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| Research progress on preparation and photocatalytic application of TiO2 hollow microspheres |
| LIU Zeyu1, XIANG Yang1, PENG Zhihang2, JI Fengchun1, SUN Shuo1 |
1. Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China;
2. Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190, China |
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Abstract TiO2 hollow microspheres, as a new type of inorganic functional material with both the intrinsic excellent properties of TiO2 and the features of hollow structures, demonstrate broad application prospects in the fields of photocatalysis, environmental governance, energy storage, and biomedicine. This paper systematically reviews six mainstream preparation methods (hard template method, Stöber method, microemulsion method, solvothermal reaction method, layer-by-layer self-assembly method, and spray reaction method) for TiO2 hollow microspheres, and provides a detailed comparative analysis of their mechanisms, advantages, and limitations. It examines the application progress in photocatalysis, including reaction mechanism, pollutant removal, and biomedical applications. It further analyzes key factors of limiting photocatalytic performance and summarizes optimization strategies such as microstructure regulation, elemental doping, and heterostructure construction. Although large-scale production and practical application of TiO2 hollow microspheres still face numerous challenges, future integration of computational simulation and artificial intelligence technologies is expected to achieve efficient, controllable, and green synthesis, advancing their transition from laboratory research to industrial application.
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Received: 07 November 2025
Published: 10 March 2026
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[1] 马晓佳, 唐学静, 靳凤先, 等. 二氧化钛基材料光催化降解VOCs的研究进展[J]. 工程科学学报, 2023, 45(4): 590-601.
MA Xiaojia, TANG Xuejing, JIN Fengxian, et al.Research advancements in the use of TiO2-based materials for the photocatalytic degradation of volatile organic compounds[J]. Chinese Journal of Engineering, 2023, 45(4): 590-601.
[2] PARAMESWARI M, JAYAMOORTHY K.A comprehensive overview of titanium dioxide for sensor and medicinal applications[J]. Microchemical Journal, 2025, 216: 114518.
[3] PARVEEN N, ANSARI S A, ALNAHDI K M, et al.Eco-friendly synthesis and applications of grapheme- titanium dioxide nanocomposites for pollutant degradation and energy storage[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2025, 459: 116096.
[4] LIU Z, ZHOU K X, WANG J B, et al.Modulation of titanium dioxide/graphene interface by Mg2+ doping: titanium dioxide coatings with conductive, corrosion- resistant and superhydrophobic features[J]. Energy, 2025, 317: 134666.
[5] XU L N, XU X L, XU Y J, et al.Photodegradation of chitosan decorated by titanium dioxide: the potential to serve as a responded microcapsule shell[J]. Carbohydrate Polymers, 2025, 357: 123482.
[6] AFSHOON E, ASADI S, LASHGARI S, et al.From surface to structure: the role of preparation techniques in shaping titanium dioxide nanotubes via anodization[J]. Ceramics International, 2025, 51(6): 6985-6992.
[7] WANG Y Z, DAI J N, MA J, et al.Rare-earth decorated hollow B-TiO2: oxygen vacancy-mediated visible-light photocatalysis for antibiotic degradation and hydrogen production[J]. Materials Science in Semiconductor Processing, 2025, 197: 109691.
[8] WANG G Z, HE W J, YUAN Z T, et al.Interfacial nanosized and oxygen vacancy engineered homojunction anatase/ rutile-TiO2 core-shell microspheres for synchronous high- capacity and ultrafast lithium storage[J]. Ceramics International, 2025, 51(18): 25399-25407.
[9] GUO Z L, LIU H P, WANG W Z, et al.Recent advances in antibacterial strategies based on TiO2 biomimetic micro/ nano-structured surfaces fabricated using the hydrothermal method[J]. Biomimetics, 2024, 9(11): 656.
[10] 马傲雪, 曾丹林, 黄刚, 等. 二氧化硅空心微球的制备及应用研究进展[J]. 化工新型材料, 2024, 52(8): 46-50.
MA Aoxue, ZENG Danlin, HUANG Gang, et al.Progress in preparation and application of silica hollow microspheres[J]. New Chemical Materials, 2024, 52(8): 46-50.
[11] 张雪, 董庆峰, 孙彦东, 等. WO3基复合材料在光催化领域的应用与研究进展[J]. 稀有金属, 2024, 48(9): 1306-1321.
ZHANG Xue, DONG Qingfeng, SUN Yandong, et al.Application and research progress of WO3-based composite materials in photocatalysis[J]. Chinese Journal of Rare Metals, 2024, 48(9): 1306-1321.
[12] YU L B, LI Z, QIAO W Q, et al.CdS/CdSe/PbS quantum dots sensitized TiO2 eggshell hollow microspheres photoanode to boost photocurrent and power conversion efficiency of QDSSC[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2024, 452: 115607.
[13] YANG X Y, CHEN L, HAN B, et al.Preparation of magnetite and tumor dual-targeting hollow polymer microspheres with pH-sensitivity for anticancer drug- carriers[J]. Polymer, 2010, 51(12): 2533-2539.
