb the nonmetal p-band configuration in the cocatalyst and optimize the orbital hybridization between the nonmetal p-band and the d-band of active sites. Such regulation enables precise modulation of the ε_d of active sites and the H* adsorption-desorption equilibrium, thereby ultimately boosting the photocatalytic H₂ evolution performance. This tactic is demonstrated by the Ni-doped CoSe₂ (NCS) cocatalyst and Bi₄Ti₃O₁₂ (BTO) semiconductor. Specifically, the introduction of Ni with higher electronegativity effectively promotes the rearrangement of outer-shell electrons of Co active sites, leading to an upward shift of its ε_d and thereby enhancing the H* adsorption capacity. Accordingly, the sample of BTO loaded with NCS delivers excellent photocatalytic H₂-evolution activity, which is approximately 20.1 and 1.8 times higher than that of pristine BTO and CoSe₂/BTO samples, respectively. This work provides a new insight into the rational design of high-efficiency H₂ evolution cocatalysts.

Key words: Photocatalytic H₂ evolution, d-band center, d-p hybridization perturbation, Heteroatom doping, Cocatalyst

Shiwen Du, Quanmei Li, Na Lu, Wei Lu, Jindou Huang, Zhenyi Zhang. Tailoring the d-band center of CoSe₂ cocatalyst via Ni-doping-induced p-d hybridization perturbation for enhanced photocatalytic H₂ production[J]. Chinese Journal of Catalysis, 2027, 92: 262-273.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65236-9

https://www.cjcatal.com/EN/Y2027/V92/I1/262

Figures/Tables 6

Scheme 1. Schematic diagram of the heteroatom doping to optimize the d-band center of active site in cocatalyst by regulating d-p orbital hybridization.

Fig. 1. (a) DOS of bulk CoSe2 and NiSe2. (b) Partial DOS of Co atom in pure CS (111) and NCS (111) slabs. (c) Charge density difference (the yellow color and green color represented the charge accumulation and depletion, respectively) and planar-averaged charge density difference of H absorbed on pure CS and NCS (111) surface and the corresponding Bader charges of H atom. The calculated pCOHP data (d) and chemisorption energy and free energy (e) of H atom absorbed on different catalysts. (f) The schematic illustrating the d-band of Co site in CS and NCS and their optimized antibonding orbital occupancy of Co-Hads. (g) Work functions of different sample slabs. (h) Schematic diagram of photogenerated electron transfer in NCS/BTO heterojunction.

Fig. 2. XRD patterns (a), high-resolution XPS spectra of Co 2p (b) and Ni 2p (c) of different samples. SEM image (d) and HAADF STEM and corresponding EDS elemental mapping images (e) of NCS/BTO sample.

Fig. 3. Photocatalytic H2 evolution amount (a) and H2 evolution rate over different samples (b). Photographs for the viewable H2 bubbles (c) and cycling stability of the photocatalytic H2 evolution activity (d) of the optimized NCS/BTO.

Fig. 4. (a) UPS spectra of pure CoSe2 and Ni-doped CoSe2 samples. H2-TPD spectra (b), LSV polarization (c) and transient photocurrent-time (I-t) curves (d) of the obtained samples. KPFM surface potential profiles of CS/BTO (e) and NCS/BTO samples (f).

Fig. 5. Pseudocolor TA spectra (pump wavelength: 343 nm) (a,d,g), TA kinetic curves (monitored at 625 nm) (b,e,h) and corresponding schematic illustration (c,f,i) of photogenerated-electron relaxation paths of BTO (a,b,c), CS/BTO (d,e,f) and NCS/BTO (g,h,i).

