01702nas a2200169 4500008004100000022001400041245012100055210006900176260000800245300001600253490000700269520105400276100002601330700002501356700002001381856013101401 2020 eng d a1144-054600aFabrication of mesoporous carbon supported Ni-Mo catalysts for the enhanced conversion of glucose to ethylene glycol0 aFabrication of mesoporous carbon supported NiMo catalysts for th cOCT a15958-159650 v443 a

Mesoporous carbon (MC)-supported Ni-Mo catalysts with varying amounts of Ni (x= 0, 3, 6 and 9 wt%) and Mo (y= 0, 10, 15 and 20 wt%) were prepared using the wet-impregnation method and characterized. Their catalytic activity in the selective conversion of aqueous glucose solution (15 wt%) to ethylene glycol (EG) in a batch reaction was investigated. A catalyst, with 3% Ni and 15% Mo on MC showed the highest activity and selectivity. The complete conversion of glucose with 63.2% yield of EG was obtained in a reaction conducted for 6 h at 200 degrees C and 40 bar hydrogen pressure. A synergistic enhancement in catalytic performance was found when both Ni and Mo were present in the catalyst composition. The dispersion of Mo enhanced in presence of Ni and a part of Mo was reduced from +6 to lower oxidation states (+5 and +4), which imparted the acidity of the catalyst. Ni facilitated the hydrogenation activity and acid sites on Mo led to the retro-aldol reaction forming higher amounts of EG. The catalyst was found to be reusable.

1 aKirali, Arun, Arunima1 aSreekantan, Sreejith1 aMarimuthu, Banu uhttp://library.ncl.res.in/content/fabrication-mesoporous-carbon-supported-ni-mo-catalysts-enhanced-conversion-glucose-ethylene02275nas a2200169 4500008004100000022001400041245011300055210006900168260000800237300001600245490000700261520163500268100002501903700002601928700002001954856013101974 2021 eng d a1144-054600aEnhanced one-pot selective conversion of cellulose to ethylene glycol over NaZSM-5 supported metal catalysts0 aEnhanced onepot selective conversion of cellulose to ethylene gl cOCT a19244-192540 v453 aThe mesopores interconnected with microporous NaZSM-5 was synthesised by sol-gel method. Reactions involving cellulose using different bimetallic and trimetallic combinations of nickel, aluminium, and tungsten metals supported on NaZSM-5 have been carried out. Different weight percentages (wt%) of Al, Ni, and W were loaded onto the NaZSM-5 support via a wet impregnation method. The prepared catalysts were characterized using PXRD, FE-SEM, HR-TEM, BET, and XPS studies to investigate the presence of mesopores, the textural properties, the metal loading, and the active oxidation states. The catalytic activities of the xAl-yNi-zW/NaZSM-5 (where x, y, and z are the wt% values of Al, Ni, and W, respectively) supported catalysts were studied during the one-pot conversion of cellulose into ethylene glycol at 220 degrees C and with a pressure of 70 bar H-2 (at the reaction temperature) in water (as a solvent). The 5%Al-8%Ni-25%W/NaZSM-5 catalyst exhibited the highest cellulose conversion of 100%, with an ethylene glycol yield as high as 89% (C mol%) under moderate reaction conditions being reported for the first time. Al3+ in the catalyst hydrolyzed cellulose, and W5+ species acted as acid centres that facilitated the retro-aldol condensation reaction and eventually led to an increased EG yield in the presence of Ni. The catalyst was moderately stable after four consecutive runs for 6 h at 220 degrees C and at a H-2 reaction pressure of 70 bar, though a 12 h reaction resulted in the highest EG yield. The high yields under moderate reaction conditions promise an energy-efficient and economically feasible process.1 aSreekantan, Sreejith1 aKirali, Arun, Arunima1 aMarimuthu, Banu uhttp://library.ncl.res.in/content/enhanced-one-pot-selective-conversion-cellulose-ethylene-glycol-over-nazsm-5-supported-metal01804nas a2200169 4500008004100000022001400041245010500055210006900160260000800229300001400237490000600251520118100257100002501438700002901463700002001492856012201512 2022 eng d a2398-490200aCatalytic conversion of sucrose to 1,2-propanediol over alumina-supported Ni-Mo bimetallic catalysts0 aCatalytic conversion of sucrose to 12propanediol over aluminasup cJUL a3681-36890 v63 a

