五氟代锰卟啉模拟酶体系快速混合停流吸收谱

采用快速混合停流技术,在实际反应条件下,考察了五氟代锰卟啉配合物Ｍｎ~Ⅲ（ＴＦＰＰ）Ｃ１与两种单氧给体亚碘酰苯ＰｈＩＯ和过氧苯甲酸ｍ－ＣＰＢＡ构建的细胞色素Ｐ－４５０模拟酶体系催化活性物种的生成及催化烯烃环氧化过程．在氧给体ＰｈＩＯ作用下,Ｍｎ~Ⅲ（ＴＦＰＰ）Ｃ１生成了高价锰氧卟啉配合物和双核μ－氧锰卟啉配合物,具有高的催化环氧化活性和催化剂稳定性．而在氧给体ｍ－ＣＰＢＡ作用下,Ｍｎ~Ⅲ（ＴＦＰＰ）Ｃ１则生成了一种较稳定物种,以致催化活性较低。     

CeO2中氧空位形成、表征及其作用机制研究进展

Ce是一种用途十分广泛的稀土金属,其丰度也是稀土元素中最高的。其金属氧化物CeO₂由于具有优异的储放氧性能,其晶格中存在的大量氧空位可以直接作为活性位点,能够捕捉气相中的O₂,产生大量的活性氧物种,表现出良好的催化性能,在各催化体系中作为载体和活性组分被普遍使用。分别从CeO₂独特的氧空位性质,CeO₂氧空位的形成途径,氧空位的表征技术以及氧空位在催化反应中的作用等方面的最新研究进展进行了综述。最后对CeO₂氧空位在氧化还原、有机物污染降解等反应过程中的应用进行了总结和展望。     

氧络锰(Ⅳ)卟啉与烯烃反应的研究

单加氧酶细胞色素P-450在生物体中温和条件下活化分子氧,选择性地催化氧化碳氢化合物,其活性中间体可能是氧络铁原卟啉Ix的配合物。锰卟啉配合物也在温和条件下活化分子氧,选择性地催化氧化碳氢化合物,其活性中间体也可能是氧络锰卟啉配合物,是细胞色素P-450的很好的模型体系。目前人们已用一系列的氧化剂,诸如氧化碘苯(PhIO)、NaOCl、KHSO_5、RCOOOH、HCIO_4和HIO_4将三价的锰卟啉氧化为氧络锰卟啉。本实验     

间位苯基桥联的锰(Ⅲ)双咔咯的合成、表征及催化氧化性质(英文)

通过间苯二甲醛与5-氟苯基二吡咯甲烷反应合成了一种新的间位苯基桥联的双咔咯1,并利用锰盐与自由咔咯反应制备了其锰的金属配合物2。采用紫外、质谱、核磁、XPS等手段对化合物进行了表征。以苯乙烯为底物考察了锰双咔咯2的催化氧化性质,探讨了时间、溶剂、氧源、轴向配体对催化反应的影响。结果表明以亚碘酰苯和间氯过氧苯甲酸为氧源时催化的主要产物为环氧苯乙烷,而以双氧水和叔丁基过氧化氢为氧源时则主要产物为苯甲醛;在极性溶剂中的催化氧化产率较高。轴向配体对催化氧化有促进作用,不同轴向配体对催化反应产率提高的顺序是:1-甲基咪唑吡啶咪唑。     

Mn(III)-saloph室温高效催化氧化仲醇的反应研究

以saloph为配体 ,醋酸碘苯 [PhI(OAc) 2 ]为氧源 ,考察了Mn等不同中心金属离子的配合物和不同溶剂对α 苯乙醇催化氧化反应的影响 ,同时又考察了不同取代基的水杨醛制备的配体所形成的锰配合物 2a～ 2g的催化氧化性能和不同底物在优化条件下的反应情况 .结果表明 ,锰配合物 2e在乙腈溶剂中催化性能最佳 .     

水溶性锰卟啉模拟酶体系快速混合停流谱研究

采用快速混合停流技术,考察了不同pH值条件下水溶性锰卟啉MnⅢ(TMPyP)与四种单氧给体m CPBA、KHSO5、NaOCl及H2O2构建的细胞色素P 450模拟酶体系催化氧化活性物种的生成及催化烯烃环氧化过程.低pH值时,主要生成四价锰氧中间体2;而在高pH值时,首先生成五价锰氧中间体1,该中间体再向四价中间体2转化.     

