共查询到20条相似文献,搜索用时 15 毫秒
1.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(21):6294-6299
The gram‐scale synthesis, stabilization, and characterization of well‐defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X‐ray snapshots of Pt02 clusters, homogenously distributed and densely packaged within the channels of a metal–organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO2 methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal clusters in solids for technically easier, cheaper, and dramatically less‐dangerous industrial reactions. 相似文献
2.
Controllable Encapsulation of “Clean” Metal Clusters within MOFs through Kinetic Modulation: Towards Advanced Heterogeneous Nanocatalysts 下载免费PDF全文
Dr. Hongli Liu Lina Chang Cuihua Bai Liyu Chen Prof. Rafael Luque Prof. Yingwei Li 《Angewandte Chemie (International ed. in English)》2016,55(16):5019-5023
Surfactant‐free tiny Pt clusters were successfully encapsulated within MOFs with controllable size and spatial distribution by a novel kinetically modulated one‐step strategy. Our synthesis relies on the rational manipulation of the reduction rate of Pt ions and/or the growth rate of MOFs by using H2 as assistant reducing agent and/or acetic acid as MOF‐formation modulator. The as‐prepared Pt@MOF core–shell composites exhibited exceedingly high activity and excellent selectivity in the oxidation of alcohols as a result of the ultrafine “clean” Pt clusters, as well as interesting molecular‐sieving effects derived from the outer platinum‐free MOF shell. 相似文献
3.
Three Series of Sulfo‐Functionalized Mixed‐Linker CAU‐10 Analogues: Sorption Properties,Proton Conductivity,and Catalytic Activity 下载免费PDF全文
Nele Reimer Bart Bueken Sebastian Leubner Christopher Seidler Prof. Michael Wark Prof. Dirk De Vos Prof. Norbert Stock 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12517-12524
Ten mixed‐linker metal–organic frameworks [Al(OH)(m‐BDC‐X)1?y(m‐BDC‐SO3H)y] (H2BDC=1,3‐benzenedicarboxylic acid; X=H, NO2, OH) exhibiting the CAU‐10‐type structure were synthesized. The compounds can be grouped into three series according to the combination of ligands employed. The three series of compounds were obtained by employing different ratios of m‐H2BDC‐X and m‐H2BDC‐SO3Li. The resulting compounds, which are denoted CAU‐10‐H/Sx, ‐N/Sx and ‐O/Sx, show exceptionally high thermal stability for sulfonated materials of up to 350 °C. Detailed characterization with special focus on polarity and acidity was performed, and the impact of the additional SO3H groups is clearly demonstrated by changes in the sorption affinities/capacities towards several gases and water vapor. In addition, selected samples were evaluated for proton conductivity and as catalysts for the gas‐phase dehydration of ethanol to ethylene. While only very low proton conductivities were observed, a pronounced increase in catalytic activity was achieved. Although reactions were performed at temperatures of 250 and 300 °C for more than 40 h, no desulfonation and no loss of crystallinity were observed, and stable ethanol conversion resulted. This demonstrates the high stability of this material. 相似文献
4.
Pengyuan Wang Dr. Jia Liu Chuanfang Liu Bin Zheng Prof. Dr. Xiaoqin Zou Prof. Dr. Mingjun Jia Prof. Dr. Guangshan Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16613-16620
It is very interesting and also a big challenge to encapsulate metal clusters within microporous solids to expand their application diversity. For this target, herein, we present an electrochemical synthesis strategy for the encapsulation of noble metals (Au, Pd, Pt) within ZIF‐8 cavities. In this method, metal precursors of AuCl42?, PtCl62?, and PdCl42? are introduced into ZIF‐8 crystals during the concurrent crystallization of ZIF‐8 at the anode. As a consequence, very small metal clusters with sizes around 1.2 nm are obtained within ZIF‐8 crystals after hydrogen reduction; these clusters exhibit high thermal stability, as evident from the good maintenance of their original sizes after a high‐temperature test. The catalytic properties of the encapsulated metal clusters within ZIF‐8 are evaluated for CO oxidations. Because of the small pore window of ZIF‐8 (0.34 nm) and the confinement effect of small pores, about 80 % of the metal clusters (fractions of 0.74, 0.77, and 0.75 for Au, Pt, and Pd in ZIF‐8, respectively) retain their catalytic activity after exposure to the organosulfur poison thiophene (0.46 nm), which is in contrast to their counterparts (fractions of 0.22, 0.25, and 0.20 for Au, Pt, and Pd on the SiO2 support). The excellent performances of metal clusters encapsulated within ZIF‐8 crystals give new opportunities for catalytic reactions. 相似文献
5.
