@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 {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 {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 {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 {48959, title = {Ligand-free one-pot synthesis of Ru/W18O49 self-assembled hierarchical coral-like nanostructures for selective conversion of glucose into glycols}, journal = {ACS Applied Nano Materials }, volume = {6}, year = {2023}, month = {DEC }, pages = {22635-22642}, type = {Journal Article}, abstract = {

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.

}, keywords = {glycols, Nanostructure, One-pot synthesis, ruthenium (Ru), selective conversion of glucose, tungsten oxide (W18O49)}, doi = {10.1021/acsanm.3c04200}, author = {Patil, Manoj Krishnat and Gaikwad, Supriya Hanmant and Kirali, Arun Arunima Balachandran and Marimuthu, Banu and Mukherjee, Shatabdi Porel} } @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} } @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} } @article {49121, title = {Enhanced catalytic conversion of disaccharides to propylene glycol using metal-supported graphitic carbon nitride}, journal = {Energy and Fuels}, volume = {38}, year = {2024}, month = {MAR }, pages = {7005-7017}, type = {Article}, abstract = {

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{\textquoteright} 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.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.3c05087}, author = {Kirali, Arun Arunima Balachandran and Narayanan, Hariprasad and Viswanathan, Balasubramanian and Yadav, Parmeshwar and Marimuthu, Banu} } @article {49574, title = {Heteropolyacid-assisted efficient one-pot synthesis of ethyl levulinate from biorenewable feedstocks}, journal = {Energy \& Fuels}, volume = {39}, year = {2025}, month = {JAN }, pages = {3131-3139}, type = {Article}, abstract = {

Amid rising environmental concerns over fossil fuel dependence, biomass-derived alkyl levulinates, particularly ethyl levulinate (EL), have gained prominence due to their versatility in applications ranging from biofuels to lubricants and green solvents. This study presents an efficient, one-pot catalytic conversion of various carbohydrates (glucose, fructose, and sucrose) into EL using a tailored Keggin-type heteropolyacid catalyst with a vanadium-to-tungsten atom ratio of 1:11. Vanadium substitution imparts higher acidity and redox properties to the catalyst, which is reflected in the catalytic performance. The catalyst demonstrated outstanding performance, achieving high EL yields of 98 +/- 1\% from sucrose, 93 +/- 2\% from fructose, and 82 +/- 2\% from glucose under batch processing conditions (180 degrees C, absolute ethanol solvent, 27 wt \% catalyst, 2 h). The high yield of EL may be assigned to the presence of both Br \& oslash;nsted and Lewis acid sites, which promotes key reactions like isomerization and ethanolysis. Moreover, a significant EL yield of 85 +/- 2\% was obtained from cellulose feedstock, which showcases the efficiency of this catalyst. The use of absolute ethanol as solvent enhanced esterification prospects, preventing hydrolysis and promoting higher EL yields, while the presence of water as cosolvent favored the formation of levulinic acid. These findings demonstrate the potential of vanadium-substituted heteropolyacid catalysts for efficient biomass valorization, offering a sustainable pathway for the large-scale production of EL from renewable feedstocks.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.4c05189}, author = {Jagannivasan, Gopika and Haridas, Suja and Marimuthu, Banu and Mukundan, Swathi} } @article {49503, title = {Upcycling solid wastes: using abundant egg shell wastes for the greener production of lactic acid under ambient conditions}, journal = {Journal of Environmental Chemical Engineering}, volume = {13}, year = {2025}, month = {APR}, pages = {115603}, type = {Article}, abstract = {

In this study, we explore a sustainable approach to repurposing eggshell waste as a catalyst for the conversion of biomass-derived sucrose, sugar syrup, xylan, and cellulose into lactic acid, a chemical in high demand. Currently, lactic acid is industrially produced using lactic acid bacteria (LAB), which require precise pH control and temperature maintenance, complicating their application. Our work demonstrates a one-pot synthesis of lactic acid using calcined eggshells in an aqueous medium via simple thermal treatment. Comprehensive characterization of the eggshell catalyst was carried out using techniques such as XRD, BET, FT-IR, FE-SEM, XPS, and TGA, revealing that calcination above 700 degrees C transformed the eggshell into CaO, drastically altering its morphology and enhancing its basicity. At 200 degrees C, using 70 wt\% of catalyst for 1 h, we achieved a remarkable 92 C-mol\% lactic acid yield with excellent carbon balance. The increased basicity played a key role in selectively driving lactic acid production. Our approach offers a green, sustainable solution with significant implications for future research in valorizing waste materials and advancing bio-based chemical production.

}, keywords = {Biomass, Lactic acid, Sustainability, Waste egg shell, Waste-to- chemicals}, issn = {2213-2929}, doi = {10.1016/j.jece.2025.115603}, author = {Sreekantan, Sreejith and Sudhakaran, Amitha Kalappurakkal and Marimuthu, Banu} }