@article { ISI:000356739400008, title = {Catalytic conversion of furfural to industrial chemicals over supported Pt and Pd catalysts}, journal = {Journal of Catalysis}, volume = {327}, year = {2015}, month = {JUL}, pages = {65-77}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

Several industrial chemicals were prepared by hydrogenation of furfural over gamma-Al2O3-supported Pt and Pd catalysts. These catalysts were active even at room temperature (25 degrees C). While the Pt catalysts were selective for C=O hydrogenation (yielding furfuryl alcohol), Pd facilitated ring hydrogenation (producing tetrahydrofurfuryl alcohol). At high temperature (240 degrees C), the Pd catalyst exhibited excellent decarbonylation activity forming furan with 85\% yield. The catalyst was reusable even in the absence of external hydrogen. The presence of hydrogen led to ring-opened products. Furan was quantitatively converted at 25 degrees C to tetrahydrofuran. Acidity of the support made a marked influence on the activity and selectivity. Pt on SO4-ZrO2 favored hydrogenolysis yielding 2-methyl furan along with furan with \>75 wt\% selectivity. Particle size, metal dispersion, and solvent influenced catalytic activity. Differences in structure and mode of furfural adsorption were also the causes for variations in selectivity of these supported Pt and Pd catalysts. (C) 2015 Elsevier Inc. All rights reserved.

}, keywords = {Biomass to fuels and chemicals, Decarbonylation, furfural, Hydrogenation, Hydrogenolysis, Supported Pt and Pd catalysts}, issn = {0021-9517}, doi = {10.1016/j.jcat.2015.04.018}, author = {Bhogeswararao, Seemala and Srinivas, D.} } @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 {45607, title = {Selective hydrogenolysis of 5-(hydroxymethyl)furfural over Pd/C catalyst to 2,5-dimethylfuran}, journal = {Journal of Saudi Chemical Society}, volume = {23}, year = {2019}, month = {MAY}, pages = {439-451}, type = {Article}, abstract = {

everal metal supported catalysts were prepared and evaluated for 5-(hydroxymethyl)furfural (5-HMF) hydrogenolysis to 2,5-dimethylfuran (2,5-DMF) which is a renewable potential fuel additive. Among the prepared catalysts, 3\%Pd/C showed excellent performance in terms of complete conversion of 5-HMF along with the highest selectivity of 99\% to 2,5-DMF. Detailed physico-chemical characterisation was done in order to understand structure-activity correlation. Uniformly dispersed Pd nanoparticles on activated carbon provided the adsorption surface to enhance the hydrogenation of 5-HMF. Reaction was well optimised and established by extensive study of different reaction parameters like temperature, pressure, reaction time, stirring effect, substrate loading and metal loading.

}, keywords = {Biomass, Fuel additive, heterogeneous catalysis, Hydrogenolysis, Palladium}, issn = {1319-6103}, doi = {10.1016/j.jscs.2018.08.009}, author = {Solanki, B. S. and Rode, C. V.} } @article {47578, title = {Active K-OMS-2 supported catalyst for hydrogenolysis of glycerol}, journal = {ChemistrySelect}, volume = {6}, year = {2021}, month = {SEP}, pages = {8700-8708}, type = {Article}, abstract = {Propanediols 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.}, keywords = {Glycerol, Hydrogenolysis, octahedral molecular sieves, Propanediols, selectivity}, issn = {2365-6549}, doi = {10.1002/slct.202101664}, author = {Gogoi, Pranjal and Chilukuri, Satyanarayana and Thirumalaiswamy, Raja} } @article {46739, title = {Advances in solid catalysts for selective hydrogenolysis of glycerol to 1,3-propanediol}, journal = {Catalysis Reviews-Science and Engineering}, year = {2021}, month = {JAN}, type = {Review}, abstract = {

Glycerol is one of the top 12 platform chemicals obtained from biomass. Its surplus availability as a by-product of biodiesel, fat-splitting and soap manufacturing industries and affordable price lends significant opportunity for its valorization, using solid catalysts, into propanediols (PDOs), particularly to 1,3-propanediol (1,3-PDO), by selective hydrogenolysis. 1,3-PDO is an important chemical with wide applications including that as a precursor in polymers manufacturing. However, the synthesis of 1,3-PDO by selective cleavage of the secondary C-O bond of glycerol in the presence of hydrogen (instead of the primary C-O bond yielding 1,2-PDO) is highly challenging. Of late, supported Pt and Ir catalysts in combination with a reducible oxide (WO(x)or ReOx) were found selective for 1,3-PDO formation. Support, metals composition and additives (co-added metals) affect the performance of these catalysts. Detailed investigations revealed that metal dispersion, electronic connectivity between metal and metal oxide/support, hydrogen activation/spillover and Bronsted acidity are some parameters that influence the activity and selectivity of these bi-functional, metal-metal oxide catalysts. This review summarizes the latest advances in these solid catalysts for selective hydrogenolysis of glycerol to 1,3-PDO, a monomer for advanced polymers.

