@article {46684, title = {Fabrication of mesoporous carbon supported Ni-Mo catalysts for the enhanced conversion of glucose to ethylene glycol}, journal = {New Journal of Chemistry}, volume = {44}, year = {2020}, month = {OCT}, pages = {15958-15965}, type = {Article}, abstract = {

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.

}, issn = {1144-0546}, doi = {10.1039/d0nj03196h}, author = {Kirali, Arun Arunima and Sreekantan, Sreejith and Marimuthu, Banu} } @article {47628, title = {Enhanced one-pot selective conversion of cellulose to ethylene glycol over NaZSM-5 supported metal catalysts}, journal = {New Journal of Chemistry}, volume = {45}, year = {2021}, month = {OCT}, pages = {19244-19254}, type = {Article}, abstract = {The 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.}, issn = {1144-0546}, doi = {10.1039/d1nj03257g}, author = {Sreekantan, Sreejith and Kirali, Arun Arunima and Marimuthu, Banu} } @article {48023, title = {Catalytic conversion of sucrose to 1,2-propanediol over alumina-supported Ni-Mo bimetallic catalysts}, journal = {Sustainable Energy \& Fuels}, volume = {6}, year = {2022}, month = {JUL}, pages = {3681-3689}, type = {Article}, abstract = {

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.

}, issn = {2398-4902}, doi = {10.1039/d2se00610c}, author = {Sreekantan, Sreejith and Kirali, Arun Arunima Balachandran and Marimuthu, Banu} } @article {48038, title = {Ce promoted Cu/?-Al2O3 catalysts for the enhanced selectivity of 1,2-pro-panediol from catalytic hydrogenolysis of glucose}, journal = {Catalysis Communications}, volume = {165}, year = {2022}, month = {MAY}, pages = {106447}, type = {Article}, abstract = {

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.

}, keywords = {2-Propanediol

,

1, Cu-Ce catalyst, ethylene glycol, Gamma alumina, Glucose hydrogenolysis}, issn = {1566-7367}, doi = {10.1016/j.catcom.2022.106447}, author = {Kirali, Arun Arunima Balachandran and Sreekantan, Sreejith and Marimuthu, Banu} } @article {48259, title = {Investigation 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.}, journal = {Chemistry-An Asian Journal}, volume = {18}, year = {2023}, month = {FEB }, type = {Article}, abstract = {

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.

}, keywords = {Cellulose hydrogenolysis, DFT studies, ethylene glycol, zeolites}, issn = {1861-4728}, doi = {10.1002/asia.202201202}, author = {Sreekantan, Sreejith and Singh, Chandrodai Pratap and Krishnamurty, Sailaja and Marimuthu, Banu} } @article {48751, title = {Review on catalytic hydrogenation of biomass-derived furfural to furfuryl alcohol: recent advances and future trends}, journal = {Energy \& Fuels}, volume = {37}, year = {2023}, month = {JUL}, pages = {11475-11496}, type = {Review}, abstract = {

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.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.3c01174}, author = {Racha, Arundhathi and Samanta, Chanchal and Sreekantan, Sreejith and Marimuthu, Banu} }