Citation: YANG Huan, WANG Gui-yun, TIAN Wei-song, TONG Chun-jie. Hydrothermal synthesis of monoclinic WO₃ and its photocatalytic hydrogen production performance[J]. Journal of Fuel Chemistry and Technology, ;2018, 46(11): 1359-1369. shu

Hydrothermal synthesis of monoclinic WO₃ and its photocatalytic hydrogen production performance

Hebei Provincial Key Laboratory of Green Chemical Technology & High Efficiency Energy Saving, Hebei University of Technology, Tianjin 300130, China

Corresponding author: WANG Gui-yun, wgy1964@hebut.edu.cn
Received Date: 17 July 2018
Revised Date: 16 September 2018

Fund Project: National Natural Science Foundation of Hebei Province B2014202004The project was supported by the National Natural Science Foundation of China (21076058) and National Natural Science Foundation of Hebei Province (B2014202004)the National Natural Science Foundation of China 21076058

Figures(15)

Monoclinic WO₃ was successfully synthesized by the hydrothermal method using sodium tungstate as tungsten source, nitric acid as acid source, and citric acid (tartaric acid) as surfactant. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet-visible diffuse reflectance (UV-vis-DR), and Brunner-Emmet-Teller (BET) were employed to characterize the structure and morphology of WO₃. The effects of molar ratios of nitric acid and citric acid (tartaric acid) to tungsten atoms on crystal phases and morphologies of WO₃ were investigated in detail. The results indicated that large amounts of nitric acid and addition of hydroxyl acids were found favorable for the formation of monoclinic WO₃. Monoclinic WO₃ was achieved under suitable conditions of molar ratios of nitric acid to tungsten atom of 2.8:1 and hydroxyl acids to tungsten atom of 0.8:1. The WO₃ was coupled with p-type semiconductor CuCrO₂ to fabricate the CuCrO₂-WO₃ composite photocatalyst. It was used for hydrogen production from photocatalytic decomposition of water. The monoclinic WO₃ with high crystalline perfection exhibited better photocatalytic properties.
- hydrothermal method,
- WO₃,
- crystal structure,
- photocatalysis,
- hydrogen production
1. [1]
  LI N, ZHAO Y, WANG Y, LU Y, SONG Y H, HUANG Z F, LI Y W, ZHAO J Z. Aqueous synthesis and visible-light photochromism of metastable h-WO₃ hierarchical nanostructures[J]. Eur J Inorg Chem, 2015,17:2804-2812.
2. [2]
  HUANG R, SHEN Y, ZHAO L, YAN M Y. Effect of hydrothermal temperature on structure and photochromic properties of WO₃ powder[J]. Adv Powder Technol, 2012,23:211-214. doi: 10.1016/j.apt.2011.02.009
3. [3]
  SONG Jing-jing, WANG Ping-ping, YAN Hui, ZHANG Xian-feng, LI Qian. Influence of malic acid dosage on structure and photochromic properties of WO₃ nano-powders[J]. J Chin Ceram Soc, 2016,44(7):976-980.
4. [4]
  JIAO Z H, WANG J M, LIN K, LIU X W, DEMIR H V, YANG M F, SUN X W. Electrochromic properties of nanostructured tungsten trioxide (hydrate) films and their applications in a complementary electrochromic device[J]. Electrochim Acta, 2012,63:153-160. doi: 10.1016/j.electacta.2011.12.069
5. [5]
  ZHENG F, MAN W K, GUO M, ZHANG M, ZHEN Q. Effects of morphology, size and crystallinity on the electrochromic properties of nanostructured WO₃ films[J]. Cryst Eng Comm, 2015,17:5440-5450. doi: 10.1039/C5CE00832H
6. [6]
  PENG Ming-dong, ZHANG Yu-zhi, SONG Li-xin, YIN Xiao-fu, WANG Pan-pan, WU Ling-nan, HU Xing-fang. Structure and electrochromic properties of titanium-doped WO₃ thin film by sputtering[J]. J Inorg Mater, 2017,32(3):287-292.
7. [7]