Xiaoying Xu Stephan M. Rummelt Flavien L. Morel Dr. Marco Ranocchiari Prof. Dr. Jeroen A. van Bokhoven 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15467-15472
Steric hindrance by a metal–organic framework (MOF) is shown to influence the outcome of a catalytic reaction by controlling the orientation of its intermediates. This is demonstrated using an organocatalyst, phosphine MOF LSK‐3, which is evaluated with the aid of molecular modeling and NMR spectroscopy techniques. This report is the first application of phosphine MOFs in organocatalysis and explores the potential of a framework steric hindrance to impose selectivity on a catalytic reaction. These findings expand the opportunities for control and design of the active site in the pocket of heterogeneous catalysts. 相似文献
6.
Silica‐Protection‐Assisted Encapsulation of Cu2O Nanocubes into a Metal–Organic Framework (ZIF‐8) To Provide a Composite Catalyst 下载免费PDF全文
Bo Li Dr. Jian‐Gong Ma Prof. Dr. Peng Cheng 《Angewandte Chemie (International ed. in English)》2018,57(23):6834-6837
The integration of metal/metal oxide nanoparticles (NPs) into metal–organic frameworks (MOFs) to form composite materials has attracted great interest due to the broad range of applications. However, to date, it has not been possible to encapsulate metastable NPs with high catalytic activity into MOFs, due to their instability during the preparation process. For the first time, we have successfully developed a template protection–sacrifice (TPS) method to encapsulate metastable NPs such as Cu2O into MOFs. SiO2 was used as both a protective shell for Cu2O nanocubes and a sacrificial template for forming a yolk–shell structure. The obtained Cu2O@ZIF‐8 composite exhibits excellent cycle stability in the catalytic hydrogenation of 4‐nitrophenol with high activity. This is the first report of a Cu2O@MOF‐type composite material. The TPS method provides an efficient strategy for encapsulating unstable active metal/metal oxide NPs into MOFs or maybe other porous materials. 相似文献
7.
Multifunctional,Defect‐Engineered Metal–Organic Frameworks with Ruthenium Centers: Sorption and Catalytic Properties 下载免费PDF全文
Olesia Kozachuk Ignacio Luz Dr. Francesc X. Llabrés i Xamena Dr. Heshmat Noei Max Kauer Dr. H. Bauke Albada Eric D. Bloch Dr. Bernd Marler Dr. Yuemin Wang Prof. Dr. Martin Muhler Prof. Dr. Roland A. Fischer 《Angewandte Chemie (International ed. in English)》2014,53(27):7058-7062
A mixed‐linker solid‐solution approach was employed to modify the metal sites and introduce structural defects into the mixed‐valence RuII/III structural analogue of the well‐known MOF family [M3II,II(btc)2] (M=Cu, Mo, Cr, Ni, Zn; btc=benzene‐1,3,5‐tricarboxylate), with partly missing carboxylate ligators at the Ru2 paddle‐wheels. Incorporation of pyridine‐3,5‐dicarboxylate (pydc), which is the same size as btc but carries lower charge, as a second, defective linker has led to the mixed‐linker isoreticular derivatives of Ru‐MOF, which display characteristics unlike those of the defect‐free framework. Along with the creation of additional coordinatively unsaturated sites, the incorporation of pydc induces the partial reduction of ruthenium. Accordingly, the modified Ru sites are responsible for the activity of the “defective” variants in the dissociative chemisorption of CO2, the enhanced performance in CO sorption, the formation of hydride species, and the catalytic hydrogenation of olefins. 相似文献
8.
Dr. Rupam Sen Debraj Saha Dr. Subratanath Koner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(19):5979-5986
The role of pH in the formation of metal–organic frameworks (MOFs) has been studied for a series of magnesium‐based carboxylate framework systems. Our investigations have revealed the formation of five different zero‐dimensional (0D) to three‐dimensional (3D) ordered frameworks from the same reaction mixture, merely by varying the pH of the medium. The compounds were synthesized by the hydrothermal method and characterized by single‐crystal X‐ray diffraction. Increase of the pH of the medium led to abstraction of the imine hydrogen from the ligand and a concomitant increase in the OH? ion concentration in the solution, facilitating the construction of higher dimensional framework compounds. A stepwise increase in pH resulted in a stepwise increase in the dimensionality of the network, ultimately leading to the formation of a 3D porous solid. A gas adsorption study of the 3D framework compound confirmed its microporosity with a BET surface area of approximately 450 m2 g?1. Notably, the 3D framework compound catalyzes aldol condensation reactions of various aromatic aldehydes with acetone under heterogeneous conditions. 相似文献
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10.
