scholarly journals Room-Temperature Metathesis of Ethylene with 2-Butene to Propene Over MoOx-Based Catalysts: Mixed Oxides as Perspective Support Materials

2021 ◽  
Author(s):  
Tatiana Otroshchenko ◽  
Qiyang Zhang ◽  
Evgenii V. Kondratenko
Keyword(s):  
Room Temperature ◽  
Mixed Oxides ◽  
Catalyst Activity ◽  
Lattice Defects ◽  
Intrinsic Activity ◽  
Metathesis Reaction ◽  
Acidic Properties ◽  
Reaction Conditions ◽  
Support Materials ◽  
Highly Dispersed

AbstractWe investigated the effect of supports based on ZrO2, TiO2, Al2O3, and SiO2 on the rate of propene formation in the metathesis of ethylene with 2-butene at 50 °C over Mo-containing catalysts possessing highly dispersed MoOx. Large improvements in this rate were achieved when using supports composed of mixed oxides (ZrO2–SiO2, ZrO2–PO4, TiO2–SiO2; Al2O3–SiO2) rather than of individual oxides (ZrO2, TiO2, Al2O3, SiO2). Although previous literature studies dealing with the metathesis reaction over Al2O3- or SiO2-suppported catalysts at higher temperatures suggest the importance of redox or acidic properties of supported MoOx species for catalyst activity, we were not able to establish any general direct correlation in this regard. Contrarily, the rate of propene formation can be significantly enhanced when promoting supports with an oxide promoter. We suggest that the created support lattice defects may facilitate the transformation of MoOx to Mo carbenes under reaction conditions or improve the intrinsic activity of the latter. Graphic Abstract

scholarly journals Chemo-Bio Catalysis Using Carbon Supports: Application in H2-Driven Cofactor Recycling

2020 ◽  
Author(s):  
Xu Zhao ◽  
Sarah Cleary ◽  
Ceren Zor ◽  
Nicole Grobert ◽  
Holly Reeve ◽  
...  
Keyword(s):  
Catalyst Activity ◽  
Carbon Support ◽  
Carbon Supports ◽  
Reaction Conditions ◽  
Support Materials ◽  
Cofactor Recycling ◽  
Metal Metal ◽  
Hydrogenation Reactions ◽  
Available Carbon ◽  
H2 Oxidation

<div>Commercially available carbon-supported metal (metal/C) catalysts are investigated here for direct H2-driven NAD+ reduction. Selected metal/C catalysts are then</div><div>used for H2 oxidation with electrons transferred via the conductive carbon support material to an adsorbed enzyme for NAD+ reduction. These chemo-bio catalysts show improved activity and selectivity for generating bioactive NADH under ambient reaction conditions compared</div><div>to metal/C catalysts. The metal/C catalysts and carbon support materials (all activated carbon or carbon black) are characterised to probe which properties potentially influence catalyst activity. The optimised chemo-bio catalysts are then used to supply NADH to an alcohol dehydrogenase for enantioselective (>99% ee) ketone reductions, leading to high cofactor turnover numbers and Pd and NAD+ reductase activities of 441 h-1 and 2,347 h-1,</div><div>respectively. This method demonstrates a new way of combining chemo- and biocatalysis on carbon supports, highlighted here for selective hydrogenation reactions.</div>

scholarly journals Chemo-Bio Catalysis Using Carbon Supports: Application in H2-Driven Cofactor Recycling

2020 ◽  
Author(s):  
Xu Zhao ◽  
Sarah Cleary ◽  
Ceren Zor ◽  
Nicole Grobert ◽  
Holly Reeve ◽  
...  
Keyword(s):  
Catalyst Activity ◽  
Carbon Support ◽  
Carbon Supports ◽  
Reaction Conditions ◽  
Support Materials ◽  
Cofactor Recycling ◽  
Metal Metal ◽  
Hydrogenation Reactions ◽  
Available Carbon ◽  
H2 Oxidation

