g-C₃N₄/Fe₃O₄微通道反应器构建与盐酸四环素降解性能

doi:10.11949/0438-1157.20251069

摘要/Abstract

摘要：

通过高温煅烧法成功制备了g-C₃N₄/Fe₃O₄异质结复合光催化剂，并将其负载于全氟烷氧基聚合物（PFA）微通道内壁，构建了一种新型光催化微通道反应器（MPR）。SEM-EDS结果表明催化剂均匀负载在管壁，并对不同前驱体浓度下形成的催化层厚度进行了表征。结合XRD、ESR、PL、XPS和FTIR等技术，系统分析了复合材料的物相结构与化学组成。以TC为目标污染物，系统评估了该微通道反应器的光催化降解性能。并深入探究了催化剂前驱体悬浮液浓度、反应器操作流速等关键参数对反应器效能的影响规律。结果表明，在紫外光照条件下，当水力停留时间为70.5s时，MPR对TC的降解率超过90%；且在经历96个小时重复使用后，仍能保持接近90%的催化活性。本研究为高浓度有机废水的高效、环境友好型处理提供了一种具有工程应用潜力的新策略。

关键词: 微通道, 催化剂载体, 异质结, 过程强化, 传质

Abstract:

A g-C₃N₄/Fe₃O₄ heterojunction composite photocatalyst was successfully prepared via a high-temperature calcination method and subsequently immobilized onto the inner wall of a perfluoroalkoxy (PFA) microchannel to construct a novel photocatalytic microchannel reactor (MPR). SEM-EDS results confirmed the uniform distribution of the catalyst on the tube wall, and the thickness of the catalytic layer formed under different precursor concentrations was characterized. The phase structure and chemical composition of the composite were systematically analyzed using techniques including XRD, ESR, PL, XPS, and FTIR. Using tetracycline (TC) as the target pollutant, the photocatalytic degradation performance of the microchannel reactor was thoroughly evaluated. The effects of key parameters, such as the precursor suspension concentration and operational flow rate, on the reactor efficiency were investigated. The results demonstrated that under UV irradiation, the MPR achieved a degradation efficiency exceeding 90% for TC at a hydraulic retention time (HRT) of 70.5 s. Furthermore, the reactor maintained nearly 90% of its initial catalytic activity after 96 hours of continuous operation. This study provides a new strategy with potential for engineering applications in the efficient and environmentally friendly treatment of high-concentration organic wastewater.

Key words: Microchannels, Catalyst carriers, Heterojunctions, Process intensification, Mass transfer

中图分类号:

TQ 032.4

孙涵, 董延茂, 张旖, 袁妍, 吴海涛, 庞舒蕾. g-C₃N₄/Fe₃O₄微通道反应器构建与盐酸四环素降解性能[J]. 化工学报, DOI: 10.11949/0438-1157.20251069.

Han SUN, Yanmao DONG, Yi ZHANG, Yan YUAN, Haitao WU, Shulei PANG. Construction and Tetracycline Hydrochloride Degradation Performance of g-C₃N₄/Fe₃O₄ Microchannel Reactor[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251069.

图/表 15

图1 (a)微通道管道示意图；(b)微通道内壁示意图

Fig.1 (a) Schematic diagram of the microchannel pipeline; (b) Schematic diagram of the inner wall of the microchannel

图2 (a)催化剂填充质量示意图；(b)理论负载量示意图；(c)实际负载量示意图；(d)催化剂保留率

Fig.2 (a) Schematic diagram of catalyst filling mass; (b) Schematic diagram of theoretical loading capacity; (c) Schematic diagram of actual loading capacity; (d) Catalyst retention rate

图3 实验流程示意图

Fig.3 Schematic diagram of the experimental process

图4 微通道内壁上的光催化剂的FE-SEM形貌：(a)g-C₃N₄, (b)Fe₃O₄, (c)20-Fe₃O₄/g-C₃N₄的SEM图； 20-Fe₃O₄/g-C₃N₄的(d)TEM图像,(e) HR TEM图像

Fig.4 FE-SEM morphology of the photocatalyst on the microchannel inner wall: SEM of (a)g-C₃N₄, (b)Fe₃O₄, (c)20-Fe₃O₄/g-C₃N₄ ;(d) TEM, (e) HRTEM of 20-Fe₃O₄/g-C₃N₄

图5 制备的g-C₃N₄、Fe₃O₄及其20-Fe₃O₄/g-C₃N₄复合材料的(a)XRD图 ,(b) FTIR光谱

Fig.5 (a) XRD patterns, (b) FTIR spectra of the prepared g-C₃N₄, Fe₃O₄, and 20-Fe₃O₄/g-C₃N₄ composite

