ITO/TiO2纳米管阵列复合材料的可见光催化性能

doi:10.15541/jim20230178

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1292-1300.DOI: 10.15541/jim20230178

所属专题：【能源环境】光催化(202312)

ITO/TiO₂纳米管阵列复合材料的可见光催化性能

王梦桃¹(), 索军¹, 方东¹(), 易健宏¹, 刘意春¹, Olim RUZIMURADOV²

1.昆明理工大学材料科学与工程学院，昆明 650031
2.塔什干都灵工业大学, 塔什干 100095, 乌兹别克斯坦

收稿日期:2023-04-11 修回日期:2023-06-15 出版日期:2023-06-25 网络出版日期:2023-06-28
通讯作者: 方东, 教授. E-mail: fangdong@kust.edu.cn
作者简介:王梦桃(1998-), 女, 硕士研究生. E-mail: m19988568478@163.com
基金资助:
科技部重点专项(China: 2021YFE0104300);科技部重点专项(Uzbekistan: MUK-2021-45)

Visible-light Catalytic Performance of ITO/TiO₂ Nanotube Array Composite

WANG Mengtao¹(), SUO Jun¹, FANG Dong¹(), YI Jianhong¹, LIU Yichun¹, Olim RUZIMURADOV²

1. Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China
2. Turin Polytechnic University in Tashkent, Tashkent 100095, Uzbekistan

Received:2023-04-11 Revised:2023-06-15 Published:2023-06-25 Online:2023-06-28
Contact: FANG Dong, professor. E-mail: fangdong@kust.edu.cn
About author:WANG Mengtao (1998-), female, Master candidate. E-mail: m19988568478@163.com
Supported by:
Key Special Projects of the Ministry of Science and Technology(China: 2021YFE0104300);Key Special Projects of the Ministry of Science and Technology(Uzbekistan: MUK-2021-45)

摘要/Abstract

摘要：

光催化以其反应条件温和、能直接利用太阳能转化为化学能的优势, 而备受科研人员的关注。如何拓展光谱吸收范围及阻止光生“电子-空穴”复合, 是目前光催化研究领域的热点。本工作通过阳极氧化制备出非晶TiO₂纳米管(TiO₂NTs), 利用机械液压法将熔融铟锡合金压入非晶TiO₂中, 得到In_9.45Sn₁/TiO₂NTs, 再经高温煅烧后得到ITO/TiO₂NTs复合材料。实验对比了TiO₂NTs、In_9.45Sn₁/TiO₂NTs与ITO/TiO₂NTs对去除水溶液中亚甲基蓝的光催化性能, 在180 min光照下, ITO/TiO₂NTs的降解效果最佳, 降解效率达96.14%。利用紫外-可见漫反射光谱(UV-Vis DRS)研究了TiO₂NTs、In_9.45Sn₁/TiO₂NTs和ITO/TiO₂NTs的光吸附性能, ITO/TiO₂NTs的吸光度最强。结合瞬态光电流响应、光电流密度电势、电化学阻抗谱和Mott-Schottky测试结果可知, ITO/TiO₂NTs比TiO₂NTs具有更高的电荷转移能力和供体密度, 抑制了空穴和电子的复合, 从而增强光电化学性能。经过五次循环后, ITO/TiO₂NTs的降解效率保持在90.28%。自由基捕获实验结果表明, •O₂^-和•OH是光催化降解的主要活性物质。

关键词: 二氧化钛, ITO, 纳米管阵列, 亚甲基蓝, 机械液压法

Abstract:

