Fabrication of porous TiO2/g-C3N4 heterojunction and investigation on its photocatalytic performance of coenzyme regeneration

doi:10.11949/0438-1157.20250443

Abstract

Abstract:

Photocatalytic coenzyme regeneration holds great significance for bio-redox reactions. Porous TiO₂-60 was prepared via sol-gel method. After calcined at 300℃, TiO₂-300 was obtained and then mixed with melamine and calcined again to get a porous TiO₂/g-C₃N₄ heterojunction. The effects of TiO₂ calcination and melamine dosage on the structure and performance of catalyst were studied, and the catalyst dosage was optimized. The results showed that TiO₂ calcination engendered the crystal phase to transform from rutile to anatase. The as-prepared TiO₂/g-C₃N₄ featured high specific surface area, broad absorption edge, narrow band gap, and better charge separation efficiency. With increasing melamine dosage, the specific surface area and pore volume first increase and then decreased, while the light absorption and charge separation properties first increase and then decreased. After optimization, the catalytic activity and yield reached 4.8 mmol/(L·g·min) and 72% respectively, about 7.4 and 5.3 times those of g-C₃N₄. Moreover, the catalyst showed stable performance over five cycles.

Key words: porous TiO₂, g-C₃N₄, heterojunction, photocatalysis, NADH regeneration

摘要：

光催化辅酶再生对生物氧化还原反应具有重要意义。采用溶胶-凝胶法制备了多孔TiO₂-60，经300℃煅烧获得TiO₂-300，再与三聚氰胺混合煅烧得到多孔TiO₂/g-C₃N₄异质结。考察了TiO₂煅烧、三聚氰胺用量对催化剂结构和性能的影响，并优化了催化剂用量。结果表明：TiO₂的煅烧使晶相从金红石相转变为锐钛矿晶型，制备的TiO₂/g-C₃N₄具有高比表面积、宽吸收边、窄带隙及更好的电荷分离效率；随着三聚氰胺用量的增加，比表面积和孔体积先增加后减小，光吸收和电荷分离性能先上升后下降；优化后，催化活性和收率分别为4.8 mmol/(L·g·min)和72%，分别是g-C₃N₄的7.4倍和5.3倍，且在5次循环中性能稳定。

关键词: 多孔TiO₂, g-C₃N₄, 异质结, 光催化, 辅酶再生

CLC Number:

TQ 028.8

Feixue SUN, Ning LIU, Wenfang LIU, Zihui MENG. Fabrication of porous TiO₂/g-C₃N₄heterojunction and investigation on its photocatalytic performance of coenzyme regeneration[J]. CIESC Journal, 2025, 76(12): 6351-6365.

孙菲雪, 刘宁, 刘文芳, 孟子晖. 多孔TiO₂/g-C₃N₄异质结的制备及其光催化辅酶再生性能研究[J]. 化工学报, 2025, 76(12): 6351-6365.

Figures/Tables 17

Fig.1 Preparation routes of porous TiO2 (a) and TiO2/g-C3N4 (b)

Fig.2 SEM images of TiO2-60 (a), TiO2-300 (b), TiO2-60/g-C3N4 (c) and TiO2-300/g-C3N4 (d)

Fig.3 XRD patterns(a), FTIR spectra (b), N2 isothermal adsorption-desorption curves (c) and pore size distribution curves (d) of TiO2-60/g-C3N4 and TiO2-300/g-C3N4

Table 1 Pore structure parameters and optical properties of TiO2-60/g-C3N4 and TiO2-300/g-C3N4

样品	S_BET/(m²/g)	V/(cm³/g)	D_ave/nm	E_g/eV	λ_g/nm
TiO₂-300/g-C₃N₄	276	0.31	18.8	2.59	455
TiO₂-60/g-C₃N₄	108	0.18	16.7	2.63	440
TiO₂-300	226	0.28	23.6	2.85	410
TiO₂-60	128	0.21	21.4	2.90	400
g-C₃N₄	13	—	—	2.65	450

