02110nas a2200205 4500008004100000022001400041245013600055210006900191260011000260300001400370490000600384520122800390100002201618700002801640700001901668700002601687700002601713700003301739856013201772 2015 eng d a2044-475300aRenewable fuels from biomass-derived compounds: Ru-containing hydrotalcites as catalysts for conversion of HMF to 2,5-dimethylfuran0 aRenewable fuels from biomassderived compounds Rucontaining hydro aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a1463-14720 v53 a

Production of transportation fuels from renewable biomass is hugely important considering the current ecological concerns over CO2 built up in the atmosphere. Ruthenium-containing hydrotalcite (HT) catalysts were applied for the selective hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). Structural and morphological features of the catalysts were examined using various physico-chemical characterization techniques. The influence of various reaction parameters, such as reaction temperature, solvent, Ru content of the catalyst, etc., was investigated with respect to HMF conversion and DMF yield. The study clearly shows that well-dispersed Ru nanoparticles are highly active and selective in the conversion of HMF to DMF. A catalyst containing only 0.56 wt% Ru converted 100 mol% HMF to yield 58 mol% DMF. This catalyst was found to be recyclable as the activity was retained even after five cycles of reaction. 2-Propanol was found to be a good solvent as it helped to improve DMF yield through transfer hydrogenation. Based on the results of the investigations, a reaction pathway for the conversion of HMF to DMF was proposed for the present Ru-based catalyst system.

1 aNagpure, Atul, S.1 aVenugopal, Ashok, Kumar1 aLucas, Nishita1 aManikandan, Marimuthu1 aThirumalaiswamy, Raja1 aChilukuri, Satyanarayana, V. uhttps://library.ncl.res.in/content/renewable-fuels-biomass-derived-compounds-ru-containing-hydrotalcites-catalysts-conversion-002331nas a2200229 4500008004100000022001400041245013900055210006900194260007300263300001200336490000800348520140400356653003601760653003101796653001801827100002601845700002801871700002101899700002401920700002601944856013101970 2016 eng d a1381-116900aRole of surface synergistic effect on the performance of Ni-based hydrotalcite catalyst for highly efficient hydrogenation of furfural0 aRole of surface synergistic effect on the performance of Nibased aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUN a153-1620 v4173 a

The selective vapor phase hydrogenation of furfural at ambient pressure has been investigated using a facile and robust hydrotalcite derived Ni containing mixed oxide catalyst. The systematic characterization results conferred that the difficulty in the reduction of Ni species due to the strong interaction between Ni and support, which facilitated from the homogeneous distribution of hydrotalcite structure. It was also found that the structure and catalytic performance of the catalysts were greatly influenced by Ni loading. Through fine-tuned surface elemental sites and reaction conditions, furfural conversion of 98% with 95% of furfuryl alcohol selectivity was achieved over a MAN-2 catalyst containing two molar ratio of Ni. The results have demonstrated that the incorporation of Mg significantly enhances the Ni-support interaction, Ni dispersion and catalytic performance. The high efficiency of the Ni-based hydrotalcite derived catalyst was mainly attributed to the surface synergistic interaction between the catalytically active metallic Ni sites and the strong basic sites, which furnished an eco-benign and sustainable catalyst for the selective hydrogenation of furfural. Furthermore, the spent catalyst analysis substantiated that no significant difference in the catalyst phase was observed even after 48 h of reaction stream. (C) 2016 Elsevier B.V. All rights reserved.

