@article { ISI:000269426900019, title = {Acetalization of glycerol using mesoporous MoO3/SiO2 solid acid catalyst}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {310}, number = {1-2}, year = {2009}, month = {SEP}, pages = {150-158}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Acetalization of glycerol with various aldehydes has been carried out using mesoporous MoO3/SiO2 as a solid acid catalyst. A series of MoO3/SiO2 catalysts with varying MoO3 loadings(1-20 mol\%) were prepared by sol-gel technique using ethyl silicate-40 and ammonium heptamolybdate as silica and molybdenum source respectively. The sol-gel derived samples were calcined at 500 degrees C and characterized using various physicochemical characterization techniques. The XRD of the calcined samples showed the formation of amorphous phase up to 10 mol\% MoO3 loading and at higher loading of crystalline alpha-MoO3 on amorphous silica support. TEM analyses of the materials showed the uniform distribution of MoO3 nanoparticles on amorphous silica support. Raman spectroscopy showed the formation of silicomolybdic acid at low Mo loading and a mixture of alpha-MoO3 and polymolybdate species at high Mo loadings. Moreover the Raman spectra of intermediate loading samples also suggest the presence of beta-MoO3. Acetalization of glycerol with benzaldehyde was carried out using series of MoO3/SiO2 catalysts with varying MoO3 loadings (1-20 mol\%). Among the series, MoO3/SiO2 With 20 mol\% MoO3 loadings was found to be the most active catalyst in acetalization under mild conditions. Maximum conversion of benzaldehyde (72\%) was obtained in 8 h at 100 degrees C with 60\% selectivity for the six-membered acetal using 20\% MoO3/SiO2. Interestingly with substituted benzaldehydes under same reaction conditions the conversion of aldehydes decreased with increase in selectivity for six-membered acetals. These results indicate the potential of this catalyst for the acetalization of glycerol for an environmentally benign process. (C) 2009 Elsevier B.V. All rights reserved.

}, keywords = {Acetalization, Aldehyde, Glycerol, Silicomolybdic acid, solid acid}, issn = {1381-1169}, doi = {10.1016/j.molcata.2009.06.010}, author = {Shubhangi B. Umbarkar and Kotbagi, Trupti V. and Biradar, Ankush V. and Pasricha, Renu and Chanale, Jyoti and Dongare, Mohan K. and Mamede, Anne-Sophie and Lancelot, Christine and Payen, Edmond} } @article { ISI:000268376100057, title = {Mannitol production from glycerol by resting cells of Candida magnoliae}, journal = {Bioresource Technology}, volume = {100}, number = {20}, year = {2009}, month = {OCT}, pages = {4911-4913}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Production of mannitol from glycerol by resting cells of Candida magnoliae under aerobic condition was investigated. The resting cells were Suspended in aqueous Solution of glycerol in Erlenmeyer flasks and incubated on rotary shaker. The samples were analyzed by ion exclusion-HPLC equipped with refractive index and UV detector. The resting cells of C. magnoliae produced mannitol from fructose, Sucrose and glycerol but not from glucose. Addition of yeast extract and/or potassium phosphate to the glycerol solution adversely affected its conversion to mannitol. The conversion of glycerol to mannitol was dependent on oxygen availability. Using testing cells, the yield of mannitol was as high as 45\%. This is probably the first report of conversion of glycerol to mannitol by osmophilic yeast. (C) 2009 Elsevier Ltd. All rights reserved.

}, keywords = {Candida magnoliae, Glycerol, Mannitol production, Resting cells}, issn = {0960-8524}, doi = {10.1016/j.biortech.2009.04.048}, author = {Khan, Asiya and Bhide, Amey J. and Gadre, Ramchandra V.} } @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:000278725100023, title = {Renewable H-2 from glycerol steam reforming: effect of La2O3 and CeO2 addition to Pt/Al2O3 catalysts.}, journal = {Chemsuschem}, volume = {3}, number = {5}, year = {2010}, month = {MAY}, pages = {619-628}, publisher = {WILEY-BLACKWELL}, address = {COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA}, abstract = {

