Boosting the catalytic activity of a step-scheme In2O3/ZnIn2S4 hybrid system for the photofixation of nitrogen

doi:10.1016/S1872-2067(21)63801-9

Abstract

Abstract:

In this study, a step-scheme photocatalytic system comprising one-dimensional In₂O₃ nanorods and two-dimensional ZnIn₂S₄ nanosheets was developed for the catalytic photofixation of nitrogen. The effects of the combination of In₂O₃ with ZnIn₂S₄ on the crystallinity, microstructure, optical absorption, and charge transfer behavior of the In₂O₃/ZnIn₂S₄ hybrid photocatalysts were investigated. Benefiting from the synergistic effects of the photogenerated vacancies and a step-scheme charge separation mechanism, the In₂O₃/ZnIn₂S₄ hybrid photocatalyst exhibited significantly enhanced catalytic activity compared to those of bare In₂O₃ and pure ZnIn₂S₄, and an optimized 50 wt% In₂O₃/ZnIn₂S₄ hybrid sample was found to exhibit superior catalytic activity for the photofixation of N₂, fixing 18.1 ±0.77 mg·L ^-1 of ammonia after exposure to simulated sunlight for 2 h. Crucially, the results of trapping experiments and electron paramagnetic resonance investigation to identify the active species confirmed that the catalytic nitrogen photofixation performance was highly correlated with the presence of ^·CO₂ ^-radicals rather than photogenerated electrons, especially when methanol was used as a hole scavenger. In summary, the reported In₂O₃/ZnIn₂S₄ hybrid photocatalysts exhibit both stability and high activity for the photofixation of N₂, making them promising catalysts for sunlight-driven artificial N₂ fixation.

Key words: In₂O₃, ZnIn₂S₄, Step-scheme, Nitrogen photofixation

Jin Zhang, Zi-Hao Pan, Ying Yang, Peng-Fei Wang, Chen-Yang Pei, Wei Chen, Guo-Bo Huang. Boosting the catalytic activity of a step-scheme In₂O₃/ZnIn₂S₄ hybrid system for the photofixation of nitrogen[J]. Chinese Journal of Catalysis, 2022, 43(2): 265-275.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63801-9

https://www.cjcatal.com/EN/Y2022/V43/I2/265

Figures/Tables 10

Fig. 1. XRD patterns of In2O3, ZnIn2S4, and the In2O3/ZnIn2S4 hybrid samples.

Fig. 2. TEM images (a,b), HRTEM image (c), and elemental maps (d) of the 50 wt% In2O3/ZnIn2S4 hybrid sample.

Fig. 3. UV-vis DRS of bare In2O3, pure ZnIn2S4, and the In2O3/ZnIn2S4 hybrid samples.

Fig. 4. XPS analyses: survey spectra (a) and the Zn 2p (b), In 3d (c), S 2p (d), and O 1s (e) spectra and EPR spectra (f) of pure In2O3, ZnIn2S4, and 50 wt% In2O3/ZnIn2S4 hybrid sample.

Fig. 5. N2 adsorption-desorption isotherms (a) and the corresponding pore size distribution curves (b) of In2O3, ZnIn2S4, and the 50 wt% In2O3/ZnIn2S4 hybrid sample.

Fig. 6. (a) Catalytic activities of the different samples and (b) catalytic stability of the 50 wt% In2O3/ZnIn2S4 hybrid sample for the photofixation of N2 under simulated sunlight.

Fig. 7. (a) Catalytic activity of the 50 wt% In2O3/ZnIn2S4 hybrid sample in the presence of different trapping agents; EPR spectra of DMPO-·CO2- on the addition of methanol (b) and EDTA-2Na (c) as hole scavengers; (d) the EPR spectra of DMPO-·OH.

Fig. 8. PL spectra (a), TRPL spectra (b), transient photocurrent data (c), electrochemical impedance spectroscopy Nyquist plots (d), and surface photovoltage spectra (e) of In2O3, ZnIn2S4, and In2O3/ZnIn2S4 hybrid samples.

Fig. 9. Mott-Schottky plots for In2O3 (a) and ZnIn2S4 (b) measured at different frequencies.

Fig. 10. Charge separation process and possible catalytic mechanism for the photofixation of N2 using the In2O3/ZnIn2S4 hybrid system.

