苯甲酸氢化还原制备苯甲醛的研究

苯甲醛是重要的有机合成中间体 ,在医药、农药、染料、香料等的合成中具有广泛的用途 .它的制备方法较多 ,而用苯甲酸为原料 ,采用催化加氢还原法文献报道较少 .该方法产率高、产品质量好、无污染 。

一氧化碳氢化中间物模型的过渡金属-烯酮(亚烯酮基)络合物

有机烯酮的化学已有80年的历史,但过渡金属-烯酮和金属-亚烯酮基络合物的研究才进行几年。由于这类络合物的化学与一碳化学的研究密切相关而引人注目,且迅速发展成为有机金属化学的一个重要分支。本文就过渡金属-烯酮和金属-亚烯酮基络合物的合成、结构、反应性能和作为一氧化碳氢化中间物模型的研究,包括作者过去的研究结果,作简要介绍。

Pt/Au双金属纳米微粒的催化性能

制备了不同比例的Pt/Au双金属纳米微粒,应用UV-VIS、TEM等手段对其结构进行了表征,并比较了它们对丁醛氢化还原反应的催化活性.

Mo(O)、W(O)络合物中配位双氮基光还原氢化反应

许多过渡金属双氮基络合物已经合成并分离出来，其中一些配位的双氮基可以被还原质子化转变成肼或氨。不过，这一过程迄今都还是化学计量反应。欲使这一反应达到催化循环，必须消耗过量的还原剂，或外加其他能量(如电能)。

芳香胺盐酸盐/硼烷体系催化的氢胺化/还原反应研究

近年来有关受限路易斯酸碱对(FLPs)化学的研究受到了国内外的广泛关注,但有关芳香胺类FLPs的应用研究却极少涉及.本工作以硅烷作为还原剂,路易斯酸三(五氟苯基)硼(BCF)作为催化剂,用芳香胺盐酸盐代替苯胺,可一步反应实现炔烃与苯胺的催化氢胺化还原反应.研究发现,取代基较多的三乙基硅烷在反应中表现出较高的反应活性,吸电子取代基取代的端基芳炔的转化率也较给电子取代基取代的端基芳炔的转化率高.对催化反应的机理研究表明,胺盐与B(C6F5)3及硅烷反应所生成的硼氢化芳胺盐活性中间体"[Ar_2NH_2]^+[H-B(C_6F_5)_3]^-"的产生和分解速度决定着中间产物亚胺的生成和还原.

Enhanced electrocatalytic activity for H_2O_2 production by the oxygen reduction reaction: Rational control of the structure and composition of multi-walled carbon nanotubes

Hydrogen peroxide(H2O2)is a very useful chemical reagent,but the current industrial methods for its production suffer from serious energy consumption problems.Using high-activity and high-selectivity catalysts to electrocatalyze the oxygen reduction reaction(ORR)through a two-electron(2e^-)pathway is a very promising route to produce H2O2.In this work,we obtained partially oxidized multi-walled carbon nanotubes(MWCNTs)with controlled structure and composition by oxidation with concentrated sulfate and potassium permanganate at 40℃ for 1 h(O-CNTs-40-1).The outer layers of O-CNTs-40-1 are damaged with defects and oxygen-containing functional groups,while the inner layers are maintained intact.The optimized structure and composition of the partially oxidized MWCNTs ensure that O-CNTs-40-1 possesses both a sufficient number of catalytic sites and good conductivity.The results of rotating ring disk electrode measurements reveal that,among all oxidized MWCNTs,O-CNTs-40-1 shows the greatest improvement in hydrogen peroxide selectivity(from ~ 30% to ~ 50%)and electron transfer number(from ~ 3.4 to ~ 3.0)compared to those of the raw MWCNTs.The results of electrochemical impedance spectroscopy measurements indicate that both the charge-transfer and intrinsic resistances of O-CNTs-40-1 are lower than those of the raw MWCNTs and of the other oxidized MWCNTs.Finally,direct tests of the H2O2 production confirm the greatly improved catalytic activity of O-CNTs-40-1 relative to that of the raw MWCNTs.

