1D/2D TiO2/ZnIn2S4 S-scheme heterojunction photocatalyst for efficient hydrogen evolution

doi:10.1016/S1872-2067(21)63875-5

Abstract

Abstract:

TiO₂ is a promising photocatalyst with limited use in practical applications owing to its wide bandgap, narrow light response range, and rapid recombination of photoexcited carriers. To address these limitations, a novel 1D/2D TiO₂/ZnIn₂S₄ heterostructure was designed according to the principles of the S-scheme heterojunction. The TiO₂/ZnIn₂S₄ (TZISx) hybrids prepared via a hydrothermal method afforded significant improvement in photocatalytic hydrogen evolution (PHE) in comparison to pristine TiO₂ and ZnIn₂S₄. In particular, the optimal TZIS2 sample (mass ratio of ZnIn₂S₄ to TiO₂ was 0.4) exhibited the highest PHE activity (6.03 mmol/h/g), which was approximately 3.7 and 2.0 times higher than those of pristine TiO₂ and ZnIn₂S₄, respectively. This improvement in the PHE of the TZIS2 sample could be attributed to the formation of an intimate heterojunction interface, high-efficiency separation of charge carriers, abundant reactive sites, and enhanced light absorption capacity. Notably, theoretical and experimental results demonstrated that the S-scheme mechanism of interfacial electron transfer in the TZISx composites facilitated the transfer and separation of photoexcited charge carriers, resulting in more isolated photoexcited electrons for the PHE reaction.

Key words: S-scheme heterojunction, TiO₂, ZnIn₂S₄, 1D/2D, Photocatalytic hydrogen evolution

Jinmao Li, Congcong Wu, Jin Li, Binghai Dong, Li Zhao, Shimin Wang. 1D/2D TiO₂/ZnIn₂S₄ S-scheme heterojunction photocatalyst for efficient hydrogen evolution[J]. Chinese Journal of Catalysis, 2022, 43(2): 339-349.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63875-5

https://www.cjcatal.com/EN/Y2022/V43/I2/339

Figures/Tables 10

Fig. 1. (a) Schematic of the synthesis of TZISx composites; (b) Zeta potential of TiO2 in ethanol aqueous solution (volume ratio of water to ethanol is 2:1).

Fig. 2. (a) XRD data, (b) nitrogen adsorption-desorption isotherms, (c) pore-size distributions, and (d) UV-vis diffuse reflectance spectra of TiO2, ZnIn2S4, and TZISx composites.

Fig. 3. (a) XPS survey data of TiO2, ZnIn2S4, and TZIS2; Ti 2p (b) andO 1s (c) high-resolution XPS data of TiO2 and TZIS2 in dark or under light irradiation; Zn 2p (d), In 3d (e), and S 2p (f) XPS data of ZnIn2S4 and TZIS2 in dark and under light irradiation.

Table 1 Physical properties of the as-prepared photocatalysts.

Sample	S_BET (m²/g)	Pore size (nm)	Pore volume (cm³/g)
TiO₂	23.6	15.5	0.09
TZIS1	26.6	14.5	0.10
TZIS2	58.3	11.9	0.17
TZIS3	81.5	10.9	0.22
ZnIn₂S₄	146.3	9.1	0.33

Fig. 4. FESEM images of TiO2 (a), ZnIn2S4 (b), and TZIS2 (c); TEM (d) and HRTEM (e) images of TZIS2; (f) Energy-dispersive X-ray mapping images of TZIS2.

Fig. 5. (a) PHE activities of the as-prepared samples in TEOA solution; (b) PHE activity of TZIS2 using different sacrificial reagents; (c) AQE of TZIS2 using different sacrificial reagents; (d) Cyclic PHE experiments of TZIS2 in TEOA aqueous solution; (e) XRD data of TZIS2 before and after reaction.

Table 2 Comparison of H2 evolution rate using representative photocatalysts.

