Boosting H2O2 evolution of CdS via constructing a ternary photocatalyst with earth-abundant halloysite nanotubes and NiS co-catalyst

doi:10.1016/S1872-2067(24)60191-9

Abstract

Abstract:

Hydrogen peroxide (H₂O₂), an environmentally friendly chemical with high value, is extensively used in industrial production and daily life. However, the traditional anthraquinone method for H₂O₂ production is associated with a highly energy-consuming and heavily polluting process. Solor-driven photocatalytic evolution of H₂O₂ is a promising, eco-friendly, and energy-efficient strategy that holds great potential to substitute the traditional approach. Here, a ternary photocatalyst, NiS/CdS/Halloysite nanotubes (NiS/CdS/HNTs) is designed and prepared with an earth-abundant clay mineral HNTs as the support and NiS as a co-catalyst. The pivotal roles of HNTs and NiS in the photocatalytic process are elucidated by experiments and theoretical calculations. HNTs serve as the carrier, which allows CdS to be uniformly dispersed onto its surface as small particles, increasing effective contact with H₂O and O₂ for H₂O₂ formation. Simultaneously, it resulted in the formation of a Schottky junction between NiS and CdS, which not only favors photogenerated charges separating efficiently but also provides a unidirectional path to transfer electrons. Consequently, the optimized NiS/CdS/HNTs composite demonstrates an H₂O₂ evolution rate of 380.5 μmol·g^-1·h^-1 without adding any sacrificial agent or extra O₂, nearly 5.0 times that of pure CdS. This work suggests a feasible idea for designing and developing highly active and low-cost solar energy catalytic composite materials.

Key words: Photocatalytic H₂O₂ evolution, Ternary photocatalyst, NiS/CdS/HNTs, Carrier separation, Schottky junction

Hongfen Li, Yihe Zhang, Jianming Li, Qing Liu, Xiaojun Zhang, Youpeng Zhang, Hongwei Huang. Boosting H₂O₂ evolution of CdS via constructing a ternary photocatalyst with earth-abundant halloysite nanotubes and NiS co-catalyst[J]. Chinese Journal of Catalysis, 2025, 69: 111-122.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60191-9

https://www.cjcatal.com/EN/Y2025/V69/I2/111

Figures/Tables 12

Fig. 1. The schematic morphology and crystal structures of HNTs and pure CdS.

Fig. 2. (a) Diagram showing the fabrication process of NiS/CdS/HNTs-1. (b) The structural schematics, microscopic morphology as well as photographs (insert) of HNTs, CdS/HNTs-1, and NiS/CdS/HNTs-1.

Fig. 3. TEM (a) and HRTEM (b) images of 5% NiS/CdS/HNTs-1. (c?h) EDX-mapping images of O, Al, Si, Cd, S, and Ni elements.

Fig. 4. (a) XRD diagrams of samples. FT-IR spectra (b) and UV-vis DRS spectra (c) of CdS, HNTs, CdS/HNTs-1, and 5% NiS/CdS/HNTs-1. N2 adsorption-desorption isotherms (d), corresponding surface area (e), and pore size distribution curves (f) of CdS, HNTs, CdS/HNTs-1, and 5% NiS/CdS/HNTs-1.

Fig. 5. (a) Total XPS spectrum of 5% NiS/CdS/HNTs-1. (b) XPS spectrum of Ni element for 5% NiS/CdS/HNTs-1. XPS spectra of O (c), Si (d), Cd (e), and S (f) elements in different samples.

Fig. 6. (a?c) Time course of H2O2 yield of different samples measured under visible light irradiation. (d) Comparison of the photocatalytic H2O2 evolution rate of different samples under the same conditions. (e) The H2O2 yield of 5% NiS/CdS/HNTs-1 under different pH value conditions. (f) The H2O2 yield of 5% NiS/CdS/HNTs-1 in 3 cycles.

Fig. 7. (a) The H2O2 yield of 5% NiS/CdS/HNTs-1 under different sacrificial agents and N2. (b,d) RRDE polarization curves over CdS and 5% NiS/CdS/HNTs-1 with ring current as well as disk current. (c) The calculated average e? transfer number (n).

Fig. 8. (a) EIS of CdS, CdS/HNTs-1, 5% NiS/CdS/HNTs-1, and HNTs (insert). (b) PL spectra of HNTs, CdS, CdS/HNTs-1, and 5% NiS/CdS/HNTs-1.

Fig. 9. ESR spectra of HNTs, CdS, CdS/HNTs-1, and 5% NiS/CdS/HNTs-1 for detection of ·O2? (a,d), e? (b,e), and h+ (c,f)under light and dark conditions.

