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Carbon Dioxide

CO2 emission causes many environmental problems. To mitigate the concentration of CO2 in the atmosphere, the fixation, activation, and capture of CO2 through chemical reactions is important. Increasingly, CO2 is used as a carbon source in syntheses.

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Ion-Conductive Properties of a Polymer Electrolyte Based on Ethylene Carbonate/Ethylene Oxide Random Copolymer

Ion‐Conductive Properties of a Polymer Electrolyte Based on Ethylene Carbonate/Ethylene Oxide Random Copolymer

A random copolymer of ethylene oxide with CO2 , namely, poly(ethylene carbonate/ethylene oxide) (P(EC/EO)), has been synthesized as a novel candidate for polymer electrolytes. Electrolyte composed of P(EC/EO) and lithium bis(fluorosulfonyl)imide is promising material for use in all-solid-state batteries because of its very high Li+ conductivity.

[Communication]
Takashi Morioka, Koji Nakano, Yoichi Tominaga
Macromol. Rapid Commun., February 21, 2017, DOI: 10.1002/marc.201600652. Read article

Study of Electrochemical Reduction of CO2 for Future Use in Secondary Microbial Electrochemical Technologies

Study of Electrochemical Reduction of CO2 for Future Use in Secondary Microbial Electrochemical Technologies

Energy storage with CO2: The electrochemical reduction of CO2 was investigated under conditions allowing microbial conversions for future use in secondary microbial electrochemical technologies (METs). A reproducible electrodeposition procedure of In on a graphite backbone allowed a systematic study of formate production from CO2 with coulombic efficiencies of 64.6±6.8 % and formate production rates of 0.013±0.002 mmolformate h−1 cm−2. The results demonstrate that the integration of electrochemical reduction of CO2 in secondary METs can become technologically relevant.

[Full Paper]
Carla Gimkiewicz, Richard Hegner, Mareike F. Gutensohn, Christin Koch, Falk Harnisch
ChemSusChem, February 20, 2017, DOI: 10.1002/cssc.201601675. Read article

Concerning the Role of Supercritical Carbon Dioxide in SN1 Reactions

Concerning the Role of Supercritical Carbon Dioxide in SN1 Reactions

Not super here: Supercritical CO2 as a solvent does not activate alkyl halides by SN1-type ionization for alkylation reactions as recently claimed.

[Full Paper]
Yun X. Qiao, Nils Theyssen, Tobias Eifert, Marcel A. Liauw, Giancarlo Franciò, Karolin Schenk, Walter Leitner, Manfred T. Reetz
Chem. Eur. J., February 20, 2017, DOI: 10.1002/chem.201604151. Read article

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals

Metallosalen‐Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals

POP catalysts: Metallosalen-based ionic porous organic polymers (POPs) catalysts (DVB@ISA and DVB@ISZ) exhibit excellent cooperative effect in CO2involved organic reactions such as the cycloaddition reaction from epoxides and N-formylation of amines with hydrosilanes, acting as bifunctional heterogeneous catalysts.

[Full Paper]
Rongchang Luo, Yaju Chen, Qian He, Xiaowei Lin, Qihang Xu, Xiaohui He, Wuying Zhang, Xiantai Zhou, Hongbing Ji
ChemSusChem, February 17, 2017, DOI: 10.1002/cssc.201601846. Read article

State-of-the-Art Aluminum Porphyrin-based Heterogeneous Catalysts for the Chemical Fixation of CO2 into Cyclic Carbonates at Ambient Conditions

State‐of‐the‐Art Aluminum Porphyrin‐based Heterogeneous Catalysts for the Chemical Fixation of CO2 into Cyclic Carbonates at Ambient Conditions

Capture by crosslinking: Aluminum porphyrin-based hyper-crosslinked polymers exhibit outstanding catalytic activity and excellent reusability in the solvent-free synthesis of cyclic carbonates from epoxides and CO2 in the presence of tetrabutylammonium bromide under mild conditions.