Glycerol is the main byproduct of biodiesel production and its increased production volume derives from the increasing demand for biofuels. The conversion of glycerol to hydrogen-rich mixtures presents an attractive route towards sustainable biodiesel production. Here we explored the use of Pt/Al2O3-based catalysts for the catalytic steam reforming of glycerol, evidencing the influence of La2O3 and CeO2 doping on the catalyst activity and selectivity. The addition of the latter metal oxides to a Pt/Al2O3 catalyst is found to significantly improve the glycerol steam reforming, with high H-2 and CO2 selectivities. A good catalytic stability is achieved for the Pt/La2O3/Al2O3 system working at 350 degrees C, while the Pt/CeO2/Al2O3 catalyst sharply deactivates after 20 h under similar conditions. Studies carried out on fresh and exhausted catalysts reveal that both systems maintain high surface areas and high Pt dispersions. Therefore, the observed catalyst deactivation can be attributed to coke deposition on the active sites throughout the catalytic process and only marginally to Pt nanoparticle sintering. This work suggests that an appropriate support composition is mandatory for preparing high-performance Pt-based catalysts for the sustainable conversion of glycerol into syngas.

}, keywords = {biofuels, Glycerol, heterogeneous catalysis, platinum, supported catalysts}, issn = {1864-5631}, doi = {10.1002/cssc.200900243}, author = {Montini, Tiziano and Singh, Rakesh and Das, Piyali and Lorenzut, Barbara and Bertero, Nicolas and Riello, Pietro and Benedetti, Alvise and Giambastiani, Giuliano and Bianchini, Claudio and Zinoviev, Sergey and Miertus, Stanislav and Fornasiero, Paolo} } @article { ISI:000338486300020, title = {1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU): a highly efficient catalyst in glycerol carbonate synthesis}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {391}, year = {2014}, month = {SEP}, pages = {144-149}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Transesterification of dimethyl carbonate (DMC) with glycerol (GLY) was investigated using various amines as catalysts. Amidines like 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) were found to be the best catalysts for this reaction. Best results: 98\% conversion of GLY with 96\% selectivity to GC (TON: 9408), were obtained with DBU as a catalyst. Effect of various reaction conditions on activity and selectivity were investigated using DBU as catalyst. The mechanism of the reaction was investigated with the help of H-1, C-13 and N-15 NMR analysis and OFT calculations. (C) 2014 Elsevier B.V. All rights reserved.

}, keywords = {DBU, Glycerol, Glycerol carbonate, transesterification}, issn = {1381-1169}, doi = {10.1016/j.molcata.2014.04.016}, author = {Munshi, Mudassir K. and Gade, Swapna M. and Mane, Manoj V. and Mishra, Deepti and Pal, Sourav and Vanka, Kumar and Rane, Vilas H. and Kelkar, Ashutosh A.} } @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 {46953, title = {Controlling and stabilization of Ru nanoparticles by tuning the nitrogen content of the support for enhanced H-2 production through aqueous-phase reforming of glycerol}, journal = {ACS Catalysis}, volume = {10}, year = {2020}, month = {FEB}, pages = {2489-2507}, type = {Article}, abstract = {

The stable activity of catalysts is an important issue in catalysis, particularly aqueous-phase reforming (APR) of renewable oxygenates, of biomass origin, to get H-2. Sintering of metal nanoparticles on supports affects catalyst stability. To alleviate this problem, a series of highly stable Ru-supported catalysts with controlled metal nanoparticle sizes have been prepared via the easy incipient wetness impregnation method. These catalysts were used for APR of glycerol to produce H-2. Nitrogen-doped mesoporous carbons (NMCs) were utlized as supports and found to have a strong influence on the catalytic performance of the catalysts. Incorporation of nitrogen in the carbon framework significantly enhanced the catalytic activity compared to Ru catalysts on nitrogen-free supports. Notably, the catalyst (5 wt \% Ru-NMC-3) with optimal N content (10.9 wt \%) demonstrated improved stability and H-2 selectivity, which are better than those of many state-of-the-art catalysts. Nitrogen in the carbon framework has a dual relationship with the activity of the catalyst: (i) it creates basic environment over the catalysts support and (ii) it acts as an anchoring site for metal nanoparticles. Anchoring of metal nanoparticles has helped to curb their sintering, thus leading to better stability of the catalysts under APR reaction conditions. Various characterization techniques were employed to understand the nature of active catalytic sites responsible for higher H-2 production while minimizing CO formation. In situ CO-FTIR studies showed that the higher catalytic activity of 5 wt \% Ru-NMC-3 catalyst was attributed to the enhanced WGS activity over this catalyst. Density functional theory calculations were performed to understand the stabilization of metal nanoparticles by different types of N present on the support and provide insights into the prefered sites of glycerol adsorption on the NMC support. Since S wt \% Ru-NMC-3 was the relatively best catalyst, it was selected for the preparation of bimetallic catalysts. Accordingly, addition of Pt to this system helped to increase the stability of the catalyst. This bimetallic catalyst may, therefore, find application for wide use in APR of biomass oxygenates.