Fig. 10. (a?c) Work functions of pure CdS, NiS, and NiS/CdS. (d) Spatial charge density difference of NiS/CdS. (e) Schematic representation of the charge transfer process of Schottky junction developed by CdS and NiS.

Fig. 11. O2 adsorption on CdS, NiS, and NiS/CdS and their theoretical calculated adsorption energies.

Fig. 12. Schematic diagram for the mechanism of the 5% NiS/CdS/HNTs-1 with efficient photocatalytic H2O2 evolution performance.

References

[1]	L. X. Wang, J. J. Zhang, Y. Zhang, H. G. Yu, Y. H. Qu, J. G. Yu, Small, 2021, 18, 2104561.
[2]	Y. Zhang, J. Y. Qiu, B. C. Zhu, M.V. Fedin, B. Cheng, J. G. Yu, L. Y. Zhang, Chem. Eng. J., 2022, 444, 126584.
[3]	Y. N. Zhang, C. S. Pan, G. M. Bian, J. Xu, Y. M. Dong, Y. Zhang, Y. Lou, W. X. Liu, Y. F. Zhu, Nat. Energy, 2023, 8, 361-371.
[4]	X. H. Xu, Y. Sui, W. T. Chen, W. Huang, X. D. Li, Y. T. Li, D. S. Liu, S. Gao, W. X. Wu, C. W. Pan, H. Zhong, H.-R. Wen, M. C. Wen, Appl. Catal. B, 2024, 341, 123271.
[5]	C. S. Pan, G. M. Bian, Y. N. Zhang, Y. Lou, Y. Zhang, Y. M. Dong, J. Xu, Y. F. Zhu, Appl. Catal. B, 2022, 316, 121675.
[6]	Y. Zhao, X. K. Li, X. Fan, H. S. Wang, Y. L. Liu, Y. Y. Chen, T. Y. Yang, J. Ye, H. Huang, H. T. Li, X. H. Zhang, Y. Liu, H. P. Lin, Y. Zhao, Z. H. Kang, Appl. Catal. B, 2022, 314, 121499.
[7]	J. Y. Yue, L. P. Song, Y. F. Fan, Z. X. Pan, P. Yang, Y. Ma, Q. Xu, B. Tang, Angew. Chem. Int. Ed., 2023, 62, e202309624.
[8]	X. Zhang, P. J. Ma, C. Wang, L. Y. Gan, X. J. Chen, P. Zhang, Y. Wang, H. Li, L. H. Wang, X. Y. Zhou, K. Zheng, Energy Environ. Sci., 2022, 15, 830-842.
[9]	Z. Chen, D. C. Yao, C. C. Chu, S. Mao, Chem. Eng. J., 2023, 451, 138489.
[10]	W. Miao, D. C. Yao, C. C. Chu, Y. Liu, Q. S. Huang, S. Mao, K. Ostrikov, Appl. Catal. B, 2023, 332, 122770.
[11]	H. N. Che, X. Gao, J. Chen, Y. H. Ao, P. F. Wang, Angew. Chem. Int. Ed., 2021, 60, 25546-25550
[12]	F. Chen, Y. H. Zhang, H. W. Huang, Chin. Chem. Lett., 2023, 34, 107523.
[13]	X. Y. Liu, M. Sayed, C. B. Bie, B. Cheng, B. W. Hu, J. G. Yu, L. Y. Zhang, J. Materiomics, 2021, 7, 419-439.
[14]	J. J. Wang, C. Hu, Y. H. Zhang, H. W. Huang, Chin. J. Catal., 2022, 43, 1277-1285.
[15]	R.-B. Wei, Z.-L. Huang, G.-H. Gu, Z. Wang, L. X. Zeng, Y. B. Chen, Z.-Q. Liu, Appl. Catal. B, 2018, 231, 101-107.
[16]	Y. G. Zhang, H. W. Huang, L. C. Wang, X. L. Zhang, Z. J. Zhu, J. J. Wang, W. Y. Yu, Y. H. Zhang, Chem. Eng. J., 2023, 454, 140420.
[17]	C. H. Li, H. M. Wang, S. B. Naghadeh, J. Z. Zhang, P. F. Fang, Appl. Catal. B, 2018, 227, 229-239.
[18]	J. H. Lee, H. Cho, S. O. Park, J. M. Hwang, Y. Hong, P. Sharma, W. C. Jeon, Y. Cho, C. Yang, S. K. Kwak, H. R. Moon, J.-W. Jang, Appl. Catal. B, 2021, 284, 119690.
[19]	P. Raizada, V. Soni, A. Kumar, P. Singh, A. A. Parwaz Khan, A. M. Asiri, V. K. Thakur, V.-H. Nguyen, J. Materiomics, 2021, 7, 388-418.