Ni-Mo supported on gamma-Al2O3 catalysts were synthesized to test its catalytic activity towards sucrose to 1,2-propanediol (1,2-PDO) conversion. The catalyst system was characterized using various physicochemical methods, including XRD, BET, py-FTIR, XPS, FE-SEM, HR-TEM and ICP. The metal combination of 8%Ni-20%Mo/gamma-Al2O3 is found to be effective in producing a good yield of 1,2-propanediol (similar to 74%) under mild reaction conditions of 180 degrees C, 40 bar H-2 pressure and a run time of 4.5 h in a batch reaction. The activity of the active catalyst over various substrates such as cellulose, glucose, fructose and real-source biomass has also been investigated. XPS analysis of the active catalyst confirms the various oxidation states of the metals Ni and Mo in the active catalyst. The py-IR results show that the optimum Lewis to Bronsted acidic site ratio is responsible for the selective conversion of sucrose to 1,2-PDO. The presence of interparticle mesopores on gamma-Al2O3 helps in the high conversion of sucrose. Furthermore, the catalyst has been found reusable for four consecutive runs without any structural or morphological changes.

1 aSreekantan, Sreejith1 aKirali, Arun, Arunima Ba1 aMarimuthu, Banu uhttp://library.ncl.res.in/content/catalytic-conversion-sucrose-12-propanediol-over-alumina-supported-ni-mo-bimetallic01528nas a2200241 4500008004100000022001400041245012700055210006900182260000800251300001100259490000800270520068800278653002200966653000900988653001900997653002001016653001801036653002701054100002901081700002501110700002001135856013101155 2022 eng d a1566-736700aCe promoted Cu/?-Al2O3 catalysts for the enhanced selectivity of 1,2-pro-panediol from catalytic hydrogenolysis of glucose0 aCe promoted CuAl2O3 catalysts for the enhanced selectivity of 12 cMAY a1064470 v1653 a

Ce promoted Cu/gamma-Al2O3 catalysts were prepared with varying amounts of Cu (x = 0-10 wt%) and Ce (y = 0-15 wt%). The prepared catalysts were characterized and tested for the conversion of aqueous glucose (5 wt%) to 1,2propanediol in a batch reactor. 10%Ce-8%Cu/gamma-Al2O3 & nbsp;showed the complete conversion of glucose with 62.7% selectivity of 1,2-propanediol and total glycols (1,2-propanediol, ethylene glycol & 1,2-butanediol) of 81% at milder reaction conditions. Cu facilitated the hydrogenation activity and Ce loading optimize the acid/base sites of Cu/gamma-Al2O3 which obtain high selectivity of 1, 2-propanediol. Catalyst reusability is reported.

10a2-Propanediol

10a

110aCu-Ce catalyst10aethylene glycol10aGamma alumina10aGlucose hydrogenolysis1 aKirali, Arun, Arunima Ba1 aSreekantan, Sreejith1 aMarimuthu, Banu uhttp://library.ncl.res.in/content/ce-promoted-cu-al2o3-catalysts-enhanced-selectivity-12-pro-panediol-catalytic-hydrogenolysis01668nas a2200253 4500008004100000245009700041210006900138260000800207300000900215490000700224520088900231653000901120653001501129653001301144653002301157653000701180653001101187653000601198100002101204700002501225700002001250700002101270856012301291 2022 eng d00aC-O hydrogenolysis of C3-C4 polyols selectively to terminal diols over Pt/W/SBA-15 catalysts0 aCO hydrogenolysis of C3C4 polyols selectively to terminal diols  cSEP a10700 v123 a

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.

10adiol10aErythritol10aGlycerol10aHydrodeoxygenation10aPt10aSBA-1510aW1 aBhowmik, Susmita1 aEnjamuri, Nagasuresh1 aMarimuthu, Banu1 aDarbha, Srinivas uhttp://library.ncl.res.in/content/c-o-hydrogenolysis-c3-c4-polyols-selectively-terminal-diols-over-ptwsba-15-catalysts02073nas a2200277 4500008004100000022001400041245013100055210006900186260000800255300001100263490000800274520114500282653001801427653001701445653001301462653002301475653001901498653002201517100002101539700002501560700001901585700002101604700002001625700002101645856012901666 2022 eng d a2468-823100aInsights into active tungsten species on Pt/W/SBA-15 catalysts for selective hydrodeoxygenation of glycerol to 1,3-propanediol0 aInsights into active tungsten species on PtWSBA15 catalysts for  cOCT a1127040 v5313 a

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.

