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171.
采用沉淀法将ZIF-67负载到CeO2上,制备了具有多重活性位点的非均相催化剂ZIF-67/CeO2,并研究其催化CO2和甲醇直接反应生成碳酸二甲酯(DMC)的性能。采用X射线衍射、N2吸附-脱附、傅里叶变换红外光谱和X射线光电子能谱研究了ZIF-67/CeO2的各种理化性质。结果表明,ZIF-67的引入使ZIF-67/CeO2催化剂产生更多的氧空位。在考察的ZIF-67/CeO2系列催化剂中,0.3-ZIF-67/CeO2(0.3为Co、Ce物质的量之比)在具有高的比表面积的同时还能保持介孔结构,具有丰富的酸碱位点,并且具有较高的CO2吸附容量,表现出最好的催化性能。在反应温度为140℃、压力为4.5 MPa的条件下反应4 h,DMC收率可达到3.79 mmolDMC·gcat-1。 相似文献
172.
Mostafa Malek-mohammadi Akram Heydari-turkmani Saeed Zakavi Nasser Nikfarjam 《应用有机金属化学》2023,37(1):e6927
In this study, the manganese complexes of N-methylated meso-tetra(2-, 3-, or 4 pyridyl)porphyrins, immobilized into the pores of the sodium salt of mesoporous amberlyst 15 nanoparticles (nanoAmbSO3Na), nanoAmbSO3@MnT(2-MePy)P (OAc), nanoAmbSO3@MnT(3-MePy)P (OAc), and nanoAmbSO3@MnT(4-MePy)P (OAc), were synthesized and characterized by field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX), thermal gravimetric analysis (TGA), nitrogen adsorption/desorption porosimetry analysis, and diffuse reflectance UV–vis spectroscopy. FESEM images revealed a particle size less than ~40 nm for the nanocomposites. The results of BET are in accord with the occupation of the larger pores of the polymer matrix in the case of MnT(2-MePy)P (OAc) as the most sterically demanding metalloporphyrin of the series, and the smaller pores in the case of the other ones. The immobilized manganese porphyrins were used as catalysts for the oxidation of olefins with sodium periodate in the presence of imidazole (ImH) as the co-catalyst. The negligible oxidative destructions of the immobilized manganese porphyrins under the oxidative conditions allowed the comparison of the inherent catalytic activity of the metalloporphyrins, decreased as nanoAmbSO3@MnT(4-MePy)P (OAc) > nanoAmbSO3@MnT(3-MePy)P (OAc) ≫ nanoAmbSO3@MnT(2-MePy)P (OAc). Contrary to the general belief that electron-deficient metalloporphyrins are more efficient catalysts than the electron-rich ones, the most electron-deficient metalloporphyrin of the series, that is, nanoAmbSO3@MnT(2-MePy)P (OAc), showed the lowest catalytic activity. Due to the high oxidative stability of the immobilized manganese porphyrins, ring opening of epoxide competes with the epoxidation reaction to decrease the yield of epoxide at longer reaction times than the optimized one. 相似文献
173.
Ramanjulu Abinaya Selvaraj Elavarasan B. Binish Dr. K. Mani Rahulan Prof. Dr. Kalpattu K. Balasubramanian Dr. Kamaraj Manokaran Dr. Elumalai Varathan Dr. Baburaj Baskar 《European journal of organic chemistry》2023,26(4):e202201098
Herein we report a simple and efficient oxidative coupling of various aryl methyl amines with diverse coupling partners, such as o-phenylenediamine (benzene-1,2-diamine), 2-aminobenzenethiol and 2-aminobenzamide, to synthesize the corresponding heterocycles using scalable and reusable heterogeneous catalysts under visible light irradiation. A systematic investigation led to the synthesis of benzimidazoles, benzothiazoles and quinazolinones under air atmosphere in very good to excellent yields. The strategy is atom economical and found to be tolerance towards different functional groups, and wide range of substrate scope. Furthermore, the methodology was demonstrated for its suitability on scale up and reusability. The density functional theory (DFT) calculations and the analysis of band structures of pristine and Ba doped CoMoO4 systems showed that the doping of Ba in place of Co improved the catalytic performance of the system. 相似文献
174.
Dr. Yukun Shi Jie Li Xuejiao Shen Peiling Xie Jiahui Gong Hongchun Sun Xiaojing Hu Baolin Zhu Prof. Dr. Weiping Huang 《Chemphyschem》2023,24(12):e202200910
The objective of the tandem hydroformylation-hydrogenation of alkenes to corresponding alcohols was to design an efficient and stable heterogeneous catalyst. To this end, a series of novel heterogeneous graphitic carbon nitride (g-CN) supported bimetallic Rh−Co nanoparticle catalysts (Rh−Co/g-CN) were prepared and subsequently studied for this one-pot two-step reaction. The lamellar structure makes Rh and Co nanoparticles with diameters of <1 nm and 20 nm, respectively, homogeneously deposited on the surface of g-CN layers, exhibit remarkable conversion of styrene (99.9 %) and chemoselectivity for alcohol (87.8 %). More importantly, Co nanoparticles are found to play an important role in the improvement of the chemoselectivity for alcohol due to the formation of catalytic active species [HCo(CO)y]. Besides the detailed investigation of the catalytic properties of Rh−Co/g-CN under different reaction conditions, the reuse of Rh−Co/g-CN was conducted for five times and no evident decrease in the activity and chemoselectivity was observed. Therefore, we expect that this work could offer an initial insight into g-CN-based heterogeneous catalyst on the tandem hydroformylation-hydrogenation reaction. 相似文献
175.
