catalysts Review Review on Carbon Dioxide Utilization for Cycloaddition of Epoxides by Ionic Liquid-Modified Hybrid Catalysts: Effect of Influential Parameters and Mechanisms Insight Jimmy Nelson Appaturi 1,*, Rajabathar. Jothi Ramalingam 2,*, Muthu Kumaran Gnanamani 3, Govindasami Periyasami 2,* , Prabhakarn Arunachalam 2 , Rohana Adnan 1, Farook Adam 1, Mohammed D. Wasmiah 2 and Hamad A. Al-Lohedan 2,4 1 School of Chemical Sciences, University Sains Malaysia (USM), Penang 11800, Malaysia; [email protected] (R.A.); [email protected] (F.A.) 2 Chemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia; [email protected] (P.A.); [email protected] (M.D.W.); [email protected] (H.A.A.-L.) 3 Center for Applied Energy Research, University of Kentucky, 2540 Research Park Drive, Lexington, KY 40511, USA; [email protected] 4 Surfactant Research Chair, Chemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia * Correspondence: [email protected] (J.N.A.); [email protected] (R.J.R.); [email protected] (G.P.) Abstract: The storage, utilization, and control of the greenhouse (CO2) gas is a topic of interest for researchers in academia and society. The present review article is dedicating to cover the overall role of ionic liquid-modified hybrid materials in cycloaddition reactions. Special emphasis is on the synthesis of various cyclic carbonate using ionic liquid-based modified catalysts. Catalytic activity Citation: Appaturi, J.N.; Ramalingam, studies have discussed with respect to process conditions and their effects on conversion and product R.J.; Gnanamani, M.K.; Periyasami, G.; selectivity for the reaction of cycloaddition of CO2 with styrene oxide. The reaction temperature and Arunachalam, P.; Adnan, R.; Adam, F.; the partial pressure of CO2 have found to play a key role in cyclic carbonate formation. The role of Wasmiah, M.D.; Al-Lohedan, H.A. other influential parameter (solvent effect) is also discussed for the conversion of cyclic/aromatic Review on Carbon Dioxide oxides to polycarbonate production. Our own research work that deals with ionic liquid-based Utilization for Cycloaddition of halide-modified mesoporous catalyst (MCM-41 type) derived from rice husk waste has also been Epoxides by Ionic Liquid-Modified discussed. Finally, the role of carbon dioxide activation and ring-opening mechanisms involved in Hybrid Catalysts: Effect of Influential the cyclic carbonate product formation from CO2 have been discussed. Parameters and Mechanisms Insight. Catalysts 2021, 11, 4. https://dx.doi.org/ Keywords: greenhouse gas; ionic liquid; mesoporous silica; cycloaddition; poly-carbonate 10.3390/catal11010004 Received: 17 November 2020 Accepted: 16 December 2020 1. Introduction Published: 23 December 2020 Greenhouse gas (carbon dioxide—CO2) in the atmosphere helps living things naturally Publisher’s Note: MDPI stays neu- by involving in photosynthesis [1]. About 32% of CO2 is being produced by hydrocarbon tral with regard to jurisdictional claims combustion and gasification process that raises concern over environmental pollution [2,3]. in published maps and institutional The transportation sector contributes nearly 30% to total carbon dioxide emissions [4]. affiliations. Figure1 shows the carbon cycle, CO 2 storage, recycle and purification, and utilization mainly of fine chemicals formation by catalysis route. Figure1 shows the global atmo- spheric CO2 concentration for about half a decade from 1958 with respect to continuous research reports carried by the Mauna Loa Observatory in Hawaii [3]. The concentration of Copyright: © 2020 by the authors. Li- atmospheric CO was 399.89 ppm till May 2013, and in 2020, it reached up to 412.78 ppm [5]. censee MDPI, Basel, Switzerland. This 2 The continuous rise in greenhouse gas (CO ) concentration creates global warming issues article is an open access article distributed 2 under the terms and conditions of the and continues damage to the green environment. In recent years, smart technologies Creative Commons Attribution (CC BY) are developed to store and utilize CO2 reduction and which makes the pollution free license (https://creativecommons.org/ atmosphere [6–8]. licenses/by/4.0/). Catalysts 2021, 11, 4. https://dx.doi.org/10.3390/catal11010004 https://www.mdpi.com/journal/catalysts Catalysts 2021, 11, x FOR PEER REVIEW 2 of 16 Catalysts 2021, 11, 4 2 of 15 Figure 1. Schematic of carbon cycle for CO2, recycle Storage and greenhouse gas utilization for possible fine chemicals Figure 1. Schematic of carbon cycle for CO2, recycle Storage and greenhouse gas utilization for production. possible fine chemicals production. Carbon dioxide is recognized as a nonflammable [9], nontoxic [10], and inexpen- sive gasCarbon [11]. dioxide It is a is renewable