环境污染与碳排放问题是影响人类社会发展所面临的重大问题。突破绿色高效光催化技术瓶颈是破解上述两大难题的重要途径。目前，制约光催化技术发展的关键科学问题是设计制备太阳光捕获及利用率高、光生载流子传输分离效率高的光催化剂，阐明光催化剂作用机理及构效关系。因此，本文针对上述科学问题，开展厚度可控的g-C₃N₄纳米片及TiLiAl-LDHs/g-C₃N₄复合材料制备与光催化性能研究。在高效光催化剂设计与制备研究基础之上，首先开展了超薄g-C₃N₄纳米片光催化降解有机污染物机理研究，以阐明超薄g-C₃N₄纳米片的结构与光催化性能的关系；其次针对CO₂光催化水还原制清洁燃料效率低的问题，以甲苯替代水，设计CO₂-甲苯光催化协同反应体系，开展了TiLiAl-LDHs/g-C₃N₄结构与光催化性能关系研究。主要研究结果如下：

（1）采用简单热聚合法，以三聚氰胺（M）和尿素（U）混合物为原料，制备出厚度可控的g-C₃N₄纳米片。采用XRD、SEM、AFM、BET 、UV-Vis和PL等手段，研究了M/U比例变化对g-C₃N₄纳米片厚度和性能的调变规律。结果表明，随着尿素含量的增加g-C₃N₄纳米片逐渐变薄，当M/U为1:8时g-C₃N₄最薄（1:8-CN），厚度仅有3.518 nm，比表面积高达85.90 m²/g是三聚氰胺为原料的g-C₃N₄（M-CN）的7倍。光电学分析表明，超薄1:8-CN具有更高的光生载流子分离效率。

（2）采用静电自组装方法，通过改变TiLiAl-LDHs与g-C₃N₄的比例制备出具有虎皮兰花簇状和阵列结构LDHs/g-C₃N₄复合材料。首先采用简单水热法通过调控金属离子比例、甲酰胺浓度及反应温度制备出了一系列TiLiAl-LDHs，并筛选出性能最优的TiLiAl-LDHs与1:8-CN通过简单的静电自组装制备出不同比例的LDHs/g-C₃N₄。结果表明：由于抑制剂甲酰胺的存在，在一定程度上抑制了TiLiAl-LDHs的横向生长，从而制的得由条状的TiLiAl-LDHs组装而成的虎皮兰花簇结构，TiLiAl-LDHs吸收波长及强度也随之增加；在甲酰胺浓度为25%，反应温度为120℃时，金属离子比例为1：3：2，得到虎皮兰花簇状0.25-Ti₁Li₃Al₂-LDHs-120，其光吸收性能最佳且比表面积最大。

进一步采用静电自组装法，将0.25-Ti₁Li₃Al₂-LDHs-120组装在1:8-CN表面，成功制备出了TiLiAl-LDHs/g-C₃N₄复合材料（LDHs/g-C₃N₄）。结合组成结构表征，研究了0.25-Ti₁Li₃Al₂-LDHs-120与1:8-CN比例对复合材料性能和结构的影响。结果表明， 在0.25-Ti₁Li₃Al₂-LDHs-120与1:8-CN比例减小至5:3可制得0.25-Ti₁Li₃Al₂-LDHs-120层片垂直于1:8-CN的阵列结构的LDHs/g-C₃N₄（5:3-LDHs/g-C₃N₄），在5:1-LDHs/g-C₃N₄和2:1-LDHs/g-C₃N₄复合材料中，由于0.25-Ti₁Li₃Al₂-LDHs-120层片过量堆叠在1:8-CN表面，因此组装成虎皮兰花簇状结构的LDHs/g-C₃N₄。在LDHs/g-C₃N₄复合材料中，0.25-Ti₁Li₃Al₂-LDHs-120与1:8-CN光吸收性能具有协同作用，提高了光生载流子分离效率。

