Electron transfer kinetics in CdS/Pt heterojunction photocatalyst during water splitting

doi:10.1016/S1872-2067(22)64108-1

Abstract

Abstract:

Noble metal cocatalysts have shown great potential in boosting the performance of CdS in photocatalytic water splitting. However, the mechanism and kinetics of electron transfer in noble-metal-decorated CdS during practical hydrogen evolution is not clearly elucidated. Herein, Pt-nanoparticle-decorated CdS nanorods (CdS/Pt) are utilized as the model system to analyze the electron transfer kinetics in CdS/Pt heterojunction. Through femtosecond transient absorption spectroscopy, three dominating exciton quenching pathways are observed and assigned to the trapping of photogenerated electrons at shallow states, recombination of free electrons and trapped holes, and radiative recombination of locally photogenerated electron-hole pairs. The introduction of Pt cocatalyst can release the electrons trapped at the shallow states and construct an ultrafast electron transfer tunnel at the CdS/Pt interface. When CdS/Pt is dispersed in acetonitrile, the lifetime and rate for interfacial electron transfer are respectively calculated to be ~5.5 ps and ~3.5 × 10¹⁰ s^-1. The CdS/Pt is again dispersed in water to simulate photocatalytic water splitting. The lifetime of the interfacial electron transfer decreases to ~5.1 ps and the electron transfer rate increases to ~4.9 × 10¹⁰ s^-1, confirming that Pt nanoparticles serve as the main active sites of hydrogen evolution. This work reveals the role of Pt cocatalysts in enhancing the photocatalytic performance of CdS from the perspective of electron transfer kinetics.

Key words: Femtosecond transient absorption spectroscopy, Photocatalytic water splitting, CdS, Electron transfer kinetics, Trap state

Jianjun Zhang, Gaoyuan Yang, Bowen He, Bei Cheng, Youji Li, Guijie Liang, Linxi Wang. Electron transfer kinetics in CdS/Pt heterojunction photocatalyst during water splitting[J]. Chinese Journal of Catalysis, 2022, 43(10): 2530-2538.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64108-1

https://www.cjcatal.com/EN/Y2022/V43/I10/2530

Figures/Tables 7

Fig. 1. (a) XRD patterns of CdS and CdS/Pt; TEM image (b), high-resolution TEM image (c) of CdS/Pt. (d) UV-vis diffuse reflection spectra of CdS and CdS/Pt.

Fig. 2. (a) Steady-state PL spectra of CdS and CdS/Pt. Schematics for the transfer pathways of photogenerated carriers in CdS (b) and CdS/Pt (c).

Fig. 3. Pseudocolor plots of CdS (a) and CdS/Pt (b). (c) fs-TAS spectra of CdS within 2000 fs. (d) Schematic for the hot exciton cooling process; (e,f) fs-TAS spectra of CdS and CdS/Pt within 6 ns. All the samples are dispersed in ACN and tested under 400 nm laser pulse excitation.

Fig. 4. Normalized decay kinetic curves at 490 nm (a,b) and the corresponding schematics (c,d) for electron quenching in CdS-ACN and CdS/Pt-ACN.

Table 1 Fitting parameters for the PB peaks of CdS and CdS/Pt in ACN and H2O.

Sample	A₁	τ₁ (ps)	A₂	τ₂ (ps)	A₃	τ₃ (ps)	τ_ave (ps)
CdS-ACN	67.4%	6.8	22.1%	58.2	10.5%	2611.9	2457.9
CdS/Pt-ACN	66.2%	5.5	18.5%	70.6	15.2%	1383.6	1287.6
CdS-H₂O	66.7%	6.8	21.8%	102.4	11.5%	1380.7	1194.2
CdS/Pt-H₂O	60.8%	5.1	21.1%	84.5	18.1%	962.0	886.3

Fig. 5. Pseudocolor plots (a,b) and fs-TAS spectra (c,d) of CdS and CdS/Pt dispersed in H2O under 400 nm laser pulse excitation.

