The work aims to prepare ternary composite catalyst UiO-66-NH2@TiO2-x@GO and study its photocatalytic degradation of formaldehyde by concrete coating. Formaldehyde, as a common indoor volatile organic compound (VOC), poses significant risks to human health, making the development of highly efficient and stable photocatalysts for its removal both scientifically important and practically valuable. In response to this gap, this study proposes and constructs a novel ternary composite catalytic system that integrates the advantages of semiconductor materials, metal-organic frameworks (MOFs), and carbon-based nanomaterials. Specifically, TiO2-x with abundant oxygen vacancies is first prepared via a combination of sol-gel synthesis followed by H2/Ar reduction treatment, which effectively introduces defect states and enhances visible light absorption. Meanwhile, UiO-66-NH2, a zirconium-based MOF with amino functional groups, is synthesized through the solvothermal method, providing a high specific surface area and strong adsorption capacity for organic pollutants. Graphene oxide (GO), known for its excellent electrical conductivity and large surface area, is incorporated to facilitate charge transfer and suppress electron-hole recombination. Based on these components, a binary organic-inorganic hybrid material consisting of TiO2-x, UiO-66-NH2, and GO is constructed, and subsequently, a well-integrated UiO-66-NH2@TiO2-x@GO ternary composite photocatalyst is successfully synthesized. To comprehensively evaluate the properties of the prepared catalyst, a series of characterization techniques are employed. The microstructure and morphology are analyzed by electron microscopy, while the specific surface area is determined through adsorption-desorption measurements. In addition, optical properties and light response performance are investigated using spectroscopic methods, confirming that the introduction of oxygen vacancies and GO significantly broadens the light absorption range into the visible region. These structural and functional features collectively contribute to improved photocatalytic performance. The photocatalytic activity of the synthesized materials is systematically evaluated with formaldehyde as a model pollutant. Comparative experiments demonstrate that the ternary composite catalyst exhibits superior degradation efficiency compared with its individual or binary counterparts. Notably, the UiO-66-NH2@TiO2-x@GO composite containing oxygen vacancies are able to effectively utilize visible light to drive the catalytic degradation of formaldehyde. When incorporated into photocatalytic coatings at loadings of 2wt.% and 3wt.%, the system achieves remarkable maximum formaldehyde removal rates of approximately 97% and 100%, respectively, highlighting its high efficiency under practical conditions. Furthermore, the stability and reusability of the prepared photocatalytic coating are also investigated. The results indicate that even after multiple cycles of use, the removal efficiency of formaldehyde remains at around 99%, demonstrating excellent durability and resistance to deactivation. This stability is crucial for real-world applications, especially in building materials that require long-term performance. In summary, this study successfully develops a novel ternary composite photocatalyst incorporating oxygen vacancies, which exhibits both high efficiency and excellent stability in the photocatalytic degradation of formaldehyde. The findings not only provide valuable insights into the design of advanced photocatalytic systems but also offer a practical and effective scientific approach for the development of environmentally friendly building coating materials capable of removing harmful chemical organic volatiles from indoor environments.
Key words
UiO-66-NH2@TiO2-x@GO /
ternary photocatalyst /
photocatalytic coating /
concrete coating /
formaldehyde
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
References
[1] 张晓杰, 罗菊芬, 古鸣, 等. 家具中挥发性有害物质检测技术的研究[J]. 家具, 2010(5): 105-107.
ZHANG X J, LUO J F, GU M, et al.The Study of VOC Test in Furniture[J]. Furniture, 2010(5): 105-107.
[2] 杜容山, 黄利民, 王少波, 等. 香溪河沿程挥发性有机物污染特征及健康风险[J]. 武汉大学学报(理学版), 2025, 71(6): 869-880.
DU R S, HUANG L M, WANG S B, et al.Pollution Characteristics and Health Risk of Volatile Organic Compounds along the Bank of Xiangxi River[J]. Journal of Wuhan University (Natural Science Edition), 2025, 71(6): 869-880.