[14] YANG Y Y, ZHENG H J, DU C C, et al.A Z-scheme photoelectrochemical biosensing platform based on Cu2O- sensitized hollow covalent organic frameworks for sensitive microcystin-LR detection[J]. Analytica Chimica Acta, 2025, 1356: 344050.
[15] CAO W, LIU H, SONG Y, et al.Biomimetic wheat-ear structured ceramic composite fibers with hollow SiO2 microsphere decoration for integrated broadband acoustic absorption and thermal insulation[J/OL]. Ceramics International, [2025-10-28]. https://doi.org/10.1016/j.ceram int.2025.10.309.
[16] BELOSTOZKY A, BRETLER S, KOLITZ-DOMB M, et al.Solidification of oil liquids by encapsulation within porous hollow silica microspheres of narrow size distribution for pharmaceutical and cosmetic applications[J]. Materials Science and Engineering C, 2019, 97: 760-767.
[17] DING H, SONG W K, CHEN Y Z, et al.Hollow engineering of carbon-based microspheres: microstructural modulation for advanced electromagnetic wave absorption[J]. Carbon, 2025, 244: 120621.
[18] LI D W, WANG C Q, ZHANG J J, et al.Efficient photo-Fenton-like catalytic system based on TiO2 hollow microspheres/g-C3N4 and peroxymonosulfate oxidation for tetracycline degradation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2025, 712: 136407.
[19] KIM J, JANG E, CHO J, et al.Porous TiO2 microspheres containing MgO nanoparticles/epoxy composite with superior thermal conductivity, EMI shielding, and electrical insulation[J]. Chemical Engineering Journal, 2024, 500: 156789.
[20] LONG Y, LI J Y, JING Y J, et al.Inorganic hollow microsphere based energy storage phase change composite materials with all-spectrum absorbing solar photothermal conversion for anti-/deicing[J]. Solar Energy, 2025, 295: 113514.
[21] WANG B C, DU J L, LIU B, et al.Exploration of the simple and green synthetic route of hollow titanium dioxide microspheres for in-depth analysis of phosphopeptides in the serum of nasopharyngeal carcinoma patients[J]. Chromatographia, 2023, 86(1): 97-105.
[22] PENNER R M, MARTIN C R.Electronically conductive composite polymer membranes[J]. Journal of the Electrochemical Society, 1986, 133(2): 310-315.
[23] YANG J X, YU Z, ZHANG F, et al.K+ doped δ-MnO2 hollow microspheres assembled from ultrathin nanosheets with controlled shell structures for aqueous zinc-ion batteries[J]. Journal of Energy Storage, 2026, 143: 119748.
[24] FENG B Y, LI H W, CHEN C, et al.Synthesis of hollow polyaniline microspheres-reinforced ferrite with super absorption performance for electromagnetic waves[J]. Surfaces and Interfaces, 2025, 73: 107531.
[25] HU Y F, LÜ J S, LI D Q, et al.Template-etched platinic defect-rich Nd-doped TiO2 hollow sphere catalysts for efficient photoelectrocatalysis[J]. International Journal of Hydrogen Energy, 2025, 156: 150387.
[26] HU X L, YANG Y Q, WANG W, et al.Hollow Fe3+-doped anatase titanium dioxide nanosphere for photocatalytic degradation of organic dyes[J]. ACS Applied Nano Materials, 2023, 6(20): 18999-19009.
[27] PARVIN N, MANDAL T K, JOO S W.Application of bimetallic heterojunction nanoparticle-based multishelled porous hollow microspheres as a two-in-one inorganic UV filter[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(45): 16133-16143.
[28] YE M P, ZHANG H M, JIANG X Q, et al.Yeast-biotemplate-assisted fabrication of self-phosphorus doped Co3O4@C hollow architecture for ciprofloxacin degradation via peroxymonosulfate activation: performance, mechanism and toxicity evaluation[J]. Separation and Purification Technology, 2024, 328: 125017.
[29] HOSSAIN M S, FURUSAWA T, SATO M.Sucrose-derived carbon template-assisted synthesis of zinc oxide hollow microspheres: investigating the effect of hollow morphology on photocatalytic activity[J]. Inorganic Chemistry Communications, 2023, 148: 110376.
[30] TIAN J Y, TIAN P, PANG H C, et al.A recyclable sacrifice-template route to prepare Al2O3 hollow microspheres[J]. Materials Letters, 2018, 210: 35-38.
[31] LIANG Z W, LIU L, ZHUANG X J, et al.Polyhedral oligomeric silsesquioxane as a recyclable soft template to synthesize mesoporous polymeric carbon nitride with enhanced photocatalytic hydrogen evolution[J]. Sustainable Energy & Fuels, 2021, 5(1): 112-116.
[32] WANG F J, PARHIZKAR M, HARKER A, et al.Constrained composite Bayesian optimization for rational synthesis of polymeric particles[J]. Digital Discovery, 2025, 4(11): 3066-3077.
[33] LI J W, JIANG C S, HU Y W, et al.Recognition of suspended particles based on Mueller matrix microscopic imaging and deep learning[J]. Marine Pollution Bulletin, 2025, 219: 118330.
[34] AHMAD Z U, CHAO B, KONGGIDINATA M I, et al.Molecular simulation and experimental validation of resorcinol adsorption on ordered mesoporous carbon (OMC)[J]. Journal of Hazardous Materials, 2018, 354: 258-265.