Newton MA Dent AJ Diaz-Moreno S Fiddy SG Jyoti B Evans J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):1975-1985
Spatially and temporally resolved energy-dispersive EXAFS (EDE) has been utilised in situ to study supported Rh nanoparticles during CO oxidation by O2 under plug-flow conditions. Three distinct phases of Rh supported upon Al2O3 were identified by using EDE at the Rh K-edge during CO oxidation. Their presence and interconversion are related to the efficiency of the catalysts in oxidising CO to CO2. A metallic phase is only found at higher temperatures (>450 K) and CO fractions (CO/O2 > 1); an oxidic phase resembling Rh2O3 dominates the active catalyst under oxygen-rich conditions. Below about 573 K, and in CO-rich environments, high proportions of isolated Rh(I)(CO)2 species are found to co-exist with metallic Rh nanoparticles. Alongside these discrete situations a large proportion of the active phase space comprises small Rh cores surrounded by layers of active oxide. Confinement of Rh to nanoscale domains induces structural lability that influences catalytic behaviour. For CO oxidation over Rh/Al2O3 there are two redox phase equilibria alongside the chemistry of CO and O adsorbed upon extended Rh surfaces. 相似文献
176.
177.
WANG Ye AN DongLi & ZHANG QingHong State Key Laboratory of Physical Chemistry of Solid Surfaces National Engineering Laboratory for Green Chemical Productions of Alcohols Ethers Esters 《中国科学:化学》2010,(2)
Selective oxidation or oxidative functionalization of methane and ethane by both homogeneous and heterogeneous catalysis is presented concerning: (1) selective oxidation of methane and ethane to organic oxygenates by hydrogen peroxide in a water medium in the presence of homogeneous osmium catalysts, (2) selective oxidation of methane to formaldehyde over highly dispersed iron and copper heterogeneous catalysts, (3) selective oxidation of ethane to acetaldehyde and formaldehyde over supported molybdenum cat... 相似文献
178.
Textile/Metal–Organic‐Framework Composites as Self‐Detoxifying Filters for Chemical‐Warfare Agents 下载免费PDF全文
Elena López‐Maya Dr. Carmen Montoro Dr. L. Marleny Rodríguez‐Albelo Dr. Salvador D. Aznar Cervantes Dr. A. Abel Lozano‐Pérez Prof. José Luis Cenís Dr. Elisa Barea Prof. Jorge A. R. Navarro 《Angewandte Chemie (International ed. in English)》2015,54(23):6790-6794
The current technology of air‐filtration materials for protection against highly toxic chemicals, that is, chemical‐warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self‐cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal–organic framework (MOF) materials to develop advanced self‐detoxifying adsorbents of chemical‐warfare agents containing hydrolysable P? F, P? O, and C? Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air‐permeation properties of the textiles with the self‐detoxifying properties of the MOF material. 相似文献
179.
Identification of tert‐Butyl Cations in Zeolite H‐ZSM‐5: Evidence from NMR Spectroscopy and DFT Calculations 下载免费PDF全文
Dr. Weili Dai Prof.Dr. Chuanming Wang Dr. Xianfeng Yi Prof. Dr. Anmin Zheng Prof. Dr. Landong Li Prof. Dr. Guangjun Wu Prof. Dr. Naijia Guan Prof. Dr. Zaiku Xie Dipl.‐Chem. Michael Dyballa Prof. Dr. Michael Hunger 《Angewandte Chemie (International ed. in English)》2015,54(30):8783-8786
Experimental evidence for the presence of tert‐butyl cations, which are important intermediates in acid‐catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with 1H/13C magic‐angle‐spinning NMR spectroscopy, the tert‐butyl cation was successfully identified on zeolite H‐ZSM‐5 upon conversion of isobutene by capturing this intermediate with ammonia. 相似文献
180.
Cuprous Oxide Catalyzed Oxidative CC Bond Cleavage for CN Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines 下载免费PDF全文
Dr. Min Wang Dr. Jianmin Lu Dr. Jiping Ma Zhe Zhang Prof. Feng Wang 《Angewandte Chemie (International ed. in English)》2015,54(47):14061-14065
Selective oxidative cleavage of a C? C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C? C bond cleavage of ketone for C? N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In‐depth studies show that both α‐C? H and β‐C? H bonds adjacent to the carbonyl groups are indispensable for the C? C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α‐C? H bond. Amines lower the activation energy of the C? C bond cleavage, and thus promote the reaction. New insight into the C? C bond cleavage mechanism is presented. 相似文献