Metal‐organic framework‐derived multifunctional photocatalysts

Metal‐organic framework(MOF)‐derived nanomaterials have attracted widespread attention,because the excellent features,such as high surface area,porosity and tunable properties are inherited from MOFs.Moreover,the derivatives avoid the poor conductivity and stability of MOFs.MOF‐derived nanomaterials can easily be regulated by a specific selection of metal nodes and organic linkers,resulting in multifunctionality in photocatalysis.MOF derivatives can be used not only as semiconductor photocatalysts,but also as co‐catalysts for photocatalytic hydrogen evolution,CO_(2) reduction,pollutants degradation,etc.This review focuses on the multifunctional applications of MOF derivatives in the field of photocatalysis.The researches in recent years are analyzed and summarized from the aspects of preparation,modification and application of MOF derivatives.At the end of the review,the development and challenges of MOF derivatives applied in photocatalysis in the future are put forward,in order to provide more references for further research in this field and bring new inspiration.

Nano Fibrous Cerium（IV） Hydrogen Phosphate Membrane Self Supported Indole Polymerization Agent

Nanosized fibrous cerium（IV） hydrogen phosphate membrane, Ce（HPO4）2·2.9H20 （nCePf）, was prepared and characterized by chemical, XRD （X-ray diffraction）, TGA （thermogravimetric analysis）, SEM （scanning electron microscopy） and TEM （transmission electron microscopy）. Novel supported nanofibrous Ce（IV） phosphate/polyiondole nanocomposite membranes were prepared via in-situ chemical oxidation of the monomer that was promoted by the reduction of Ce（IV） ions present in the inorganic matrix. The presence of Ce（IV） ions allows redox reactions necessary to oxidative polymerization to occur. The resultant material was characterized by TGA, elemental （C, H, N） analysis and FT-IR （Fourier transform spectroscopy）. SEM images of the resulting nanocomposite reveals a uniform distribution of the polymer on the inorganic matrix. Amount of polyindole polymer present in the composite is found to be - 7.0%.

Enantioselective Hydrogenation of β-keto Esters Using Homogeneous and Heterogeneous Catalysts, a Case Study for Comparison of Different Catalytic Methodologies

The asymmetric reduction of β-keto esters to their corresponding hydroxy alcohols can be performed by employing homogeneous and heterogeneous chemo- and bio-catalysis. This review covers the scope and limitations of different catalysts and methodologies that were employed for the reaction and compare between them on the basis of catalytic performance, product separation and catalyst recycling procedure. In general, heterogeneous catalytic systems are advantageous from industrial point of views as they can be easily separated by filtration and re-used. Nickel modified with tartaric acid and sodium bromide was found to be suitable heterogeneous catalyst for the enantioselective hydrogenation, yet its performance is lower than this of homogeneous chiral metal catalysts such as Ru-BINAP. Heterogenization of the chiral complex via immobilization or entrapment using organic and inorganic supports was thus tested. However, though the resulted heterogeneous analogues were highly enantioselective and could be re-used, the activity of the system is often very low compared to homogeneous system due to mass transfer limitations. Alternatively, performing liquid phase hydrogenation under homogeneous conditions, using Ru-BINAP soluble derivatives, yielded high activit5＇ and enantioselectivity. Product separation and catalysts recycling were facilitated by either extraction of the product with solvent that does not dissolve the complex or by selective filtration of the product. Alternatively, precipitation of the complex at the end of the reaction was also reported.

NiMoCo layered double hydroxides for electrocatalyst and supercapacitor electrode

Non-noble-metal electrode materials with high durability and efficiency have become the frontiers of energy conversion and storage fields.However,conventional electrode materials often show high overpotential and low conductivity.To solve this problem,we fabricate a NiMoxCo2−x layered double hydroxide(LDH)/Ni foam(NF)product through a facile hydrothermal route.The as-prepared NiMo-Co-LDH/NF catalyst possesses an overpotential of 123 mV for hydrogen evolution reaction(HER)at 10 mA cm^−2 and 279 mV for oxygen evolution reaction(OER)at 20 mA cm^−2.The as obtained product exhibits excellent overall water splitting performances.Meanwhile,as the electrode material for supercapacitor,it delivers high specific capacitance and excellent cyclic performance.The asymmetric supercapacitor assembled with NiMoCo-LDH/NF//active carbon exhibits 93%of its initial capacity after 8000 cycles.

