Light‐Assisted CO 2 Hydrogenation over Pd 3 Cu@UiO‐66 Promoted by Active Sites in Close Proximity

2022 ◽  
Author(s):  
Li‐Li Ling ◽  
Weijie Yang ◽  
Peng Yan ◽  
Min Wang ◽  
Hai‐Long Jiang
Keyword(s):  
2013 ◽  
Vol 67 (8) ◽  
Author(s):  
Robert Kosydar ◽  
Monika Goral ◽  
Alicja Drelinkiewicz ◽  
Jaroslav Stejskal

AbstractTwo polyaniline (PANI) samples of various molecular masses were used for the preparation of palladium catalysts (with 2 mass % of Pd). The physicochemical features of starting polyanilines were found to substantially affect the size and extent of palladium nanoparticles aggregation. Strongly aggregated large palladium particles appeared in the PANI sample of more compact morphology (PANI-H), higher crystallinity and lower specific surface area. Pd nanoparticles of a definitively smaller size were formed in the more amorphous PANI sample of looser morphology (PANI-L) and the extent of particles aggregation was markedly lower. The catalytic properties of Pd/PANI samples were studied in a liquid phase hydrogenation of unsaturated triple bond (C≡C) in alkynes reactants, phenylacetylene, and cyclohexylacetylene. The 2 mass % Pd/PANI-L catalyst prepared using polymer of less compact texture exhibited much higher activity in both reactions. In the presence of the 2 mass % Pd/PANI-L catalyst, alkene products were formed with a high selectivity (approximately 90 %) attained at the almost complete conversion of alkynes. This highly selective hydrogenation of the C≡C to the C=C bond was related to the presence of an electroactive polymer, PANI, in close proximity with Pd active sites. Polyaniline could have a role in a steric effect as well as in a modification of adsorptive properties of Pd centres.


2019 ◽  
Author(s):  
Marius Arz ◽  
Tim Kratky ◽  
Sebastian Günther ◽  
Katia Rodewald ◽  
Thomas Burger ◽  
...  

We report the immobilization of the ultrarigid <i>ansa</i>-hafnocene complexes [Me<sub>2</sub>Si(Ind*)<sub>2</sub>HfCl<sub>2</sub>] (Ind* = 7,(3',5'-Di-<i>tert</i>-butylphenyl)-4-methoxy-2-methylindenyl) on silica as heteregeneous catalysts for propene polymerization. A sequential three-step synthesis on the siliceous surface led to pre-catalysts of the generalized structure SiO<sub>2</sub>-Si(Ind*)<sub>2</sub>HfCl<sub>2</sub>, which possess the silylene bridge of the substituted bis(indenyl) ligand directly attached to the surface. The immobilized pre-catalysts show very poor performance in the polymerization of propene, independent on the reaction conditions and the employed silica. Based on the results, we suggest that the close proximity of the catalyst to the surface combined with the steric congestion provoked by the ligand prevents a continuous polymerization, most likely due to a blockage of the catalytically active sites with growing polymer.<br>


2021 ◽  
Vol 25 ◽  
Author(s):  
Nicoletta Gaggero ◽  
Domenico C. M. Albanese

: Cascade reactions catalyzed by immobilized multi enzymatic systems are emerging as a tool to address the increasing need for green and sustainable chemistry. In this regard, the carrier-free immobilization strategy of combined cross-linked enzymes aggregates (combi-CLEAs) is of great interest. In a combi-CLEAs two or more enzymes are co-immobilized into a single unit where they are accommodated in close proximity in order to minimize the intermediates diffusion in the reaction medium, at the same time allowing the access of substrates and coenzymes to the active sites. The use of CLEAs provides a simple and low cost methodology that enhances operational and storage enzyme stability and facilitates biocatalyst recovery and recycle. Some significant applications of cascade reactions catalyzed by combi-CLEAs are reported in this mini-review. These examples have been applied on a multigram scale and have furnished practical steps towards the implementation of enzymes on an industrial scale.


2019 ◽  
Author(s):  
Marius Arz ◽  
Tim Kratky ◽  
Sebastian Günther ◽  
Katia Rodewald ◽  
Thomas Burger ◽  
...  