[35] STÖBER W, FINK A, BOHN E. Controlled growth of monodisperse silica spheres in the micron size range[J]. Journal of Colloid and Interface Science, 1968, 26(1): 62-69.
[36] GHIMIRE P P, JARONIEC M.Renaissance of Stöber method for synthesis of colloidal particles: new developments and opportunities[J]. Journal of Colloid and Interface Science, 2021, 584: 838-865.
[37] DA SILVA A D S, DOS SANTOS J H Z. Stöber method and its nuances over the years[J]. Advances in Colloid and Interface Science, 2023, 314: 102888.
[38] FENG Z L, WEI W R, WANG L T, et al.Hollow mesoporous titania microspheres: new technology and enhanced photocatalytic activity[J]. Applied Surface Science, 2015, 357: 759-765.
[39] PENG L H, REN D F, ZHANG A, et al.Weaving of silica nanoparticles with tunable morphologies in the improved Stöber system via interfacial nucleation and competitive growth strategy[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2025, 709: 136168.
[40] CHENG S R, LI Y M, LI K, et al.Preparation and properties of SiO2 wrapped γ-(CeLa)2S3 orange-red pigment by Stober method[J]. Journal of the Indian Chemical Society, 2025, 102(10): 102057.
[41] WANG Y R, JIANG L, LI B H, et al.Superhydrophobic fluorescent micro-/nano-composites from carbon dots encapsulated in CaCO3-SiO2[J]. Composite Interfaces, 2024, 31(4): 401-415.
[42] CHEN Z Y, REN X C, YANG L H, et al.Self-templating synthesis and photocatalytic activity of hollow TiO2 microspheres prepared by the sol-gel + solvothermal method[J]. Applied Surface Science, 2023, 619: 156731.
[43] JI L J, LIU X, XU T, et al.Preparation and photocatalytic properties of carbon/carbon-doped TiO2 double-layer hollow microspheres[J]. Journal of Sol-Gel Science and Technology, 2020, 93(2): 380-390.
[44] DU T, LI H, SANT G, et al.New insights into the sol-gel condensation of silica by reactive molecular dynamics simulations[J]. The Journal of Chemical Physics, 2018, 148(23): 234504.
[45] ALBERT E, BASA P, FODOR B, et al.Experimental and computational synthesis of TiO2 sol-gel coatings[J]. Langmuir, 2025, 41(1): 704-718.
[46] KAHLWEIT M.Microemulsions[J]. Science, 1988, 240(4852): 617-621.
[47] 陈云霞, 程兰兰, 施玮, 等. 乳液法制备SiO2核壳结构复合材料的研究进展[J]. 陶瓷学报, 2017, 38(1): 1-7.
CHEN Yunxia, CHENG Lanlan, SHI Wei, et al.Progress of silica-coated core-shell structured composite materials prepared by microemulsion method[J]. Journal of Ceramics, 2017, 38(1): 1-7.
[48] ZHANG Y H, ZHANG Z Y, LIU X, et al.Spherical polyelectrolyte brush nanoreactor: preparation of hollow TiO2 nanospheres and characterization by small angle X-ray scattering[J]. Chinese Journal of Polymer Science, 2024, 42(9): 1393-1400.
[49] MAZINANI B, BEITOLLAHI A, MASROM A K, et al.Synthesis and photocatalytic performance of hollow sphere particles of SiO2-TiO2 composite of mesocellular foam walls[J]. Ceramics International, 2017, 43(15): 11786-11791.
[50] ZHANG J W, CHEN L, WANG A L, et al.Dissipative particle dynamics simulation of ionic liquid-based microemulsion: quantitative properties and emulsification mechanism[J]. Industrial & Engineering Chemistry Research, 2020, 59(2): 763-773.
[51] DÜCHS D, GANESAN V, FREDRICKSON G H, et al. Fluctuation effects in ternary AB + A + B polymeric emulsions[J]. Macromolecules, 2003, 36(24): 9237-9248.
[52] KOPANICHUK I V, VANIN A A, BRODSKAYA E N.The effect of water on the shape of aggregates in water-in-oil microemulsions according to data of computer simulation[J]. Colloid Journal, 2017, 79(3): 328-332.
[53] TALAPATRA A, NOJABAEI B, KHODAPARAST P.A data driven predictive viscosity model for the microemulsion phase[J]. Scientific Reports, 2025, 15: 13462.
[54] 张霞, 张永翠, 王浩然, 等. 水热与溶剂热法在合成材料中的应用[J]. 现代技术陶瓷, 2024, 45(3): 247-258.
ZHANG Xia, ZHANG Yongcui, WANG Haoran, et al.The application of hydrothermal and solvothermal methods in preparing materials[J]. Advanced Ceramics, 2024, 45(3): 247-258.
[55] 董敏, 苗鸿雁, 谈国强. 溶剂热合成纳米材料技术及其进展[J]. 材料导报, 2005, 19(F05): 27-29.
DONG Min, MIAO Hongyan, TAN Guoqiang.Technology and progress of solvothermal preparation of nano materials[J]. Materials Reports, 2005, 19(F05): 27-29.
