@article { ISI:000275090400021, title = {Cu:Al Nano catalyst for selective hydrogenolysis of glycerol to 1,2-propanediol}, journal = {Catalysis Letters}, volume = {135}, number = {1-2}, year = {2010}, month = {MAR}, pages = {141-147}, publisher = {SPRINGER}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Non-chromium Cu:Al nano catalyst prepared by simultaneous co-precipitation and digestion method without any template or stabilizer, showed three times higher activity than the bulk Cu-Cr catalyst for hydrogenolysis of glycerol in both isopropanol and water solvents, with the selectivity to 1,2-Propanediol (1,2-PDO) as high as 91\% at 493 K and H(2) pressure of 7 MPa in 5 h. XRD pattern showed the presence of Cu(+) species in the activated Cu: Al nano catalyst. Although Cu(+) is catalytically inactive in glycerol hydrogenolysis reaction, the presence of Cu(+) helps to stabilize the particle size in a narrow range of 7-11 nm by inhibiting the sintering of copper particles under reaction conditions.

}, keywords = {1, 2-Propanediol, Cu:Al nano catalyst, Glycerol, Selective hydrogenolysis}, issn = {1011-372X}, doi = {10.1007/s10562-010-0276-5}, author = {Mane, Rasika B. and Hengne, Amol M. and Ghalwadkar, Ajay A. and Vijayanand, Subramanian and Mohite, Pravin H. and Potdar, Hari S. and Rode, Chandrashekhar V.} } @article { ISI:000304129100035, title = {Continuous dehydration and hydrogenolysis of glycerol over non-chromium copper catalyst: laboratory-scale process studies}, journal = {Organic Process Research \& Development}, volume = {16}, number = {5}, year = {2012}, month = {MAY}, pages = {1043-1052}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

A non-chromium Cu:Al catalyst was developed for glycerol dehydration under N-2 atmosphere to acetol and hydrogenolysis to 1,2-propanediol (1,2-PDO). Among the various copper-based catalysts screened in this work, Cu:Al-1 catalyst showed the highest activity and acetol selectivity in water medium, whereas transfer hydrogenation in 2-propanol as the reaction medium led to the formation of 1,2-PDO (10-38\%). The same catalyst was also found to catalyze the direct hydrogenolysis of glycerol to 1,2-PDO. Time on stream activity (TOS) of our Cu:Al-1 catalyst for both continuous dehydration and hydrogenolysis of glycerol was found to be 400 h with an average glycerol conversion of 90\% and 65\%, respectively. Maximum acetol selectivity was 55\% while 1,2-PDO selectivity was 91\% in dehydration and hydrogenolysis reactions separately. Effects of various reaction conditions on conversion, selectivity, and global rates of the two processes were also investigated.

}, issn = {1083-6160}, doi = {10.1021/op200383r}, author = {Mane, Rasika B. and Rode, Chandrashekhar V.} } @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:000309139400020, title = {Simultaneous glycerol dehydration and in situ hydrogenolysis over Cu-Al oxide under an inert atmosphere}, journal = {Green Chemistry}, volume = {14}, number = {10}, year = {2012}, month = {JUL}, pages = {2780-2789}, publisher = {ROYAL SOC CHEMISTRY}, type = {Article}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Among various catalysts screened, the Cu-Al oxide catalyst, prepared by a co-precipitation method, exhibited excellent activity for simultaneous glycerol dehydration and its hydrogenolysis without external hydrogen. Detailed characterization by XRD, XPS, HR-TEM, TPR, etc., showed evidence of Cu2+ in the form of CuO and CuAl2O4, along with Cu-0 and Cu1+ species, which are responsible for their multifunctional roles in glycerol APR, dehydration and hydrogenolysis reactions under inert conditions. This catalyst also presented consistent activity for a duration of 400 h for autogeneous hydrogenolysis of refined glycerol with 36\% selectivity to 1,2-propanediol (1,2-PDO). Manipulating the temperature and feed flow rate conditions, meant that the selectivity to acetol and 1,2-PDO could be tailored as desired. Substantial enhancement in 1,2-PDO selectivity (75\%) was achieved for an aqueous bio-glycerol feed over the same catalyst for 50 h of testing.

}, issn = {1463-9262}, doi = {10.1039/c2gc35661a}, author = {Mane, Rasika B. and Rode, Chandrashekhar V.} } @article { ISI:000323842900043, title = {Active sites in modified copper catalysts for selective liquid phase dehydration of aqueous glycerol to acetol}, journal = {RSC Advances}, volume = {3}, number = {37}, year = {2013}, month = {JUL}, pages = {16499-16508}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

We report here the influence of oxides of various metals viz. Ba, Mg, Zr, Zn, Al, and Cr in modified copper catalysts, on the formation of different copper species and acid sites responsible for dehydration of aqueous glycerol to acetol. These catalysts were prepared by a co-precipitation method, among which the catalysts having higher acid strength and predominant Bronsted acidity (Cu-Mg, Cu-Zr and Cu-Al) gave the highest acetol selectivity (76-92\%), while the catalysts with lower acidity such as Cu-Zn showed very poor (25\%) selectivity to acetol in spite of the highest conversion of 68\%. Nevertheless, catalysts exhibiting higher activity and acetol selectivity also showed the presence of metallic Cu confirmed by XRD and XANES-EXAFS characterization. Based on these results, two different catalytic pathways have been proposed highlighting the role of Lewis and Bronsted acidity along with the metal sites in individual steps of glycerol dehydration reaction.