图 6 (a)20-Fe₃O₄/g-C₃N₄样品的XPS全谱扫描谱图；( b) Fe 2p, (c)O 1s, (d) N 1s 和 (e) C 1s的高分辨率 XPS 谱图；(f)催化剂的紫外可见光谱； (g)催化剂的能隙计算图

Fig.6 (a) XPS survey spectrum of the 20-Fe₃O₄/g-C₃N₄ sample; high-resolution XPS spectra of (b) Fe 2p, (c) O 1s, (d) N 1s, and (e) C 1s; (f) UV-vis spectrum of the catalyst; (g) band gap calculation plot of the catalyst

图7 (a)催化剂的EIS图；(b) 催化剂的的光电流；(c) 催化剂的的PL光谱

Fig.7 (a) EIS plot of the catalyst; (b) photocurrent response of the catalyst; (c) PL spectrum of the catalyst

图8 Fe₃O₄/g-C₃N₄催化剂作用下TC溶液的可见光吸收光谱

Fig.8 Visible light absorption spectrum of TC solution with Fe₃O₄/g-C₃N₄ catalyst

图 9 空白对照实验示意图：(a) 紫外光照和管道吸附对结果影；(b) 催化剂吸附对结果影响

Fig.9 Schematic diagram of blank control experiments: (a) Effect of UV irradiation and pipeline adsorption on results; (b) Effect of catalyst adsorption on results

图 10 (a) 不同催化剂对TC的降解率；(b) 不同催化剂降解TC的表观反应速率；(c) 不同浓度的催化剂对TC的降解率；(d) 不同浓度的催化剂降解TC的表观反应速率；(e) 不同管径对TC的降解率；(f) 不同g管径降解TC的表观反应速率

Fig.9 (a) Degradation rates of TC by different catalysts; (b) Apparent reaction rates of TC degradation by different catalysts; (c) Degradation rate of TC by catalysts at different concentrations; (d) Apparent reaction rate of TC degradation by catalysts at different concentrations; (e) Degradation rate of TC by different pipe diameters; (f) Apparent reaction rate of TC degradation by different pipe diameters.

图 11 (a) 不同ph对TC的降解率；(b) 不同ph降解TC的表观反应速率；(c) 对不同浓度的TC的降解率；(d) 降解不同浓度的TC的表观反应速率；(e)、(f) 不同反应器降解TC的效率对比

Fig.11 (a) Degradation rate of TC at different pH levels; (b) Apparent reaction rate of TC degradation at different pH levels; (c) Degradation rate of TC at different concentrations; (d) Apparent reaction rate of degrading TC at different concentrations; (e), (f) Comparison of TC degradation efficiency among different reactors.

图 12 自由基清除剂对复合催化剂降解TC的影响

Fig.12 Effect of radical scavengers on TC degradation by composite catalyst

图 13 光催化机理中的EPR光谱分析:(a) DMPO-•O₂⁻;(b) DMPO-•OH

Fig.13 EPR Spectral Analysis in the Photocatalytic Mechanism: (a) DMPO-•O₂⁻;(b) DMPO-•OH