Photocatalysis has received extensive attention due to its advantages of mild reaction conditions and direct conversion of solar energy to chemical energy. Improving the solar absorption range and reducing the recombination of photo-generated “electron-hole” pairs are the hot topics in the field of photocatalysis. In this work, the amorphous TiO₂ nanotube arrays (TiO₂NTs) were prepared by anodic oxidation, and indium-tin (In-Sn) alloy was pressed into the amorphous TiO₂NTs by a mechanical hydraulic method to make In_9.45Sn₁/TiO₂NTs, then the In_9.45Sn₁/TiO₂NTs were annealed in air to obtain indium tin oxide (ITO)/TiO₂NTs. The photocatalytic properties of the obtained TiO₂NTs, In_9.45Sn₁/TiO₂NTs and ITO/TiO₂NTs on the removal of methylene blue in aqueous solution were studied and compared. After 180 min visible light irradiation, the degradation efficiency of the ITO/TiO₂NTs reaches 96.14%. The applying UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) to explore the optical adsorption abilities of the samples shows the strongest absorbance of ITO/TiO₂NTs. Combining the results of transient photocurrent responses, photocurrent density-potential, electrochemical impedance spectroscopy, and Mott-Schottky plots, the ITO/TiO₂NTs have higher charge transfer capability and donor density than do other samples, which can reduce the recombination of holes and electrons, thus improving the visible-light catalytic performance. After five cycles, the degradation rate of the ITO/TiO₂NTs still maintains 90.28%. Results of free radicals trapping experiments reveal that •O₂^- and •OH are the main active substances for the photocatalytic degradation.

Key words: titania, ITO, nanotube array, methylene blue, mechanical hydraulic method

中图分类号:

O643

王梦桃, 索军, 方东, 易健宏, 刘意春, Olim RUZIMURADOV. ITO/TiO₂纳米管阵列复合材料的可见光催化性能[J]. 无机材料学报, 2023, 38(11): 1292-1300.

WANG Mengtao, SUO Jun, FANG Dong, YI Jianhong, LIU Yichun, Olim RUZIMURADOV. Visible-light Catalytic Performance of ITO/TiO₂ Nanotube Array Composite[J]. Journal of Inorganic Materials, 2023, 38(11): 1292-1300.

图/表 10

图1 ITO/TiO2NTs的合成过程图

Fig. 1 Synthesis schematic diagram of ITO/TiO2NTs

图2 直接制备的TiO2NTs(非晶TiO2NTs)、450 ℃煅烧得到的TiO2NTs(TiO2NTs)、In9.45Sn1/TiO2NTs和ITO/TiO2NTs的XRD图谱

Fig. 2 XRD patterns of the as-prepared TiO2NTs (amorphous TiO2NTs), TiO2NTs after calcined at 450 ℃ (TiO2NTs), In9.45Sn1/TiO2NTs and ITO/TiO2NTs

图3 TiO2NTs、In9.45Sn1/TiO2NTs和ITO/TiO2NTs样品的XPS图谱

Fig. 3 High resolution XPS spectra of In9.45Sn1/TiO2NTs and ITO/TiO2NTs (a) Ti2p; (b) In3d; (c) Sn3d

图4 (a~c)TiO2NTs、In9.45Sn1/TiO2NTs和ITO/TiO2NTs的SEM照片, (d, e)In9.45Sn1/TiO2NTs和ITO/TiO2NTs的TEM照片, (f)是(e)中红色虚线框区域的放大图, (f1)和(f2)是(f)中区域1和2相对应的快速傅里叶变换图像和样品相对应晶面间距

Fig. 4 (a-c) SEM images of TiO2NTs, In9.45Sn1/TiO2NTs and ITO/TiO2NTs; (d, e) TEM images of In9.45Sn1/TiO2NTs and ITO/TiO2NTs; (f) HRTEM image recorded at the red dotted box region in (e); (f1, f2) Fast Fourier Transform images and interplanar spacing images of sample in the regions 1 and 2 of (f), respectively

图5 (a)紫外-可见漫反射光谱和(b)使用Tauc图计算样品的带隙

Fig. 5 (a) UV-Vis DRS spectra and (b) band gaps of the samples calculated using Tauc plots

图6 (a) TiO2NTs、In9.45Sn1/TiO2NTs和ITO/TiO2NTs对MB的光催化降解性能, (b)降解MB的伪一级动力学拟合, (c)循环光降解MB的ITO/TiO2NTS光催化剂的光稳定性测试

Fig. 6 (a) Photocatalytic degradation of MB by TiO2NTs, In9.45Sn1/TiO2NTs and ITO/TiO2NTs; (b) Pseudo-first-order kinetic plots of MB photodegradation; (c) Photostability tests over ITO/TiO2NTs photocatalyst for the cycling photodegradation of MB

图7 TiO2NTs、In9.45Sn1/TiO2NTs和ITO/TiO2NTs的(a)瞬时光电流密度-时间曲线(i-t), (b)光电流密度-电位曲线(J-V)(扫描速率: 10 mV/s)、(c)电化学交流阻抗谱(EIS)和(d)莫特-肖特基(M-S)曲线