<div>Commercially available carbon-supported metal (metal/C) catalysts are investigated here for direct H2-driven NAD+ reduction. Selected metal/C catalysts are then</div><div>used for H2 oxidation with electrons transferred via the conductive carbon support material to an adsorbed enzyme for NAD+ reduction. These chemo-bio catalysts show improved activity and selectivity for generating bioactive NADH under ambient reaction conditions compared</div><div>to metal/C catalysts. The metal/C catalysts and carbon support materials (all activated carbon or carbon black) are characterised to probe which properties potentially influence catalyst activity. The optimised chemo-bio catalysts are then used to supply NADH to an alcohol dehydrogenase for enantioselective (>99% ee) ketone reductions, leading to high cofactor turnover numbers and Pd and NAD+ reductase activities of 441 h-1 and 2,347 h-1,</div><div>respectively. This method demonstrates a new way of combining chemo- and biocatalysis on carbon supports, highlighted here for selective hydrogenation reactions.</div>

scholarly journals Combined Reforming of Clean Biogas over Nanosized Ni–Rh Bimetallic Clusters

Catalysts ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 1345
Author(s):  
Nicola Schiaroli ◽  
Carlo Lucarelli ◽  
Maria Carmela Iapalucci ◽  
Giuseppe Fornasari ◽  
Antonio Crimaldi ◽  
...  
Keyword(s):  
Active Sites ◽  
Carbon Deposition ◽  
Bimetallic Nanoparticles ◽  
Catalyst Activity ◽  
Dry Reforming ◽  
Bimetallic Clusters ◽  
Low Carbon ◽  
Reaction Conditions ◽  
Active Particles ◽  
Highly Dispersed

The combined steam/dry reforming of clean biogas (CH4/CO2 = 50/50 v/v) represents an innovative way to produce synthesis gas (CO + H2) using renewable feeds, avoiding to deplete the fossil resources and increase CO2 pollution. The reaction was carried out to optimize the reaction conditions for the production of a syngas with a H2/CO ratio suitable for the production of methanol or fuels without any further upgrading. Ni-Rh/Mg/Al/O catalysts obtained from hydrotalcite-type precursors showed high performances in terms of clean biogas conversion due to the formation of very active and resistant Ni-Rh bimetallic nanoparticles. Through the utilization of a {Ni10Rh(CO)19}{(CH3CH2)4N}3 cluster as a precursor of the active particles, it was possible to promote the Ni-Rh interaction and thus obtain low metal loading catalysts composed by highly dispersed bimetallic nanoparticles supported on the MgO, MgAl2O4 matrix. The optimization of the catalytic formulation improved the size and the distribution of the active sites, leading to a better catalyst activity and stability, with low carbon deposition with time-on-stream.

Naturally Occurring Organic Acid-catalyzed Facile Diastereoselective Synthesis of Biologically Active (E)-3-(arylimino)indolin-2-one Derivatives in Water at Room Temperature

2019 ◽  
Vol 23 (16) ◽  
pp. 1778-1788 ◽  
Author(s):  
Gurpreet Kaur ◽  
Arvind Singh ◽  
Kiran Bala ◽  
Mamta Devi ◽  
Anjana Kumari ◽  
...  
Keyword(s):  
Room Temperature ◽  
Biologically Active ◽  
Environmentally Benign ◽  
Diastereoselective Synthesis ◽  
Substituted Anilines ◽  
Reaction Conditions ◽  
Naturally Occurring ◽  
Acid Catalyzed ◽  
Reaction Media ◽  
Column Chromatographic

A simple, straightforward and efficient method has been developed for the synthesis of (E)-3-(arylimino)indolin-2-one derivatives and (E)-2-((4-methoxyphenyl)imino)- acenaphthylen-1(2H)-one. The synthesis of these biologically-significant scaffolds was achieved from the reactions of various substituted anilines and isatins or acenaphthaquinone, respectively, using commercially available, environmentally benign and naturally occurring organic acids such as mandelic acid or itaconic acid as catalyst in aqueous medium at room temperature. Mild reaction conditions, energy efficiency, good to excellent yields, environmentally benign conditions, easy isolation of products, no need of column chromatographic separation and the reusability of reaction media are some of the significant features of the present protocol.

A Facile, Efficient and Selective Deprotection of P - Methoxy Benzyl Ethers Using Zinc (II) Trifluoromethanesulfonate

2019 ◽  
Vol 16 (12) ◽  
pp. 955-958
Author(s):  
Reddymasu Sireesha ◽  
Reddymasu Sreenivasulu ◽  
Choragudi Chandrasekhar ◽  
Mannam Subba Rao
Keyword(s):  
Room Temperature ◽  
Protecting Groups ◽  
Side Reactions ◽  
Reaction Conditions ◽  
Acid Sensitivity ◽  
Time Period ◽  
Protective Groups ◽  
Benzyl Ethers ◽  
Last Stage ◽  
Zinc Triflate

