基于能带结构理论的半导体光催化材料改性策略

doi:10.15541/jim20140648

无机材料学报 ›› 2015, Vol. 30 ›› Issue (7): 683-693.DOI: 10.15541/jim20140648

基于能带结构理论的半导体光催化材料改性策略

王丹军^{1, 2}, 张洁¹, 郭莉¹, 申会东¹, 付峰¹, 薛岗林², 方轶凡¹

(1. 延安大学化学与化工学院, 陕西省化学反应工程重点实验室, 延安 716000; 2. 西北大学化学与材料科学学院, 教育部合成与天然产物重点实验室, 西安 710069)

收稿日期:2014-12-16 修回日期:2015-01-17 出版日期:2015-07-20 网络出版日期:2015-06-25
基金资助:
国家自然科学基金重点项目(20973133);教育部合成与天然产物重点实验室基金(338080055);陕西省科技厅工业攻关项目(2013K11-08, 2013SZS20-P01);陕西省教育厅基金(13JK0669);延安市工业攻关项目(2011kg-13);大学生创新项目(1242)

Modification Strategies for Semiconductor Photocatalyst Based on Energy Band Structure Theory

WANG Dan-Jun^{1, 2}, ZHANG Jie¹, GUO Li¹, SHEN Hui-Dong¹, FU Feng¹, XUE Gang-Lin², FANG Yi-Fan¹

(1. College of Chemistry & Chemical Engineering, Yan'an University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an 716000, China; 2. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Educational), College of Chemistry & Materials Science, Northwest University, Xi’an 710069, China)

Received:2014-12-16 Revised:2015-01-17 Published:2015-07-20 Online:2015-06-25
Supported by:
National Natural Science Foundation of China(20973133);Open Foundation of Key Laboratory of Synthetic and Natural Functional Molecule Chemistry(Ministry of Educational)(338080055);Natural Science Program of Education Department of Shaanxi Province (2013K11-08, 2013SZS20-P01);Shaanxi Provincial Education Department Fund(13JK0669);Key Industry Plan of Yan’an City (2011kg-13);College students’ Innolvative Projects(1242)

摘要/Abstract

摘要：

作为一种新型的环境净化技术, 半导体光催化技术已引起全世界范围的广泛关注。然而, 传统光催化剂对太阳能利用率低、且光生电子-空穴对易于复合, 极大限制了该技术的实际应用。因此, 通过不同的改性手段合成具有可见光响应活性的光催化材料成为光催化领域研究的热点课题。提高光催化剂的活性, 除了合成方法的优选(调控尺寸、形貌、结晶度、微结构)外, 改性也是提高催化剂活性的主要手段。本文从半导体光催化的基本原理出发, 概述了半导体光催化剂改性的基本思想: 即拓宽太阳光利用范围和提高光生电子-空穴的寿命。围绕这一思想, 常用的改性策略有化学结构调控(能带调控), 以拓宽光谱响应范围; 表面修饰(表面敏化、半导体耦合和贵金属沉积)以提高电荷的分离效率。合适的能带结构是拓展催化剂的可见光响应范围和提高电荷分离效率的关键。

关键词: 催化剂, 光催化, 能带结构, 改性, 策略, 综述

Abstract:

Design and controllable synthesis of catalyst and its property tuning are an interesting subject for physical chemistry, materials chemistry and catalytic chemistry. As a new environmental-purifying technology, semiconductor photocatalytic oxidation technology has arosen worldwide attention. However, conventional photocatalyst exhibits poor utilization of solar energy and low efficient of photogenerated charge separation, which restricts the practical application of the technology. Therefore, it is still a challenging topic to design and synthesize visible-light-response photocatalytic materials with higher utilization efficiency of solar energy. Besides tuning synthesis method (by controlling particle size, morphology, crystallinity and other microstructures, etc), modification is a crucial strategy for the activity enhancement of photocatalyst. In this paper, we reviewed the basic mechanism for the photocatalyst modification from the view of semiconductor energy structure. Taking consideration of the basic mechanism and process of photocatalysis, there are two key modification strategies: chemical structure modification (energy band modification) to broaden the light absorption and surface modification (surface sensitization, semiconductor combinations and noble metal deposition) to increase life-time of carrier. Suitable band structure is responsible for the visible-light harvesting and effective separation of carrier of semiconductor photocatalyst.

Key words: catalyst, photocatalysis, energy band structure, modification, strategies, review

中图分类号:

O614

王丹军, 张洁, 郭莉, 申会东, 付峰, 薛岗林, 方轶凡. 基于能带结构理论的半导体光催化材料改性策略[J]. 无机材料学报, 2015, 30(7): 683-693.