Fig. 7 (a) Instantaneous current density-time curves (i-t); (b) Photocurrent density-potential curves (J-V) (scanning rate: 10 mV/s); (c) Electrochemical impedance spectra (EIS); (d) Mott-Schottky curves (M-S) of TiO2NTs, In9.45Sn1/TiO2NTs and ITO/TiO2 NTs All electrolytes used in the above tests are 0.2 mol/L Na2SO4 aqueous solution with pH 7

图8 在可见光照射下, 用EDTA-2Na、异丙醇和氮氧自由基哌啶醇作为捕获剂进行光催化反应期间活性物种的捕获实验

Fig. 8 Tests of active species trapping during the photocatalytic reaction with sacrificial reagents of EDTA-2Na, IPA and 4-Hydroxy-TEMPO under visible optical irradiation

图9 ITO/TiO2复合材料光催化机理示意图

Fig. 9 Schematic illustration of the photocatalytic mechanism of ITO/TiO2

图10 ITO/TiO2NTs上沉积(a) Pt和(b) PbO2的SEM照片和元素分布图

Fig. 10 SEM images and elemental distribution mappings of (a) Pt and (b) PbO2 deposited on ITO/TiO2NTs

参考文献 47

[1]	CHEN J, ZENG T, CHANG S, et al. Discharged titanium oxide nanotube arrays coated with Ni as a high-performance lithium battery electrode material. Energy Technology, 2022, 10(11): 2200494. DOI URL
[2]	SU C, HONG B Y, TSENG C M. Sol-gel preparation and photocatalysis of titanium dioxide. Catalysis Today, 2004, 96(3): 119. DOI URL
[3]	BURASO W, LACHOM V, SIRIYA P, et al. Synthesis of TiO₂ nanoparticles via a simple precipitation method and photocatalytic performance. Materials Research Express, 2018, 5(11): 115003. DOI URL
[4]	REHAN M, LAI X, KALE G.M. Hydrothermal synthesis of titanium dioxide nanoparticles studied employing in situ energy dispersive X-ray diffraction. CrystEngComm, 2011, 13(11): 3725. DOI URL
[5]	MAMAGHANI A H, HAGHIGHAT F, LEE C S. Hydrothermal/ solvothermal synthesis and treatment of TiO₂ for photocatalytic degradation of air pollutants: preparation, characterization, properties, and performance. Chemosphere, 2019, 219: 804. DOI URL
[6]	SUN H, WANG C, PANG S, et al. Photocatalytic TiO₂ films prepared by chemical vapor deposition at atmosphere pressure. Journal of Non-Crystalline Solids, 2008, 354(12/13): 1440. DOI URL
[7]	NASSAR Z M, YÜKSELICI M H. The effect of strain and grain size on phonon and electron confinements in TiO₂ thin films. Physica Status Solidi (b), 2018, 255(6): 1700636. DOI URL
[8]	CHIGANE M, SHINAGAWA T, TANI J I. Preparation of titanium dioxide thin films by indirect-electrodeposition. Thin Solid Films, 2017, 628: 203. DOI URL
[9]	VIJAYALAKSHMI R, RAJENDRAN V. Synthesis and characterization of nano-TiO₂ via different methods. Archives of Applied Science Research, 2012, 4(2): 1183.
[10]	HASHIMOTO K, IRIE H, FUJISHIMA A. TiO₂ photocatalysis: a historical overview and future prospects. Japanese Journal of Applied Physics, 2005, 44(12R): 8269. DOI
[11]	YOSHIDA T, MISU Y, YAMAMOTO M, et al. Effects of the amount of Au nanoparticles on the visible light response of TiO₂ photocatalysts. Catalysis Today, 2020, 352: 34. DOI URL
[12]	XIA J, DONG L, SONG H, et al. Preparation of doped TiO₂ nanomaterials and their applications in photocatalysis. Bulletin of Materials Science, 2023, 46(1): 13. DOI
[13]	AYDIN E B, SEZGINTÜRK M K. Indium tin oxide (ITO): a promising material in biosensing technology. TrAC Trends in Analytical Chemistry, 2017, 97: 309. DOI URL
[14]	BANERJEE S, MANDAL S, BARUA A K, et al. Hierarchical indium tin oxide (ITO) nano-whiskers: electron beam deposition and sub-bandgap defect levels mediated visible light driven enhanced photocatalytic activity. Catalysis Communications, 2016, 87: 86. DOI URL