[20]	W. N. Xing, L. Ni, P. W. Huo, Z. Y. Lu, X. L. Liu, Y. Y. Luo, Y. S. Yan, Appl. Surf. Sci., 2012, 259, 698-704.
[21]	H. Zhang, L. Wang, Z. L. Liu, Y. G. Su, C. F. Du, J. Colloid Interface Sci., 2023, 650, 1211-1224.
[22]	D. Papoulis, Appl. Clay Sci., 2019, 168, 164-174.
[23]	M. Massaro, C. G. Colletti, G. Lazzara, S. Milioto, R. Noto, S. Riela, J. Mater. Chem. A, 2017, 5, 13276-13293.
[24]	M. Hojamberdiev, M. M. Khan, Z. Kadirova, K. Kawashima, K. Yubuta, K. Teshima, R. Riedel, M. Hasegawa, Renewable Energy, 2019, 138, 434-444.
[25]	E. H. Zhang, Q. H. Zhu, J. H. Huang, J. Liu, G. Q. Tan, C. J. Sun, T. Li, S. Liu, Y. M. Li, H. Z. Wang, X. D. Wan, Z. H. Wen, F. T. Fan, J. T. Zhang, K. Ariga, Appl. Catal. B, 2021, 293, 120213.
[26]	W. L. Fang, L. Wang, X. C. Meng, C. H. Li, J. Alloys Compd., 2023, 947, 169606.
[27]	K. L. Li, H. Pan, F. Wang, Z. G. Zhang, S. X. Min, Appl. Catal. B, 2023, 321, 122028.
[28]	B. C. Zhu, J. J. Liu, J. Sun, F. Xie, H. Y. Tan, B. Cheng, J. J. Zhang, J. Mater. Sci. Technol., 2023, 162, 90-98.
[29]	Q. Zhang, T. F. Wu, H. N. Che, C. M. Tang, B. Liu, Y. H. Ao, Surf. Interfaces, 2024, 47, 104205.
[30]	X. L. Zhang, F. Wu, G. C. Li, L. Wang, J. F. Huang, A. Meng, Z. J. Li, Appl. Catal. B, 2024, 342, 123398.
[31]	W. Zhong, X. H. Wu, Y. P. Liu, X. F. Wang, J. J. Fan, H. G. Yu, Appl. Catal. B, 2021, 280, 119455.
[32]	Y. R. Wang, J. J. Zhao, W. Q. Hou, Y. M. Xu, Appl. Catal. B, 2022, 310, 121350.
[33]	Y. Z. Zhang, W. Zhou, Y. Tang, Y. C. Guo, Z. K. Geng, L. Q. Liu, X. Tan, H. Y. Wang, T. Yu, J. H. Ye, Appl. Catal. B, 2022, 305, 121055.
[34]	D. D. Gao, J. C. Xu, L. X. Wang, B. C. Zhu, H. G. Yu, J. G. Yu, Adv. Mater., 2021, 34, 2108475.
[35]	M. C. Liu, Y. B. Chen, J. Z. Su, J. W. Shi, X. X. Wang, L. J. Guo, Nat. Energy, 2016, 1, 16151.
[36]	Y. Zhang, Z. J. Peng, S. D. Guan, X. L. Fu, Appl. Catal. B, 2018, 224, 1000-1008.
[37]	Z. M. Qin, C. M. Yang, W. J. Shuai, J. Jin, X. Tang, F. Chen, T. R. Shi, Y. Ye, Y. R. Liang, Y. H. Wang, Sep. Purif. Technol., 2023, 307, 122816.
[38]	G. Mishra, M. Mukhopadhyay, Sci. Rep., 2019, 9, 4345.
[39]	X. Cao, H. Z. Liu, X. H. Yang, J. H. Tian, B. H. Luo, M. X. Liu, Compos. Sci. Technol., 2020, 191, 108071.
[40]	H. X. Yu, Y. T. Zhang, X. B. Sun, J. D. Liu, H. Q. Zhang, Chem. Eng. J., 2014, 237, 322-328.
[41]	S. Kandula, P. Jeevanandam, J. Alloys Compd, 2014, 615, 167-176.
[42]	S. Chawla, K. Jayanthi, H. Chander, D. Haranath, S. K. Halder, M. Kar, J. Alloys Compd., 2008, 459, 457-460.
[43]	J. J. Luo, M. Wang, L. S. Chen, J. L. Shi, J. Energy Chem., 2022, 66, 52-60.
[44]	W. Y. Tan, Y. L. Li, W. S. Jiang, C. L. Gao, C. Q. Zhuang, ACS Appl. Energy Mater., 2020, 3, 8048-8054.
[45]	B. W. He, C. B. Bie, X. G. Fei, B. Cheng, J. G. Yu, W. K. Ho, A. A. Al-Ghamdi, S. Wageh, Appl. Catal. B, 2021, 288, 119994.
[46]	X. Gao, L. An, D. Qu, W. S. Jiang, Y. X. Chai, S. R. Sun, X. Y. Liu, Z. C. Sun, Sci. Bull., 2019, 64, 918-925.

