Citation: REN Yumei, XU Qun. Construction of Advanced Two-dimensional Heterostructure Ag/WO_3−x for Enhancing Photoelectrochemical Performance[J]. Acta Physico-Chimica Sinica, ;2019, 35(10): 1157-1164. doi: 10.3866/PKU.WHXB201812054 shu

Construction of Advanced Two-dimensional Heterostructure Ag/WO_3−x for Enhancing Photoelectrochemical Performance

REN Yumei ,
XU Qun ^,

College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China

Corresponding author: XU Qun, qunxu@zzu.edu.cn
Received Date: 30 December 2018
Revised Date: 24 January 2019
Accepted Date: 28 January 2019
Available Online: 20 October 2019
Fund Project: The project was supported by the National Natural Science Foundation of China 21571157The project was supported by the National Natural Science Foundation of China (21773216, 51173170, 21571157) and the Innovation Talents Award of Henan Province, China (114200510019)Innovation Talents Award of Henan Province, China 114200510019The project was supported by the National Natural Science Foundation of China 21773216The project was supported by the National Natural Science Foundation of China 51173170

Solar energy, which is clean, affordable and reliable, can help alleviate the current environmental pollution and energy crisis efficiently. In the past few decades, great progress has been made in harvesting and converting solar energy into chemical energy. Among various technologies, plasmon-induced photoelectrochemistry has been proposed as a promising alternative for solar energy conversion. The hot electrons generated from plasmon excitation and transfer from metal nanostructures to semiconductors is a potential new paradigm for solar energy conversion. However, the ultrafast decay of the hot carriers is unfavorable for the improvement of photocatalytic efficiency. Therefore, finding more efficient photocatalysts, with enhanced light absorption and a longer carrier lifetime, is of paramount importance for improving the conversion efficiency of solar energy, but their fabrication is challenging. In this work, a plasmonic metal/semiconductor heterostructure based on Ag nanoparticles embedded in two-dimensional (2D) amorphous sub-stoichiometric tungsten trioxide (a-WO_3−x), followed by annealing, was successfully fabricated. Firstly, the peculiar nanostructure of 2D a-WO_3−x was successfully constructed from WS₂ nanosheets with supercritical CO₂ (SC CO₂) at 200 ℃. Secondly, the Ag/a-WO_3−x heterostructure was synthesized using an in situ reduction method. Finally, the obtained 2D heterostructure of Ag/WO_3−x was annealed at 400 ℃ in N₂ to further improve its stability and conductivity. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure, morphology, and composition of the material, respectively. UV-Vis spectra were also measured to evaluate light adsorption. Characterization results show that the amorphous structure can effectively anchor metal nanoparticles, and the metal nanoparticles are uniformly dispersed in the amorphous region and have a small size. The as-prepared nanocomposites showed efficient photoelectrochemical (PEC) water splitting when serving as photoelectrode materials, and efficient PEC activity towards photo-oxidation degradation currents under excitation of Ag localized surface plasmon