水滑石衍生的复合氧化物催化氧化挥发性有机气体的研究进展（英文）

挥发性有机化合物(VOCs)是大气颗粒污染物(PM2.5)和臭氧污染的主要前体物,来源于工业活动(如溶剂使用过程)、汽车尾气以及植物排放等,具有毒性,对人类和自然生命产生危害.催化氧化技术是在催化剂表面,在较低的操作温度(200-450℃)下,将VOCs非均相催化氧化成CO2和H2O,是一种最为有效的分解VOCs的方法,具有副产物少,能耗低的优点.VOCs分解用催化剂主要分为贵金属和金属氧化物两大类.贵金属催化剂活性高,但价格昂贵.因此科研工作者一直在诸多方面调控过渡金属氧化物,例如制备方法、组分协同、结构缺陷等,期望获得高活性、低成本的催化剂.水滑石(LDHs)是一种层状双金属氢氧化物,由带正电荷的金属氢氧化物层板和层间阴离子组成,可以表示为[M1-x^2+Mx^3+(OH)2](An-)x/n·mH2O.鉴于LDHs特有的结构特点,层板元素可调、比例可调等,其在一定温度下煅烧可以得到过渡金属复合氧化物(MMO)材料.由于LDHs的拓扑焙烧转变得到的MMO材料显示出许多利于多相催化反应的优点,如大表面积和多孔性、高热稳定性、良好的金属氧化物分散性等.水滑石基催化材料用于VOCs催化分解也引起了科研工作者的持续关注和研究,文献大多选择苯、甲苯、乙酸乙酯等工业活动中常用的挥发性有机溶剂作为探针分子来评估催化剂的活性、稳定性等参数.本综述将LDHs衍生的VOCs降解催化剂分为4类,整理了其近10年的研究进展:(1)含过渡金属的LDHs焙烧转变成MMO催化剂:系统论述了层板元素组成、层板元素比例、焙烧温度、制备方法等条件对催化活性的影响规律,阐明了不同处理条件下催化剂的物理化学特性(比表面积、孔结构、表面元素价态、氧缺陷、还原性)与催化活性的关联;(2)贵金属/MMO催化剂:比较了贵金属种类、LDHs载体种类、负载方式等因素对催化活性的影响规律,总结了贵金属负载在LDHs载体的优势;(3)核壳型MMO催化剂:分析了在氧化铝球、MOF等载体上原位负载LDHs的方法构筑多级结构的MMO催化剂,利于促进VOCs分解活性;(4)整体型MMO催化剂:满足VOCs分解实际应用,提出铝片基底上原位生长-煅烧制备高活性位点暴露的整体式催化剂的优点.在催化活性基础上着重介绍了水蒸气对活性的影响以及VOCs分解催化机理.同时提出了3点仍需努力的方向:LDHs向MMO拓扑转变机制认识不足;LDHs衍生的催化剂的VOCs分解机制研究不深入;催化剂活性降低-再生研究不透彻.     

Molecular complexes in water oxidation: Pre-catalysts or real catalysts

Artificial photosynthesis is considered a promising method to produce clean and renewable energy by sunlight. To accomplish this aim, development of efficient and robust catalysts for water oxidation and hydrogen production is extremely important. Owing to the advantages of easily modified structures and traceable catalytic processes, molecular water oxidation catalysts (WOCs) attract much attention during the past decade. However, the transformation of molecular WOCs to metal oxides/hydroxides or metal ions may occur under the harsh catalytic conditions, making the identification of true active species difficult. In this article, recent progress on molecular complexes acting as real catalysts or precursors toward water oxidation was briefly reviewed. We summarized the commonly used physical techniques and chemical methods that enable to distinguish homogeneous catalysts from heterogeneous catalysts. The factors that affect the nature of WOCs, such as reaction conditions, transition metal centers, and supporting ligands were discussed as well.     