Boosting H₂O₂ evolution of CdS via constructing a ternary photocatalyst with earth-abundant halloysite nanotubes and NiS co-catalyst

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 12

References

Related Articles 11

Recommended Articles

Metrics

[1]	Lu Zhang, Hourui Zhang, Dongyang Zhu, Zihan Fu, Shuangshi Dong, Cong Lyu. Construction of multivariate donor-acceptor heterojunction in covalent organic frameworks for enhanced photocatalytic oxidation: Regulating electron transfer and superoxide radical generation [J]. Chinese Journal of Catalysis, 2024, 66(11): 181-194.
[2]	Lijuan Sun, Weikang Wang, Ping Lu, Qinqin Liu, Lele Wang, Hua Tang. Enhanced photocatalytic hydrogen production and simultaneous benzyl alcohol oxidation by modulating the Schottky barrier with nano high-entropy alloys [J]. Chinese Journal of Catalysis, 2023, 51(8): 90-100.
[3]	Xiu-Qing Qiao, Chen Li, Zizhao Wang, Dongfang Hou, Dong-Sheng Li. TiO_2-_x@C/MoO₂Schottky junction: Rational design and efficient charge separation for promoted photocatalytic performance [J]. Chinese Journal of Catalysis, 2023, 51(8): 66-79.
[4]	Meiyu Zhang, Kongming Li, Chunlian Hu, Kangwei Ma, Wanjun Sun, Xianqiang Huang, Yong Ding. Co nanoparticles modified phase junction CdS for photoredox synthesis of hydrobenzoin and hydrogen evolution [J]. Chinese Journal of Catalysis, 2023, 47(4): 254-264.
[5]	Aixia Wang, Linhe Zhang, Xuli Li, Yangqin Gao, Ning Li, Guiwu Lu, Lei Ge. Synthesis of ternary Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S composite materials with significantly improved photocatalytic H₂ production performance [J]. Chinese Journal of Catalysis, 2022, 43(5): 1295-1305.
[6]	Li Wang, Yukun Li, Chao Wu, Xin Li, Guosheng Shao, Peng Zhang. Tracking charge transfer pathways in SrTiO₃/CoP/Mo₂C nanofibers for enhanced photocatalytic solar fuel production [J]. Chinese Journal of Catalysis, 2022, 43(2): 507-518.
[7]	Zhiming Zhou, Chuanbiao Bie, Peize Li, Bien Tan, Yan Shen. A thioether-functionalized pyrene-based covalent organic framework anchoring ultrafine Au nanoparticles for efficient photocatalytic hydrogen generation [J]. Chinese Journal of Catalysis, 2022, 43(10): 2699-2707.
[8]	Ying Liu, Donglai Pan, Mingwen Xiong, Ying Tao, Xiaofeng Chen, Dieqing Zhang, Yu Huang, Guisheng Li. In-situ fabrication SnO₂/SnS₂ heterostructure for boosting the photocatalytic degradation of pollutants [J]. Chinese Journal of Catalysis, 2020, 41(10): 1554-1563.
[9]	Huishan Zhai, Xiaolei Liu, Zeyan Wang, Yuanyuan Liu, Zhaoke Zheng, Xiaoyan Qin, Xiaoyang Zhang, Peng Wang, Baibiao Huang. ZnO nanorod decorated by Au-Ag alloy with greatly increased activity for photocatalytic ethylene oxidation [J]. Chinese Journal of Catalysis, 2020, 41(10): 1613-1621.
[10]	Yanrui Li, Yu Guo, Ran Long, Dong Liu, Daming Zhao, Yubo Tan, Chao Gao, Shaohua Shen, Yujie Xiong. Steering plasmonic hot electrons to realize enhanced full-spectrum photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2018, 39(3): 453-462.
[11]	LU Ying, CHEN Shuo, QUAN Xie, YU Hong-Tao. Fabrication of a TiO₂/Au Nanorod Array for Enhanced Photocatalysis [J]. Chinese Journal of Catalysis, 2011, 32(12): 1838-1843.