Fig.4 TEM (a) and HRTEM (b) image of TiO2-300/g-C3N4

Fig.5 In-situ XPS of TiO2-300/g-C3N4

Fig.6 VB XPS of g-C3N4, TiO2-300 and TiO2-300/g-C3N4(a) and band structure diagram (b)

Fig.7 UV-vis DRS (a), PL spectra (b), electrochemical impedance (c) and photocurrent test results (d) of TiO2-60/g-C3N4 and TiO2-300/g-C3N4

Fig.8 Reaction kinetic curves (a) and catalytic activity and NADH yield (b) of TiO2-60/g-C3N4 and TiO2-300/g-C3N4; (c) UV-vis spectra of TiO2-300/g-C3N4 system under different illumination times

Fig.9 SEM images of TiO2/g-C3N4-m

Fig.10 XRD patterns (a)； FTIR spectra (b)； N2 isothermal adsorption-desorption curves (c) and pore size distribution curves (d) of TiO2/g-C3N4-m

Table 2 Pore structure parameters and optical properties of TiO2/g-C3N4-m

样品	S_BET/(m²/g)	V/(cm³/g)	D_ave/nm	E_g/eV	λ_g/nm
TiO₂/g-C₃N₄-1.5	243	0.29	17.5	2.71	430
TiO₂/g-C₃N₄-1.8	276	0.31	18.8	2.59	455
TiO₂/g-C₃N₄-2.1	176	0.28	13.2	2.64	450

Fig.11 UV-vis DRS (a) and PL spectra (b) of TiO2/g-C3N4-m

Fig.12 Reaction kinetic curves (a) and catalytic activity and NADH yield (b) of TiO2/g-C3N4-m

Fig.13 Reaction kinetic curves (a) and catalytic activity and NADH yield (b) with different dosage of TiO2/g-C3N4

Fig.14 Reusability of TiO2/g-C3N4: reaction kinetic curves(a); XRD patterns(b); SEM photos(c),(d)

Fig.15 Biological activity of regenerated NADH

References 52

[1]	Gupta N, Sarkar A, Biswas S K. In situ NADH regeneration coupled to enzymatic CO₂ reduction: from fundamental concepts to recent advances[J]. Journal of Environmental Chemical Engineering, 2025, 13(3): 116657.
[2]	Zhao H, Wang L R, Liu G H, et al. Hollow Rh-COF@COF S-scheme heterojunction for photocatalytic nicotinamide cofactor regeneration[J]. ACS Catalysis, 2023, 13(10): 6619-6629.
[3]	Escaliante L C, de Jesus Pereira A L, Affonço L J, et al. MultilayeredTiO₂/TiO_2- _x /TiO₂ films deposited by reactive sputtering for photocatalytic applications[J]. Journal of Materials Research, 2021, 36(15): 3096-3108.
[4]	Batista J A F, Mendes J, Moretto W E, et al. Sunlight removal of diclofenac using g-C₃N₄, g-C₃N₄/Cl, g-C₃N₄/Nb₂O₅ and g-C₃N₄/TiO₂ photocatalysts[J]. Journal of Environmental Chemical Engineering, 2024, 12(3): 113016.
[5]	Liu N, Jiang J L, Zhang S Q, et al. Arrangement of ordered D-a components in a metal-organic framework for cocatalyst-free photocatalytic hydrogen evolution with efficient proton conduction[J]. Angewandte Chemie International Edition, 2025, 64(19): e202501141.
[6]	Sun F X, Chong R Q, Yang J, et al. Activated-carbon supported two dimensional covalent organic frameworks for high-efficient coenzyme photo-regeneration[J]. Journal of Environmental Chemical Engineering, 2025, 13(1): 115142.
[7]	Li Z, Ao J L, Wang Z, et al. Boosting the photocatalytic CO₂ reduction activity of g-C₃N₄ by acid modification[J]. Separation and Purification Technology, 2024, 338: 126577.
[8]	Lee J H, Jeong S Y, Son Y D, et al. Facile fabrication of TiO₂ quantum dots-anchored g-C₃N₄ nanosheets as 0D/2D heterojunction nanocomposite for accelerating solar-driven photocatalysis[J]. Nanomaterials, 2023, 13(9): 1565.
[9]	Ismael M. A review on graphitic carbon nitride (g-C₃N₄) based nanocomposites: synthesis, categories, and their application in photocatalysis[J]. Journal of Alloys and Compounds, 2020, 846: 156446.
[10]	孙世平. g-C₃N₄的制备、改性及其光催化性能研究[D]. 郑州: 郑州大学, 2019.
	Sun S P. Preparation, modification and photocatalytic properties of g-C₃N₄ [D]. Zhengzhou: Zhengzhou University, 2019.
[11]	Deng C H, Wang T, Ye F, et al. Construction of 0D/2D CuO/BiOBr hierarchical heterojunction for the enhanced photocatalytic degradation of benzene-containing pollutants under visible light[J]. Journal of Environmental Chemical Engineering, 2022, 10(3): 107365.
[12]	Yu C X, Li M X, Yang D C, et al. NiO nanoparticles dotted TiO₂ nanosheets assembled nanotubes P-N heterojunctions for efficient interface charge separation and photocatalytic hydrogen evolution[J]. Applied Surface Science, 2021, 568: 150981.
[13]	Li J J, Guo C P, Li L H, et al. Construction of Z-scheme WO₃-Cu₂O nanorods array heterojunction for efficient photocatalytic degradation of methylene blue[J]. Inorganic Chemistry Communications, 2022, 138: 109248.
[14]	孙萌, 周思源, 王涵, 等. 复合光催化剂TiO₂/g-C₃N₄的光催化性能的研究[J]. 化学工程与技术, 2021, 11(2): 45-54.
	Sun M, Zhou S Y, Wang H, et al. Study on photocatalytic performance of composites photocatalyst TiO₂/g-C₃N₄ [J]. Hans Journal of Chemical Engineering and Technology, 2021, 11(2): 45-54.
[15]	Qu A L, Xu X M, Xie H L, et al. Effects of calcining temperature on photocatalysis of g-C₃N₄/TiO₂ composites for hydrogen evolution from water[J]. Materials Research Bulletin, 2016, 80: 167-176.
[16]	Deng Z J, Osuga R, Matsubara M, et al. Morphological effect of TiO₂ nanoparticles in TiO₂/g-C₃N₄ heterojunctions on photocatalytic dye degradation[J]. Chemistry Letters, 2024, 53(9): upae171.
[17]	Pestana C J, Hui J N, Camacho-Muñoz D, et al. Solar-driven semi-conductor photocatalytic water treatment (TiO₂, g-C₃N₄, and TiO₂+g-C₃N₄) of cyanotoxins: proof-of-concept study with microcystin-LR[J]. Chemosphere, 2023, 310: 136828.