Mn(Ⅲ)-saloph室温高效催化氧化仲醇的反应研究

以saloph为配体，醋酸碘苯[PhI(OAc)2]为氧源，考察了Mn等不同中心金属离子的配合物和不同溶剂对α-苯乙醇催化氧化反应的影响，同时又考察了不同取代基的水杨醛制备的配体所形成的锰配合物2a-2g的催化氧化性能和不同底物在优化条件下的反应情况．结果表明，锰配合物2e在乙腈溶剂中催化性能最佳．     

金属氧化物中氧空位缺陷的催化作用机制

金属氧化物由于其良好的活性、选择性和稳定性,在实验和工业催化领域已被广泛研究,用于一些重要的反应过程如CO₂还原、水煤气转化、氮还原反应、析氧反应等。现已证明,很多金属氧化物的缺陷是发生催化反应的活性位点,其中氧空位缺陷的作用最具代表性。氧空位缺陷作为一种重要的点缺陷可以影响材料的局域几何结构和电子结构,从而影响其催化活性,因此具有非常重要的研究意义。本文从金属氧化物中氧空位缺陷的形成机制出发,介绍其分类及调控策略,重点综述了氧空位缺陷在热催化、电催化和光催化反应中的作用特点及催化反应机制,最后对具有非金属空位缺陷催化剂的潜在应用及未来挑战进行了总结与展望。     

间位苯基桥联的锰（Ⅲ）双咔咯的合成、表征及催化氧化性质

通过间苯二甲醛与5-氟苯基二吡咯甲烷反应合成了一种新的间位苯基桥联的双咔咯1,并利用锰盐与自由咔咯反应制备了其锰的金属配合物2。采用紫外、质谱、核磁、XPS等手段对化合物进行了表征。以苯乙烯为底物考察了锰双咔咯2的催化氧化性质,探讨了时间、溶剂、氧源、轴向配体对催化反应的影响。结果表明以亚碘酰苯和间氯过氧苯甲酸为氧源时催化的主要产物为环氧苯乙烷,而以双氧水和叔丁基过氧化氢为氧源时则主要产物为苯甲醛;在极性溶剂中的催化氧化产率较高。轴向配体对催化氧化有促进作用,不同轴向配体对催化反应产率提高的顺序是：1-甲基咪唑 >吡啶 >咪唑。     

LaBO3(B=Fe,Co)中氧的迁移与光催化反应活性

以柠檬酸法合成的钙钛矿型复合氧化物LaBO3(B=Fe,Co)为催化剂,对水溶性染料进行光催化降解,实验结果表明,其光催化活性与钙钛矿型结构中氧空位沿BO6八面体棱边以曲线而非直线的迁移机制有关.在光催化氧化过程中,光生电子首先被表面氧空位束缚,再与表面的吸附氧反应生成超氧基(O2-·)而加速对染料分子的降解.钙钛矿型复合氧化物中的氧空位是由氧的迁移产生的,它可以作为电子的陷阱而捕俘电子,并作为氧的吸附中心而提高催化剂表面的吸附氧量.     

Improving visible-light-driven photocatalytic NO oxidation over BiOBr nanoplates through tunable oxygen vacancies

In this work, a series of BiOBr nanoplates with oxygen vacancies (OVs) were synthesized by a solvothermal method using a water/ethylene glycol solution. The number of OVs and facets of BiOBr were tuned by changing the water/ethylene glycol ratio. Although the role of OVs in photocatalysis has been investigated, the underlying mechanisms of charge transfer and reactant activation remain unknown. To unravel the effect of OVs on the reactant activation and photocatalytic NO oxidation process, in situ diffuse reflectance infrared Fourier transform spectroscopy, so-called DRIFTS, and theoretical calculations were performed and their results combined. The photocatalytic efficiency of the as-prepared BiOBr was significantly increased by increasing the amount of OVs. The oxygen vacancies had several effects on the photocatalysts, including the introduction of intermediate energy levels that enhanced light absorption, promoted electron transfer, acted as active sites for catalytic reaction and the activation of oxygen molecules, and facilitated the conversion of the intermediate products to the final product, thus increasing the overall visible light photocatalysis efficiency. The present work provides new insights into the understanding of the role of OVs in photocatalysts and the mechanism of photocatalytic NO oxidation.     