recognized carbon as a nonfla sourcemmable [12] and [9], thermodynamically nontoxic [10], and inexpensive stable com- poundgas [11]. [13 It, 14is ].a Interestingly,renewable carbon carbon source oxide [12] can and replace thermodynamically the following toxic stable chemical compound com- [13,14]. Interestingly, carbon oxide can replace the following toxic chemical compounds pounds such as carbonyl dichloride known as phosgene (COCl2), carbon monoxide (CO), andsuchisocyanides as carbonyl (R-NCO)dichloride for known fine chemical as phosgene applications. (COCl2), carbon Carbon monoxide dioxide can (CO), be utilizedand iso- ascyanides a mild (R-NCO) oxygen source for fine [15 chemical]. It can applications. be used as an Carbon alternate dioxide medium can be or solventutilized [as16 a], mild also workoxygen as source a supercritical [15]. It can fluid be (sc)used [17 as], an and alternate act as a medium carbon source. or solvent It can [16], be usedalso work based as on a itssupercritical unique chemical fluid (sc) properties [17], and to act be as incorporated a carbon source. with It high can “atombe used efficiency” based on suchits unique as in carboxylationchemical properties synthesis to be or incorporated in catalyst synthesis with high [16 “atom]. Hutchings efficiency” [15,17 such] used as in supercritical carboxyla- COtion2 synthesisas an antisolvent or in catalyst for the synthesis preparation [16]. of Hutchings Au/scCO2 [15,17]and sc-VPO used supercritical (vanadium phosphate) CO2 as an catalysts.antisolvent Currently, for the preparation CO2 has been of Au/scCO used in various2 and sc-VPO industrial (vanadium applications phosphate) such as chemical,catalysts. pharmaceutical,Currently, CO2 has foodstuff, been used laboratories in various and industrial analysis, applications beverage, and such pulp as and chemical, paper indus-phar- triesmaceutical, [16]. The foodstuff, application laboratories of CO2 as and C1 analysis, raw material beverage, in the and chemical pulp and industry paper was industries started in[16]. past The few application decades. Itof hasCO2 been as C1 reported raw material that approximately in the chemical 110 industry million was metric started tons ofin COpast2 feware currentlydecades. usedIt has every been yearreported in the that chemical approximately industry. 110 In themillion present metric decade, tons carbonof CO2 dioxideare currently utilization used hasevery reached year in around the chemical 110 million industry. MT (metric In the present tons) [18 decade,]. Carbon carbon dioxide di- isoxide also utilization playing major has reached role in the around production 110 million of urea, MT [ 17(metric] methanol tons) [[18].18], salicylic-acidCarbon dioxide [19 is], formic-acidalso playing [ 20major], cyclic role carbonates in the production [21–23], copolymers,of urea, [17] polymermethanol building [18], salicylic-acid blocks, and [19], fine chemicalsformic-acid [24 [20],–27 ].cyclic Urea carbonates is one of the [21–23], major fertilizers,copolymers, and polymer CO2 is thebuilding source blocks, for it [ 26and]. Thefine ureachemicals is prepared [24–27]. from Urea ammonia is one of andthe major CO2 in fertilizers, fertilizer and [28] CO and2 is also the in source fabrication for it [26]. process The ofurea various is prepared types from of polymers, ammonia such and asCO melamine2 in fertilizer and [28] urea-formaldehyde and also in fabrication resin [process29–32]. Salicylicof various acid types is producedof polymers, from such phenol as mela andmine CO 2andvia urea-formaldehyde the Kolbe-Schmitt reactionresin [29–32]. [33]. TheSal- producticylic acid is is used produced to produce from acetyl phenol salicylic and CO acid2 via which the Kolbe-Schmitt is also known reaction as aspirin, [33]. used The mostly prod- inuct healthcare is used to applicationsproduce acetyl [34 salicylic–36]. Everyday acid which monitoring is also known of Carbon as aspirin, dioxide used emission mostly inin atmospherehealthcare applications have shown [34–36]. in online Everyday website (monitoringwww.co2.earth of Carbon) to monitor dioxide the emission Keeling Curve in at- ofmosphere Atmospheric have shown CO2 concentration in online website emission (www.co2.earth between 1958 ) toto 16monitor August the 2020 Keeling [5,35]. Curve of AtmosphericThe cyclic carbonatesCO2 concentration are odorless, emission colorless, between and 1958 biodegradable to 16 August [37 2020,38]. [5,35]. The cyclic carbonatesThe cyclic are used carbonates in industries are odorless, as aprotic colorl polaress, solvents and biodegradable [39], as a monomer [37,38]. for The polymer cyclic synthesis,carbonates and are asused additives in industries [40]. Besides, as aprotic it