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Parmar et al. [44] synthesized [Co(BDC)(L)·2H2O]·xG}n or CoMOF-2 (Figure 8b) with nitrogen- rich pyridine as basic site. They demonstrated an excellent catalytic activity of CoMOF-2 and KI as binary catalyst in epoxide−CO2 cycloaddition. SEO conversion of 85% was obtained at room temperature for 48 h. In addition, 99% conversions were achieved within 24 h, with increasing temperature to 40 °C. The recyclability remained constant with 99% conversion and yield through Processes 2020, 8, 548 14 of 22 five successive cycles. (a) (b) (c) (d) Figure 8. The 3D structure of MOFs: (a) In2(OH)(btc)(Hbtc)0.4(L)0.6·3H2O (reprinted with permission Figure 8. The 3D structure of MOFs: (a) In2(OH)(btc)(Hbtc)0.4(L)0.6·3H2O (reprinted with permission from Liu, L.; Wang, S.M.; Han, Z.B.; Ding, M.; Yuan, D.Q.; Jiang, H.L. Exceptionally Robust In-Based from Liu, L.; Wang, S.M.; Han, Z.B.; Ding, M.; Yuan, D.Q.; Jiang, H.L. Exceptionally Robust In-Based Metal-Organic Framework for Highly Efficient Carbon Dioxide Capture and Conversion. Inorg. Chem. Metal-Organic Framework for Highly Efficient Carbon Dioxide Capture and Conversion. Inorg. Chem. 2016, 55, 3558–3565. Copyright (2016) American Chemical Society.); (b) {[Co(BDC)(L)]·2H2O·xG}n 2016, 55, 3558–3565. Copyright (2016) American Chemical Society.); (b) {[Co(BDC)(L)]·2H2O·xG}n (CoMOF-2) (reprinted with permission from Parmar, B.; Patel, P.; Pillai, R.S.; Tak, R.K.; Kureshy, R.I.; (CoMOF-2) (reprinted with permission from Parmar, B.; Patel, P.; Pillai, R.S.; Tak, R.K.; Kureshy, Khan, N.H.; Suresh, E. Cycloaddition of CO2 with an Epoxide-Bearing Oxindole Scaffold by a Metal– R.I.; Khan, N.H.; Suresh, E. Cycloaddition of CO2 with an Epoxide-Bearing Oxindole Scaffold by a Organic Framework-Based Heterogeneous Catalyst under Ambient Conditions. Inorg. Chem. 2019, 58, Metal–Organic Framework-Based Heterogeneous Catalyst under Ambient Conditions. Inorg. Chem. 10084–10096. Copyright (2019) American Chemical Society.); (c) {Cu2[(C20H12N2O2)(COO)4]}n 2019, 58, 10084–10096. Copyright (2019) American Chemical Society.); (c) {Cu2[(C20H12N2O2)(COO)4]}n ((rreepprrinintteedwiitthpeerrmiisssiionffrromLii,,P.Z.Z.;.;Waanngg,,XX.J..J;.;LLiuiu,,JJ.;.;Phang,,H..S..;; Li,, Y..;;Zhao,, Y..Hiighlly EfffefecctitviveeCCarabrobnonFixFaitxiaotniovniavCiataClyataiclyCtiocnvCeornsivoenrsoifoCnOof bCyOan2 AbycyalanmAidcey-lCaomnitdaein-CinognMtaientainl-gOrMgaentaicl- 2 FOrargmaenwicoFrrka.mCewheomr.k.MChaetmer.M2a0t1er7.,22091,7,9295,69–295266–19.26C1.oCpoypriygrhigth(2t0(21071)7A)AmmereirciacnanCChheemicicaallSociety..);; ((dd)){C{Cuu4[[((C57H32N12)()C(COOO)8)]}]n}(r(erperpirnitnetdedwwitihthpperemrmisisisoinonfrforommLLi,i,PP.Z.Z.;.;Wang, X.J.; Liu, J.; Lim, J..S..;; 4573212 8n Zoou,,RR.;.Z;hZahoa,oY,.AY.TrAiazTorliea-zColne-tCaionnintaginMinegtalM-Oertgaaln-OicrgFaranmicewFroarmkeawsaorHkigahslyaEHffeigcthivlyeaEnfdfeSctuivbestranted SSizueb-sDtreaptenSdieznet-DCeaptaelnysdtefnotr COatalCyostnvfeorsiConO.2J.CAomn.vCerhseimon. .SoJ.c.A2m01.6C, 1h3e8m,.21S4o2c–.22104156.,C1o3p8y,ri2g1h4t2(–201465). 2 ACmoperyirciagnhtC(h2e0m16i)caAlmSoecriectayn.).Chemical Society.). Parmaretal.