Hydrothermal synthesis of monoclinic WO3 and its photocatalytic hydrogen production performance
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摘要: 利用水热合成法，以钨酸钠为钨源，硝酸为酸源，柠檬酸与酒石酸为辅助剂，制备了单斜相且形貌规整的WO3。对WO3样品进行了X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）及紫外可见漫反射（UV-vis-DR）分析，测试了样品的BET比表面积，考察了硝酸与钨原子物质的量比，柠檬酸、酒石酸与钨原子物质的量比对样品晶相与形貌的影响。结果表明，大量硝酸及羟基酸的加入都有利于WO3单斜相的形成，当硝酸与钨原子的物质的量比为2.8:1，羟基酸与钨原子的物质的量比为0.8:1时，能够制得单斜相、形貌规整的WO3样品。将WO3与p型半导体物质CuCrO2复合得到CuCrO2-WO3复合催化剂用于光催化分解水产氢的实验，高结晶度的单斜相WO3具有较好的光催化性能。Abstract: 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.
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Key words:
- hydrothermal method /
- WO3 /
- crystal structure /
- photocatalysis /
- hydrogen production
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图 1 不同nN:nW条件下制得WO3样品的XRD谱图
Figure 1 XRD patterns of WO3 prepared with different molar ratio of nitric acid to tungsten atom
nN:nW: a: 2.0:1; b: 2.8:1; c: 5.8:1; d: 10.0:1; e: 15.0:1; f: 20.0:1
图 2 不同nN:nW条件下制得WO3的SEM照片
Figure 2 SEM images of WO3 prepared with different molar ratio of nitric acid to tungsten atom
nN:nW: (a): 2.8:1; (b): 10:1; (c): 15:1; (d): 20:1
图 3 不同nN:nW条件下制得WO3样品的XRD谱图
Figure 3 XRD patterns of WO3 prepared with different molar ratio of nitric acid to tungsten atom
nN:nW: a: 1.6:1; b: 2.0:1; c: 2.4:1; d: 2.8:1; e: 3.2:1
图 4 不同nN:nW条件下制得WO3的SEM照片
Figure 4 SEM images of WO3 prepared with different molar ratio of nitric acid to tungsten atom
nN:nW: (a): 1.6:1; (b): 2.0:1; (c): 2.8:1; (d): 3.2:1
图 5 不同nN:nW条件下制得WO3样品的XRD谱图
Figure 5 XRD patterns of WO3 prepared with different molar ratio of nitric acid to tungsten atom
nN:nW: a: 2.0:1; b: 2.4:1; c: 2.8:1; d: 3.2:1
图 6 不同nN:nW条件下制得WO3的SEM照片
Figure 6 SEM images of WO3 prepared with different molar ratio of nitric acid to tungsten atom
nN:nW: (a): 2.0:1; (b): 2.8:1; (c): 3.2:1
图 7 不同nC:nW条件下制得WO3样品的XRD谱图
Figure 7 XRD patterns of WO3 prepared with different molar ratio of citric acid to tungsten atom
nC:nW: a: 0.2:1; b: 0.4:1; c: 0.8:1; d: 1.2:1
图 8 不同nC:nW条件下制得WO3样品的SEM照片
Figure 8 SEM images of WO3 prepared with different molar ratio of citric acid to tungsten atom
nC:nW: (a): 0.2:1; (b): 0.8:1; (c): 1.2:1
图 9 nC:nW=0.8:1条件下制得WO3样品的TEM照片
Figure 9 TEM images of WO3 prepared with molar ratio of citric acid to tungsten atom of 0.8:1
图 10 不同nT:nW条件下制得WO3的XRD谱图
Figure 10 XRD patterns of WO3 prepared with different molar ratio of tartaric acid to tungsten atom
nT:nW: a: 0.2:1; b: 0.4:1; c: 0.8:1; d: 1.2:1
图 11 不同nT:nW条件下制得WO3样品的SEM照片
Figure 11 SEM images of WO3 prepared with different molar ratio of tartaric acid to tungsten atom
nT:nW: (a): 0.4:1; (b): 0.8:1; (c): 1.2:1
图 12 nN:nW =2.8:1，nT:nW =0.8:1条件下制得WO3样品的TEM照片
Figure 12 TEM images of WO3 prepared with molar ratio of tartaric acid to tungsten atom of 0.8:1 and nitric acid to tungsten atom of 2.8:1
图 14 样品C2、C2c与T2、T2c的UV-vis-DR谱图
Figure 14 UV-vis-DR spectra of samples C2, C2c and T2, T2c
表 1 不同条件下制得的WO3的性能及其与CuCrO2复合后CuCrO2-WO3的光催化活性
Table 1 Photocatalytic activity of the CuCrO2-WO3 catalysts using WO3 prepared at different conditions
No System nN/nW nC/nW
(nT/nW)Treatment condition ABET/
(m2·g-1)Crystalline phases Amount of hydrogen/μmol mercury lamp xenon lamp S1 W+N 10:1 0 - 33.6007 O+H+M 8.2 - S1c W+N 10:1 0 500 ℃, 2 h 3.8621 M 42.5 - S2 W+N 20:1 0 - 10.0510 M 14.5 - S2c W+N 20:1 0 500 ℃, 2 h 7.5436 M 76.3 2.8 C1 W+N+C 2.8:1 0.2:1 - 30.6146 O+M 5.5 - C1c W+N+C 2.8:1 0.2:1 500 ℃, 2 h 4.4787 M 82.8 1.2 C2 W+N+C 2.8:1 0.8:1 - 8.9656 M 30.8 - C2c W+N+C 2.8:1 0.8:1 500 ℃, 2 h 4.2363 M 108.6 5.0 T1 W+N+T 2.8:1 0.2:1 - 32.7801 O+M 13.4 - T1c W+N+T 2.8:1 0.2:1 500 ℃, 2 h 4.5723 M 68.4 - T2 W+N+T 2.8:1 0.8:1 - 11.8887 M 28.6 - T2c W+N+T 2.8:1 0.8:1 500 ℃, 2 h 3.5759 M 100.9 4.6 W-sodium tungstate; N-nitric acid; C-citric acid; T-tartaric acid; O-orthorhombic; H-hexagonal; M-monoclinic 
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