Iron Coordination to Hollow Microporous Metal-Free Disalphen Networks: Heterogeneous Iron Catalysts for CO2 Fixation to Cyclic Carbonates

This work shows that a hollow and microporous metal-free N,N′-phenylenebis(salicylideneimine) (salphen) network (H-MSN) can be engineered by Sonogashira coupling of [tetraiodo{di(Zn-salphen)}] building blocks with 1,4-diethynylbenzene in the presence of silica templates and by successive Zn and silica etching. Iron(III) ions could be incorporated into the H-MSN to form hollow and microporous Fe–disalphen networks (H-MFeSN) with enhanced microporosity and surface area. The H-MFeSN showed efficient catalytic performance and recyclability in the CO₂ conversion to cyclic carbonates.     

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。     

Characterization of Hydrocarbon Soluble Metal Oxides. Precursors to Supported Catalysts

Abstract

The metal oxide carboxylate complexes described in the previous chapter have been characterized by infrared spectroscopy, x-ray diffraction, electron microscopy, and analytical ultracentrifugation. The molecular weights and solution particle diameters have been determined for a number of the hydrocarbon soluble particles by analytical ultracentrifugation methods, and the use of a spherical model consistent with the particulate shape observed by electron microscopy. The size of the soluble complexes has been studied as a function of: metal, metal/acid ratio, acid composition, and solvent. The molecular weights for the ultimate particles are reasonably independent of the metal employed in the synthesis and are relatively constant for materials with similar metal/acid equivalents ratios. The single particle molecular weights for the complexes studied ranged from approximately 5×10⁴ to 1.5×10⁶g mole^?1. The solution size distribution was polydisperse in all cases, with aggregates of the ultimate particles prevalent. Weight average molecular weights in excess of 10⁹g mole^?1 have been observed. The aggregation is dependent on the surface acid composition and on the solvent in which the soluble complex is dispersed. Solubility and stability of these materials have been examined in a number of solvents. The metal oxide particles are initially soluble in octane, isooctane, cyclohexane, mineral spirits, carbon tetrachloride, benzene, and tetrahydrofuran. However, most of the complexes eventually precipitate from dilute solutions in carbon tetrachloride, benzene, and tetrahydrofuran. The stability of the particles is decreased in the presence of oxygen, or when carboxylic acids, alcohols, or ketones are present even in small amounts, and is decreased even further at temperatures above 100°C. Heterogeneous catalysts have been prepared by deposition of several of the soluble metal oxides onto supports such as alumina, silica, or kieselguhr followed by oxidation to yield supported metal oxides or reduction to yield supported metal. The application of few supported metals and metal oxides in hydrogenations of olefins, benzene, and naphthalene is described.     

Molecular Mixed‐Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts

Well‐defined mixed‐metal [CoMn₃O₄] and [NiMn₃O₄] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure‐function relationships of the electrocatalysts’ heterometallic composition. Depending on preparation conditions, the Co‐Mn oxide was found to change metal composition during catalysis, while the Ni–Mn oxides maintained the NiMn₃ ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn₃O₄ cubane‐like geometry was maintained in the absence of thermal treatment ( 2‐Ni ). In contrast, the thermally generated 3‐Ni develops an oxide‐like extended structure. Both 2‐Ni and 3‐Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen‐evolving complex in Photosystem II, including the MMn₃O₄ cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.     

Preparation of YSZ Microporous Membranes on Porous a-Alumina with Metal Chlorides as Precursor

A sol-gel process for YSZ membrane prepared with less expensive chemicals, ZrOCI₂·8H₂0 and YC1₃, has been developed. The sol viscosity as a function of concentration, acidity and temperature was brane formation processes were also studied. investigated. And gelation and Based on an optimized procedure memhole and crack-free YSZ membranes with the pore size less than 100 nm have obtained on coarse porous a-alumina.     