Nanostructured CdS for efficient photocatalytic H2 evolution: A review

Cadmium sulfide(Cd S)-based photocatalysts have attracted extensive attention owing to their strong visible light absorption,suitable band energy levels,and excellent electronic charge transportation properties.This review focuses on the recent progress related to the design,modification,and construction of Cd S-based photocatalysts with excellent photocatalytic H2 evolution performances.First,the basic concepts and mechanisms of photocatalytic H2 evolution are briefly introduced.Thereafter,the fundamental properties,important advancements,and bottlenecks of Cd S in photocatalytic H2 generation are presented in detail to provide an overview of the potential of this material.Subsequently,various modification strategies adopted for Cd S-based photocatalysts to yield solar H2 are discussed,among which the effective approaches aim at generating more charge carriers,promoting efficient charge separation,boosting interfacial charge transfer,accelerating charge utilization,and suppressing charge-induced self-photocorrosion.The critical factors governing the performance of the photocatalyst and the feasibility of each modification strategy toward shaping future research directions are comprehensively discussed with examples.Finally,the prospects and challenges encountered in developing nanostructured Cd S and Cd S-based nanocomposites in photocatalytic H2 evolution are presented.

Engineering two-dimensional metal oxides and chalcogenides for enhanced electro-and photocatalysis

Two-dimensional(2D)metal oxides and chalcogenides(MOs&MCs)have been regarded as a new class of promising electro-and photocatalysts for many important chemical reactions such as hydrogen evolution reaction,CO_(2) reduction reaction and N2 reduction reaction in virtue of their outstanding physicochemical properties.However,pristine 2D MOs&MCs generally show the relatively poor catalytic performances due to the low electrical conductivity,few active sites and fast charge recombination.Therefore,considerable efforts have been devoted to engineering 2D MOs&MCs by rational structural design and chemical modification to further improve the catalytic activities.Herein,we comprehensively review the recent advances for engineering technologies of 2D MOs&MCs,which are mainly focused on the intercalation,doping,defects creation,facet design and compositing with functional materials.Meanwhile,the relationship between morphological,physicochemical,electronic,and optical properties of 2D MOs&MCs and their electro-and photocatalytic performances is also systematically discussed.Finally,we further give the prospect and challenge of the field and possible future research directions,aiming to inspire more research for achieving high-performance 2D MOs&MCs catalysts in energy storage and conversion fields.

Sulfur defect-rich WS nanosheet electrocatalysts for N reduction

Seeking catalysts with high electrocatalytic activity for ambient-condition N2 reduction reaction (NRR) remains an ongoing challenge due to the chemical inertness of N2.Herein,defect-rich WS2 nanosheets (WS2-x) were designed as an efficient electrocatalyst for NRR,which were prepared via vulcanizing the oxygen-vacancy-rich tungsten oxide in a vacuum tube.The sulfur defects were conducive to the adsorption and activation of N2.In neutral electrolyte of 0.1 mol L^(-1)Na2SO_(4) at-0.60 V vs.reversible hydrogen electrode,such WS2-xoffered a high Faradaic efficiency of 12.1%with a NH3generation rate of 16.38μg h-1mg-1cat..

间氨基苯酚N-烷基衍生物的合成新方法

开发了一种合成间氨基苯酚N-烷基衍生物的新方法。以间二硝基苯与过量的苯甲醇在碳酸钾的存在下发生亲核取代反应,生成的产物(间硝基苄基苯酚)不分离,直接转移到压力釜中,添加乙醛或正丁醛,经氢化-裂解-还原-胺化反应得到间氨基苯酚N-烷基衍生物,同时副产甲苯。整个反应过程不需要用水。