[56] ZHANG Z P, LI X, GUAN D Y, et al.Photocatalytic oxidation of gas-phase Hg0 by Fe-doped TiO2 hollow microspheres[J]. Materials Letters, 2021, 291: 129538.
[57] SONG H B, LIU Z, WANG Y J, et al.Template-free synthesis of hollow TiO2 nanospheres supported Pt for selective photocatalytic oxidation of benzyl alcohol to benzaldehyde[J]. Green Energy & Environment, 2019, 4(3): 278-286.
[58] CHU Y Q, ZHANG H X, ZHOU H H, et al.L-tyrosine- assisted synthesis of nanosilver/titanium nitride with hollow microsphere structure for electrochemical detection of hydrogen peroxide[J]. Journal of Solid State Electrochemistry, 2023, 27(3): 753-761.
[59] LIU B J, CHEN Q, MO Q L, et al.Robust, versatile, green and emerging layer-by-layer self-assembly platform for solar energy conversion[J]. Coordination Chemistry Reviews, 2023, 493: 215285.
[60] ILER R K.Multilayers of colloidal particles[J]. Journal of Colloid and Interface Science, 1966, 21(6): 569-594.
[61] SHENDE P, PATIL A, PRABHAKAR B.Layer-by-layer technique for enhancing physicochemical properties of actives[J]. Journal of Drug Delivery Science and Technology, 2020, 56: 101519.
[62] SUN P X, ZHANG H J, LENG Y, et al.Fabrication of wood composites with embedded carbon dot based on layer-by- layer self-assembly with flame retardant and hydrophobic capabilities[J]. Journal of Cleaner Production, 2025, 523: 146428.
[63] SHEN C, XU L S, ZHANG G L, et al.Layer-by-layer self-assembly of core/shell pH-responsive MOF microcarriers coated with polyelectrolyte hydrogels for controlled antimicrobial delivery[J]. Chemical Engineering Journal, 2025, 524: 169139.
[64] GUAN M F, LI J Q, FANG Y, et al.Fabrication and performance investigation of flame retardant flexible polyurethane composites via polyethyleneimine/phytic acid LBL self‐assembly coatings[J]. Journal of Applied Polymer Science, 2025, 142(9): e56535.
[65] 郝晏, 李巧玲, 李建强, 等. 逐层自组装法制备纳米二氧化钛空心微球[J]. 天津化工, 2011, 25(1): 13-14.
HAO Yan, LI Qiaoling, LI Jianqiang, et al.Preparation of layer-by-layer self-assembled nano-titania hollow microsphere[J]. Tianjin Chemical Industry, 2011, 25(1): 13-14.
[66] CARUSO R A, SUSHA A, CARUSO F.Multilayered titania, silica, and laponite nanoparticle coatings on polystyrene colloidal templates and resulting inorganic hollow spheres[J]. Chemistry of Materials, 2001, 13(2): 400-409.
[67] ZALDIVAR G, SIRKIN Y A P, DEBAIS G, et al. Molecular theory: a tool for predicting the outcome of self-assembly of polymers, nanoparticles, amphiphiles, and other soft materials[J]. ACS Omega, 2022, 7(43): 38109-38121.
[68] KADUPITIYA J C S, SUN F B, FOX G, et al. Machine learning surrogates for molecular dynamics simulations of soft materials[J]. Journal of Computational Science, 2020, 42: 101107.
[69] JUNG H, COVINO R, ARJUN A, et al.Machine-guided path sampling to discover mechanisms of molecular self-organization[J]. Nature Computational Science, 2023, 3(4): 334-345.
[70] BERGEK J, ELGH B, PALMQVIST A E C, et al. Formation of titanium dioxide core-shell microcapsules through a binary-phase spray technique[J]. Physical Chemistry Chemical Physics, 2017, 19(35): 23878-23886.
[71] WANG A J, LU Y P, SUN R X. Recent progress on the fabrication of hollow microspheres[J]. Materials Science and Engineering A, 2007, 460/461: 1-6.
[72] VELÁZQUEZ-PALENZUELA A, WANG H, YANG N L, et al. Preparation of TiO2-based hollow microspheres by spray drying and their use as novel active pigments for photocatalytic coatings[J]. Progress in Organic Coatings, 2021, 160: 106518.
[73] VO T K.Spray pyrolysis synthesis and UV-driven photocatalytic activity of mesoporous Al2O3@TiO2 microspheres[J]. Environmental Science and Pollution Research, 2022, 29(28): 42991-43003.
[74] MINOSHIMA H, MATSUSHIMA K, LIANG H, et al.Basic model of spray drying granulation[J]. Journal of Chemical Engineering of Japan, 2001, 34(4): 472-478.
[75] PETERSEN L N, POULSEN N K, NIEMANN H H, et al.An experimentally validated simulation model for a four- stage spray dryer[J]. Journal of Process Control, 2017, 57: 50-65.
[76] SCHMITT J M, BAUMANN J M, MORGEN M M.Predicting spray dried dispersion particle size via machine learning regression methods[J]. Pharmaceutical Research, 2022, 39(12): 3223-3239.