References

[1]	A. J. Esswein, D. G. Nocera, Chem. Rev., 2007, 107, 4022-4047.
[2]	C. Bie, J. Yu, EcoEnergy, 2026, 4, e70040.
[3]	M. Z. Rahman, M. G. Kibria, C. B. Mullins, Chem. Soc. Rev., 2020, 49, 1887-1931.
[4]	W. Yu, M. H. Richter, P. Buabthong, I. A. Moreno-Hernandez, C. G. Read, E. Simonoff, B. S. Brunschwig, N. S. Lewis, Energy Environ. Sci., 2021, 14, 6007-6020.
[5]	X. Wu, M. Sayed, G. Wang, W. Yu, B. Zhu, Adv. Mater., 2026, 38, e11322.
[6]	L. Zhang, J. Zhang, J. Yu, Chem, 2026, 12, 102719.
[7]	B. Zhu, J. Xu, Chin. J. Struct. Chem., 2024, 43, 100327.
[8]	F. Fan, H. Xiu, Y. Wang, Y. Cui, Y. Wang, Acta Phys. Chim. Sin., 2026, 42, 100143.
[9]	C. Pornrungroj, A. Bin Mohamad Annuar, Q. Wang, M. Rahaman, S. Bhattacharjee, V. Andrei, E. Reisner, Nat. Water, 2023, 1, 952-960.
[10]	J. Hu, M. Zhu, Z. Ali Ghazi, Y. Cao, Chin. J. Catal., 2025, 71, 319-329.
[11]	B. Xia, G. Liu, K. Fan, R. Chen, X. Liu, L. Li, Chin. J. Catal., 2025, 69, 315-326.
[12]	Y. Zhang, L. Wang, Chin. J. Catal., 2025, 71, 1-4.
[13]	R. Liu, P. Wang, X. Wang, F. Chen, H. Yu, Acta Phys. Chim. Sin., 2025, 41, 100137.
[14]	M. Cabrero-Antonino, A. Uscategui-Linares, R. Ramírez-Grau, P. García-Aznar, G. Sastre, J. Zhang, S. Goberna-Ferrón, J. Albero, J. Yu, H. García, F. Xu, A. Primo, Angew. Chem. Int. Ed., 2025, 64, e202503860.
[15]	S. Zhang, C. Bie, Rare Met., 2025, 44, 9289-9292.
[16]	D. Gao, H. Yu, H. García, J. Yu, Prog. Mater. Sci., 2026, 159, 101663.
[17]	X. Xiang, B. Cheng, B. Zhu, C. Jiang, G. Liang, Chin. J. Catal., 2025, 68, 326-335.
[18]	W. Li, Z. Ni, O. Akdim, T. Liu, B. Zhu, P. Kuang, J. Yu, Adv. Mater., 2025, 37, 2503742.
[19]	S. M. Wu, M. Antonietti, X. Y. Yang, Natl. Sci. Rev., 2023, 10, nwad188.
[20]	S. Lai, J. Su, S. Jiang, J. Zhang, S. Song, Chin. J. Catal., 2024, 65, 185-194.
[21]	C. Bie, C. Jiang, J. Yang, X. Sun, X. Zeng, J. Zhang, B. Zhu, J. Mater. Sci. Technol., 2025, 229, 48-57.
[22]	H. Long, X. Zhang, Z. Zhang, J. Zhang, J. Yu, H. Yu, Nat. Commun., 2025, 16, 946.
[23]	H. Long, R. Li, C. Bie, J. Zhang, J. Yu, H. García, H. Yu, J. Am. Chem. Soc., 2026, 148, 17146-17156.
[24]	B. Hammer, J. K. Norskov, Nature, 1995, 376, 238-240.
[25]	W. Chen, G. Qian, H. Wang, D. Chen, X. Zhou, W. Yuan, X. Duan, J. Am. Chem. Soc., 2025, 147, 46729-46744.
[26]	S. Jiao, X. Fu, H. Huang, Adv. Funct. Mater., 2022, 32, 2107651.
[27]	B. Ghosh, C. Zhang, S. Frick, E. J. Cho, T. Woods, Y. Yang, N. H. Perry, A. Klein, H. Yang, J. Am. Chem. Soc., 2024, 146, 18524-18534.
[28]	S. Zhao, C. Wang, W. Che, C. Li, Y. Chen, L. Cai, Z. Li, A. Chen, Z. Zhu, J.-B. Baek, Nano Energy, 2026, 151, 111844.
[29]	Z. Wang, C. Bie, J. Mater. Sci. Technol., 2026, 243, 206-208.
[30]	Y. Wang, S. Jiang, C. Sun, S. Song, J. Mater. Sci. Technol., 2024, 190, 210-217.
[31]	J. Liu, A. Wei, H. Zhang, S. Duo, Acta Phys.-Chim. Sin., 2025, 41, 100185.
[32]	Y. Miao, Y. Zhao, S. Zhang, R. Shi, T. Zhang, Adv. Mater., 2022, 34, 2200868.
