Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Comparative study on catalytic hydrodehalogenation of halogenated aromatic compounds over Pd/C and Raney Ni catalysts.

ABSTRACT: Catalytic hydrodehalogenation (HDH) has proved to be an efficient approach to dispose halogenated aromatic compounds (HACs). Liquid-phase HDH of single and mixed halobenzenes/4-halophenols with H2 over 5% Pd/C and Raney Ni catalyst are investigated and compared. For liquid-phase HDH of single HACs, hydrogenolytic scission reactivity of C-X bonds decreases in order of C-Br > C-Cl > C-I > C-F over Pd/C catalyst, and in order of C-I > C-Br > C-Cl > C-F over Raney Ni catalyst. To clarify the reason why hydrogenolytic scission reactivity of C-X bonds over Pd/C and Raney Ni catalysts exhibits different trends, liquid-phase HDH of mixed HACs over Pd/C and Raney Ni catalysts were studied, and catalysts are characterized by SEM, EDX, and XRD techniques. It was found that the high adsorption of iodoarenes on Pd/C catalyst caused the HDH reactivity of iodoarenes to be lower than that of chloroarenes and bromoarenes in the HDH of single HACs. Moreover, the adsorption of in situ produced iodine ion (I(-)) to catalyst surface would result in the decline of catalytic activity, which might be the main reason why the HDH reactivity of HACs in the presence of NaI is rather low.

SUBMITTER: Ma X

PROVIDER: S-EPMC4844995 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Pure Acetylene Semihydrogenation over Ni-Cu Bimetallic Catalysts: Effect of the Cu/Ni Ratio on Catalytic Performance.

Project description:Ethylene is an important chemical raw material and with the increasing consumption of petroleum resources, the production of ethylene through the calcium carbide acetylene route has important research significance. In this work, a series of bimetallic catalysts with different Cu/Ni molar ratios are prepared by co-impregnation method for the hydrogenation of calcium carbide acetylene to ethylene. The introduction of an appropriate amount of Cu effectively inhibits not only the formation of ethane and green oil, thus increasing the selectivity of ethylene, but also the formation of carbon deposits, which improves the stability of the catalyst. The ethylene selectivity of the Ni-Cu bimetallic catalyst increases from 45% to 63% compared with the Ni monometallic counterpart and the acetylene conversion still can reach 100% at the optimal conditions of 250 °C, 8000 mL·g-1·h-1 and V(H2)/V(C2H2) = 3. X-ray diffraction and transmission electron microscopy confirmed that the metal particles were highly dispersed on the support, High-resolution transmission electron microscopy and H2-Temperature programmed reduction proved that there was an interaction between Ni and Cu, combined with X-ray photoelectron spectroscopy and density functional theory calculations results, Cu transferred electrons to Ni changed the Ni electron cloud density in NiCux catalysts, thus reducing the adsorption of acetylene and ethylene, which is favorable to ethylene selectivity.

| S-EPMC7153591 | biostudies-literature

Chemical structure and biodegradability of halogenated aromatic compounds. Halogenated muconic acids as intermediates.

Project description:Substituted muconic acids were prepared from the corresponding catechols by pyrocatechase II from Pseudomonas sp. B13. The stabilities of substituted muconic acids were compared under different pH conditions. 3-Substituted cis, cis-muconic acids cycloisomerized readily in slightly acidic solutions, whereas 2-chloro- and 2-fluoro-cis,cis-muconic acids were stable under these conditions and could be isolated as crystalline compounds. They were isomerized to the cis, trans-form in highly acidic solution (pH 1), particularly when heated to 80 degrees C. Cycloisomerization of 2-chloro-cis,cis-muconic acid in 75% (v/v) H2SO4 yields 4-carboxymethyl-2-chloro-but-2-en-4-olide (4-chloro-2,5-dihydro-5-oxo-3H-furan-2-ylacetic acid). THe cis,cis-configuration of 2-chloromuconic acid was certified by 1H n.m.r. spectroscopy and by enzymic cycloisomerization. Although the cis,cis-configuration of 2-fluoromuconic acid was confirmed by corresponding spectroscopic data, it was not cycloisomerized by crude extracts or cycloisomerase II preparations from Pseudomonas sp. B13.

| S-EPMC1162338 | biostudies-other

Chemical structure and biodegradability of halogenated aromatic compounds. Substituent effects on 1,2-dioxygenation of catechol.

