ROSHITH KURUPPATHPARAMBIL ROSHAN
@vssc.gov.in
SCIENTIST/ENGINEER, POLYMERS & SPECIAL CHEMICALS DIVISION
VIKRAM SARABHAI SPACE CENTRE, INDIAN SPACE RESEARCH ORGANIZATION (ISRO
RESEARCH INTERESTS
Polymeric systems for space applications, high temperature performing composites, metal organic frameworks, green chemistry, catalysis, ionic liquids, CO2 conversion to fine chemicals.
Scopus Publications
Scholar Citations
Scholar h-index
Scholar i10-index
Scopus Publications
Hye-Min Jeong, Roshith Roshan, Robin Babu, Hyeon-Jun Kim, and Dae-Won Park
Springer Science and Business Media LLC
Two highly stable isoreticular metal-organic frameworks comprising chains of zirconium coordinated with linkers of 1,4-H2BDC (1,4-benzenedicarboxylic acid) and 4,4′-H2BPDC (4,4′-biphenyldicarboxylic acid), denoted as MIL-140A and MIL-140C, were synthesized. The catalytic activity of these frameworks was studied for the coupling reaction of CO2 and epoxides to produce cyclic carbonates under solvent-free conditions. Excellent activity was observed for both catalysts: they yielded high epoxide conversion with >99% selectivity toward the cyclic carbonate, and were fully reusable even after four cycles without any considerable loss of initial activity. The enhancement in the catalytic activity was explained based on acidity/basicity studies. The influence of various reaction parameters such as catalyst amount, reaction time, reaction temperature, and CO2 pressure was also investigated. Reaction mechanism was proposed on the basis of experimental evidence and our previous DFT (density functional theory) studies.
Hyeongseok Ryu, Roshith Roshan, Moon-Il Kim, Dong-Woo Kim, Manickam Selvaraj, and Dae-Won Park
Springer Science and Business Media LLC
Zeolitic imidazolate framework ZIF-23 was prepared and used as catalyst for the solventless synthesis of cyclic carbonate from CO2 and propylene oxide with or without TBAB co-catalyst. ZIF-23 catalysts were prepared by a solvothermal or microwave method and they were characterized by various physicochemical techniques such as XRD, FT-IR, BET, TGA, and FE-SEM. The effects of reaction parameters such as temperature, reaction time, CO2 pressure, and co-catalyst on the reactivity of catalyst were investigated. ZIF-23 was recyclable up to four times without any considerable loss of its initial activity. Reaction mechanism containing the role of ZIF-23 with TBAB co-catalyst was also proposed.
Robin Babu, Roshith Roshan, Yeongrok Gim, Yun Hee Jang, Jintu Francis Kurisingal, Dong Woo Kim, and Dae-Won Park
Royal Society of Chemistry (RSC)
The correlation between dimensionality and active sites on deciding the catalytic performance of an MOF catalyst in CO2–epoxide cycloaddition reactions has been studied.
Han-Ung Kim, Robin Babu, Roshith Roshan, and Dae-Won Park
Elsevier BV
Abstract Two types of metal azolate frameworks (MAFs) with uncoordinated and coordinated nitrogen atoms composed of zinc coordinated with 3-amino-1,2,4-triazole and 3,5-dimethyl-1,2,4-triazole linkers denoted as MAF-66 and MAF-X5, respectively have been synthesized and characterized using various physicochemical techniques. The uncoordinated N donors present in the MAFs show high adsorption affinity for carbon dioxide. The synthesized MAFs showed promising catalytic activity towards the cycloaddition of carbon dioxide and epoxides under solvent-free conditions with excellent selectivity towards the desired five-membered cyclic carbonates. The importance of uncoordinated N donors and amine groups in the effective catalysis of the cycloaddition of CO 2 and epoxides was investigated. Both catalysts were separable by simple filtration and reusable without any considerable loss in the initial activity. Various reaction parameters including temperature, reaction time, and CO 2 pressure were studied. A possible reaction mechanism explaining the role of amine groups in the cycloaddition reaction was proposed based on literature and experimental inferences.
