共查询到20条相似文献,搜索用时 15 毫秒
1.
2.
This review article summarizes our recent researches for molecular design of polyoxometalates (POMs) and their related compounds
for environmentally-friendly functional group transformations. The divacant POM [γ-SiW10O34(H2O)2]4− exhibits high catalytic performance for mono-oxygenation-type reactions including epoxidation of olefins and allylic alcohols,
sulfoxidation, and hydroxylation of organosilanes with H2O2. We have successfully synthesized several POM-based molecular catalysts (metal-substituted POMs) with controlled active sites
by the introduction of metal species into the divacant POM as a “structural motif”. These molecular catalysts can efficiently
activate H2O2 (vanadium-substituted POM for epoxidation) and alkynes (copper-substituted POM for click reaction and oxidative homocoupling
of alkynes). The aluminum-substituted POM exhibits Lewis acidic catalysis for diastereoselective cyclization of (+)-citronellal
to (−)-isopulegol. In addition, we have developed POM-based “molecular heterogeneous catalysts” by the “solidification” and
“immobilization” of catalytically active POMs. 相似文献
3.
Dr. Volodymyr Semeniuchenko Dr. Wilfried M. Braje Prof. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(49):12535-12539
NaBHT (sodium 2,6-di-tert-butyl-4-methylphenolate), a strong, but hindered and lipophilic base, has been effectively paired with similarly lipophilic, high-reactivity Pd-NHC (N-heterocyclic carbene) catalysts to produce an ideal combination for performing solvent-free (melt) cross-coupling amination. The mild nucleophilicity of NaBHT, coupled with the anti-oxidant properties of its conjugate acid byproduct, BHT means the process seems to have no functional group incompatibilities. Highly effective coupling of base-sensitive and redox-active functional groups was observed in all cases with only 0.1–0.2 mol percent catalyst. Comparisons using the standard base for this reaction, KOtBu, led to poor couplings or complete degradation in most applications – only NaBHT works. 相似文献
4.
Aaron Garg Maria Milina Madelyn Ball Prof. Daniela Zanchet Sean T. Hunt Prof. James A. Dumesic Prof. Yuriy Román-Leshkov 《Angewandte Chemie (International ed. in English)》2017,56(30):8828-8833
Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. The ability to control shell coverage and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties. 相似文献
5.
6.
聚烯烃弹性体(POE)是一类有高性能、高附加值的高分子材料,随着其应用领域的不断拓展,在国内外得到迅速发展,国内各大相关企业纷纷投入巨资进行研究开发。作为聚烯烃产业核心技术的催化剂,核心技术目前主要控制在西方公司手中,开发具有自主知识产权的催化剂是当前的POE领域研究热点。为了给国内同行提供参考,课题组结合国内外的研究工作,对目前主流的POE催化剂——限定几何构型茂金属催化剂(CGC) 、桥连双配体结构茂金属和苯氧基亚胺催化剂(FI)的发展历程进行了评述,对近五年这三类催化剂的微观结构、催化活性以及结构与催化性能的关系,特别是催化乙烯/1-辛烯共聚反应的活性以及1-辛烯插入率进行详细的比较,考察了各类不同的有机配体对催化剂催化行为、聚合物组成的影响,揭示了均相催化条件下通过改变配体结构以提高聚合反应温度和1-辛烯插入率的技术方案,本文摘录了67篇文献,涉及到109种催化剂,相信本文的工作对于国内同行设计、合成新型POE催化剂将具有重要的参考作用。 相似文献
7.
8.
费托合成钴基催化剂的研究进展 总被引:1,自引:0,他引:1
费托合成油技术是煤炭、天然气等含碳资源清洁优化利用的重要途径, 其关键问题之一是催化剂选择性的调控, 即抑制甲烷生成和提高馏分油含量. 近 10 年来, 中国科学院山西煤炭化学研究所系统地开展了钴基费托合成催化剂及制备放大的工程基础研究, 包括钴分散度、还原度与甲烷生成之间的关系, 载体表面疏水性对催化剂性能的影响, 以及采用孔道限域等手段初步实现了产物的选择性调控. 同时, 初步阐明了甲烷生成的结构基础, 并指明了新型馏分油催化剂研发方向. 在此基础上, 研制了新型钴基催化剂, 其具有低甲烷选择性、高重质烃选择性和良好稳定性的特点. 目前, 对 I 型催化剂完成了实验室稳定性验证并实现了工业示范; 对 II 型催化剂 (甲烷选择性约 2%~3%) 完成了稳定性验证. 相似文献
9.