Fig. 6. Normalized decay kinetic curves at 500 nm (a,b) and corresponding schematics (c,d) for the electron quenching processes of CdS-H2O and CdS/Pt-H2O.

References

[1]	L. Wang, B. Zhu, B. Cheng, J. Zhang, L. Zhang, J. Yu, Chin. J. Catal., 2021, 42, 1648-1658.
[2]	M. Qi, M. Conte, M. Anpo, Z. Tang, Y. Xu, Chem. Rev., 2021, 121, 13051-13085.
[3]	J. Zhang, X. Li, L. Wang, J. Yu, S. Wageh, A. Al-Ghamdi, Appl. Surf. Sci., 2021, 564, 150464.
[4]	J. Wu, J. Liu, W. Xia, Y. Ren, F. Wang, Acta Phys.-Chim. Sin., 2021, 37, 2008043.
[5]	J. Zhang, J. Fan, B. Cheng, J. Yu, W. Ho, Solar RRL, 2020, 4, 2000502.
[6]	W. Yu, M. Richter, P. Buabthong, I. Moreno-Hernandez, C. Read, E. Simonoff, B. Brunschwig, N. Lewis, Energy Environ. Sci., 2021, 14, 6007-6020.
[7]	H. Xu, R. Xiao, J. Huang, Y. Jiang, C. Zhao, X. Yang, Chin. J. Catal., 2021, 42, 107-114.
[8]	T. Su, C. Men, L. Chen, B. Chu, X. Luo, H. B. Ji, J. Chen, Z. Qin, Adv. Sci., 2022, 9, 2103715.
[9]	J. Liu, H. Wu, F. Li, X. Feng, P. Zhang, L. Gao, Adv. Sustain. Syst., 2020, 4, 2000151.
[10]	S. Wageh, A. Al-Ghamdi, O. Al-Hartomy, M. Alotaibi, L. Wang, Chin. J. Catal., 2022, 43, 586-588.
[11]	Y. Wu, Y. Li, L. Zhang, Z. Jin, ChemCatChem, 2022, 14, e202101656.
[12]	X. Ma, H. Lin, Y. Li, L. Wang, X. Pu, X. Yi, Chin. J. Struct. Chem., 2021, 40, 7-22.
[13]	D. Gao, J. Xu, L. Wang, B. Zhu, H. Yu, J. Yu, Adv. Mater., 2022, 34, 2108475.
[14]	L. Jian, H. Zhang, B. Liu, C. Pan, Y. Dong, G. Wang, J. Zhong, Y. Zheng, Y. Zhu, Chin. J. Catal., 2022, 43, 536-545.
[15]	X. Kang, J. Shi, H. Lu, G. Zhang, J. Yao, L. Hou, F. Chen, S. Mao, V. Binas, S. Shen, Adv. Sustain. Syst., 2021, 5, 2100138.
[16]	R. Shen, X. Lu, Q. Zheng, Q. Chen, Y. Ng, P. Zhang, X. Li, Solar RRL, 2021, 5, 2100177.
[17]	S. Wageh, A. Al-Ghamdi, Q. Xu, Acta Phys.-Chim. Sin., 2022, 38, 2202001.
[18]	C. Cheng, B. He, J. Fan, B. Cheng, S. Cao, J. Yu, Adv. Mater., 2021, 33, 2100317.
[19]	R. Shen, D. Ren, Y. Ding, Y. Guan, Y. Ng, P. Zhang, X. Li, Sci. China Mater., 2020, 63, 2153-2188.
[20]	J. Bai, R. Shen, Z. Jiang, P. Zhang, Y. Li, X. Li, Chin. J. Catal., 2022, 43, 359-369.
[21]	S. Tang, Y. Xia, J. Fan, B. Cheng, J. Yu, W. Ho, Chin. J. Catal., 2021, 42, 743-752.
[22]	X. Li, S. Song, Y. Gao, L. Ge, W. Song, T. Ma, J. Liu, Small, 2021, 17, 2101315.