10aalcohol-hydrotalcites-selective10aBiomass-frurfural-furfuryl10aHydrogenation1 aManikandan, Marimuthu1 aVenugopal, Ashok, Kumar1 aPrabu, Kandasamy1 aJha, Ratnesh, Kumar1 aThirumalaiswamy, Raja uhttps://library.ncl.res.in/content/role-surface-synergistic-effect-performance-ni-based-hydrotalcite-catalyst-highly-efficient02316nas a2200229 4500008004100000022001400041245006900055210006700124260000800191300001400199490000600213520159900219653001301818653001901831653003201850653001701882653001601899100001901915700002901934700002601963856009701989 2021 eng d a2365-654900aActive K-OMS-2 supported catalyst for hydrogenolysis of glycerol0 aActive KOMS2 supported catalyst for hydrogenolysis of glycerol cSEP a8700-87080 v63 aPropanediols are very important chemical intermediates, which need to be prepared through commercially viable routes. Cryptomelane type octahedral molecular sieve-2 (K-OMS-2), a cheap and environmentally benign microporous oxide was employed to support Ru and used as a catalyst to get 1,2-propanediol (1,2-PDO) selectively through hydrogenolysis of glycerol. Three catalysts with different Ru content were prepared and evaluated for glycerol hydrogenolysis. Among these, 1 wt.% Ru-K-OMS-2 showed reasonably good activity towards 1,2-PDO formation under moderate reaction conditions even at lower Ru loading (0.9 wt.%). When other metals such as Cu and Ni were supported on K-OMS-2, their performance was inferior compared to Ru-supported catalysts. All the catalysts were characterized using various physicochemical techniques like XRD, N-2-sorption, TPD, H-2-TPR, TGA, ICP-OES, FE-SEM and TEM. The enhanced catalytic activity with the 1 wt.%Ru-K-OMS-2 catalyst was attributed to the better Ru metal dispersion, higher active metal surface area, basic strength, and porosity of the support. The catalyst was found to be recyclable. Analysis of spent catalyst by TEM showed disintegration of Ru nanoparticles to smaller ones, under high H-2 pressure at the reaction temperature. Smaller Ru particles are expected to promote C-C bond cleavage thus suppressing 1,2-PDO formation. Furthermore, a relationship between the TOF value, Ru nanoparticles size, and the basic strength of the catalysts was established, which provides dipper insight into the different catalytic behavior of the catalysts.10aGlycerol10aHydrogenolysis10aoctahedral molecular sieves10aPropanediols10aselectivity1 aGogoi, Pranjal1 aChilukuri, Satyanarayana1 aThirumalaiswamy, Raja uhttps://library.ncl.res.in/content/active-k-oms-2-supported-catalyst-hydrogenolysis-glycerol01988nas a2200241 4500008004100000022001400041245009600055210006900151260000800220300001100228490000800239520117000247653000901417653001401426653001401440653002301454653003401477100003701511700002101548700003101569700002601600856012001626 2021 eng d a1566-736700aPromoted mesoporous Fe-alumina catalysts for the non-oxidative dehydrogenation of isobutane0 aPromoted mesoporous Fealumina catalysts for the nonoxidative deh cFEB a1062630 v1503 a

Production of isobutene is commercially consequential and highly demanding from the end-use industries being a key platform molecule as well as an intermediate for a variety of value-added chemicals. Traditionally, isobutene is prepared via steam cracking and fluid catalytic cracking methods. However, the catalysts used in these conventional methods have disadvantages like coke formation, sintering, etc. In this study, the catalytic non-oxidative dehydrogenation of isobutane over acidic, alkaline, and noble metal promoted mesoporous iron-doped catalysts was investigated. Iron doping has a significant function in controlling isobutene selectivity. The synthesis method is crucial to achieve successful metal doping in the mesoporous alumina matrix. Promoted catalysts exhibited a notable difference in isobutane conversion with a marginal change in dehydrogenation selectivity. Silver promoted catalyst showed slightly higher isobutene yield due to the optimal catalytic properties. This catalyst was stable for a considerable duration, and coke deposition, as well as particle agglomeration, were observed to faintly inhibit the catalytic activity.

10airon10aIsobutane10aIsobutene10aMesoporous alumina10aNon-oxidative dehydrogenation1 aVenugopalan, Aswathy, Thareparam1 aKandasamy, Prabu1 aGupta, Nikitra, Nihalchand1 aThirumalaiswamy, Raja uhttps://library.ncl.res.in/content/promoted-mesoporous-fe-alumina-catalysts-non-oxidative-dehydrogenation-isobutane01853nas a2200277 4500008004100000022001400041245012800055210006900183260000800252300001400260490000800274520094000282653000601222653001301228653001601241653001101257653000901268653001901277653003001296100002901326700002101355700001901376700002201395700002601417856013201443 2021 eng d a1011-372X00aUtilizing the oxygen carrier property of cerium iron oxide for the low-temperature synthesis of 1,3-butadiene from 1-butene0 aUtilizing the oxygen carrier property of cerium iron oxide for t cOCT a3057-30660 v1513 a