: Deprotection is significant and conducted over mild reaction conditions, in order to restrict any more side reactions with sensitive functional groups as well as racemization or epimerization of stereo center because the protective groups are often cleaved at last stage in the synthesis. P - Methoxy benzyl (PMB) ether appears unique due to its easy introduction and removal than the other benzyl ether protecting groups. A facile, efficient and highly selective cleavage of P - methoxy benzyl ethers was reported by using 20 mole% Zinc (II) Trifluoromethanesulfonate at room temperature in acetonitrile solvent over 15-120 min. time period. To study the generality of this methodology, several PMB ethers were prepared from a variety of substrates having different protecting groups and subjected to deprotection of PMB ethers using Zn(OTf)2 in acetonitrile. In this methodology, zinc triflate cleaves only PMB ethers without affecting acid sensitivity, base sensitivity and also chiral epoxide groups.

One-pot Synthesis of Pyrazolone Sulfones by Iodine-catalyzed Sulfenylation of Pyrazolones with Aryl Sulfonyl Hydrazides Followed by Oxidation in Water

2018 ◽  
Vol 15 (3) ◽  
pp. 380-387
Author(s):  
Xia Zhao ◽  
Xiaoyu Lu ◽  
Lipeng Zhang ◽  
Tianjiao Li ◽  
Kui Lu
Keyword(s):  
Double Bond ◽  
Efficient Method ◽  
Room Temperature ◽  
Sulfonyl Chloride ◽  
Antibacterial Activities ◽  
Oxidation Reactions ◽  
Reaction Conditions ◽  
One Pot ◽  
X Ray ◽  
Amide Form

Aim and Objective: Pyrazolone sulfones have been reported to exhibit herbicidal and antibacterial activities. In spite of their good bioactivities, only a few methods have been developed to prepare pyrazolone sulfones. However, the substrate scope of these methods is limited. Moreover, the direct sulfonylation of pyrazolone by aryl sulfonyl chloride failed to give pyrazolone sulfones. Thus, developing a more efficient method to synthesize pyrazolone sulfones is very important. Materials and Method: Pyrazolone, aryl sulphonyl hydrazide, iodine, p-toluenesulphonic acid and water were mixed in a sealed tube, which was heated to 100°C for 12 hours. The mixture was cooled to 0°C and m-CPBA was added in batches. The mixture was allowed to stir for 30 min at room temperature. The crude product was purified by silica gel column chromatography to afford sulfuryl pyrazolone. Results: In all cases, the sulfenylation products were formed smoothly under the optimized reaction conditions, and were then oxidized to the corresponding sulfones in good yields by 3-chloroperoxybenzoic acid (m-CPBA) in water. Single crystal X-ray analysis of pyrazolone sulfone 4aa showed that the major tautomer of pyrazolone sulfones was the amide form instead of the enol form observed for pyrazolone thioethers. Moreover, the C=N double bond isomerized to form an α,β-unsaturated C=C double bond. Conclusion: An efficient method to synthesize pyrazolone thioethers by iodine-catalyzed sulfenylation of pyrazolones with aryl sulfonyl hydrazides in water was developed. Moreover, this method was employed to synthesize pyrazolone sulfones in one-pot by subsequent sulfenylation and oxidation reactions.

Rh(III)-Catalyzed Olefination and Alkylation of Arenes with Maleimides: A Tunable Strategy for C(sp2)–H Functionalization

Synthesis ◽  
2021 ◽  
Author(s):  
Hongji Li ◽  
Wenjie Zhang ◽  
Xueyan Liu ◽  
Zhenfeng Tian
Keyword(s):  
Room Temperature ◽  
Functional Group ◽  
Reaction Conditions ◽  
Bond Functionalization ◽  
Alkylation Process ◽  
Coupling Partner

AbstractWe herein report a new nitrogen-directed Rh(III)-catalyzed C(sp2)–H bond functionalization of N-nitrosoanilines and azoxybenzenes with maleimides as a coupling partner, in which the olefination/alkylation process can be finely controlled at room temperature by variation of the reaction conditions. This method shows excellent functional group tolerance, and presents a mild access to the resulting olefination/alkylation products in moderate to good yields.

