@article { ISI:000284494800013, title = {Selective hydrogenolysis of glycerol to 1,2-propanediol: comparison of batch and continuous process operations}, journal = {Organic Process Research \& Development}, volume = {14}, number = {6}, year = {2010}, month = {NOV}, pages = {1393-1400}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The screening of copper chromite catalysts with various promoters such as Al, Zn, and Ba for glycerol hydrogenolysis to 1,2-propanediol (1,2-PDO) in a batch reaction showed that Cu-Cr (Ba) catalyst gave the highest conversion of 34\% and selectivity of 84\% to 1,2-PDO. In a continuous operation (23 g catalyst bed) the same catalyst showed higher conversion of glycerol and selectivity for 1,2-PDO of 65\% and \> 90\%, respectively, with an on-stream activity of similar to 800 h. Better performance in a continuous operation could be due to the in situ activation of the catalyst, suppression of glycerol cracking to ethylene glycol, as well as excessive hydrogenation of 1,2-PDO to 2-propanol due to lower contact time of 1.3 h as compared to that in a batch operation (5 h). Effects of various process parameters on conversion and selectivity also have been compared for batch and continuous operations.

}, issn = {1083-6160}, doi = {10.1021/op1001897}, author = {Rode, Chandrashekhar V and Ghalwadkar, Ajay A. and Mane, R. B. and Hengne, Amol M. and Jadkar, Sachin T. and Biradar, Narayan S.} } @article { ISI:000289764000056, title = {Control of competing hydrogenation of phenylhydroxylamine to aniline in a single-step hydrogenation of nitrobenzene to p-aminophenol }, journal = {Industrial \& Engineering Chemistry Research}, volume = {50}, number = {9}, year = {2011}, month = {MAY}, pages = {5478-5484}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Two steps involving catalytic hydrogenation of nitrobenzene to phenylhydroxylamine (PHA) in acid medium and its rearrangement to p-aminophenol (PAP) were studied separately in a batch reactor, using a well-characterized 3\% Pt/C catalyst. The first step of hydrogenation of nitrobenzene to PHA could be carried out at 303 K and a H(2) pressure of 0.69 MPa with complete conversion of nitrobenzene, while the achieved selectivity to PHA was higher than 90\% with some formation of aniline, even at lower temperature. The second step of PHA rearrangement to PAP could be achieved under a hydrogen atmosphere at elevated temperature of 353 K to give a maximum selectivity to PAP of 74\%.

}, issn = {0888-5885}, doi = {10.1021/ie102544a}, author = {Nadgeri, Jayprakash M. and Biradar, Narayan S. and Patil, Priyanka B. and Jadkar, Sachin T. and Garade, Ajit C. and Rode, Chandrashekhar V.} } @article { ISI:000294374900007, title = {Liquid phase oxidation of p-vanillyl alcohol over synthetic Co-saponite catalyst}, journal = {Applied Clay Science}, volume = {53}, number = {2, SI}, year = {2011}, month = {AUG}, pages = {157-163}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Effect of cobalt loading on porosity of synthetic Co-saponite catalysts and on the air oxidation of p-vanillyl alcohol was studied by varying Co content in the range of 5\% to 30\% using in situ precipitation method. The pore size increased from 1.29 to 3.69 nm indicating a transition from micro to meso porosity, with increase in Co loading from 5\% to 30\%. The distribution ratio of Co(3)O(4)/CoO phases as estimated from TPR studies, also increased from 0.84 to 1.67 with increase in Co loading from 5\% to 13\% and remained almost constant (1.7) with further increase in Co loading up to 30\%. The highest activity (conversion 55\%) and selectivity of 99\% to p-vanillin obtained for 13\% Co-saponite in p-vanillyl alcohol oxidation was due to the highest distribution ratios of Co(3)O(4)/CoO phases. (C) 2010 Elsevier B.V. All rights reserved.