溶剂化金属原子浸渍法制备高分散负载型催化剂——ⅩⅣ.Pd催化剂的表面组成及CO_2甲烷化催化性能

用元素分析、热脱附和H_2还原脱附等方法分析了Pd/γ-Al_2O_3、Pd/MgO、Pd/TiO_2溶剂化金属原子浸渍(SMAI)催化剂的表面组成和孔结构。结果表明Pd颗粒表面覆盖着一些有机碎片,这些碎片主要由C_1和少量C_2,C_3及C_3以上物种组成。SMAI催化剂的比表面积均高于相应纯载体的比表面积。而平均孔径均小于后者,CO_2甲烷化反应中,SMAI催化剂的活性均高于相应的普通浸渍法(CI)催化剂,而活化能却低于后者。在SMAI催化剂上CO_2甲烷化反应机理与Solymosi机理相同。     

Manipulating Catalytic Pathways: Deoxygenation of Palmitic Acid on Multifunctional Catalysts

The mechanism of the catalytic reduction of palmitic acid to n‐pentadecane at 260 °C in the presence of hydrogen over catalysts combining multiple functions has been explored. The reaction involves rate‐determining reduction of the carboxylic group of palmitic acid to give hexadecanal, which is catalyzed either solely by Ni or synergistically by Ni and the ZrO₂ support. The latter route involves adsorption of the carboxylic acid group at an oxygen vacancy of ZrO₂ and abstraction of the α‐H with elimination of O to produce the ketene, which is in turn hydrogenated to the aldehyde over Ni sites. The aldehyde is subsequently decarbonylated to n‐pentadecane on Ni. The rate of deoxygenation of palmitic acid is higher on Ni/ZrO₂ than that on Ni/SiO₂ or Ni/Al₂O₃, but is slower than that on H‐zeolite‐supported Ni. As the partial pressure of H₂ is decreased, the overall deoxygenation rate decreases. In the absence of H₂, ketonization catalyzed by ZrO₂ is the dominant reaction. Pd/C favors direct decarboxylation (?CO₂), while Pt/C and Raney Ni catalyze the direct decarbonylation pathway (?CO). The rate of deoxygenation of palmitic acid (in units of mmol mol_{total metal}^?1 h^?1) decreases in the sequence r_{(Pt black)}≈r_{(Pd black)}>r_{(Raney Ni)} in the absence of H₂. In situ IR spectroscopy unequivocally shows the presence of adsorbed ketene (C?C?O) on the surface of ZrO₂ during the reaction with palmitic acid at 260 °C in the presence or absence of H₂.     

Dynamic Combinatorial Chemistry: A New Methodology Comes of Age

Dynamic combinatorial chemistry (DCC) has repeatedly proven to be an effective approach to generate directed ligand libraries for macromolecular targets. In the absence of an external stimulus, a dynamic library forms from reversibly reacting building blocks and reaches a stable thermodynamic equilibrium. However, upon addition of a macromolecular host which can bind and stabilize certain components of the library, the equilibrium composition changes and induces an evolution-like selection and enrichment of high-affinity ligands. A valuable application of this so-called target-directed DCC (tdDCC) is the identification of potent ligands for pharmacologically relevant targets. Over time, the term tdDCC has been applied to describe a number of different experimental setups, leading to some ambiguity concerning its definition. This article systematically classifies known procedures for tdDCC and related approaches, with a special focus on the methods used for analysis and evaluation of experiments.     

Combinatorial Approach to Chiral Tris‐ligated Carbophilic Platinum Complexes: Application to Asymmetric Catalysis

A straightforward methodology for the synthesis of libraries of chiral tris‐ligated cationic platinum complexes and their in situ evaluation as asymmetric carbophilic catalysts in a model domino hydroarylation/cyclization reaction of a 1,6‐enyne was developed. A catalyst‐generation process based on a combination of a monodentate and a bidentate phosphorus ligand allowed the formation of 108 chiral complexes. One‐pot screening of the stereoinduction obtained with this library in a test domino addition/cyclization reaction validated this approach and stressed the key role played by the monodentate ligand partner in obtaining high enantioselectivities. In the case of two challenging substrate/nucleophile combinations, the combinatorial approach resulted in a significant gain in enantioselectivity.     

Molecular Clusters in Mesoporous Materials as Precursors to Nanoparticles of a New Lacunar Ternary Compound Pd x Mo y P

Bimetallic clusters of composition Pd₂Mo₂(η⁵-C₅H₅)₂(μ₃-CO)₂(μ₂-CO)₄(PR₃)₂ (R = ethyl or phenyl) were incorporated by impregnation from solution into two different silica matrices, amorphous xerogels and ordered SBA-15, and a study of their thermal decomposition under a reducing atmosphere is reported. With both matrices, a suitable thermal treatment afforded nanoparticles of a new bimetallic phosphide. Although nanoparticles of composition Pd _x Mo _y P, isostructural with Mo₃P, were formed in both matrices, they were more uniformly distributed in the SBA-15 framework and showed a narrower size distribution. The samples have been characterized by powder XRD, chemical analysis, FT-IR spectroscopy, TEM and electron tomography (3D TEM). Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Rhodium Catalysts for Enantioselective Hydrosilylation—A New Concept in the Development of Asymmetric Catalysts

