Visible Light Photocatalytic Activity of Porphyrin Tin(IV) Sensitized TiO2 Nanoparticles for the Degradation of 4-Nitrophenol and Methyl Orange

A stable metalloporphyrin sensitized TiO₂ (Degussa P25) photocatalyst was prepared by using trans-dihydroxo[5,10,15,20-tetraphenylporphyrin]tin(IV) (SnP) as a sensitizer in a simple impregnation process. The solid diffuse reflectance ultraviolet-visible (UV-vis) spectrum of the SnP sensitized TiO₂ photocatalyst (SnP-TiO₂) indicated that there existed interaction between SnP and TiO₂. It was found that SnP-TiO₂ exhibited an enhanced visible light photocatalytic activity as compared with that over P25 for the degradation of 4-nitrophenol (4-NP) and methyl orange (MO) in aqueous solutions. The mechanism exploration showed that the degradation of MO and 4-NP experienced two different ways, that is, MO was photodegraded by reactive oxygen species and 4-NP was directly photodegraded by the excited state of SnP. Furthermore, it was found that the loading content of SnP had an important influence on the photocatalytic activity of TiO₂. The maximum photocatalytic efficiency was achieved when the contents of SnP were 25 mg and 30 mg per gram TiO₂ for MO and 4-NP, respectively. Importantly, SnP-TiO₂ was particularly stable and the photocatalytic activity was hardly decreased after being recycled seven times in the presence of oxygen, which could be attributed to the easy reductive regeneration of SnP.     

Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

The first visible‐light‐mediated synthesis of trifluoromethylselenolated arenes under metal‐free conditions is reported. The use of an organic photocatalyst enables the trifluoromethylselenolation of arene diazonium salts using the shelf‐stable reagent trifluoromethyl tolueneselenosulfonate at room temperature. The reaction does not require the presence of any additives and shows high functional‐group tolerance, covering a very broad range of starting materials. Mechanistic investigations, including EPR spectroscopy, luminescence investigations, and cyclic voltammetry allow rationalization of the reaction mechanism.     

负载于多壁碳纳米管上卟啉锡的可见光催化活性

采用超声-回流方法制备了反式-二羟基-5,10,15,20-四苯基卟啉锡髧(SnP)和多壁碳纳米管(MWNTs)复合物光催化剂(SnP/MWNTs),用红外光谱、紫外-可见吸收光谱、X射线光电子能谱等方法对其进行了表征。研究了SnP/MWNTs在可见光照射下对罗丹明B催化降解的性能,并结合电化学阻抗谱和伏安特性等测试对其可见光催化降解机理进行了讨论。结果表明,SnP优异的可见光吸收能力结合MWNTs强的电子转移能力,有效地促进了光生电子的转移,使SnP/MWNTs显示出优异的可见光催化活性,可见光照射5h后,对罗丹明B的降解效率达92%。     

离子交换法制备AgBr/Ag2WO4复合催化剂及其可见光催化性能

以Ag₂WO₄为载体,采用离子交换法合成了新型的AgBr/Ag₂WO₄复合光催化剂.利用XRD、SEM和UV-Vis对AgBr/Ag₂WO₄催化剂进行了表征,在可见光条件下(500 W、λ>420 nm)、以甲基橙(MO)为染料模型研究了AgBr/Ag₂WO₄的光催化活性.结果表明,AgBr/Ag₂WO₄具有比单独的AgBr和Ag₂WO₄更佳的催化活性,其中30%-AgBr/Ag₂WO₄复合催化剂具有最大光催化活性.机理研究表明,在MO的降解过程中,·O₂^-起主要作用,h⁺次之而·OH可以忽略.AgBr和Ag₂WO₄之间构成的异质结有效分离了光生电子和空穴,提高了催化剂的活性.     