[77] PRZYBYŁ K, SAMBORSKA K, KOSZELA K, et al.Artificial neural networks in the evaluation of the influence of the type and content of carrier on selected quality parameters of spray dried raspberry powders[J]. Measurement, 2021, 186: 110014.
[78] XI H M, ZHU A, KLINZING G R, et al.Characterization of spray dried particles through microstructural imaging[J]. Journal of Pharmaceutical Sciences, 2020, 109(11): 3404-3412.
[79] ZHANG S, STROUD P A, ZHU A, et al.Characterizing the impact of spray dried particle morphology on tablet dissolution using quantitative X-ray microscopy[J]. European Journal of Pharmaceutical Sciences, 2021, 165: 105921.
[80] PAVLENKO V, KHOSRAVI H S, ŻÓŁTOWSKA S, et al. A comprehensive review of template-assisted porous carbons: modern preparation methods and advanced applications[J]. Materials Science and Engineering: R: Reports, 2022, 149: 100682.
[81] MALGRAS V, TANG J, WANG J, et al.Fabrication of nanoporous carbon materials with hard- and soft-templating approaches: a review[J]. Journal of Nanoscience and Nanotechnology, 2019, 19(7): 3673-3685.
[82] LI W, ZHAO D Y.Extension of the Stöber method to construct mesoporous SiO2 and TiO2 shells for uniform multifunctional core-shell structures[J]. Advanced Materials, 2013, 25(1): 142-149.
[83] KOSARI M, BORGNA A, ZENG H C.Transformation of Stöber silica spheres to hollow nanocatalysts[J]. ChemNanoMat, 2020, 6(6): 889-906.
[84] MALIK M A, WANI M Y, HASHIM M A.Microemulsion method: a novel route to synthesize organic and inorganic nanomaterials[J]. Arabian Journal of Chemistry, 2012, 5(4): 397-417.
[85] SALABAT A, MIRHOSEINI F.Polymer‐based nanocomposites fabricated by microemulsion method[J]. Polymer Composites, 2022, 43(3): 1282-1294.
[86] BELEW A A, ASSEGE M A.Solvothermal synthesis of metal oxide nanoparticles: a review of applications, challenges, and future perspectives[J]. Results in Chemistry, 2025, 16: 102438.
[87] LIU L, WANG S Z, JIANG G Y, et al.Solvothermal synthesis of zirconia nanomaterials: latest developments and future[J]. Ceramics International, 2022, 48(22): 32649-32676.
[88] RAWTANI D, AGRAWAL Y K.Emerging strategies and applications of layer-by-layer self-assembly[J]. Nanobiomedicine, 2014, 1: 8.
[89] JAVAID S, REHMAN S U, IBRAHIM A B M, et al. Layer-by-layer self-assembled dip coating: an eco-friendly approach toward multi-functional durable textile finishing[J]. Chemical Papers, 2025, 79(6): 3659-3678.
[90] BARBOSA J, TEIXEIRA P.Development of probiotic fruit juice powders by spray-drying: a review[J]. Food Reviews International, 2017, 33(4): 335-358.
[91] SÁNCHEZ-OSORNO D M, LÓPEZ-JARAMILLO M C, PAZ A V C, et al. Recent advances in the microencapsulation of essential oils, lipids, and compound lipids through spray drying: a review[J]. Pharmaceutics, 2023, 15(5): 1490.
[92] XU G, ZHANG Y, LU C Y, et al.Carbon sphere template derived TiO2 hollow sphere with nitrogen doping and carbon sensitization for visible-light driven cyclohexane oxidation and tetracycline hydrochloride degradation[J]. Journal of Water Process Engineering, 2025, 80: 109178.
[93] 张英东. 碳点掺杂二氧化钛中空微球的制备及性能研究[D]. 北京: 北京化工大学, 2018.
ZHANG Yingdong.Preparation and application of CDs@TiO2 hollow microspheres[D]. Beijing: Beijing University of Chemical Technology, 2018.
[94] WANG Z L, CHEN Y F, ZHANG L Y, et al.Step-scheme CdS/TiO2 nanocomposite hollow microsphere with enhanced photocatalytic CO2 reduction activity[J]. Journal of Materials Science & Technology, 2020, 56: 143-150.
[95] WANG J L, WANG X Q, CHEN Q H, et al.Microstructural modification of hollow TiO2 nanospheres and their photocatalytic performance[J]. Applied Surface Science, 2021, 535: 147641.
[96] ARUN J, NACHIAPPAN S, RANGARAJAN G, et al.Synthesis and application of titanium dioxide photocatalysis for energy, decontamination and viral disinfection: a review[J]. Environmental Chemistry Letters, 2023, 21(1): 339-362.
[97] 景学杰. 改性TiO2中空微球的制备及其光催化性能的研究[D]. 吉林: 东北电力大学, 2022.
JING Xuejie.Preparation and photocatalytic properties to research of modified TiO2 hollow microspheres[D]. Jilin: Northeast Electric Power University, 2022.
[98] WANG H, GAO Q, LI H T, et al.Hydrous titania nanosheets constructed hierarchical hollow microspheres as a highly efficient dual-use decontaminant for elimination of heavy metal ions and organic pollutants[J]. Chemical Engineering Journal, 2020, 381: 122638.