Following a survey of the asymmetric hydrogenation of prochiral olefins with transition metal/phosphane catalysts, the problem of chirality transfer from the optically active ligands of the catalyst to the substrate is discussed. A new concept for this chirality transfer is introduced; the conformational analysis of model compounds as well as the development of catalysts for enantioselective hydrosilylation demonstrate the usefulness of this concept.     

多孔材料化学:从无机微孔化合物到金属有机多孔骨架

本文主要从无机微孔化合物和金属有机多孔骨架的合成化学和结构化学这两方面来介绍多孔材料化学的研究进展。多孔材料是一类具有规则孔结构的固态化合物,它们在催化、分离、离子交换等工业领域有着广泛的应用。硅铝酸盐是最为人们所熟知的微孔分子筛,经过半个多世纪的发展,人们又相继开发出磷酸盐、砷酸盐、锗酸盐、亚磷酸盐、硫酸盐、亚硒酸盐以及金属硫化物等类沸石无机微孔化合物。近十多年来,配位聚合物与金属有机多孔骨架开始大量兴起,为微孔化合物的多样化与组成的复杂性增添了新的领域。     

Tetraammineplatinum(II) and Tetraamminepalladium(II) Chromates as Precursors of Metal Oxide Catalysts

[M(NH₃)₄]A (M=Pt, Pd; A=CrO₄, Cr₂O₇) and [Pt(NH₃)₄(NO₂)(Cr₂O₇)]NO₃ complex salts were synthesized and characterized by a number of physicochemical methods of analysis (IR, single-crystal and powder XRD, and simultaneous thermogravimetry and differential scanning calorimetry with evolved gas analysis mass spectrometry). Thermolysis of the salts obtained in a hydrogen atmosphere proceeds with the partial reduction of chromium to a metallic state and the formation of M_xCr_1−x (M=Pt, Pd) metal solid solution with a chromium content of up to 22 at % and chromium(III) oxide. The thermal decomposition of salts in an inert and oxidizing atmosphere passes through the formation stage of the MCrO₂ phase with the delafossite structure followed by its subsequent decomposition into chromium(III) oxide and noble metal. Nanosized Pt−Cr₂O₃ and Pd−Cr₂O₃ composites obtained by the thermolysis of precursor salts in air at 500 °C and being held at this temperature for 1 h showed a high catalytic activity in the CO total oxidation (TOX) and preferential oxidation in the excess of hydrogen (PROX) processes compared with that of monometallic Pt and Pd powders.     

Noble Metal Nanoparticles Stabilized by Hyper-Cross-Linked Polystyrene as Effective Catalysts in Hydrogenation of Arenes

This work is addressing the arenes’ hydrogenation—the processes of high importance for petrochemical, chemical and pharmaceutical industries. Noble metal (Pd, Pt, Ru) nanoparticles (NPs) stabilized in hyper-cross-linked polystyrene (HPS) were shown to be active and selective catalysts in hydrogenation of a wide range of arenes (monocyclic, condensed, substituted, etc.) in a batch mode. HPS effectively stabilized metal NPs during hydrogenation in different medium (water, organic solvents) and allowed multiple catalyst reuses.     

Applications of Transition‐Metal Catalysts to Textile and Wood‐Pulp Bleaching

From an economic perspective, textile and paper bleaching are amongst the most important oxidation processes. The removal of unwanted chromophores, be it stains on cloths or residual lignin in wood pulp, consumes more than 60 % of the world production of hydrogen peroxide. However, existing technologies have their limitations. At ambient temperature, hydrogen peroxide gives little stain bleaching and is used inefficiently. Hence the high product dosages and washing temperatures required limit its application to predominantly European markets, to the exclusion of the majority of the world's population. In paper manufacture, the use of chlorine‐based oxidants results in the formation of chlorinated waste products, which show poor biodegradability. On the other hand, hydrogen peroxide requires higher temperatures, longer reaction times and is more expensive. Transition‐metal catalysts offer an alternative. This review discusses the main classes of known bleach catalysts and their possible modes of action.