Oxygen Vacancy‐Mediated Photocatalysis of BiOCl: Reactivity,Selectivity, and Perspectives

Semiconductor photocatalysis is a trustworthy approach to harvest clean solar light for energy conversions, while state‐of‐the‐art catalytic efficiencies are unsatisfactory because of the finite light response and/or recombination of robust charge carriers. Along with the development of modern material characterization techniques and electronic‐structure computations, oxygen vacancies (OVs) on the surface of real photocatalysts, even in infinitesimal concentration, are found to play a more decisive role in determining the kinetics, energetics, and mechanisms of photocatalytic reactions. This Review endeavors to clarify the inherent functionality of OVs in photocatalysis at the surface molecular level using 2D BiOCl as the platform. Structure sensitivity of OVs on reactivity and selectivity of photocatalytic reactions is intensely discussed via confining OVs onto prototypical BiOCl surfaces of different structures. The critical understanding of OVs chemistry can help consolidate and advance the fundamental theories of photocatalysis, and also offer new perspectives and guidelines for the rational design of catalysts with satisfactory performance.     

分子氧催化氧化苯直接合成苯酚

苯酚是重要的有机合成中间体,当前主要通过异丙苯法合成苯酚的技术路线存在制备流程长、消耗丙烯、副产丙酮等不足。以分子氧为氧化剂由苯氧化直接合成苯酚则具有潜在重大的经济效益、社会效益和环境效益，已成为催化与有机合成等研究领域中极具挑战性的热点课题之一。本文较为系统地总结了分子氧氧化苯通过一步法合成苯酚的研究工作，着重综述了用于该反应的催化剂如Pd、Cu、V等金属或其化合物，也归纳了影响此反应的主要因素，并介绍相应的反应机理。最后，对分子氧催化氧化苯合成苯酚反应的研究提供了一些建议和展望。     

Surface Engineering of g‐C3N4 by Stacked BiOBr Sheets Rich in Oxygen Vacancies for Boosting Photocatalytic Performance

BiOBr containing surface oxygen vacancies (OVs) was prepared by a simple solvothermal method and combined with graphitic carbon nitride (g‐C₃N₄) to construct a heterojunction for photocatalytic oxidation of nitric oxide (NO) and reduction of carbon dioxide (CO₂). The formation of the heterojunction enhanced the transfer and separation efficiency of photogenerated carriers. Furthermore, the surface OVs sufficiently exposed catalytically active sites, and enabled capture of photoexcited electrons at the surface of the catalyst. Internal recombination of photogenerated charges was also limited, which contributed to generation of more active oxygen for NO oxidation. Heterojunction and OVs worked together to form a spatial conductive network framework, which achieved 63 % NO removal, 96 % selectivity for carbonaceous products (that is, CO and CH₄). The stability of the catalyst was confirmed by cycling experiments and X‐ray diffraction and transmission electron microscopy after NO removal.     

苯直接羟基化制苯酚研究进展*

综述了苯直接羟基化制苯酚的几种催化反应,包括阳极氧化法、N₂O氧化法、H₂O₂氧化法、O₂直接氧化法,这些反应均具有良好的原子经济性和环境效益.同时重点介绍了相关的催化剂及其活性中心,探讨了这些新型方法的工业应用前景.     