图 14 光催化微通道反应器的耐久性

Fig.14 Durability of the photocatalytic microchannel reactor

图15 TC的降解机理

Fig.15 Degradation mechanism of TC

参考文献 54

[1]	Klein E Y, Impalli I, Poleon S, et al. Global trends in antibiotic consumption during 2016–2023 and future projections through 2030[J]. Proceedings of the National Academy of Sciences of the United States of America, 2024, 121(49): e2411919121.
[2]	Wang F, Xu J, Wang Z P, et al. Unprecedentedly efficient mineralization performance of photocatalysis-self-Fenton system towards organic pollutants over oxygen-doped porous g-C3N4 nanosheets[J]. Applied Catalysis B: Environmental, 2022, 312: 121438.
[3]	Khan M A, Mutahir S, Shaheen I, et al. Recent advances over the doped g-C3N4 in photocatalysis: a review[J]. Coordination Chemistry Reviews, 2025, 522: 216227.
[4]	Kumari M, Kumar N, Sharma R K, et al. Construction, characterization, and DFT analysis of Li, P Co-doped g-C₃N₄ multifunctional materials with boosted performance as photocatalyst and supercapacitor electrode[J]. Sustainable Materials and Technologies, 2025, 45: e01426.
[5]	Mubashir M, Dumée L F, Fong Y Y, et al. Cellulose acetate-based membranes by interfacial engineering and integration of ZIF-62 glass nanoparticles for CO2 separation[J]. Journal of Hazardous Materials, 2021, 415: 125639.
[6]	He S A, Li W, Wang X, et al. High-efficient precious-metal-free g-C3N4-Fe3O4/β-FeOOH photocatalyst based on double-heterojunction for visible-light-driven hydrogen evolution[J]. Applied Surface Science, 2020, 506: 144948.
[7]	Tennakone K, Tilakaratne C T K, Kottegoda I R M. Photocatalytic degradation of organic contaminants in water with TiO2 supported on polythene films[J]. Journal of Photochemistry and Photobiology A: Chemistry, 1995, 87(2): 177-179.
[8]	Jayswal S, Mohapatra S. ZnO-modified glass capillaries as a portable photocatalytic reactor for real-time measurements[J]. Materials Research Express, 2024, 11(9): 096401.
[9]	He Z Y, Li Y G, Zhang Q H, et al. Capillary microchannel-based microreactors with highly durable ZnO/TiO2 nanorod arrays for rapid, high efficiency and continuous-flow photocatalysis[J]. Applied Catalysis B: Environmental, 2010, 93(3/4): 376-382.
[10]	Ramos B, Ookawara S, Matsushita Y, et al. Low-cost polymeric photocatalytic microreactors: Catalyst deposition and performance for phenol degradation[J]. Journal of Environmental Chemical Engineering, 2014, 2(3): 1487-1494.
[11]	Bongiovanni R, Nelson A, Vitale A, et al. Ultra-thin films based on random copolymers containing perfluoropolyether side chains[J]. Thin Solid Films, 2012, 520(17): 5627-5632.
[12]	Li X R, Chen Y, Tao Y, et al. Challenges of photocatalysis and their coping strategies[J]. Chem Catalysis, 2022, 2(6): 1315-1345.
[13]	Geyer K, Codée J D C, Seeberger P H. Microreactors as tools for synthetic chemists: the chemists' round-bottomed flask of the 21st century?[J]. Chemistry – A European Journal, 2006, 12(33): 8434-8442.
[14]	Singh S, Mahalingam H, Singh P K. Polymer-supported titanium dioxide photocatalysts for environmental remediation: a review[J]. Applied Catalysis A: General, 2013, 462/463: 178-195.
[15]	ROBERGE D M, GOTTSPONER M, EYHOLZER M, et al. Industrial design, scale-up, and use of microreactors [J]. Chimica Oggi, 2009, 27(4): 8-11.
[16]	HESSEL V, RENKEN A, SCHOUTEN J C, et al. Micro Process Engineering (A Comprehensive Handbook) \|\| Development and Scale-Up of a Microreactor Pilot Plant Using the Concept of Numbering-Up [J]. 2009, 10.1002/9783527631445: 255-61.
[17]	朱艳, 刘海龙, 贾仕奎, 等. Fe3O4/g-C3N4复合异质结的构建及紫外光降解罗丹明B[J]. 材料导报, 2024, 38(23):39-45.
	Zhu Y, Liu H L, Jia S K, et al. Preparation of Fe3O4/g-C3N4 composite heterojunction and its photodegradation of rhodamine B[J]. Materials Reports, 2024, 38(23): 39-45.
[18]	Zhou X S, Jin B, Chen R Q, et al. Synthesis of porous Fe3O4/g-C3N4 nanospheres as highly efficient and recyclable photocatalysts[J]. Materials Research Bulletin, 2013, 48(4): 1447-1452.
