NH2-MIL-125（Ti）/C3N5复合材料的制备及光热催化还原CO2性能

doi:10.3969/j.issn.2097-2806.2025.09.004

摘要/Abstract

摘要： 采用溶剂热法构建了S型富氮氮化碳（C₃N₅）负载金属有机框架化合物NH₂-MIL-125（Ti）[NH₂-MIL-125（Ti）/C₃N₅]异质结复合材料，通过XRD、XPS、SEM、TEM、UV-vis DRS和PL等手段对复合材料的物相晶型、元素组成、微观形貌、光谱吸收和光电子-空穴重组进行了表征。评价了复合材料光热催化还原CO₂活性和稳定性，同时讨论了光热催化还原CO₂的机理。结果表明，相比单一组分材料，NH₂-MIL-125（Ti）/C₃N₅表现出显著提升光热催化还原CO₂的活性，CH₃OH和CO的产率分别为3.33和0.34 μmol/（g·h）。显著提升的光热催化还原CO₂活性得益于复合材料高达674.916 m²/g的比表面积以及高效的光电子-空穴分离效率。通过原位XPS和普通XPS谱结合能位置的变化证明了NH₂-MIL-125（Ti）和C₃N₅之间S型异质结的构建，电荷由NH₂-MIL-125（Ti）向C₃N₅转移，弯曲能带和内建电场实现了光电子-空穴的高效分离，在C₃N₅的导带和NH₂-MIL-125（Ti）的价带保留高还原和氧化活性的电子和空穴，在电子和热效应的作用下CO₂被还原为CH₃OH，同时生成了少量的CO。

关键词: NH₂-MIL-125（Ti）, 富氮氮化碳, S型异质结, 光热催化, CO₂还原, 复合材料

Abstract:

Photocatalytic reduction of CO₂ to hydrocarbon fuel is of great significance to alleviate the energy crisis and greenhouse effect. However, the recombination of photoelectron-holes greatly limits the catalytic activity of single-component material. In order to solve this problem, a S scheme nitrogen-rich carbon nitride （C₃N₅） supported metal-organic framework NH₂-MIL-125（Ti）[NH₂-MIL-125（Ti）/C₃N₅] heterojunction composite material was constructed by solvothermal method. The crystal phase, elemental composition, microstructure, spectral absorption and photoelectron-hole recombination of the composite material were characterized by XRD, XPS, SEM, TEM, UV-vis DRS and PL. The activity and stability of the composites for photothermal catalytic reduction of CO₂ were evaluated, and the mechanism of photothermal catalytic reduction of CO₂ was discussed. The results show that NH₂-MIL-125（Ti）/C₃N₅ exhibits significantly enhanced photothermal composite material reduction of CO₂ activity compared to the single component composite material. The yields of CH₃OH and CO are 3.33 and 0.34 μmol/ （g·h）, respectively. The significantly improved photothermal composite material reduction of CO₂ activity is due to the high specific surface area of the composite material up to 674.916 m²/g and efficient photoelectron-hole separation efficiency. The construction of S scheme heterojunction between NH₂-MIL-125（Ti） and C₃N₅ is proved by the change of binding energy position of in-situ XPS and ordinary XPS spectra. The charge ias transferred from NH₂-MIL-125（Ti） to C₃N₅, and the bending energy band and built-in electric field realize the efficient separation of photoelectron-holes. The electrons and holes with high reduction and oxidation activity are retained in the conduction band of C₃N₅ and the valence band of NH₂-MIL-125（Ti）. Under the action of electron and thermal effects, CO₂ is reduced to CH₃OH and a small amount of CO is generated.

Key words: NH₂-MIL-125（Ti）, nitrogen-rich carbon nitride, S scheme heterojunction, photothermal catalysis, CO₂ reduction, composite material

中图分类号:

O644.1

胡红丹, 赵鑫. NH₂-MIL-125（Ti）/C₃N₅复合材料的制备及光热催化还原CO₂性能[J]. 日用化学工业（中英文）, 2025, 55(9): 1112-1119.

Hongdan Hu, Xin Zhao. Preparation of NH₂-MIL-125 (Ti)/C₃N₅ composite and its photothermal catalytic reduction of CO₂ performance[J]. China Surfactant Detergent & Cosmetics, 2025, 55(9): 1112-1119.