}, keywords = {aqueous-phase reforming, Glycerol, H-2 production, Ru/NMC catalyst, synergistic effect}, issn = {2155-5435}, doi = {10.1021/acscatal.9b04063}, author = {Gogoi, Pranjal and Kanna, Narsimharao and Begum, Pakiza and Deka, Ramesh C. and Satyanarayana, C. V. V. and Raja, Thirumalaiswamy} } @article {46928, title = {Synthesis and characterization of supported heteropoly acid: efficient solid acid catalyst for glycerol esterification to produce biofuel additives}, journal = {Inorganic and Nano-Metal Chemistry}, volume = {50}, year = {2020}, month = {NOV }, pages = {1157-1165}, type = {Article}, abstract = {

Esterification of glycerol with acetic acid has been studied with different solid acid catalysts, prepared by impregnating phospotungustic, silicotungstic, and phosphomolybdic acids on polymeric material polyvinylpyrrolidone. These results were compared with commercially available montmorillonite KSFO catalyst showed that PVP-DTP gave higher selectivity to di- and triacetins. This study was mainly focused on increasing the selectivity toward triacetin which is an excellent alternative to fossil fuel based fuel additives. The detail characterization was done for the PVP-DTP catalyst which gave complete conversion of glycerol and maximum selectivity of 34\% toward triacetin. Complete conversion of glycerol was achieved at 110 degrees C within 6 h of reaction time. The characterization of the catalyst was performed by SEM/EDX, X-ray diffraction, thermogravimetic techniques, and FT-IR analysis.TPD-NH3 characterization showed that DTP supported on PVP increases the catalyst acidity of PVP. The highest acidity of PVP-DTP is also confirmed using NH3-TPD analysis.

}, keywords = {Glycerol, phospostugustic acid, povidone, solid acid catalyst, triacetin}, issn = {2470-1556}, doi = {10.1080/24701556.2020.1737817, Early Access Date = MAR 2020}, author = {Magar, Subhash and Mohanraj, Govindraj T. and Jana, Sumit Kumar and Rode, V, Chandrashekhar} } @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 {47114, title = {Bioglycerol (C3) upgrading to 2,3-butanediol (C4) by cell-free extracts of Enterobacter aerogenes NCIM 2695}, journal = {Journal of Chemical Technology and Biotechnology}, volume = {96}, year = {2021}, month = {MAY}, pages = {1316-1325}, type = {Article}, abstract = {

BACKGROUND Production of biobased chemicals from renewable resources is a green starring approach that serves as a substitute to petroleum derivatives. Bioglycerol, with its growing production as a co-product of biodiesel, is an attractive low-cost feedstock for the synthesis of platform chemicals by microbial fermentation. 2,3-butanediol (2,3-BDO) is amongst the top biorefinery platform chemicals that can be produced by glycerol fermentation. RESULTS The {\textquoteleft}Circular Economy{\textquoteright} concept is demonstrated by converting the by-product bioglycerol using a cell-free extract of Enterobacter aerogenes NCIM 2695 (National Collection of Industrial Microorganisms, NCIM), yielding 22 g L-1 2,3-BDO, in 96 h, 98\% atom economy and 0.4 g/g E factor. The cell-free bioglycerol conversion to 2,3-BDO was proved using a modified procedure for determining glycerol dehydrogenase enzyme assay by protein analysis and it was also shown to be cell-bounded. CONCLUSION Our study offers an effective utilization of the leftover material (i.e. cell-free extract) that biocatalysed C3 to C4 diol, which adds value to the overall economics of the process using only crude glycerol (C3) itself as a fermentative medium.