Bo Li Dr. Jian‐Gong Ma Prof. Dr. Peng Cheng 《Angewandte Chemie (International ed. in English)》2018,57(23):6945-6945
11.
Feifan Wang Jie Tian Mengzhu Li Weizhen Li Lifang Chen Xiaozhi Liu Jian Li Aidaer Muhetaer Qi Li Yuan Wang Lin Gu Ding Ma Dongsheng Xu 《Angewandte Chemie (International ed. in English)》2020,59(21):8203-8209
Fully utilizing solar energy for catalysis requires the integration of conversion mechanisms and therefore delicate design of catalyst structures and active species. Herein, a MOF crystal engineering method was developed to controllably synthesize a copper–ceria catalyst with well‐dispersed photoactive Cu‐[O]‐Ce species. Using the preferential oxidation of CO as a model reaction, the catalyst showed remarkably efficient and stable photoactivated catalysis, which found practical application in feed gas treatment for fuel cell gas supply. The coexistence of photochemistry and thermochemistry effects contributes to the high efficiency. Our results demonstrate a catalyst design approach with atomic or molecular precision and a combinatorial photoactivation strategy for solar energy conversion. 相似文献
12.
Encapsulation of Silver Nanoparticles in an Amine‐Functionalized Porphyrin Metal–Organic Framework and Its Use as a Heterogeneous Catalyst for CO2 Fixation under Atmospheric Pressure 下载免费PDF全文
《化学:亚洲杂志》2018,13(18):2677-2684
A new porphyrin‐based compound, [Zn3(C40H24N8)(C20H8N2O4)2(DEF)2](DEF)3 ( 1 ; DEF=N,N‐diethylformamide), has been synthesized by employing 5,10,15,20‐tetrakis(4‐pyridyl)porphyrin, 1,2‐diamino‐3,6‐bis(4‐carboxyphenyl)benzene, and Zn2+ salt at 100 °C under solvothermal conditions. The structure, as determined by single‐crystal XRD studies, is three‐dimensional with threefold interpenetration. The usefulness of free −NH2 groups in the ligand was exploited for anchoring silver nanoparticles through a simple solution‐based route. The silver‐loaded sample, Ag@ 1 , was characterized by powder XRD, energy‐dispersive X‐ray spectroscopy, high‐resolution TEM, SEM, X‐ray photoelectron spectroscopy, and inductively coupled plasma MS analysis, which clearly indicated that silver nanoparticles with a size of 3.83 nm were uniformly distributed within the metal–organic framework (MOF). The Ag@ 1 sample was evaluated for possible catalytic activity for the carboxylation of a terminal alkyne by employing CO2 under atmospheric pressure; this gave excellent results. The Ag@ 1 catalyst was found to be robust, active, and recyclable. The present studies suggest that porphyrin MOFs not only exhibit interesting structures, but also show good heterogeneous catalytic activity towards the fixation of CO2. 相似文献
13.
Selective catalytic reduction (SCR) of NOx with H2 as a reductant is the most promising denitration technology at low temperature. Achieving the conversion of NOx into N2 at ambient temperature not only prolongs the service life of the catalyst, but also provides more freedom for the arrangement of denitration units throughout the flue gas treatment equipment. However, the development of highly efficient, stable, and environmentally benign supported platinum‐based catalysts for H2‐SCR at ambient temperature is still a major challenge. Herein, a 0.5 wt % Pt/ZrO2@C catalyst, which was composed of carbon‐coated octahedral ZrO2 with highly dispersed Pt particles, was prepared by using a new stabilization strategy based on UiO‐66‐NH2 (a zirconium metal–organic framework) as a template. The catalytic performance of this Pt/ZrO2@C in H2‐SCR was tested and confirmed to achieve near 100 % NOx conversion at 90 °C. Also, 70 % N2 selectivity of the catalyst was achieved. The morphology, structure, and porous properties of the as‐synthesized nanocomposites were characterized by using data obtained from field‐emission SEM, TEM, XRD, Raman spectroscopy, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and N2 adsorption–desorption isotherms. The results show that residual carbon formed by pyrolysis treatment is coated on octahedral ZrO2, and effectively prevents the agglomeration of platinum particles on the surface. 相似文献
14.
