氨基酞菁-二氧化钛可见-近红外光催化剂的制备及其性能

以可溶性氨基酞菁3,3′,3″,3?-四(二甲氨基)铜酞菁(α-TDMACu Pc)为敏化剂,采用溶胶-凝胶法制备了氨基酞菁-二氧化钛(α-TDMACu Pc-Ti O2)光催化剂,通过紫外-可见吸收光谱(UV-Vis)、X射线衍射(XRD)对其进行了表征,并通过对甲基紫的光催化降解考察了α-TDMACu Pc-Ti O2光催化剂的催化性能。结果表明,α-TDMACu Pc在近红外光区有较强的吸收,敏化后的二氧化钛吸收可被拓展至可见-近红外光区,而且二氧化钛呈金红石晶型。α-TDMACu Pc敏化后的二氧化钛在可见-近红外光区的催化活性明显提高,在α-TDMACu Pc质量分数为1%时催化活性达到最高,而且光催化剂具有较好的稳定性。     

磷钨酸掺杂二氧化钛光催化剂的吸附性能及光催化活性

以钛酸四丁酯和无水乙醇为原料,采用溶胶-凝胶法制备了磷钨酸掺杂二氧化钛(H₃PW₁₂O₄₀-TiO₂)光催化剂,并利用XRD、SEM、DRS等对掺杂前后二氧化钛的结构进行了表征。在光催化实验初期的暗反应之后,发现H₃PW₁₂O₄₀-TiO₂光催化剂的吸附效果很好。对H₃PW₁₂O₄₀-TiO₂光催化剂的吸附性能进行了研究,结果表明,相比于Freundlich方程,Langmuir方程能更好地描述其吸附平衡。H₃PW₁₂O₄₀-TiO₂光催化剂与纯TiO₂相比有更好的吸附性能,吸附时间为70 min的条件下H₃PW₁₂O₄₀-TiO₂对亚甲基蓝(MB)的脱色率可达90%以上。通过自行设计的光催化反应器考察了光催化剂用量、磷钨酸掺杂量等因素对光催化降解MB性能的影响。结果表明:H₃PW₁₂O₄₀-TiO₂在紫外和可见光区域有较强的吸收,对MB溶液具有更好的光催化降解效果,而且该复合材料有较高的循环回收利用率。     

BaTiO3-TiO2复合光催化剂降解盐酸四环素及机理研究

以钛酸丁酯(TBOT)和钛酸钡(BaTiO₃)为原料,采用水热法制备了BaTiO₃-TiO₂复合光催化剂,研究了不同煅烧温度(400,500,600,700℃)对复合光催化剂结构、形貌及对盐酸四环素(TCH)光催化性能的影响。结果表明：煅烧温度的升高促进了部分TiO₂向BaTiO₃的转变,BaTiO₃的衍射峰增强,晶粒尺寸逐渐增大,球状颗粒的生长成型更为完全。BaTiO₃-TiO₂复合光催化剂的禁带宽度为3.03 eV,煅烧温度的变化没有改变BaTiO₃-TiO₂的吸收带边,复合光催化剂的吸收强度随煅烧温度的升高先增大后减小,600℃退火处理的BaTiO₃-TiO₂光催化剂吸收强度最高。在180 min时,600℃退火的BaTiO₃-TiO₂光催化剂对TCH的降解率最高可达92.80...     

2-氨基酞菁铝的合成及其催化活性研究

由于油品中的含硫化合物随着油品的燃烧,转化成污染环境的硫氧化物,因此必须除去油品中的含硫化合物。合成了2-硝基酞菁铝配合物以及2-氨基酞菁铝配合物,通过元素分析、红外光谱以及紫外—可见光谱对其的结构进行表征,然后以2-氨基酞菁铝和2-硝基酞菁铝作为乙硫醇的催化剂,结果表明:以2-氨基酞菁铝作为催化剂,乙硫醇的去除率达到了94.2%,540 min后催化活性才开始下降,而2-硝基酞菁铝的催化活性能达到91%,270 min后就开始下降。主要是因为氨基是一个供电子基团,增加了酞菁环上的电子云密度,有利于电子的传递,使催化活性提高。     

α-TPMPc/TiO_2复合材料的制备及光催化性能研究

采用原位化学合成的方法合成了均匀掺杂的1,8,15,22-四苯氧基酞菁钴/二氧化钛(简称α-TP Co(Ⅱ)Pc/TiO_2)和1,8,15,22-四苯氧基酞菁铜/二氧化钛(简称α-TPCu(Ⅱ)Pc/TiO_2)复合材料。通过UV-Vis、XRD、TG进行了表征,并通过对罗丹明B的降解来考察材料的光催化性能。结果表明,α-TPMPc/TiO_2对罗丹明B降解具有较好的光催化活性,α-TPMPc敏化能有效地提高TiO_2的可见光光催化活性,且α-TPCo(Ⅱ)Pc/TiO_2的催化活性明显优于α-TPCu(Ⅱ)Pc/TiO_2。     