[33]	Y. Qin, Z. Ou, C. Guo, Y. Liu, R. Jin, C. Xu, H. Chen, Y. Si, H. Li, Appl. Catal. B, 2025, 360, 124553.
[34]	X.-W. Lv, J. Gong, S. Wang, X. Yan, C. Sun, X. Hu, Z. Lai, Y. Liu, H. Wang, Z.-Y. Yuan, J. Geng, Adv. Energy Mater., 2025, 15, 2501129.
[35]	W. Tu, K. Mao, Y. Huang, J. Shao, X. Tian, P. Xu, S. Yang, F. Wang, Y. Gao, P. Zhang, X. Lu, Angew. Chem. Int. Ed., 2025, 64, e202513523.
[36]	J. Zhu, X. Li, Chin. J. Catal., 2025, 72, 1-3.
[37]	J. Zhao, Y. Zhang, Z. Zhuang, Y. Deng, G. Gao, J. Li, A. Meng, G. Li, L. Wang, Z. Li, D. Wang, Angew. Chem. Int. Ed., 2024, 63, e202404968.
[38]	Z. Wang, J. Huang, L. Wang, Y. Liu, W. Liu, S. Zhao, Z.-Q. Liu, Angew. Chem. Int. Ed., 2022, 61, e202114696.
[39]	Z. Wang, Z. Lin, J. Deng, S. Shen, F. Meng, J. Zhang, Q. Zhang, W. Zhong, L. Gu, Adv. Energy Mater., 2021, 11, 2003023.
[40]	C. Liu, Y. Hu, F. Liu, H. Liu, X. Xu, Y. Xue, J. Zhang, Y. Li, C. Tang, Int. J. Hydrogen Energy, 2021, 46, 17133-17142.
[41]	Z. Liu, D. Gao, L. Hu, H. Liu, Y. Li, Y. Xue, F. Liu, J. Zhang, C. Tang, Colloids Surf. A, 2022, 646, 128903.
[42]	J. Li, X. Zhang, J. Li, X. Zheng, M. Li, J. Zhou, E. Song, Y. Zhou, Adv. Mater., 2026, 38, e10760.
[43]	N. Li, Y. Qiu, L. Li, J. Zhang, Y. Gao, L. Ge, Small, 2025, 21, 2408057.
[44]	Y. Deng, Y. Chen, L. Zhang, H. Jin, Y. Yang, Q. Xu, S. Wang, Acta Phys.-Chim. Sin., 2026, 42, 100193.
[45]	C. Yuan, W. Xia, J. Wang, X. Zhu, Y. Zhang, B. Zhu, J. Yu, Acta Phys.-Chim. Sin., 2026, 42, 100244.
[46]	Z. Chen, H. Jiang, W. Jin, C. Shi, Appl. Catal. B, 2016, 180, 698-706.
[47]	H. Zhang, P. Xiao, C. Hu, D. Tao, D. Zhang, Y. Cao, T. Li, F. Xu, Adv. Funct. Mater., 2025, 35, 2426006.
[48]	G. Li, Z. Chen, Y. Wang, H. Su, L. Chen, J. Chen, J. Xiao, R. Wang, S. Zhang, Q. Zhong, J. Li, Angew. Chem. Int. Ed., 2026, 65, e4308936.
[49]	X. Cheng, S. Wan, D. Guo, W. Wang, B. Cheng, J. Xu, G. Luo, S. Cao, Appl. Catal. B, 2026, 390, 126636.
[50]	J. Jiang, J. Sun, Y. Chen, L. Zhang, P. Dong, Acta Phys.-Chim. Sin., 2025, 41, 100145.
[51]	M. M. Kržmanc, N. Daneu, K. M. Kamal, B. Likozar, A. Čontala, M. Spreitzer, J. C. S. Wu, S. Gupta, Chem. Eng. J., 2026, 527, 171758.
[52]	J. Lei, J. Wang, W. Zhang, G. Wang, Z. Liang, J. Li, Acta Phys. Chim. Sin., 2025, 41, 100174.
[53]	C. Ge, J. Hu, X. Liu, Y. Song, C. Liu, Z. Zou, Acta Phys.-Chim. Sin., 2026, 42, 100154.
[54]	D. Kim, S. Jo, J. I. Jeon, J. I. Sohn, J. Hong, Energy Environ. Mater., 2026, 9, e70136.
[55]	H. Ma, W. Li, B. Liu, H. Hu, Y. Li, W. Xu, R. Fang, F. Dong, Chem. Eng. J., 2025, 505, 159421.
[56]	F. Xu, L. Zheng, J. Zhang, Y. He, H. Cao, X. Zheng, H. García, J. Yu, Nat. Catal., 2026, 9, 363.
[57]	C. Chen, H. Shi, X. Cai, L. Mao, Z. Chen, Acta Phys.-Chim. Sin., 2025, 41, 100155.
[58]	S. Wei, J. Liu, F. Lv, T. Wang, H. Jiang, J. Zhu, Y. Zhao, Y. Zheng, Nano Res., 2025, 18, 94908022.
[59]	T. Erdil, C. Ozgur, U. Geyikci, E. Lokcu, C. Toparli, ACS Appl. Energy Mater., 2024, 7, 7775-7786.