[3] LI F, CHENG Z K, LI X, et al.Facile and Scalable Method to Synthesize MOFs/PET Composite Fibers for Indoor VOCs Adsorption[J]. Separation and Purification Technology, 2025, 357: 130007.
[4] 刘意, 谭彩霞. 工业废水处理装置中的废气治理技术研究分析[J]. 中国科技期刊数据库工业A, 2024(003): 000.
LIU Y, TAN C X.Research and Analysis of Waste Gas Treatment Technology in Industrial Wastewater Treatment Plant[J]. China Science and Technology Journal Database Industry A, 2024(003): 000.
[5] BRALEWSKA K, ROGULA-KOZŁOWSKA W, BIAŁAS J. Seasonal and Spatial Variability of Volatile Organic Compounds and Formaldehyde Concentrations at the Fire Station[J]. Building Research & Information, 2025, 53(4): 509-531.
[6] CORDERO J M, HINGORANI R, JIMENEZ-RELINQUE E, et al.NOx Removal Efficiency of Urban Photocatalytic Pavements at Pilot Scale[J]. Science of the Total Environment, 2020, 719: 137459.
[7] 吴波. 建材有害物质释放对室内空气质量的影响研究[J]. 四川建材, 2025, 51(7): 18-20.
WU B.Study on the Influence of the Release of Harmful Substances in Building Materials on Indoor Air Quality[J]. Sichuan Building Materials, 2025, 51(7): 18-20.
[8] HUANG J Y, LI Q Y, HE J Y, et al.Dye-Sensitized N-n Heterojunction {001}TiO2@NH2-MIL-101(Fe) for Degradation of Rhodamine B under Visible Light[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2025, 707: 135886.
[9] 刘金婷. 室内墙体内甲醛等有害物质的环保检测研究[J]. 中国住宅设施, 2025(4): 93-95.
LIU J T.Study on Environmental Protection Detection of Harmful Substances Such as Formaldehyde in Indoor Walls[J]. China Housing Facilities, 2025(4): 93-95.
[10] GAO F Y, ZHANG J Y, JIANG J Y, et al.Visible Light-Induced Photocatalytic Oxidation of Gaseous Ammonia on C Surface-Coated N-TiO2 Catalyst: Synthesis, Properties and Mechanism[J]. Separation and Purification Technology, 2025, 358: 130349.
[11] BENGTSSON N, CASTELLOTE M.Photocatalytic Activity for NO Degradation by Construction Materials: Parametric Study and Multivariable Correlations[J]. Journal of Advanced Oxidation Technologies, 2010, 13(3): 341-349.
[12] DIAMANTI M V, DEL CURTO B, ORMELLESE M, et al.Photocatalytic and Self-Cleaning Activity of Colored Mortars Containing TiO2[J]. Construction and Building Materials, 2013, 46: 167-174.
[13] 程锦, 李朝维, 李奇, 等. 纳米二氧化钛光催化涂料的制备及其甲醛降解效果研究[J]. 涂料工业, 2014, 44(11): 41-45.
CHENG J, LI (C /Z)W, LI Q, et al. Preparation of Nano-TiO2 Photocatalytic Coatings and Its Function of Formaldehyde Degradation[J]. Paint & Coatings Industry, 2014, 44(11): 41-45.
[14] 董瑞, 沈卫国, 钟景波, 等. 光催化自洁净混凝土研究进展[J]. 混凝土, 2011(8): 62-66.
DONG R, SHEN W G, ZHONG J B, et al.Progress of Research on Photocatalytic Self-Cleaning Concrete[J]. Concrete, 2011(8): 62-66.
[15] 夏群, 陈培鑫, 赵善宇, 等. 不同体积掺量的TiO2-SiO2气凝胶对复合砂浆光催化性能的研究[J]. 混凝土, 2018(7): 101-104.
XIA Q, CHEN P X, ZHAO S Y, et al.Effect on the Photocatalytic Performance of Mortar Using Different Volume Content of TiO2-SiO2 Aerogels[J]. Concrete, 2018(7): 101-104.