高黏度指数聚α-烯烃合成润滑油的制备方法

以AlCl₃-乙酰丙酮络合物为催化剂,1-辛烯为原料齐聚合成了聚α-烯烃合成润滑油。考察了AlCl₃物质的量分数、n(AlCl₃)∶n(乙酰丙酮)、反应温度及反应时间对聚α-烯烃合成润滑油收率和性能的影响。结果表明,最佳工艺条件为AlCl₃物质的量分数4%,n(AlCl₃)∶n(乙酰丙酮)=2∶1,反应温度25 ℃,反应时间4 h,此条件下,可以合成黏度指数为173和凝点-40 ℃的聚α-烯烃合成润滑油。     

光催化剂对土壤中有机污染物的分解

研究掺杂型TiO₂光催化剂对土壤中有机污染物的分解效果及其催化剂的催化活性，考察不同金属离子掺杂型TiO₂光催化剂在土壤中加入量、光催化剂分散方式、光照时间、土壤的水分与厚度等因素的变化，通过超声萃取-高效液相色谱测定了光催化剂对有机污染物五氯酚的分解效果。结果显示，掺杂型TiO₂光催化剂的光催化活性不仅与自身对光的响应范围、吸收强度以及掺杂金属离子种类有关，还与晶体结构及分解的物质有关，表明光催化剂的催化活性是多方面因素共同作用的结果。     

Ag3PO4/AgI光催化剂的制备及降解2-氨基-4-乙酰氨基苯甲醚机理

研究了Ag₃PO₄复合棒状AgI光催化剂的制备及降解2-氨基-4-乙酰氨基苯甲醚（AMA）的性能和机理,利用X射线衍射（XRD）、扫描电镜（SEM）、紫外可见漫反射（UV-Vis）、光电子能谱（XPS）等方法对合成样品的物相组成和形貌结构进行了表征。通过可见光催化降解AMA来评价光催化剂的催化性能。实验结果显示,Ag₃PO₄/AgI复合光催化剂比Ag₃PO₄和AgI单体具有更强的光催化氧化与还原能力,其中以I和P的比例为1∶5时效果最佳,且在五次循环使用之后仍有较好的光催化活性。自由基捕获实验证明光催化过程中光生空穴（h⁺）是主要的活性物种。投加量为30mg、光照时间60min的条件下可将AMA几乎完全去除。本文研究结果为构筑新型可见光光催化剂提供了新视角,为促进光催化降解有机污染物提供了新途径。     

无定形态H3PW12O40/TiO2光催化剂降解有机染料

以钛酸丁酯和磷钨酸为主要原料,采用溶胶-凝胶法制备H₃PW₁₂O₄₀/TiO₂光催化剂,采用红外光谱、X射线衍射、热重分析和比表面分析对光催化剂进行表征。结果表明,H₃PW₁₂O₄₀/TiO₂光催化剂为无定形态,比表面积202 m²·g^-1,杂多阴离子保持了Keggin骨架结构。在TiO₂中掺杂H₃PW₁₂O₄₀,使催化剂的光响应范围扩展到可见光区,从而提高光催化活性。光催化剂对甲基橙、酸性红、罗丹明B和亚甲基蓝均有较好的光催化降解活性,催化剂易于分离,重复使用稳定性较好。对甲基橙降解的适宜条件为：1.7×10-5 mol·L^-1甲基橙溶液50 mL,H₃PW₁₂O₄₀/TiO2光催化剂用量0.03 g,500 W碘钨灯照射60 min,此条件下,甲基橙脱色率可达到96%。     

磁性氧化石墨烯负载酞菁铜的制备及去除2,4-二氯苯酚研究

以Fe Cl₃、Fe Cl₂、氧化石墨烯(GO)和二磺酸酞菁铜为原料,首先采用化学共沉淀法制备了磁性氧化石墨烯(MGO),再用共混法制备了磁性氧化石墨烯负载酞菁铜(CuPc@MGO),采用红外光谱、XRD、拉曼光谱等手段对其进行结构表征。以CuPc@MGO为去除剂,采用紫外可见吸收光谱法研究反应时间、温度、催化剂用量、初始浓度和溶液pH值对目标污染物2,4-二氯酚(2,4-DCP)去除效果的影响。实验结果表明,在25℃,CuPc@MGO用量为60 mg/L,p H值=6.5时,浓度为40 mg/L的2,4-DCP,在300 min时的去除率最高,为56.3%。     