  TAKÁCS M, DÜCSÖ C, LÁBADI Z, PAP A E. Effect of hexagonal WO₃ morphology on NH₃ sensing[J]. Procedia Eng, 2014,87:1011-1014. doi: 10.1016/j.proeng.2014.11.331
8. [8]
  MIAO B, ZENG W, MU Y J, YU W J, HUSSAIN S, XU S B, ZHANG H, LI T M. Controlled synthesis of monodisperse WO₃·H₂O square nanoplates and their gas sensing properties[J]. Appl Surf Sci, 2015,349:380-386. doi: 10.1016/j.apsusc.2015.04.226
9. [9]
  CAO S X, ZHAO C, HAN T, PENG L L. Hydrothermal synthesis, characterization and gas sensing properties of the WO₃ nanofibers[J]. Mater Lett, 2016,169:17-20. doi: 10.1016/j.matlet.2016.01.053
10. [10]
  LUO Jian-yi, ZHANG Yu, CHEN Xue-xian, LI Wei-da, DENG Wei-yuan, ZHOU Yang-yang. Study on the sensing property of Pt coated WO₃ nanowire film for high concentration of H₂ gas[J]. J Synth Cryst, 2013,42(10):2109-2120. doi: 10.3969/j.issn.1000-985X.2013.10.026
11. [11]
  CHEN D, YE J H. Hierarchical WO₃ hollow shells:Dendrite, sphere, dumbbell, and their photocatalytic properties[J]. Adv Funct Mater, 2010,18:1922-1928.
12. [12]
  XIE Y P, LIU G, YIN L C, CHENG H M. Crystal facet-dependent photocatalytic oxidation and reduction reactivity of monoclinic WO₃ for solar energy conversion[J]. J Mater Chem, 2012,22:6746-6751. doi: 10.1039/c2jm16178h
13. [13]
  BATHE S R, PATIL P S. Electrochromic characteristics of pulsed spray pyrolyzed polycrystalline WO₃ thin films[J]. Smart Mater Struct, 2009,18:1-7.
14. [14]
  GUERY C, CHOQUET C, DUJEANCOURT F, TARASCON J C, LASSEGUES J C. Infrared and X-ray studies of hydrogen intercalation in different tungsten trioxides and tungsten trioxide hydrates[J]. J Solid State Electrochem, 1997,1:199-207. doi: 10.1007/s100080050049
15. [15]
  CHEN D L, WANG H L, ZHANG R, GAO L, SUGAHARAC Y. YASUMORI A.. Single-crystalline tungsten oxide nanoplates[J]. J Ceram Process Res, 2008,9:596-600.
16. [16]
  CHEN D L, GAO L, YASUMORI A, KURODA K, SUGAHARA Y. Size-and shape-controlled conversion of tungstate-based inorganic-organic hybrid belts to WO₃ nanoplates with high specific surface areas[J]. Small, 2008,4:1813-1822. doi: 10.1002/smll.v4:10
17. [17]
  LI X X, ZHANG G Y, CHENG F Y, GUO B. CHEN J.. Synthesis, characterization, and gas-sensor application of WO₃ nanocuboids[J]. J Electrochem Soc, 2006,153:133-137.
18. [18]
  CHEN Q P, LI J H, ZHOU B X, LONG M C, CHEN H C, LIU Y B, CAI W M, SHANGGUAN W F. Preparation of well-aligned WO₃ nanoflake arrays vertically grown on tungsten substrate as photoanode for photoelectrochemical water splitting[J]. Electrochem Commun, 2012,20:153-156. doi: 10.1016/j.elecom.2012.03.043
19. [19]
  XIN G, GUO W, MA T L. Effect of annealing temperature on the photocatalytic activity of WO₃ for O₂ evolution[J]. Appl Surf Sci, 2009,256:165-169. doi: 10.1016/j.apsusc.2009.07.102
20. [20]
  ZHANG H L, YANG J Q, LI D, GUO W, QIN Q, ZHU L J, ZHENG W J. Template-free facile preparation of monoclinic WO₃ nanoplates and their high photocatalytic activities[J]. Appl Surf Sci, 2014,305:274-280. doi: 10.1016/j.apsusc.2014.03.061
21. [21]
  ZHU W Y, LIU J C, YU S Y, ZHOU Y, YAN X L. Ag loaded WO₃ nanoplates for efficient photocatalytic degradation of sulfanilamide and their bactericidal effect under visible light irradiation[J]. J Hazard Mater, 2016,318:407-416. doi: 10.1016/j.jhazmat.2016.06.066
22. [22]
  DIRANY N, ARAB M, LEROUX C, VILLAIN S, MADIGOU V, GAVARRI J R. Effect of WO₃ nanoparticles morphology on the catalytic properties[J]. Mater Today:Proc, 2016,3:230-234. doi: 10.1016/j.matpr.2016.01.062
23. [23]
  ZHOU J C, LIN S W, CHEN Y J, GASKOV A M. Facile morphology control of WO₃ nanostructure arrays with enhanced photoelectrochemical performance[J]. Appl Surf Sci, 2017,403:274-281. doi: 10.1016/j.apsusc.2017.01.209