}, keywords = {1, 3-Propanediol, bifunctional metal-metal oxide catalyst, biomass valorization, Glycerol, Hydrogenolysis}, issn = {0161-4940}, doi = {10.1080/01614940.2020.1794737}, author = {Bhowmik, Susmita and Darbha, Srinivas} } @article {47689, title = {Hydrogenolysis of benzofuran using aqueous ethanol solution over graphite-supported platinum catalyst}, journal = {Journal of the Indian Chemical Society}, volume = {98}, year = {2021}, month = {FEB}, pages = {100021}, type = {Article}, abstract = {Graphite-supported platinum catalysts (Pt/G) were highly active for the hydrogenolysis of benzofuran to o-ethylphenol in aqueous ethanol solution at 523 K without using any external hydrogen gas. The hydrogenolysis activities and selectivity to o-ethylphenol in ethanol solution over Pt/G were higher than those with a conventional method using externally supplied hydrogen gas. Both water and ethanol were indispensable for the hydrogenolysis in aqueous ethanol solution at 523 K.}, keywords = {Biomass conversion, Graphite support, Hydrogenolysis, platinum catalysts}, issn = {0019-4522}, doi = {10.1016/j.jics.2021.100021}, author = {Hiraishi, Yushi and Minakawa, Naohiro and Taniguchi, Kenkichi and Nagasawa, Yoshiyuki and Nanao, Hidetaka and Rode, V, Chandrashekhar and Sato, Osamu and Yamaguchi, Aritomo and Shirai, Masayuki} } @article {48187, title = {Insights into active tungsten species on Pt/W/SBA-15 catalysts for selective hydrodeoxygenation of glycerol to 1,3-propanediol}, journal = {Molecular Catalysis}, volume = {531}, year = {2022}, month = {OCT}, pages = {112704}, type = {Article}, abstract = {

Diols are important class of industrial chemicals. Their synthesis from bio-resources (instead from fossil feed-stocks) is sustainable. In this study, we probed active tungsten species on Pt/W/SBA-15 catalysts for selective synthesis of 1,3-propanediol (1,3-PDO) from aqueous glycerol through a liquid-phase hydrodeoxygenation re-action. A synergistic enhancement in glycerol conversion and 1,3-PDO selectivity was observed when both Pt and W were present on the catalyst. A volcano-shape variation followed with a gradual increase in glycerol conversion and 1,3-PDO yield with W-loading (0.25-15 wt\%) was observed. Pt dispersion and acidity of the catalyst dis-played similar variations with the W-loading confirming their critical role in the reaction. Structure-function relationships inferred that oligomeric WOx with moderate Bro center dot nsted acidity (predominant at 1 wt\% W-loading) in contact with dispersed Pt are the active species for 1,3-PDO formation and crystalline WO3 with strong Bro center dot nsted acidity (prevalent above 4 wt\% W-loading) in association with Pt nanoparticles lead to 1-propanol formation.