resonance (LSPR). The photocurrent response of the Ag/WO_3−x heterostructure was approximately five times greater than that of a-WO_3−x. Moreover, the PEC degradation efficiency of Ag/WO_3−x reached 96.7% for MO under Vis light illumination (after reaction for 120 min), while the PEC degradation efficiency of WO_3−x was only 63.6%. The high PEC performance of the composite photoanode can be ascribed to the local surface plasmon resonance (LSPR) effect of the Ag nanoparticles, which can enhance the light absorption and hot electron transformation. Moreover, the construction of local crystalline-amorphous interfaces can further promote the separation efficiency of the photogenerated electron-hole pairs, and thus increase conductivity. This work provides a positive strategy for the fabrication of advanced photocatalysts, and a new perspective on understanding of the synergistic effects of structural and electronic regulations.
- Two-dimensional material,
- Plasmonic metal/semiconductor heterostructure,
- PEC conversion
1. [1]
  Wang, F, F.; Li, Q., Xu, D. S. Adv. Energy Mater. 2017, 7 (23), 1700529. doi: 10.1002/aenm.201700529 doi: 10.1002/aenm.201700529
2. [2]
  Wu, N. Q. Nanoscale 2018, 10, 2679. doi: 10.1039/C7NR08487K doi: 10.1039/C7NR08487K
3. [3]
  Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q.; Santori, E. A.; Lewis, N. S. Chem. Rev. 2010, 110 (11), 6446. doi: 10.1021/cr1002326 doi: 10.1021/cr1002326
4. [4]
  Li, J. T.; Wu, N. Q. Catal. Sci. Tech. 2015, 5, 1360. doi: 10.1039/C4CY00974F doi: 10.1039/C4CY00974F
5. [5]
  Xia, H. C.; Xu, Q.; Zhang, J. N. Nano Micro Lett. 2018, 10 (4), 66. doi: 10.1007/s40820-018-0219-z doi: 10.1007/s40820-018-0219-z
6. [6]
  Chen, X. B.; Shen, S. H.; Guo, L. J.; Mao, S. S. Chem. Rev. 2010, 110 (11), 6503. doi: 10.1021/cr1001645 doi: 10.1021/cr1001645
7. [7]
  Vuong, N. M.; Kim, D.; Kim, H. Sci. Rep. 2015, 5, 11040. doi: 10.1038/srep11040 doi: 10.1038/srep11040
8. [8]
  Kong, Y. Q.; Sun, H. G.; Fan, W. L.; Wang, L.; Zhao, H. K.; Zhao, X.; Yuan, S. Z. RSC Adv. 2017, 7, 15201. doi: 10.1039/c7ra01426k doi: 10.1039/c7ra01426k
9. [9]
  Ling, C. Y.; Wang, J. L. Acta Phys.-Chim. Sin. 2017, 33 (5), 869.[ doi: 10.3866/PKU.WHXB201702088
10. [10]
  Shang, Y.; Chen, Y.; Shi, Z. B.; Zhang, D. F.; Guo, L. Acta Phys.-Chim. Sin. 2013, 29 (8), 1819.[ doi: 10.3866/PKU.WHXB201305281
11. [11]
  Cushing, S. K.; Wu, N. J. Phys. Chem. Lett. 2016, 7 (4), 666. doi: 10.1021/acs.jpclett.5b02393 doi: 10.1021/acs.jpclett.5b02393
12. [12]
  Zhang, Y. C.; He, S.; Guo, W. X.; Hu, Y.; Huang, J. W.; Mulcahy, J. R.; Wei, W. D. Chem. Rev. 2018, 118 (6), 2927. doi: 10.1021/acs.chemrev.7b00430 doi: 10.1021/acs.chemrev.7b00430
13. [13]
  Clavero, C. Nat. Photonics 2014, 8, 95. doi: 10.1038/NPHOTON.2013.238 doi: 10.1038/NPHOTON.2013.238
14. [14]
  Tian, Y.; Tatsuma, T. J. Am. Chem. Soc. 2005, 127 (20), 7632. doi: 10.1021/ja042192u doi: 10.1021/ja042192u
15. [15]
  Naseri, N.; Qorbani, M.; Kim, H.; Choi, W.; Moshfegh, A. Z. J. Phys. Chem. C 2015, 119 (3), 1271. doi: 10.1021/jp507988c doi: 10.1021/jp507988c
16. [16]
  Du, X. H.; L. Y.; Y. H.; Xiang, Q. J. Acta Phys.-Chim. Sin. 2018, 34 (4), 414.[ doi: 10.3866/PKU.WHXB201708283
17. [17]
  Nie, L. H.; Hu Y.; Zhang, W. X. Acta Phys.-Chim. Sin. 2012, 28 (1), 154.[ doi: 10.3866/PKU.WHXB201228154