Robin Babu, Roshith Roshan, Amal Cherian Kathalikkattil, Dong Woo Kim, and Dae-Won Park
American Chemical Society (ACS)
A dual-porous, three-dimensional, metal-organic framework [Zn4O(2,6-NDC)(BTB)4/3] (MOF-205, BET = 4200 m2/g) has been synthesized using microwave power as an alternative energy source for the first time, and its catalytic activity has been exploited for CO2-epoxide coupling reactions to produce five-membered cyclic carbonates under solvent-free conditions. Microwave synthesis was performed at different time intervals to reveal the formation of the crystals. Significant conversion of various epoxides was obtained at room temperature, with excellent selectivity toward the desired five-membered cyclic carbonates. The importance of the dual porosity and the synergistic effect of quaternary ammonium salts on efficiently catalyzed CO2 conversion were investigated using various experimental and physicochemical characterization techniques, and the results were compared with those of the solvothermally synthesized MOF-205 sample. On the basis of literature and experimental inferences, a rationalized mechanism mediated by the zinc center of MOF-205 for the CO2-epoxide cycloaddition reaction has been proposed.
Gyu-Young Hwang, Roshith Roshan, Hyeong-Seok Ryu, Hye-Min Jeong, Seenu Ravi, Moon-Il Kim, and Dae-Won Park
Elsevier BV
Abstract A zeolitic imidazolate framework possessing LTA topology is investigated for its catalytic potential in the synthesis of cyclic carbonates from CO2 and epoxides. The synthesized ZIF-22 was chemically and thermally stable and was analyzed using multiple physico-chemical characterizations such as XRD, FT-IR, FE-SEM, XPS, TGA, ICP-OES and EA. ZIF-22 was found to afford excellent heterogeneous catalysis with high turnover frequencies (TOF) and selectivity, outperforming the activities exhibited by the previously reported ZIF catalysts. Parameter studies were carried out with various temperature, CO2 pressure, catalyst amount and reaction time and the catalyst was found to have reusable properties over three times with negligible or no loss in catalytic activity.
Jose Tharun, Kyung-Mi Bhin, Roshith Roshan, Dong Woo Kim, Amal Cherian Kathalikkattil, Robin Babu, Hye Young Ahn, Yong Sun Won, and Dae-Won Park
Royal Society of Chemistry (RSC)
Covalent post functionalized ZIF-90 with pyridinium based ionic liquid was prepared and used as catalyst for the solventless synthesis of propylene carbonate.
Amal Cherian Kathalikkattil, Roshith Roshan, Jose Tharun, Robin Babu, Gyeong-Seon Jeong, Dong-Woo Kim, Sung June Cho, and Dae-Won Park
Royal Society of Chemistry (RSC)
A water-stable zinc-glutamate-MOF catalyst, prepared using a facile and eco-friendly method at room temperature, was employed for room temperature wet CO2fixation reactions.
Robin Babu, Amal Cherian Kathalikkattil, Roshith Roshan, Jose Tharun, Dong-Woo Kim, and Dae-Won Park
Royal Society of Chemistry (RSC)
An approach employing a dual-porous metal organic framework as a catalyst for room temperature CO2 fixation via cyclic carbonate synthesis with high selectivity towards cyclic carbonates under solvent free conditions was demonstrated.
Amal Cherian Kathalikkattil, Robin Babu, Jose Tharun, Roshith Roshan, and Dae-Won Park
Springer Science and Business Media LLC
Global warming has begun to show its impact on the environment, and it is time to take steps to manage CO2 emissions, so as to regain the balance of carbon cycle. In addition to various capture and sequestration techniques, conversion of CO2 to value added products is high relevant. However, the inertness of CO2 makes catalysts an indispensable part of the process. CO2 undergoes cycloaddition with epoxides to produce cyclic carbonates, which have utility in various applications. Considering the necessity for heterogeneity and activity under ambient conditions, metal organic framework (MOF) catalysts have recently emerged as prospective candidates for cyclic carbonate synthesis. These porous hybrid inorganic–organic crystals are also excellent materials for gas storage and separation, including CO2 gas. Thus, MOFs could efficiently capture CO2 and catalytically convert them to cyclic carbonates. In this review, we discuss the recent advancements in the design of MOF catalysts for cyclic carbonate synthesis.