[23]	B. Zhu, B. Cheng, J. Fan, W. Ho, J. Yu, Small Struct., 2021, 2, 2100086.
[24]	Y. Bao, S. Song, G. Yao, S. Jiang, Solar RRL, 2021, 5, 2100118.
[25]	L. Zhang, J. Zhang, H. Yu, J. Yu, Adv. Mater., 2022, 34, 2107668.
[26]	L. Wang, B. Cheng, L. Zhang, J. Yu, Small, 2021, 17, 2103447.
[27]	Z. Jiang, Q. Chen, Q. Zheng, R. Shen, P. Zhang, X. Li, Acta Phys.-Chim. Sin., 2021, 37, 2010059.
[28]	W. Yu, S. Zhang, J. Chen, P. Xia, M. Richter, L. Chen, W. Xu, J. Jin, S. Chen, T. Peng, J. Mater. Chem. A, 2018, 6, 15668-15674.
[29]	S. Zhang, G. Chen, Z. Zhu, Y. Wang, L. Wang, S. Meng, X. Zheng, X. Fu, F. Zhang, W. Huang, S. Chen, J. Catal., 2021, 402, 72-82.
[30]	R. Feng, K. Wan, X. Sui, N. Zhao, H. Li, W. Lei, J. Yu, X. Liu, X. Shi, M. Zhai, G. Liu, H. Wang, L. Zheng, M. Liu, Nano Today, 2021, 37, 101080.
[31]	Y. Shen, D. Li, Y. Dang, J. Zhang, W. Wang, B. Ma, Appl. Surf. Sci., 2021, 564, 150432.
[32]	X. Xiang, B. Zhu, B. Cheng, J. Yu, H. Lv, Small, 2020, 16, 2001024.
[33]	G. Yang, S. Shi, X. Zhang, S. Zhou, D. Liu, Y. Liang, Z. Chen, G. Liang, Opt. Express, 2021, 29, 9012-9020.
[34]	J. Liu, G. Hodes, J. Yan, S. Liu, Chin. J. Catal., 2021, 42, 205-216.
[35]	J. Zhang, L. Wang, C. Jiang, B. Cheng, T. Chen, J. Yu, Adv. Sci., 2021, 8, 2102648.
[36]	Z. Wei, W. Wang, W. Li, X. Bai, J. Zhao, E. Tse, D. Phillips, Y. Zhu, Angew. Chem. Int. Ed., 2021, 60, 8236-8242.
[37]	Z. Yan, W. Wang, L. Du, J. Zhu, D. Phillips, J. Xu, Appl. Catal. B, 2020, 275, 119151.
[38]	Y. Wang, W. Zhang, D. Li, J. Guo, Y. Yu, K. Ding, W. Duan, X. Li, H. Liu, P. Su, B. Liu, J. Li, Adv. Sci., 2021, 8, 2004456.
[39]	K. Wu, H. Zhu, Z. Liu, W. Rodriguez-Cordoba, T. Lian, J. Am. Chem. Soc., 2012, 134, 10337-10340.
[40]	H. Dong, J. Feng, J. Liu, X. Wan, J. Zhang, Z. Wang, H. Chen, Y. Weng, J. Phys. Chem. C, 2021, 125, 19906-19913.
[41]	B. He, C. Bie, X. Fei, B. Cheng, J. Yu, W. Ho, A. Al-Ghamdi, S. Wageh, Appl. Catal. B, 2021, 288, 119994.
[42]	W. Wei, Q. Tian, H. Sun, P. Liu, Y. Zheng, M. Fan, J. Zhuang, Appl. Catal. B, 2020, 260, 118153.
[43]	T. Di, B. Cheng, W. Ho, J. Yu, H. Tang, Appl. Surf. Sci., 2019, 470, 196-204.
[44]	B. Wang, S. He, L. Zhang, X. Huang, F. Gao, W. Feng, P. Liu, Appl. Catal. B, 2019, 243, 229-235.
[45]	Z. Wang, L. Wang, B. Cheng, H. Yu, J. Yu, Small Methods, 2021, 5, 2100979.