[Full Paper]
Yaju Chen, Rongchang Luo, Qihang Xu, Wuying Zhang, Xiantai Zhou, Hongbing Ji
ChemCatChem, February 17, 2017, DOI: 10.1002/cctc.201601578. Read article

Explicit Water Molecules Play a Key Role in the Mechanism of Rhodium-Substituted Human Carbonic Anhydrase

Explicit Water Molecules Play a Key Role in the Mechanism of Rhodium‐Substituted Human Carbonic Anhydrase

A pocketful of water: A plausible mechanism of action for a rhodium-substituted human carbonic anhydrase, with potential impact on the environmentally important problem of carbon dioxide capture and conversion into formic acid, was elucidated through a series of quantum mechanical computations. Two water molecules assist directly in the reaction by altering the enzyme pocket. This lowers the activation barrier for the rate-limiting step dramatically.

[Full Paper]
Paolo Piazzetta, Tiziana Marino, Nino Russo, Dennis R. Salahub
ChemCatChem, February 15, 2017, DOI: 10.1002/cctc.201601433. Read article

Synthesis of Asymmetrical Organic Carbonates using CO2 as a Feedstock in AgCl/Ionic Liquid System at Ambient Conditions

Synthesis of Asymmetrical Organic Carbonates using CO2 as a Feedstock in AgCl/Ionic Liquid System at Ambient Conditions

Asymmetry is all! A series of asymmetrical organic carbonates can be synthesized efficiently by the reaction of CO2 with propargylic alcohols and primary alcohols under ambient conditions using AgCl/[Bmim][OAc] as catalyst and solvent, and the yields of the desired products can approach 100 %.

[Full Paper]
Jiayin Hu, Jun Ma, Lu Lu, Qingli Qian, Zhaofu Zhang, Chao Xie, Buxing Han
ChemSusChem, February 07, 2017, DOI: 10.1002/cssc.201601773. Read article

Strategies for Enhancing the Catalytic Performance of Metal–Organic Frameworks in the Fixation of CO2 into Cyclic Carbonates

Strategies for Enhancing the Catalytic Performance of Metal–Organic Frameworks in the Fixation of CO2 into Cyclic Carbonates

A stable MOF: The metal–organic framework MIL-100(Cr) is presented as a promising new heterogeneous catalyst with high activity, selectivity and reusability in the solvent-free synthesis of styrene carbonate from CO2 at mild conditions. Two strategies to increase the reusability of the MOF catalysts are proposed.

[Full Paper]
Masoumeh Taherimehr, Ben Van de Voorde, Lik H. Wee, Johan A. Martens, Dirk E. De Vos, Paolo P. Pescarmona
ChemSusChem, February 06, 2017, DOI: 10.1002/cssc.201601768. Read article

Aluminum-Mediated Formation of Cyclic Carbonates: Benchmarking Catalytic Performance Metrics

Aluminum‐Mediated Formation of Cyclic Carbonates: Benchmarking Catalytic Performance Metrics

Take a pick: The reactivities of a small series of binary catalysts derived from various combinations of Al complexes and nucleophiles are examined. These benchmarking studies provide a useful comparison of their overall performances in the coupling of both terminal and internal epoxides, and CO2 to afford their cyclic carbonates. The results are explained from a mechanistic point of view, and the crucial role of the nucleophile, its amount and catalyst concentration are discussed.

[Full Paper]
Jeroen Rintjema, Arjan W. Kleij
ChemSusChem, February 03, 2017, DOI: 10.1002/cssc.201601712. Read article

Cyanuric Acid-Based Organocatalyst for Utilization of Carbon Dioxide at Atmospheric Pressure

Cyanuric Acid‐Based Organocatalyst for Utilization of Carbon Dioxide at Atmospheric Pressure

1 bar? Wunderbar! Economical and readily available cyanuric acid was demonstrated to be an excellent organocatalyst for the utilization of atmospheric pressure carbon dioxide. The catalytic system was applicable to various propargylamines and 2-aminobenzonitriles for the synthesis of 2-oxazolidinones and quinazoline-2,4(1H,3H)-diones. In particular, CO2 in air was directly converted into 2-oxazolidinone in excellent yields without external reagents.