18. [18]
  Xia, H. C.; Zhang, J. N.; Chen, Z. M.; Xu, Q. Appl. Surf. Sci. 2018, 440, 91. doi: 10.1016/j.apsusc.2017.12.263. doi: 10.1016/j.apsusc.2017.12.263
19. [19]
  Xia, H. C.; Zhang, J. N.; Yang, Z.; Guo, S. Y.; Guo, S. H.; Xu, Q. Nano Micro Lett. 2017, 9 (4), 43. doi: 10.1007/s40820-017-0144-6 doi: 10.1007/s40820-017-0144-6
20. [20]
  Tian, Y.; Tatsuma, T. Chem. Commun. 2004, 1810. doi: 10.1039/B405061D doi: 10.1039/B405061D
21. [21]
  Tian, Y.; Tatsuma, T. J. Am. Chem. Soc. 2005, 127 (20), 7632. doi: 10.1021/ja042192u doi: 10.1021/ja042192u
22. [22]
  Lee, S. H.; Lee, S. W.; Oh, T.; Petrosko, S. H.; Mirkin, C. A.; Jang, J. W. Nano Lett. 2018, 18 (1), 109. doi: 10.1021/acs.nanolett.7b03540 doi: 10.1021/acs.nanolett.7b03540
23. [23]
  Li, J.; Cushing, S. K.; Chu, D.; Zheng, P.; Bright, J.; Castle, C.; Manivannan, A.; Wu, N. J. Mater. Res. 2016, 31 (11), 1608. doi: 10.1557/jmr.2016.102 doi: 10.1557/jmr.2016.102
24. [24]
  Ren, Y. M.; Li, C.; Xu, Q.; Yan, J.; Li, Y. Z.; Yuan, P. F.; Xia, H. C.; Niu, C. Y.; Yang, X. A.; Jia, Y. Appl. Catal. B: Environ. 2019, 245, 648. doi: 10.1016/j.apcatb.2019.01.015 doi: 10.1016/j.apcatb.2019.01.015
25. [25]
  Ren, Y. M.; Xu, Q. Energ. Environ. Mater. 2018, 1 (2), 46. doi: 10.1016/j.apcatb.2019.01.015 doi: 10.1016/j.apcatb.2019.01.015
26. [26]
  Ren, Y. M.; Wang, C. Z.; Qi, Y. H.; Chen, Z. M.; Jia, Y.; Xu, Q. Appl. Surf. Sci. 2017, 419, 573. doi: 10.1016/j.apsusc.2017.05.058 doi: 10.1016/j.apsusc.2017.05.058
27. [27]
  Wang, N.; Xu, Q.; Xu, S. S.; Qi, Y. H.; Chen, M.; Li, H. X.; Han, B. X. Sci. Rep. 2015, 5, 16764. doi: 10.1038/srep16764 doi: 10.1038/srep16764
28. [28]
  Ren, Y. M.; Xu, Q.; Zheng, X. L.; Fu, Y. Z.; Wang, Z.; Chen, H. L.; Weng, Y. X.; Zhou, Y. C. Appl. Catal. B: Environ. 2018, 231, 381. doi: 10.1016/j.apcatb.2018.03.040 doi: 10.1016/j.apcatb.2018.03.040
29. [29]
  Wang, Y. L.; Cui, X. B.; Yang, Q. Y.; Liu, J.; Gao, Y.; Sun, P.; Lu, G. Y. Sensor. Actuat. B 2016, 225, 544. doi: 10.1016/j.snb.2015.11.065 doi: 10.1016/j.snb.2015.11.065
30. [30]
  Chen, F.; Yang, Q.; Li, X. M.; Zeng, G. M.; Wang, D. B.; Niu, C. G.; Zhao, J. W.; An, H. X.; Xie, T.; Deng, Y. C. Appl. Catal. B: Environ. 2017, 200, 330. doi: 10.1016/j.apcatb.2016.07.021 doi: 10.1016/j.apcatb.2016.07.021
31. [31]
  Shi, Y.; Wang, J.; Wang, C.; Zhai, T. T.; Bao, W. J.; Xu, J. J.; Xia, X. H.; Chen, H. Y. J. Am. Chem. Soc. 2015, 137 (23), 7365. doi: 10.1021/jacs.5b01732 doi: 10.1021/jacs.5b01732
32. [32]
  Zafra, M. C.; Lavela, P.; Rasines, G.; Macías, C.; Tirado, J. L.; Ania, C. O. Electrochim. Acta 2014, 135, 208. doi: 10.1016/j.electacta.2014.04.182. doi: 10.1016/j.electacta.2014.04.182
33. [33]
  Lewera, A., Timperman, L., Roguska, A.; Alonso-Vante, N. J. Phys. Chem. C 2011, 115 (41), 20153. doi: 10.1021/jp2068446 doi: 10.1021/jp2068446
34. [34]
  Yin, L.; Chen, D. L.; Feng, M. J.; Ge, L. F.; Yang, D. W.; Song, Z. H.; Fan, B. B.; Zhang, R.; Shao, G. S. RSC Adv. 2015, 5, 328. doi: 10.1039/c4ra10500a doi: 10.1039/c4ra10500a
35. [35]
  Cheng, H. F.; Huang, B. B; Wang, P.; Wang, Z. Y.; Lou, Z. Z.; Wang, J. P.; Qin, X. Y.; Zhang, X. Y.; Dai, Y. Chem. Commun. 2011, 47, 7054. doi: 10.1039/c1cc11525a doi: 10.1039/c1cc11525a
36. [36]
  Dong, P. Y.; Yang, B. R.; Liu, C.; Xu, F. H.; Xi, X. G.; Hou, G. H.; Shao, R. RSC Adv. 2017, 7, 947. doi: 10.1039/c6ra25272a doi: 10.1039/c6ra25272a
