不同晶相MnS制备及光解H2S制氢性能研究

doi:10.15541/jim20170104

摘要/Abstract

摘要：

采用溶剂热法成功制备了具有立方结构的α-MnS和六方结构的γ-MnS。通过X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM)、高分辨透射电镜(HRTEM)、选区电子衍射(SAED)和紫外-可见吸收光谱(UV-Vis), 对样品的物相组成、显微形貌、光学性质进行了研究, 并对不同晶相MnS在可见光(λ > 420 nm)和全光谱下光解H₂S制氢性能进行了研究。结果表明: α, γ-MnS在可见光下都具有光解H₂S制氢活性, 且相比于热力学稳定相的α-MnS (4.24 μmol/(g·h)), 亚稳态的γ-MnS (23.38 μmol/(g·h))具有更好的催化性能。相对于可见光, α, γ-MnS在全光谱下的产氢速率明显提高, 其中γ-MnS在全光谱下具有最大的光解H₂S制氢活性, 其产氢速率可达 2272.69 μmol/(g·h)。值得注意的是, 在6 h的光催化测试过程中, α, γ-MnS都展示较好的抗光腐蚀能力和光催化稳定性。此外, 对α, γ-MnS光催化分解H₂S制氢机理进行了分析, 通过对α, γ-MnS光电化学性质的研究, 对其光催化活性存在差异的原因进行了探讨。

关键词: 硫化锰, 光催化, 硫化氢, 氢气, 晶体结构

Abstract:

Cubic α-MnS and hexagonal γ-MnS were successfully prepared by a one-pot solvothermal method. X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and UV-Vis absorption spectrum were used to investigate the phase, microstructure, morphology, and optical property of the obtained samples. The photocatalytic H₂ production performances from H₂S of α-MnS and γ-MnS were evaluated both under visible light (λ > 420 nm) and UV-Vis light irradiation. The results revealed that both α-MnS and γ-MnS possess photo-splitting H₂S activity under visible light, and the metastable state γ-MnS showed better photocatalytic H₂ evolution performance (23.38 μmol/(g·h)) than the stable form α-MnS (4.24 μmol/(g·h)). Comparing the photocatalytic activity under visible light, it was found that the hydrogen production rate of α, γ-MnS under the full spectrum irradiation increased remarkably. A maximum H₂ production rate of 2272.69 μmol/(g·h) was achieved over γ-MnS under the full spectrum irradiation. It is noteworthy that during the process of 6 h photocatalytic testing, α, γ-MnS displayed a good stability and resistance to the photocorrosion. In addition, the catalytic mechanism of α, γ-MnS was investigated. Finally, the reason for the difference in photocatalytic activity between these two MnS phases was explored.

Key words: manganese sulfide, photocatalysis, hydrogen sulfide, hydrogen, crystal structure

中图分类号:

TQ174

淡猛, 张骞, 钟云倩, 周莹. 不同晶相MnS制备及光解H₂S制氢性能研究[J]. 无机材料学报, 2017, 32(12): 1308-1314.

DAN Meng, ZHANG Qian, ZHONG Yun-Qian, ZHOU Ying. Preparation of MnS with Different Crystal Phases for Photocatalytic H₂Production from H₂S[J]. Journal of Inorganic Materials, 2017, 32(12): 1308-1314.

图/表 9

图1 H2S光分解装置示意图

Fig. 1 Schematic diagram of photo-splitting H2S reaction equipment

图2 采用吡啶(a)和水(b)作为反应溶剂制备的MnS样品的XRD图谱

Fig. 2 XRD patterns of MnS sample prepared with pyridine (a) and water (b) as the reaction solvents

图3 (a) α-MnS和(b) γ-MnS样品的SEM照片

Fig. 3 SEM images of samples (a) α-MnS and (b) γ-MnS

图4 α-MnS(a,b)和γ-MnS(c,d)的TEM和HRTEM照片

Fig. 4 TEM and HRTEM images of the α-MnS (a, b) and γ-MnS (c, d)^Insets are the corresponding SAED patterns

图5 样品MnS的紫外-可见漫反射光谱图

Fig. 5 UV-Vis DRS of MnS sample

图6 MnS产氢性能图

Fig. 6 Photocatalytic H2 production of MnSUnder reaction conditions: catalyst, 2.5 mg; light source, 300 W Xe lamp

表1 不同晶相MnS在不同光照条件下光解H2S制氢性能

Table 1 Photocatalytic H2 production under different light irradiation over two different MnS

Samples	H₂ production/(μmol·g^-1·h^-1)
Samples	Visible light (λ>420 nm)	Full spectrum
α-MnS	4.24	877.68
γ-MnS	23.38	2272.69

图7 MnS光解H2S制氢机理示意图

Fig. 7 Schematic representation of the mechanism for photo- splitting H2S by MnS

图8 MnS样品在0.1 mol/L Na2S和0.6 mol/L Na2SO3溶液中的EIS电化学阻抗谱

Fig. 8 EIS of MnS samples in 0.1 mol/L Na2S and 0.6 mol/L Na2S solution

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不同晶相MnS制备及光解H₂S制氢性能研究

Preparation of MnS with Different Crystal Phases for Photocatalytic H₂Production from H₂S

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