Effects of carrier and Mn loading on supported manganese oxide catalysts for catalytic combustion of methane

Supported manganese oxide catalysts were prepared by incipient wetness impregnation method for methane catalytic combustion, and effects of the support （Al2O3, SiO2 and TiO2） and Mn loading were investigated. These catalysts were characterized with N2 adsorption, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Methane conversion varied in a large range depending on supports or Mn loading. Al2O3 supported 15% Mn catalyst exhibited better activity toward methane catalytic oxidation. The manganese state and oxygen species played an important role in the catalytic performance,     

Kinetics of Lab Prepared Manganese Oxide Catalyzed Oxidation of Benzyl Alcohol in the Liquid Phase

The oxidation of benzyl alcohol in the liquid phase was studied over manganese oxide catalyst using molecular oxygen as an oxidant. Manganese oxide was prepared by a mechanochemical process in solid state and was characterized by chemical and physical techniques. The catalytic performance of manganese oxide was explored by carrying out the oxidation of benzyl alcohol at 323–373 K temperature and 34–101 kPa partial pressure of oxygen. Benzaldehyde and benzoic acid were identified as the reaction products. Typical batch reactor kinetic data were obtained and fitted to the Langmuir–Hinshelwood, Eley–Rideal, and Mars–van Krevelene models of heterogeneously catalyzed reactions. The Langmuir–Hinshelwood model was found to give a better fit. Adsorption of benzyl alcohol at the surface of the catalyst followed the Langmuir adsorption isotherm. The heat of adsorption for benzyl alcohol was determined as –18.14 kJ mol^?1. The adsorption of oxygen followed the Temkin adsorption isotherm. The maximum heat of adsorption for oxygen was –31.12 kJ mol^?1. The value of activation energy was 71.18 kJ mol^?1, which was apparently free from the influence of the heat of adsorption of both benzyl alcohol and oxygen.     

Cooperative Catalysis for Selective Alcohol Oxidation with Molecular Oxygen

The activation of dioxygen for selective oxidation of organic molecules is a major catalytic challenge. Inspired by the activity of nitrogen‐doped carbons in electrocatalytic oxygen reduction, we combined such a carbon with metal‐oxide catalysts to yield cooperative catalysts. These simple materials boost the catalytic oxidation of several alcohols, using molecular oxygen at atmospheric pressure and low temperature (80 °C). Cobalt and copper oxide demonstrate the highest activities. The high activity and selectivity of these catalysts arises from the cooperative action of their components, as proven by various control experiments and spectroscopic techniques. We propose that the reaction should not be viewed as occurring at an ‘active site’, but rather at an ‘active doughnut’–the volume surrounding the base of a carbon‐supported metal‐oxide particle.     

锰基氧化物与冷等离子体协同催化氧化VOCs研究进展

挥发性有机化合物(VOCs)对环境的严重污染和对人体的危害引起了人们的重视。冷等离子体与催化剂耦合形成的协同效应可显著提高VOCs低温转化速率,减少二次污染和降低能耗,具有较好的应用前景。协同催化效果主要取决于催化剂物化性能,可通过调控催化剂的组成、粒径和结构改善协同催化活性。锰基氧化物因其具有较高的储氧能力、稳定的晶体结构、较好的氧气活化性能和良好的抗中毒能力等优点而被广泛应用于冷等离子体协同催化净化VOCs的应用研究。通过金属离子掺杂调控锰基氧化物的离子价态、氧迁移率和氧气吸附量,是改善催化剂与等离子体协同催化性能主要方法。本文总结了近年来锰基氧化物与冷等离子体协同催化氧化VOCs的研究进展,主要包括氧化锰晶型、分散度和掺杂金属离子对协同催化氧化VOCs的活性影响趋势及反应机理。分析冷等离子体与锰基氧化物催化剂协同氧化VOCs中存在的问题并对其发展前景进行了展望。     

Surface characterization and catalytic evaluation of manganese nodule leached residue toward oxidation of benzene to phenol

Water washed manganese nodule leached residue (WMNLR) calcined at different temperatures was characterized by XRD, FTIR, TG-DTA, surface area, surface oxygen, and surface acid sites. Surface area, surface oxygen, surface hydroxyl group, and surface acid sites increase up to 400 degrees C and then decrease with further rise in calcination temperature up to 700 degrees C. The catalytic activity of the calcined samples was tested for single-step oxidation of benzene to phenol using hydrogen peroxide as the oxidant and acetic acid as the solvent at room temperature. The influence of various reaction parameters such as solvent, concentration of solvent, oxidant amount, time, temperature, and catalyst amount was studied to optimize the reaction conditions. WMNLR calcined at 400 degrees C showed the highest catalytic activity towards oxidation of benzene with 12.7% conversion and 98% selectivity.