37. [37]
  Miyauchi, M. Phys. Chem. Chem. Phys. 2008, 10, 6258. doi: 10.1039/b807426g doi: 10.1039/b807426g
38. [38]
  Wang, Q.; Moser, J. E.; Gra1tzel, M. J. Phys. Chem. B 2005, 109 (31), 14945. doi: 10.1021/jp052768h doi: 10.1021/jp052768h
39. [39]
  Chen, X. Q.; Li, P.; Tong, H.; Kako, T.; Ye, J. H. Sci. Technol. Adv. Mater. 2011, 12, 044604. doi: 10.1088/1468-6996/12/4/044604 doi: 10.1088/1468-6996/12/4/044604
40. [40]
  Pu, Y. C.; Wang, G. M.; Chang, K. D.; Ling, Y. C.; Lin, Y. K.; Fitzmorris, B. C.; Liu, C. M.; Lu, X. L.; Tong, Y. X.; Zhang, J. Z.; et al. Nano Lett. 2013, 13 (8), 3817. doi: 10.1021/nl4018385 doi: 10.1021/nl4018385
41. [41]
  Robatjazi, H.; Bahauddin, S. M.; Doiron, C.; Thomann, I. Nano Lett. 2015, 15 (9), 6155. doi: 10.1021/acs.nanolett.5b02453 doi: 10.1021/acs.nanolett.5b02453
42. [42]
  Xu, F.; Yao, Y. W.; Bai, D. D.; Xu, R. S.; Mei, J. J.; Wu, D. P.; Gao, Z. Y.; Jiang, K. RSC Adv. 2015, 5, 60339. doi: 10.1039/c5ra06241a doi: 10.1039/c5ra06241a
43. [43]
  Hisatomi, T.; Kubota, J.; Domen, K. Chem. Soc. Rev. 2014, 43, 7520. doi: 10.1039/c3cs60378d doi: 10.1039/c3cs60378d
44. [44]
  Chen, H. R.; Shen, K.; Chen, J. Y.; Chen, X. D.; Li; Y. E. J. Mater. Chem. A 2017, 5, 9937. doi: 10.1039/c7ta02184d. doi: 10.1039/c7ta02184d
45. [45]
  Li, D.; Xing, Z. P.; Yu, X. J.; Cheng, X. W. Electrochim. Acta 2015, 170, 182. doi: 10.1016/j.electacta.2015.04.148 doi: 10.1016/j.electacta.2015.04.148
1. [1]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
2. [2]
  Xinghong Cai , Qiang Yang , Yao Tong , Lanyin Liu , Wutang Zhang , Sam Zhang , Min Wang . AlO₂: A novel two-dimensional material with a high negative Poisson's ratio for the adsorption of volatile organic compounds. Chinese Chemical Letters, 2025, 36(2): 109586-. doi: 10.1016/j.cclet.2024.109586
3. [3]
  Muhammad Riaz , Rakesh Kumar Gupta , Di Sun , Mohammad Azam , Ping Cui . Selective adsorption of organic dyes and iodine by a two-dimensional cobalt(II) metal-organic framework. Chinese Journal of Structural Chemistry, 2024, 43(12): 100427-100427. doi: 10.1016/j.cjsc.2024.100427
4. [4]
  Pengyu Dong , Yue Jiang , Zhengchi Yang , Licheng Liu , Gu Li , Xinyang Wen , Zhen Wang , Xinbo Shi , Guofu Zhou , Jun-Ming Liu , Jinwei Gao . NbSe₂纳米片优化钙钛矿太阳能电池的埋底界面. Acta Physico-Chimica Sinica, 2025, 41(3): 2407025-. doi: 10.3866/PKU.WHXB202407025
5. [5]
  Huayan Liu , Yifei Chen , Mengzhao Yang , Jiajun Gu . 二维材料基超级电容器的容量与倍率性能提升策略. Acta Physico-Chimica Sinica, 2025, 41(6): 100063-. doi: 10.1016/j.actphy.2025.100063
6. [6]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127
7. [7]
  Tian Yang , Yi Liu , Lina Hua , Yaoyao Chen , Wuqian Guo , Haojie Xu , Xi Zeng , Changhao Gao , Wenjing Li , Junhua Luo , Zhihua Sun . Lead-free hybrid two-dimensional double perovskite with switchable dielectric phase transition. Chinese Chemical Letters, 2024, 35(6): 108707-. doi: 10.1016/j.cclet.2023.108707
8. [8]
  Zhuoer Cai , Yinan Zhang , Xiu-Ni Hua , Baiwang Sun . Phase transition arising from order-disorder motion in stable layered two-dimensional perovskite. Chinese Journal of Structural Chemistry, 2024, 43(11): 100426-100426. doi: 10.1016/j.cjsc.2024.100426
9. [9]