Photocatalyst	Light source	Electron donor	H₂ evolution rate (mmol/h/g)	Ref.
ZnIn₂S₄/TiO_2‒_x	LED lamp (420 nm)	Na₂S/Na₂SO₃	0.53	[14]
ZnIn₂S₄@SiO₂@TiO₂	300 W Xe lamp	TEOA	0.62	[16]
rGO/TiO₂/ZIS	300 W Xe lamp	Na₂S/Na₂SO₃	0.46	[38]
TiO₂@ZnIn₂S₄	300 W Xe lamp	Lactic acid	1.24	[40]
Ti₃C₂@TiO₂/ZIS	300 W Xe lamp	Na₂S/Na₂SO₃	1.19	[50]
TiO₂ nanobelt/ZnIn₂S₄	300 W Xe lamp	Na₂S/Na₂SO₃	0.35	[60]
TiO₂ nanofiber/ZnIn₂S₄	300 W Xe lamp	TEOA Lactic acid Methanol Na₂S/Na₂SO₃	6.03 2.32 1.92 1.56	This work

Fig. 6. (a) PL spectra of the as-prepared samples; (b) TRPL of TiO2 and TZIS2; Transient photocurrent (c) and EIS plots (d) of TiO2, ZnIn2S4, and TZIS2.

Fig. 7. XPS valence band spectra (a) and Tauc plots (b) of TiO2 and ZnIn2S4; Calculated electrostatic potentials of TiO2 (c) and ZnIn2S4 (d).

Fig. 8. Schematic showing the S-scheme electron transfer between TiO2 and ZnIn2S4.