（3）在可见光下，超薄1:8-CN对罗丹明B（RhB）具有最佳的降解效率，并揭示了其光催化降解机理。在CEL-SPH2N光催化活性评价系统上，以氙灯为光源，研究了g-C₃N₄纳米片厚度对光催化降解RhB反应的影响，通过自由基捕获实验研究了其光催化反应机理。结果表明：1:8-CN对RhB的光催化降解率可以达到96.2%，是M-CN的1.9倍。1:8-CN光催化降解RhB的反应机理表现为：1:8-CN光生电子-空穴对高效分离产生的电子与O₂结合生成·O₂^-是提高RhB光催化降解的关键。

（4）在以LDHs/g-C₃N₄为光催化剂的CO₂-甲苯光催化反应体系上，可实现光催化CO₂弱氧化甲苯转化为精细化学品，并同时实现CO₂光催转化。在高压光催化反应器上，以氙灯为光源，研究了LDHs/g-C₃N₄复合材料光催化剂组成变化对CO₂-甲苯光催化反应产物转化率和选择性的影响规律。结果表明，在5:1-LDHs/g-C₃N₄光催化剂上，反应压力1MPa时，苯甲酸苄酯选择性最高，产量最大达至3.98 mmol/g_cat；在2:1-LDHs/g-C₃N₄上，反应压力1.5MPa时，苯甲醛选择性最高，产量最高达到8.66 mmol/g_cat。反应过程中，CO₂同时被还原为CO等产物。光催化CO₂-甲苯协同反应机理为：甲苯与CO₂在光照下分别产生苯甲基和 ，再结合生成苯甲醛；苯甲醛通过Tishchenko反应生成苯甲酸苄酯。

Environmental pollution and carbon emissions are major issues that affect the development of human society. Breaking through the bottleneck of green and efficient photocatalysis technology is an important way to solve the above two major problems. At present, the key scientific issue that restricts the development of photocatalysis technology is to design and prepare photocatalysts with higher solar light capture and utilization, and higher photogenerated carrier transport and separation efficiency. In addition, the structure-activity relationship and catalytic mechanism of the photocatalysts are worth in-depth study. In this work, novel g-C₃N₄ nanosheets with controllable thickness and corresponding TiLiAl-LDHs/g-C₃N₄ heterojunction were prepared, and their photocatalytic performance was investigated. by the degradation of and toluene oxidation by CO₂ under visible light irradiation, respectively Based on the design and preparation of the high-efficiency photocatalysts, the photocatalytic degradation of Rhodamine B (RhB) on the ultra-thin g-C₃N₄ nanosheets was carried out, and the structure-activity relationship of the g-C₃N₄ was further studied to explore the photocatalytic mechanism. In view of the low efficiency of photocatalytic CO₂ reduction with water to clean fuel, toluene was used to replace water and photocatalytic toluene oxidation by CO₂-over the TiLiAl-LDHs/g-C₃N₄ catalyst was conducted. The relationship between the catalyst structure and photocatalytic performance was investigated. The main findings are as follows:

(1) The g-C₃N₄ nanosheets with controllable thickness were prepared via a simple thermal polymerization method, using a mixture of melamine (M) and urea (U) as raw materials. XRD, SEM, AFM, BET, UV-Vis and PL were used to study the regulation of the nanosheet thickness and the optical properties of the g-C₃N₄. The results show that with the increase of the content of urea, g-C₃N₄ nanosheets gradually become thinner. When the ratio of melamine to urea is 1:8, the thickness of the g-C₃N₄ nanosheet (1:8-CN) is only 3.518 nm, and the specific surface area is 85.90 m²/g, which is 7 times that of g-C₃N₄ (M-CN) made of melamine. Photoelectric analysis shows that ultra-thin 1:8-CN has a higher separation efficiency of photogenerated carriers.