Project description:1. The influence of halogen substituents on the 1,2-dioxygenation of catechols was investigated. The results obtained with the two isoenzymes pyrocatechase I and pyrocatechase II from the haloarene-utilizing Pseudomonas sp. B 13 and the pyrocatechase from benzoate-induced cells of Alcaligenes eutrophus B.9 were compared. 2. Substituents on catechol were found to interfere with O2 binding by the two isoenzymes from Pseudomonas sp. B 13, whereas the Km value for catechol kept constant at different O2 concentrations. 3. Electron-attracting substituents decreased the Km values for catechols. 4. Results from binding studies with substituted catechols demonstrated narrow stereospecificities of pyrocatechase I from pseudomonas sp. B 13 and the pyrocatechase from alcaligenes eutrophus B.9. In contrast, a low steric hindrance by substituents in the binding of catechols with pyrocatechase II was observed. 5. Low pK'1 values of substituted catechols resulted in low Michaelis constants. 6. Electron-attracting substituents such as halogen decreased the reaction rates of catechol 1,2-dioxygenation. The correlation of the Vmax. values observed with pyrocatechase II from Pseudomonas sp. B 13 with the substituent constant sigma+ (Okamoto--Brown equation) was distinctly greater than with Hammett's sigma values. The corresponding logVmax. against sigma+ correlation for pyrocatechase I was considerably disturbed by steric influences of the substituents.

| S-EPMC1185888 | biostudies-other

Transformation of Jatropha Oil into High-Quality Biofuel over Ni-W Bimetallic Catalysts.

Project description:The production of fuel from the hydrodeoxygenation of vegetable oils has been extensively investigated on account of the decline of petroleum-based fuels and increase of ecological problems. The conversion of jatropha oil over Al-MCM-41-supported Ni, W, and Ni-W catalysts was studied at 3 MPa and 360 °C. Over the monometallic Ni and W catalysts, the biofuel yield was low, about 19.3 and 12.5 wt %, respectively, whereas the highest biofuel yield reached 63.5 wt % over the Ni-W bimetallic catalysts. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and high-resolution TEM results suggested that the proper amount of Ni and W would form a Ni17W3 active phase, the particle size of which varied with the content of Ni and W or preparation methods. The crystalline Ni17W3 phase formed when the content of both Ni and W reached 10%. With further increase of the content of W or Ni to 15%, the crystal size of Ni17W3 grew from 7 to 14 nm or to 20 nm, whereas the biofuel yield decreased with the increase of the Ni17W3 crystal size. The 10Ni-10W/Al-MCM-41 catalyst with the Ni17W3 crystal size of 7 nm showed the best performance for the transformation of jatropha oil into high-grade biofuel.

| S-EPMC6648155 | biostudies-literature

Mixed-ligand complexes of paddlewheel dinuclear molybdenum as hydrodehalogenation catalysts for polyhaloalkanes.

Project description:We developed a hydrodehalogenation reaction of polyhaloalkanes catalyzed by paddlewheel dimolybdenum complexes in combination with 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) as a non-toxic H-atom source as well as a salt-free reductant. A mixed-ligated dimolybdenum complex Mo2(OAc)2[CH(NAr)2]2 (3a, Ar = 4-MeOC6H4) having two acetates and two amidinates exhibited high catalytic activity in the presence of n Bu4NCl, in which [ n Bu4N]2[Mo2{CH(NAr)2}2Cl4] (9a), derived by treating 3a with ClSiMe3 and n Bu4NCl, was generated as a catalytically-active species in the hydrodehalogenation. All reaction processes, oxidation and reduction of the dimolybdenum complex, were clarified by control experiments, and the oxidized product, [ n Bu4N][Mo2{CH(NAr)2}2Cl4] (10a), was characterized by EPR and X-ray diffraction studies. Kinetic analysis of the hydrodehalogenation reaction as well as a deuterium-labelling experiment using MBTCD-d8 suggested that the H-abstraction was the rate-determining step for the catalytic reaction.

| S-EPMC5659211 | biostudies-literature

Chemical structure and biodegradability of halogenated aromatic compounds. Conversion of chlorinated muconic acids into maleoylacetic acid.

Project description:1. An enzyme for the cycloisomerization of 2- and 3-chloro-cis,cis-muconic acid was isolated from 3-chlorobenzoate-grown cells of Pseudomonas sp. B13. It was named muconate cycloisomerase II, because it could it clearly be differentiated by its Km and Vmax. values from an ordinary muconate cycloisomerase, which functioned in benzoate catabolism and exhibited low activity with the chlorinated substrates. 2-Chloro-cis,cis-muconic acid was converted into trans- and 3-chloro-cis,cis--muconic acid into cis-4-carboxymethylenebut-2-en-4-olide together with dehalogenation. 2. An enzyme was isolated from chlorobenzoate-grown cells, which converted the 4-carboxymethylenebut-2-en-4-olides into maleoylacetic acid.

| S-EPMC1162339 | biostudies-other

Experimental Study on Dry Reforming of Biogas for Syngas Production over Ni-Based Catalysts.