[18]	Wu M, Gong Y S, Nie T, et al. Template-free synthesis of nanocage-like g-C₃N₄ with high surface area and nitrogen defects for enhanced photocatalytic H₂ activity[J]. Journal of Materials Chemistry A, 2019, 7(10): 5324-5332.
[19]	Li L W, Cai Z X, Wu Q H, et al. Rational design of porous conjugated polymers and roles of residual palladium for photocatalytic hydrogen production[J]. Journal of the American Chemical Society, 2016, 138(24): 7681-7686.
[20]	Ceccio G, Vacik J, Siegel J, et al. Etching and doping of pores in polyethylene terephthalate analyzed by ion transmission spectroscopy and nuclear depth profiling[J]. Membranes, 2022, 12(11): 1061.
[21]	Ding Y, Yang G X, Xiang Z M, et al. Design of two-dimensional porous photocatalysts and their applications in solar fuel and valuable chemical production[J]. Journal of Environmental Chemical Engineering, 2024, 12(5): 113483.
[22]	Asasian-Kolur N, Sharifian S, Haddadi B, et al. Ordered porous carbon preparation by hard templating approach for hydrogen adsorption application[J]. Biomass Conversion and Biorefinery, 2024, 14(16): 18381-18416.
[23]	Zhang D Y, Huang G, Zhang H, et al. Soft template-induced self-assembly strategy for sustainable production of porous carbon spheres as anode towards advanced sodium-ion batteries[J]. Chemical Engineering Journal, 2024, 495: 153646.
[24]	Sun X, Shi L, Bai Q, et al. Synthesis of BiOCl/Bi₃NbO₇ heterojunction by in situ chemical etching with enhanced photocatalytic performance for the degradation of organic pollutants[J]. Applied Surface Science, 2022, 587: 152633.
[25]	Liao J Y, Jiang X H, Duan Y N, et al. Rational design and construction of novel hierarchical Au/BPNSs/ZnIn₂S₄ heterojunction photocatalyst for enhancing photocatalytic H₂ production under visible light[J]. Journal of Alloys and Compounds, 2023, 938: 168501.
[26]	Hao R R, Wang G H, Tang H, et al. Template-free preparation of macro/mesoporous g-C₃N₄/TiO₂ heterojunction photocatalysts with enhanced visible light photocatalytic activity[J]. Applied Catalysis B: Environmental, 2016, 187: 47-58.
[27]	Hong Z H, Shen B, Chen Y L, et al. Enhancement of photocatalytic H₂ evolution over nitrogen-deficient graphitic carbon nitride[J]. Journal of Materials Chemistry A, 2013, 1(38): 11754-11761.
[28]	Yu J G, Su Y R, Cheng B. Template-free fabrication and enhanced photocatalytic activity of hierarchical macro-/ mesoporous titania[J]. Advanced Functional Materials, 2007, 17(12): 1984-1990.
[29]	Hussain H, Tocci G, Woolcot T, et al. Structure of a model TiO₂ photocatalytic interface[J]. Nature Materials, 2017, 16(4): 461-466.
[30]	Wang X C, Yu J C, Ho C, et al. Photocatalytic activity of a hierarchically macro/mesoporous titania[J]. Langmuir, 2005, 21(6): 2552-2559.
[31]	Yu J G, Wang S H, Low J, et al. Enhanced photocatalytic performance of direct Z-scheme g-C₃N₄-TiO₂ photocatalysts for the decomposition of formaldehyde in air[J]. Physical Chemistry Chemical Physics, 2013, 15(39): 16883-16890.
[32]	Yang D, Zhang Y S, Zou H J, et al. Phosphorus quantum dots-facilitated enrichment of electrons on g-C₃N₄ hollow tubes for visible-light-driven nicotinamide adenine dinucleotide regeneration[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(1): 285-295.
[33]	Xiong X Y, Ding L Y, Wang Q Q, et al. Synthesis and photocatalytic activity of BiOBr nanosheets with tunable exposed {010} facets[J]. Applied Catalysis B: Environmental, 2016, 188: 283-291.
[34]	Liu Y Q, Ren M, Zhang X Y, et al. Ti—N coordination bonds boost Z-scheme interfacial charge transfer in TiO₂/C-deficient g-C₃N₄ heterojunctions for enhanced photocatalytic phenolic pollutant degradation[J]. Applied Surface Science, 2023, 614: 156118.