References

[1]	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.
[2]	P. C. Yan, X. J. She, X. W. Zhu, L. Xu, J. C. Qian, J. X. Xia, J. M. Zhang, H. Xu, H. N. Li, H. M. Li, Appl. Surf. Sci., 2020,507, 145085.
[3]	Z. L. Wang, J. J. Fan, B. Cheng, J. G. Yu, J. S. Xu, Mater. Today Phys., 2020,15, 100279.
[4]	C. Cheng, B. W. He, J. J. Fan, B. Cheng, S. W. Cao, J. G. Yu, Adv. Mater., 2021,33, 2100317.
[5]	J. M. Li, J. Li, C. C. Wu, Z. H. Li, L. W. Cai, H. Tang, Z. Z. Zhou, G. H. Wang, J. Wang, L. Zhao, S. M. Wang, Carbon, 2021,179, 387-399.
[6]	Y. W. Liao, G. H. Wang, J. Wang, K. Wang, S. D. Yan, Y. R. Su, J. Colloid Interface Sci., 2021,587, 110-120.
[7]	R. A. He, H. J. Liu, H. M. Liu, D. F. Xu, L. Y. Zhang, J. Mater. Sci. Technol., 2020,52, 145-151.
[8]	H. N. Ge, F. Y. Xu, B. Cheng, J. G. Yu, W. K. Ho, ChemCatChem, 2019,11, 6301-6309.
[9]	G. Liu, G. H. Wang, Z. H. Hu, Y. R. Su, L. Zhao, Appl. Surf. Sci., 2019,465, 902-910.
[10]	G. C. Huang, X. Y. Liu, S. R. Shi, S. T. Li, Z. T. Xiao, W. Q. Zhen, S. W. Liu, P. K. Wong, Chin. J. Catal., 2020,41, 50-61.
[11]	J. Wang, G. H. Wang, X. H. Wei, G. Liu, J. Li, Appl. Surf. Sci., 2018,456, 666-675.
[12]	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.
[13]	A. Y. Meng, L. Y. Zhang, B. Cheng, J. G. Yu, ACS Appl. Mater. Interfaces, 2019,11, 5581-5589.
[14]	Y. F. Wang, X. Y. Meng, Q. Y. Hu, M. Y. Zhang, X. H. Cao, C. J. Xu, Y. Ding, Int. J. Hydrogen Energy, 2021,46, 6262-6271.
[15]	M. Tahir, B. Tahir, J. Colloid Interface Sci., 2021,591, 20-37.
[16]	L. Wang, H. H. Zhou, H. Z. Zhang, Y. L. Song, H. Zhang, X. H. Qian, Inorg. Chem., 2020,59, 2278-2287.
[17]	Y. C. Lu, X. Y. Ou, W. G. Wang, J. J. Fan, K. L. Lv, Chin. J. Catal., 2020,41, 209-218.
[18]	J. Wang, G. H. Wang, B. Cheng, J. G. Yu, J. J. Fan, Chin. J. Catal., 2021,42, 56-68.
[19]	A. Y. Meng, L. Y. Zhang, B. Cheng, J. G. Yu, Adv. Mater., 2019,31, 1807660.
[20]	S. Wageh, A. A. Al-Ghamdi, L. J. Liu, Acta Phys.-Chim. Sin., 2021,37, 2010024.
[21]	I. B. Assaker, M. Gannouni, J. B. Naceur, M. A. Almessiere, A. L. Al-Otaibi, T. Ghrib, S. W. Shen, R. Chtourou, Appl. Surf. Sci., 2015,351, 927-934.
[22]	Y. J. Zou, J. W. Shi, D. D. Ma, Z. Y. Fan, L. Lu, C. M. Niu, Chem. Eng. J., 2017,322, 435-444.
[23]	F. He, A. Y. Meng, B. Cheng, W. K. Ho, J. G. Yu, Chin. J. Catal., 2020,41, 9-20.
[24]	Y. H. Jiang, Z. Y. Peng, S. B. Zhang, F. Li, Z. C. Liu, J. M. Zhang, Y. Liu, K. Wang, Ceram. Int., 2018,44, 6115-6126.
[25]	F. Y. Xu, K. Meng, B. Cheng, S. Y. Wang, J. S. Xu, J. G. Yu, Nat. Commun., 2020,11, 4613.
[26]	P. F. Xia, S. W. Cao, B. C. Zhu, M. J. Liu, M. S. Shi, J. G. Yu, Y. F. Zhang, Angew. Chem. Int. Ed., 2020,59, 5218-5225.
[27]	X. G. Fei, H. Y. Tan, B. Cheng, B. C. Zhu, L. Y. Zhang, Acta Phys.-Chim. Sin., 2021,37, 2010027.
[28]	X. B. Li, J. Y. Liu, J. T. Huang, C. Z. He, Z. J. Feng, Z. Chen, L. Y. Wan, F. Deng, Acta Phys.-Chim. Sin., 2021,37, 2010030.
[29]	A. Y. Meng, B. Cheng, H. Y. Tan, J. J. Fan, C. L. Su, J. G. Yu, Appl. Catal. B, 2021,289, 120039.
[30]	M. T. Song, Y. H. Wu, C. F. Du, Y. G. Su, J. Colloid Interface Sci., 2021,588, 357-368.
[31]	X. C. Hu, G. H. Wang, J. Wang, Z. F. Hu, Y. R. Su, Appl. Surf. Sci., 2020,511, 145499.
[32]	S. S. Wu, X. Yu, J. L. Zhang, Y. M. Zhang, Y. Zhu, M. S. Zhu, Chem. Eng. J., 2021,411, 128555.
[33]	M. N. Huang, J. H. Yu, Q. Hu, W. L. Su, M. G. Fan, B. Li, L. H. Dong, Appl. Surf. Sci., 2016,389, 1084-1093.