[15]	WEI N, CUI H, WANG X, et al. Hierarchical assembly of In₂O₃ nanoparticles on ZnO hollow nanotubes using carbon fibers as templates: enhanced photocatalytic and gas-sensing properties. Journal of Colloid and Interface Science, 2017, 498: 263. DOI URL
[16]	KANEHARA M, KOIKE H, YOSHINAGA T, et al. Indium tin oxide nanoparticles with compositionally tunable surface plasmon resonance frequencies in the near-IR region. Journal of the American Chemical Society, 2009, 131(49): 17736. DOI PMID
[17]	NAIK G.V, KIM J, BOLTASSEVA A. Oxides and nitrides as alternative plasmonic materials in the optical range. Optical Materials Express, 2011, 1(6): 1090. DOI URL
[18]	LI S, LIANG J, WEI P, et al. ITO@TiO₂ nanoarray: an efficient and robust nitrite reduction reaction electrocatalyst toward NH₃ production under ambient conditions. eScience, 2022, 2(4): 382. DOI URL
[19]	DUNG T N, DANG TRAN C, TRINH DUC T, et al. Fabrication and characteristics of Zn_1-_xSn_xO nanorod/ITO composite photocatalytic films. Materials Research Express, 2020, 7(4): 045504. DOI
[20]	SIVASAKTHI P, SANGARANARAYANAN M V, GURUMALLESH PRABU H. Micro-nanoarchitectures of electrodeposited Ni-ITO nanocomposites on copper foil as electrocatalysts for the oxygen evolution reaction. New Journal of Chemistry, 2021, 45(11): 5146. DOI URL
[21]	CHEN A, BAI S, SHI B, et al. Methane gas-sensing and catalytic oxidation activity of SnO₂-In₂O₃ nanocomposites incorporating TiO₂. Sensors and Actuators B: Chemical, 2008, 135(1): 7. DOI URL
[22]	WENDERICH K, MUL G. Methods, mechanism, and applications of photodeposition in photocatalysis: a review. Chemical Reviews, 2016, 116(23): 14587. PMID
[23]	CHEN L, SONG X L, REN J T, et al. Precisely modifying Co₂P/ black TiO₂ S-scheme heterojunction by in situ formed P and C dopants for enhanced photocatalytic H₂ production. Applied Catalysis B: Environmental, 2022, 315: 121546. DOI URL
[24]	JIANG W, QU D, AN L, et al. Deliberate construction of direct Z-scheme photocatalysts through photodeposition. Journal of Materials Chemistry A, 2019, 7(31): 18348. DOI URL
[25]	SUO J, JIAO K, FANG D, et al. Visible photocatalytic properties of Ag-Ag₂O/ITO NWs fabricated by mechanical injection-discharge- oxidation method. Vacuum, 2022, 204: 111338. DOI URL
[26]	WANG Z, LUO C, ZHANG Y, et al. Construction of hierarchical TiO₂ nanorod array/graphene/ZnO nanocomposites for high-performance photocatalysis. Journal of Materials Science, 2018, 53(22): 15376. DOI
[27]	EL JOUAD Z, LOUARN G, PRAVEEN T, et al. Improved electron collection in fullerene via caesium iodide or carbonate by means of annealing in inverted organic solar cells. EPJ Photovoltaics, 2014, 5: 50401. DOI URL
[28]	DANG M.T, LEFEBVRE J, WUEST J.D. Recycling indium tin oxide (ITO) electrodes used in thin-film devices with adjacent hole-transport layers of metal oxides. ACS Sustainable Chemistry & Engineering, 2015, 3(12): 3373.
[29]	PAN Q, LI A, ZHANG Y, et al. Rational design of 3D hierarchical ternary SnO₂/TiO₂/BiVO₄ arrays photoanode toward efficient photoe lectrochemical performance. Advanced Science, 2020, 7(3): 1902235. DOI URL
[30]	WANG Z, KONG D, WANG M, et al. Sealing effect of surface porosity of Ti-P composite films on tinplates. RSC Advances, 2019, 9(23): 12990. DOI
[31]	BAUER F J, BRAEUER P A B, AßMANN S, et al. Characterisation of the transition type in optical band gap analysis of in- flame soot. Combustion and Flame, 2022, 243: 111986. DOI URL
