可见光“全”分解水的类纳光电化学(PEC)电池模型

本文在对新型TiO2的光、电性质和形貌学研究基础上,首次提出"可见光‘全’分解水的类纳PEC电池模型",将水的redox反应分别放在新型TiO2纳米管内、外表面上进行。模型还提出以合适电化学性质的可变价金属氧化物作为放氧催化剂,表面晶格氧参与放O2过程,克服"全"光解水中四电子转移放O2的困难。此模型期望更多同行进行探索、验证。     

Enhancement of Visible-Light Photocatalytic Degradation of Tetracycline by Co-Doped TiO2 Templated by Waste Tobacco Stem Silk

In this study, Co-doped TiO₂ was synthesized using waste tobacco stem silk (TSS) as a template via a one-pot impregnation method. These samples were characterized using various physicochemical techniques such as N₂ adsorption/desorption analysis, diffuse reflectance UV–visible spectroscopy, X-ray diffraction, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and electron paramagnetic resonance spectroscopy. The synthesized material was used for the photodegradation of tetracycline hydrochloride (TCH) under visible light (420–800 nm). No strong photodegradation activity was observed for mesoporous TiO₂ synthesized using waste TSS as a template, mesoporous Co-doped TiO₂, or TiO₂. In contrast, Co-doped mesoporous TiO₂ synthesized using waste TSS as a template exhibited significant photocatalytic degradation, with 86% removal of TCH. Moreover, owing to the unique chemical structure of Ti-O-Co, the energy gap of TiO₂ decreased. The edge of the absorption band was redshifted, such that the photoexcitation energy for generating electron–hole pairs decreased. The electron–hole separation efficiency improved, rendering the microstructured biotemplated TiO₂ a much more efficient catalyst for the visible-light degradation of TCH.     

微波水热两步法合成高可见光响应Ag2S/ZnO及其光催化性能、机理

在不同的制备条件下,通过微波水热两步法获得了一系列Ag₂S/ZnO光催化剂,采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis/DRS)、扫描电子显微镜(SEM)和N₂吸附-脱附等测试手段对产物结构和形貌进行了表征。结果表明,产物以六方纤锌矿ZnO为主,其晶型结构并未随着反应温度和Ag₂S物质的量的增加而改变。Ag₂S的引入显著增强了光催化剂在可见光区的吸收,使吸收边带发生红移,同时抑制了ZnO(001)晶面的生长。另外,所得产物的形貌随着Ag₂S物质的量的增加从爆米花状转变为少量的柱体颗粒,且BET比表面积经过复合后明显减小。以罗丹明B为目标降解物,研究并比较了一系列Ag₂S/ZnO光催化剂对罗丹明B的光降解性能。结果表明,n_Ag2S/n_ZnO为1:10时,光催化剂在紫外光、可见光和模拟日光的照射下具有最好的光催化效果,优于目前应用最广泛的市售P25。另外,所制备的光催化材料Ag₂S/ZnO经4次循环使用后,其降解效率没有明显下降,表明该催化材料具有一定的光催化稳定性。经捕获实验研究发现,在Ag₂S/ZnO的光催化反应中空穴起主要作用,并根据绝对电负性估算了复合材料Ag₂S/ZnO的能带位置,据此提出了可能的光催化反应机理。     

F-Tag Induced Acyl Shift in the Photochemical Cyclization of o-Alkynylated N-Alkyl-N-acylamides to Indoles**

A photochemical cyclization of F-tagged, o-alkynylated N-alkylamides to indoles catalyzed by [Ir(dF(CF₃)ppy)₂(dtbpy)]PF₆ is presented. This straightforward and efficient reaction involves an intramolecular rearrangement due to the presence of an electron withdrawing group in the acyl moiety and is the first example of photochemically induced 1,3-acyl shift in the cyclization towards 3-acylindoles. A four-step reaction sequence including the photoreaction as a key step to the desired indoles has been developed and optimized. The compatibility of differently substituted F-tagged precursors with the photocyclization step was investigated and the robustness of this step towards modifications could be shown. In total, 16 so far unknown derivatives with diverse modifications in positions N1 and C2, bearing a pentadecafluorooctanoyl moiety as F-tag, were synthesized in very good yields and fully characterized.     