[34]	B. Chai, T. Y. Peng, J. Mao, K. Lia, L. Zan, Phys. Chem. Chem. Phys., 2012,14, 16745-16752.
[35]	F. He, B. C. Zhu, B. Cheng, J. G. Yu, W. K. Ho, W. Macyk, Appl. Catal. B, 2020,272, 119006.
[36]	X. L. Guo, Y. H. Peng, G. B. Liu, G. W. Xie, Y. N. Guo, Y. Zhang, J. Q. Yu, J. Phys. Chem. C, 2020,124, 5934-5943.
[37]	X. W. Shi, L. Mao, P. Yang, H. J. Zheng, M. Fujitsuka, J. Y. Zhang, T. Majima, Appl. Catal. B, 2020,265, 118616.
[38]	H. Q. An, M. Li, W. Wang, Z. T. Lv, C. Y. Deng, J. Y. Huang, Z. Yin, Ceram. Int., 2019,45, 14976-14982.
[39]	G. C. Zuo, Y. T. Wang, W. L. Teo, A. M. Xie, Y. Guo, Y. X. Dai, W. Q. Zhou, D. Jana, Q. M. Xian, W. Dong, Y. L. Zhao, Angew. Chem. Int. Ed., 2020,59, 11287-11292.
[40]	H. Li, Z. H. Chen, L. Zhao, G. D. Yang, Rare Metals, 2019,38, 420-427.
[41]	Z. H. Mei, G. H. Wang, S. D. Yan, J. Wang, Acta Phys.-Chim. Sin., 2021,37, 2009097.
[42]	Y. W. Zhu, L. L. Wang, Y. T. Liu, L. H. Shao, X. N. Xia, Appl. Catal. B, 2019,241, 483-490.
[43]	Q. L. Xu, L. Y. Zhang, B. Cheng, J. J. Fan, J. G. Yu, Chem, 2020,6, 1543-1559.
[44]	F. Y. Xu, H. Y. Tan, J. J. Fan, B. Cheng, J. G. Yu, J. S. Xu, Sol. RRL, 2021,5, 2000571.
[45]	Y. Y. Duan, L. Liang, K. L. Lv, Q. Li, M. Li, Appl. Surf. Sci., 2018,456, 817-826.
[46]	L. Wang, C. B. Zhang, F. Gao, G. Mailhot, G. Pan, Chem. Eng. J., 2017,314, 622-630.
[47]	S. B. Kale, R. S. Kalubarme, M. A. Mahadadalkar, H. S. Jadhav, A. P. Bhirud, J. D. Ambekar, C. J. Park, B. B. Kale, Phys. Chem. Chem. Phys., 2015,17, 31850-31861.
[48]	Y. Xia, Q. Li, K. L. Lv, M. Li, Appl. Surf. Sci., 2017,398, 81-88.
[49]	Y. Xia, B. Cheng, J. J. Fan, J. G. Yu, G. Liu, Sci. China Mater., 2020,63, 552-565.
[50]	K. L. Huang, C. H. Li, X. C. Meng, J. Colloid Interface Sci., 2020,580, 669-680.
[51]	M. A. Alcudia-Ramos, M. O. Fuentez-Torres, F. Ortiz-Chi, C. G. Espinosa-Gonzalez, N. Hernandez-Como, D. S. Garcia-Zaleta, M. K. Kesarla, J. G. Torres-Torres, V. Collins-Martinez, S. Godavarthi, Ceram. Int., 2020,46, 38-45.
[52]	K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A. Pierotti, J. Rouquerol, T. Siemieniewska, Pure Appl. Chem., 1985,57, 603-619.
[53]	Q. Li, Y. Xia, C. Yang, K. L. Lv, M. Lei, M. Li, Chem. Eng. J., 2018,349, 287-296.
[54]	Q. Tang, X. F. Meng, Z. Y. Wang, J. W. Zhou, H. Tang, Appl. Surf. Sci., 2018,430, 253-262.
[55]	X. B. Li, J. Xiong, Y. Xu, Z. J. Feng, J. T. Huang, Chin. J. Catal., 2019,40, 424-433.
[56]	Z. L. Wang, Y. F. Chen, L. Y. Zhang, B. Cheng, J. G. Yu, J. J. Fan, J. Mater. Sci. Technol., 2020,56, 143-150.
[57]	G. Yang, D. M. Chen, H. Ding, J. J. Feng, J. Z. Zhang, Y. F. Zhu, S. Hamid, D. W. Bahnemann, Appl. Catal. B, 2017,219, 611-618.
[58]	Y. Wu, H. Wang, W. G. Tu, S. Y. Wu, J. W. Chew, Appl. Catal. B, 2019,256, 117810.
[59]	J. M. Li, L. Zhao, S. M. Wang, J. Li, G. H. Wang, J. Wang, Appl. Surf. Sci., 2020,515, 145922.
[60]	N. Wei, Y. H. Wu, M. L. Wang, W. X. Sun, Z. K. Li, L. Ding, H. Z. Cui, Nanotechnology, 2019,30, 045701.
[61]	Q. Xie, W. M. He, S. W. Liu, C. H. Li, J. F. Zhang, P. K. Wong, Chin. J. Catal., 2020,41, 140-153.
[62]	J. Wang, G. H. Wang, J. Jiang, Z. Wan, Y. R. Su, H. Tang, J. Colloid Interface Sci., 2020,564, 322-332.
[63]	Y. Y. Ren, Y. Li, X. Y. Wu, J. L. Wang, G. K. Zhang, Chin. J. Catal., 2021,42, 69-77.
[64]	Z. F. Li, Z. H. Wu, R. G. He, L. Wan, S. Y. Zhang, J. Mater. Sci. Technol., 2020,56, 151-161.
[65]	D. R. Qin, Y. Xia, Q. Li, C. Yang, Y. M. Qin, K. L. Lv, J. Mater. Sci. Technol., 2020,56, 206-215.