References

[1]	G. N. Schrauzer, T. D. Guth , J. Am. Chem. Soc., 1977,99, 7189-7193.
[2]	S. Wang, F. Ichihara, H. Pang, H. Chen, J. Ye , Adv. Funct. Mater., 2018,28, 1803309.
[3]	G. Zhang, C.D. Sewell, P. Zhang, H. Mi, Z. Lin , Nano Energy, 2020,71, 104645.
[4]	C. Li, T. Wang, Z.-J. Zhao, W. Yang, J.-F. Li, A. Li, Z. Yang, G. A. Ozin, J. Gong , Angew. Chem. Int. Ed., 2018,57, 5278-5282.
[5]	H. Li, J. Shang, Z. Ai, L. Zhang , J. Am. Chem. Soc., 2015,137, 6393-6399.
[6]	X. Hu, Y. Yong, Y. Xu, X. Hong, Y. Weng, X. Wang, X. Yao , Appl. Surf. Sci., 2020,531, 147348.
[7]	F. Xu, K. Meng, B. Cheng, S. Wang, J. Xu, J. Yu , Nat. Commun., 2020,11, 4613.
[8]	Q. Xu, L. Zhang, B. Cheng, J. Fan, J. Yu , Chem, 2020,6, 1543-1559.
[9]	J. Fu, Q. Xu, J. Low, C. Jiang, J. Yu , Appl. Catal. B, 2019,243, 556-565.
[10]	Y. Sun, Q. Zhu, B. Bai, Y. Li, C. He , Chem. Eng. J., 2020,390, 124518.
[11]	J. Li, F. Wei, C. Dong, W. Mu, X. Han , J. Mater. Chem. A, 2020,8, 6524-6531.
[12]	Z. Wan, Q. Mao, Q. Chen , Chem. Eng. J., 2021,403, 126389.
[13]	N. Zhang, A. Jalil, D. Wu, S. Chen, Y. Liu, C. Gao, W. Ye, Z. Qi, H. Ju, C. Wang, X. Wu, L. Song, J. Zhu, Y. Xiong , J. Am. Chem. Soc., 2018,140, 9434-9443.
[14]	F. Zhang, X. Li, Q. Zhao, G. Chen, Q. Zhang , Appl. Catal. B, 2020,263, 118278.
[15]	C. Han, X. Li, Y. Liu, X. Li, C. Shao, J. Ri, J. Ma, Y. Liu, , J. Hazard. Mater., 2021,403, 124093.
[16]	Q. Shen, L. Sun, Y. Zhuang, W. Zhan, X. Wang, X. Han , Inorg. Chem., 2020,59, 17650-17658.
[17]	M. Zhang, J. Yao, M. Arif, B. Qiu, H. Yin, X. Liu, S.M. Chen , Appl. Surf. Sci., 2020,526, 145749.
[18]	W. Chen, R. Q. Yan, J. Q. Zhu, G. B. Huang, Z. Chen , Appl. Surf. Sci., 2020,504, 144406.
[19]	Y. Qin, H. Li, J. Lu, Y. Feng, F. Meng, C. Ma, Y. Yan, M. Meng , Appl. Catal. B, 2020,277, 119254.
[20]	W. Chen, T. Y. Liu, T. Huang, X. H. Liu, X. J. Yang , Nanoscale, 2016,8, 3711-3719.
[21]	G. Zhang, J. Sun, D. Chen, N. Li, Q. Xu, H. Li, J. He, J. Lu , J. Hazard. Mater., 2020,398, 122889.
[22]	Q. Zhu, Y. Sun, S. Xu, Y. Li, X. Lin, Y. Qin , J. Hazard. Mater., 2020,382, 121098.
[23]	W. Gao, L. Wang, C. Gao, J. Liu, Y. Yang, L. Yang, Q. Shen, C. Wu, Y. Zhou, Z. Zou , Nanoscale, 2020,12, 14676-14681.
[24]	S. Wang, B. Y. Guan, X. W. D. Lou , J. Am. Chem. Soc., 2018,140, 5037-5040.
[25]	Y. X. Pan, Y. You, S. Xin, Y. Li, G. Fu, Z. Cui, Y.-L. Men, F.-F. Cao, S.-H. Yu, J. B. Goodenough , J. Am. Chem. Soc., 2017,139, 4123-4129.