Synthesis of Pyrrolo[1,2-a][1,6]- and [1,8]naphthyridines by Alkyne-Carbonyl Metathesis

Synthesis ◽  
2020 ◽  
Author(s):  
Peter Ehlers ◽  
Peter Langer ◽  
Marian Blanco Ponce ◽  
Silvio Parpart ◽  
Alexander Villinger ◽  
...  
Keyword(s):  
Heterocyclic Compounds ◽  
Metathesis Reaction ◽  
Synthetic Methodology ◽  
Facile Synthesis ◽  
Reaction Conditions ◽  
One Pot ◽  
Metal Free ◽  
Modular Synthesis

AbstractA concise and modular synthesis of pyrrolo[1,2-a][1,6]- and [1,8]naphthyridines by a one-pot two-step reaction consisting of electrophilic acylation followed by an alkyne-carbonyl-metathesis reaction as the final cyclization step is reported. This developed synthetic methodology allows the facile synthesis of these heterocyclic core structures in mainly high overall yields under metal-free conditions. Reaction conditions are carefully optimized and display a novel supplement to access these tricyclic heterocyclic compounds.

scholarly journals Bio-DEE Synthesis and Dehydrogenation Coupling of Bio-Ethanol to Bio-Butanol over Multicomponent Mixed Metal Oxide Catalysts

Catalysts ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 660
Author(s):  
Izabela S. Pieta ◽  
Alicja Michalik ◽  
Elka Kraleva ◽  
Dusan Mrdenovic ◽  
Alicja Sek ◽  
...  
Keyword(s):  
Active Sites ◽  
Internal Combustion Engines ◽  
Mixed Oxides ◽  
Catalyst Activity ◽  
Product Distribution ◽  
Coke Deposition ◽  
Precipitation Method ◽  
Mixed Metal Oxide ◽  
Low Carbon ◽  
Municipal Solid Wastes

Within the Waste2Fuel project, innovative, high-performance, and cost-effective fuel production methods from municipal solid wastes (MSWs) are sought for application as energy carriers or direct drop-in fuels/chemicals in the near-future low-carbon power generation systems and internal combustion engines. Among the studied energy vectors, C1-C2 alcohols and ethers are mainly addressed. This study presents a potential bio-derived ethanol oxidative coupling in the gas phase in multicomponent systems derived from hydrotalcite-containing precursors. The reaction of alcohol coupling to ethers has great importance due to their uses in different fields. The samples have been synthesized by the co-precipitation method via layered double hydroxide (LDH) material synthesis, with a controlled pH, where the M(II)/M(III) ≈ 0.35. The chemical composition and topology of the sample surface play essential roles in catalyst activity and product distribution. The multiple redox couples Ni2+/Ni3+, Cr2+/Cr3+, Mn2+/Mn3+, and the oxygen-vacant sites were considered as the main active sites. The introduction of Cr (Cr3+/Cr4+) and Mn (Mn3+/Mn4+) into the crystal lattice could enhance the number of oxygen vacancies and affect the acid/base properties of derived mixed oxides, which are considered as crucial parameters for process selectivity towards bio-DEE and bio-butanol, preventing long CH chain formation and coke deposition at the same time.

Process intensification for enzyme assisted turmeric starch hydrolysis in hydrotropic and supercritical conditions

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Yogita P. Labrath ◽  
Prafulla V. Belge ◽  
Uma G. Kulkarni ◽  
Vilas G. Gaikar
Keyword(s):  
Residence Time ◽  
Filtration Rate ◽  
Room Temperature ◽  
Curcuma Longa ◽  
Process Intensification ◽  
Enzyme Treatment ◽  
Starch Hydrolysis ◽  
Reaction Conditions ◽  
Natural Form ◽  
Hydrolysis Of

Abstract The turmeric rhizome (Curcuma longa) contains curcuminoids embedded in the starch matrix. It is thus important to target starch hydrolysis to enhance extraction of curcuminoids. In the case of starch hydrolysis, α-amylase is more efficient when the starch is in a gelatinised form than when it is in its natural form. The present work includes hydrolysis of turmeric starch in its natural and gelatinised forms using α-amylase in hydrotrope solution (HS) and scCO2. The optimum rate of starch hydrolysis was obtained using 200 IU cm−3 of α-amylase, at reaction conditions of 6.5 pH at 328 K when 10% w/w of turmeric powder was stirred at 900 rpm in HSs. The hydrolysis in 15 MPa scCO2 at room temperature required a phase modifier and 40 min of residence time (RT). The enzyme treatment of turmeric powder in HSs increased the filtration rate for curcuminoid extraction (gelatinised and native) compared to untreated turmeric powder.

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