}, keywords = {2, 3-Butanediol, atom economy, circular economy, E factor, Glycerol, glycerol dehydrogenase}, issn = {0268-2575}, doi = {10.1002/jctb.6650, Early Access Date = JAN 2021}, author = {Parate, Roopa and Borgave, Mrunal and Dharne, Mahesh and Rode, Chandrashekhar} } @article {47653, title = {Glycerol-triazole conjugated rhodamine as colorimetric and fluorimetric sensor for Cu2+}, journal = {ChemistrySelect}, volume = {6}, year = {2021}, month = {SEP}, pages = {9288-9292}, type = {Article}, abstract = {{A glycerol-triazole tethered rhodamine based colorimetric and fluorimetric sensor 3 {\textquoteleft},6 {\textquoteleft}-bis(diethylamino)-2-(((1-(1,3-dihydroxypropan-2-yl)-1H-1,2,3-triazol-4 -yl)methylene)aminospiro [isoindoline-1,9 {\textquoteleft}-xanthen]-3-one (L1) is designed and synthesized for the selective recognition of Cu2+ ion. The sensor L1 allows naked eye detection of Cu2+ ion with a fast response (<1 min). Among the various metal ions tested, the sensor L1 shows selective binding with Cu2+ through turn-on fluorescence mechanism. The sensor shows 1 : 2 binding stoichiometry with binding constant}, keywords = {Cu2+ Sensor, DFT, Glycerol, Rhodamine B, Triazole}, issn = {2365-6549}, doi = {10.1002/slct.202102145}, author = {Verma, Abhishek and Gahlyan, Parveen and Bawa, Rashim and Dash, Soumya Ranjan and Prasad, Ashok K. and Kumar, Rakesh} } @article {47641, title = {Role of preparation parameters of Cu-Zn mixed oxide catalyst in solvent free glycerol carbonylation with urea}, journal = {Journal of the Indian Chemical Society}, volume = {98}, year = {2021}, month = {JUL}, pages = {100090}, type = {Article}, abstract = {Solvent-free carbonylation of glycerol with urea to glycerol carbonate (GC) was achieved over heterogeneous Cu-Zn mixed oxide catalyst. Cu-Zn catalysts with different ratios of Cu:Zn were prepared using co-precipitation (CP) and oxalate gel (OG) methods. As compared to CuO-ZnO(2:1) catalyst prepared by oxalate gel (OG) method, much higher conversion of glycerol and highest selectivity towards glycerol carbonate (GC) was achieved with CuO-ZnO_CP(2:1) catalyst. Physicochemical properties of prepared catalysts were investigated by using XRD, FT-IR, BET, TPD of CO2 and NH3 and TEM techniques. The effect of stoichiometric ratio of Cu/Zn, calcination temperature of CuO-ZnO catalysts and effect of reaction parameters such as molar ratio of substrates, time and temperature on glycerol conversion to GC were critically studied. Cu/Zn of 2:1 ratio, glycerol-urea 1:1 molar ratio, 145 degrees C reaction temperatures were found to be optimized reaction conditions to achieve highest glycerol conversion of 86\% and complete selectivity towards GC. The continuous expel of NH 3 from reaction the mixture avoided formation of ammonia complex with CuO-ZnO catalyst. As a result of this, CuO-ZnO catalyst could be recycled up to three times without losing its initial activity.}, keywords = {Co-precipitation (CP), Glycerol, Glycerol carbonate, Oxalate gel (OG)}, issn = {0019-4522}, doi = {10.1016/j.jics.2021.100090}, author = {Charate, Shrinivas and Shinde, Suhas and Kondawar, Sharda and Desai, Uday and Wadgaonkar, Prakash and Rode, Chandrashekhar} } @article {48020, title = {C-O hydrogenolysis of C3-C4 polyols selectively to terminal diols over Pt/W/SBA-15 catalysts}, journal = {Catalysts}, volume = {12}, year = {2022}, month = {SEP}, pages = {1070}, type = {Article}, abstract = {