[44]synthesized[Co(BDC)(L)·2H O]·xG}norCoMOF-2(Figure8b)withnitrogen-rich Li et al. [43] synthesized Cu2[(C20H12N2O2)(COO)4] (Figure 8c), which incorporated both pyridine as basic site. They demonstrated an excellent catalytic activity of CoMOF-2 and KI as binary accessible nitrogen-rich acylamide groups and exposed Cu metal sites expressing a high CO2 catalystinepoxide−CO cycloaddition.SEOconversionof85%wasobtainedatroomtemperaturefor adsorptioncapability.T2heresultsshowed96%forpropyleneoxide,85%forbutyleneoxide,88%for 48 h. In addition, 99% conversions were achieved within 24 h, with increasing temperature to 40 ◦C. epichlorohydrin, and 10% 1-octene oxide (1,2-epoxyoctane) on cycloaddition at 1.01 bar of CO2 and The recyclability remained constant with 99% conversion and yield through five successive cycles. room temperature, which demonstrated high selectivity toward size and shape of substrate. The Li et al. [43] synthesized Cu [(C H N O )(COO) ] (Figure 8c), which incorporated both accessible catalyst displayed slight decre2ase20of1c2on2ver2sion of4propylene oxide after second run within five nitrogen-richacylamidegroupsandexposedCumetalsitesexpressingahighCO adsorptioncapability. cycles. 2 The results showed 96% for propylene oxide, 85% for butylene oxide, 88% for epichlorohydrin, and Li et al. [45] utilized a highly porous triazole-based MOF, Cu4[(C57H32N12)(COO)8] (Figure 8d), 10% 1-octene oxide (1,2-epoxyoctane) on cycloaddition at 1.01 bar of CO and room temperature, which showed high activity towards size- and shape-selective synthe2sis of carbonates. MOF which demonstrated high selectivity toward size and shape of substrate. The catalyst displayed slight incorporating both unsaturated metal sites and accessible nitrogen-rich triazole units exhibited a high decrease of conversion of propylene oxide after second run within five cycles. affinity towards CO2. The MOF exhibited high catalytic selectivity to small epoxide substrate—96% Li et al. [45] utilized a highly porous triazole-based MOF, Cu [(C H N )(COO) ] (Figure 8d), forpropyleneoxide,83%forbutyleneoxide,and85%forepichlor4ohy5d7rin32,w1i2thavery8lowyieldfor which showed high activity towards size- and shape-selective synthesis of carbonates. MOF incorporating large epoxide substrate. The catalyst displayed slight (≈1%) decrease of conversion after the third run both unsaturated metal sites and accessible nitrogen-rich triazole units exhibited a high affinity towards within five cycles. On the basis of this observation, MOF is an effective catalyst for CO2 cycloaddition CO . The MOF exhibited high catalytic selectivity to small epoxide substrate—96% for propylene oxide, rea2ction, specifically in terms of recyclability and selectivity. 83% for butylene oxide, and 85% for epichlorohydrin, with a very low yield for large epoxide substrate. T4h. eScuasttaliynsat bdliespElpayoexdidseligShotu(r≈ce1%s f)odreCcryecalsoeaodfdciotinovnerRsieoanctaifotner the third run within five cycles. On the basis of this observation, MOF is an effective catalyst for CO2 cycloaddition reaction, specifically in terms Ethylene oxide and propylene oxide are the most employed epoxides at the industrial scale for of recyclability and selectivity. CO2/epoxide coupling synthesis. Epoxides are still mainly derived from petrochemical feedstock such as ethylene and propylene, and increasing interest has focused on developing bio-based routes 4. Sustainable Epoxide Sources for Cycloaddition Reaction Ethylene oxide and propylene oxide are the most employed epoxides at the industrial scale for CO2/epoxide coupling synthesis. Epoxides are still mainly derived from petrochemical feedstock such as ethylene and propylene, and increasing interest has focused on developing bio-based routes to produce these two compounds. On the basis of three platforms of biomass feedstock, includingPDF Image | Green Pathway Utilizing CO2 Cycloaddition Reaction Epoxide
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