[Communication]
Bing Yu, Daeun Kim, Seoksun Kim, Soon Hyeok Hong
ChemSusChem, January 31, 2017, DOI: 10.1002/cssc.201601684. Read article

Coupling Reactions of Carbon Dioxide with Epoxides Catalyzed by Vanadium Aminophenolate Complexes

Coupling Reactions of Carbon Dioxide with Epoxides Catalyzed by Vanadium Aminophenolate Complexes

Making good use of CO2: Four epoxide-soluble vanadium complexes with ionic co-catalysts convert epoxides such as propylene oxide, styrene oxide, and cyclohexene oxide to carbonates. For propylene oxide, turnover numbers up to 4000 and turnover frequencies over 500 h−1 are obtained. In situ IR spectroscopic monitoring of carbonate formation allows activation energies to be determined (45.6–54.7 kJ mol−1).

[Full Paper]
Ali I. Elkurtehi, Francesca M. Kerton
ChemSusChem, January 31, 2017, DOI: 10.1002/cssc.201601548. Read article

Mechanistic Insights into the Carbon Dioxide/Cyclohexene Oxide Copolymerization Reaction: Is One Metal Center Enough?

Mechanistic Insights into the Carbon Dioxide/Cyclohexene Oxide Copolymerization Reaction: Is One Metal Center Enough?

Two better than one: A computational study of several reaction mechanisms for CO2/cyclohexene oxide copolymerization mediated by an [Al{amino- tri(phenolate)}]/NBu4X binary catalyst suggests that a new non-covalent dimeric complex formed in situ in the reaction medium is the catalytically active species because it presents the most favorable free-energy pathway.

[Full Paper]
Joan González-Fabra, Fernando Castro-Gómez, Arjan W. Kleij, Carles Bo
ChemSusChem, January 30, 2017, DOI: 10.1002/cssc.201601520. Read article

Organocatalytic Coupling of CO2 with a Propargylic Alcohol: A Comprehensive Mechanistic Study

Organocatalytic Coupling of CO2 with a Propargylic Alcohol: A Comprehensive Mechanistic Study

A better understanding: The catalytic efficiency and selectivity of bicyclic guanidines (1,5,7-triazabicyclo[4.4.0]dec-5-ene, TBD, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, MTBD) for the coupling of a propargylic alcohol with CO2 under mild conditions is investigated in detail through the combination of DFT calculations and online kinetic studies by in situ attenuated-total reflection (ATR)–IR spectroscopy.

[Full Paper]
Amélie Boyaval, Raphaël Méreau, Bruno Grignard, Christophe Detrembleur, Christine Jerome, Thierry Tassaing
ChemSusChem, January 27, 2017, DOI: 10.1002/cssc.201601524. Read article

Telescoped Synthesis of γ-Bromo-β-Lactones from Allylic Bromides Employing Carbon Dioxide

Telescoped Synthesis of γ‐Bromo‐β‐Lactones from Allylic Bromides Employing Carbon Dioxide

[Communication]
Sreekumar Vellalath, Daniel Romo
Isr. J. Chem., January 18, 2017, DOI: 10.1002/ijch.201600125. Read article

Elimination of the Crystallinity of Long Polyethylene Oxide-Based Copolymers for Gas Separation Membranes by Using Electron Beam Irradiation

Elimination of the Crystallinity of Long Polyethylene Oxide‐Based Copolymers for Gas Separation Membranes by Using Electron Beam Irradiation

Electron beam irradiation appears as a novel and effective approach for the elimination of the crystallinity in polyethylene oxide (PEO)-based polymer films. Electron beam produces mainly cross-linking between the PEO chains, improving the gas separation performance of these materials at certain optimal doses.

[Full Paper]
Angel Marcos-Fernández, Esbaide Adem, Alejandra Rubio Hernández-Sampelayo, Jose E. Báez, Laura Palacio, Pedro Prádanos, Alberto Tena, Antonio Hernández
Macromol. Chem. Phys., January 05, 2017, DOI: 10.1002/macp.201600441. Read article

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