CsTi2NbO7@N-TiO2杂化核壳结构的制备及其可见光催化性能

doi:10.11901/1005.3093.2020.382

材料研究学报

2021, Vol. 35

Issue (3): 221-230 DOI: 10.11901/1005.3093.2020.382

研究论文

本期目录 | 过刊浏览

CsTi₂NbO₇@N-TiO₂杂化核壳结构的制备及其可见光催化性能

程婷¹^,², 董鹏玉²(

), 高欣¹^,², 孟承启³, 王艳³, 陈小卫³, 张蓓蓓³, 奚新国³(

)

^1.江苏大学材料科学与工程学院镇江 212013
^2.盐城工学院材料科学与工程学院盐城 224051
^3.盐城工学院化学化工学院盐城 224051

Synthesis and Visible-light-driven Photocatalytic Activity of CsTi₂NbO₇@N-doped TiO₂ Hybrid Core-shell Structure

CHENG Ting¹^,², DONG Pengyu²(

), GAO Xin¹^,², MENG Chengqi³, WANG Yan³, CHEN Xiaowei³, ZHANG Beibei³, XI Xinguo³(

)

^1.School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
^2.School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China
^3.School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng 224051, China

引用本文:

程婷, 董鹏玉, 高欣, 孟承启, 王艳, 陈小卫, 张蓓蓓, 奚新国. CsTi₂NbO₇@N-TiO₂杂化核壳结构的制备及其可见光催化性能[J]. 材料研究学报, 2021, 35(3): 221-230.
Ting CHENG, Pengyu DONG, Xin GAO, Chengqi MENG, Yan WANG, Xiaowei CHEN, Beibei ZHANG, Xinguo XI. Synthesis and Visible-light-driven Photocatalytic Activity of CsTi₂NbO₇@N-doped TiO₂ Hybrid Core-shell Structure[J]. Chinese Journal of Materials Research, 2021, 35(3): 221-230.

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摘要:

将CsTi₂NbO₇与异丙醇钛混合后与尿素在空气中煅烧制备出CsTi₂NbO₇@N-TiO₂核壳杂化材料，用XRD、SEM、TEM、UV-Vis DRS和XPS等手段对样品进行了表征。结果表明，N掺杂使TiO₂带隙变窄和吸收边红移，实现了可见光响应。杂化、核壳结构和N掺杂的协同作用不仅使CsTi₂NbO₇@N-TiO₂杂化核壳结构材料具有较强的可见光吸收特性，异质结面的存在还导致光生载流子分离和迁移效率增强，从而提高了可见光降解亚甲基蓝(MB)的光催化活性，其反应速率常数约为CsTi₂NbO₇的5.8倍。同时，这种材料还具有良好的光催化循环稳定性。

关键词 ：无机非金属材料, 核壳结构, 氮掺杂, 二氧化钛, 可见光光降解

Abstract：

A novel CsTi₂NbO₇@N-TiO₂ core-shell hybrid material was successfully prepared by mixing CsTi₂NbO₇ with titanium isopropoxide and then calcining with urea in atmosphere. The prepared products were characterized by means of X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet–visible diffuse reflectance absorption spectrum (UV-Vis DRS) and X-ray photoelectron spectroscopy (XPS). It was found that the N doping resulted in the shortening of the band gap of TiO₂ and the red-shift of absorption edge, thus achieving the visible light response. Because of the synergistic effect of hybridization, core-shell structure, and N doping, the as-prepared CsTi₂NbO₇@N-TiO₂ hybrid core-shell structural materials not only have strong visible absorption properties, but also exhibit enhanced photocatalytic activity for degradation of methylene blue (MB) under visible light irradiation, resulting from the improvement of carrier separation and migration efficiency due to the existence of the built-in electric field. Moreover, the reaction rate constant of CsTi₂NbO₇@N-TiO₂ hybrid core-shell structural material is about 5.8 times that of CsTi₂NbO₇. Therefore, it shows good photocatalytic cycle stability.