Pt/W/SBA-15 catalysts (with Pt-loading = 0.5-4 wt\% and W-loading = 1 wt\%) prepared by the sequential impregnation method were evaluated for selective C-O cleavage of erythritol and glycerol in an aqueous medium. The Pt and W particles dispersed on SBA-15 approached close proximity at higher Pt loadings and afforded synergistic enhancement in C-O hydrogenolysis activity/selectivity. 1,4-Butanediol yields of 30.9\% (at 190 degrees C, 50 bar H-2 and 24 h) and 1,3-propanediol yields of 34.4\% (at 190 degrees C, 50 bar H-2 and 12 h of reaction) were obtained over these catalysts. Pt nanoparticles (facilitating dissociative H-2 adsorption and spillover) and W (present as acidic oligomeric WOx species; activating and coordinating the polyol via 1 degrees-OH group) worked in tandem for the selective hydrogenolysis of polyols yielding terminal diols of industrial demand.

}, keywords = {diol, Erythritol, Glycerol, Hydrodeoxygenation, Pt, SBA-15, W}, doi = {10.3390/catal12091070}, author = {Bhowmik, Susmita and Enjamuri, Nagasuresh and Marimuthu, Banu and Darbha, Srinivas} } @article {48156, title = {Influence of catalyst reduction temperature on autogenous glycerol hydrogenolysis over NiAl catalyst}, journal = {Asian Journal of Organic Chemistry}, volume = {11}, year = {2022}, month = {FEB}, pages = {e202100704}, type = {Article}, abstract = {

Autogenous glycerol hydrogenolysis to 1,2-propanediol by aqueous phase reforming (APR) was investigated over supported nickel catalysts. Effect of reduction temperature on physico-chemical properties of catalysts played a significant role in tuning conversion and product selectivities. The formation of nickel aluminate (NiAl2O4) spinel phase during catalyst reduction led to rearrangement of Ni species to obtain small and stable Ni particles. The catalyst activation temperature alters the extent of reduction of multivalent Ni species (Ni-0, Ni+2/+3) which facilitated glycerol dehydration and hydrogenation while suppressing C-C cleavage and thus avoiding undesirable side products. Additionally, presence of moderate Bronsted/Lewis acid ratio of the catalyst promoted higher 1,2-PDO selectivity. In-situ glycerol hydrogenolysis involves glycerol dehydration to acetol with simultaneous reforming to H-2 and CO2 and this hydrogen converts acetol to 1,2-PDO.

}, keywords = {APR, autogenous hydrogenolysis, Glycerol, Propanediols, reduction temperature, spinel}, issn = {2193-5807}, doi = {10.1002/ajoc.202100704}, author = {Pandya, Rajan and Mane, Rasika and Rode, Chandrashekhar} } @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 {48072, title = {Perception of glycerol carbonate as green chemical: synthesis and applications}, journal = {Catalysis Communications}, volume = {172}, year = {2022}, month = {DEC}, pages = {106542}, type = {Article}, abstract = {

Glycerol carbonate (GC) is a prominent component in industrial practice and has a remarkable potential for the sophisticated applications. While GC has come into prominence due to the perceived overflow of glycerol (GLY) as a coproduct of biodiesel industry, its contemporary and future downstream applications are driving tremendous interest in recent years. This review comprises strategies for glycerol carbonate synthesis, properties and its applications. The conversion of GLY to GC via transesterification has appeared in consensus to be the most promising route. A detailed explanation of the effect of the catalysts and operating conditions on the GC yield to provide an updated understanding of the process are summarized. Future directions for GC production through catalytic transesterification are also discussed.

}, keywords = {Biodiesel, biofuels, catalysis, Glycerol, Glycerol carbonate, green chemistry, transesterification}, issn = {1566-7367}, doi = {10.1016/j.catcom.2022.106542}, author = {Gade, Swapna M. and Saptal, Vitthal B. and Bhanage, Bhalchandra M.} }