Noble Metal Nanoparticles Stabilized by Hyper-Cross-Linked Polystyrene as Effective Catalysts in Hydrogenation of Arenes.
Ontology highlight
ABSTRACT:
SUBMITTER: Bakhvalova ES
PROVIDER: S-EPMC8348316 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Nickel-tungsten carbide catalysts convert furfural to high value products in a liquid phase catalytic reaction. The product distribution depends on the solvent and the Ni-W-ratio of the catalyst. In isopropyl alcohol a combination of Ni and W x C enables the opening of the furan ring to yield 1,2-pentanediol. Nickel accelerates the tungsten oxide reduction in the tungsten carbide catalyst synthesis and facilitates the carbon insertion. Nickel modified tungsten carbide is a promising, noble metal-free catalyst system for the upgrading of furfural based renewable resources. Its preparation is facilitated compared to unmodified tungsten carbide catalysts.
| S-EPMC9055482 | biostudies-literature
Project description:Among different polymers nanostructured cross-linked aromatics have the greatest potential as catalytic supports due to their exceptional thermal and chemical stability and preservation of the active phase morphology. This work studies the ability of hyper-cross-linked polystyrene (HPS) to stabilize small Pdn and Ptn (n = 4 or 9) clusters. Unrestricted DFT calculations were carried out for benzene (BZ) adsorption at the BP level of theory using triple-zeta basis sets. The adsorption of BZ rings (stepwise from one to four) was found to result in noticeable gain in energy and stabilization of resulting adsorption complexes. Moreover, the interaction of metal clusters with HPS micropores was also addressed. For the first time, the incorporation of small clusters in the HPS structure was shown to influences its geometry resulting in the stabilization of polymer due to its partial relaxation.
| S-EPMC8433677 | biostudies-literature
Project description:The control of product distribution in a multistep catalytic selective hydrogenation reaction is challenging. For instance, the deep hydrogenation of dimethyl oxalate (DMO) is inclined to proceed over Cu/SiO2 catalysts because of inevitable coexistence of Cu+ and Cu0, leading to hard acquisition of the preliminary hydrogenation product, methyl glycolate (MG). Here, the oriented DMO hydrogenation into MG is achieved over the sputtering (SP) Cu/SiO2 catalysts with a selectivity of more than 87% via freezing Cu in a zero-valence state. Our density functional theory calculation results revealed that Cu0 is the active site of the preliminary hydrogenation step, selectively converting DMO to MG via •H addition, while Cu+ is a key factor for deep hydrogenation. The prominent Coster-Kronig transition enhancement is observed over SP-Cu/SiO2 from Auger spectra, indicating that the electron density of inner shells in Cu atoms is enhanced by high-energy argon plasma bombardment during the SP process. Thus, the "penetration effect" of outermost electrons could also be enhanced, making these Cu nanoparticles exhibit high oxidation resistance ability and present noble metal-like behaviors as Au or Ag. Therefore, the regulation of Cu chemical properties by changing the electron structure is a feasible strategy to control the hydrogenation products, inspiring the rational design of selective hydrogenation catalysts.
| S-EPMC6303123 | biostudies-literature
Project description:Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.
| S-EPMC5993471 | biostudies-other
Project description:In recent decades, fuel cell technology has been undergoing revolutionary developments, with fundamental progress being the replacement of electrolyte solutions with polymer electrolytes, making the device more compact in size and higher in power density. Nowadays, acidic polymer electrolytes, typically Nafion, are widely used. Despite great success, fuel cells based on acidic polyelectrolyte still depend heavily on noble metal catalysts, predominantly platinum (Pt), thus increasing the cost and hampering the widespread application of fuel cells. Here, we report a type of polymer electrolyte fuel cells (PEFC) employing a hydroxide ion-conductive polymer, quaternary ammonium polysulphone, as alkaline electrolyte and nonprecious metals, chromium-decorated nickel and silver, as the catalyst for the negative and positive electrodes, respectively. In addition to the development of a high-performance alkaline polymer electrolyte particularly suitable for fuel cells, key progress has been achieved in catalyst tailoring: The surface electronic structure of nickel has been tuned to suppress selectively the surface oxidative passivation with retained activity toward hydrogen oxidation. This report of a H2–O2 PEFC completely free from noble metal catalysts in both the positive and negative electrodes represents an important advancement in the research and development of fuel cells.
| S-EPMC2634878 | biostudies-literature
Project description:Selective hydrogenations of (hetero)arenes represent essential processes in the chemical industry, especially for the production of polymer intermediates and a multitude of fine chemicals. Herein, we describe a new type of well-dispersed Ru nanoparticles supported on a nitrogen-doped carbon material obtained from ruthenium chloride and dicyanamide in a facile and scalable method. These novel catalysts are stable and display both excellent activity and selectivity in the hydrogenation of aromatic ethers, phenols as well as other functionalized substrates to the corresponding alicyclic reaction products. Furthermore, reduction of the aromatic core is preferred over hydrogenolysis of the C-O bond in the case of ether substrates. The selective hydrogenation of biomass-derived arenes, such as lignin building blocks, plays a pivotal role in the exploitation of novel sustainable feedstocks for chemical production and represents a notoriously difficult transformation up to now.