[46]	F. Zhang, W. Liu, Y. Liu, J. Wang, G. Ji, J. Nanopart. Res., 2015, 17, 62.
[47]	X. Zhou, Y. Liu, Z. Jin, M. Huang, F. Zhou, J. Song, J. Qu, Y. Zeng, P. Qian, W. Wong, Adv. Sci., 2021, 8, 2002465.
[48]	D. Sun, J. Shi, D. Ma, Y. Zou, G. Sun, S. Mao, L. Sun, Y. Cheng, Chin. J. Catal., 2020, 41, 1421-1429.
[49]	J. Peng, J. Shen, X. Yu, H. Tang, Zulfiqar, Q. Liu, Chin. J. Catal., 2021, 42, 87-96.
[50]	B. Qiu, L. Cai, N. Zhang, X. Tao, Y. Chai, Adv. Sci., 2020, 7, 1903568.
[51]	N. Zhao, J. Peng, J. Wang, M. Zhai, Acta Phys.-Chim. Sin., 2022, 38, 2004046.
[52]	X. Jiao, Z. Chen, X. Li, Y. Sun, S. Gao, W. Yan, C. Wang, Q. Zhang, Y. Lin, Y. Luo, Y. Xie, J. Am. Chem. Soc., 2017, 139, 7586-7594.
[53]	J. Zhang, J. Tian, J. Fan, J. Yu, W. Ho, Small, 2020, 16, 1907290.
[54]	D. A. Valverde-Chavez, C. S. Ponseca, C. Stoumpos, A. Yartsev, M. G. Kanatzidis, V. Sundstrom, D. G. Cooke, Energy Environ. Sci., 2015, 8, 3700-3707.
[55]	K. Wu, H. Zhu, T. Lian, Acc. Chem. Res., 2015, 48, 851-859.
[56]	A. Sacra, D. J. Norris, C. B. Murray, M. G. Bawendi, J. Chem. Phys., 1995, 103, 5236-5245.
[57]	A. Boulesbaa, A. Issac, D. Stockwell, Z. Huang, J. Huang, J. Guo, T. Lian, J. Am. Chem. Soc., 2007, 129, 15132-15133.
[58]	V. I. Klimov, Annu. Rev. Phys. Chem., 2007, 58, 635-673.
[59]	H. Zhu, N. Song, T. Lian, J. Am. Chem. Soc., 2011, 133, 8762-8771.
[60]	H. Zhu, N. Song, T. Lian, J. Am. Chem. Soc., 2010, 132, 15038-15045.
[61]	L. Zhang, Q. Zhang, Y. Luo, J. Phys. Chem. Lett., 2017, 8, 5680-5686.
[62]	J. Chen, X. Wu, L. Yin, B. Li, X. Hong, Z. Fan, B. Chen, C. Xue, H. Zhang, Angew. Chem. Int. Ed., 2015, 54, 1210-1214.
[63]	Z. Yan, L. Du, D. Phillips, RSC Adv., 2017, 7, 55993-55999.
[64]	S. Habas, P. Yang, T. Mokari, J. Am. Chem. Soc., 2008, 130, 3294-3295.
[65]	H. Liu, Z. Chen, L. Zhang, D. Zhu, Q. Zhang, Y. Luo, X. Shao, J. Phys. Chem. C, 2018, 122, 6388-6396.
[66]	Y. Liu, W. Yang, Q. Chen, D. Cullen, Z. Xie, T. Lian, J. Am. Chem. Soc., 2022, 144, 2705-2715.
[67]	W. Guo, H. Luo, Z. Jiang, W. Shangguan, Chin. J. Catal., 2022, 43, 316-328.
[68]	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.
[69]	E. Nikoloudakis, M. Pigiaki, M. N. Polychronaki, A. Margaritopoulou, G. Charalambidis, E. Serpetzoglou, A. Mitraki, P. A. Loukakos, A. G. Coutsolelos, ACS Sustainable Chem. Eng., 2021, 9, 7781-7791.