10a3-Propanediol10aActive sites10aGlycerol10aHydrodeoxygenation10aHydrogenolysis10aSupported Pt-WO x1 aBhowmik, Susmita1 aEnjamuri, Nagasuresh1 aSethia, Govind1 aAkula, Venugopal1 aMarimuthu, Banu1 aDarbha, Srinivas uhttp://library.ncl.res.in/content/insights-active-tungsten-species-ptwsba-15-catalysts-selective-hydrodeoxygenation-glycerol02030nas a2200217 4500008004100000022001400041245018000055210006900235260000900304490000700313520118900320653002901509653001601538653002001554653001301574100002501587700003001612700002601642700002001668856012401688 2023 eng d a1861-472800aInvestigation of the effect of zeolite supports and the role of W-species for one-pot catalytic conversion of cellulose to ethylene glycol: theoretical & experimental studies.0 aInvestigation of the effect of zeolite supports and the role of  cFEB 0 v183 a

Endeavors were made to study the influence of various zeolite (HY, NaY, NaZSM-5 and HZSM-5) supports with (Al)-Ni-W metal combination catalysts for the ethylene glycol (EG) production, selectively from cellulose. From the experimental results ZSM-5 (NaZSM-5/73.3% & HZSM-5/67.7%) support is superior over HY & NaY support in selective EG production from cellulose. It was understood that W- species with oxygen vacancies (WO3-x, XPS analysis) plays an important role in producing the glycolaldehyde (GA) intermediate (via C-C cleavages), which on hydrogenation over Ni- sites selectively produce EG. Further, the studies based on the Density Functional Theory (DFT) were conducted to substantiate the involvement of the WO3-x species in the reaction. The adsorption energies and structural changes establish that the C-2-C-3 bond of the glucose elongates and thereby activates on adsorbing to WO3-x sites supporting the formation of GA. Activation of GA on Ni- sites is distinguished by an increase of 0.1 angstrom in C=O bond length, which facilitates the hydrogenation of C=O resulting in EG. The reaction pathway is explained through an analysis of CDD and DOS.

10aCellulose hydrogenolysis10aDFT studies10aethylene glycol10azeolites1 aSreekantan, Sreejith1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja1 aMarimuthu, Banu uhttp://library.ncl.res.in/content/investigation-effect-zeolite-supports-and-role-w-species-one-pot-catalytic-conversion02225nas a2200253 4500008004100000245015100041210006900192260000900261300001600270490000600286520128100292653001201573653001801585653002201603653001901625653003601644653002801680100002701708700003001735700002901765700002001794700003101814856012601845 2023 eng d00aLigand-free one-pot synthesis of Ru/W18O49 self-assembled hierarchical coral-like nanostructures for selective conversion of glucose into glycols0 aLigandfree onepot synthesis of RuW18O49 selfassembled hierarchic cDEC  a22635-226420 v63 a

In this study, we report a simple inorganic route for the synthesis of Ru/W18O49 self-assembled coral-like nanostructures, with the following advantages: It is one step and requires no surfactant or stabilizing agent; Ru loading is easily tuned, and the as-synthesized nanomaterials can be used as a catalyst without any further processing. The preliminary investigations of the catalytic performance of these as-synthesized Ru/W18O49 nanomaterials appear quite promising for converting glucose to glycols. The total glycol selectivity of 82.6% with 100% conversion of glucose was obtained over 0.03 wt % Ru loading on tungsten nanostructures, which turns out to be the lowest Ru loading% on support reported to date to achieve the highest total glycol selectivity among the previously reported catalyst based on Ru-nano/composite materials. Additionally, preliminary results show that the concentration of Ru on W18O49 significantly affects the selectivity of the glycol production. Thus, our methodology will open up a wide range of opportunities regarding the choice of metals, stoichiometric/nonstoichiometric WOx (x=1-3) as support, and the viability of further catalytic manipulations. A probable catalytic mechanism for this catalytic process is also proposed.

10aglycols10aNanostructure10aOne-pot synthesis10aruthenium (Ru)10aselective conversion of glucose10atungsten oxide (W18O49)1 aPatil, Manoj, Krishnat1 aGaikwad, Supriya, Hanmant1 aKirali, Arun, Arunima Ba1 aMarimuthu, Banu1 aMukherjee, Shatabdi, Porel uhttp://library.ncl.res.in/content/ligand-free-one-pot-synthesis-ruw18o49-self-assembled-hierarchical-coral-nanostructures01903nas a2200277 4500008004100000022001400041245011700055210006900172260000900241300001100250490000800261520097300269653002301242653001501265653001901280653001201299653002901311653001801340653003901358100002101397700002101418700001901439700002001458700002101478856012601499 2023 eng d a0926-860X00aPromoting effect of titanium on C-O hydrogenolysis of erythritol to 1,4-butanediol over Pt/W/Ti-SBA-15 catalysts0 aPromoting effect of titanium on CO hydrogenolysis of erythritol  cSEP  a1194250 v6663 a

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).