}, keywords = {3-Propanediol, Active sites, Glycerol, Hydrodeoxygenation, Hydrogenolysis, Supported Pt-WO x}, issn = {2468-8231}, doi = {10.1016/j.mcat.2022.112704}, author = {Bhowmik, Susmita and Enjamuri, Nagasuresh and Sethia, Govind and Akula, Venugopal and Marimuthu, Banu and Darbha, Srinivas} } @article {47731, title = {Selective production of C9 monomeric phenols via hydrogenolysis of lignin using Pd-(W/Zr/Mo oxides)-supported on biochar catalyst}, journal = {Fuel}, volume = {308}, year = {2022}, month = {JAN }, pages = {121818}, type = {Article}, abstract = {Valorizing lignin to phenolic monomers and fine chemicals is an essential component of a sustainable biorefinery that uses lignocellulosic feedstocks. In this study, Pd-metal oxides (ZrO2, WOx, MoO3) supported on activated biochar (ABC) catalysts were developed for hydrogenolysis of lignin. The metals (2\% Pd, 5\% Zr, 5\% W, 5\% Mo) were supported on activated biochar using the wetness impregnation method, and the catalysts were extensively characterized. The effect of addition of secondary metals on active surface properties such as acidity, Pd metal particle size and dispersion were also evaluated. The selectivity to C9 monomeric phenols followed the trend: 2Pd-5Mo/ABC (57.3\%) > 2Pd-5Zr/ABC (49.2\%) > 2Pd-5W/ABC (45\%) > 2Pd/ABC (42.9\%). The maximum C9 phenolic monomer yield achieved in this study was similar to 22 wt\%. The fractional conversion of lignin was 67-69\% with Pd-metal oxide catalysts. The presence of Mo in the catalyst inhibited the hydrogenation of aliphatic C-alpha = C-beta in lignin and led to the formation of t-isoeugenol, while the presence of W and Zr resulted in selective formation of the hydrogenated product, propyl guaiacol. Using model compounds, it is proved that the formation of propyl guaiacol is via hydrogenation of t-isoeugenol, and not through dehydroxylation of propanol guaiacol. The dehydroxylation activity of the catalysts is attributed to the higher Lewis acidity and electropositive nature of the metals. A notable carbon atom economy of 47-50\% towards total phenolic monomers was achieved with 2Pd/ABC, 2Pd-5Mo/ABC and 2Pd-5Zr/ABC catalysts.}, keywords = {Activated biochar, Guaiacol, Hydrogenolysis, lignin, Metal oxides, Palladium}, issn = {0016-2361}, doi = {10.1016/j.fuel.2021.121818}, author = {Gurrala, Lakshmiprasad and Kumar, M. Midhun and Sharma, Shweta and Paek, Changyub and Vinu, R.} } @article {47732, title = {Unraveling the reaction mechanism of selective C9 monomeric phenols formation from lignin using Pd-Al2O3-activated biochar catalyst}, journal = {Bioresource Technology}, volume = {344}, year = {2022}, month = {JAN}, pages = {126204}, type = {Article}, abstract = {The conversion of biomass-derived lignin to valuable monomeric phenols at high selectivity is of paramount importance for sustainable biorefineries. In this study, a novel Pd-Al2O3 supported on activated biochar catalyst is developed for lignin hydrogenolysis. The catalyst characterization revealed that the (1 1 1) planes of both of Pd-0 and Al2O3 were exposed to the surface. The maximum lignin conversion of 70.4\% along with high liquid yield (similar to 57 wt\%) was obtained at 240 degrees C, 3 h and 3 MPa H-2 pressure. The total monomeric phenols yield in the liquid was 51.6 wt\%, out of which C9 monomeric guaiacols constituted similar to 30.0 wt\% with 38.0\% selectivity to 4-propyl guaiacol. Using the reaction intermediate, coniferyl alcohol, chemoselective hydrogenation of C-alpha=C-beta is proved to occur over the Pd site, while dehydroxylation of C-gamma-OH is shown to occur over the alumina site. An impressive carbon atom economy of 60\% was achieved for the production of monomeric phenols.}, keywords = {Hydrogenolysis, lignin, Mechanism, Pd-Al/activated biochar, Propanol guaiacol, Propyl guaiacol}, issn = {0960-8524}, doi = {10.1016/j.biortech.2021.126204}, author = {Gurrala, L. and Kumar, M. M. and Yerrayya, Attada and Kandasamy, Prabu and Castano, Pedro and Raja, T. and Pilloni, Giovanni and Paek, C. and Vinu, R.} } @article {48789, title = {Promoting effect of titanium on C-O hydrogenolysis of erythritol to 1,4-butanediol over Pt/W/Ti-SBA-15 catalysts}, journal = {Applied Catalysis A-General}, volume = {666}, year = {2023}, month = {SEP }, pages = {119425}, type = {Article}, abstract = {

The C-O hydrogenolysis of erythritol was investigated using Pt/W/Ti-SBA-15 catalysts (4 wt\% Pt, 1 wt\% W and Si/Ti molar ratio = 50, 33, 20 and 10). Ti-incorporation enhanced the hydrogenolysis activity and the yield of 1,4-butanediol (1,4-BDO). A catalyst with Si/Ti = 20 afforded erythritol conversion of 94 mol\% with 1,4-BDO yield of 32.6 mol\% and total BDOs yield of 51.7 mol\% at 190 degrees C, 50 bar H2 and 12 h. For the catalyst with no titanium (Pt/W/SBA-15), a double the time was required to achieve such yield. There observed electronic connectivity amongst Ti, Pt and W. For the catalyst with Si/Ti = 20, a greater amount of interfacial Pt-O-W(Ti) sites with Pt in + 2 oxidation state was present. The enhanced catalytic performance of these catalysts was corresponded to dispersed Pt (that facilitate hydrogen activation and spillover) and acidic interfacial Pt-O-W sites (that promote the adsorption and hydrogenolysis of erythritol to diols).

}, keywords = {Biomass conversion, Erythritol, Hydrogenolysis, Polyols, Promotional effect of Ti, Terminal diol, Ti-SBA-15-supported Pt/W catalysts}, issn = {0926-860X}, doi = {10.1016/j.apcata.2023.119425}, author = {Bhowmik, Susmita and Akula, Venugopal and Sethia, Govind and Marimuthu, Banu and Darbha, Srinivas} }