[99] YANG J, LONG Q X, ZHU Y, et al.Multifunctional self-assembled adsorption microspheres based on waste bamboo shoot shells for multi-pollutant water purification[J]. Environmental Research, 2024, 249: 118452.
[100] LIU H, CHEN S, ZHANG Y, et al.An effective Z-scheme hybrid photocatalyst based on zinc porphyrin derivative and anatase titanium dioxide microsphere for carbon dioxide reduction[J]. Materials Today Sustainability, 2022, 19: 100164.
[101] WYNS K, GYS N, VARELA A D, et al.Iron(III) removal from acidic solutions using mesoporous titania microspheres prepared by vibrational droplet coagulation[J]. Journal of Environmental Chemical Engineering, 2021, 9(5): 106257.
[102] GERHARDS L, KLÜNER T. Quantum chemical investigation of photocatalytical sulfoxidation of hydrocarbons on TiO2[J]. The Journal of Physical Chemistry C, 2021, 125(24): 13313-13323.
[103] ZHANG S Y, WANG Q, DAI F N, et al.Novel TiO2 nanoparticles/polysulfone composite hollow microspheres for photocatalytic degradation[J]. Polymers, 2021, 13(3): 336.
[104] XIAO Y G, SUN X D, LI L Y, et al.Simultaneous formation of a C/N-TiO2 hollow photocatalyst with efficient photocatalytic performance and recyclability[J]. Chinese Journal of Catalysis, 2019, 40(5): 765-775.
[105] ZHANG Y, HAN M, TAO Y J, et al.Sol-gel synthesis of suspensible titanium dioxide-hollow glass microsphere composites for photocatalytic degradation of acid red 1[J]. Ceramics International, 2020, 46(14): 22846-22853.
[106] MATSUNAGA T, TOMODA R, NAKAJIMA T, et al.Photoelectrochemical sterilization of microbial cells by semiconductor powders[J]. FEMS Microbiology Letters, 1985, 29(1/2): 211-214.
[107] SUN J Q, YU S S, CUI Z H, et al.Synthesis, characterization, and photocatalytic antibacterial activities of porous Ce-doped TiO2 microspheres using pine pollen as novel biotemplates[J]. Journal of Materials Science, 2022, 57(32): 15276-15297.
[108] SHEIKH M, MAKKAD S, SHENDE S, et al.Antimicrobial efficacy of metal-doped titanium dioxide nanoparticles: a comprehensive review[J]. International Journal of Pharmaceutical Investigation, 2024, 14(4): 1042-1051.
[109] CHU M Z, MA H X, LIU Z J, et al.Template-synthesized CdWO4/Cd0.5Zn0.5S hollow microsphere photocatalyst for high-efficient hydrogen evolution under visible light[J]. International Journal of Hydrogen Energy, 2024, 90: 874-884.
[110] 谢川. PBAT微球的制备及其载药应用研究[D]. 贵阳: 贵州大学, 2023.
XIE Chuan.Preparation and drug loading application of PBAT microspheres[D]. Guiyang: Guizhou University, 2023.
[111] LI P C, YU J, ZHAO K, et al.Efficient enhancement of electrochemiluminescence from tin disulfide quantum dots by hollow titanium dioxide spherical shell for highly sensitive detection of chloramphenicol[J]. Biosensors and Bioelectronics, 2020, 147: 111790.
[112] 刘迪. 介孔TiO2、中空TiO2及其复合材料的制备及性能研究[D]. 广州: 广东药科大学, 2019.
LIU Di.Preparation and properties of mesoporous TiO2, hollow TiO2 and its composite[D]. Guangzhou: Guangdong Pharmaceutical University, 2019.
[113] HURUM D C, AGRIOS A G, GRAY K A, et al.Explaining the enhanced photocatalytic activity of Degussa P25 mixed-phase TiO2 using EPR[J]. The Journal of Physical Chemistry B, 2003, 107(19): 4545-4549.
[114] 於煌. N掺杂二氧化钛的制备、可见光活性与机理研究[D]. 重庆: 重庆工商大学, 2007.
YU Huang.Preparation, visible light activity, and mechanism study of N-doped titanium dioxide[D]. Chongqing: Chongqing Technology and Business University, 2007.
[115] FENG P, TIAN H F, YANG F, et al.Reduced graphene oxide-mediated electron-hole separation using titanium dioxide increases the photocatalytic antibacterial activity of bone scaffolds[J]. Bio-Design and Manufacturing, 2025, 8(1): 100-115.
[116] WEI Z S, JANCZAREK M, ENDO M, et al.Noble metal- modified faceted anatase titania photocatalysts: octahedron versus decahedron[J]. Applied Catalysis B: Environmental, 2018, 237: 574-587.
[117] 李俊, 马丹丹, 邹雅珺, 等. 石墨相氮化碳的改性及其在光催化中的应用进展[J]. 中国材料进展, 2024, 43(7): 565-578.
LI Jun, MA Dandan, ZOU Yajun, et al.The modification of graphite carbon nitride and its applications in photocatalysis[J]. Materials China, 2024, 43(7): 565-578.