[16] YAN W J, LI N, YAN Z Y, et al.Pd/Au Bimetallic Nanoparticle-Anchored BiVO4/TiO2 Nanotube Arrays Toward Efficient Photoelectrocatalytic Suzuki-Miyaura Reactions[J]. Catalysis Science & Technology, 2023, 13(20): 6059-6067.
[17] SONG C Y.Enhancing Photocatalytic Degradation of Hydrolyzed Polyacrylamide in Oilfield Wastewater Using BiVO4/TiO2 Heterostructure Nano-Photocatalyst under Visible Light Irradiation[J]. International Journal of Electrochemical Science, 2023, 18(12): 100363.
[18] AHMADI M, ALAVI S M, LARIMI A.Highly Active Platinum Decorated BiVO4 Nanosheet/TiO2 Nanobelt Heterojunction for Photocatalytic CO2 Reduction[J]. Surfaces and Interfaces, 2024, 45: 103908.
[19] 朱玉杰, 刘璧源, 盖浩南, 等. 室内典型半挥发性有机物的光催化降解[J]. 中国环境科学, 2025, 45(5): 2390-2398.
ZHU Y J, LIU B Y, GAI H N, et al.Photocatalytic Degradation of Typical Semi-Volatile Organic Compounds in Indoor Environments[J]. China Environmental Science, 2025, 45(5): 2390-2398.
[20] YOU F F, ZHOU T H, LI J X, et al.Rich Oxygen Vacancies in Confined Heterostructured TiO2@In2S3 Hybrid for Boosting Solar-Driven CO2 Reduction[J]. Journal of Colloid and Interface Science, 2024, 660: 77-86.
[21] 黄福杨, 梁馨予, 王彬, 等. 胡敏酸对纳米二氧化钛光催化降解土霉素的影响[J]. 安全与环境学报, 2024, 24(12): 4835-4845.
HUANG F Y, LIANG X Y, WANG B, et al.Effect of Humic Acid on the Photocatalytic Degradation of Oxytetracycline Using Nano-Titanium Dioxide[J]. Journal of Safety and Environment, 2024, 24(12): 4835-4845.
[22] FARHAN S, RAZA A H, LI L, et al.Designed 2D/2D F-Doped TiO2@ZnIn2S4 Heterojunction for Efficient Photo-Utilization Hydrogen Generation[J]. Journal of Colloid and Interface Science, 2025, 681: 1-15.
[23] KAMANI H, ASHRAFI S D, LIMA E C, et al.Synthesis of N-Doped TiO2 Nanoparticle and Its Application for Disinfection of a Treatment Plant Effluent from Hospital Wastewater[J]. Desalination and Water Treatment, 2023, 289: 155-162.
[24] 陆瑶瑶, 叶俊涛, 阮承祥, 等. 二氧化钛/多孔碳纳米纤维复合材料的制备及其光催化性能[J]. 纺织学报, 2024, 45(4): 67-75.
LU Y Y, YE J T, RUAN C X, et al.Preparation and Photocatalytic Performance of Titanium Dioxide/Porous Carbon Nanofibers Composite Material[J]. Journal of Textile Research, 2024, 45(4): 67-75.
[25] 周易, 欧阳威龙, 王岳军. 核壳结构NH2-UiO-66@TiO2的制备及其可见光下的甲苯降解性能研究[J]. 物理化学学报, 2021, 37(8): 107-114.
ZHOU Y, OUYANG W L, WANG Y J, et al.Core-Shell Structured NH2-UiO-66@TiO2 Photocatalyst for the Degradation of Toluene under Visible Light Irradiation[J]. Acta Physico-Chimica Sinica, 2021, 37(8): 107-114.
[26] CHEN J F, WANG B H, LI J Z, et al.Enhanced Photocatalytic Performance of TiO2 with Tunable Oxygen Vacancies Induced by H2/N2 Mixture Treatment[J]. Solid State Sciences, 2024, 157: 107726.
Funding
2022 Guidance Project of the Scientific Research Program of the Department of Education of Hubei Province, China (B2022612); 2023 Key Project of the Hubei Provincial Education Science Planning (2023GA084)
PDF(2989 KB)