硼氮共掺杂TiO2粉末制备及光催化活性研究

采用溶胶-凝胶法制备硼氮共掺杂TiO₂光催化剂,利用X射线衍射、X射线光电子能谱及紫外-可见光漫反射光谱手段对制备的催化剂进行表征。结果表明,硼和氮均以间隙方式进入TiO₂晶格中,形成Ti-O-B、Ti-O-N和Ti-O-B-N结构,提高了催化剂活性;B-N-TiO₂吸收带边明显红移,表明催化剂对可见光吸收增强。可见光降解甲基橙结果表明,B-N-TiO₂的活性明显高于B-TiO₂和N-TiO₂,说明硼氮共掺杂改性对提高TiO₂可见光活性具有协同作用。     

Photocatalytic degradation of organic compounds diluted in water using visible light-responsive metal ion-implanted TiO2 catalysts: Fe ion-implanted TiO2

The application of metal ion-implantation method has been made to improve the electronic properties of the TiO₂ photocatalyst to realize the utilization of visible light. The photocatalytic properties of these unique TiO₂ photocatalysts for the purification of water have been investigated. By the metal ion-implantation method, metal ions (Fe⁺, Mn⁺, V⁺, etc.) are accelerated enough to have the high kinetic energy (150 keV) and can be implanted into the bulk of TiO₂. TiO₂ photocatalysts which can absorb visible light and work as a photocatalyst efficiently under visible light irradiation were successfully prepared using this advanced technique. The UV-Vis absorption spectra of these metal ion-implanted TiO₂ photocatalysts were found to shift toward visible light regions depending on the amount and the kind of metal ions implanted. They were found to exhibit an effective photocatalytic reactivity for the liquid-phase degradation of 2-propanol diluted in water at 295 K under visible light (λ>450 nm) irradiation. The investigation using XAFS analysis suggested that the substitution of Ti ions in TiO₂ lattice with implanted metal ions is important to modify TiO₂ to be able to adsorb visible light.     

Au/TiO2复合物的制备、表征及其增强光催化灭菌活性

为提升TiO₂光催化活性克服其可见光响应能力差的问题,采用沉积-沉淀法制备了Au/TiO₂复合物光催化剂,利用X射线衍射（XRD）、傅里叶红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-vis DRS）、荧光发射光谱等对样品进行了表征。XRD、FTIR和XPS结果表明,Au/TiO₂中TiO₂为锐钛矿相且Au成功沉积至TiO₂。UV-vis DRS和荧光发射光谱结果表明,适量Au修饰不仅能提高TiO₂对可见光的吸收,还可促进TiO₂光生电子-空穴对分离,有利于增强其光催化活性。自由基捕获实验证实,形成?OH的数量与光照时间成正比且?OH生成量越多,光催化活性越高。对比考察了Au/TiO₂和TiO₂在氙灯光源照射下对大肠杆菌的光催化杀灭作用,并探讨了Au负载量、光照时间、光照强度、光催化剂浓度等因素对灭菌性能的影响。结果表明：Au/TiO₂的光催化灭菌活性优于TiO₂,且与光照时间和光照强度均成正比;Au的适宜负载量为3%（质量分数）;3%Au/TiO₂在光照时间60min、光照强度7mW/cm²、光催化剂浓度100μg/mL的条件下,对大肠杆菌的杀灭效率高达91.3%。     

The preparation of coupled WO3/TiO2 photocatalyst by ball milling

The coupled photocatalyst WO₃/TiO₂ is prepared by ball milling by doping WO₃ into TiO₂ and using H₂O solution as disperser. The coupled photocatalyst WO₃/TiO₂ is characterized by UV–VIS diffuse reflection spectrum, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Transmission electron microscopy (TEM). The results show that the optimum percentage of WO₃ doped is 3% and that the photocatalytic activity of the coupled WO₃/TiO₂ photocatalyst is much higher than that of TiO₂ and WO₃–TiO₂ with no ball milling. Compared with TiO₂, the photoexcited wavelength range of the WO₃/TiO₂ photocatalyst red-shifts about 50 nm, and the light absorption intensity is also improved. The crystal phase of TiO₂ is not changed and new crystal phases are not found during the process of ball milling. WO₃ and TiO₂ coupled highly, forming the WO₃/TiO₂ photocatalyst. The increased photocatalytic activity of the coupled photocatalyst may be attributed to the enhance charge separation efficiency and the extend wavelength range of photoexcitation.     

