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( Robin Babu ),( Jose Tharun ),박대원 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1
Metal Organic Frameworks (MOFs) have been widely accepted as new generation materials for various applications including CO<sub>2</sub> capture and transformations because of its high surface area, accessible pore volume, ordered porous structures, high adsorption capacity, and diverse means available for functionalization etc. Synthesis of cyclic carbonates from CO<sub>2</sub> and epoxides is 100% atom economical and the most promising pathways that do not utilize phosgene or isocyanate as raw material. UMCM-1-NH<sub>2</sub>, a mesoporous Metal Organic Framework has been synthesized and characterized for its crystallinity and textural properties using various physicochemical techniques. The framework consists of Zn<sub>4</sub>O clusters linked by dicarboxylate and tricarboxylate linkers forming a central mesoporous hexagonal channel surrounded by six microcages. The cooperative influence of Zn<sup>2+</sup> and NH<sub>2-</sub> of UMCM-1-NH<sub>2</sub> was studied for the cycloaddition reaction of CO<sub>2</sub> and allyl glycidyl ether (AGE) to form allyl glycidyl carbonate (AGC). Scope of various parameters like catalyst loading, time, temperature and pressure etc. were studied.
( Robin Babu ),박대원,김설희,( Jintu Francis K ) 한국공업화학회 2017 한국공업화학회 연구논문 초록집 Vol.2017 No.1
A zinc containing 3D non-interpenetrated metal organic framework, UMCM-15 was found to display excellent synergistic catalysis with alkyl ammonium halides (TBAX) in the room temperature fixation of CO<sub>2</sub> with epoxide to cyclic carbonate. The favorable role of noninterpenetrated pillared structures in promoting room temperature CO<sub>2</sub>-epoxide cycloaddition reactions was explained by comparing the catalytic efficiency of the three-linker extended pillar-layered noninterpenetrated UMCM-15 with its analogous pillared structures built from two- and three-fold interpenetrated ([Zn<sub>2</sub>(BDC)<sub>2</sub>(4,4'-bipy)] and [Zn<sub>2</sub>(NDC)<sub>2</sub>(4,4'-bipy)]) catalytic systems with a single dicarboxylate linker. Reaction parameters were optimized by altering the conditions. In addition, a plausible mechanism for the synergistic operation of the Lewis acid sites and nucleophiles was suggested.
Babu, Robin,Roshan, Roshith,Gim, Yeongrok,Jang, Yun Hee,Kurisingal, Jintu Francis,Kim, Dong Woo,Park, Dae-Won The Royal Society of Chemistry 2017 Journal of materials chemistry. A, Materials for e Vol.5 No.30
<P>The correlation between dimensionality and active sites on deciding the catalytic performance of an MOF catalyst in CO2-epoxide cycloaddition reactions has been studied. Seven In(iii) based MOFs built from carboxylic and N-donor ligands possessing different dimensionalities and distinct coordination environments were chosen as solid acid catalysts for this study. The origin of the catalytic activity of an In<SUP>3+</SUP>/TBAB bifunctional system in a CO2-PO reaction was studied in detail by performing density functional theory (DFT) calculations at the M06/LACVP**++ level. The energy barrier of the propylene oxide ring opening in the presence of In<SUP>3+</SUP>/Br<SUP>−</SUP>is 11.5 kcal mol<SUP>−1</SUP>, which is significantly lower than those of un-catalyzed (55-63 kcal mol<SUP>−1</SUP>) and Br<SUP>−</SUP>-catalyzed (19.5 kcal mol<SUP>−1</SUP>) reactions, which confirms the importance of the In<SUP>3+</SUP>/Br<SUP>−</SUP>binary catalytic system in the CO2-epoxide cycloaddition reactions. The one-dimensional (1D) MOF with unsaturated metal centers exhibited higher catalytic activity (PO conversion: 91%, temperature: 50 °C, and time: 12 h) than the two- and three-dimensional MOFs. The roles of dimensionality and unsaturated metal centers in cycloaddition reactions were explained on the basis of the results of activity testing and structural investigations. In addition, a plausible reaction mechanism for the catalytic activity of the 1D MOF was proposed with reference to our structure-density functional theory correlations.</P>
Babu, Robin,Kurisingal, Jintu Francis,Chang, Jong-San,Park, Dae-Won WILEY-VCH 2018 CHEM SUS CHEM Vol.11 No.5