10aBiomass conversion10aErythritol10aHydrogenolysis10aPolyols10aPromotional effect of Ti10aTerminal diol10aTi-SBA-15-supported Pt/W catalysts1 aBhowmik, Susmita1 aAkula, Venugopal1 aSethia, Govind1 aMarimuthu, Banu1 aDarbha, Srinivas uhttp://library.ncl.res.in/content/promoting-effect-titanium-c-o-hydrogenolysis-erythritol-14-butanediol-over-ptwti-sba-1501952nas a2200181 4500008004100000022001400041245012100055210006900176260000800245300001600253490000700269520127400276100002201550700002201572700002501594700002001619856013101639 2023 eng d a0887-062400aReview on catalytic hydrogenation of biomass-derived furfural to furfuryl alcohol: recent advances and future trends0 aReview on catalytic hydrogenation of biomassderived furfural to  cJUL a11475-114960 v373 a

Biomass is one of the highly abundantrenewable resourcesavailablethat can be converted into several high-value-added products, includingchemicals, biofuels, and advanced materials. To achieve net-zero emissionsand improve biomass application, researchers around the world haverecently focused on expanding biomass processing techniques to value-addedproducts with the eventual goal of industrializing some of the products.In this review, we summarize lignocellulosic biomass derived furfural(FA) and its subsequent hydrogenation to furfuryl alcohol (FAL). Thiswork reviews the various types of hydrogenation catalysts and theirutility in the production of value-added products from FA. There willbe an increase in the demand for selective catalysts and process technologies,as well as an increase in the challenges during valorization, as theusage of biomass to achieve carbon neutrality increases. The reviewaims to provide a concise overview of the advancements in this fieldand the potential for sustainable FAL production. In this paper, wepresent a simple strategy for selecting catalyst systems and associatedprocess parameters that facilitate the highly efficient and selectivevalorization of FA to chemicals or fuel (bioadditives) for industrialuse.

1 aRacha, Arundhathi1 aSamanta, Chanchal1 aSreekantan, Sreejith1 aMarimuthu, Banu uhttp://library.ncl.res.in/content/review-catalytic-hydrogenation-biomass-derived-furfural-furfuryl-alcohol-recent-advances-and02106nas a2200193 4500008004100000022001400041245011800055210006900173260000900242300001400251490000700265520137900272100002901651700002601680700003301706700002201739700002001761856013101781 2024 eng d a0887-062400aEnhanced catalytic conversion of disaccharides to propylene glycol using metal-supported graphitic carbon nitride0 aEnhanced catalytic conversion of disaccharides to propylene glyc cMAR  a7005-70170 v383 a

Propylene glycol (or) 1,2-propanediol (1,2-PD) is an important polyol widely used for pharmaceuticals, polyester resins, paints, cosmetics, antifreeze, etc. Sucrose has emerged as a promising feedstock to produce 1,2-PD, as indicated by recent research findings. Graphitic carbon nitride (g-C3N4/gCN) was synthesized by using different crucibles. Ni-Mo was loaded on different g-C3N4 supports via the wetness impregnation method for sucrose hydrogenolysis. Effects of different g-C3N4 supports were studied. Catalysts with varying Ni (x = 0-8 wt %) and Mo (y = 0-15 wt %) contents were characterized using XRD, BET, XPS, FE-SEM, Py-FTIR, HR-TEM, TPD (CO2)and Raman spectroscopy. An attempt was made on sucrose conversion into 1,2-PD using a Ni-Mo/g-C3N4 catalyst. The catalyst containing 8% Ni and 10% Mo on Gr-gCN exhibited the best performance, achieving complete sucrose conversion with a 76% yield of 1,2-PD under mild reaction conditions. The presence of highly dispersed nanoparticles and the nature of graphitic carbon nitride help improve the reactions' yield by allowing reactions at lower temperatures, reducing the occurrence of side reactions, and increasing recycling rates. A straightforward approach to material preparation, coupled with the exceptional dispersion of metal nanoparticles, paves the way for a novel platform for biomass conversion.

1 aKirali, Arun, Arunima Ba1 aNarayanan, Hariprasad1 aViswanathan, Balasubramanian1 aYadav, Parmeshwar1 aMarimuthu, Banu uhttp://library.ncl.res.in/content/enhanced-catalytic-conversion-disaccharides-propylene-glycol-using-metal-supported-graphitic