Chemical Fixation of CO2 and Other Heterogeneous Catalytic Studies by Employing a Layered Cu‐Porphyrin Prepared Through Single‐Crystal to Single‐Crystal Exchange of a Zn Analogue 下载免费PDF全文
A solvothermal reaction of Zn(NO3)2 ? 6 H2O, tetra‐(4‐pyridyl)porphyrin (H2TPyP), and 4,4′‐oxybis(benzoic acid) (H2OBA) resulted in a new two‐dimensional Zn‐ porphyrin metal–organic framework compound, [Zn2(C40H24N8)0.5(C14H8O5)(DMA)](DMA)(H2O)6 ( 1 ; DMA=N,N‐dimethylacetamide). The ZnII ions present in 1 could be exchanged by using a solution of Cu(NO3)2 ? 3 H2O in DMA at room temperature to give [Cu2(C40H24N8)0.5(C14H8O5)(DMA)](DMA)(H2O)3 ( Cu∈1 ). The extra‐framework solvent molecules have been shown to be reversibly removed or exchanged without collapse of the framework. Solvent‐free Cu∈1 was explored as an active heterogeneous catalyst towards three different organic reactions: 1) the chemical fixation of CO2 into cyclic carbonate at room temperature and 1 atm; 2) the nitroaldol reaction under solvent‐free conditions, and 3) the three‐component coupling of aminopyridine, benzaldehyde, and aryl alkynes followed by 5‐exo‐dig cyclization to produce the important pharmacophore imidazopyridine. 相似文献
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A Chromium Hydroxide/MIL‐101(Cr) MOF Composite Catalyst and Its Use for the Selective Isomerization of Glucose to Fructose 下载免费PDF全文
Dr. Qiang Guo Dr. Limin Ren Prashant Kumar Dr. Viktor J. Cybulskis Prof. K. Andre Mkhoyan Prof. Mark E. Davis Prof. Michael Tsapatsis 《Angewandte Chemie (International ed. in English)》2018,57(18):4926-4930
A metal–organic framework (MOF)‐based catalyst, chromium hydroxide/MIL‐101(Cr), was prepared by a one‐pot synthesis method. The combination of chromium hydroxide particles on and within Lewis acidic MIL‐101 accomplishes highly selective conversion of glucose to fructose in the presence of ethanol, matching the performance of optimized Sn‐containing Lewis acidic zeolites. Differently from zeolites, NMR spectroscopy studies with isotopically labeled molecules demonstrate that isomerization of glucose to fructose on this catalyst, proceeds predominantly via a proton transfer mechanism. 相似文献
17.
Ge Huang Li Yang Qi Yin Zhi‐Bin Fang Xiao‐Jing Hu An‐An Zhang Jun Jiang Tian‐Fu Liu Rong Cao 《Angewandte Chemie (International ed. in English)》2020,59(11):4385-4390
Although many ionic metal–organic frameworks (MOFs) have been reported, little is known about how the charge of the skeleton affects the properties of the MOF materials. Herein we report how the chemical stability of MOFs can be substantially improved through embedding electrostatic interactions in structure. A MOF with a cationic skeleton is impervious to extremely acidic, oxidative, reductive, and high ionic strength conditions, such as 12 m HCl (301 days), aqua regia (86 days), H2O2 (30 days), and seawater (30 days), which is unprecedented for MOFs. DFT calculations suggested that steric hinderance and the repulsive interaction of the cationic framework toward positively charged species in microenvironments protects the vulnerable bonds in the structure. Diverse functionalities can be bestowed by substituting the counterions of the charged framework with identically charged functional species, which broadens the horizon in the design of MOFs adaptable to a demanding environment with specific functionalities. 相似文献
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María C. Bernini Felipe Gándara Marta Iglesias Dr. Natalia Snejko Dr. Enrique Gutiérrez‐Puebla Prof. Elena V. Brusau Dr. Griselda E. Narda Dr. M. Ángeles Monge Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(19):4896-4905
The novel Yb succinate metal–organic framework exhibits a reversible single‐crystal to single‐crystal polymorphic transformation (see figure) when it is heated above 130 °C, returning to its initial form when back at room temperature. This transformation produces a change in the coordination sphere of the Yb atoms, which influences the catalytic activity of the material.