Seenu Ravi, Roshith Roshan, Jose Tharun, Amal Cherian Kathalikkattil, and Dae Won Park
Elsevier BV
Abstract A sulfonic acid tethered mesoporous silica material (SBA-15-SO3H) was successfully synthesized and characterized using SAXS, N2 physisorption studies, TEM, EA and XPS. This metal-free heterogeneous catalyst with terabutyl ammonium bromide (TBAB) co-catalyst was found to be an efficient catalyst system for styrene carbonate synthesis from CO2 and styrene oxide. The synergistic mechanistic pathways of SBA-15-SO3H with TBAB have been explained by hydrogen bond interactions and nucleophilic effects. A turn over number of 920 was obtained at mild reaction temperature of 80 °C. The catalyst was thermally stable and reused for five times without loss of any significant activity.
Jose Tharun, George Mathai, Amal Cherian Kathalikkattil, Roshith Roshan, Yong-Sun Won, Sung June Cho, Jong-San Chang, and Dae-Won Park
Wiley
Reported is the application of ZIF-90, which is a highly porous zeolitic imidazolate framework, as a novel catalyst for the cycloaddition of propylene oxide (PO) with CO2 in the absence of co-catalysts and solvents under moderate reaction conditions. The effects of various reaction parameters were investigated. The activity of ZIF-90 was compared with that of various metal-organic-framework (MOF)-based catalysts for the cycloaddition of PO with CO2 . Density functional theory calculations elucidated the role of ZIF-90 in creating a favorable environment for the PO-CO2 cycloaddition reaction. A reaction mechanism for the ZIF-90-catalyzed PO-CO2 cycloaddition on the basis of DFT calculations is proposed and the regeneration of ZIF-90 is discussed.
Seenu Ravi, Dong Heon Kang, Roshith Roshan, Jose Tharun, Amal Cherian Kathalikkattil, and Dae Won Park
Royal Society of Chemistry (RSC)
Mesoporous silica materials tethered with the sulphonate salts of organic bases were synthesized and they were highly active in CO2–epoxide cycloaddition.
Amal Cherian Kathalikkattil, Robin Babu, Roshith Kuruppathparambil Roshan, Hankyul Lee, Hyungjun Kim, Jose Tharun, Eringathodi Suresh, and Dae-Won Park
Royal Society of Chemistry (RSC)
A Zn(ii)-amino acid MOF catalyst and its use for CO2fixation are reported, in addition to corresponding structure-topology-DFT studies.
Seenu Ravi, Roshith Roshan, Jose Tharun, Dae-Won Park, Ho-Hwan Chun, Hyun Park, and Manickam Selvaraj
Royal Society of Chemistry (RSC)
A newly synthesized giant mesoporous silica particle has been used for arsenate and chromate adsorption studies.
Jose Tharun, Amal Cherian Kathalikkattil, Roshith Roshan, Dong-Heon Kang, Hee-Chul Woo, and Dae-Won Park
Elsevier BV
Abstract This study investigated the use of pyridinium-based ionic liquids (ILs) as an efficient catalyst for the rapid solvent-free microwave-assisted cycloaddition of allyl glycidyl ether (AGE) and CO 2 to yield allyl glycidyl carbonate (AGC) under moderate reaction conditions. The cycloaddition reaction occurred over a short reaction time of 30 s, resulting in a high turnover frequency (TOF) ranging from 200 to 7000 h − 1 . The effects of alkyl chain length and anion of pyridinium-based catalysts on the cycloaddition reactivity were studied. The effects of reaction parameters such as the amount of catalyst, microwave power, CO 2 pressure, and reaction time were also investigated.
Amal Cherian Kathalikkattil, Dong-Woo Kim, Jose Tharun, Han-Geul Soek, Roshith Roshan, and Dae-Won Park
Royal Society of Chemistry (RSC)
A carboxyl-containing coordination polymer catalyst {Cu(Hip)2(Bpy)}n (CHB) was synthesized rapidly in an aqueous medium using microwave energy and characterized for its structure, morphology, acid-base sites and heterogeneity using experimental and physicochemical techniques. The microwave route was established as competent with the hydrothermal pathway. Exploration of the coordination modes of metal–organic framework (MOF) ligands, especially carboxyl spacers, in achieving reactive functional groups is herein illustrated as crucial rather than focusing merely on the porosity of MOF catalysts. The work represents the first report of a carboxyl-containing MOF class material employed for synthesizing cyclic carbonates from epoxide and CO2. The metal–carboxyl mediated cycloaddition of allyl glycidyl ether and CO2 by the cooperative influence of Cu2+ and the COOH of CHB was synergistically enhanced by an ionic liquid co-catalyst to obtain allyl glycidyl carbonate in 89% yield at optimised reaction conditions. The epoxide substrate scope, effect of reaction parameters and catalyst recyclability (up to 5 cycles) were also studied.
Amal Cherian Kathalikkattil, Roshith Roshan, Jose Tharun, Han-Geul Soek, Hyeong-Seok Ryu, and Dae-Won Park
Wiley
The sulfonate anion is proposed as a remarkable partaker in catalyzing epoxide–CO2 cycloaddition for cyclic carbonate synthesis. The role is illustrated by the concerted action of a sulfonate‐rich cobalt–amino acid framework catalyst [{Co(4,4′‐bipy)(L‐cys)(H2O)}⋅H2O]n (2 D‐CCB) and a quaternary ammonium bromide co‐catalyst in synthesizing styrene carbonate (SC) at a turnover number of 228. SC yield at atmospheric pressure is presumed to result from the activation of CO2 by the sulfonate group. The involvement of SO3− anions as basic sites in 2 D‐CCB is ascertained from the initial rate (r0) for catalyzing Knoevenagel condensation reactions and by using CO2 temperature programmed desorption. Microwave pulses are used for synthesizing 2 D‐CCB at a rate that is 288‐fold faster than conventionally employed solvothermal methods. Unambiguous evidence for the pulsating role‐play of sulfonate groups in 2 D‐CCB is perceived by comparing the activity of an analogous metal organic framework (3 D‐CCB) in which the sulfonate oxyanions are jammed by coordination with cobalt. 2 D‐CCB is analyzed for heterogeneity, and reused four times.
Dong-Woo Kim, Roshith Roshan, Jose Tharun, Amal Cherian, and Dae-Won Park
Springer Science and Business Media LLC
The catalytic applicability of ionic liquids immobilized on various support materials such as silica, polystyrene and biopolymers in the cycloaddition of carbon dioxide with epoxides is reviewed in this work. Comparisons of the catalytic efficiency of these various catalysts have been done from the aspect of turnover number and reusability. The studies revealed that ionic liquids or support materials possessing hydrogen bonding capable groups exhibited enhanced catalytic activity towards cyclic carbonate synthesis. Moreover, the increased quest towards environmentally benign materials has renewed the search for biocompatible materials as support for ionic liquids.
Jose Tharun, Dong Woo Kim, Roshith Roshan, Amal Cherian Kathalikkattil, Manickam Selvaraj, and Dae-Won Park
Royal Society of Chemistry (RSC)
This paper reports the effectiveness of carrying out the cycloaddition reaction of styrene oxide (SO) and CO2 without the use of any catalysts. A naturally abundant and cheap material, urea, was utilized in promoting the reaction by controlling the reaction conditions. The influence of reaction temperature, carbon dioxide (CO2) pressure, amount of urea, and the reaction time on the selectivity of styrene carbonate (SC) was investigated.
Jose Tharun, George Mathai, Roshith Roshan, Amal Cherian Kathalikkattil, Kim Bomi, and Dae-Won Park
Royal Society of Chemistry (RSC)
Microwave-assisted quaternization of glycine (GLY) resulted in the synthesis of an efficient catalyst, quaternized glycine (QGLY), for the solventless synthesis of cyclic carbonates from epoxides and CO2 under mild reaction conditions. Density functional theory was used to simulate the synergistic influence of the COOH group and the halide ion of QGLY in enhancing the catalytic activity.
Jose Tharun, Dong Woo Kim, Roshith Roshan, Yeseul Hwang, and Dae-Won Park
Elsevier BV
Abstract An efficient method of utilizing microwave irradiation for the quaternization of chitosan (QCHT) has been investigated. QCHT catalysts have been characterized by various physicochemical methods such as FT-IR, XRD, XPS, TGA, EDS, SEM, EA, and BET. They exhibited excellent activity for the solvent-free cycloaddition of CO 2 and allyl glycidyl ether (AGE). The influences of alkyl chain length and anion of the QCHT catalyst on the cycloaddition reactivity were studied. The effects of reaction parameters such as catalyst amount, reaction time, temperature, and CO 2 pressure were also investigated. QCHT prepared by microwave irradiation exhibited higher catalytic activity than the conventional QCHT.
Jose Tharun, George Mathai, Amal Cherian Kathalikkattil, Roshith Roshan, Joo-Young Kwak, and Dae-Won Park
Royal Society of Chemistry (RSC)
An environment-friendly synthesis of cyclic carbonates from CO2 and epoxides with a HCOOH/KI catalytic system was performed in a microwave reactor. Various epoxide substrates were subjected to microwave irradiated cycloaddition using a HCOOH/KI catalyst. The effects of reaction parameters like catalyst composition, microwave power, CO2 pressure, and reaction time have been investigated. The synergistic influence of the COOH/KI catalyst in the reaction has been compared with that of an OH/KI system and was theoretically simulated using density functional theory.
Amal Cherian Kathalikkattil, Jose Tharun, Roshith Roshan, Han-Geul Soek, and Dae-Won Park
Elsevier BV
Abstract Biopolymers made of polysaccharide chains are emerging as promising materials for designing efficient, cheap, environmental friendly and recyclable heterogeneous catalysts. In this study, we synthesized a series of covalently functionalized chitosan-alkyl pyridinium halides (CS-RPX, R = ethyl, propyl, butyl, hexyl and X = Cl, Br) and evaluated their potential application as catalysts for the chemical transformation of CO2 to 4-methyl-2-oxazolidinone using 2-methylaziridine under mild reaction conditions. The catalysts were characterized using different physicochemical methods, including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermo gravimetric analysis (TGA), elemental analysis (EA) and field emission scanning electron microscopy (FE-SEM). 1H NMR, GC–MS, EA and FT-IR were used to confirm successful oxazolidinone formation. Cycloaddition was found to proceed through the synergistic effect of the hydroxyl and amine groups of chitosan together with the anion. The catalyst was reused five times after the cycloaddition reaction, with a loss of 2–6% in conversion and 1–3% in selectivity per cycle. The effect of different reaction parameters, such as catalyst amount, time, temperature and CO2 pressure were studied to determine the reaction conditions that resulted in the highest conversion and selectivity.
Jose Tharun, Yeseul Hwang, Roshith Roshan, Sohyun Ahn, Amal Cherian Kathalikkattil, and Dae-Won Park
Royal Society of Chemistry (RSC)
A novel attempt of using quaternized chitosan (QCHT) as a catalyst for the cycloaddition reaction of allyl glycidyl ether (AGE) and CO2 under solvent-free conditions has been made. The surface quaternization of CHT has been characterized by means of various physicochemical methods, such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and elemental analysis. The effects of reaction parameters like catalyst amount, reaction time, reaction temperature, and CO2 pressure have been investigated. The catalyst system was recyclable and was reused. It has been demonstrated that the inherently present hydroxyl group in the catalyst had a synergistic effect with halide anions, and a high yield of cyclic carbonates and excellent selectivity could be obtained under optimum conditions. These results reveal that QCHT is an efficient and environmentally friendly catalyst for the cycloaddition reaction.