Incorporation Of Carbon Dioxide Research Articles

Making C–C Bonds from Carbon Dioxide via Transition-Metal Catalysis

Developing more green and sustainable strategies for organic synthesis is an important modern challenge. Although carbon dioxide is an attractive reagent, because of its availability, the low reactivity of this small molecule renders it challenging to use widely in organic synthesis. The discovery of new catalysts thus plays a central role in advancing the science and impact of CO2 utilization. This perspective describes advances in metal-catalyzed carbon dioxide incorporation since Aresta’s report of the first metal-CO2 complex.

Measuring ecological total-factor energy efficiency incorporating regional heterogeneities in China

This paper proposes a metafrontier slack-based efficiency measure (MSBM) approach to model ecological total-factor energy efficiency. This new advanced approach incorporates group heterogeneities of regions, total slacks, and undesirable outputs simultaneously into energy efficiency analysis. We incorporate global environmental technology into the proposed model so as to improve its discriminating power. We conduct an empirical analysis of regional ecological energy efficiency by incorporating carbon dioxide (CO2) and sulfur dioxide (SO2) emissions and the chemical oxygen demand (COD) of China during 2001-2010. The results indicate that most of the provinces are not performing at high ecological energy efficiency. Significant regional technology gaps in ecological energy efficiency exist in three areas. We present some policy suggestions based on the empirical results.

Fabrication of microstructured Mg5(CO3)4(OH)2·4H2O and MgCO3 in flue gas absorption technology

Basic magnesium carbonate/magnesium carbonate microstructured materials have been synthesized as by-products in a simulative flue gas absorption technology through a direct carbonation of Mg-based (brucite) slurry. A probable carbonation mechanism from brucite to magnesite is proposed via a couple of gas–solid reaction pathways. Experimental results demonstrate that the reactions undergo transitional basic magnesium carbonate carnations constructed by microflakes and then development of rhombohedral magnesium carbonate microstructured crystals with further incorporation of carbon dioxide. Furthermore, the carbonation parameters of brucite are also studied in detail. Since the novel approach is simple and has a high additional value in combination with the flue gas absorption technology, the process could bring significant progress for residue treatment in chemical CO2 capture.

Isotope geochemistry of Swan Lake Basin in the Nebraska Sandhills, USA: Large 13C enrichment in sediment-calcite records

This study presents isotope geochemical analyses conducted on water column samples and core sediments collected from the Swan Lake Basin. Water analyses include the dissolved methane (CH4) content and the ratio of carbon-13 to carbon-12 (δ13C) in dissolved inorganic carbon (DIC). The core sediments – sandy muds containing inorganic calcite, organic matter, and opal phases±ostracods – were examined by X-ray diffraction, dated by radiocarbon (14C), analyzed for wt% organic carbon, wt% organic nitrogen, wt% organic matter, wt% calcite, δ13C of bulk-sediment insoluble organic matter (kerogen), 18O:16O ratio (δ18O) and δ13C of bulk and ostracod calcite. Of particular significance is the large enrichment in carbon-13 (δ13C=+4.5 to +20.4‰ V-PDB) in the calcite of these sediments. The 13C-enriched calcite is primarily formed from DIC in the water column of the lake as a result of the following combined processes: (i) the incorporation of 13C enriched residual carbon dioxide (CO2) after partial reduction to CH4 in the sediments and its migration into the water column-DIC pool; (ii) the preferential assimilation of 12C by phytoplankton during photosynthesis; (iii) the removal of 13C-depleted CH4 by ebullition and of organic matter by sedimentation and burial. The 13C enrichment was low between 3624 and 2470yr BP; high between 2470 and 1299yr BP; and moderate since 1299yr BP. Low 13C enrichment was formed under low water-column carbon levels while higher ones were formed under elevated rates of biomass and calcite deposition. These associations seem to imply that biological productivity is the main reason for carbon-13 enrichments.

ChemInform Abstract: Carbon Dioxide Incorporation into Alkyne Compounds Mediated by Silver Catalysts

AbstractReview: [27 refs.

Novel Method of Tetramic Acid Synthesis: Silver-Catalyzed Carbon Dioxide Incorporation into Propargylic Amine and Intramolecular Rearrangement

Tetramic acid derivatives have been studied as biologically active heterocycle structures for pharmaceutical or agricultural chemicals. Conventional preparative approaches often require highly functionalized starting materials and harsh heating conditions in basic media. The present report provides a conceptually new synthetic strategy for the synthesis of tetramic acid derivatives from easily available propargylic amines and carbon dioxide with a silver salt and DBU under mild reaction conditions.

