MCNOs/CdS双效光催化剂的制备及其性能研究

水热合成法制备了不同磁性纳米洋葱碳(MCNOs)负载量(0%、1%、3%、5%)的MCNOs/CdS光催化剂。并通过X射线衍射分析(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)、紫外可见光光谱(UV-Vis)、磁滞回线测定仪(VSM)对其进行表征,探究了MCNOs负载比例对催化剂在可见光下降解RhB性能及机理的影响。结果表明,MCNOs能有效提高CdS的光催化效果,复合3%MCNOs后降解率为96%,与纯CdS相比降解率提高了30%,磁性分析表明,其具有良好的顺磁性并能实现催化剂的有效回收。MCNOs/CdS在可见光下催化降解RhB的一级反应动力学直线有较好的拟合度,表明制备的催化剂有较好的催化活性。     

Surface Engineering of Conjugated Polybenzothiadiazoles and Integration with Cobalt Oxides for Photocatalytic Water Oxidation

Conjugated polymers feature promising structure and properties for photocatalytic water splitting. Herein, a hydrolysis strategy was demonstrated to rationally modulate the surface hydrophilicity and band structures of conjugated poly-benzothiadiazoles. High hydrophilicity not only enhances the dispersions of polymeric solids in an aqueous solution but also reduces the absorption energy of water molecules. Besides, both theoretical and experimental results reveal that a more positive valence band potential is generated, which contributes to enhancing the photocatalytic water oxidation performance. Accordingly, the surface-modified conjugated polymers show largely promoted photocatalytic water oxidation activities by deposition of cobalt oxides as cocatalysts.     

自掺杂SnO2微球的水热合成及其可见光催化性能

本研究采用水热法,以柠檬酸为螯合剂,通过控制n(Sn⁴⁺)/n(Sn²⁺)的数值,合成了由具有丰富氧空位的SnO₂纳米晶体组装成的微球。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)及UV-Vis漫反射光谱对SnO₂纳米微球进行表征分析,结果表明:在酸性水热条件和柠檬酸的螯合作用下,二氧化锡纳米晶体聚集形成微球;在Sn⁴⁺/Sn²⁺摩尔比例为3:7时,其微球尺寸最小,整体分散性较好;同时适量二价锡离子的掺杂使得该样品氧空位浓度达到最佳,氧空位的存在将使得样品光吸收范围拓展至可见光,因而该样品显示出较强的可见光催化效率,在8 min内完全降解甲基橙。     

Applications of photocatalytic titanium dioxide-based nanomaterials in sustainable agriculture

Photocatalytic materials are attracting attention as emerging resources for agricultural applications. This timely review assesses the current developments in the use of biocompatible titanium dioxide (TiO₂)-based photocatalytic nanomaterials (TiO₂-PN) as models to unravel agricultural growth, harvest, and post-harvest problems. Such developments can lead to technological innovations aimed at addressing the pressing global environmental challenges faced by farming. TiO₂-PN have been used as antimicrobial, growth-regulating, and fertilizer-like agents. The promising agricultural research applications of TiO₂-PN are highlighted along with a discussion of the main challenges that will need to be overcome to fully understand the roles of TiO₂-PN in the sustainable and productive exploitation of land and water for agricultural applications under natural conditions. In particular, rhizosphere internalization, translocation, and plant bioaccumulation pathways of photocatalytic materials from environmental exposition are outlined to illustrate the effect of TiO₂ on the agricultural cycle. Nanotoxicology and regulations are also discussed to illustrate the importance of biocompatibility and green synthesis of nanomaterials for safe use in real applications. This overview is focused on motivating and intensifying our understanding of on-site agricultural studies. Complementary biological approaches and structural damage observed by biological transmission electron, scanning electron, and optical microscopies should accelerate the practical contribution of TiO₂-PN to sustainable agriculture in conjunction with plant factories and plasma nitrogen fixation technology. Loadings below 10 μg/L of TiO₂-PN with a size of 40 nm benefit seed germination and root elongation as well as partially suppressing metal root translocation. However, only approximately 5% of current studies were carried out in real agricultural settings.     