}, keywords = {Co-saponite, Cobalt oxide phase ratio, p-Vanillin, p-Vanillyl alcohol oxidation, Porosity transition, Temperature programmed reduction}, issn = {0169-1317}, doi = {10.1016/j.clay.2010.10.026}, author = {Garade, Ajit C. and Biradar, Narayan S. and Joshi, S. M. and Kshirsagar, V. S. and Jha, Ratnesh Kumar and Rode, Chandrashekhar V.} } @article { ISI:000291908500016, title = {Reply to the comments of vicente et al. on {\textquoteleft}{\textquoteleft}liquid phase oxidation of p-vanillyl alcohol over synthetic co-saponite catalyst{\textquoteright}{\textquoteright} applied clay science (2010), doi:10.1016/j.clay.2010.10.026}, journal = {Applied Clay Science}, volume = {52}, number = {4}, year = {2011}, month = {JUN}, pages = {432}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, issn = {0169-1317}, doi = {10.1016/j.clay.2011.04.008}, author = {Rode, Chandrashekhar V. and Garade, Ajit C. and Biradar, Narayan S. and Kshirsagar, V. S.} } @article { ISI:000311864500004, title = {Selectivity tuning options in hydrogenation of m-chloronitrobenzene to m-chloroaniline over mono- and bimetallic supported Pt catalysts}, journal = {Industrial \& Engineering Chemistry Research}, volume = {51}, number = {48}, year = {2012}, month = {DEC}, pages = {15564-15572}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Supported monometallic (Pt, Ni,) and bimetallic (Ni-Pt) catalysts were prepared for the selective liquid phase hydrogenation of m-chlronitrobenzene to m-chloroaniline (m-CAN). It was found that the use of sodium carbonate as an additive substantially reduced the extent of dehydrohalogenation in the case of monometallic, 1\% Pt/C catalyst, to give the highest selectivity of 96\% to m-CAN. Ni-Pt bimetallic catalyst although showed almost complete selectivity (\>99\%) to m-chloroaniline; its activity was several fold lower than that of 1\% Pt/C Na2CO3 system. However, compared with Ni monometallic catalyst, bimetallic Ni-Pt showed higher activity and selectivity due to the presence of electron rich surface metallic Pt stabilized by Ni having lower ionization potential compared with Pt.

}, issn = {0888-5885}, doi = {10.1021/ie301363x}, author = {Mane, Rasika B. and Potdar, Aparna S. and Nadgeri, Jayprakash M. and Biradar, Narayan S. and Rode, Chandrashekhar V.} } @article { ISI:000304401600015, title = {Surface species of supported ruthenium catalysts in selective hydrogenation of levulinic esters for bio-refinery application}, journal = {Catalysis Letters}, volume = {142}, number = {6}, year = {2012}, month = {JUN}, pages = {779-787}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Several supported noble metal catalysts were screened for the hydrogenation of methyl levulinate to gamma-valerolactone (GVL). Among these catalysts 5 \% Ru/C showed the highest conversion of 95 \% of methyl levulinate with 91 \% selectivity to GVL. A detailed characterization was carried out using TPR, XRD, XPS and BET techniques. XPS studies revealed that higher extent of Ru-0 species in case of carbon supported Ru was responsible for its higher hydrogenation activity as compared to Ru on other supports. Effect of process parameters such as temperature, H-2 pressure, catalyst and substrate concentration and metal loading on methyl LA conversion and selectivity to GVL also has been studied. 5 \% Ru/C catalyst was found to be stable up to five reuses.

}, keywords = {5 \% Ru/C, Biofeedstock, gamma-Valerolactone, H-2-TPR, Hydrogenation, Methyl levulinate, XPS}, issn = {1011-372X}, doi = {10.1007/s10562-012-0822-4}, author = {Hengne, Amol M. and Biradar, Narayan S. and Rode, Chandrashekhar V.} } @article { ISI:000330812400022, title = {Single-pot formation of THFAL via catalytic hydrogenation of FFR over Pd/MFI catalyst}, journal = {ACS Sustainable Chemistry \& Engineering}, volume = {2}, number = {2}, year = {2014}, month = {FEB}, pages = {272-281}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Furfural (FFR) was selectively hydrogenated in a single pot to tetrahydrofurfuryl alcohol (THFAL) over a Si MFI molecular sieve supported Pd catalyst. Studies on catalyst screening revealed that both the metal function and the support were critical for directing the selectivity to the ringhydrogenated product, THFAL. The structural feature of MFI as shown by XRD was completely retained in the used sample of the 3\% Pd/MFI catalyst confirming its stability under reaction conditions. XRD, along with SEM characterization of the used samples, established retention of morphology of the structured silicate, suggesting a strong interaction between hexagonal porous silicate and Pd particles. The complete conversion of FFR with an enhanced selectivity of 95\% to THFAL could be achieved by recycling the crude of the first hydrogenation experiment over the same 3\% Pd/MFI catalyst.