We report the immobilization of the ultrarigid <i>ansa</i>-hafnocene complexes [Me<sub>2</sub>Si(Ind*)<sub>2</sub>HfCl<sub>2</sub>] (Ind* = 7,(3',5'-Di-<i>tert</i>-butylphenyl)-4-methoxy-2-methylindenyl) on silica as heteregeneous catalysts for propene polymerization. A sequential three-step synthesis on the siliceous surface led to pre-catalysts of the generalized structure SiO<sub>2</sub>-Si(Ind*)<sub>2</sub>HfCl<sub>2</sub>, which possess the silylene bridge of the substituted bis(indenyl) ligand directly attached to the surface. The immobilized pre-catalysts show very poor performance in the polymerization of propene, independent on the reaction conditions and the employed silica. Based on the results, we suggest that the close proximity of the catalyst to the surface combined with the steric congestion provoked by the ligand prevents a continuous polymerization, most likely due to a blockage of the catalytically active sites with growing polymer.<br>


Author(s):  
John L. Beggs ◽  
John D. Waggener ◽  
Wanda Miller

Microtubules (MT) are versatile organelles participating in a wide variety of biological activity. MT involvement in the movement and transport of cytoplasmic components has been well documented. In the course of our study on trauma-induced vasogenic edema in the spinal cord we have concluded that endothelial vesicles contribute to the edema process. Using horseradish peroxidase as a vascular tracer, labeled endothelial vesicles were present in all situations expected if a vesicular transport mechanism was in operation. Frequently,labeled vesicles coalesced to form channels that appeared to traverse the endothelium. The presence of MT in close proximity to labeled vesicles sugg ested that MT may play a role in vesicular activity.


Author(s):  
Alexis T. Bell

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.


Author(s):  
Oliver C. Wells ◽  
Mark E. Welland

Scanning tunneling microscopes (STM) exist in two versions. In both of these, a pointed metal tip is scanned in close proximity to the specimen surface by means of three piezos. The distance of the tip from the sample is controlled by a feedback system to give a constant tunneling current between the tip and the sample. In the low-end STM, the system has a mechanical stability and a noise level to give a vertical resolution of between 0.1 nm and 1.0 nm. The atomic resolution STM can show individual atoms on the surface of the specimen.A low-end STM has been put into the specimen chamber of a scanning electron microscope (SEM). The first objective was to investigate technological problems such as surface profiling. The second objective was for exploratory studies. This second objective has already been achieved by showing that the STM can be used to study trapping sites in SiO2.


Author(s):  
R.H.M. Cross ◽  
C.E.J. Botha ◽  
A.K. Cowan ◽  
B.J. Hartley

Senescence is an ordered degenerative process leading to death of individual cells, organs and organisms. The detection of a conditional lethal mutant (achloroplastic) of Hordeum vulgare has enabled us to investigate ultrastructural changes occurring in leaf tissue during foliar senescence.Examination of the tonoplast structure in six and 14 day-old mutant tissue revealed a progressive degeneration and disappearance of the membrane, apparently starting by day six in the vicinity of the mitochondria associated with the degenerating proplastid (Fig. 1.) where neither of the plastid membrane leaflets is evident (arrows, Fig. 1.). At this stage there was evidence that the mitochondrial membranes were undergoing retrogressive changes, coupled with disorganization of cristae (Fig. 2.). Proplastids (P) lack definitive prolamellar bodies. The cytoplasmic matrix is largely agranular, with few endoplasmic reticulum (ER) cisternae or polyribosomal aggregates. Interestingly, large numbers of actively-budding dictysomes, associated with pinocytotic vesicles, were observed in close proximity to the plasmalemma of mesophyll cells (Fig. 3.). By day 14 however, mesophyll cells showed almost complete breakdown of subcellular organelle structure (Fig. 4.), and further evidence for the breakdown of the tonoplast. The final stage of senescence is characterized by the solubilization of the cell wall due to expression and activity of polygalacturonase and/or cellulose. The presence of dictyosomes with associated pinocytotic vesicles formed from the mature face, in close proximity to both the plasmalemma and the cell wall, would appear to support the model proposed by Christopherson for the secretion of cellulase. This pathway of synthesis is typical for secretory glycoproteins.


Author(s):  
C. Jacobsen ◽  
J. Fu ◽  
S. Mayer ◽  
Y. Wang ◽  
S. Williams

In scanning luminescence x-ray microscopy (SLXM), a high resolution x-ray probe is used to excite visible light emission (see Figs. 1 and 2). The technique has been developed with a goal of localizing dye-tagged biochemically active sites and structures at 50 nm resolution in thick, hydrated biological specimens. Following our initial efforts, Moronne et al. have begun to develop probes based on biotinylated terbium; we report here our progress towards using microspheres for tagging.Our initial experiments with microspheres were based on commercially-available carboxyl latex spheres which emitted ~ 5 visible light photons per x-ray absorbed, and which showed good resistance to bleaching under x-ray irradiation. Other work (such as that by Guo et al.) has shown that such spheres can be used for a variety of specific labelling applications. Our first efforts have been aimed at labelling ƒ actin in Chinese hamster ovarian (CHO) cells. By using a detergent/fixative protocol to load spheres into cells with permeabilized membranes and preserved morphology, we have succeeded in using commercial dye-loaded, spreptavidin-coated 0.03μm polystyrene spheres linked to biotin phalloidon to label f actin (see Fig. 3).


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