[118] YAN Z Y, HUANG W X, JIANG X R, et al.Hollow structured black TiO2 with thickness-controllable microporous shells for enhanced visible-light-driven photocatalysis[J]. Microporous and Mesoporous Materials, 2021, 323: 111228.
[119] WANG H, SHI G D, ZHANG X S, et al.In-situ synthesis of TiO2 rutile/anatase heterostructure by DC magnetron sputtering at room temperature and thickness effect of outermost rutile layer on photocatalysis[J]. Journal of Environmental Sciences, 2017, 60: 33-42.
[120] 王丽, 师兆忠, 崔伟娜, 等. BiVO4/GO纳米复合材料制备及其光催化性能研究[J]. 钢铁钒钛, 2024, 45(2): 51-57.
WANG Li, SHI Zhaozhong, CUI Weina, et al.Preparation of BiVO4/GO composites and their photocatalytic performance[J]. Iron Steel Vanadium Titanium, 2024, 45(2): 51-57.
[121] WANG H J, WU D P, WU W P, et al.Preparation of TiO2 microspheres with tunable pore and chamber size for fast gaseous diffusion in photoreduction of CO2 under simulated sunlight[J]. Journal of Colloid and Interface Science, 2019, 539: 194-202.
[122] CHEN K, FAN Q H, CHEN C L, et al.Insights into the crystal size and morphology of photocatalysts[J]. Journal of Colloid and Interface Science, 2019, 538: 638-647.
[123] XIA J X, GE Y P, ZHAO D X, et al.Microwave-assisted synthesis of few-layered MoS2/BiOBr hollow microspheres with superior visible-light-response photocatalytic activity for ciprofloxacin removal[J]. CrystEngComm, 2015, 17(19): 3645-3651.
[124] PANIGRAHI R, SRIVASTAVA S K.Ultrasound assisted synthesis of a polyaniline hollow microsphere/Ag core/shell structure for sensing and catalytic applications[J]. RSC Advances, 2013, 3(21): 7808-7815.
[125] GOPINATH K P, MADHAV N V, KRISHNAN A, et al.Present applications of titanium dioxide for the photocatalytic removal of pollutants from water: a review[J]. Journal of Environmental Management, 2020, 270: 110906.
[126] KANAKARAJU D, KUTIANG F D A, LIM Y C, et al. Recent progress of Ag/TiO2 photocatalyst for wastewater treatment: doping, co-doping, and green materials functionalization[J]. Applied Materials Today, 2022, 27: 101500.
[127] BASHIR N, SAWAIRA T, JAMIL A, et al.Challenges and prospects of main-group metal-doped TiO2 photocatalysts for sustainable water remediation[J]. Materials Today Sustainability, 2024, 27: 100869.
[128] MADANI H, SAEPURAHMAN. Low-energy light-activated Sn2+-SnO2/TiO2 photocatalyst for water pollutant removal[J]. Journal of Water Process Engineering, 2025, 77: 108425.
[129] GUO X H, YESZHAN Y, BEXEITOVA K, et al.Photocatalytic degradation of microplastics in aquatic system using metal and non metal-doped TiO2 catalyst[J]. Journal of Water Process Engineering, 2025, 79: 108956.
[130] ZHANG J, LI X H, PENG M L, et al.Ag-doped TiO2 hollow microspheres with visible light response by template-free route for removal of tetracycline hydrochloride from aqueous solution[J]. Materials Research Express, 2018, 5(6): 065008.
[131] DAI H L, LIU Z C, OU L, et al.Iron nanoparticles decorated TiO2 hollow microspheres for boosting degradation of tetracycline in a photo-Fenton catalytic system[J]. Journal of Environmental Chemical Engineering, 2023, 11(5): 110797.
[132] JIN C Z, WANG C Y, HUANG T, et al.Hollow amorphous N-doped TiO2 microspheres with uniform shell thickness and high carrier separation efficiency for photocatalytic of high- concentration Cr(VI)[J]. Optical Materials, 2025, 159: 116516.
[133] ZHENG B Z, FAN J Y, CHEN B, et al.Rare-earth doping in nanostructured inorganic materials[J]. Chemical Reviews, 2022, 122(6): 5519-5603.
[134] KHAN F U, AHMAD H, ALOMAIRY S, et al.Electronic and optical properties of titanium dioxide (TiO2) by tri-doping of cerium (Ce), nitrogen (N) and phosphorus (P)[J]. Next Research, 2025, 2(4): 101089.
[135] OWOLABI T O, GONDAL M A.A hybrid intelligent scheme for estimating band gap of doped titanium dioxide semiconductor using crystal lattice distortion[J]. Computational Materials Science, 2017, 137: 249-256.
[136] ZHANG J, LIU Q Y, LONG Y, et al.A study on determining the solid solution position of Ag-doped TiO2 based on electronegativity theory[J]. Journal of Alloys and Compounds, 2025, 1039: 183058.
[137] YANG R M, LI Y T, ZHAO X Y, et al.Strongly conductive coating: titanium dioxide enhances graphene dispersion through Coδ+ self-transformation valence[J]. Journal of Alloys and Compounds, 2025, 1037: 182397.
[138] BU H K, GUO F J, ZHAO Y, et al.Influence of element doping and surface oxidation on CoP for overall water splitting: a first-principles study[J]. The Journal of Physical Chemistry C, 2023, 127(4): 1808-1821.
[139] JIANG M X, YANG Z H, LU T, et al.Machine learning accelerated study for predicting the lattice constant and substitution energy of metal doped titanium dioxide[J]. Ceramics International, 2024, 50(1): 1079-1086.
[140] LIN M Y, YANG X X, LU F H.Crystal and band structures of N-doped Ti3O5 coatings: experiments and first-principles calculations[J]. Thin Solid Films, 2024, 803: 140484.
[141] TANEJA Y, DUBE D, SINGH R.Recent advances in elemental doping and simulation techniques: improving structural, photophysical and electronic properties of titanium dioxide[J]. Journal of Materials Chemistry C, 2024, 12(37): 14774-14808.
[142] CHEN Q C, HU G X, ZHANG Y J, et al.Heat transfer characteristics of MgO/ZnO doped Ca-based sorbents in temperature range of 300-1 123 K: a combined in-situ experimental and molecular dynamics study[J]. International Communications in Heat and Mass Transfer, 2026, 171: 110081.
[143] HU S R, BI A X, XUE F, et al.Diverse design strategies and machine learning evaluation for improving titanium-based ion sieve performance: a review[J]. Desalination, 2026, 619: 119553.
[144] CHEN T T, WANG Y C, WANG G, et al.Machine learning-guided investigation of substitutional doping effects on the hydrogen evolution activity of two-dimensional heterojunctions of WS2/MS2 (M=Mo, Cr)[J]. International Journal of Hydrogen Energy, 2025, 189: 152060.
[145] HE L J, ZHANG L L, ZHOU H, et al.Boosting photocatalytic upcycling of liquid biomass into biodiesel via microenvironment modulation[J]. Advanced Energy Materials, 2025, 15(5): 2403168.
[146] WU X, YAN Q, WANG H, et al.Heterostructured catalytic materials as advanced electrocatalysts: classification, synthesis, characterization, and application[J]. Advanced Functional Materials, 2024, 34(42): 2404535.
[147] HAN Z Y, SONG Y D, JIA Y B, et al. Classification and characterization methods for heterojunctions[J]. Advanced Materials Interfaces, 2025, 12(15): 2500191.
[148] ZHOU S S, NING J L, SUN J W, et al. Composition-induced type I and direct bandgap transition metal dichalcogenides alloy vertical heterojunctions[J]. Nanoscale, 2020, 12(1): 201−209.
[149] SHABBIR A, SARDAR S, MUMTAZ A. Mechanistic investigations of emerging type-II, Z-scheme and S-scheme heterojunctions for photocatalytic applications: a review[J]. Journal of Alloys and Compounds, 2024, 1003: 175683.
[150] CHEN H J, HUANG L X, LI X X, et al. Interfacial engineering strategies in bio-heterojunctions for antibacterial therapeutics and biomedical applications[J]. Acta Biomaterialia, 2025, 209: 120−147.
[151] WANG C H, ZHAO Y Y, CHENG C, et al. S-scheme heterojunction photocatalysts: mechanism, challenges and opportunities[J]. Coordination Chemistry Reviews, 2024, 521: 216177.
[152] SU J, LI G D, LI X H, et al. 2D/2D heterojunctions for catalysis[J]. Advanced Science, 2019, 6(7): 1801702.
[153] WANG X S, YUAN Z Y. Insights into semiconductor heterojunctions for enhanced photocatalytic performance and applications[J]. Coordination Chemistry Reviews, 2026, 548: 217184.
[154] XU S W, LI Z W, WEN J H, et al. Review of TiO2-based heterojunction coatings in photocathodic protection[J]. ACS Applied Nano Materials, 2024, 7(8): 8464−8488.
[155] VERMA P, AHIR P, KUMAR P, et al. A systematic review on nanostructured heterojunctions and their biomedical applications[J]. Materials Chemistry and Physics, 2026, 348: 131687.
[156] TAN J Z Y, GAVRIELIDES S, BELEKOUKIA M, et al. Synthesis of TiO2−x/W18O49 hollow double-shell and core- shell microspheres for CO2 photoreduction under visible light[J]. Chemical Communications, 2020, 56(81): 12150− 12153.
[157] WEI H, MCMASTER W A, TAN J Z Y, et al. Tricomponent brookite/anatase TiO2/g-C3N4 heterojunction in mesoporous hollow microspheres for enhanced visible-light photocatalysis[J]. Journal of Materials Chemistry A, 2018, 6(16): 7236−7245.
[158] ZHAO X, XIAO S J, YAO B M, et al. DFT-based mechanistic exploration and application in photocatalytic heterojunctions[J]. Journal of Chemical Theory and Computation, 2024, 20(22): 9770−9786.
[159] CHEN G P, ZHANG G F, YANG F C. The elaboration of multifunctional hollow core-shell Fe3O4@PDA@TiO2 architecture with dual magnetic-and photo-responsive performance[J]. New Journal of Chemistry, 2020, 44(8): 3487−3492. |
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2026, Vol. 31 