[35]	Zhang L, Jing D W, She X L, 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(7): 2071-2078.
[36]	Dong G H, Ho W, Li Y H, et al. Facile synthesis of porous graphene-like carbon nitride (C₆N₉H₃) with excellent photocatalytic activity for NO removal[J]. Applied Catalysis B: Environment and Energy, 2015, 174: 477-485.
[37]	Huang Z A, Sun Q, Lv K L, et al. Effect of contact interface between TiO₂ and g-C₃N₄ on the photoreactivity of g-C₃N₄/TiO₂ photocatalyst: (001) vs (101) facets of TiO₂ [J]. Applied Catalysis B: Environmental, 2015, 164: 420-427.
[38]	Chang F, Zhang J, Xie Y C, et al. Fabrication, characterization, and photocatalytic performance of exfoliated g-C₃N₄-TiO₂ hybrids[J]. Applied Surface Science, 2014, 311: 574-581.
[39]	Yu J G, Ran J R. Facile preparation and enhanced photocatalytic H₂-production activity of Cu(OH)₂ cluster modified TiO₂ [J]. Energy & Environmental Science, 2011, 4(4): 1364-1371.
[40]	Sing K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984)[J]. Pure and Applied Chemistry, 1985, 57(4): 603-619.
[41]	Yu J G, Su Y R, Cheng B. Template-free fabrication and enhanced photocatalytic activity of hierarchical macro-/ mesoporous titania[J]. Advanced Functional Materials, 2007, 17(12): 1984-1990.
[42]	Wu Y Z, Ward-Bond J, Li D L, et al. G-C₃N₄@α-Fe₂O₃/C photocatalysts: synergistically intensified charge generation and charge transfer for NADH regeneration[J]. ACS Catalysis, 2018, 8(7): 5664-5674.
[43]	Singh S, Choi S Y, et al. Enhancing photocatalytic CO₂ reduction and photo-oxidative coupling over CdS/S-g-C₃N₄ heterojunction interface into solar chemicals[J]. Energy & Fuels, 2025, 39(3): 1746-1758.
[44]	Biesinger M C, Lau L W M, Gerson A R, et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn[J]. Applied Surface Science, 2010, 257(3): 887-898.
[45]	Yang Y X, Guo Y N, Liu F Y, et al. Preparation and enhanced visible-light photocatalytic activity of silver deposited graphitic carbon nitride plasmonic photocatalyst[J]. Applied Catalysis B: Environmental, 2013, 142: 828-837.
[46]	Zang Y P, Li L P, Xu Y S, et al. Hybridization of brookite TiO₂ with g-C₃N₄: a visible-light-driven photocatalyst for As³⁺ oxidation, MO degradation and water splitting for hydrogen evolution[J]. Journal of Materials Chemistry A, 2014, 2(38): 15774-15780.
[47]	Wang W G, Yu J G, Xiang Q J, et al. Enhanced photocatalytic activity of hierarchical macro/mesoporous TiO₂-graphene composites for photodegradation of acetone in air[J]. Applied Catalysis B: Environmental, 2012, 119/120: 109-116.
[48]	Wang W G, Wang M X, Feng X J, et al. Effects of deposition temperature on the structural and optical properties of single crystalline rutile TiO₂ films[J]. Materials Chemistry and Physics, 2018, 211: 172-176.
[49]	Xu J, Wang Y J, Zhu Y F. Nanoporous graphitic carbon nitride with enhanced photocatalytic performance[J]. Langmuir, 2013, 29(33): 10566-10572.
[50]	Zhang P Y, Hu J D, Shen Y B, et al. Photoenzymatic catalytic cascade system of a pyromellitic diimide/g-C₃N₄ heterojunction to efficiently regenerate NADH for highly selective CO₂ reduction toward formic acid[J]. ACS Applied Materials & Interfaces, 2021, 13(39): 46650-46658.
[51]	Wang Y Z, Sun J, Zhang H H, et al. Tetra(4-carboxyphenyl)porphyrin for efficient cofactor regeneration under visible light and its immobilization[J]. Catalysis Science & Technology, 2018, 8(10): 2578-2587.
[52]	Poizat M, Arends I W C E, Hollmann F. On the nature of mutual inactivation between [Cp*Rh(bpy)(H₂O)]²⁺ and enzymes-analysis and potential remedies[J]. Journal of Molecular Catalysis B: Enzymatic, 2010, 63(3/4): 149-156.