过渡金属基层状双羟基化合物的调控及其在电化学水氧化中的应用

过渡金属基层状双羟基化合物(transition metals based layered double hydroxides,TM LDHs)由于大的比表面积,开放的微观结构,可调的层间距和化学成分等优势,近年来被广泛应用于催化领域。 本综述文章将集中介绍TM LDH在电催化水氧化中的应用,从其化学成分和微观结构的调控两方面入手,详述TM LDH具有优异催化水性能的原因,并对其催化性能未来进一步的可能发展进行展望。     

Effects of Cerium Oxides on the Catalytic Performance of Pd/CNT for Methanol Oxidation

The carbon nanotubes supported palladium(Pd/CNT)nanocatalysts were modified by cerium oxides/ hydroxides and their catalytic performances for methanol oxidation were evaluated.Electrochemical measurements indicate that the introduction of cerium remarkably improves the catalytic activity of Pd/CNT catalysts towards methanol oxidation.X-Ray photoelectron spectra results reveal an interaction between palladium and cerium oxides.It is also observed that cerium-modified catalysts have excellent poison resistances,which is attributed to the poison-removal ability of cerium oxides/hydroxides.The highly oxidized cerium oxides/hydroxides have a strong ability to inhibit the accumulation of carbonaceous intermediates on the active sites of Pd catalysts.     

Colloidal FeIII,MnIII, CoIII,and CuII Hydroxides Stabilized by Starch as Catalysts of Water Oxidation Reaction with One Electron Oxidant Ru(bpy)33+

Colloidal catalysts for oxidation of water to dioxygen, which are stable on storage and under the reaction conditions, are synthesized based on Co^III, Mn^III, Fe^III and Cu^II hydroxides. Stabilization of the colloids with dextrated starch allows the process of hydroxide ageing to be stopped at the stage of the formation of primary nuclei (ca. 2–3 nm from transmission electron microscopy data). Molecular mechanics and dynamic light scattering studies indicate a core-shell type structure of the catalysts, where the hydroxide core is stabilized by the molecular starch network (ca. 5–7 nm). The colloidal catalysts are highly efficient in oxidizing water with one electron oxidant Ru(bpy)₃³⁺ at pH 7 to 10. The influence of pH, catalyst concentration, and buffer nature on the oxygen yield is studied. The maximal yields are 72, 53, and 78 % over Fe-, Mn- and Co-containing catalysts, respectively, and turnover numbers are 7.8; 54 and 360, respectively. The Cu-containing catalyst is poorly effective to the water oxidation (the maximal yield is 28 % O₂). The synthesized catalysts are of interest for stopped-flow kinetic studies of the mechanism of the water oxidation and as precursors for anchoring nanosized hydroxides onto various supports in order to develop biomimetic systems for artificial photosynthesis.     

铁基阳极析氧催化剂的研究进展与展望

利用电解水制氢来储存太阳能是未来能源发展的一大趋势。 水的阳极氧化是这一过程中最重要也是最复杂的一步。 因此,设计稳定而高效的水氧化催化剂是电解水制氢的关键。 目前,研究比较成熟的是基于贵金属钌的水氧化催化剂,但由于其价格昂贵、储量较少无法大规模利用。 铁作为钌的同族元素用于水氧化催化近年来受到了越来越多的关注。 本文从铁基阳极水氧化催化剂研究现状、制备方法、催化体系及机理3个方面对电解水铁基阳极催化剂进行了综述。 分析其当前存在的问题,为水氧化催化剂的进一步研究设计提供参考。     

Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts

Iron cations are essential for the high activity of nickel and cobalt‐based (oxy)hydroxides for the oxygen evolution reaction, but the role of iron in the catalytic mechanism remains under active investigation. Operando X‐ray absorption spectroscopy and density functional theory calculations are used to demonstrate partial Fe oxidation and a shortening of the Fe?O bond length during oxygen evolution on Co(Fe)O_xH_y. Cobalt oxidation during oxygen evolution is only observed in the absence of iron. These results demonstrate a different mechanism for water oxidation in the presence and absence of iron and support the hypothesis that oxidized iron species are involved in water‐oxidation catalysis on Co(Fe)O_xH_y.     

Metal hydroxides as catalysts for the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide

This paper reports the results obtained in the Baeyer-Villiger oxidation of cyclohexanone with a hydrogen peroxide/benzonitrile mixture as oxidant in the presence of synthetic metal hydroxides or their calcined products as catalysts. The metal hydroxides were obtained by coprecipitation. The best ε-caprolactone conversion results were provided by magnesium hydroxide.     

