Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H2O2 production by using femtosecond transient absorption spectroscopy

doi:10.1016/S1872-2067(24)60069-0

Abstract

Abstract:

Abstract: Hydrogen peroxide (H₂O₂) has gained widespread attention as a versatile oxidant and a mild disinfectant. Here, an electrostatic self-assembly method is applied to couple ZnSe quantum dots (QDs) with a flower-like covalent organic framework (COF) to form a step-scheme (S-scheme) photocatalyst for H₂O₂ production. The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF. The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies. Photoluminescence, time-resolved photoluminescence, photocurrent response, electrochemical impedance spectroscopy, and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability, resulting in enhanced photocatalytic performance. Remarkably, a 10%-ZnSe QD/COF has excellent photocatalytic H₂O₂-production activity, and the optimal S-scheme composite with ethanol as the hole scavenger yields a H₂O₂-production rate of 1895 mol g^-1 h^-1. This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H₂O₂ production.

Key words: ZnSe quantum dot, Covalent organic framework, S-scheme heterojunction, Carrier migration and separation, H₂O₂ production

Yanyan Zhao, Chunyan Yang, Shumin Zhang, Guotai Sun, Bicheng Zhu, Linxi Wang, Jianjun Zhang. Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H₂O₂ production by using femtosecond transient absorption spectroscopy[J]. Chinese Journal of Catalysis, 2024, 63: 258-269.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60069-0

https://www.cjcatal.com/EN/Y2024/V63/I8/258

Figures/Tables 11

Fig. 1. (a) Schematic illustrating the preparation process for Z/T composites. TEM image (b) and HRTEM images (c,d) of Z/T-10%. (e) HAADF image of Z/T-10% and the corresponding EDS maps of C, N, O, Se, and Zn.

Fig. 2. (a) XRD patterns of ZnSe QDs, Ta-Dva COF, and Z/T-10%. The blue lines represent the standard diffraction pattern of cubic ZnSe crystals. (b) FTIR spectra of the as-prepared ZnSe QDs, Ta-Dva COF, and Z/T-10%.

Fig. 3. (a) UV-vis DRS spectra of ZnSe QDs, Ta-Dva COF, and Z/T-10%. Tauc plots (b) and Mott-Schottky plots (c) of ZnSe QDs and Ta-Dva COF. (d) Band diagrams of ZnSe QDs and Ta-Dva COF, and standard potentials of O2/?O2- and OH-/?OH.

Fig. 4. O 1s (a) and N 1s (b) spectra of Ta-Dva COF and Z/T-10% (in dark and under 365-nm LED irradiation). Zn 2p (c) and Se 3d (d) spectra of ZnSe QDs and Z/T-10% (in dark and under 365-nm LED irradiation).

Fig. 5. Calculated work functions of Ta-Dva COF (a) and ZnSe QDs (311) (b). (c) Schematic illustration of the S-scheme carrier transfer mechanism in Z/T composites before contact, after contact, and under light illumination.

Fig. 6. PL spectra (a), TRPL spectra (b), transient photocurrent density (c), and Nyquist plots (d) of Ta-Dva COF, ZnSe QDs, and Z/T-10%.

Fig. 7. Pseudocolor TA plots of pristine ZnSe QDs (a), bare Ta-Dva COF (b), and Z/T-10% S-scheme heterojunction (c). fs‐TAS spectra of pristine ZnSe QDs (d), bare Ta-Dva COF (e), and Z/T-10% S-scheme heterojunction (f) recorded at indicated delay times under 325 nm pump pulse with average pump power of ~73 μW.

Fig. 8. Normalized decay kinetics of pristine ZnSe QD probe at 440 nm (a), bare Ta-Dva COF probe at 480 nm (b), and Z/T-10% composite probe at 550 nm (c). (d) Schematic for the decay pathways of photogenerated electrons in Z/T-10% S-scheme heterojunction.

Fig. 9. (a) Photocatalytic production of H2O2 over the as-prepared samples with ethanol as sacrificial agent under 1-h light irradiation. (b) H2O2 yield over Z/T-10% with ethanol as the sacrificial agent under 5-h light irradiation. (c) H2O2 yield over Z/T-10% under different conditions. (d) H2O2 yield over Z/T-10% with Rhodamine B (10 mg L-1) as the sacrificial agent. (e) Photocatalytic decomposition of H2O2 (1 mmol L-1) over different samples in N2-saturated DI water. (f) Formation rate (Kf) and decomposition rate (Kd) over the photocatalyst.