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参考文献 31

[1]	Zhao R, Nie Y H, et al. Construction and performance study of ZIF-based foam for photocatalytic CO₂ reduction and oil-water separation[J]. Journal of Environmental Chemical Engineering, 2025, 13: 115813.
[2]	Zhang H D, Chen M, Qian W M, et al. Photo-assisted thermal catalytic CO₂ reduction over Ru-TiO₂ catalysts[J]. Journal of Environmental Sciences, 2025, 155: 501-509.
[3]	Tian M Z, Wang Z S, et al. Constructing a stable CdS/Nb₂O₅ Z-scheme heterojunction for efficient photocatalytic conversion of CO₂[J]. Molecular Catalysis, 2025, 576: 114930.
[4]	Wu F, Zhou C W, Tang Y G, et al. Engineering nickel doped cobalt phosphide as a photocatalyst toward visible-light-driven CO₂ reduction[J]. Molecular Catalysis, 2025, 576: 114940.
[5]	Wen X Y, Chen L, et al. Non-toxic, low-resistance Ni-based gel driven charge transfer in carbon nitride for photocatalytic CO₂ reduction[J]. Journal of Environmental Chemical Engineering, 2025, 13: 115968.
[6]	Zhao R F, Shi C D, et al. Structure-tailored superlattice Bi₇Ti₄NbO₂₁: coupling octahedral tilting and rotation induced high ferroelectric polarization for efficient piezo-photocatalytic CO₂ reduction[J]. Advanced Powder Materials, 2025, 4: 100265.
[7]	Meng Q, Yang X Y, et al. Metal-free 2D/2D C₃N₅/GO nanosheets with customized energy-level structure for radioactive nuclear wastewater treatment[J]. Journal of Hazardous Materials, 2022, 422: 126912.
[8]	Wang X Q, Wang F, Chen B, et al. Promotion of phenol photodecomposition and the corresponding decomposition mechanism over g-C₃N₄/TiO₂ nanocomposites[J]. Applied Surface Science, 2018, 453: 320-329.
[9]	Long J Q, Wei L, Huang H Z, et al. Facile fabrication of biochar-coupled g-C₃N₅/C and its enhanced photocatalytic properties[J]. Journal of Physics and Chemistry of Solids, 2022, 171: 111029.
[10]	Yin H F, Yuan C Y, et al. Fabrication of 2D/1D Bi₂WO₆/C₃N₅ heterojunctions for efficient antibiotics removal[J]. Powder Technology, 2023, 413: 118083.
[11]	Zhang X W, Li D, et al. Flower-like Co₃O₄/C₃N₅ composite as solid-phase microextraction coating for high-efficiency adsorption and preconcentration of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in water[J]. Chemical Engineering Journal, 2022, 443: 136293.
[12]	Fang Z J, Zhu Z X, et al. The efficient removal of tetracycline using copper-based MOFs under visible light[J]. Materials Research Bulletin, 2025, 188: 113431.
[13]	Li Y, Yang X Y, Wang M Y, et al. Constructing NH₂-MIL-125(Ti) derived evaporator for simultaneous photocatalytic decontamination and water evaporation[J]. Separation and Purification Technology, 2025, 361: 131567.
[14]	Wang L, Chen R J, Zhang Z Q, et al. Constructing direct Z-scheme heterojunction g-C₃N₅/BiOBr for efficient photocatalytic CO₂ reduction with H₂O[J]. Journal of Environmental Chemical Engineering, 2023, 11: 109345.
[15]	Yang J, Long J Q, Huang H Z, et al. Synthesis of visible-light driven CeO₂/g-C₃N₅ heterojunction with enhanced photocatalytic performance for organic dyes[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 660: 130846.
[16]	Liu S L, Cheng S, et al. Preparation of g-C₃N₅/g-C₃N₄ heterojunction for methyl orange photocatalytic degradation: Mechanism analysis[J]. Journal of Water Process Engineering, 2023, 54: 104019.
[17]	Wang M, Synthesis of S scheme 2D/2D g-C₃N₅/g-C₃N₄ heterojunction for photocatalytic degradation tetracycline[J]. Surfaces and Interfaces, 2024, 50: 104487.