Catalytic performance of Ni-Al layered double hydroxides in CO purification processes

Ni-Al layered double hydroxides with Ni²⁺/Al³⁺ molar ratios of 1.5 and 3.0 have been synthesized by co-precipitation and studied as catalyst precursors for purification of CO-containing gas-mixtures by means of CO oxidation to CO₂ and conversion of CO by water vapor (water-gas shift reaction). The influence of the alkali additives (K⁺ ions) on the water-gas shift activity has been also examined. It was established that the catalytic activity of both reactions increases with the temperature and the nickel content. Hypothetic schemes are proposed about activation of the catalysts in the WGSR and CO oxidation including redox Ni²⁺ ? Ni³⁺ transition on the catalyst surface. The activity in WGSR is positively affected by the presence of potassium promoter, depending on its amount. The sample with higher nickel loading is the most effective catalyst as for CO oxidation as well as for WGSR at intermediate temperatures after potassium promotion.     

A Dinuclear Ruthenium‐Based Water Oxidation Catalyst: Use of Non‐Innocent Ligand Frameworks for Promoting Multi‐Electron Reactions

Insight into how H₂O is oxidized to O₂ is envisioned to facilitate the rational design of artificial water oxidation catalysts, which is a vital component in solar‐to‐fuel conversion schemes. Herein, we report on the mechanistic features associated with a dinuclear Ru‐based water oxidation catalyst. The catalytic action of the designed Ru complex was studied by the combined use of high‐resolution mass spectrometry, electrochemistry, and quantum chemical calculations. Based on the obtained results, it is suggested that the designed ligand scaffold in Ru complex 1 has a non‐innocent behavior, in which metal–ligand cooperation is an important part during the four‐electron oxidation of H₂O. This feature is vital for the observed catalytic efficiency and highlights that the preparation of catalysts housing non‐innocent molecular frameworks could be a general strategy for accessing efficient catalysts for activation of H₂O.     

Promoting Proton Transfer and Stabilizing Intermediates in Catalytic Water Oxidation via Hydrophobic Outer Sphere Interactions

The outer coordination sphere of metalloenzyme often plays an important role in its high catalytic activity, however, this principle is rarely considered in the design of man-made molecular catalysts. Herein, four Ru-bda (bda=2,2′-bipyridine-6,6′-dicarboxylate) based molecular water oxidation catalysts with well-defined outer spheres are designed and synthesized. Experimental and theoretical studies showed that the hydrophobic environment around the Ru center could lead to thermodynamic stabilization of the high-valent intermediates and kinetic acceleration of the proton transfer process during catalytic water oxidation. By this outer sphere stabilization, a 6-fold rate increase for water oxidation catalysis has been achieved.     

环己烷氧化微孔催化剂的研究进展

环己烷氧化是化工生产中的重要反应之一,其氧化产物为重要的化工生产中间体,因此开发高效的环己烷氧化多相催化剂体系具有重要的理论意义和应用前景。本文综述了国内外环己烷选择氧化微孔催化剂的研究进展,分别对Y沸石、ZSM-5沸石及MOFs三大类微孔催化剂体系的组成及催化性能进行了介绍,最后展望了环己烷多相催化体系的发展趋势。     

Supramolecular Water Oxidation with Ru–bda‐Based Catalysts

Extremely slow and extremely fast new water oxidation catalysts based on the Ru–bda (bda=2,2′‐bipyridine‐6,6′‐dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s^?1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π‐stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.     