}, issn = {2046-2069}, doi = {10.1039/c3ra42348d}, author = {Mane, Rasika B. and Yamaguchi, Aritomo and Malawadkar, Atul V. and Shirai, Masayuki and Rode, Chandrashekhar V.} } @article { ISI:000337689900034, title = {Effect of composition and pretreatment parameters on activity and stability of Cu-Al catalysts for water-gas shift reaction}, journal = {ChemCatChem}, volume = {6}, number = {6}, year = {2014}, month = {JUN}, pages = {1698-1706}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

We investigated various Cu species responsible for highly efficient Cu-Al oxide catalyst for the water-gas shift reaction (WGSR). The formation of various Cu species was achieved by systematically varying the Cu-Al composition in the coprecipitated mixed Cu-Al oxides. The Cu-Al composition of 70:30 (Cu-Al-7) was the best for WGSR using the reformate gas composition. In addition, the Cu-Al-7 catalyst reduced under 100\% H-2, was relatively stable with time on stream of 100 h, at higher gas hourly space velocity of 36201 h(-1). The structural investigation of our coprecipitated catalysts with varying Cu-Al compositions revealed the formation of nonzero oxidation state copper and metallic Cu to be essential for the observed WGSR activity. In addition, the highest activity and stability of Cu-Al-7 catalysts reduced under 100\% H-2 at lower temperature was attributed to particle-size stabilization and a lower extent of Cu aggregation by Cu2O and boehmite phases, respectively, along with the formation of various Cu species during the activation protocol for 12 h. Complete CO2 selectivity without methanation was observed for all the Cu-Al compositions irrespective of their pretreatment conditions.

}, keywords = {aluminum, Copper, fuel cells, Hydrogen, reduction}, issn = {1867-3880}, doi = {10.1002/cctc.201301049}, author = {Mane, Rasika B. and Jeong, Dae-Woon and Malawadkar, Atul V. and Roh, Hyun-Seog and Rode, Chandrashekhar V.} } @article {44014, title = {Influence of carbon based supports on selectivity behavior of diols and propanol in Ru catalyzed glycerol hydrogenolysis}, journal = {Applied Catalysis B: Environmental}, volume = {204}, year = {2017}, month = {MAY}, chapter = {134-146}, abstract = {

Activated carbon (AC) and three graphite materials were studied as supports for Ru catalyzed glycerol hydrogenolysis to propanediols and 1-propanol. Structural characteristics of AC and graphite materials were found to greatly affect the reducibility and particle size of supported Ru and hence, the activity and product distribution in glycerol hydrogenolysis. XRD of graphite materials showed distinctly (002) plane having highly organized layered structure and the peak intensity decreased in the order of Ru/KS150 \> Ru/HSAG100 \> Ru/KS6 due to decrease in the graphite sheet thickness. In Raman, the intense D band in HSAG100 compared to that in KS6 and KS150 samples indicated its highly amorphous nature or mixed carbon hybridization. Glycerol conversion for Ru on AC was higher than that on graphite and among different graphites, it showed a descending activity order of Ru/KS6 \> Ru/HSAG100 \> Ru/KS150. The product distribution for AC and HSAG100 supported Ru was similar, giving 1-propanol (45\%) alongwith 1,2-propanediol (1,2-PDO) (37\%) and 1,3-propanediol (1,3-PDO) (9{\textendash}11\%). For graphite supports, availability of Ru although bigger in size (4{\textendash}5 nm), would be higher on the surface than in case of AC which formed deep hydrogenolysis products like 1-, 2- propanol, ethanol etc.

}, keywords = {activated carbon, Amorphous carbon, catalysis, Glycerol, Glycerol conversions, Glycerol hydrogenolysis, graphite composites, Graphite supports, Hydrogenolysis, Hydrolysis, layered structures, Particle size, Product distributions, Propanediols, Propanol, Selectivity behavior, Structural characteristics, Structural effect, Structural effects}, issn = {0926-3373}, doi = {10.1016/j.apcatb.2016.11.032}, author = {Mane, Rasika B. and Patil, S. and Shirai, Masayuki and Rayalu, Sadhana S. and Rode, Chandrashekhar V.} } @article {43794, title = {Microwave-assisted synthesis of 5-substituted 1H-tetrazoles via [3+2] cycloaddition over a heterogeneous Cu-based catalyst: application to the preparation of N-13-labelled tetrazoles}, journal = {New Journal of Chemistry}, volume = {41}, year = {2017}, month = {AUG}, pages = {8084-8091}, type = {Article}, abstract = {The [3+2] cycloaddition between various nitriles and sodium azide proceeds smoothly in the presence of a new Cu-II catalyst in N-methyl-2-pyrrolidone (NMP) to give the corresponding 5-substituted 1H-tetrazoles. The desired tetrazoles were obtained in high yields within 3-30 min by employing controlled microwave heating. The reaction most probably proceeds through the activation of the nitrile groups by the Cu-II species, followed by a successive [3+2] cycloaddition with the sodium azide. The good performance of the catalyst enabled the preparation of selected tetrazoles labelled with the positron emitter nitrogen-13 even under conventional heating. The short reaction time, simple work-up procedure, and recyclability of the catalyst are advantages of the method reported here.}, doi = {10.1039/c7nj00568g}, author = {Joshi, Sameer M. and Mane, Rasika B. and Pulagam, Krishna R. and Gomez-Vallejo, Vanessa and Llop, Jordi and Rode, Chandrashekhar} }