}, keywords = {Biomass conversion, Hydrogenation, Pd/MFI, Recyclability, THFAL}, issn = {2168-0485}, doi = {10.1021/sc400302b}, author = {Biradar, Narayan S. and Hengne, Amol M. and Birajdar, Shobha N. and Niphadkar, Prashant S. and Joshi, Praphulla N. and Rode, Chandrashekhar V.} } @article { ISI:000331191200046, title = {Surface synergism of an Ag-Ni/ZrO2 nanocomposite for the catalytic transfer hydrogenation of bio-derived platform molecules}, journal = {RSC Advances}, volume = {4}, number = {19}, year = {2014}, month = {FEB}, pages = {9730-9736}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Levulinic acid was completely and selectively converted to GVL, in the presence of formic acid over an Ag-Ni/ZrO2 catalyst. The synergism between Ag and Ni in transfer hydrogenation eliminates the need for external hydrogen, making the process safer. The magnetic nature of the catalyst offers easy recovery for efficient recycling. This approach is standardized for the hydrogenation of several C-3-C-6 platform molecules in an aqueous medium.

}, issn = {2046-2069}, doi = {10.1039/c3ra46495d}, author = {Hengne, Amol M. and Malawadkar, Atul V. and Biradar, Narayan S. and Rode, Chandrashekhar V.} } @article {45973, title = {Tailoring the product dstribution with batch and continuous process options in catalytic hydrogenation of furfural}, journal = {Organic Process Research \& Development}, volume = {18}, year = {2014}, month = {NOV}, pages = {1434-1442}, type = {Artical}, abstract = {

Various noble metal catalysts were screened in a batch operation for a furfural (FFR) single-step decarbonylation and hydrogenation reaction to obtain THF in high selectivity. Among these, the 3\% Pd/C showed complete FFR conversion with a total of 80\% selectivity to ring hydrogenated products including tetrahydrofuran (THF). The order of activity exhibited by other noble metals was Pt/C \> Re/C \> Ru/C. Although Pt/C exhibited the highest activity, its decarbonylation and ring hydrogenation ability were the least (24\%) with a major product selectivity of 66\% to furfuryl alcohol (FAL). Similarly, the Cu catalyst gave almost complete selectivity to FAL. In a continuous operation (23 g catalyst bed), the 3\% Pd/C catalyst showed higher selectivity of \>40\% compared to THF alone with complete FFR conversion and on-stream activity of similar to 100 h. The reaction pathway elucidated from some control experiments revealed that the decarbonylation of FFR to furan over the Pd/C catalyst is a prerequisite for THF formation.

}, issn = {1083-6160}, doi = {10.1021/op500196x}, author = {Biradar, Narayan S. and Hengne, Amol A. and Birajdar, Shobha N. and Swami, Rameshwar and Rode, Chandrashekhar V.} } @article { ISI:000336158700036, title = {Triple nanocomposites of CoMn2O4, Co3O4 and reduced graphene oxide for oxidation of aromatic alcohols}, journal = {Catalysis Science \& Technology}, volume = {4}, number = {6}, year = {2014}, month = {MAY}, pages = {1771-1778}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A composite of reduced graphene oxide (RGO) with oxides of manganese and cobalt together was prepared by a solvothermal method. During synthesis, both the reduction of graphene oxide as well as the growth of nanorod shaped CoMn2O4 and Co3O4 occurred simultaneously having a crystallite size of similar to 8 nm calculated from X-ray diffraction (XRD). The as-obtained triple nanocomposite material designated as RGO-MnCoO exhibited excellent activity for the liquid phase aerobic oxidation of aromatic alcohols under base-free conditions selectively giving the corresponding aldehydes (\>85\%). RGO loading was varied in the range of 1-10\%, among which 1\% RGO-MnCoO showed maximum catalytic activity enhancement of 24\% as compared to the bare mixed oxide (MnCo-MO) for the oxidation of vanillyl alcohol. HR-TEM of RGO-MnCoO revealed that it was a composite material having uniform nanotubes of similar to 25 nm length and 6 nm diameter with a fringe pattern showing the (103) and (004) planes and lattice spaces of 0.26 nm and 0.22 nm, respectively, for the spinel CoMn2O4. The detailed studies on the morphology, size and composition of the as-prepared RGO-MnCoO nanocomposite by XRD, XPS, N-2-adsorption/desorption and O-2-TPD techniques were used to understand the role of RGO in the enhancement of catalytic activity for oxidation reaction.