铝基类水滑石和复合氧化物负载Pt催化剂的制备及对甲基苯酚加氢脱氧反应的催化性能

采用共沉淀法制备了多种铝基类水滑石,焙烧后得到对应的复合氧化物;以水滑石或复合氧化物为载体,制备了系列Pt基催化剂,研究了该催化剂对甲基苯酚加氢脱氧反应的催化性能。结果表明,Pt基催化剂的性能与载体的组分组成和结构相关;当以不经焙烧的类水滑石做载体时,所制备的Pt基催化剂具有较高的活性。其中,Pt-Ni-Al-H催化剂的加氢脱氧活性最高,对甲基苯酚转化率达到99.8%,甲苯选择性为1.4%,而Pt-Zn-Al-H催化剂的直接脱氧活性最高,在275℃和氢压2MPa下反应1h后,甲苯选择性达到84.1%。研究发现,反应过程中所生成的甲基环己烷可进一步发生脱氢反应转化为甲苯,说明所制备的Pt基催化剂具有较好的脱氢活性,可节省脱氧过程中的氢气消耗量。     

缓冲溶液阴离子对三价铜催化剂催化水氧化过程的影响

水氧化是光解水制氢气的瓶颈反应,认识和理解水氧化机制并研发廉价稳定的催化剂对解决这一问题尤为重要.自1982年Meyer课题组报道了第一例分子型双核钌水氧化催化剂(blue dimer)以来,过渡金属配合物被广泛应用于探索这一氧化过程的规律和机理,特别是近几年廉价金属配合物在水氧化领域的应用也备受关注.由于水氧化一般在苛刻的氧化条件下才可以实现,如何提高过渡金属配合物在催化条件下的稳定性一直是分子催化剂结构设计的一个难点.利用部分分子催化剂的不稳定性,将其作为前体制备非均相金属氧化物催化剂,广泛用于水氧化研究.然而,对于催化水氧化过程中造成分子催化剂不稳定的因素却鲜有探讨.因此,了解分子催化剂和异相活性物种之间原位转化的机理对于分子催化剂设计至关重要.本文考察了大环配体(TAML)的三价铜配合物(TAML-CuⅢ)的氧化还原性质及其电催化水氧化的反应性能.实验结果表明,TAML-CuⅢ的催化水氧化活性与缓冲溶液种类有关,在磷酸盐溶液与碳酸氢钠溶液中均无催化活性,而在硼酸溶液中表现出较高的催化活性.此外,TAML-CuⅢ工具有与本课题组之前报道的TAML-CoⅢ截然不同的电化学行为.TAML-CuⅢ只能发生配体的单电子氧化生成TAML·+-CdⅢ,且该物种无法实现对水分子的活化.进一步实验结果表明,生成的TAML·+-CuⅢ在硼酸根的协助下可以发生进一步氧化和配体的水解,从而生成具有高活性的非均相物种.研究表明该活性物种为含硼的氧化铜物种(B/CuOx).通过本文研究可得出两个结论:(1)具有平面四方构型的三价铜配合物不是一种有效催化水氧化的分子型催化剂;(2)缓冲阴离子在分子催化剂的分解中起到了关键作用.因此,缓冲溶液的选择对催化剂的电化学行为以及稳定性有着重要的影响.     

天然光合放氧反应的理论研究进展

光合放氧复合物是位于光系统II中氧化水的催化中心。对其结构、性质以及催化机理的研究不仅能够深入了解植物光合作用机制,也是人工合成稳定、高效、廉价的水氧化催化剂的基础。由于光合放氧复合物结构的复杂性,现代计算量子化学方法在对其研究中起着极为重要的作用。本文综述了天然水氧化催化剂的理论研究进展,总结了理论研究工作的重点,并展望了未来的发展方向。     