Key words： inorganic non-metallic materials core-shell structure nitrogen doping titanium dioxide Visible-light photo-degradation

收稿日期: 2020-09-09

ZTFLH:

O643

基金资助:国家自然科学基金(51772258);国家重点研发计划(2016YFC0209202);住房和城乡建设部科学技术项目(2018-K1-004);江苏省研究生科研与实践创新计划项目（SJCX19_1037,KYCX20_2965）

作者简介: 程婷，女，1996年生，硕士生

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	程婷
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	陈小卫
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https://www.cjmr.org/CN/10.11901/1005.3093.2020.382 或 https://www.cjmr.org/CN/Y2021/V35/I3/221

图1 CsTi2NbO7的晶体结构[24]

图2 CsTi2NbO7@N-TiO2核壳结构的设计原理

图3 CsTi2NbO7、TiO2、TNT和TNNT样品的XRD谱

图4 样品CsTi2NbO7和TNNT的SEM照片

图5 TNNT的透射电镜照片和高分辨率透射电镜照片

图6 TNNT样品的XPS谱

图7 不同样品的紫外-可见漫反射吸收光谱

图8 CsTi2NbO7、TNT和TNNT样品的光电流响应

图9 不同样品的可见光催化MB溶液降解和光催化反应速率常数

图10 在可见光照射下样品TNNT不同降解时间后MB溶液的紫外-可见吸收光谱(插图为MB溶液的颜色随照射时间变化图)和光催化降解MB的循环稳定性

图11 TNNT可见光降解MB机理的示意图

1	Chen Y, Lu C, Xu L, et al. Single-crystalline orthorhombic molybdenum oxide nanobelts: synthesis and photocatalytic properties [J]. CrystEngComm. 2010, 12: 3740
2	Xu L, Yang X, Zhai Z, et al. EDTA-mediated shape-selective synthesis of Bi₂WO₆ hierarchical self-assemblies with high visible-light-driven photocatalytic activities [J]. CrystEngComm. 2011, 13: 7267
3	Zhu G, Hojamberdiev M, Tan C, et al. Photodegradation of organic dyes with anatase TiO₂ nanoparticles-loaded BiOCl nanosheets with exposed {001} facets under simulated solar light [J]. Materials Chemistry and Physics. 2014, 147: 1146
4	Du G, Guo Z, Wang S, et al. Superior stability and high capacity of restacked molybdenum disulfide as anode material for lithium ion batteries [J]. Chemical communications. 2010, 46: 1106
5	Pelaez M, Nolan N T, Pillai S C, et al. A review on the visible light active titanium dioxide photocatalysts for environmental applications [J]. Applied Catalysis B: Environmental. 2012, 125: 331
6	Linsebigler A L, Lu G, Yates Jr T, Photocatalysis on TiO2surfaces: principles, mechanisms, and selected results [J]. Chemical reviews. 1995, 95: 735
7	Zhang Y C, Yang M, Zhang G, et al. HNO₃-involved one-step low temperature solvothermal synthesis of N-doped TiO₂ nanocrystals for efficient photocatalytic reduction of Cr (VI) in water [J]. Applied Catalysis B: Environmental. 2013, 142: 249
8	Zhang Y C, Li J, Xu H Y, One-step in situ solvothermal synthesis of SnS2/TiO₂ nanocomposites with high performance in visible light-driven photocatalytic reduction of aqueous Cr(VI) [J]. Applied Catalysis B: Environmental. 2012, 123: 18
9	Wang S, Yun J H, Luo B, et al. Recent progress on visible light responsive heterojunctions for photocatalytic applications [J]. Journal of Materials Science & Technology. 2017, 33: 1
10	He J, Li Q, Tang Y, et al. Characterization of HNbMoO₆, HNbWO₆ and HTiNbO₅ as solid acids and their catalytic properties for esterification reaction [J]. Applied Catalysis A: General. 2012, 443: 145
11	Zhang L, Hu C, Zhang J, et al. Sulfur and iron Co-doped titanoniobate nanosheets: a novel efficient solid acid catalyst for alcoholysis of styrene epoxide at room temperature [J]. Chemical communications. 2013, 49: 7507
12	He J, Xu A, Hu L, et al. Layered KTiNbO₅ photocatalyst modified with transitional metal ions (Mn²⁺, Ni²⁺): Investigation of microstructure and photocatalytic reaction pathways for the oxidation of dimethyl sulfide and ethyl mercaptan [J]. Powder Technology. 2015, 270: 154