[26]	Z. Wang, Y. Chen, L. Zhang, B. Cheng, J. Yu, J. Fan , J. Mater. Sci. Technol., 2020,56, 143-150.
[27]	C. Y. Pei, Y. G. Chen, L. Wang, W. Chen, G. B. Huang , Appl. Surf. Sci., 2021,535, 147682.
[28]	L. Han, F. Jing, J. Zhang, X. Z. Luo, Y. L. Zhong, K. Wang, S. H. Zang, D. H. Teng, Y. Liu, J. Chen, C. Yang, Y. T. Zhou , Appl. Catal. B, 2021,282, 119602.
[29]	M. Tang, Y. Ao, P. Wang, C. Wang , J. Hazard. Mater., 2020,387, 121713.
[30]	Z. Li. Z. Wu, R. He, L. Wan, S. Zhang , J. Mater. Sci. Technol., 2020,56, 151-161.
[31]	M. Zhang, M. Arif, Y. Hua, B. Qiu, Y. Mao, X. Liu , Nanoscale Adv., 2021,3, 812-822.
[32]	M. M. Fang, J. X. Shao, X. G. Huang, J. Y. Wang, W. Chen , J. Mater. Sci. Technol., 2020,56, 133-142.
[33]	W. Chen, G. B. Huang, H. Song, J. Zhang , J. Mater. Chem. A, 2020,8, 20963-20969.
[34]	X. Sun, X. Luo, X. Zhang, J. Xie, S. Jin, H. Wang, X. Zheng, X. Wu, Y. Xie , J. Am. Chem. Soc., 2019,141, 3797-3801.
[35]	T. Wang, J. Liu, P. Wu, C. Feng, D. Wang, H. Hu, G. Xue , J. Mater. Chem. A, 2020, 8, 16590-16598.
[36]	S. Wang, X. Hai, X. Ding, K. Chang, Y. Xiang, X. Meng, Z. Yang, H. Chen, J. Ye , Adv. Mater., 2017,29, 1701774.
[37]	L. Cai, J. He, Q. Liu, T. Yao, L. Chen, W. Yan, F. Hu, Y. Jiang, Y. Zhao, T. Hu, Z. Sun, S. Wei , J. Am. Chem. Soc., 2015,137, 2622-2627.
[38]	X. Gao, Y. Shang, L. Liu, F. Fu , J. Catal., 2019,371, 71-80.
[39]	G. Hosamani, B. N. Jagadale, J. Manjanna, S. M. Shivaprasad, D. K. Shukla, J. S. Bhat , J. Electron. Mater., 2021,50, 52-58.
[40]	S. Mukherjee, K. Sarkar, G. P. Wiederrecht, R. D. Schaller, D. J. Gosztola, M. A. Stroscio, M. Dutta , Nanotechnology, 2018,29, 175201.
[41]	L. Ding, D. Li, H. Shen, X. Qiao, H. Shen, W. Shi , J. Alloys Compd., 2021,853, 157328.
[42]	J. Gan, X. Lu, J. Wu, S. Xie, T. Zhai, M. Yu, Z. Zhang, Y. Mao, S. C. I. Wang, Y. Shen, Y. Tong , Sci. Rep., 2012,3, 1021.
[43]	F. Gu, C. Li, D. Han, Z. Wang , ACS Appl. Mater. Interfaces, 2018,10, 933-942.
[44]	H. Yin, Y. Cao, T. Fan, M. Zhang, J. Yao, P. Li, S. Chen, X. Liu , Sci. Total Environ., 2021,754, 141926.
[45]	S. Chen, D. Huang, G. Zeng, X. Gong, W. Xue, J. Li, Y. Yang, C. Zhou, Z. Li, X. Yan, T. Li, Q. Zhang , Chem. Eng. J., 2019,370, 1087-1100.
[46]	M. Thommes, K. Kaneko, A. V. Neimark, J. P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K. S. W. Sing , Pure Appl. Chem., 2015,87, 1051-1069.