10.
11.
Advantages and drawbacks of commercial catalysts for gas-phase hydrogenation are considered. The use of modified catalysts, including nickel catalysts modified with heteropoly compounds, is promising. Data on the selective reduction of carbonyl compounds and hydrogenation of aromatic hydrocarbons over these catalysts are presented. Palladium films are shown to be the best catalysts for the selective reduction of acetylene compounds to olefins. 相似文献
12.
甲酸燃料电池是一种近年发展起来的新型燃料电池,具有极好的商业化前景,但其发展受到很多因素的制约,其中阳极催化剂是影响其性能的关键因素。本文从催化剂的制备方法、催化剂载体和掺杂其他元素等方面介绍了近年来国内外在提高催化剂的活性和抗毒性方面所做的重要研究工作。具体包括:电沉积法、有机溶胶法等重要制备方法,碳纳米管、石墨烯和复合材料作为催化剂载体的研究以及通过掺杂其他元素制备合金催化剂和复合催化剂来提高催化剂活性和抗毒性的相关研究工作。本文还对甲酸燃料电池的发展做了展望。 相似文献
13.
Holger Elsen Christian Fischer Christian Knüpfer Dr. Ana Escalona Prof. Dr. Sjoerd Harder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(70):16141-16147
The efficient catalytic reduction of imines with phenylsilane is achieved by using the potassium, calcium and strontium based catalysts [(DMAT)K (THF)]∞, (DMAT)2Ca⋅(THF)2 and (DMAT)2Sr⋅(THF)2 (DMAT=2-dimethylamino-α-trimethylsilylbenzyl). Eight different aldimines and the ketimine Ph2C=NPh could be successfully reduced by PhSiH3 at temperatures between 25–60 °C with catalyst loadings down to 2.5 mol %. Also, simple amides like KN(SiMe3)2 or Ae[N(SiMe3)2]2 (Ae=Ca, Sr, Ba) catalyze this reaction. Activities increase with metal size. For most substrates the activity increases along the row K<Ca<Sr<Ba. Fastest conversion was found for imines with alkyl substituents at N and aryl rings at C, for example, PhC(H)=NtBu, while tBuC(H)=NtBu or PhC(H)=NPh react much slower. Reasonable functional group tolerance is observed. The proposed metal hydride mechanism is supported by stoichiometric reactions using a catalyst model system, isolation of intermediates and DFT calculations. 相似文献
14.
15.
16.
17.
均相催化剂产生于50年代末期,但由于活性很低而末引起重视。80年代初,由于发现MAO具有良好的助催化能力而使均相催化剂得到了很大发展,涌现了多种催化体系,广泛地使α-烯烃及其衍生物立体选择性聚合,开辟了配位聚合研究的新领域,本文对均相催化剂的产生,发展及现状作了综述评述。 相似文献
18.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(30):8954-8959
Core–shell architectures offer an effective way to tune and enhance the properties of noble‐metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X‐ray photoelectron spectroscopy revealed significant core‐level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d‐states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. The ability to control shell coverage and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties. 相似文献
19.
20.
Preparation and Catalytic Application of Novel Water Tolerant Solid Acid Catalysts of Zirconium Sulfate/HZSM-5 总被引:2,自引:0,他引:2
JIANG Ya-jie JUAN Joon Ching MENG Xiu-juan CAO Wei-liang YARMO Mohd Ambar ZHANG Jing-chang 《高等学校化学研究》2007,23(3):349-354
Esterification of acrylic acid(AA) to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorption, TGA-DTA, XPS, and ammonia adsorption FTIR. The effects of Si/Al ratio, zirconium sulfate(ZS) loading on HZSM-5 and calcination temperature on the esterification were investigated. When 20%(mass fraction) ZS is loaded on HZSM-5, the conversion of AA reaches 100%. XRD analysis indicates that ZS is highly dispersed on HZSM-5 because no crystalline structure assigned to ZS is found. Catalytic activity and hydrophobicity of ZS supported on HZSM-5 are higher compared with those of parent ZS or HZSM-5. Results show that this kind of novel catalysts is an efficient water tolerant solid acid catalyst for esterification reactions. 相似文献