Zn掺杂二维层状δ-Bi2O3纳米片的光催化固氮性能研究

doi:10.15541/jim20180595

摘要/Abstract

摘要：

通过掺杂修饰催化剂形成捕获陷阱, 可以有效抑制光生载流子的复合, 获得高效的光催化固氮效率。以Bi(NO₃)₃·5H₂O、Zn(CH₃COO)₂为原料, 采用溶剂热法制备了Zn掺杂的δ-Bi₂O₃光催化剂。采用X射线衍射(XRD)、扫描电镜(SEM)、能谱分析(EDS)、X射线光电子能谱(XPS)、透射电镜(TEM)、紫外-可见漫反射(UV-Vis DRS)等表征手段对其形貌、元素组成、光吸收等性质进行表征。结果表明, 利用这种简单的水热合成方法获得2D薄层状结构的Zn-δ-Bi₂O₃。在常温常压下, 研究了Zn-δ-Bi₂O₃的光催化固氮性能, 并考察了Zn的添加量对光催化固氮活性的影响。结果表明, 可见光照射3 h, 4wt% Zn-δ-Bi₂O₃的氨生成量可达301.6 μmol·L ^-1。采用荧光、光电流、光阻抗等手段探讨了光催化固氮机理, 发现掺杂Zn不仅可以促进价带和导带的轨道杂化, 拓宽可见光的利用范围, 而且可以在δ-Bi₂O₃表面形成陷阱, 降低光生电子和空穴的复合速率, 从而提高光催化固氮效率。

关键词: Zn掺杂, δ-Bi₂O₃, 光催化固氮, 2D层状结构

Abstract:

Surface traps are formed by doping element into catalyst, which effectively inhibits the recombination of photogenerated carriers and achieves excellent photocatalytic nitrogen fixation performance consequently. Two-dimensional Zn-δ-Bi₂O₃nanosheets were prepared via solvothermal method using Bi(NO₃)₃·5H₂O and Zn(CH₃COO)₂as raw materials. The morphology, element composition and light-harvesting capability were characterized by XRD, SEM, EDS, XPS, TEM, and UV-Vis DRS. The results show that Zn doping attributs to interstitial deposition, and Zn-δ-Bi₂O₃ microspheres are assembled from 2D nanosheets. The ability of photocatalytic nitrogen fixation over photocatalyst was explored under room temperature and atmospheric pressure with visible light irradiation. The results show that the ammonia production over 4wt% Zn-δ-Bi₂O₃ could reach 301.6 μmol·L ^-1 after 3 h irradiation. The mechanism of photocatalytic ammonia synthesis was investigated by means of fluorescence, photocurrent and impedance spectra. Zn doping not only broadens the utilization range of visible light-harvesting, but also inhibits the recombination of photogenerated electron-hole pairs, and thus improves the performance of photocatalytic nitrogen fixation.

Key words: Zn doping, δ-Bi₂O₃, nitrogen fixation, 2D layered structure

中图分类号:

O643

高晓明,尚艳岩,刘利波,聂卫. Zn掺杂二维层状δ-Bi₂O₃纳米片的光催化固氮性能研究[J]. 无机材料学报, 2019, 34(9): 967-973.

GAO Xiao-Ming,SHANG Yan-Yan,LIU Li-Bo,NIE Wei. Zn doping 2D Layered δ-Bi₂O₃ Nanosheets for Photocatalytic Nitrogen Fixation[J]. Journal of Inorganic Materials, 2019, 34(9): 967-973.

图/表 8

图1 (a)样品的XRD图谱, (b)4wt% Zn-δ-Bi2O3的XPS宽谱图, (c)Bi元素, (d)O元素和(e)Zn元素的XPS窄谱图

Fig. 1 (a) XRD patterns of the as-prepared samples, (b) XPS spectra of 4wt% Zn-δ-Bi2O3, and high-resolution XPS spectra of (c) Bi4f, (d) O1s, (e) Zn2s

图2 (a~c)δ-Bi2O3的SEM照片; 4wt% Zn-δ-Bi2O3的SEM(d~f)、TEM(g)和HRTEM(h)照片

Fig. 2 SEM images of δ-Bi2O3 (a-c), SEM(d-f), TEM (g) and HRTEM (h) images of 4wt% Zn-δ-Bi2O3

图3 4wt% Zn-δ-Bi2O3的SEM照片(a)和EDS面扫描分布图(元素总分布(b), Bi(c)、O(d)、Zn(e))

Fig. 3 SEM image (a) and EDS mapping ((b) of total elements, (c) Bi, (d) O, (e) Zn) of 4wt% Zn-δ-Bi2O3

图4 样品的UV-Vis DRS图谱

Fig. 4 UV-Vis-DRS spectra of the as-prepared samples

图5 不同样品的光催化氨生成量随时间变化图(a)和光催化固氮速率图(b)

Fig. 5 (a) NH4+ concentration in water and (b) photocatalytic nitrogen fixation rate over different catalysts

表1 样品的光载流子寿命

Table 1 Life and relative strength of the as-prepared samples

Sample	(Decay time, τ₁/ns) /(Intensity/%)	(Decay time, τ₁/ns) /(Intensity/%)	Fitting factor, χ²	Fluorescence lifetime, τ/ns
δ-Bi₂O₃	0.1/94.93	1.92/5.07	1.194	0.192
2wt% Zn-δ-Bi₂O₃	0.18/96.53	1.23/3.47	1.192	0.216
4wt% Zn-δ-Bi₂O₃	0.18/94.75	1.89/5.25	1.282	0.300
6wt% Zn-δ-Bi₂O₃	0.18/93.85	1.87/6.15	1.135	0.284
8wt% Zn-δ-Bi₂O₃	0.19/93.08	1.28/6.92	1.230	0.267
10wt% Zn-δ-Bi₂O₃	0.19/94.37	1.36/5.63	1.124	0.256

图6 样品的PL图(a)、瞬态稳态图(b)、未光照阻抗图(c)、光阻抗图(d)、光电流密度(e)和莫特肖特基图(f)

Fig. 6 (a) Photoluminescence spectra, (b) time-resolved fluorescence decay spectra, Nyqiust flots (c) without and (d) with irradiation of 400 W xenon lamp, (e) transient photocurrent responses with on/off cycles of the irradiation of 400 W xenon lamp, and (f) Mott-Schottky plots of the as-prepared samples

图7 光催化固氮机理图

Fig. 7 Schematic of photocatalytic nitrogen fixation mechanism

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Zn掺杂二维层状δ-Bi₂O₃纳米片的光催化固氮性能研究

Zn doping 2D Layered δ-Bi₂O₃ Nanosheets for Photocatalytic Nitrogen Fixation

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