[19]	Fabiyi M E, Skelton R L. Photocatalytic mineralisation of methylene blue using buoyant TiO2-coated polystyrene beads[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2000, 132(1/2): 121-128.
[20]	Sahar Shafaq, Zeb Akif, 刘亚男, 等. Fe3O4/g-C3N4复合催化剂增强芬顿/光-芬顿和类过氧化酶反应的活性及稳定性[J]. 催化学报, 2017, 38(12): 2110-2119.
	Sahar S, Zeb A, Liu Y N, et al. Fe3O4/g-C3N4 composite catalyst enhances the activity and stability of Fenton/photo-Fenton and peroxidase-like reaction[J]. Chinese Journal of Catalysis, 2017, 38(12): 2110-2119.
[21]	周银, 张平, 邹赛, 等. 可磁分离Fe3O4/g-C3N4复合材料的制备及其性能[J]. 复合材料学报, 2018(11): 3189-3195.
	Zhou Y, Zhang P, Zou S, et al. Preparation and properties of magnetically separable Fe3O4/g-C3N4 composites[J]. Acta Materiae Compositae Sinica, 2018(11): 3189-3195.
[22]	舒适, 王元有, 封娜, 等. 球片型Fe3O4/g-C3N4复合材料光催化性能研究[J]. 化学研究与应用, 2019, 31(8): 1558-1562.
	Shu S, Wang Y Y, Feng N, et al. Study on photocatalytic performance of spherical Fe3O4/g-C3N4 composites[J]. Chemical Research and Application, 2019, 31(8): 1558-1562.
[23]	Alshammari M, Alhassan S, Alshammari K, et al. Hydrogen catalytic performance of hybrid Fe3O4/FeS2/g-C3N4 nanocomposite structures[J]. Diamond and Related Materials, 2023, 138: 110214.
[24]	Pei J X, Li H F, Yu D C, et al. G-C3N4-based heterojunction for enhanced photocatalytic performance: a review of fabrications, applications, and perspectives[J]. Catalysts, 2024, 14(11): 825.
[25]	于笑潇. 分等级纳米复合光催化材料的制备及其光催化性能研究[D]. 武汉: 武汉理工大学, 2010.
	Yu X X. Study on Preparation and Photocatalytic Performance of Hierarchical Nanocomposite Photocatalytic Materials[D]. Wuhan: Wuhan University of Technology, 2010.
[26]	WEI X, WEN X, LIU Y, et al. Oxygen Vacancy-Mediated Selective C-N Coupling toward Electrocatalytic Urea Synthesis [J]. J Am Chem Soc, 2022, 144(26): 11530-5.
[27]	Che Y P, Liu Q Q, Lu B X, et al. Plasmonic ternary hybrid photocatalyst based on polymeric g-C3N4 towards visible light hydrogen generation[J]. Scientific Reports, 2020, 10: 721.
[28]	Vavilapalli D S, Peri R G, Sharma R K, et al. G-C3N4/Ca2Fe2O5 heterostructures for enhanced photocatalytic degradation of organic effluents under sunlight[J]. Scientific Reports, 2021, 11: 19639.
[29]	Iqbal N, Afzal A, Khan I, et al. Molybdenum impregnated g-C3N4 nanotubes as potentially active photocatalyst for renewable energy applications[J]. Scientific Reports, 2021, 11: 16886.
[30]	Chandrakanta K, Jena R, Pal P, et al. Enhanced magnetic and magnetodielectric properties of Co-doped brownmillerite KBiFe2O5 at room temperature[J]. Journal of Alloys and Compounds, 2021, 886: 161294.
[31]	LOW J, YU J, JARONIEC M, et al. Heterojunction Photocatalysts [J]. Adv Mater, 2017, 29(20).
[32]	Lianos P. Production of electricity and hydrogen by photocatalytic degradation of organic wastes in a photoelectrochemical cell: the concept of the Photofuelcell: a review of a re-emerging research field[J]. Journal of Hazardous Materials, 2011, 185(2/3): 575-590.
[33]	Zhang L W, Mohamed H H, Dillert R, et al. Kinetics and mechanisms of charge transfer processes in photocatalytic systems: a review[J]. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2012, 13(4): 263-276.
[34]	Cui P P, Hu Y, Zheng M M, et al. Enhancement of visible-light photocatalytic activities of BiVO4 coupled with g-C3N4 prepared using different precursors[J]. Environmental Science and Pollution Research, 2018, 25(32): 32466-32477.
[35]	Jia L Y, Jin Y, Li J, et al. Study on high-efficiency photocatalytic degradation of oxytetracycline based on a spiral microchannel reactor[J]. Industrial & Engineering Chemistry Research, 2022, 61(1): 554-565.
[36]	Ren Z L, Zhao Z W, Ma X, et al. Construction of magnetically retrievable g-C3N4/CeO2-Fe3O4-reduced graphene oxide composites with enhanced visible-light photocatalytic activity and antibacterial properties[J]. Catalysis Letters, 2024, 154(12): 6271-6289.
[37]	安小英, 蔡漪, 姜韵婕, 等. g-C3N4/HNTs复合光催化剂的制备及其降解盐酸四环素研究[J]. 化工新型材料, 2017, 45(5): 161-163, 172.