Fig. 10. EPR signals of DMPO-·OH (a) and DMPO-·O2- (b). (c) In-situ DRIFTS spectra of Z/T-10% S-scheme heterojunction under H2O and O2.

Fig. 11. Proposed reaction pathway for H2O2 production over Z/T-10% S-scheme photocatalysts.

References

[1]	K. Bryliakov, Chem. Rev., 2017, 117, 11406-11459.
[2]	Y. Shao, J. Hu, T. Yang, X. Yang, J. Qu, Q. Xu, C. Li, Carbon 2022, 190, 337-347.
[3]	J. Xu, X. Zheng, Z. Feng, Z. Lu, Z. Zhang, W. Huang, Y. Li, D. Vuckovic, Y. Li, S. Dai, G. Chen, K. Wang, H. Wang, J. Chen, W. Mitch, Y. Cui, Nat. Sustain., 2021, 4, 233-241.
[4]	J. Tang, T. Zhao, D. Solanki, X. Miao, W. Zhou, S. Hu, Joule, 2021, 5, 1432-1461.
[5]	C. Yang, S. Wan, B. Zhu, J. Yu, S. Cao, Angew. Chem. Int. Ed., 2022, 61, e202208438.
[6]	M. Gu, Y. Yang, L. Zhang, B. Zhu, G. Liang, J. Yu, Appl. Catal. B, 2023, 324, 122227.
[7]	J. Lee, H. Cho, S. Park, J. Hwang, Y. Hong, P. Sharma, W. Jeon, Y. Cho, C. Yang, S. Kwak, H. Moon, J. Jang, Appl. Catal. B, 2021, 284, 119690.
[8]	R. He, D. Xu, X. Li, J. Mater. Sci. Technol., 2023, 138, 256-258.
[9]	B. Zhu, J. Liu, J. Sun, F. Xie, H. Tan, B. Cheng, J. Zhang, J. Mater. Sci. Technol., 2023, 162, 90-98.
[10]	Z. Jiang, Q. Long, B. Cheng, R. He, L. Wang, J. Mater. Sci. Technol., 2023, 162, 1-10.
[11]	H. Zhang, J. Liu, Y. Zhang, B. Cheng, B. Zhu, L. Wang, J. Mater. Sci. Technol., 2023, 166, 241-249.
[12]	H. Li, B. Zhu, B. Cheng, G. Luo, J. Xu, S. Cao, J. Mater. Sci. Technol., 2023, 161, 192-200.
[13]	S. Li, G. Dong, R. Hailili, L. Yang, Y. Li, F. Wang, Y. Zeng, C. Wang, Appl. Catal. B, 2016, 190, 26-35.
[14]	L. Yang, G. Dong, D.L. Jacobs, Y. Wang, L. Zang, C. Wang, J. Catal., 2017, 352, 274-281.
[15]	J. Zhang, L. Zheng, F. Wang, C. Chen, H. Wu, S.A.K. Leghari, M. Long, Appl. Catal. B, 2020, 269, 118770.
[16]	H. Zhu, S. Yan, Z. Li, Z. Zou, ACS Appl. Mater. Interfaces, 2017, 9, 33887-33895.
[17]	Y. Wang, M. Kim, A.S. Chabungbam, D. Kim, H. Park, Appl. Surf. Sci., 2022, 579, 152170.
[18]	X. Geng, L. Wang, L. Zhang, H. Wang, Y. Peng, Z. Bian, Chem. Eng. J., 2021, 420, 129722.
[19]	Z. Jiang, Y. Zhang, L. Zhang, B. Cheng, L. Wang, Chin. J. Catal., 2022, 43, 226-233.
[20]	H. Chen, S. Gao, G. Huang, Q. Chen, Y. Gao, J. Bi, Appl. Catal. B, 2024, 343, 123545.