[47]	F. He, A. Meng, B. Cheng, W. Ho, J. Yu , Chin. J. Catal., 2020,41, 9-20.
[48]	P. Li, Z. Zhou, Q. Wang, M. Guo, S. Chen, J. Low, R. Long, W. Liu, P. Ding, Y. Wu, Y. Xiong , J. Am. Chem. Soc., 2020,142, 12430-12439.
[49]	H. Yin, Y. Cao, T. Fan, B. Qiu, M. Zhang, J. Yao, P. Li, X. Liu, S. Chen , J. Alloys Compd., 2020,824, 153915.
[50]	J. Xi, H. Xia, X. Ning, Z. Zhang, J. Liu, Z. Mu, S. Zhang, P. Du, X. Lu , Small, 2019,15, 1902744.
[51]	X. Li, B. Kang, F. Dong, Z. Zhang, X. Luo, L. Han, J. Huang, Z. Feng, Z. Chen, J. Xu, B. Peng, Z.L. Wang , Nano Energy, 2021,81, 105671.
[52]	Z. Li, G. Gu, S. Hu, X. Zou, G. Wu , Chin. J. Catal., 2019,40, 1178-1186.
[53]	Z. Wei, M. Xu, J. Liu, W. Guo, Z. Jiang, W. Shangguan , Chin. J. Catal., 2020,41, 103-113.
[54]	D. Qin, Y. Xia, Q. Li, C. Yang, Y. Qin, K. Lv , J. Mater. Sci. Technol., 2020,56, 206-215.
[55]	J. Luo, Z. Lin, Y. Zhao, S. Jiang, S. Song , Chin. J. Catal., 2020,41, 122-130.
[56]	X. Y. Shangguan, B. L. Fang, C. X. Xu, Y. Tan, Y. G. Chen, Z. J. Xia, W. Chen , Ceram. Int., 2021,47, 6318-6328.
[57]	C. Yang, Q. Li, Y. Xia, K. Lv, M. Li , Appl. Surf. Sci., 2019,464, 388-395.
[58]	Y. Lu, X. Ou, W. Wang, J. Fan, K. Lv , Chin. J. Catal., 2020,41, 209-218.
[59]	X. Hu, G. Wang, J. Wang, Z. Hu, Y. Su , Appl. Surf. Sci., 2020,511, 145499.
[60]	L. Huang, B. Li, B. Su, Z. Xiong, C. Zhang, Y. Hou, Z. Ding, S. Wang , J. Mater. Chem. A, 2020,8, 7177-7183.
[61]	X. Li, J. Xiong, Y. Xu, Z. Feng, J. Huang , Chin. J. Catal., 2019,40, 424-433.
[62]	G. Fan, R. Ning, Z. Yan, J. Luo, B. Du, J. Zhan, L. Liu, J. Zhang , J. Hazard. Mater., 2021,403, 123964.
[63]	L. J. Zhang, S. Li, B. K. Liu, D. J. Wang, T. F. Xie , ACS Catal., 2014,4, 3724-3729.
[64]	J. Wang, G. Wang, B. Cheng, J. Yu, J. Fan , Chin. J. Catal., 2021,42, 56-68.
[65]	X. Sun, X. Luo, X. Zhang, J. Xie, S. Jin, H. Wang, X. Zheng, X. Wu, Y. Xie , J. Am. Chem. Soc., 2019,141, 3797-3801.
[66]	Z. Mei, G. Wang, S. Yan, J. Wang , Acta Phys.-Chim. Sin., 2021,37, 2009097.
[67]	Y. Chen, F. Su, H. Xie, R. Wang, C. Ding, J. Huang, Y. Xue, L. Ye , Chem. Eng. J., 2021,404, 126498.
[68]	X. Jia, Q. Han, H. Liu, S. Li, H. Bi , Chem. Eng. J., 2020,399, 125701.
[69]	L. Liu, T. Hu, K. Dai, J. Zhang, C. Liang , Chin. J. Catal., 2021,42, 46-55.
[70]	J. Wei, Y. Chen, H. Zhang, Z. Zhuang, Y. Yu , Chin. J. Catal., 2021,42, 78-86.
[71]	W. Wu, G. Liu, Q. Xie, S. Liang, H. Zheng, R. Yuan, W. Su, L. Wu , Green Chem., 2012,14, 1705-1709.