  Jiahao Li , Guinan Chen , Chunhong Chen , Yuanyuan Lou , Zhihao Xing , Tao Zhang , Chengtao Gong , Yongwu Peng . Modulated synthesis of stoichiometric and sub-stoichiometric two-dimensional covalent organic frameworks for enhanced ethylene purification. Chinese Chemical Letters, 2025, 36(1): 109760-. doi: 10.1016/j.cclet.2024.109760
10. [10]
  Xi Zhou , Shengyao Wang . Dynamic two-dimensional covalent organic frameworks via ‘wine rack' design. Chinese Journal of Structural Chemistry, 2025, 44(4): 100464-100464. doi: 10.1016/j.cjsc.2024.100464
11. [11]
  Zhihong LUO , Yan SHI , Jinyu AN , Deyi ZHENG , Long LI , Quansheng OUYANG , Bin SHI , Jiaojing SHAO . Two-dimensional silica-modified polyethylene oxide solid polymer electrolyte to enhance the performance of lithium-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 1005-1014. doi: 10.11862/CJIC.20230444
12. [12]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
13. [13]
  Xuan Zhu , Lin Zhou , Xiao-Yun Huang , Yan-Ling Luo , Xin Deng , Xin Yan , Yan-Juan Wang , Yan Qin , Yuan-Yuan Tang . (Benzimidazolium)2GeI4: A layered two-dimensional perovskite with dielectric switching and broadband near-infrared photoluminescence. Chinese Journal of Structural Chemistry, 2024, 43(6): 100272-100272. doi: 10.1016/j.cjsc.2024.100272
14. [14]
  Yuting Wu , Haifeng Lv , Xiaojun Wu . Design of two-dimensional porous covalent organic framework semiconductors for visible-light-driven overall water splitting: A theoretical perspective. Chinese Journal of Structural Chemistry, 2024, 43(11): 100375-100375. doi: 10.1016/j.cjsc.2024.100375
15. [15]
  Yan Fan , Jiao Tan , Cuijuan Zou , Xuliang Hu , Xing Feng , Xin-Long Ni . Unprecedented stepwise electron transfer and photocatalysis in supramolecular assembly derived hybrid single-layer two-dimensional nanosheets in water. Chinese Chemical Letters, 2025, 36(4): 110101-. doi: 10.1016/j.cclet.2024.110101
16. [16]
  Yiwen Xu , Chaozheng He , Chenxu Zhao , Ling Fu . Single-atom Ti doping on S-vacancy two-dimensional CrS₂ as a catalyst for ammonia synthesis: A DFT study. Chinese Chemical Letters, 2025, 36(4): 109797-. doi: 10.1016/j.cclet.2024.109797
17. [17]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
18. [18]
  Shenhao QIU , Qingquan XIAO , Huazhu TANG , Quan XIE . First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2250-2258. doi: 10.11862/CJIC.20240104
19. [19]
  Shu-Ran Xu , Fang-Xing Xiao . Metal halide perovskites quantum dots: Synthesis, and modification strategies for solar CO2 conversion. Chinese Journal of Structural Chemistry, 2023, 42(12): 100173-100173. doi: 10.1016/j.cjsc.2023.100173
20. [20]
  Qingyan JIANG , Yanyong SHA , Chen CHEN , Xiaojuan CHEN , Wenlong LIU , Hao HUANG , Hongjiang LIU , Qi LIU . Constructing a one-dimensional Cu-coordination polymer-based cathode material for Li-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 657-668. doi: 10.11862/CJIC.20240004

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(660)
HTML views(58)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Construction of Advanced Two-dimensional Heterostructure Ag/WO3−x for Enhancing Photoelectrochemical Performance

Metrics

通讯作者: 陈斌, bchen63@163.com

Construction of Advanced Two-dimensional Heterostructure Ag/WO_3−x for Enhancing Photoelectrochemical Performance