13	Zhang G, Lin B, Yang W, et al. Highly efficient photocatalytic hydrogen generation by incorporating CdS into ZnCr-layered double hydroxide interlayer [J]. RSC Advances. 2015, 5: 5823
14	Liu C, Zhu H, Zhu Y, et al. Ordered layered N-doped KTiNbO₅/g-C₃N₄ heterojunction with enhanced visible light photocatalytic activity [J]. Applied Catalysis B: Environmental. 2018, 228: 54
15	Li H, Li N, Wang M, et al. Synthesis of novel and stable g-C₃N₄-Bi₂WO₆ hybrid nanocomposites and their enhanced photocatalytic activity under visible light irradiation [J]. Royal Society open science. 2018, 5: 171419
16	Li J, Xu L, He J, et al. Synthesis, characterization and enhanced visible-light photocatalytic activity of novel NiO/HTi₂NbO₇ nanocomposite [J]. New Journal of Chemistry. 2018, 42: 10279
17	Cai W, Lu G, He J, et al. The adsorption feature and photocatalytic oxidation activity of K_1-2_xM_xTiNbO₅ (M=Mn, Ni) for methyl mercaptan in methane [J]. Ceramics International, 2012, 38: 3167
18	Cheng K S, Li Y, Tian H, et al. Synthesis and Photocatalytic Performance of Heterostructured Nano-Composite Bi₄Ti₃O₁₂/TiO₂ [J]. Chin. J. Mater. Res., 2014, 28: 503
18	陈侃松, 黎旸, 田寒等. Bi₄Ti₃O₁₂/TiO₂异质结的制备及其光催化性能 [J]. 材料研究学报, 2014, 28: 503
19	Chen H Y, He F, Zhang X H, et al. Photocatalytic Reduction Properties of Palladium and Nitrogen Co-Doped TiO₂ Thin Films [J]. Chin. J. Mater. Res., 2017, 31: 255
19	陈海洋, 何菲, 张旭海等. 钯氮共掺杂TiO₂薄膜的光催化还原性能 [J]. 材料研究学报. 2017, 31: 255
20	Asahi R, Morikawa T, Irie H, et al. Nitrogen-doped titanium dioxide as visible-light-sensitive photocatalyst: designs, developments, and prospects [J]. Chemical reviews. 2014, 114: 9824
21	Trevisan V, Olivo A, Pinna F, Signoretto M, et al. CN/TiO₂ photocatalysts: Effect of Co-doping on the catalytic performance under visible light [J]. Applied Catalysis B: Environmental. 2014, 160: 152
22	Liu C, Wu L, Chen J, et al. The nanocomposite of polyaniline and nitrogen-doped layered HTiNbO₅ with excellent visible-light photocatalytic performance [J]. Physical Chemistry Chemical Physics. 2014, 16: 13409
23	Liu C, Zhang C, Wang J, et al. N-doped CsTi₂NbO₇@ g-C₃N₄ core-shell nanobelts with enhanced visible light photocatalytic activity [J]. Materials Letters. 2018, 217: 235
24	Hervieu M, Raveau B. A layer structure: The titanoniobate CsTi₂NbO₇ [J]. Journal of Solid State Chemistry. 1980, 32: 161
25	Dias A S, Lima S, Carriazo D, et al. Exfoliated titanate, niobate and titanoniobate nanosheets as solid acid catalysts for the liquid-phase dehydration of D-xylose into furfural [J]. Journal of Catalysis. 2006, 244: 23
26	Takagaki A, Yoshida T, Lu D, et al. Titanium niobate and titanium tantalate nanosheets as strong solid acid catalysts [J]. The Journal of Physical Chemistry B. 2004, 108: 11549
27	Jang J S, Kim H G, Reddy V R, et al. Photocatalytic water splitting over iron oxide nanoparticles intercalated in HTiNb(Ta)O₅ layered compounds [J]. Journal of Catalysis. 2005, 231: 213
28	Zhang Y, Wang N, He J, et al. Synthesis of CeO₂/e-HTiNbO₅ nanocomposite and its application for photocatalytic oxidation desulfurization [J]. Nano. 2016, 11: 1650018
29	Liu C, Han R, Ji H, et al. S-doped mesoporous nanocomposite of HTiNbO₅ nanosheets and TiO₂ nanoparticles with enhanced visible light photocatalytic activity [J]. Physical Chemistry Chemical Physics. 2016, 18: 801
30	Li J, Xu L, He J, et al. The structure feature of novel Cu₂O/e-HTi₂NbO₇ Nanocomposite and their enhanced photocatalytic Activity [J]. Nano. 2017, 12: 1750100