Boosting the catalytic activity of a step-scheme In₂O₃/ZnIn₂S₄ hybrid system for the photofixation of nitrogen

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 10

References

Related Articles 15

Recommended Articles

Metrics

[1]	Zicong Jiang, Bei Cheng, Liuyang Zhang, Zhenyi Zhang, Chuanbiao Bie. A review on ZnO-based S-scheme heterojunction photocatalysts [J]. Chinese Journal of Catalysis, 2023, 52(9): 32-49.
[2]	Bowen Liu, Jiajie Cai, Jianjun Zhang, Haiyan Tan, Bei Cheng, Jingsan Xu. Simultaneous benzyl alcohol oxidation and H₂ generation over MOF/CdS S-scheme photocatalysts and mechanism study [J]. Chinese Journal of Catalysis, 2023, 51(8): 204-215.
[3]	Xuan Li, Xingxing Jiang, Yan Kong, Jianju Sun, Qi Hu, Xiaoyan Chai, Hengpan Yang, Chuanxin He. Interface engineering of a GaN/In₂O₃ heterostructure for highly efficient electrocatalytic CO₂ reduction to formate [J]. Chinese Journal of Catalysis, 2023, 50(7): 314-323.
[4]	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.
[5]	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.
[6]	Jinman Yang, Xingwang Zhu, Qing Yu, Minqiang He, Wei Zhang, Zhao Mo, Junjie Yuan, Yuanbin She, Hui Xu, Huaming Li. Multidimensional In₂O₃/In₂S₃ heterojunction with lattice distortion for CO₂ photoconversion [J]. Chinese Journal of Catalysis, 2022, 43(5): 1286-1294.
[7]	Jing-Yu Li, Ming-Yu Qi, Yi-Jun Xu. Efficient splitting of alcohols into hydrogen and C-C coupled products over ultrathin Ni-doped ZnIn₂S₄ nanosheet photocatalyst [J]. Chinese Journal of Catalysis, 2022, 43(4): 1084-1091.
[8]	Hui Yang, Jin feng Zhang, Kai Dai. Organic amine surface modified one-dimensional CdSe_0.8S_0.2-diethylenetriamine/two-dimensional SnNb₂O₆ S-scheme heterojunction with promoted visible-light-driven photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2022, 43(2): 255-264.
[9]	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.
[10]	Jie Jiang, Guohong Wang, Yanchi Shao, Juan Wang, Shuang Zhou, Yaorong Su. Step-scheme ZnO@ZnS hollow microspheres for improved photocatalytic H₂ production performance [J]. Chinese Journal of Catalysis, 2022, 43(2): 329-338.
[11]	Mengyu Zhao, Sen Liu, Daimei Chen, Sushu Zhang, Sónia A. C. Carabineiro, Kangle Lv. A novel S-scheme 3D ZnIn₂S₄/WO₃ heterostructure for improved hydrogen production under visible light irradiation [J]. Chinese Journal of Catalysis, 2022, 43(10): 2615-2624.
[12]	Lele Wang, Tao Yang, Lijie Peng, Qiqi Zhang, Xilin She, Hua Tang, Qinqin Liu. Dual transfer channels of photo-carriers in 2D/2D/2D sandwich-like ZnIn₂S₄/g-C₃N₄/Ti₃C₂ MXene S-scheme/Schottky heterojunction for boosting photocatalytic H₂ evolution [J]. Chinese Journal of Catalysis, 2022, 43(10): 2720-2731.
[13]	Lizhong Liu, Taiping Hu, Kai Dai, Jinfeng Zhang, Changhao Liang. A novel step-scheme BiVO₄/Ag₃VO₄ photocatalyst for enhanced photocatalytic degradation activity under visible light irradiation [J]. Chinese Journal of Catalysis, 2021, 42(1): 46-55.
[14]	Juan Wang, Guohong Wang, Bei Cheng, Jiaguo Yu, Jiajie Fan. Sulfur-doped g-C₃N₄/TiO₂ S-scheme heterojunction photocatalyst for Congo Red photodegradation [J]. Chinese Journal of Catalysis, 2021, 42(1): 56-68.
[15]	Kai Zhu, Jie Ou-Yang, Qian Zeng, Sugang Meng, Wei Teng, Yanhua Song, Sheng Tang, Yanjuan Cui. Fabrication of hierarchical ZnIn₂S₄@CNO nanosheets for photocatalytic hydrogen production and CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2020, 41(3): 454-463.