WANG Dan-Jun, ZHANG Jie, GUO Li, SHEN Hui-Dong, FU Feng, XUE Gang-Lin, FANG Yi-Fan. Modification Strategies for Semiconductor Photocatalyst Based on Energy Band Structure Theory[J]. Journal of Inorganic Materials, 2015, 30(7): 683-693.

图/表 14

图 1 半导体光催化剂的带隙位置和水中不同物质的氧化还原电势( pH =7)

Fig. 1 Band-edge position of semiconductor photocatalyst and various redox couples in water (pH=7)

图 2 半导体的光催化机理示意图[4]

Fig. 2 Schematic illustration of basic mechanism of a semiconductor photocatalytic process[4]

图3 提高半导体光催化性能的基本思想

Fig. 3 Elementary ideology to improve photocatalytic activity of semiconductor

图4 半导体带隙调控的三种策略

Fig. 4 Three strategies to narrow the band gap of semiconductor photocatalysts to match the solar spectrum

图5 (A)TiO2的成键图和(B)金属离子掺杂TiO2-xAxO2 (A=V、Cr、Mn、Fe, Ni)的态密度分布[9]

Fig. 5 (A) Bonding diagram of TiO2 and (B) DOS of metal-doped TiO2-xAxO2 (A=V、Cr、Mn、Fe、Co, or Ni)[9]

图6 (A)掺杂TiO2的总态密度分布和(B)阴离子取代锐钛矿型TiO2的氧原子态密度分布[10]

Fig. 6 (A) Total DOSs of doped TiO2 and (B) DOSs of the dopants anion located at a substitutional site for O atom in the anatase TiO2 crystal[10] Ni-doped stands for N doping at an interstitial sites, and Ni-s-doped stands for doping at both substitutional and interstitial sites

图 7 (A)S掺杂TiO2的总态密度分布和(B)F掺杂TiO2的总态密度分布[18]

Fig. 7 (A) Total DOS of S-doped TiO2 and (B) total DOS of F-doped TiO2[18] Eg indicates the band gap energy. The impurity states are labeled (I) and (II)

图8 系列α-AgMO2 (M=Al, Ga, In)催化剂的电子结构和光催化活性比较[28]

Fig. 8 Serial electronic structures of α-AgMO2(M=A1, Ga, In) and comparation of their photo catalytic activity (A) Electronic structures of α-AgMO2 (M=Al, Ga, In), (B) Photocatalytic degradation of isopropanol using α-AgGaO2 and α-AgInO2 under visible light irradiation (400 nm<λ<520 nm) and (C) Apparent photonic efﬁciency of acetone evolution using α-AgGaO2 for various wavelength ranges within the UV-visible absorption spectrum[28]

图9 Ag3PO4(A)和Ag2O(B)的能带结构[29]

Fig. 9 Energy band structures for (A) Ag3PO4 and (B) Ag2O

图10 GaN、ZnO和固溶体(ZnO)x(GaN)1-x的能带结构示意图[31]

Fig. 10 Schematic illustration of band structures of GaN and ZnO, and their solid solution[31]

图11 固溶体AgAlO2、AgGaO2和AgAl1-xGaxO2的能带结构示意图(A), 固溶体β-AgAl1-xGaxO2吸收光谱(B), 丙酮产生速率、带隙以及β-AgAl1-xGaxO2 的颜色随组成的变化(C)和异丙醇在β-AgAl1-xGaxO2 上降解的表观量子产率(D)[32]

Fig. 11 (A)Schematic electronic structures of AgAlO2, AgGaO2 and AgAl1-xGaxO2 solid solutions; (B) UV-visible absorption spectra of β-AgAl1-xGaxO2 solid solutions; (C) Rate of acetone evolution, band-gap, and color of β-AgAl1-xGaxO2 as a function of x; (D) Apparent quantum efﬁciency of IPA photodegradation over β-AgAl0.6Ga0.4O2 in various wavelength ranges within the V-visible absorption spectrum[32]

图 12 染料分子敏化剂的激发过程

Fig. 12 Excitation process of dye molecule sensitizer

图13 AgBr/Bi2WO6异质结的能带结构[39]

Fig. 13 Energy band structure aof AgBr/Bi2WO6 heterojunction[39]

图14 Ag负载Bi2WO6光催化剂的光催化活性增强机理[48]

Fig. 14 Photocatalytic activity enhancement of Ag-loaded Bi2WO6[48] (Left: room temperature photoluminescence (PL) spectra of Bi2WO6 (a), and Ag-loaded Bi2WO6 nanoarchitecture, λexcitation=300 nm; Right: Energy band diagram and photocatalytic scheme of the Ag-loaded Bi2WO6)

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基于能带结构理论的半导体光催化材料改性策略

Modification Strategies for Semiconductor Photocatalyst Based on Energy Band Structure Theory

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