Zn0.4(CuGa)0.3Ga2S4/CdS光催化材料的制备及其CO2还原性能

doi:10.15541/jim20210480

无机材料学报 ›› 2022, Vol. 37 ›› Issue (1): 15-21.DOI: 10.15541/jim20210480

所属专题：【能源环境】CO2绿色转换

• 专栏: CO ₂ 绿色转化(特邀编辑: 欧阳述昕, 王文中) • 上一篇下一篇

Zn_0.4(CuGa)_0.3Ga₂S₄/CdS光催化材料的制备及其CO₂还原性能

刘彭(), 吴仕淼, 吴昀峰, 张宁()

中南大学材料科学与工程学院, 长沙 410083

收稿日期:2021-07-29 修回日期:2021-08-17 出版日期:2022-01-20 网络出版日期:2021-09-27
通讯作者: 张宁, 副教授. E-mail: nzhang@csu.edu.cn
作者简介:刘彭(1999-), 男, 硕士研究生. E-mail: 203112101@csu.edu.cn
基金资助:
国家自然科学基金(22072183);长沙市自然科学基金(kq2014119)

Synthesis of Zn_0.4(CuGa)_0.3Ga₂S₄/CdS Photocatalyst for CO₂ Reduction

LIU Peng(), WU Shimiao, WU Yunfeng, ZHANG Ning()

School of Materials Science and Engineering, Central South University, Changsha 410083, China

Received:2021-07-29 Revised:2021-08-17 Published:2022-01-20 Online:2021-09-27
Contact: ZHANG Ning, associate professor. E-mail: nzhang@csu.edu.cn
About author:LIU Peng (1999-), male, Master candidate. E-mail: 203112101@csu.edu.cn
Supported by:
National Natural Science Foundation of China(22072183);Changsha Municipal Natural Science Foundation(kq2014119)

摘要/Abstract

摘要：

利用光催化技术将CO₂转化为燃料有望解决能源危机和温室效应。Zn_1-2_x(CuGa)_xGa₂S₄具有可见光响应及较高的导带电势, 从热力学上看是较为理想的CO₂还原材料, 但是其光催化CO₂还原活性仍然较低, 亟待从动力学角度提高其活性。本研究采用Zn_0.4(CuGa)_0.3Ga₂S₄与不同比例的CdS纳米颗粒复合, 制备了Zn_0.4(CuGa)_0.3Ga₂S₄/CdS异质结半导体材料。通过材料表征证明CdS在Zn_0.4(CuGa)_0.3Ga₂S₄微米颗粒上均匀生长并形成了全固态Z型异质结的复合结构。这种结构有效抑制了电子空穴对的复合, 保持了较高的还原电势, 有利于提高光催化性能。在溶液体系中, 所制备的Zn_0.4(CuGa)_0.3Ga₂S₄/CdS能够有效地将CO₂光催化还原为CO。研究表明, 当Zn_0.4(CuGa)_0.3Ga₂S₄与CdS的摩尔比为2 : 1时, 样品的光催化活性达到最优, 是Zn_0.4(CuGa)_0.3Ga₂S₄材料的1.7倍, CdS材料的1.6倍。本工作通过构造异质结构, 提高了Zn_0.4(CuGa)_0.3Ga₂S₄半导体材料的光催化CO₂还原活性, 对人工光合成材料的设计与制备具有较大的参考价值。

关键词: 光催化, Z型异质结, 二氧化碳还原, 硫化物

Abstract:

Conversion of CO₂ into fuels by photocatalysis is promising in solving the energy crisis and the greenhouse effect. Among various photocatalytic materials, Zn_1-2_x(CuGa)_xGa₂S₄ materials possess visible light response and high conduction band potential, which are ideal CO₂ reduction materials from thermodynamics aspect. However, their photocatalytic CO₂ reduction activity is still low which is urgent to improve its activity in terms of kinetics. In this study, Zn_0.4(CuGa)_0.3Ga₂S₄ was synthesized and composited with CdS nanoparticles with different proportions to form Zn_0.4(CuGa)_0.3Ga₂S₄/CdS heterojunction photocatalysts. A series of characterizations suggest that CdS is uniformly grown on surface of Zn_0.4(CuGa)_0.3Ga₂S₄ microcrystals to form a Z-scheme type all-solid heterojunction composite materials. Such a structure effectively suppresses the recombination of electron-hole pairs and improve the photocatalytic performance. In the solution CO₂ reduction system, the as-prepared Zn_0.4(CuGa)_0.3Ga₂S₄/CdS can effectively reduce CO₂ into CO under visible light irradiation. The optimal molar ratio of Zn_0.4(CuGa)_0.3Ga₂S₄ and CdS in composite materials is 2 : 1, whose photocatalytic performance is 1.7 times of that of Zn_0.4(CuGa)_0.3Ga₂S₄/ CdS and 1.6 times of that of CdS. This work constructs all solid Z-scheme type Zn_0.4(CuGa)_0.3Ga₂S₄/CdS heterojunction materials with enhanced photocatalytic activity for CO₂ reduction, which is promising for designing novel photocatalysts in field of artificial photosynthesis.

Key words: photocatalysis, Z-scheme heterojunction, carbon dioxide reduction, sulfide

中图分类号:

TQ174

刘彭, 吴仕淼, 吴昀峰, 张宁. Zn_0.4(CuGa)_0.3Ga₂S₄/CdS光催化材料的制备及其CO₂还原性能[J]. 无机材料学报, 2022, 37(1): 15-21.

LIU Peng, WU Shimiao, WU Yunfeng, ZHANG Ning. Synthesis of Zn_0.4(CuGa)_0.3Ga₂S₄/CdS Photocatalyst for CO₂ Reduction[J]. Journal of Inorganic Materials, 2022, 37(1): 15-21.

图/表 9

图1 样品的XRD图谱

Fig. 1 XRD patterns of as-prepared products

图2 Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1的(a,b)SEM照片, (c,d)TEM照片和(e)HRTEM照片

Fig. 2 (a,b) SEM images, (c,d) TEM images, (e) HRTEM image of Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1

图3 Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1的EDS线扫描元素分析

Fig. 3 EDS elemental line scanning analyses of Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1

图4 样品Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1、Zn0.4(CuGa)0.3Ga2S4和CdS的(a)Cu2p, (b)C3d, (c)S2p, (d)Ga3d的XPS图谱

Fig. 4 (a) Cu2p, (b) C3d, (c) S2p, (d) Ga3d XPS spectra of Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1, Zn0.4(CuGa)0.3Ga2S4 and CdS

图5 样品的UV-Vis图谱(a)及带隙能量计算图(b)

Fig. 5 UV-Vis adsorption spectra (a) and band gap energy calculation diagram (b) of samples

图6 Zn0.4(CuGa)0.3Ga2S4和CdS的VB-XPS图谱

Fig. 6 VB-XPS spectra of Zn0.4(CuGa)0.3Ga2S4 and CdS

图7 Zn0.4(CuGa)0.3Ga2S4和CdS的能带结构示意图

Fig. 7 Scheme of relatively energy band position for Zn0.4(CuGa)0.3Ga2S4 and CdS

图8 样品Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1、Zn0.4(CuGa)0.3Ga2S4和CdS的时间分辨光致发光光谱

Fig. 8 TRPL spectra of samples Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1, Zn0.4(CuGa)0.3Ga2S4 and CdS Colorful figures are available on website

图9 样品Zn0.4(CuGa)0.3Ga2S4/CdS-4 : 1、Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1、Zn0.4(CuGa)0.3Ga2S4/CdS-1 : 1、Zn0.4(CuGa)0.3Ga2S4和CdS的(a)CO动力学曲线, (b)CO产率柱状图, (c) H2动力学曲线和(d) H2产率柱状图

Fig. 9 (a) CO evolution vs. irradiation time, (b) CO evolution rate, (c) H2 evolution vs. irradiation time, and (d) H2 evolution rate over Zn0.4(CuGa)0.3Ga2S4/CdS-4 : 1, Zn0.4(CuGa)0.3Ga2S4/CdS-2 : 1, Zn0.4(CuGa)0.3Ga2S4/CdS-1 : 1, Zn0.4(CuGa)0.3Ga2S4, and CdS Colorful figures are available on website

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Zn_0.4(CuGa)_0.3Ga₂S₄/CdS光催化材料的制备及其CO₂还原性能

Synthesis of Zn_0.4(CuGa)_0.3Ga₂S₄/CdS Photocatalyst for CO₂ Reduction

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