[21]	S. Zhou, Y. Shi, G. Chen, W. Kong, H. Hu, H. Xie, C. Li, J. Qin, Z. Zhang, L. Peng, X. Ke, Y. Kong, Chem. Eng. J., 2023, 477, 146946.
[22]	Y. Zhao, X. Fan, H. Zheng, E. Liu, J. Fan, X. Wang, J. Mater. Sci. Technol., 2024, 170, 200-211.
[23]	K. Fuku, R. Takioka, K. Iwamura, M. Todoroki, K. Sayama, N. Ikenaga, Appl. Catal. B, 2020, 272, 119003.
[24]	W. Xue, H. Sun, X. Hu, X. Bai, J. Fan, E. Liu, Chin. J. Catal., 2022, 43, 234-245.
[25]	G. Han, F. Xu, B. Cheng, Y. Li, J. Yu, L. Zhang, Acta Phys. Chim. Sin., 2022, 38, 2112037.
[26]	S. Li, K. Dong, M. Cai, X. Li, X. Chen, Science, 2024, 4, 100208.
[27]	C. Wang, C. You, K. Rong, C. Shen, F. Yang, S. Li, Acta Phys. Chim. Sin., 2024, 40, 2307045.
[28]	B. Zhu, J. Sun, Y. Zhao, L. Zhang, J. Yu, Adv. Mater., 2024, 36, 2310600.
[29]	J. Fu, Q. Xu, J. Low, C. Jiang, J. Yu, Appl. Catal. B, 2019, 243, 556-565.
[30]	F. He, A. Meng, B. Cheng, W. Ho, J. Yu, Chin. J. Catal., 2020, 41, 9-20.
[31]	Z. Zhou, H. Yao, Y. Wu, T. Li, N. Tsubaki, Z. Jin, Acta Phys. Chim. Sin., 2024, 40, 2312010.
[32]	W. Wang, S. Mei, H. Jiang, L. Wang, H. Tang, Q. Liu, Chin. J. Catal., 2023, 55, 137-158.
[33]	A. Kumar, A. Khosla, S. K. Sharma, P. Dhiman, G. Sharma, L. Gnanasekaran, M. Naushad, F. J. Stadler, Fuel, 2023, 333, 126267.
[34]	Z. Wang, B. Cheng, L. Zhang, J. Yu, H. Tan, Sol. RRL, 2022, 6, 2100587.
[35]	Y. Fu, Y. Xu, Y. Mao, M. Tan, Q. He, H. Mao, H. Du, D. Hao, Q. Wang, Sep. Purif. Technol., 2023, 317, 123922.
[36]	Z. Wang, Y. Chen, L. Zhang, B. Cheng, J. Yu, J. Fan, J. Mater. Sci. Technol., 2020, 56, 143-150.
[37]	K. Zhang, Y. Li, S. Yuan, L. Zhang, Q. Wang, Acta Phys. Chim. Sin., 2023, 39, 2212010.
[38]	X. Wu, G. Chen, J. Wang, J. Li, G. Wang, Acta Phys. Chim. Sin., 2023, 39, 2212016.
[39]	T. Sun, C. Li, Y. Bao, J. Fan, E. Liu, Acta Phys. Chim. Sin., 2023, 39, 2212009.
[40]	Y. Wu, Y. Yang, M. Gu, C. Bie, H. Tan, B. Cheng, J. Xu, Chin. J. Catal., 2023, 53, 123-133.
[41]	H. Yan, Y. Liu, Y. Yang, H. Zhang, X. Liu, J. Wei, L. Bai, Y. Wang, F. Zhang, Chem. Eng. J., 2022, 431, 133404.
[42]	D. Shang, D. Li, B. Chen, B. Luo, Y. Huang, W. Shi, ACS Sustain. Chem. Eng., 2021, 9, 14238-14248.
[43]	X. Zhong, Y. Liu, S. Wang, Y. Zhu, B. Hu, Sep. Purif. Technol., 2021, 279, 119627.