1D/2D TiO₂/ZnIn₂S₄ S-scheme heterojunction photocatalyst for efficient hydrogen evolution

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

share this article

Figures/Tables 10

References

Related Articles 15

Recommended Articles

Metrics

[1]	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.
[2]	Mingming Song, Xianghai Song, Xin Liu, Weiqiang Zhou, Pengwei Huo. Enhancing photocatalytic CO₂ reduction activity of ZnIn₂S₄/MOF-808 microsphere with S-scheme heterojunction by in situ synthesis method [J]. Chinese Journal of Catalysis, 2023, 51(8): 180-192.
[3]	Jiaming Li, Yuan Li, Xiaotian Wang, Zhixiong Yang, Gaoke Zhang. Atomically dispersed Fe sites on TiO₂ for boosting photocatalytic CO₂ reduction: Enhanced catalytic activity, DFT calculations and mechanistic insight [J]. Chinese Journal of Catalysis, 2023, 51(8): 145-156.
[4]	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.
[5]	Zhihan Yu, Chen Guan, Xiaoyang Yue, Quanjun Xiang. Infiltration of C-ring into crystalline carbon nitride S-scheme homojunction for photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2023, 50(7): 361-371.
[6]	Defa Liu, Bin Sun, Shuojie Bai, Tingting Gao, Guowei Zhou. Dual co-catalysts Ag/Ti₃C₂/TiO₂ hierarchical flower-like microspheres with enhanced photocatalytic H₂-production activity [J]. Chinese Journal of Catalysis, 2023, 50(7): 273-283.
[7]	Houwei He, Zhongliao Wang, Kai Dai, Suwen Li, Jinfeng Zhang. LSPR-enhanced carbon-coated In₂O₃/W₁₈O₄₉ S-scheme heterojunction for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2023, 48(5): 267-278.
[8]	Han Li, Shanren Tao, Sijie Wan, Guogen Qiu, Qing Long, Jiaguo Yu, Shaowen Cao. S-scheme heterojunction of ZnCdS nanospheres and dibenzothiophene modified graphite carbon nitride for enhanced H₂ production [J]. Chinese Journal of Catalysis, 2023, 46(3): 167-176.
[9]	Chenggong Yang, Donge Wang, Rong Huang, Jianqiang Han, Na Ta, Huaijun Ma, Wei Qu, Zhendong Pan, Congxin Wang, Zhijian Tian. Highly active and stable MoS₂-TiO₂ nanocomposite catalyst for slurry-phase phenanthrene hydrogenation [J]. Chinese Journal of Catalysis, 2023, 46(3): 125-136.
[10]	Zhijie Zhang, Xuesheng Wang, Huiling Tang, Deben Li, Jiayue Xu. Modulation of Fermi level gap and internal electric field over Cs₃Bi₂Br₉@V_O-In₂O₃S-scheme heterojunction for boosted charge separation and CO₂ photoconversion [J]. Chinese Journal of Catalysis, 2023, 55(12): 227-240.
[11]	You Wu, Yi Yang, Miaoli Gu, Chuanbiao Bie, Haiyan Tan, Bei Cheng, Jingsan Xu. 1D/0D heterostructured ZnIn₂S₄@ZnO S-scheme photocatalysts for improved H₂O₂ preparation [J]. Chinese Journal of Catalysis, 2023, 53(10): 123-133.
[12]	Yang Lei, Jian-Feng Huang, Xin-Ao Li, Chu-Ying Lv, Chao-Ping Hou, Jun-Min Liu. Direct Z-scheme photochemical hybrid systems: Loading porphyrin-based metal-organic cages on graphitic-C₃N₄ to dramatically enhance photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2022, 43(8): 2249-2258.
[13]	Xiu Qian, Yanjiao Wei, Mengjie Sun, Ye Han, Xiaoli Zhang, Jian Tian, Minhua Shao. Heterostructuring 2D TiO₂ nanosheets in situ grown on Ti₃C₂T_x MXene to improve the electrocatalytic nitrogen reduction [J]. Chinese Journal of Catalysis, 2022, 43(7): 1937-1944.
[14]	Zhongliao Wang, Bei Cheng, Liuyang Zhang, Jiaguo Yu, Youji Li, S. Wageh, Ahmed A. Al-Ghamdi. S-Scheme 2D/2D Bi₂MoO₆/BiOI van der Waals heterojunction for CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2022, 43(7): 1657-1666.
[15]	Zhenlong Zhao, Ji Bian, Lina Zhao, Hongjun Wu, Shuai Xu, Lei Sun, Zhijun Li, Ziqing Zhang, Liqiang Jing. Construction of 2D Zn-MOF/BiVO₄ S-scheme heterojunction for efficient photocatalytic CO₂ conversion under visible light irradiation [J]. Chinese Journal of Catalysis, 2022, 43(5): 1331-1340.