分子催化剂催化水氧化过程及其O–O成键机理

随着化石燃料的不断消耗和生存环境的日益恶化,可再生、清洁且环境友好的新能源逐渐受到广泛关注与利用.太阳能作为一种洁净的可再生能源,在自然界中,植物可以通过光合作用将太阳能转换成化学能.在该过程中,水分子在光系统II中被氧化而释放出氧气,伴随生成的质子和电子进一步将二氧化碳转化为蕴含生物质能的碳水化合物.在光系统II中,叶绿素P680被光照激发生成阳离子自由基P680^·+,其具有很强的氧化能力,可以从附近的析氧中心中夺取电子.析氧中心通过这一过程失去4个电子,可以将两分子水氧化生成一分子氧气和4个质子.作为水裂解的半反应之一,水氧化在热力学方面需要很多能量来断裂4个O-H键(ΔE=1.23 V vs.NHE),在动力学方面涉及4个氢原子与2个氧原子的重组以及氧气的释放,因而水氧化析氧是一个非常缓慢的过程,如何高效稳定地催化水氧化一直是人们研究的热点和难点.研究发现,自然界中存在的析氧中心为Mn₄CaO(x)的钙锰簇合物,在水氧化过程中生成的Mn=O物种可以被游离的水分子亲核进攻形成O-O键,也可以与桥连μ-O(H)反应生成O-O键.通过对析氧中心持续的研究,在过去几十年中设计合成了一系列具有水氧化催化活性的基于金属配合物的分子催化剂.分子催化剂催化水氧化一般主要分为金属-氧物种的演化过程以及O-O成键过程.通常,金属-氧物种可以通过失电子或质子耦合的失电子过程逐步生成高价态的金属-氧物种,其引发的O-O成键过程通常是水氧化催化循环的决速步骤.基于之前的研究成果,目前主要报道了五种不同的O-O成键机理:(1)水亲核进攻金属-氧物种的WNA机理,(2)金属-氧自由基耦合的I2M机理,(3)金属-羟基自由基耦合的HC机理,(4)分子内进攻桥连氧的IOC机理以及(5)氧化还原异构的RI机理.本文综述了过去几十年水氧化分子催化剂的发展,总结了贵金属钌和铱配合物到第一过渡金属锰、铁、钴、镍和铜配合物催化水氧化过程中金属-氧物种的生成与演化,重点阐述了引发O-O成键过程的高价态金属-氧物种的种类及其不同的O-O成键机理.重点总结了O-O成键中WNA机理与I2M机理的异同,并阐述了催化剂设计对WNA与I2M机理选择性的影响.通过对金属-氧物种种类和O-O成键机理的总结,将有助于进一步设计合成高效稳定的水氧化分子催化剂.     

Water oxidation catalysed by manganese compounds: from complexes to 'biomimetic rocks'

One of the most fundamental processes of the natural photosynthetic reaction sequence is the light-driven oxidation of water to molecular oxygen. In vivo, this reaction takes place in the large protein ensemble Photosystem II, where a μ-oxido-Mn(4)Ca- cluster, the oxygen-evolving-complex (OEC), has been identified as the catalytic site for the four-electron/four-proton redox reaction of water oxidation. This Perspective presents recent progress for three strategies which have been followed to prepare functional synthetic analogues of the OEC: (1) the synthesis of dinuclear manganese complexes designed to act as water-oxidation catalysts in homogeneous solution, (2) heterogeneous catalysts in the form of clay hybrids of such Mn(2)-complexes and (3) the preparation of manganese oxide particles of different compositions and morphologies. We discuss the key observations from the studies of such synthetic manganese systems in order to shed light upon the catalytic mechanism of natural water oxidation. Additionally, it is shown how research in this field has recently been motivated more and more by the prospect of finding efficient, robust and affordable catalysts for light-driven water oxidation, a key reaction of artificial photosynthesis. As manganese is an abundant and non-toxic element, manganese compounds are very promising candidates for the extraction of reduction equivalents from water. These electrons could consecutively be fed into the synthesis of "solar fuels" such as hydrogen or methanol.     

水/有机两相体系中催化氧化反应的研究进展

论述了水／有机两相体系中催化氧化反应的一些最新进展。由于采用水溶性催化剂，使得水／有机两相体系中的催化反应具有催化剂与产物容易分离的优点。阐述了水溶性催化剂在催化氧化反应中的应用，列举了一些典型的水溶性配体、水溶性催化剂以及催化氧化反应实例。参考文献21篇。     

Effects of Catalyst Heating Rates Upon the Activity of Silica-Supported Silicomolybdic Acid Catalysts for Methane Partial Oxidation

Silica-supported silicomolybdic acid (SMA) catalysts showed a very high activity for partial oxidation of methane into formaldehyde at 873 K in the presence of an excess amount of water vapor in feed. However, the high activity was observed only when the catalysts were heated to 873 K with very high heating rates such as 100 K min^-1. In this article, the reason why these high heating rates are necessary to exhibit the higher catalytic activity into formaldehyde will be discussed based on the structural changes in SMA during heating the catalysts to 873 K.