[44]	J. Ming, A. Liu, J. Zhao, P. Zhang, H. Huang, H. Lin, Z. Xu, X. Zhang, X. Wang, J. Hofkens, M.B.J. Roeffaers, J. Long, Angew. Chem. Int. Ed., 2019, 58, 18290-18294.
[45]	Y. Yang, J. Liu, M. Gu, B. Cheng, L. Wang, J. Yu, Appl. Catal. B, 2023, 333, 122780.
[46]	Y. Zhang, J. Qiu, B. Zhu, M. V. Fedin, B. Cheng, J. Yu, L. Zhang, Chem. Eng. J., 2022, 444, 136584.
[47]	Y. Zheng, Z. Yang, J. Y. Ying, Adv. Mater., 2007, 19, 1475-1479.
[48]	C. Zhang, Z. Shao, X. Zhang, G. Liu, Y. Zhang, L. Wu, C. Liu, Y. Pan, F. Su, M. Gao, Y. Li, S. Yu, Angew. Chem. Int. Ed., 2023, 62, e202305571.
[49]	Y. Zhao, X. Liang, H. Shi, Y. Wang, Y. Ren, E. Liu, X. Zhang, J. Fan, X. Hu, Chem. Eng. J., 2018, 353, 56-68.
[50]	W. Ma, Q. Zheng, Y. He, G. Li, W. Guo, Z. Lin, L. Zhang, J. Am. Chem. Soc., 2019 141, 18271-18277.
[51]	Q. Sun, B. Aguila, J. Perman, L. D. Earl, C. W. Abney, Y. Cheng, H. Wei, N. Nguyen, L. Wojtas, S. Ma, J. Am. Chem. Soc., 2017, 139, 2786-2793.
[52]	W. Ma, G. Li, C. Zhong, Y. Yang, Q. Sun, D. Ouyang, W. Tong, W. Tian, L. Zhang, Z. Lin, Chem. Commun., 2021, 57, 7362-7365.
[53]	Y. Yao, J. Cao, W. Yin, L. Yang, X. Wei, J. Phys. D, 2020, 53, 055108.
[54]	J. Zhang, P. Tian, T. Tang, G. Huang, J. Zeng, B. Cui, Z. Shen, H. Wang, Z. Kong, J. Xi, Z. Ji, Int. J. Hydrogen Energy, 2020, 45, 8526-8539.
[55]	Y. Zhao, H. Guo, J. Liu, Q. Xia, J. Liu, X. Liang, E. Liu, J. Fan, J. Colloid Interface Sci., 2022, 627, 180-193.
[56]	L. Wang, J. Zhang, H. Yu, I. H. Patir, Y. Li, S. Wageh, A. A. Al-Ghamdi, J. Yu, J. Phys. Chem. Lett., 2022, 13, 4695-4700.
[57]	D. Gao, P. Deng, J. Zhang, L. Zhang, X. Wang, H. Yu, J. Yu, Angew. Chem. Int. Ed., 2023, 62, e202304559.
[58]	J. Zhang, G. Yang, B. He, B. Cheng, Y. Li, G. Liang, L. Wang, Chin. J. Catal., 2022, 43, 2530-2538.
[59]	J. Zhu, S. Wageh, A. A. Al-Ghamdi, Chin. J. Catal., 2023, 49, 5-7.
[60]	C. Cheng, J. Zhang, B. Zhu, G. Liang, L. Zhang, J. Yu, Angew. Chem. Int. Ed., 2023, 62, e202218688.
[61]	B. He, P. Xiao, S. Wan, J. Zhang, T. Chen, L. Zhang, J. Yu, Angew. Chem. Int. Ed., 2023, 62, e202313172.
[62]	E. A. Pogna, M. Marsili, D. D. Fazio, S. D. Conte, C. Manzoni, D. Sangalli, D. Yoon, A. Lombardo, A. C. Ferrari, A. Marini, G. Cerullo, D. Prezzi, ACS Nano, 2016, 10, 1182-1188.

Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H₂O₂ production by using femtosecond transient absorption spectroscopy

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 11

References

Related Articles 15

Recommended Articles

Metrics

[1]	Fulin Wang, Xiangwei Li, Kangqiang Lu, Man Zhou, Changlin Yu, Kai Yang. Molten salt construction of core-shell structured S-scheme CuInS₂@CoS₂ heterojunction to boost charge transfer for efficient photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2024, 63(8): 190-201.
[2]	Qiqi Zhang, Hui Miao, Jun Wang, Tao Sun, Enzhou Liu. Self-assembled S-scheme In_2.77S₄/K⁺-doped g-C₃N₄ photocatalyst with selective O₂ reduction pathway for efficient H₂O₂ production using water and air [J]. Chinese Journal of Catalysis, 2024, 63(8): 176-189.
[3]	Chao Li, Shuo Wang, Yuan Liu, Xihe Huang, Yan Zhuang, Shuhong Wu, Ying Wang, Na Wen, Kaifeng Wu, Zhengxin Ding, Jinlin Long. Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2024, 63(8): 164-175.
[4]	Chunguang Chen, Jinfeng Zhang, Hailiang Chu, Lixian Sun, Graham Dawson, Kai Dai. Chalcogenide-based S-scheme heterojunction photocatalysts [J]. Chinese Journal of Catalysis, 2024, 63(8): 81-108.
[5]	Gaoxiong Liu, Rundong Chen, Bingquan Xia, Zhen Wu, Shantang Liu, Amin Talebian-Kiakalaieh, Jingrun Ran. Synthesis of H₂O₂ and high-value chemicals by covalent organic framework-based photocatalysts [J]. Chinese Journal of Catalysis, 2024, 61(6): 97-110.
[6]	Haoming Huang, Qingqing Lin, Qing Niu, Jiangqi Ning, Liuyi Li, Jinhong Bi, Yan Yu. Metal-free photocatalytic reduction of CO₂ on a covalent organic framework-based heterostructure [J]. Chinese Journal of Catalysis, 2024, 60(5): 201-208.
[7]	Miaoli Gu, Yi Yang, Bei Cheng, Liuyang Zhang, Peng Xiao, Tao Chen. Unveiling product selectivity in S-scheme heterojunctions: Harnessing charge separation for tailored photocatalytic oxidation [J]. Chinese Journal of Catalysis, 2024, 59(4): 185-194.
[8]	Baolong Zhang, Fangxuan Liu, Bin Sun, Tingting Gao, Guowei Zhou. Hierarchical S-scheme heterojunctions of ZnIn₂S₄-decorated TiO₂ for enhancing photocatalytic H₂ evolution [J]. Chinese Journal of Catalysis, 2024, 59(4): 334-345.
[9]	Junxian Bai, Rongchen Shen, Guijie Liang, Chaochao Qin, Difa Xu, Haobin Hu, Xin Li. Topology-induced local electric polarization in 2D thiophene-based covalent organic frameworks for boosting photocatalytic H₂ evolution [J]. Chinese Journal of Catalysis, 2024, 59(4): 225-236.
[10]	Jinkang Pan, Aicaijun Zhang, Lihua Zhang, Pengyu Dong. Construction of S-scheme heterojunction from protonated D-A typed polymer and MoS₂ for efficient photocatalytic H₂ production [J]. Chinese Journal of Catalysis, 2024, 58(3): 180-193.
[11]	Yong Zhang, Junyi Qiu, Bicheng Zhu, Guotai Sun, Bei Cheng, Linxi Wang. Hollow spherical covalent organic framework supported gold nanoparticles for photocatalytic H₂O₂ production [J]. Chinese Journal of Catalysis, 2024, 57(2): 143-153.
[12]	Yucheng Jin, Xiaolin Liu, Chen Qu, Changjun Li, Hailong Wang, Xiaoning Zhan, Xinyi Cao, Xiaofeng Li, Baoqiu Yu, Qi Zhang, Dongdong Qi, Jianzhuang Jiang. Perylene diimide covalent organic frameworks super-reductant for visible light-driven reduction of aryl halides [J]. Chinese Journal of Catalysis, 2024, 57(2): 171-183.
[13]	Cheng Yang, Xin Li, Mei Li, Guijie Liang, Zhiliang Jin. Anchoring oxidation co-catalyst over CuMn₂O₄/graphdiyne S-scheme heterojunction to promote eosin-sensitized photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2024, 56(1): 88-103.
[14]	Xin Liu, Maodi Wang, Yiqi Ren, Jiali Liu, Huicong Dai, Qihua Yang. Construction of modularized catalytic system for transfer hydrogenation: Promotion effect of hydrogen bonds [J]. Chinese Journal of Catalysis, 2023, 52(9): 207-216.
[15]	Lijuan Sun, Xiaohui Yu, Liyong Tang, Weikang Wang, Qinqin Liu. Hollow dodecahedron K₃PW₁₂O₄₀/CdS core-shell S-scheme heterojunction for photocatalytic synergistic H₂ evolution and benzyl alcohol oxidation [J]. Chinese Journal of Catalysis, 2023, 52(9): 164-175.