[32]	NIMSHI R E, VIJAYA J J, KENNEDY L J, et al. Effective microwave assisted synthesis of CoFe₂O₄@TiO₂@rGO ternary nanocomposites for the synergic sonophotocatalytic degradation of tetracycline and c antibiotics. Ceramics International, 2023, 49(9): 13762. DOI URL
[33]	SOLTANI T, TAYYEBI A, LEE B K. Enhanced photoelectrochemical (PEC) and photocatalytic properties of visible-light reduced graphene-oxide/bismuth vanadate. Applied Surface Science, 2018, 448: 465. DOI URL
[34]	GU S, LI W, WANG F, et al. Synthesis of buckhorn-like BiVO₄ with a shell of CeO_x nanodots: effect of heterojunction structure on the enhancement of photocatalytic activity. Applied Catalysis B: Environmental, 2015, 170: 186.
[35]	CHEN F, YANG Q, YAO F, et al. Synergetic transformations of multiple pollutants driven by BiVO₄-catalyzed sulfite under visible light irradiation: reaction kinetics and intrinsic mechanism. Chemical Engineering Journal, 2019, 355: 624. DOI URL
[36]	GHANNADI S, ABDIZADEH H, RAKHSHA A, et al. Sol-electrophoretic deposition of TiO₂ nanoparticle/nanorod array for photoanode of dye-sensitized solar cell. Materials Chemistry and Physics, 2021, 258: 123893. DOI URL
[37]	CHINARRO E, MORENO B, JURADO J R. Combustion synthesis and EIS characterization of TiO₂-SnO₂ system. Journal of the European Ceramic Society, 2007, 27(13): 3601. DOI URL
[38]	CHONG L W, CHIEN H T, LEE Y L. Assembly of CdSe onto mesoporous TiO₂ films induced by a self-assembled monolayer for quantum dot-sensitized solar cell applications. Journal of Power Sources, 2010, 195(15): 5109. DOI URL
[39]	YANG Y, LIAO S, SHI W, et al. Nitrogen-doped TiO₂ (B) nanorods as high-performance anode materials for rechargeable sodium-ion batteries. RSC Advances, 2017, 7(18): 10885. DOI URL
[40]	ZHOU T, WANG J, ZHANG Y, et al. Oxygen vacancy-abundant carbon quantum dots as superfast hole transport channel for vastly improving surface charge transfer efficiency of BiVO₄ photoanode. Chemical Engineering Journal, 2022, 431: 133414. DOI URL
[41]	WEI R B, KUANG P Y, CHENG H, et al. Plasmon-enhanced photoelectrochemical water splitting on gold nanoparticle decorated ZnO/CdS nanotube arrays. ACS Sustainable Chemistry & Engineering, 2017, 5(5): 4249.
[42]	LUO X L, CHEN Z Y, YANG S Y, et al. Two-step hydrothermal synthesis of peanut-shaped molybdenum diselenide/bismuth vanadate (MoSe₂/BiVO₄) with enhanced visible-light photocatalytic activity for the degradation of glyphosate. Journal of Colloid and Interface Science, 2018, 532: 456. DOI URL
[43]	BI Y, YANG Y, SHI X L, et al. Full-spectrum responsive photocatalytic activity via non-noble metal Bi decorated mulberry-like BiVO₄. Journal of Materials Science & Technology, 2021, 83: 102.
[44]	ZHANG X, CHEN C, JIANG C, et al. Construction and mechanism of Ag₃PO₄/UiO-66-NH₂ Z-Scheme heterojunction with enhanced photocatalytic activity. Catalysis Letters, 2021, 151(3): 734. DOI
[45]	BAO Y, CHEN K. Novel Z-scheme BiOBr/reduced graphene oxide/ protonated g-C₃N₄ photocatalyst: synthesis, characterization, visible light photocatalytic activity and mechanism. Applied Surface Science, 2018, 437: 51. DOI URL
[46]	GUO F, CHEN J, ZHAO J, et al. Z-scheme heterojunction g-C₃N₄@PDA/BiOBr with biomimetic polydopamine as electron transfer mediators for enhanced visible-light driven degradation of sulfamethoxazole. Chemical Engineering Journal, 2020, 386: 124014. DOI URL
[47]	OHNO T, SARUKAWA K, MATSUMURA M. Crystal faces of rutile and anatase TiO₂ particles and their roles in photocatalytic reactions. New Journal of Chemistry, 2002, 26(9): 1167. DOI URL