| S-EPMC4853427 | biostudies-literature
Project description:Ligand control of metal nanoparticles (MNPs) is rapidly gaining importance as ligands can stabilize the MNPs and regulate their catalytic properties. Herein we report the first example of Pt NPs ligated by imidazolium-amidinate ligands that bind strongly through the amidinate anion to the platinum surface atoms. The binding was established by 15N NMR spectroscopy, a precedent for nitrogen ligands on MNPs, and XPS. Both monodentate and bidentate coordination modes were found. DFT showed a high bonding energy of up to -48 kcal mol-1 for bidentate bonding to two adjacent metal atoms, which decreased to -28 ± 4 kcal mol-1 for monodentate bonding in the absence of impediments by other ligands. While the surface is densely covered with ligands, both IR and 13C MAS NMR spectra proved the adsorption of CO on the surface and thus the availability of sites for catalysis. A particle size dependent Knight shift was observed in the 13C MAS NMR spectra for the atoms that coordinate to the surface, but for small particles, ∼1.2 nm, it almost vanished, as theory for MNPs predicts; this had not been experimentally verified before. The Pt NPs were found to be catalysts for the hydrogenation of ketones and a notable ligand effect was observed in the hydrogenation of electron-poor carbonyl groups. The catalytic activity is influenced by remote electron donor/acceptor groups introduced in the aryl-N-substituents of the amidinates; p-anisyl groups on the ligand gave catalysts several times faster the ligand containing p-chlorophenyl groups.
| S-EPMC5376718 | biostudies-literature
Project description:Size effect plays a crucial role in catalytic hydrogenation. The highly dispersed ultrasmall clusters with a limited number of metal atoms are one candidate of the next generation catalysts that bridge the single-atom metal catalysts and metal nanoparticles. However, for the unfavorable electronic property and their interaction with the substrates, they usually exhibit sluggish activity. Taking advantage of the small size, their catalytic property would be mediated by surface binding species. The combination of metal cluster coordination chemistry brings new opportunity. CO poisoning is notorious for Pt group metal catalysts as the strong adsorption of CO would block the active centers. In this work, we will demonstrate that CO could serve as a promoter for the catalytic hydrogenation when ultrasmall Pd clusters are employed. By means of DFT calculations, we show that Pd n (n = 2-147) clusters display sluggish activity for hydrogenation due to the too strong binding of hydrogen atom and reaction intermediates thereon, whereas introducing CO would reduce the binding energies of vicinal sites, thus enhancing the hydrogenation reaction. Experimentally, supported Pd2CO catalysts are fabricated by depositing preestablished [Pd2(μ-CO)2Cl4]2- clusters on oxides and demonstrated as an outstanding catalyst for the hydrogenation of styrene. The promoting effect of CO is further verified experimentally by removing and reintroducing a proper amount of CO on the Pd cluster catalysts.
| S-EPMC7382763 | biostudies-literature
Project description:We report a robust, universal "soft" nitriding method to grow in situ ligand-free ultrasmall noble metal nanocatalysts (UNMN; e.g., Au, Pd, and Pt) onto carbon. Using low-temperature urea pretreatment at 300 °C, soft nitriding enriches nitrogen-containing species on the surface of carbon supports and enhances the affinity of noble metal precursors onto these supports. We demonstrated sub-2-nm, ligand-free UNMNs grown in situ on seven different types of nitrided carbons with no organic ligands via chemical reduction or thermolysis. Ligand-free UNMNs supported on carbon showed superior electrocatalytic activity for methanol oxidation compared to counterparts with surface capping agents or larger nanocrystals on the same carbon supports. Our method is expected to provide guidelines for the preparation of ligand-free UNMNs on a variety of supports and, additionally, to broaden their applications in energy conversion and electrochemical catalysis.
| S-EPMC4852704 | biostudies-literature
Project description:Developing a low-cost and robust catalyst for efficient transformation of biomass-derived platform chemicals plays a crucial role in the synthesis of future transportation fuels. Herein, a post-synthetic strategy was employed to develop a noble metal-free and robust ZrY zeolite catalyst, which is efficient for the hydrogenation of biomass-derived levulinic acid (LA) into biofuel γ-valerolactone (GVL), whereas over 95% yield of GVL was achieved in 10 h at 220°C. The effects of acidic properties from ZrY catalysts and various reaction parameters on the catalytic performance were then discussed in detail. Subsequently, different characterization tools were used to compare the difference and relationship of structure activity between the fresh and spent ZrY catalysts. It was found that acidity and the metal-support interaction were important for the direct synthesis of GVL. This work provides a guideline to design a noble metal-free catalyst for high-value utilization of biomass-derived sources.
| S-EPMC8546667 | biostudies-literature