31	Liu Y, Zhang M, Li L, et al. One-dimensional visible-light-driven bifunctional photocatalysts based on Bi₄Ti₃O₁₂ nanofiber frameworks and Bi₂XO₆ (X=Mo, W) nanosheets [J]. Applied Catalysis B: Environmental. 2014, 160: 757
32	Zhang L, Jing D, She X, et al. Heterojunctions in g-C₃N₄/TiO₂ (B) nanofibres with exposed (001) plane and enhanced visible-light photoactivity [J]. Journal of Materials Chemistry A. 2014, 2: 2071
33	Liu C., Wu Q., Ji M., et al. Constructing Z-scheme charge separation in 2D layered porous BiOBr/graphitic C₃N₄ nanosheets nanojunction with enhanced photocatalytic activity [J]. Journal of Alloys & Compounds. 2017, 723: 1121
34	Liu C, Xu Q, Zhang Q, et al. Layered BiOBr/Ti₃C₂ MXene composite with improved visible-light photocatalytic activity [J]. Journal of Materials Science. 2019, 54: 2458
35	Wu T, Zhang Q, Hou Y, et al. Monocopper Doping in Cd-In-S Supertetrahedral Nanocluster via Two-Step Strategy and Enhanced Photoelectric Response [J]. Journal of the American Chemical Society. 2013, 135(28): 10250
36	Wu N, Wang J, Tafen D N, et al. Shape-enhanced photocatalytic activity of single-crystalline anatase TiO₂ (101) nanobelts [J]. Journal of the American Chemical Society. 2010, 132: 6679
37	Mor G K, Varghese O K, Paulose M, et al. A review on highly ordered, vertically oriented TiO₂ nanotube arrays: Fabrication, material properties, and solar energy applications [J]. Solar Energy Materials and Solar Cells. 2006, 90: 2011
38	Ye L, Liu J, Jiang Z, et al. The pure shape effect with a removing facet effect of single-crystalline anatase TiO₂ (101) for photocatalytic application [J]. Nanoscale. 2013, 5: 9391
39	Lee S H, Yamasue E, Ishihara K N, et al. Photocatalysis and surface doping states of N-doped TiO_x films prepared by reactive sputtering with dry air [J]. Applied Catalysis B: Environmental. 2010, 93(3-4): 217
40	Li H, Li J, Huo Y, Highly active TiO2N photocatalysts prepared by treating TiO₂ precursors in NH3/ethanol fluid under supercritical conditions [J]. The Journal of Physical Chemistry B., 2006, 110: 1559
41	Yang X, Cao C, Erickson L, et al. Photo-catalytic degradation of Rhodamine B on C-, S-, N-, and Fe-doped TiO₂ under visible-light irradiation [J]. Applied Catalysis B: Environmental., 2009, 91: 657
42	Ou H H, Lo S L, Liao C H. N-Doped TiO₂ Prepared from Microwave-Assisted Titanate Nanotubes (Na_xH_2-_xTi₃O₇): The Effect of Microwave Irradiation during TNT Synthesis on the Visible Light Photoactivity of N-Doped TiO₂ [J]. The Journal of Physical Chemistry C, 2011, 115: 4000
43	Lee H U, Lee S C, Choi S, et al. Influence of visible-light irradiation on physicochemical and photocatalytic properties of nitrogen-doped three-dimensional (3D) titanium dioxide [J]. Journal of hazardous materials, 2013, 258: 10
44	Chaudhari N S, Warule S S, Dhanmane S A, et al. Nano structured N-doped TiO₂ marigold flowers for an efficient solar hydrogen production from H₂S [J]. Nanoscale, 2013, 5: 9383
45	Liu H, Yang D, Zheng Z, et al. A Raman spectroscopic and TEM study on the structural evolution of Na₂Ti₆O₁₃ during the transition to Na₂Ti₆O₁₃ [J]. Journal of Raman Spectroscopy, 2010, 41: 1331
46	Tauc J. Absorption edge and internal electric fields in amorphous semiconductors [J]. Materials Research Bulletin, 1970, 5: 721

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