	An X Y, Cai Y, Jiang Y J, et al. Preparation of g-C3N4/HNTs composite photocatalyst and its degradation of tetracycline hydrochloride[J]. New Chemical Materials, 2017, 45(5): 161-163, 172.
[38]	Charles G, Roques-Carmes T, Becheikh N, et al. Determination of kinetic constants of a photocatalytic reaction in micro-channel reactors in the presence of mass-transfer limitation and axial dispersion[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2011, 223(2/3): 202-211.
[39]	Chen S Y, Lv Q R, Li F J, et al. Flat-plate mesophotoreactor with a serpentine channel and inclined baffles for balancing mixing performance and reaction throughput[J]. Reaction Chemistry & Engineering, 2025, 10(4): 894-905.
[40]	Sayed M, Ren B X, Ali A M, et al. Solar light induced photocatalytic activation of peroxymonosulfate by ultra-thin Ti3+ self-doped Fe2O3/TiO2 nanoflakes for the degradation of naphthalene[J]. Applied Catalysis B: Environmental, 2022, 315: 121532.
[41]	González-Galán C, Luna-Triguero A, Vicent-Luna J M, et al. Exploiting the π-bonding for the separation of benzene and cyclohexane in zeolites[J]. Chemical Engineering Journal, 2020, 398: 125678.
[42]	Shi Z X, Zhao J W, Li C F, et al. Fully exposed edge/corner active sites in Fe substituted-Ni(OH)2 tube-in-tube arrays for efficient electrocatalytic oxygen evolution[J]. Applied Catalysis B: Environmental, 2021, 298: 120558.
[43]	Samuel M S, Selvarajan E, Sarswat A, et al. Nanomaterials as adsorbents for As(III) and As(V) removal from water: a review[J]. Journal of Hazardous Materials, 2022, 424: 127572.
[44]	Liu T C, Yin K, Liu C B, et al. The role of reactive oxygen species and carbonate radical in oxcarbazepine degradation via UV, UV/H2O2: Kinetics, mechanisms and toxicity evaluation[J]. Water Research, 2018, 147: 204-213.
[45]	谢钦崟, 黄晓连, 李元, 等. TiO2平板微反应器设计优化及光催化性能研究[J]. 化工学报, 2021, 72(7): 3626-3636.
	Xie Q Y, Huang X L, Li Y, et al. Design optimization and photocatalytic performance research of TiO2 planar microreactor[J]. CIESC Journal, 2021, 72(7): 3626-3636.
[46]	Priya A, Arumugam M, Arunachalam P, et al. Fabrication of visible-light active BiFeWO6/ZnO nanocomposites with enhanced photocatalytic activity[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020, 586: 124294.
[47]	Song Y, Mei Z H, Kang Y H, et al. Recyclable ternary composite photocatalyst Fe3O4@mTiO2/carbon deficient g-C3N4 for efficient degrading sodium ethyl xanthate in mining wastewater[J]. Journal of Alloys and Compounds, 2025, 1022: 179818.
[48]	Girish Y R, Udayabhanu, Alnaggar G, et al. Facile and rapid synthesis of solar-driven TiO2/g-C3N4 heterostructure photocatalysts for enhanced photocatalytic activity[J]. Journal of Science: Advanced Materials and Devices, 2022, 7(2): 100419.
[49]	Adeleke J T, Theivasanthi T, Thiruppathi M, et al. Photocatalytic degradation of methylene blue by ZnO/NiFe2O4 nanoparticles[J]. Applied Surface Science, 2018, 455: 195-200.
[50]	Qiu L, Pang D D, Zhang C L, et al. In situ IR studies of Co and Ce doped Mn/TiO2 catalyst for low-temperature selective catalytic reduction of NO with NH3[J]. Applied Surface Science, 2015, 357: 189-196.
[51]	Kumar S, Surendar T, Kumar B, et al. Synthesis of magnetically separable and recyclable g-C3N4–Fe3O4 hybrid nanocomposites with enhanced photocatalytic performance under visible-light irradiation[J]. The Journal of Physical Chemistry C, 2013, 117(49): 26135-26143.
[52]	Xi G C, Yue B, Cao J Y, et al. Fe3O4/WO3 hierarchical core–shell structure: high-performance and recyclable visible-light photocatalysis[J]. Chemistry – A European Journal, 2011, 17(18): 5145-5154.
[53]	Wang J L, Zhuan R. Degradation of antibiotics by advanced oxidation processes: an overview[J]. Science of the Total Environment, 2020, 701: 135023.
[54]	Gligorovski S, Strekowski R, Barbati S, et al. Environmental implications of hydroxyl radicals (•OH)[J]. Chemical Reviews, 2015, 115(24): 13051-13092.