(2) Using the electrostatic self-assembly method, the LDHs/g-C₃N₄ composite material with tiger skin orchid cluster and array structure was prepared by changing the ratio of TiLiAl-LDHs vs. g-C₃N₄. A series of TiLiAl-LDHs were prepared by a simple hydrothermal method with different ratios of metal ions, different concentrations of formamide and different treatment  temperatures. TiLiAl-LDHs/g-C₃N₄ heterojunction was prepared by a simple electrostatic self-assembly method. The results showed that the lateral growth of TiLiAl-LDHs was inhibited to a certain extent, due to the presence of the inhibitor formamide, leading to the formation of a tiger skin orchid structure assembled from TiLiAl-LDHs strips. In this orchid  structure, the light absorption wavelength and intensity of TiLiAl-LDHs also increase. When the concentration of formamide is 25%, the treatment temperature is 120℃ and the ratio of metal ions is 1:3:2, the resulting TiLiAl-LDHs (marked as 0.25-Ti₁Li₃Al₂-LDHs-120) shows the best light absorption performance and the largest specific surface area. Then, 0.25-Ti₁Li₃Al₂-LDHs-120 was assembled on the surface of 1:8-CN by a electrostatic self-assembly method, so TiLiAl-LDHs/g-C₃N₄ composite material was successfully synthesized. Combined with the characterization of the composition structure, the influence of the ratio of 0.25-Ti₁Li₃Al₂-LDHs-120 and 1:8-CN on the properties and structure of the composite was studied. The results show that when the ratio of 0.25-Ti₁Li₃Al₂-LDHs-120 to 1:8-CN is reduced to 5:3 (5:3-LDHs/g-C₃N₄), the 0.25-Ti₁Li₃Al₂-LDHs-120 layer is perpendicular to the 1:8-CN array structure.When 5:1-LDHs/g-C₃N₄ and 2:1-LDHs/g-C₃N₄ are Over-stacked 0.25-Ti₁Li₃Al₂-LDHs-120 layers were assembled on the surface of 1:8-CN to form LDHs/g-C₃N₄ with a tiger skin orchid cluster structure. In the composite material, the light absorption properties of 0.25-Ti₁Li₃Al₂-LDHs-120 and 1:8-CN have a synergistic effect, which improves the separation efficiency of photogenerated carriers.

(3) The ultra-thin 1:8-CN has the best degradation efficiency for rhodamine B (RhB) under visible light, and its photocatalytic degradation mechanism was revealed. In the CEL-SPH2N photocatalysis evaluation system with a xenon lamp as a light source, the effect of the thickness of the g-C₃N₄ nanosheets on the photocatalytic degradation of RhB was studied, and the photocatalytic reaction mechanism was studied by free radical trapping experiments. The results show that the photocatalytic degradation rate of RhB by 1:8-CN can reach 96.2%, which is 1.9 times that of M-CN. The significantly improved photocatalytic activity is mainly attributed to the enhanced separation efficiency of photogenerated carriers, providing more electrons for the conversion of O₂ to O₂^-.

(4) For CO₂-toluene photocatalytic reaction system over the TiLiAl-LDHs/g-C₃N₄ photocatalyst, toluene can be weakly oxidized by CO₂ into some fine chemicals. Using a high-pressure photocatalytic reactor with a xenon lamp as the light source, the effect of the composition of TiLiAl-LDHs and g-C₃N₄ on the  activity and selectivity of the CO₂-toluene photocatalytic reaction was studied. The results show that the selectivity of benzyl benzoate is the highest over 5:1-LDHs/g-C₃N₄ at 1MPa, and the maximum yield is 3.98 mmol/g_cat. For 2:1-LDHs/g-C₃N₄, the selectivity of benzaldehyde reaches the highest at 1.5MPa with the yield of 8.66 mmol/g_cat. The mechanism of the photocatalytic toluene oxidation by CO₂ was also studied. Toluene and CO₂ react with photogenerated holes and electrons to produce benzyl and  species, respectively. Benzyl and  further combine to form benzaldehyde. Then, benzaldehyde can be converted to benzyl benzoate through Tishchenko reaction.

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