Semi‐heterogeneous Dual Nickel/Photocatalysis using Carbon Nitrides: Esterification of Carboxylic Acids with Aryl Halides

Cross‐coupling reactions mediated by dual nickel/photocatalysis are synthetically attractive but rely mainly on expensive, non‐recyclable noble‐metal complexes as photocatalysts. Heterogeneous semiconductors, which are commonly used for artificial photosynthesis and wastewater treatment, are a sustainable alternative. Graphitic carbon nitrides, a class of metal‐free polymers that can be easily prepared from bulk chemicals, are heterogeneous semiconductors with high potential for photocatalytic organic transformations. Here, we demonstrate that graphitic carbon nitrides in combination with nickel catalysis can induce selective C?O cross‐couplings of carboxylic acids with aryl halides, yielding the respective aryl esters in excellent yield and selectivity. The heterogeneous organic photocatalyst exhibits a broad substrate scope, is able to harvest green light, and can be recycled multiple times. In situ FTIR was used to track the reaction progress to study this transformation at different irradiation wavelengths and reaction scales.     

Three‐in‐One Oxygen Vacancies: Whole Visible‐Spectrum Absorption,Efficient Charge Separation,and Surface Site Activation for Robust CO2 Photoreduction

A facile and controllable in situ reduction strategy is used to create surface oxygen vacancies (OVs) on Aurivillius‐phase Sr₂Bi₂Nb₂TiO₁₂ nanosheets, which were prepared by a mineralizer‐assisted soft‐chemical method. Introduction of OVs on the surface of Sr₂Bi₂Nb₂TiO₁₂ extends photoresponse to cover the whole visible region and also tremendously promotes separation of photoinduced charge carriers. Adsorption and activation of CO₂ molecules on the surface of the catalyst are greatly enhanced. In the gas‐solid reaction system without co‐catalysts or sacrificial agents, OVs‐abundant Sr₂Bi₂Nb₂TiO₁₂ nanosheets show outstanding CO₂ photoreduction activity, producing CO with a rate of 17.11 μmol g^?1 h^?1, about 58 times higher than that of the bulk counterpart, surpassing most previously reported state‐of‐the‐art photocatalysts. Our study provides a three‐in‐one integrated solution to advance the performance of photocatalysts for solar‐energy conversion and generation of renewable energy.     

Total Synthesis of Zephycarinatines via Photocatalytic Reductive Radical ipso-Cyclization

We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses.     

Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light

Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl₄^?_(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O₂ through the transfer of SPR‐excited hot electrons to O₂ molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O₂ molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O₂ charge‐transfer process.     

二氧化钛包裹金纳米棒核壳材料的制备及其光解水制氢

利用溶胶凝胶法制备了金纳米棒(GNR)与TiO₂的核壳结构复合材料--GNR@TiO₂,粒径为200 nm左右。 经水热晶化后的材料粒径为300 nm左右,GNR形貌和局域表面等离子共振(LSPR)峰保持稳定,其外边包裹着树枝状的锐钛矿相TiO₂壳层。 采用X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱分析(XPS)、紫外可见吸收光谱、光催化制氢性能等技术手段测试表征了样品的结构及性能。 结果表明,晶化后的GNR@TiO₂在可见光范围内制氢速率为31.0 μmol/(g·h),相较与晶化前7.3 μmol/(g·h)得到了明显提升。 最后结合实验结果和时域有限差分(FDTD)分析了催化产氢机理:LSPR促进了可见光吸收,锐钛矿TiO₂对电场的增强促进了光生电子-空穴分离,同时晶化后的TiO₂壳层疏松多介孔,增加了活性位点,有利于传质。     

Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton-Coupled Electron Transfer

We report a catalytic, light-driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible-light irradiation in the presence of an Ir^III-based photoredox catalyst, a Brønsted base catalyst, and a hydrogen-atom transfer (HAT) co-catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O−H bonds through a proton-coupled electron-transfer mechanism. This method exhibits a broad substrate scope and high functional-group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented.