I have completed my Ph.D. from CSIR-National Chemical Laboratory, India in November 2016. My thesis work was focused on the hydrolysis and dehydration reactions of saccharides using Brønsted acidic ionic liquids (BAILs). Presently, I am working at National Taiwan University, Taiwan as a postdoctoral researcher. Here the current focus of my research is complete conversion (lignin, hemicellulose, and cellulose) of lignocellulosic biomass into chemicals in the one-pot fashion.
In recent years, conjugated microporous polymers (CMPs) have become important precursors for envi... more In recent years, conjugated microporous polymers (CMPs) have become important precursors for environmental and energy applications, compared with inorganic electrode materials, due to their ease of preparation, facile charge storage process, π-conjugated structures, relatively high thermal and chemical stability, abundance in nature, and high surface areas. Therefore, in this study, we designed and prepared new benzobisthiadiazole (BBT)-linked CMPs (BBT–CMPs) using a simple Sonogashira couplings reaction by reaction of 4,8-dibromobenzo(1,2-c;4,5-c′)bis(1,2,5)thiadiazole (BBT–Br2) with ethynyl derivatives of triphenylamine (TPA-T), pyrene (Py-T), and tetraphenylethene (TPE-T), respectively, to afford TPA–BBT–CMP, Py–BBT–CMP, and TPE–BBT–CMP. The chemical structure and properties of BBT–CMPs such as surface areas, pore size, surface morphologies, and thermal stability using different measurements were discussed in detail. Among the studied BBT–CMPs, we revealed that TPE–BBT–CMP displa...
We report a one-step facile 1,2,6-hexanetriol synthesis from HMF under milder conditions using an... more We report a one-step facile 1,2,6-hexanetriol synthesis from HMF under milder conditions using an Pt@Al2O3 catalyst.
We report an acid-free effective furfural-to-MA conversion system using a nitrogen-doped carbon c... more We report an acid-free effective furfural-to-MA conversion system using a nitrogen-doped carbon catalyst and H2O2 oxidant.
Over the past decade, the development in the valorization of biomass technologies keeps increasin... more Over the past decade, the development in the valorization of biomass technologies keeps increasing because the biomass utilization for manufacturing fine chemicals and fuels has diverse advantages over fossil feedstock. The review focuses on the utilization of metal–organic framework-derived (MOF-derived) materials as effective solid catalysts for the valorization of biomass into platform chemicals. MOFs compose of abundant organic ligands and metal cluster, and additional functional groups, could be modified on ligands (or metal clusters) serving as active sites. On the other hand, MOFs could also be converted into porous carbons or metal oxide composites by calcination at nitrogen or air, respectively, for catalytic reactions. These MOF-derived catalysts feature advantages like high specific surface area, porosity, and active sites from mother MOFs. More importantly, stronger interactions between guests (i.e., metal or alloy NPs) and hosts (i.e., MOF-derived carbons or metal oxides) make these catalysts...
Journal of visualized experiments : JoVE, Jun 1, 2018
Recently, ionic liquids (ILs) are used for biomass valorization into valuable chemicals because o... more Recently, ionic liquids (ILs) are used for biomass valorization into valuable chemicals because of their remarkable properties such as thermal stability, lower vapor pressure, non-flammability, higher heat capacity, and tunable solubility and acidity. Here, we demonstrate a method for the synthesis of C5 sugars (xylose and arabinose) from the pentosan present in jute biomass in a one-pot process by utilizing a catalytic amount of Brønsted acidic 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate IL. The acidic IL is synthesized in the lab and characterized using NMR spectroscopic techniques for understanding its purity. The various properties of BAIL are measured such as acid strength, thermal and hydrothermal stability, which showed that the catalyst is stable at a higher temperature (250 °C) and possesses very high acid strength (Ho 1.57). The acidic IL converts over 90% of pentosan into sugars and furfural. Hence, the presenting method in this study can also be employed for ...
The conversion of raw biomass into C5-sugars and furfural was demonstrated with the one-pot metho... more The conversion of raw biomass into C5-sugars and furfural was demonstrated with the one-pot method using Brønsted acidic ionic liquids (BAILs) without any mineral acids or metal halides. Various BAILs were synthesized and characterized using NMR, FT-IR, TGA, and CHNS microanalysis and were used as the catalyst for raw biomass conversion. The remarkably high yield (i.e. 88%) of C5 sugars from bagasse can be obtained using 1-methyl-3(3-sulfopropyl)-imidazolium hydrogen sulfate ([C3SO3HMIM][HSO4]) BAIL catalyst in a water medium. Similarly, the [C3SO3HMIM][HSO4] BAIL also converts the bagasse into furfural with very high yield (73%) in one-pot method using a water/toluene biphasic solvent system.
Using recyclable and green ionic liquids in catalytic amounts, renewable sugars are dehydrated in... more Using recyclable and green ionic liquids in catalytic amounts, renewable sugars are dehydrated into furans with high yields.
Brönsted acidic ionic liquids were synthesized, characterized and used in the conversion of assor... more Brönsted acidic ionic liquids were synthesized, characterized and used in the conversion of assorted hemicelluloses to yield C5 sugars in 87% yield.
Efficient liquid-phase hydrogenolysis of benzyl phenyl ether using Ni/CB in an EtOH/H2O co-solven... more Efficient liquid-phase hydrogenolysis of benzyl phenyl ether using Ni/CB in an EtOH/H2O co-solvent system.
New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in thi... more New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on 1H and 13C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and salicylaldehyde and the subsequent reaction with CH2O. Thermal properties of the product formed through ring-opening polymerization (ROP) of Por-BZ were measured using DSC, TGA and FTIR spectroscopy. Because of the rigid structure of the porphyrin moiety appended to the benzoxazine unit, the temperature required for ROP (314 °C) was higher than the typical Pa-type benzoxazine monomer (ca. 260 °C); furthermore, poly(Por-BZ) possessed a high thermal decomposition temperature (Td10 = 478 °C) and char yield (66 wt%) after thermal polymerization at 240 °C. An investigation of the thermal and luminescence properties of metal–porphyrin complexes revealed that the insertion of Ni and Zn ions decreased the thermal ROP temperatures of the Por-...
Biomass valorization to building block chemicals in food and pharmaceutical industries has tremen... more Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K2CO3 as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al2O3 or SiO2 as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K2CO3 extracted lignin catalyzed by Cu-Fe/SiO2 catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al2O3 catalyst was lower (49.52 wt%) compar...
Lignocellulosic biomass is an abundantly available byproduct obtained after the separation of edi... more Lignocellulosic biomass is an abundantly available byproduct obtained after the separation of edible parts from various crops that is a potential source to produce renewable and sustainable biofuels, chemicals, materials, and polymers, without altering the greenhouse gas emissions relative to fossil feedstocks. Valorisation of lignocellulosic biomass focuses on polysaccharides conversion to value-added chemicals and polymers. However, lignin rich of high carbon burned to generate energy and chemicals. For the development of an effective lignocellulosic biomass conversion technology to biofuels and chemicals, biomass composition analysis and their properties need to be characterized prior to biomass reactions, including polysaccharide hydrolysis and lignin depolymerization. In this work, we have determined alpha-, beta- and gamma- cellulose, pentosan, lignin, and silica percentages of wheat straw (WS) and two bagasse (BG I and II) samples. The impact of different types of biomass sam...
Sewage sludge (SS) is an organic biomass from wastewater treatment plants, but the use of SS to p... more Sewage sludge (SS) is an organic biomass from wastewater treatment plants, but the use of SS to produce bio-based chemicals under acid-catalyzed hydrolysis (ACH) processes is not well investigated. In this study, ACH processes were performed at 120, 150, and 180 °C using sulfuric acid (H2SO4) with concentrations of 0–0.5 M within a reaction time of 90–180 min to produce bio-based chemicals from SS. The results showed that the reaction temperature, reaction time, and concentrations of H2SO4 affected the yields of sugars, levulinic acid (LA), and 5-hydroxymethylfurfural (HMF). The highest xylose and glucose yields were 7.69 mol% and 5.22 mol% at 120 °C with 0.5 M H2SO4 during the 180 min of reaction time, respectively. Besides, under the ACH process at 180 °C and 180 min, the yield of LA reached a maximum value of 0.48 mol% at 0.5 M H2SO4, and the highest yield of HMF was 1.66 mol% at 0.1 M H2SO4. The data obtained also indicated that the ACH process led to an increase in soluble chem...
Synthesis of biomass-derived N-doped porous carbon for energy storage and catalysis applications ... more Synthesis of biomass-derived N-doped porous carbon for energy storage and catalysis applications is a sustainable and environmentally friendly approach.
In recent years, conjugated microporous polymers (CMPs) have become important precursors for envi... more In recent years, conjugated microporous polymers (CMPs) have become important precursors for environmental and energy applications, compared with inorganic electrode materials, due to their ease of preparation, facile charge storage process, π-conjugated structures, relatively high thermal and chemical stability, abundance in nature, and high surface areas. Therefore, in this study, we designed and prepared new benzobisthiadiazole (BBT)-linked CMPs (BBT–CMPs) using a simple Sonogashira couplings reaction by reaction of 4,8-dibromobenzo(1,2-c;4,5-c′)bis(1,2,5)thiadiazole (BBT–Br2) with ethynyl derivatives of triphenylamine (TPA-T), pyrene (Py-T), and tetraphenylethene (TPE-T), respectively, to afford TPA–BBT–CMP, Py–BBT–CMP, and TPE–BBT–CMP. The chemical structure and properties of BBT–CMPs such as surface areas, pore size, surface morphologies, and thermal stability using different measurements were discussed in detail. Among the studied BBT–CMPs, we revealed that TPE–BBT–CMP displa...
We report a one-step facile 1,2,6-hexanetriol synthesis from HMF under milder conditions using an... more We report a one-step facile 1,2,6-hexanetriol synthesis from HMF under milder conditions using an Pt@Al2O3 catalyst.
We report an acid-free effective furfural-to-MA conversion system using a nitrogen-doped carbon c... more We report an acid-free effective furfural-to-MA conversion system using a nitrogen-doped carbon catalyst and H2O2 oxidant.
Over the past decade, the development in the valorization of biomass technologies keeps increasin... more Over the past decade, the development in the valorization of biomass technologies keeps increasing because the biomass utilization for manufacturing fine chemicals and fuels has diverse advantages over fossil feedstock. The review focuses on the utilization of metal–organic framework-derived (MOF-derived) materials as effective solid catalysts for the valorization of biomass into platform chemicals. MOFs compose of abundant organic ligands and metal cluster, and additional functional groups, could be modified on ligands (or metal clusters) serving as active sites. On the other hand, MOFs could also be converted into porous carbons or metal oxide composites by calcination at nitrogen or air, respectively, for catalytic reactions. These MOF-derived catalysts feature advantages like high specific surface area, porosity, and active sites from mother MOFs. More importantly, stronger interactions between guests (i.e., metal or alloy NPs) and hosts (i.e., MOF-derived carbons or metal oxides) make these catalysts...
Journal of visualized experiments : JoVE, Jun 1, 2018
Recently, ionic liquids (ILs) are used for biomass valorization into valuable chemicals because o... more Recently, ionic liquids (ILs) are used for biomass valorization into valuable chemicals because of their remarkable properties such as thermal stability, lower vapor pressure, non-flammability, higher heat capacity, and tunable solubility and acidity. Here, we demonstrate a method for the synthesis of C5 sugars (xylose and arabinose) from the pentosan present in jute biomass in a one-pot process by utilizing a catalytic amount of Brønsted acidic 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate IL. The acidic IL is synthesized in the lab and characterized using NMR spectroscopic techniques for understanding its purity. The various properties of BAIL are measured such as acid strength, thermal and hydrothermal stability, which showed that the catalyst is stable at a higher temperature (250 °C) and possesses very high acid strength (Ho 1.57). The acidic IL converts over 90% of pentosan into sugars and furfural. Hence, the presenting method in this study can also be employed for ...
The conversion of raw biomass into C5-sugars and furfural was demonstrated with the one-pot metho... more The conversion of raw biomass into C5-sugars and furfural was demonstrated with the one-pot method using Brønsted acidic ionic liquids (BAILs) without any mineral acids or metal halides. Various BAILs were synthesized and characterized using NMR, FT-IR, TGA, and CHNS microanalysis and were used as the catalyst for raw biomass conversion. The remarkably high yield (i.e. 88%) of C5 sugars from bagasse can be obtained using 1-methyl-3(3-sulfopropyl)-imidazolium hydrogen sulfate ([C3SO3HMIM][HSO4]) BAIL catalyst in a water medium. Similarly, the [C3SO3HMIM][HSO4] BAIL also converts the bagasse into furfural with very high yield (73%) in one-pot method using a water/toluene biphasic solvent system.
Using recyclable and green ionic liquids in catalytic amounts, renewable sugars are dehydrated in... more Using recyclable and green ionic liquids in catalytic amounts, renewable sugars are dehydrated into furans with high yields.
Brönsted acidic ionic liquids were synthesized, characterized and used in the conversion of assor... more Brönsted acidic ionic liquids were synthesized, characterized and used in the conversion of assorted hemicelluloses to yield C5 sugars in 87% yield.
Efficient liquid-phase hydrogenolysis of benzyl phenyl ether using Ni/CB in an EtOH/H2O co-solven... more Efficient liquid-phase hydrogenolysis of benzyl phenyl ether using Ni/CB in an EtOH/H2O co-solvent system.
New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in thi... more New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on 1H and 13C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and salicylaldehyde and the subsequent reaction with CH2O. Thermal properties of the product formed through ring-opening polymerization (ROP) of Por-BZ were measured using DSC, TGA and FTIR spectroscopy. Because of the rigid structure of the porphyrin moiety appended to the benzoxazine unit, the temperature required for ROP (314 °C) was higher than the typical Pa-type benzoxazine monomer (ca. 260 °C); furthermore, poly(Por-BZ) possessed a high thermal decomposition temperature (Td10 = 478 °C) and char yield (66 wt%) after thermal polymerization at 240 °C. An investigation of the thermal and luminescence properties of metal–porphyrin complexes revealed that the insertion of Ni and Zn ions decreased the thermal ROP temperatures of the Por-...
Biomass valorization to building block chemicals in food and pharmaceutical industries has tremen... more Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K2CO3 as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al2O3 or SiO2 as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K2CO3 extracted lignin catalyzed by Cu-Fe/SiO2 catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al2O3 catalyst was lower (49.52 wt%) compar...
Lignocellulosic biomass is an abundantly available byproduct obtained after the separation of edi... more Lignocellulosic biomass is an abundantly available byproduct obtained after the separation of edible parts from various crops that is a potential source to produce renewable and sustainable biofuels, chemicals, materials, and polymers, without altering the greenhouse gas emissions relative to fossil feedstocks. Valorisation of lignocellulosic biomass focuses on polysaccharides conversion to value-added chemicals and polymers. However, lignin rich of high carbon burned to generate energy and chemicals. For the development of an effective lignocellulosic biomass conversion technology to biofuels and chemicals, biomass composition analysis and their properties need to be characterized prior to biomass reactions, including polysaccharide hydrolysis and lignin depolymerization. In this work, we have determined alpha-, beta- and gamma- cellulose, pentosan, lignin, and silica percentages of wheat straw (WS) and two bagasse (BG I and II) samples. The impact of different types of biomass sam...
Sewage sludge (SS) is an organic biomass from wastewater treatment plants, but the use of SS to p... more Sewage sludge (SS) is an organic biomass from wastewater treatment plants, but the use of SS to produce bio-based chemicals under acid-catalyzed hydrolysis (ACH) processes is not well investigated. In this study, ACH processes were performed at 120, 150, and 180 °C using sulfuric acid (H2SO4) with concentrations of 0–0.5 M within a reaction time of 90–180 min to produce bio-based chemicals from SS. The results showed that the reaction temperature, reaction time, and concentrations of H2SO4 affected the yields of sugars, levulinic acid (LA), and 5-hydroxymethylfurfural (HMF). The highest xylose and glucose yields were 7.69 mol% and 5.22 mol% at 120 °C with 0.5 M H2SO4 during the 180 min of reaction time, respectively. Besides, under the ACH process at 180 °C and 180 min, the yield of LA reached a maximum value of 0.48 mol% at 0.5 M H2SO4, and the highest yield of HMF was 1.66 mol% at 0.1 M H2SO4. The data obtained also indicated that the ACH process led to an increase in soluble chem...
Synthesis of biomass-derived N-doped porous carbon for energy storage and catalysis applications ... more Synthesis of biomass-derived N-doped porous carbon for energy storage and catalysis applications is a sustainable and environmentally friendly approach.
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Papers by Babasaheb Matsagar