可见光光催化剂的研究进展

综述TiO_2、改性TiO_2光催化剂和非TiO_2体系光催化剂在可见光催化领域的研究进展,概述了光催化剂的光催化原理和应用方向,针对可见光光催化剂发展现状中存在的量子效率和可见光利用率低、且回收难等问题进行阐述,并指出制备组成可控、形貌可控、易于回收利用且可见光利用率高的新型光催化剂是研究首要方向。     

Photocatalytic decomposition of 4-nitrophenol on Ti-containing MCM-41

A series of Ti-containing MCM-41 samples, such as Ti-MCM-41 with variable Si/Ti ratios and Cr–Ti-substituted TiO₂-loaded MCM-41 having different TiO₂ loading, were prepared and studied for the photocatalytic decomposition of 4-nitrophenol in UV and visible light. The samples were characterized using surface area measurement, XRD, FT-IR, and UV–vis DRS techniques. In the case of the Ti-MCM-41 samples with Si/Ti ratios higher than 20 which were found to have typical mesoporous structure, the framework incorporation of Ti into MCM-41 increased with decreasing Si/Ti ratio. On the contrary, the Ti-MCM-41 with lower Si/Ti ratio (Si/Ti = 10) shows low structural integrity and the formation of Ti-oxide species, leading to a considerable decrease in surface area. In the case of Cr–Ti-substituted TiO₂-loaded MCM-41 samples, significant absorption occurs in visible light and the absorption in both UV and visible region increases with increasing TiO₂ loading. However, when the amount of TiO₂ loaded on Cr–Ti-MCM-41 increased above 33 wt.%, the absorption in visible light increased slightly. Thus, it seems that, at higher TiO₂ loading, some TiO₂ particles are not closely bound to the wall of Cr–Ti-MCM-41. The photocatalytic activities of Ti-containing MCM-41 samples were strongly influenced by the amount of Ti. Under UV illumination, the highest photocatalytic activity for photocatalytic decomposition of 4-NP was observed for the Ti-MCM-41 having Si/Ti ratio of 20. Among various Ti-containing MCM-41 materials prepared in this work, only Cr–Ti-substituted TiO₂-loaded MCM-41 catalysts exhibited discernable photocatalytic activities in visible light, and their photocatalytic activities increased considerably with increasing TiO₂ loading up to 33 wt.%. Further increase in TiO₂ loading enhanced photocatalytic activity slightly.     

Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2

A visible-light-active TiO₂ photocatalyst was prepared through carbon doping by using glucose as carbon source. Different from the previous carbon-doped TiO₂ prepared at high temperature, our preparation was performed by a hydrothermal method at temperature as low as 160 °C. The resulting photocatalyst was characterized by XRD, XPS, TEM, nitrogen adsorption, and UV–vis diffuse reflectance spectroscopy. The characterizations found that the photocatalyst possessed a homogeneous pore diameter about 8 nm and a high surface area of 126 m²/g. Comparing to undoped TiO₂, the carbon-doped TiO₂ showed obvious absorption in the 400–450 nm range with a red shift in the band gap transition. It was found that the resulting carbon-doped TiO₂ exhibits significantly higher photocatalytic activity than the undoped counterpart and Degussa P25 on the degradation of rhodamine B (RhB) in water under visible light irradiation (λ > 420 nm). This method can be easily scaled up for industrial production of visible-light driven photocatalyst for pollutants removal because of its convenience and energy-saving.     

纳米N掺杂TiO2的制备及可见光催化活性研究

N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.     

B掺杂对负载型TiO_2光催化剂脱硝性能的影响

采用超声辅助溶胶-凝胶法制备活化半焦负载B掺杂TiO_2光催化剂,即B-TiO_2/ASC。在相同实验条件下,分别在紫外和可见光下研究其对模拟烟气的光催化氧化脱硝性能。结果表明,在紫外和可见光下,B掺杂光催化剂的活性得到提高,在可见光下的活性增加更加显著,反应180 min后仍可保持80%以上的脱硝率。结合XRD和FT-IR分析,可以看出B以取代掺杂的方式存在于TiO_2中并且导致TiO_2表面缺陷。表面缺陷有助于光生载流子的分离,从而延长光生电子的寿命并增加参与光催化反应的光生电子数量,从而产生更多的羟基自由基氧化NO,最终提高光催化脱硝率。     

柔性Ag@TiO2/碳纳米纤维膜的制备及光催化性能

首先通过静电纺丝、预氧化煅烧法制备出自支撑的柔性TiO₂/碳纳米纤维膜(TiO₂/CNFs),然后在AgNO3溶液中通过光沉积法制备出三元复合Ag@TiO₂/CNFs光催化剂。该纤维膜可以直接从废水中取出,减少了过滤、离心等工艺步骤。同时,TiO₂分散在碳纤维中,防止了纳米颗粒的团聚。相对于纯粉体TiO₂,三元复合Ag@TiO₂/CNFs膜对可见光的吸收明显提高,并表现出优异的光催化性能。当Ag占膜质量的理论百分比为1%时,Ag@TiO₂/CNFs对罗丹明B的降解效果最好,光照150 min后降解率可达到95.30%。