原位合成CoPc/SnO2的键合特性及可见光光催化活性

报道了酞菁钴(CoPc)分子原位自组装于纳米SnO2颗粒表面, CoPc大环分子与SnO2表面形成Co—O轴向相互作用, 测定了原位合成方法(标记为i)制备的CoPc/SnO2(i)与浸渍法(标记为d)制备CoPc/SnO2(d)间的结合特性, 并进行了可见光光催化表征及CoPc敏化机理探讨. 结果表明, 在结合位点数相当的情况下, CoPc/SnO2(i)结合常数比CoPc/SnO2(d)的高两个数量级, 前者的光催化效率亦比后者高32.5%(光照150 min), 且CoPc/SnO2(i)光催化稳定性较高(重复十次循环使用). 其CoPc敏化SnO2的机理为, 由于敏化剂与半导体之间存在的强相互作用, 不仅增强了光生电荷在CoPc的LUMO与SnO2半导体导带间的导入效率及光生电荷对的分离效率, 而且提高了敏化剂的负载稳定性与循环光催化效率的持续性.     

可见光照射下丙炔光催化水解反应的研究 Ⅱ．钒离子对二氧化钛催化性能的影响

 研究了几种不同粒径的TiO2在CH3CCH和H2O的光催化反应中的催化活性．结果表明,利用离子注入法可以拓展纳米TiO2催化剂的光吸收区域,使其吸收带向可见光方向偏移,且偏移程度随着TiO2粒径的增大而增大;特别是注入V离子使TiO2催化剂在可见光区域具有光催化活性．V离子注入后,TiO2催化剂在紫外区域的光催化活性没有下降,但在可见光区域的光催化活性有所提高．在五种光催化剂中,具有中等粒径大小的P－25注入V离子后表现出最高的光催化活性．在太阳光直接照射下,这些光催化剂也具有较高的催化活性．     

可见/红外宽光谱分色片偏振调控的设计

针对光学系统中可见/红外宽光谱分色片的偏振特性,采用诱导透射法设计了满足偏振遥感光学系统能量要求的可见/红外宽光谱分色片,并对其偏振特性进行了分析.通过计算获得了透射带400～900 nm可见/红外宽光谱分色片的偏振情况,采用等效层理论在其基底背面设计了偏振调控膜系,对分色片透射带的偏振度加以调控.使用needle优化...     

Visible‐Light Photocatalysis: Does It Make a Difference in Organic Synthesis?

Visible‐light photocatalysis has evolved over the last decade into a widely used method in organic synthesis. Photocatalytic variants have been reported for many important transformations, such as cross‐coupling reactions, α‐amino functionalizations, cycloadditions, ATRA reactions, or fluorinations. To help chemists select photocatalytic methods for their synthesis, we compare in this Review classical and photocatalytic procedures for selected classes of reactions and highlight their advantages and limitations. In many cases, the photocatalytic reactions proceed under milder reaction conditions, typically at room temperature, and stoichiometric reagents are replaced by simple oxidants or reductants, such as air, oxygen, or amines. Does visible‐light photocatalysis make a difference in organic synthesis? The prospect of shuttling electrons back and forth to substrates and intermediates or to selectively transfer energy through a visible‐light‐absorbing photocatalyst holds the promise to improve current procedures in radical chemistry and to open up new avenues by accessing reactive species hitherto unknown, especially by merging photocatalysis with organo‐ or metal catalysis.     

空间目标的可见光散射与红外辐射

利用Lowtran7大气传输模型计算0.4～0.8μm可见光波段的太阳辐射、大气自身的热辐射以及天地背景辐射.依据粗糙面光散射理论与双向反射分布函数计算空中目标表面对太阳辐射和云层对阳光反射的散射.利用传热学和背景辐射理论,根据能量守恒定律建立空间目标表面温度的热平衡方程.以气球为例,计算不同表面涂层材料的气球,在不同地理位置、不同高度和不同时间条件下,其温度及辐射功率的变化.分析空间目标红外辐射特性的一般规律和特征.