<P>A pyridinium-based ionic-liquid-decorated 1D metal-organic framework (MOF; IL-[In-2(dpa)(3)(1,10-phen)(2)]; IL = ionic liquid; dpa = diphenic acid; 1,10-phen = 1,10-phenanthroline) was developed as a bifunctional heterogeneous catalyst system for CO2-oxirane coupling reactions. An aqueous-microwave route was employed to perform the hydrothermal reaction for the synthesis of the [In-2(dpa)(3)(1,10-phen)(2)] MOF, and the IL-[In-2(dpa)(3)(1,10-phen)(2)] catalyst was synthesized by covalent postfunctionalization. As a result of the synergetic effect of the dual-functional sites, which include Lewis acid sites (coordinatively unsaturated In sites) and the I- ion in the IL functional sites, IL-[In-2(dpa)(3)(1,10-phen)(2)] displayed a high catalytic activity for CO2-epoxide cycloaddition reactions under mild and solvent-free conditions. Microwave pulses were employed for the first time in MOF-catalyzed CO2-epoxide cycloaddition reactions to result in a high turnover frequency of 2000-3100 h(-1). The catalyst had an excellent reusability and maintained a continuous high selectivity. Furthermore, only a small amount of leaching was observed from the spent catalyst. A plausible reaction mechanism based on the synergistic effect of the dual-functional sites that catalyze the CO2-epoxide cycloaddition reaction effectively is proposed.</P>
( Robin Babu ),박대원,김현준,최각규 한국공업화학회 2017 한국공업화학회 연구논문 초록집 Vol.2017 No.1
A novel energy-efficient bimetallic heterogeneous catalyst system consisting of Zn and Co as active centers was synthesized at room temperature using low-boiling solvents. The newly synthesized material possesses RHO topology, similar to that of the parent monometallic zeolitic imidazolate frameworks (ZIFs), and the similar ionic radii of Zn<sup>2+</sup> and Co<sup>2+</sup> allow uniform distribution throughout the framework, as was confirmed through various physicochemical analytical techniques. The structural peculiarities of the newly synthesized bimetallic ZIF (denoted as ZnCo-ZIF) were exploited for CO<sub>2</sub>-epoxide cycloaddition reactions at room temperature and atmospheric pressure. The synergistic effects of multiple metal centers that cooperatively activate the epoxides led to superior catalytic activity compared to those of the corresponding monometallic ZIFs. In addition, a mechanism for the solvent-free CO<sub>2</sub>-epoxide cycloaddition reaction catalyzed by the bimetallic ZIF was proposed.
김설희,박대원,( Robin Babu ),김가형,( Jintu Francis K ) 한국공업화학회 2017 한국공업화학회 연구논문 초록집 Vol.2017 No.1
The conversion of CO<sub>2</sub> to cyclic carbonates via cycloaddition with epoxides is a 100% atom economy reaction, but necessitates the use of a catalyst to be economically viable. In this work, a microporous metal-organic framework (MOF) Ni(HBTC)(4,4’-bipy) has been synthesized and its synergistic catalytic activity with a co-catalyst containing strong nucleophilic anion has been studied for the solventless cycloaddition of CO<sub>2</sub> with epoxides under mild reaction conditions. The structure of Ni(HBTC)(4,4’-bipy) consists of honeycomb grid layers built by Ni<sup>2+</sup> ions and BTC groups, and are linked by 4,4’-bipy pillars to form a 3D highly porous framework. Significant conversion of various epoxides was obtained with excellent selectivity toward the desired five-membered cyclic carbonates.
정혜민,Roshith Roshan,Robin Babu,김현준,박대원 한국화학공학회 2018 Korean Journal of Chemical Engineering Vol.35 No.2
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.
Room temperature CO2 fixation via cyclic carbonate synthesis over vanadium-MOF catalysts
Roshith Roshan Kuruppathparambil,Robin Babu,정호찬,장윤희,이미혜,박대원 한국화학공학회 2019 Korean Journal of Chemical Engineering Vol.36 No.5
Vanadium containing 3D MOF, MIL-47 displayed excellent synergistic catalysis with alkyl ammonium halides (TBAX) in the room temperature fixation of CO2. Theoretical intrinsic-reaction-coordinate calculations were performed at the level of M06/LACVP**++ implemented in Jaguar v8.5 software to ascertain the mechanistic pathways of catalysis. A homogeneous complex of vanadium, vanadium acetyl acetonato [VO(acac)2], was used as a model system to investigate the mechanism behind the synergistic activity of the MIL-47/TBAX, which indeed shows that the activation energy of the CO2 fixation is considerably lowered by about 30-35 kcal compared to the uncatalyzed reactions.