[18]	Huang R T, Zhang Y Y, et al. Catalytic activity of microcystis aeruginosa in Fe-Co-MOFs system for efficient CO₂ fixation and high-value conversion[J]. Applied Catalysis B: Environment and Energy, 2025, 367: 125120.
[19]	Wang T T, Zhu P F, Wang M Y, et al. Insights into morphology-dependent MIL-100(Fe) catalyst towards high efficiency photothermal reduction of CO₂ by H₂O [J]. Molecular Catalysis, 2025, 576: 114948.
[20]	Zhang D L, Zhang C, Song H B, et al. Advanced bio-inspired Cu₃P/g-C₃N₅@Cu with highly dispersed Cu₃P nanoclusters for superior visible-light-driven pollutant degradation[J]. Journal of Cleaner Production, 2023, 427: 139273.
[21]	Cai Z Q, Huang Y N, et al. Type-II surface heterojunction of bismuth-rich Bi₄O₅Br₂ on nitrogen-rich g-C₃N₅ nanosheets for efficient photocatalytic degradation of antibiotics[J]. Separation and Purification Technology, 2022, 280: 119772.
[22]	Zhang H, Xiao Z R, Zhang C X, et al. Pt-supported on N-doped carbon/TiO₂ nanomaterials derived from NH₂-MIL-125 for efficient photo-thermal RWGS reaction[J]. Journal of Colloid and Interface Science, 2025, 680: 407-416.
[23]	Low J X, Jaroniec M, et al. Heterojunction photocatalysts[J]. Advanced Materials, 2017, 20: 1601694.
[24]	Jiang Z C, Zhang J J, Cheng B, et al. Hollow TiO₂@TpPa S-scheme photocatalyst for efficient H₂O₂ production through ¹O₂ in deionized water using phototautomerization[J]. Small (Weinheim an der Bergstrasse, Germany), 2025, 21: 2409079.
[25]	Huang G Z, Liu S L, Tian C, et al. Construction of S scheme ZnO/g-C₃N₄ heterojunction for the removal of pyridine from coal chemical wastewater[J]. Optical Materials, 2024, 150: 115288.
[26]	Wang C C, Cai M J, et al. Designing oxygen vacancy mediated bismuth molybdate (Bi₂MoO₆)/Nrich carbon nitride (C₃N₅)S-scheme heterojunctions for boosted photocatalytic removal of tetracycline antibiotic and Cr(Ⅵ): intermediate toxicity and mechanism insight[J]. Journal of Colloid and Interface Science, 2022, 624: 219-232.
[27]	Yue L, Yang Z C, Wang M F, et al. Construction of Sn/Bi-BDC(NH₂) and molybdenum trioxide S heterojunction enhanced photocatalytic degradation of acid red 18 and mechanism perspective[J]. Journal of Molecular Structure, 2025, 1321: 139588.
[28]	Ren C J, et al. Construct a novel CoAl-LDH/CdSe S scheme heterojunction with enhanced charge separation for efficient photocatalytic hydrogen evolution[J]. Journal of the Taiwan Institute of Chemical Engineers, 2023, 146: 104888.
[29]	Xia C H, Yuan L, Song H, et al. Spatial specific janus S-Scheme photocatalyst with enhanced H₂O₂ production performance[J]. Small (Weinheim an der Bergstrasse, Germany), 2023, 19: 2300292.
[30]	Yang X Y, Yang N, Zhou T, et al. Preventing O₂ release from CeO₂ endow P25/CeO₂ S-scheme heterojunction visible light driven hydrogen evolution[J]. Journal of Alloys and Compound, 2025, 1021: 179678.
[31]	Wang P, Wu Q, Liang J, et al. Oxygen vacancy-enhanced Mn₃O₄/PbTiO₃ S-scheme heterostructures for visible-light-driven photocatalytic CO₂ reduction by H₂O[J]. Journal of Alloys and Compounds, 2025, 1021: 179681.

Sample	S_BET/ （m²/g）	Pore size/nm	Pore volume/（cm³/g）
C₃N₅	19.436	6.425	0.203
NH₂-MIL-125（Ti）	453.354	3.599	0.522
NH₂-MIL-125（Ti）/C₃N₅	674.916	8.332	0.731

NH₂-MIL-125（Ti）/C₃N₅复合材料的制备及光热催化还原CO₂性能

Preparation of NH₂-MIL-125 (Ti)/C₃N₅ composite and its photothermal catalytic reduction of CO₂ performance

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