Fabrication of porous TiO₂/g-C₃N₄heterojunction and investigation on its photocatalytic performance of coenzyme regeneration

多孔TiO₂/g-C₃N₄异质结的制备及其光催化辅酶再生性能研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 17

References 52

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Lili TONG, Ying CHEN, Minhua AI, Yumei SHU, Xiangwen ZHANG, Jijun ZOU, Lun PAN. ZnO/WO₃ heterojunction modulated [2+2] photocycloaddition of cycloolefins for high-energy-density fuels production [J]. CIESC Journal, 2025, 76(9): 4882-4892.
[2]	Wei ZHAO, Wenle XING, Zhaoxu HAN, Xingzhong YUAN, Longbo JIANG. Progress of g-C₃N₄-based metal-free heterojunction photocatalytic degradation of organic pollutants in water [J]. CIESC Journal, 2025, 76(9): 4752-4769.
[3]	Fenhong SONG, Wenguang WANG, Liang GUO, Jing FAN. Modulation of TiO₂ by C-element modified g-C₃N₄ and photocatalytic hydrogen production performance of composites [J]. CIESC Journal, 2025, 76(6): 2983-2994.
[4]	Lili LU, Chen LI, Liuyun CHEN, Xinling XIE, Xuan LUO, Tongming SU, Zuzeng QIN, Hongbing JI. Morphology regulation of BiOBr and study on its performance of photocatalytic CO₂ reduction [J]. CIESC Journal, 2025, 76(6): 2687-2700.
[5]	Sanlong WANG, Yuelin WANG, Yu CAO. Research on the performance of inorganic perovskite solar cells based on phase heterojunction [J]. CIESC Journal, 2025, 76(3): 1346-1352.
[6]	Yanbei LIU, Ruoming WANG, Juan LIU, Taimoor Raza, Yuzheng LU, Rizwan Raza, Bin ZHU, Songbo LI, Shengli AN, Sining YUN. Preparation of CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ electrolyte and its property in semiconductor ionic fuel cells performance [J]. CIESC Journal, 2025, 76(3): 1353-1362.
[7]	Yuejun LI, Tieping CAO, Dawei SUN. Bi nanoparticles loading modulates interfacial charge separation in CeO₂/PANI S-scheme heterojunction for enhanced CO₂ photoreduction performance [J]. CIESC Journal, 2025, 76(12): 6387-6397.
[8]	Ruobing PI, Yunlong ZHOU. Research progress on photocatalytic reduction of carbon dioxide in direct Z-scheme heterojunctions system [J]. CIESC Journal, 2024, 75(10): 3379-3400.
[9]	Yong LI, Jiaqi GAO, Chao DU, Yali ZHAO, Boqiong LI, Qianqian SHEN, Husheng JIA, Jinbo XUE. Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation [J]. CIESC Journal, 2023, 74(6): 2458-2467.
[10]	Yin XU, Jie CAI, Lu CHEN, Yu PENG, Fuzhen LIU, Hui ZHANG. Advances in heterogeneous visible light photocatalysis coupled with persulfate activation for water pollution control [J]. CIESC Journal, 2023, 74(3): 995-1009.
[11]	Mengxin LIANG, Yan GUO, Shidong WANG, Hongwei ZHANG, Pei YUAN, Xiaojun BAO. Study on preparation of Pd catalyst supported on carbon nitride for the selective hydrogenation of SBS [J]. CIESC Journal, 2023, 74(2): 766-775.
[12]	Mai ZHANG, Yao TIAN, Zhiqi GUO, Ye WANG, Guangjin DOU, Hao SONG. Design and optimization of photocatalysis-biological hybrid system for green synthesis of fuels and chemicals [J]. CIESC Journal, 2022, 73(7): 2774-2789.
[13]	DAI Xiaoye, AN Qingsong, XU Yunting, SHI Lin. Review of waste refrigerant destruction methods [J]. CIESC Journal, 2021, 72(S1): 1-6.
[14]	Yan LI, Liang JIAN, Qinyi MAO, Chengsi PAN, Pingping JIANG, Yongfa ZHU, Yuming DONG. Construction of Bi₂O₂CO₃/g-C₃N₄ heterojunction photocatalytic complete oxidation of benzyl alcohol to benzaldehyde [J]. CIESC Journal, 2021, 72(8): 4166-4176.
[15]	XIE Qinyin, HUANG Xiaolian, LI Yuan, LI Ling, GE Xuehui, QIU Ting. Design optimization and photocatalytic performance research of TiO₂ planar microreactor [J]. CIESC Journal, 2021, 72(7): 3626-3636.