24. [24]
  ZHANG R K, NING F Y, LEI S X, ZHOU L, SHAO M F, WEI M. Oxygen vacancy engineering of WO₃ toward largely enhanced photoelectrochemical water splitting[J]. Electrochim Acta, 2018,274:217-223. doi: 10.1016/j.electacta.2018.04.109
25. [25]
  ARIENZO M D, ARMELAO L, MARI C M, POLIZZI S, RUFFO R, SCOTTI R, MORAZZONI F. Surface interaction of WO₃ nanocrystals with NH₃ role of the exposed crystal surfaces and porous structure in enhancing the electrical response[J]. RSC Adv, 2014,4:11012-11022. doi: 10.1039/c3ra46726k
26. [26]
  ZHANG H L, LIU Z F, Yang J Q, GUO W, ZHU L J, ZHENG W J. Temperature and acidity effects on WO₃ nanostructures and gas-sensing properties of WO₃ nanoplates[J]. Mater Res Bull, 2014,57:260-267. doi: 10.1016/j.materresbull.2014.06.013
27. [27]
  WANG J M, KHOO E, LEE P S, MA J. Controlled synthesis of WO₃ nanorods and their electrochromic properties in H₂SO₄ electrolyte[J]. J Phys Chem C, 2009,113:9655-9658. doi: 10.1021/jp901650v
28. [28]
  JARUPAT S, TITIPUN T, SOMCHAI T. Large-scale synthesis of WO₃ nanoplates by a microwave-hydrothermal method[J]. Ceram Int, 2012,38:1051-1055. doi: 10.1016/j.ceramint.2011.08.030
29. [29]
  SU X T, XIAO F, LI Y N, JIAN J K, SUN Q J, WANG J D. Synthesis of uniform WO₃ square nanoplates via an organic acid-assisted hydrothermal process[J]. Mater Lett, 2010,64:1232-1234. doi: 10.1016/j.matlet.2010.02.063
30. [30]
  ZHANG H, ZHAO H, JIANG Y Q, HOU S Y, ZHOU Z H, WAN H L. pH-and mol-ratio dependent tungsten(Ⅵ)/citrate speciation from aqueous solutions:syntheses, spectroscopic properties and crystal structures[J]. Inorg Chim Acta, 2003,351:311-318. doi: 10.1016/S0020-1693(03)00177-4
1. [1]
  Shuang Cao , Bo Zhong , Chuanbiao Bie , Bei Cheng , Feiyan Xu . Insights into Photocatalytic Mechanism of H₂ Production Integrated with Organic Transformation over WO₃/Zn_0.5Cd_0.5S S-Scheme Heterojunction. Acta Physico-Chimica Sinica, 2024, 40(5): 2307016-0. doi: 10.3866/PKU.WHXB202307016
2. [2]
  Wenjun Zhu , Jin Shi , Yong Zhang , Panpan Yan , Meng Li , Chuanbiao Bie . Interfacial electron transfer in WO₃/In₂S₃ S-scheme heterojunctions via W−S bonds for enhanced photocatalytic H₂O₂ production. Acta Physico-Chimica Sinica, 2026, 42(11): 100357-0. doi: 10.1016/j.actphy.2026.100357
3. [3]
  Haitao Wang , Lianglang Yu , Jizhou Jiang , Arramel , Jing Zou . S-Doping of the N-Sites of g-C₃N₄ to Enhance Photocatalytic H₂ Evolution Activity. Acta Physico-Chimica Sinica, 2024, 40(5): 2305047-0. doi: 10.3866/PKU.WHXB202305047
4. [4]
  Jiawei Hu , Kai Xia , Ao Yang , Zhihao Zhang , Wen Xiao , Chao Liu , Qinfang Zhang . Interfacial Engineering of Ultrathin 2D/2D NiPS₃/C₃N₅ Heterojunctions for Boosting Photocatalytic H₂ Evolution. Acta Physico-Chimica Sinica, 2024, 40(5): 2305043-0. doi: 10.3866/PKU.WHXB202305043
5. [5]
  Chenye An , Sikandaier Abiduweili , Xue Guo , Yukun Zhu , Hua Tang , Dongjiang Yang . Hierarchical S-scheme Heterojunction of Red Phosphorus Nanoparticles Embedded Flower-like CeO₂ Triggering Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(11): 2405019-0. doi: 10.3866/PKU.WHXB202405019
6. [6]
  Jiajie Cai , Chang Cheng , Bowen Liu , Jianjun Zhang , Chuanjia Jiang , Bei Cheng . CdS/DBTSO-BDTO S-scheme photocatalyst for H₂ production and its charge transfer dynamics. Acta Physico-Chimica Sinica, 2025, 41(8): 100084-0. doi: 10.1016/j.actphy.2025.100084
7. [7]
  Yahui HAN , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395