ITO/TiO₂纳米管阵列复合材料的可见光催化性能

Visible-light Catalytic Performance of ITO/TiO₂ Nanotube Array Composite

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 47

相关文章 15

编辑推荐

Metrics

本文评价

[1]	薛虹云, 王聪宇, MAHMOOD Asad, 于佳君, 王焱, 谢晓峰, 孙静. 二维g-C₃N₄与Ag-TiO₂复合光催化剂降解气态乙醛抗失活研究[J]. 无机材料学报, 2022, 37(8): 865-872.
[2]	迟聪聪, 屈盼盼, 任超男, 许馨, 白飞飞, 张丹洁. SiO₂@Ag@SiO₂@TiO₂核壳结构的制备及其光催化降解性能[J]. 无机材料学报, 2022, 37(7): 750-756.
[3]	周帆, 毕辉, 黄富强. 用稻壳制备亚甲基蓝高吸附容量的超高比表面积活性炭[J]. 无机材料学报, 2021, 36(8): 893-903.
[4]	潘碧宸,任鹏禾,周特军,蔡圳阳,赵小军,周宏明,肖来荣. 树脂基复合材料表面隔热涂层的组织与性能研究[J]. 无机材料学报, 2020, 35(8): 947-952.
[5]	朱本必,张旺,张志坚,章建忠,IMRAN Zada,张荻. 光热增强光催化性能二氧化钛(B)/玻纤布复合研究[J]. 无机材料学报, 2019, 34(9): 961-966.
[6]	张晓锋,张冠华,孟跃,薛继龙,夏盛杰,倪哲明. 席夫碱钴改性CoCr-LDHs材料光催化降解亚甲基蓝研究[J]. 无机材料学报, 2019, 34(9): 974-982.
[7]	张亚萍, 丁文明, 朱海丰, 黄承兴, 于濂清, 王永强, 李哲, 徐飞. 电还原MoSe₂修饰TiO₂纳米管光电化学性能研究[J]. 无机材料学报, 2019, 34(8): 797-802.
[8]	李远洋,江波. 具有超亲水光催化性能的λ/4-λ/2型两层宽频增透膜的制备和性能研究[J]. 无机材料学报, 2019, 34(2): 159-163.
[9]	隋丽丽,王润,赵丹,申书昌,孙立,徐英明,程晓丽,霍丽华. 多级结构α-MoO₃空心微球的构筑及其对有机染料的吸附性能[J]. 无机材料学报, 2019, 34(2): 193-200.
[10]	苏琨, 张亚茹, 陆飞, 张君, 王熙. 铂修饰二氧化钛纳米片的制备及其光电催化析氢反应研究[J]. 无机材料学报, 2019, 34(11): 1200-1204.
[11]	盛鹏, 赵广耀, 徐丽, 刘双宇, 王博, 刘海镇, 马光, 韩钰, 陈新. 铝沉积还原制备蓝色二氧化钛[J]. 无机材料学报, 2018, 33(9): 942-948.
[12]	范闻, 武利民. 硅油两步脱水法可控制备纳米二氧化钛透镜[J]. 无机材料学报, 2018, 33(12): 1337-1342.
[13]	赵海兵, 徐海峰, 杨克伟, 林辰学, 冯苗, 于岩. Mg掺杂TiO₂纳米晶光氧化还原染料的可逆颜色转变研究[J]. 无机材料学报, 2018, 33(10): 1124-1130.
[14]	林景诚, 唐笑, 楚婉怡. 液相合成超小TiO₂纳米簇及其光催化性质[J]. 无机材料学报, 2017, 32(8): 863-869.
[15]	鲍艳, 康巧玲. 中空TiO₂微球的制备及其对聚丙烯酸酯薄膜保温性能的影响[J]. 无机材料学报, 2017, 32(6): 581-586.