非金属S掺杂对NaTaO3可见光下光催化性能的影响

doi:10.15541/jim20170252

摘要/Abstract

摘要：

以Ta₂O₅为前驱体, Na₂S₂O₃为S源, 采用水热法成功合成了新型S掺杂NaTaO₃, 并以甲基橙为目标降解物,研究S元素掺杂对提高纳米NaTaO₃的可见光光催化机理和反应历程。采用场发射扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱仪(UV-Vis DRS)和X射线衍射仪(XRD)等对所得样品进行分析。实验结果表明, 掺入S元素后, NaTaO₃晶体的表面电荷和表面形貌没有发生明显变化。UV-Vis漫反射光谱分析结果表明S^2-部分取代晶格中的O^2-离子形成Ta-S-Ta键, 掺杂后的NaTaO_3-_xS_x样品的光响应范围拓展至可见光区域。光降解实验结果表明, S掺杂NaTaO₃在可见光下其光催化活性明显高于纯相NaTaO₃。这是因为在NaTaO_3-_xS_x晶体内S^2-离子取代了部分O^2-离子形成掺杂态。GC-MS实验结果表明, NaTaO_3-_xS_x样品能够在可见光条件下将甲基橙(质荷比m/z=304)降解至m/z=156, 226和276的化合物, 随着降解时间增加, 可继续降解至m/z=156或m/z=212的化合物, 并最终转化为无机小分子(SO₄^2-, NO₃^-和NH₄⁺)。而且, NaTaO_3-_xS_x在光降解过程中非常稳定, 重复使用10次后光催化活性因催化剂损失而略微下降。

关键词: 钙钛矿, 非金属元素掺杂, 钽酸钠, 光催化

Abstract:

A novel NaTaO_3-_xS_x catalysts were successfully synthesized by one-step hydrothermal method using Ta₂O₅ as starting material and Na₂S₂O₃ as sulfur source. Its catalytic mechanism and reaction process were tested by degradation experiment. The samples were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XRS), UV-Vis diffuse reflectance spectra (UV-Vis DRS) and X-ray diffraction (XRD). The results showed that the as-prepared S-doped NaTaO₃ did not display obvious variations to the surface charge and micro-morphology of NaTaO₃. UV-Vis diffuse reflectance spectrum analysis indicated that S^2- partially substitute of O^2- ions in the lattice to form Ta-S-Ta bonds, and the light response range of the doped NaTaO_3-_xS_x samples extends to the visible region. The results of degradation experiment indicated that NaTaO_3-_xS_x exhibited much higher activity than that of pure NaTaO₃. The reason is that in the crystal lattice of NaTaO_3-_xS_x, S^2-ions replace part of the O^2-ions, which form a mixed valence band energy levels. The results of GC-MS showed that the monohydroxylated species (m/z = 304) results in the production at m/z = 156, 226 and 276, which is further degraded into species of m/z = 212 and 156. Finally, the photogenerated oxidative species forming over S-doped NaTaO₃ catalyst surface further decompose these intermediates into the final carbon dioxide and some non-toxic inorganic products (SO₄^2-, NO₃^-and NH₄⁺). In addition, in a ten-time recycling test, S-doped NaTaO₃ displayed reliable recycling photocatalytic performance, whose photocatalytic efficiency kept at a high level and only existed very slight drop, due to the loss of photocatalyst during the reclaiming process.

Key words: perovskite, nonmetal element doping, NaTaO₃, photocatalysis

中图分类号:

TQ174

刘大锐. 非金属S掺杂对NaTaO₃可见光下光催化性能的影响[J]. 无机材料学报, 2018, 33(4): 409-415.

LIU Da-Rui. Influence of Sulfur Anion Doping on Visible-light Photocatalytic Activity of NaTaO₃[J]. Journal of Inorganic Materials, 2018, 33(4): 409-415.

图/表 12

图1 不同Na2S2O3添加量NaTaO3样品的XRD图谱

Fig. 1 XRD patterns of Na2S2O3-doped NaTaO3 powders with various doping amounts

图2 Na2S2O3添加量为20mol%的NaTaO3样品XPS谱图

Fig. 2 XPS spectrum of Na2S2O3-doped NaTaO3 with doping amounts of 20mol%

表1 Na2S2O3添加量对NaTaO3-xSx中x值的影响

Table 1 The x values in NaTaO3-xSx catalysts with different S-doped contents

S addition	x in NaTaO_3-_xS_x
0	0
5mol%	0
10mol%	0
15mol%	0
20mol%	0.031
50mol%	0.032

图3 NaTaO3(a)和NaTaO2.969S0.031(b)的SEM照片

Fig. 3 SEM images of S-doped NaTaO3 (a) and pure NaTaO3 (b)

图4 NaTaO3-xSx和NaTaO3的UV-Vis漫反射光谱

Fig. 4 UV-Vis diffuse reflectance spectra of NaTaO3-xSx and NaTaO3 powders

图5 NaTaO3-xSx和NaTaO3的可见光活性测试图

Fig. 5 Photocatalytic degradation of MO by S-doped NaTaO3 and pure NaTaO3

图6 不同pH溶液中NaTaO3-xSx和NaTaO3的可见光活性测试结果

Fig. 6 Effects of initial pH on photocatalytic degradation of MO on S-doped NaTaO3 and pure NaTaO3

图7 不同NaTaO3-xSx和NaTaO3用量的可见光活性测试结果

Fig. 7 Effects of the catalyst dose on photocatalytic degradation of MO on S-doped NaTaO3 and pure NaTaO3

图8 NaTaO2.969S0.031光催化使用寿命测试结果

Fig. 8 Cyclic photocatalytic test of the reaction of NaTaO2.969S0.031

图9 NaTaO3-xSx光催化过程中的动力学分析

Fig. 9 Kinetic data of the degradation of MO over NaTaO3-xSx

表2 甲基橙在不同催化剂下光降解的一级动力学参数

Table 2 Kinetic parameter of MO photocatalytic degradation for different catalysts

Catalysts	Kinetic parameter of first order reaction	k/h^-1	R²
NaTaO₃	y=0.02962x+1.0491	0.02962	0.9683
S-doped NaTaO₃	y=1.4350x+1.1365	1.43500	0.9949

图10 甲基橙分子降解过程图

Fig. 10 Proposed degradation products of MO

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非金属S掺杂对NaTaO₃可见光下光催化性能的影响

Influence of Sulfur Anion Doping on Visible-light Photocatalytic Activity of NaTaO₃

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