Carbon Dioxide Incorporation into Alkyne Compounds Mediated by Silver Catalysts

We have reported that a silver catalyst with a base was an effective system for the incorporation and utilization of carbon dioxide in organic syntheses under mild reaction conditions. The C≡C triple bond activation by the silver catalysts was assumed to be a key step in these reactions, which was supported by DFT calculations with a model substrate. Based on these reports, we recently developed three new CO2 incorporations under the mild reaction conditions using our silver catalyst system. In this Personal Account, we describe the silver-catalyzed CO2 incorporation with C-C bond formation to afford the corresponding γ-lactone derivatives and the synthesis of benzoxazin-2-one derivatives and 4-hydroxyquinolin-2(1H)-one derivatives from alkynylanilines with carbon dioxide catalyzed by silver salts.

ChemInform Abstract: Efficient Preparation of 4‐Hydroxyquinolin‐2(1H)‐one Derivatives with Silver‐Catalyzed Carbon Dioxide Incorporation and Intramolecular Rearrangement.

AbstractThe use of catalytic amounts of AgNO3 and DBU as base renders possible the preparation of the title compounds (III) and (V) from o‐alkynylanilines and carbon dioxide under mild conditions.

Multivariable greenhouse climate control using dynamic decoupling controllers

Multivariable greenhouse climate control is presented. The greenhouse environment is described using a dynamic nonlinear model in state equation form incorporating carbon dioxide concentration, ambient air temperature and humidity concentration. The use of a dynamic linear input/output decoupling controller is described and simulation results are illustrated. The advantages of applying the specific control technique are highlighted as it does not only achieve input/output decoupling but also decreases significantly the settling time of all state variables maintaining control input constraints.

Efficient Preparation of 4-Hydroxyquinolin-2(1H)-one Derivatives with Silver-Catalyzed Carbon Dioxide Incorporation and Intramolecular Rearrangement

Although 4-hydroxyquinolin-2(1H)-one derivatives have attracted much attention due to their biological benefits, conventional reactions under harsh heat conditions must be employed to provide these key compounds. In the presence of a catalytic amount of silver salt, various o-alkynylanilines were treated with carbon dioxide and a base under mild reaction conditions to afford the corresponding 4-hydroxyquinolin-2(1H)-one derivatives in high yield.

ChemInform Abstract: Silver‐Catalyzed Incorporation of Carbon Dioxide into o‐Alkynylaniline Derivatives.

AbstractBenzoxazine‐2‐one derivatives are important heterocyclic structures due to their various pharmaceutical activities.

ChemInform Abstract: One‐Pot Synthesis of α‐Amino Acids from CO2 Using a Bismetal Reagent with Si—B Bond.

AbstractA commercially available silylboron is successfully applied to the synthesis of α‐amino acid esters from α‐amidosulfones via carbon dioxide incorporation and subsequent esterification with diazomethane.

Exploiting microbial hyperthermophilicity to produce an industrial chemical, using hydrogen and carbon dioxide

Microorganisms can be engineered to produce useful products, including chemicals and fuels from sugars derived from renewable feedstocks, such as plant biomass. An alternative method is to use low potential reducing power from nonbiomass sources, such as hydrogen gas or electricity, to reduce carbon dioxide directly into products. This approach circumvents the overall low efficiency of photosynthesis and the production of sugar intermediates. Although significant advances have been made in manipulating microorganisms to produce useful products from organic substrates, engineering them to use carbon dioxide and hydrogen gas has not been reported. Herein, we describe a unique temperature-dependent approach that confers on a microorganism (the archaeon Pyrococcus furiosus, which grows optimally on carbohydrates at 100°C) the capacity to use carbon dioxide, a reaction that it does not accomplish naturally. This was achieved by the heterologous expression of five genes of the carbon fixation cycle of the archaeon Metallosphaera sedula, which grows autotrophically at 73°C. The engineered P. furiosus strain is able to use hydrogen gas and incorporate carbon dioxide into 3-hydroxypropionic acid, one of the top 12 industrial chemical building blocks. The reaction can be accomplished by cell-free extracts and by whole cells of the recombinant P. furiosus strain. Moreover, it is carried out some 30°C below the optimal growth temperature of the organism in conditions that support only minimal growth but maintain sufficient metabolic activity to sustain the production of 3-hydroxypropionate. The approach described here can be expanded to produce important organic chemicals, all through biological activation of carbon dioxide.