Low-temperature oxidative dehydrogenation (ODH) of 1-butene to 1,3-butadiene is one of the challenging reactions in the polymer industry. Towards this a highly dispersed cerium iron oxide was synthesized by citrate gel combustion method and employed for the synthesis of 1,3-butadiene (BD) from 1-butene. The reaction was carried out at low temperature under an oxygen-free atmosphere in a continuous flow mode fixed bed reactor. A decrease in the lattice parameters observed from PXRD and high-resolution TEM analysis proved that iron occupies cerium sites in the crystal lattice. XPS, TPR, and oxygen uptake studies quantified the nature and abundance of different oxygen species. ODH was observed through consuming lattice oxygens. The vacancies generated could be filled by re-oxidation with an external supply of oxygen which will restore the catalytic activity demonstrating the Mars van Krevelen mechanism. [GRAPHICS] .

10a110a1-butene10a3-butadiene10aCerium10airon10aLattice oxygen10aoxidative dehydrogenation1 aVenugopalan, Aswathy, T.1 aKandasamy, Prabu1 aGogoi, Pranjal1 aRatneshkumar, Jha1 aThirumalaiswamy, Raja uhttps://library.ncl.res.in/content/utilizing-oxygen-carrier-property-cerium-iron-oxide-low-temperature-synthesis-13-butadiene-101473nas a2200229 4500008004100000022001400041245009200055210006900147260000800216300001100224490000800235520069800243100001900941700002000960700002500980700001901005700002201024700002601046700002101072700002601093856012401119 2022 eng d a1566-736700aMicrowave-assisted selective N-alkylation of aniline over molybdenum supported catalyst0 aMicrowaveassisted selective Nalkylation of aniline over molybden cAUG a1064640 v1683 a

Selective N-alkylation of aniline is a tough and challenging reaction due to over alkylation, therefore, catalyst with specific characteristics is needed to accomplish such transformations. In this work, a series of catalysts with molybdenum supported on alumina are prepared and subjected to various reaction conditions, out of which 30 PMA (Phosphomolybdic acid) showed the best result due to its proper combination of acidic sites. This reaction is sustainable and environmentally friendly as it is carried out with methanol as an alkylating source in the presence of microwave radiation at low temperature. The reaction data was compared with various other reactor systems too.

1 aBhatkar, Akash1 aMane, Samruddhi1 aMekala, Siva, Prasad1 aGogoi, Pranjal1 aMohapatra, Gourab1 aRamakrishnan, Archana1 aMarimuthu, Prabu1 aThirumalaiswamy, Raja uhttps://library.ncl.res.in/content/microwave-assisted-selective-n-alkylation-aniline-over-molybdenum-supported-catalyst03096nas a2200301 4500008004100000245011200041210006900153260000800222300000800230490000700238520212000245653001102365653001402376653001802390653001402408653001502422653001402437653001702451653002602468100002302494700002102517700002402538700002602562700002902588700002102617700002602638856013002664 2022 eng d00aSynthesis and crystal structures of Mn(II) and Co(II) complexes as catalysts for oxidation of cyclohexanone0 aSynthesis and crystal structures of MnII and CoII complexes as c cJUL a1000 v103 a