[60]	D. Gao, X. Zhang, P. Wang, J. Yu, H. Yu, Adv. Funct. Mater., 2025, 35, 2424527.
[61]	K. Wongyai, S. Kaewmorakot, Y. Injongkol, M. Siaj, S. Poorahong, ACS Appl. Nano Mater., 2025, 8, 20363-20373.
[62]	J. Tian, C. Guan, H. Hu, E. Liu, D. Yang, Acta Phys.-Chim. Sin., 2025, 41, 100068.
[63]	A. Kareem, K. Thenmozhi, S. Ramasamy, E. Jose, A. K. Kunhiraman, S. Pitchaimuthu, S. Senthilkumar, ACS Appl. Energy Mater., 2024, 7, 6278-6288.
[64]	H. Shan, J. Qin, J. Wang, H. M. K. Sari, L. Lei, W. Xiao, W. Li, C. Xie, H. Yang, Y. Luo, G. Zhang, X. Li, Adv. Sci., 2022, 9, 2200341.
[65]	H. Yang, C. Li, L. Lü, Z. Li, S. Zhang, Z. Huang, R. Ma, S. Liu, M. Ge, W. Zhou, X. Yuan, J. Colloid Interface Sci., 2025, 678, 300-308.
[66]	Y. Yao, X. Wei, H. Zhou, K. Wei, B. Kui, F. Wu, L. Chen, W. Wang, F. Dai, P. Gao, N. Wang, W. Ye, ACS Catal., 2024, 14, 16205-16213.
[67]	Q. Huang, W. Yang, Y. Yan, S. Xie, A. Yu, T. Xu, Y. Zhao, P. Peng, F.-F. Li, Adv. Funct. Mater., 2024, 34, 2409406.
[68]	G. Jia, F. Sun, T. Zhou, Y. Wang, X. Cui, Z. Guo, F. Fan, J. C. Yu, Nat. Commun., 2024, 15, 4746.
[69]	S. Du, S. Lin, K. Ren, C. Li, F. Zhang, Appl. Catal. B, 2023, 328, 122503.
[70]	Y. Hao, H. Yang, Y. Lin, Q. Guo, X. Hao, Z. Jin, Appl. Catal. B, 2026, 382, 125934.
[71]	E.-J. Shin, A. Spiller, G. Tavoularis, M. A. Keane, Phys. Chem. Chem. Phys., 1999, 1, 3173-3181.
[72]	W. C. Conner Jr, J. L. Falconer, Chem. Rev., 1995, 95, 759-788.
[73]	J. Tian, C. Guan, Q. Zhang, T. Sun, H. Hu, E. Liu, J. Mater. Sci. Technol., 2025, 231, 308-321.
[74]	W. Zhong, A. Meng, Y. Su, H. Yu, P. Han, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202425038.
[75]	J. Cai, C. Cheng, B. Liu, J. Zhang, C. Jiang, B. Cheng, Acta Phys.-Chim. Sin., 2025, 41, 100084.
[76]	J. Yang, X. Hao, J. Jing, Y. Hao, Z. Jin, Acta Phys.-Chim. Sin., 2025, 41, 100131.
[77]	X. Hao, W. Deng, Y. He, Z. Jin, Appl. Catal. B, 2025, 363, 124836.
[78]	M. Wei, X. Zhou, C. Cheng, J. Zhang, C. Jiang, B. Cheng, J. Mater. Sci. Technol., 2025, 232, 302-312.
[79]	B. Liu, K. Meng, B. Cheng, L. Wang, G. Liang, C. Bie, J. Mater. Sci. Technol., 2025, 231, 286-295.
[80]	D. Gao, J. Zhang, H. Yu, C. Jiang, H. García, J. Yu, Angew. Chem. Int. Ed., 2026, 65, e2317803.
[81]	X. Yin, D. Gao, J. Zhang, H. García, J. Yu, H. Yu, J. Am. Chem. Soc., 2025, 147, 34881-34890.
[82]	M. Wei, C. Cheng, B. He, B. Cheng, K. Qi, C. Bie, Acta Phys.-Chim. Sin., 2025, 41, 100158.
[83]	Q. Yao, H. Li, J. Xue, S. Jiang, Q. Zhang, J. Bao, Angew. Chem. Int. Ed., 2023, 62, e202308140.
[84]	B. Yang, H. Li, H. Mi, G. Zhang, Small, 2025, 21, e08481.
[85]	Y. Zhang, J. Pan, X. Ni, F. Mo, Y. Xu, P. Dong, Chin. J. Catal., 2025, 74, 250-263.

Tailoring the d-band center of CoSe₂ cocatalyst via Ni-doping-induced p-d hybridization perturbation for enhanced photocatalytic H₂ production

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