Project description:Syngas production from dry reforming of biogas (DRB) is studied experimentally in this work. Ni/Al2O3, Pt/Al2O3, and Pt-Ni/Al2O3 are used as catalysts to examine the effect of CO2 content in biogas and H2O addition on DRB performance for reaction temperatures in the 600–800 °C range. It is found that the bimetallic Pt–Ni catalyst exhibits the best activity and thermal stability among the three types of catalysts studied due to better carbon deposition resistance. Because CO2 functions as the oxidant in combustion, CH4 conversion is enhanced when the biogas contains more CO2. One hundred percent CO2 conversion can be reached for biogas containing a less amount of CO2 at high temperatures. With H2O addition in DRB, the steam reforming of methane (SRM) reaction is the dominant reaction, resulting in higher H2 and CO yields with biogas containing lesser amounts of CO2. However, lower CH4 conversion and negative CO2 conversion do result. With higher CO2 content in the biogas, higher CH4 and CO2 conversions can be obtained. Lower yields of H2 and CO are obtained due to less SRM dominance. With H2O addition in biogas, the H2/CO ratio with a value greater than 1 can be obtained from DRB. It is also found that the H2/CO ratio with a value of 2.1 can be obtained for reactant composition with a molar ratio of CH4/CO2/H2O = 1:0.25:1 and reaction temperature of 800 °C.

| S-EPMC6921260 | biostudies-literature

Three-Dimensional Network Pd-Ni/γ-Al<sub>2</sub>O<sub>3</sub> Catalysts for Highly Active Catalytic Hydrogenation of Nitrobenzene to Aniline under Mild Conditions.

Project description:In view of the current situation of high cost and low catalytic efficiency of the commercial Pd-based catalysts, adding transition metals (Ni, Co, etc.) to form the Pd-M bimetallic catalyst not only reduces the consumption of Pd but also greatly improves the catalytic activity and stability, which has attracted increasing attention. In this work, the three-dimensional network Pd-Ni bimetallic catalysts were prepared successfully by a liquid-phase in situ reduction method with the hydroxylated γ-Al2O3 as the support. Through investigating the effects of the precursor salt amount, reducing agent concentration, stabilizer concentration, and reducing stirring time on the synthesis of the Pd-Ni nanocatalyst, the three-dimensional network Pd-Ni bimetallic nanostructures with four different atomic ratios were prepared under an optimal condition. The obtained wire-like Pd-Ni catalysts have a uniform diameter size of about 5 nm and length up to several microns. After closely combining with the hydroxylated γ-Al2O3, the supported Pd-Ni/γ-Al2O3 catalysts exhibit nearly 100% conversion rate and selectivity for the hydrogenation of nitrobenzene to aniline at low temperature and normal pressure. The stability testing of the supported Pd-Ni/γ-Al2O3 catalysts shows that the conversion rate still remained above 99% after 10 cycles. There is no doubt that the supported catalysts show significant catalytic efficiency and recyclability, which provides important theoretical basis and technical support for the preparation of low-cost, highly efficient catalysts for the hydrogenation of nitrobenzene to aniline.

| S-EPMC8047756 | biostudies-literature

Monometallic Cerium Layered Double Hydroxide Supported Pd-Ni Nanoparticles as High Performance Catalysts for Lignin Hydrogenolysis.

Project description:Monometallic cerium layered double hydroxides (Ce-LDH) supports were successfully synthesized by a homogeneous alkalization route driven by hexamethylenetetramine (HMT). The formation of the Ce-LDH was confirmed and its structural and compositional properties studied by XRD, SEM, XPS, iodometric analyses and TGA. HT-XRD, N2-sorption and XRF analyses revealed that by increasing the calcination temperature from 200 to 800 °C, the Ce-LDH material transforms to ceria (CeO2) in four distinct phases, i.e., the loss of intramolecular water, dehydroxylation, removal of nitrate groups and removal of sulfate groups. When loaded with 2.5 wt% palladium (Pd) and 2.5 wt% nickel (Ni) and calcined at 500 °C, the PdNi-Ce-LDH-derived catalysts strongly outperform the PdNi-CeO2 benchmark catalyst in terms of conversion as well as selectivity for the hydrogenolysis of benzyl phenyl ether (BPE), a model compound for the ?-O-4 ether linkage in lignin. The PdNi-Ce-LDH catalysts showed full selectivity towards phenol and toluene while the PdNi-CeO2 catalysts showed additional oxidation of toluene to benzoic acid. The highest BPE conversion was observed with the PdNi-Ce-LDH catalyst calcined at 600 °C, which could be related to an optimum in morphological and compositional characteristics of the support.

| S-EPMC7040693 | biostudies-literature

3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid.

Project description:Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects.

| S-EPMC3943891 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data