The global demand on adipic usage in the production of plasticizers and synthetic polyamide is increasing. In line with the search for an efficient and energy-conserving way to isolate adipic acid (AA) in good yields, this paper introduces the oxidization of cyclohexanone utilizing two new coordination compounds, [Mn(2,6-pydc)(2)](imi) (1) and [Co(H(2)pza)(2)(H2O)(2)(NO3)].NO3 (2), as catalysts. Compounds 1 and 2 were synthesized by room temperature and refluxing methods, and characterized by spectral analyses (IR and UV-Vis.), SEM, BET, TGA, elemental, and X-ray crystallography. The single crystal structure of compound 1 revealed that pyridinedicarboxylate (2,6-pydc) and imidazole (imi) moieties were coordinated to the Mn(II) atom through imine nitrogen and deprotonated oxygen atoms, to form an undistorted octahedral coordination geometry with the N2O4 donor set. The axial and equatorial planes containing O2, O4, O5, and O7 atoms were from two adjacent 2,6-pydc ligands which formed the unidendate donor ligand; imi, on the other hand, acted as a bidendate donor ligand. For compound 2, the Co(II) atom was being coordinated by two pyrazinamide (H(2)pza) moieties, which acted as an unidendate donor ligand; two water molecules occupying the axial position, and one nitrate molecule occupying the apical position, were within the coordination sphere; a nitrate molecule was disordered outside the coordination sphere. The distance, 4.658 angstrom, between the Co1 atom and the N8 atom of the uncoordinated nitrate molecule, was within the range reported elsewhere. Cyclohexanone peroxidation experiments revealed that compound 1 exhibited unique catalytic performance by giving a 72.8% yield in adipic acid, in comparison to the 71.3% yield obtained with compound 2. The yields in AA were maintained by way of recyclability evaluation. The reaction kinetics of compound 2 gave less activation energy, E-a 2938 J mol(-1), while the thermodynamic parameters indicated that the chemical reactivity of cyclohexanone on the active surfaces of compounds 1 and 2 was via monolayer physisorption.

10acobalt10aComplexes10acyclohexanone10aImidazole10amanaganese10aOxidation10apyrazinamide10apyridinedicarboxylate1 aTella, Adedibu, C.1 aIsaac, Aaron, Y.1 aClayton, Hadley, S.1 aOgunlaja, Adeniyi, S.1 aVenugopalan, Aswathy, T.1 aPrabu, Marimuthu1 aThirumalaiswamy, Raja uhttps://library.ncl.res.in/content/synthesis-and-crystal-structures-mnii-and-coii-complexes-catalysts-oxidation-cyclohexanone02711nas a2200301 4500008004100000022001400041245013500055210006900190260000900259300001100268490000800279520168000287653001801967653003001985653002802015653002402043653001602067653002002083100002802103700001902131700001902150700002102169700002302190700002602213700001602239700002502255856012902280 2026 eng d a2468-823100aEffect of sulfonation density on acid strength in ion exchange resins: Insights from solid-state NMR and density functional theory0 aEffect of sulfonation density on acid strength in ion exchange r cMAR  a1157940 v5933 a

Ion-exchange (IE) resins are widely used as solid acid catalysts; however, their surface acidity remains poorly characterized because their limited thermal stability precludes conventional NH3-based acidity measurements. Moreover, acid-site accessibility in IE resins is strongly governed by solvent- or reactant-induced swelling. Here, we investigate the surface acidity of commercial Amberlyst and Indion IE resins using & sup3;& sup1;P MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance), employing TMPO as a molecular probe dispersed on the resin with moderately swelling dichloromethane, thereby capturing the swollen-state acidity relevant for predicting catalytic activity. The deconvolution of the P-31 MAS NMR spectra reveals three distinct acid-strength zones arising from inhomogeneous sulfonation of the polymer matrix. The overall acidity, quantified by the area-weighted average P-31 chemical shift (delta), increases monotonically with sulfonation density. Notably, only resins containing acid sites stronger than similar to 80 ppm exhibited measurable catalytic activity in alpha-pinene isomerization, establishing a direct correlation between acidity and activity. Density functional theory (DFT) calculations on representative resin models, supported by electron-density analyses, attribute the enhancement of acid strength at higher sulfonation densities to cooperative hydrogen-bonding networks among neighboring sulfonic acid groups. Together, these findings establish P-31 MAS NMR-derived surface acidity as a catalytically relevant descriptor for the rational selection of IE resins in liquid phase acid-catalyzed chemistries.

10aAcid strength10aDensity functional theory10aheterogeneous catalysis10aIon-exchange resins10aSolid acids10aSolid-state NMR1 aTumulu, Goutam, Narayan1 aDatar, Sarvesh1 aShelke, Ankita1 aSwain, Gitanjali1 aAjithkumar, T., G.1 aThirumalaiswamy, Raja1 aMohan, Ojus1 aMahajani, Sanjay, M. uhttps://library.ncl.res.in/content/effect-sulfonation-density-acid-strength-ion-exchange-resins-insights-solid-state-nmr-and