8. [8]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . Construction of 4-Amino-1H-imidazole-5-carbonitrile Modified Carbon Nitride-Based Donor-Acceptor Photocatalyst for Efficient Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-0. doi: 10.3866/PKU.WHXB202406026
9. [9]
  Chengxiao Zhao , Zhaolin Li , Dongfang Wu , Xiaofei Yang . SBA-15 templated covalent triazine frameworks for boosted photocatalytic hydrogen production. Acta Physico-Chimica Sinica, 2026, 42(1): 100149-0. doi: 10.1016/j.actphy.2025.100149
10. [10]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
11. [11]
  Ze Luo , Yukun Zhu , Yadan Luo , Guangmin Ren , Yonghong Wang , Hua Tang . Photocatalytic selective oxidation of 5-hydroxymethylfurfural coupled with H₂ evolution over In₂O₃/ZnIn₂S₄ S-scheme heterojunction. Acta Physico-Chimica Sinica, 2026, 42(3): 100166-0. doi: 10.1016/j.actphy.2025.100166
12. [12]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
13. [13]
  Sumiya Akter Dristy , Md Ahasan Habib , Shusen Lin , Mehedi Hasan Joni , Rutuja Mandavkar , Young-Uk Chung , Md Najibullah , Jihoon Lee . Exploring Zn doped NiBP microspheres as efficient and stable electrocatalyst for industrial-scale water splitting. Acta Physico-Chimica Sinica, 2025, 41(7): 100079-0. doi: 10.1016/j.actphy.2025.100079
14. [14]
  Qinghong Cai , Xingyan Liu , Yuhan Li , Youzhou He , Xianyan Xu , Jia Zeng , Siping Wei . Strong built-in electric field promoted by π–π stacking charge-transfer channels in HOFs/MOFs S-scheme heterojunction for boosting photocatalytic H₂ or H₂O₂ production. Acta Physico-Chimica Sinica, 2026, 42(11): 100329-0. doi: 10.1016/j.actphy.2026.100329
15. [15]
  Peipei Sun , Jinyuan Zhang , Yanhua Song , Zhao Mo , Zhigang Chen , Hui Xu . Built-in Electric Fields Enhancing Photocarrier Separation and H₂ Evolution. Acta Physico-Chimica Sinica, 2024, 40(11): 2311001-0. doi: 10.3866/PKU.WHXB202311001
16. [16]
  Ke Li , Chuang Liu , Jingping Li , Guohong Wang , Kai Wang . Architecting Inorganic/Organic S-Scheme Heterojunction of Bi₄Ti₃O₁₂ Coupling with g-C₃N₄ for Photocatalytic H₂O₂ Production from Pure Water. Acta Physico-Chimica Sinica, 2024, 40(11): 2403009-0. doi: 10.3866/PKU.WHXB202403009
17. [17]
  Linfeng Xiao , Wanlu Ren , Shishi Shen , Mengshan Chen , Runhua Liao , Yingtang Zhou , Xibao Li . Enhancing Photocatalytic Hydrogen Evolution through Electronic Structure and Wettability Adjustment of ZnIn₂S₄/Bi₂O₃ S-Scheme Heterojunction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308036-0. doi: 10.3866/PKU.WHXB202308036
18. [18]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . Designing thermodynamically stable noble metal single-atom photocatalysts for highly efficient non-oxidative conversion of ethanol into high-purity hydrogen and value-added acetaldehyde. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-0. doi: 10.1016/j.actphy.2025.100067
19. [19]
  Xi YANG , Chunxiang CHANG , Yingpeng XIE , Yang LI , Yuhui CHEN , Borao WANG , Ludong YI , Zhonghao HAN . Co-catalyst Ni₃N supported Al-doped SrTiO₃: Synthesis and application to hydrogen evolution from photocatalytic water splitting. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 440-452. doi: 10.11862/CJIC.20240371
20. [20]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(1752)
HTML views(224)

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

Hydrothermal synthesis of monoclinic WO3 and its photocatalytic hydrogen production performance

Metrics

通讯作者: 陈斌, bchen63@163.com

Hydrothermal synthesis of monoclinic WO₃ and its photocatalytic hydrogen production performance