可见光催化C(sp3)-C(sp3)键的构筑

本文对近年来可见光催化构筑C(sp ³)-C(sp ³)键的国内外最新研究成果进行概述,着重阐述了各类催化的催化体系、反应机理及在合成生物活性分子或药物分子方面的应用。在可见光催化的反应体系中引入过渡金属或手性催化剂,构建新颖的协同催化体系,可以实现在温和的条件下对C—C键构筑的精确控制,对于手性药物的设计、开发具有重要的意义。最后,对未来可见光催化构筑C—C键的发展进行展望。     

Simultaneous Construction of C−Se And C−S Bonds via the Visible‐Light‐Mediated Multicomponent Cascade Reaction of Diselenides,Alkynes, and SO2

A visible‐light mediated multicomponent cascade reaction of diselenides, alkynes, and sulfur dioxide was developed, in which multiple C?Se and C?S bonds were constructed, and unexpected β‐sulfonylvinylselane compounds were generated with high selectivity for E configuration. β‐Sulfonylvinylselane transformation into 1,4‐oxathiine‐4,4‐dioxide and sulfonylethyne derivates was then investigated. A plausible mechanism involving a selenium radical‐initiated cascade reaction and sulfur dioxide insertion was proposed.     

一维Fe2 O3/α-MoO3异质结的制备及其可见光光催化性能

利用沉积法获得了一维Fe2 O3/α-MoO3异质结光催化剂,通过XRD、SEM-EDS、STEM、XPS、UV-Vis-DRS等测试手段对其组成、形貌、光吸收性质进行了表征,同时在可见光区测试了光催化氧化降解罗丹明B溶液的性能。测试结果表明,Fe2 O3修饰一维α-MoO3纳米带可将其光响应扩展至可见光区域,提高光催化性能。1wt;Fe2 O3/α-MoO3异质结作为光催化剂时,光照40 min后罗丹明B降解率可达到99;,分别是纯α-MoO3纳米带和纯Fe2 O3的光催化活性的3.8倍和26倍。     

磁性LDHs复合材料的制备及可见光光催化性能研究

材料复合过程组成单元间的相互作用有利于光生电子空穴对的分离,是提高材料光催化活性的一条有效途径.以Mg-Al-LDHs为主,利用直接包覆法在Fe3O4表面垂直生长生长LDHs,并引入Cu元素,得到了可见光光催化性能良好的Fe3O4/Cu-Mg-Al-LDHs复合材料.利用X-射线衍射、扫描电镜、X射线光电子能谱、红外光谱和交变梯度磁强计等测试方法研究了样品的形貌、粒径、结晶性、磁性能和元素.对比分析了单一材料、单一材料简单混合样品和Fe3O4/Cu-Mg-Al-LDHs复合材料对甲基橙光催化降解效果.实验结果表明,Fe3O4/Cu-Mg-Al-LDHs复合材料对甲基橙表现出良好的光催化效果,同时良好的磁性能有利于吸附剂的回收.     

ZnS/g-C3N4复合型催化剂的制备及其可见光光催化性能

利用共沉淀的方法制备了ZnS/g-C3N4复合型催化剂,并考察其在可见光区对罗丹明B的光降解性能的影响机制.采用TEM、BET、XRD、ICP、FT-IR和XPS等分析手段表征了样品,并评价了样品的光催化活性.结果表明,与g-C3N4相比,ZnS负载量为5wt;的ZnS/g-C3N4催化剂活性会更高一些,且经过四次循环实验后样品的光催化性能未明显失活.这可能归因于ZnS和g-C3N4所形成的异质结构提高了光催化效率.     

EAST 装置边缘局域模细丝宽度的高速CCD可见光相机系统诊断

利用高速CCD 可见光相机系统研究了EAST 上的边缘局域模(ELMs)细丝动力学特性。采用Tsai 两步标定法对CCD 相机进行标定,以实现将CCD 图像坐标转换为真实空间坐标。选取CCD 图像中与边缘局域模细丝垂直方向上的图像灰度值,绘制了灰度分布图。灰度分布图中的一个凸起的尖峰代表了一条边缘局域模细丝结构,细丝的位置坐标由尖峰顶点确定。运用Sobel 边缘检测算子检测细丝边缘轮廓,从而得到细丝的宽度。通过对边缘局域模细丝宽度特性的分析,发现边缘局域模细丝在从最外层封闭磁面向外传播的过程中宽度不断减小。这表明细丝在向外传播的过程中其能量和粒子不断耗散。I-型边缘局域模的细丝宽度比III-型边缘局域模细丝的宽度更大。