}, issn = {2044-4753}, doi = {10.1039/c3cy01025b}, author = {Jha, Ajay and Mhamane, Dattakumar and Suryawanshi, Anil and Joshi, Sameer M. and Shaikh, Parvez and Biradar, Narayan S. and Ogale, Satishchandra and Rode, Chandrashekhar V.} } @article {43403, title = {Reductive cyclization of levulinic acid to gamma-valerolactone over non-noble bimetallic nanocomposite}, journal = {Industrial \& Engineering Chemistry Research}, volume = {55}, year = {2016}, month = {DEC}, pages = {13032-13039}, abstract = {Bimetallic nanoparticles have diverse applications in catalytic processes owing to the differences in individual properties that contribute to their increased catalytic activity. To further improve the efficiency, they are dispersed in an inert support that enhances the catalytic activity toward organic transformations. In this study, we report simple, facile, and cost-effective chemical route for the fabrication of nanocomposites with Fe-Ni bimetallic nanoparticles supported on montmorillonite (MMT) possessing variation in the Fe and Ni content. These composites are characterized with X-ray diffraction, transmission electron microscopy surface area, and NH3-TPD. Fe Ni bimetallic nanoparticles are well-dispersed within MMT structure having particle sizes of about 30-40 nm. Among various compositions of Fe-Ni/MMT catalysts, composite with 25\% Fe and 25\% Ni exhibits >99\% LA conversion with 98\% selectivity to GVL within 1 h. IPA is found to be better solvent for levulinic acid (LA) to gamma-valerolactone (GVL) conversion, while substantial leaching of iron takes place when water is used as a solvent. It is observed that bimetallic sites are responsible for reduction of LA, while strong acidic sites of MMT are favoring subsequent cyclization to GVL. XPS analysis of fresh and reused Fe-Ni/MMT composites suggest that the catalyst surface does not undergo any chemical change during successive cycles, and the catalytic activity is retained up to six cycles. The plausible mechanism for LA to GVL conversion involves reductive cyclization processes through formation of levulinate ester that undergoes lactonization due to synergism in bimetallic nanoparticles and MMT clay.}, doi = {10.1021/acs.iecr.6b03900}, author = {Kadu, Brijesh S. and Hengne, Amol M. and Biradar, Narayan S. and Rode, Chandrashekhar V. and Chikate, Rajeev C.} } @article { ISI:000381122100030, title = {Single pot transfer hydrogenation and aldolization of furfural over metal oxide catalysts}, journal = {Catalysis Letters}, volume = {146}, number = {8}, year = {2016}, month = {AUG}, pages = {1611-1619}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

One pot catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol (FAL) by using hydrogen producing alcohols and simultaneous aldolization of carbonyl compounds produced during CTH, with furfural was achieved over non-noble metal oxides with bifunctional sites. Basic sites of MgO responsible for abstraction of proton showed complete conversion of furfural to give FAL and C8 monomer in a ratio of 3:1, respectively, the later altered to 1:1 by incorporating Al into MgO. Catalyst stability was established by its four cycles study. [GRAPHICS]

}, keywords = {Aldol, furfural, Furfuryl alcohol, Metal oxides, transfer hydrogenation}, issn = {1011-372X}, doi = {10.1007/s10562-016-1786-6}, author = {Biradar, Narayan S. and Hengne, Amol M. and Sakate, S. S. and Swami, R. K. and Rode, Chandrashekhar V.} } @article { ISI:000379350100109, title = {Transfer hydrogenation of biomass-derived levulinic acid to gamma-valerolactone over supported Ni catalysts}, journal = {RSC Advances}, volume = {6}, number = {64}, year = {2016}, month = {JUN}, pages = {59753-59761}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

A sustainable process of catalytic transfer hydrogenation (CTH) of levulinic acid (LA) to gamma-valerolactone (GVL) was investigated over Ni on various supports (Al2O3, ZnO, MMT and SiO2) in the presence of isopropanol (IPA) as the H-donor. Among these, the montmorillonite (MMT) supported Ni catalyst showed almost complete LA conversion (\>99\%) and selectivity (\>99\%) to GVL within 1 h. XRD and XPS results showed that the concentration of the metallic species significantly enhanced (two to four times) in the recovered sample as compared to the freshly prepared Ni/MMT. This was due to the in situ reduction of Ni2+ species present on the catalyst surface, through liberated H-2 under the reaction conditions. The strong acid strength of MMT, evidenced by NH3-TPD and py-IR, facilitated the esterification of LA as well as cyclization to GVL. The conversion-selectivity pattern was found to decrease in the IPA-water mixture while, it remained unchanged in the IPA-acetone mixture. Our catalyst could be efficiently recycled up to five times with consistent CTH activity and selectivity to GVL. The plausible mechanism of LA to GVL conversion involves the formation of a levulinate ester with IPA that favours its simultaneous hydrogenation and cyclization in a spontaneous manner to give GVL and regenerating IPA for sustainability.

}, issn = {2046-2069}, doi = {10.1039/c6ra08637c}, author = {Hengne, Amol M. and Kadu, Brijesh S. and Biradar, Narayan S. and Chikate, Rajeev C. and Rode, Chandrashekhar V.} }