Silver-Catalyzed Incorporation of Carbon Dioxide into o-Alkynylaniline Derivatives

Benzoxazine-2-one derivatives are important heterocycle structures because of their various pharmaceutical activities, though their synthetic methods had been limited. In some cases, toxic reagents, such as phosgene or carbon monoxide, are required. It was found that a silver catalyst successfully promoted the incorporation of CO(2) into o-alkynylanilines to afford the corresponding benzoxazine-2-ones bearing Z exo-olefin via 6-exo-dig cyclization at the activated C-C triple bond.

Microstructure and mechanical properties of Mg-Al alloys with in situ Al<SUB align="right">4C<SUB align="right">3 phase synthesised by CO<SUB align="right">2 incorporation during liquid state processing

In this work, Mg–Al alloys containing 7 wt.% and 9 wt.% Al were synthesised by the incorporation of carbon dioxide during casting, using the disintegrated melt deposition technique and were characterised after extrusion. Microstructural studies revealed fine–grained structure and phase analyses of Mg–7Al–CO2 and Mg–9Al–CO2 showed the presence of Al4C3 phase formed in situ during processing. Evaluation of mechanical properties of these alloys phase showed improvements in hardness, yield strength and ultimate tensile strength when compared to those without the incorporation of CO2. The observed enhancement in mechanical properties was attributed to the dispersion strengthening effect brought forth by the in situ Al4C3 phase. Based on the processing–structure–property correlation, the significant influence of CO2 incorporation and the processing methods on the microstructural and mechanical properties of the alloys are discussed.

Aluminium coordination complexes in copolymerization reactions of carbon dioxide and epoxides

Al complexes are widely used in a range of polymerization reactions (ROP of cyclic esters and cationic polymerization of alkenes). Since the discovery in 1978 that an Al porphyrin complex could copolymerize propylene oxide with carbon dioxide, Al coordination compounds have been studied extensively as catalysts for epoxide-carbon dioxide copolymerizations. The most widely studied catalysts are Al porphyrin and Al salen derivatives. This is partially due to their ability to act as mechanistic models for more reactive, paramagnetic Cr catalysts. However, this in depth mechanistic understanding could be employed to design more active Al catalysts themselves, which would be beneficial given the wide availability of this metal. Polymerization data (% CO3 linkages, M(n), M(w)/M(n) and TON) for these complexes are presented and mechanisms discussed. In most cases, especially those employing square-based pyramidal Al complexes, co-catalysts are required to obtain high levels of carbon dioxide incorporation. However, in some cases, the use of co-catalysts inhibits the copolymerization reaction. Lewis acidic Al phenolate complexes have been used as activators in CHO-carbon dioxide copolymerizations to increase TOF and this has recently led to the development of asymmetric copolymerization reactions. Given the ready availability of Al, the robustness of many complexes (e.g. use in immortal polymerizations) and opportunity to prepare block copolymers and other designer materials, Al complexes for copolymerization of carbon dioxide are surely worth a second look.

Interactions among Carbon Dioxide, Heat, and Chemical Lures in Attracting the Bed Bug,Cimex lectulariusL. (Hemiptera: Cimicidae)

Commercial bed bug (Cimex lectulariusL.) monitors incorporating carbon dioxide (CO2), heat, and chemical lures are being used for detecting bed bugs; however, there are few reported studies on the effectiveness of chemical lures in bed bug monitors and the interactions among chemical lure, CO2, and heat. We screened 12 chemicals for their attraction to bed bugs and evaluated interactions among chemical lures, CO2, and heat. The chemical lure mixture consisting of nonanal, 1-octen-3-ol, spearmint oil, and coriander Egyptian oil was found to be most attractive to bed bugs and significantly increased the trap catches in laboratory bioassays. Adding this chemical lure mixture when CO2was present increased the trap catches compared with traps baited with CO2alone, whereas adding heat did not significantly increase trap catches when CO2was present. Results suggest a combination of chemical lure and CO2is essential for designing effective bed bug monitors.

Properties of yeast free bread produced by supercritical fluid extrusion (SCFX) and vacuum baking

Abstract A novel technology, supercritical fluid extrusion (SCFX), allows for continuous production of yeast-free dough leavened via incorporation of supercritical carbon dioxide (SC-CO 2 ). In this study, an optimum dough formulation, SCFX leavened dough production and baking procedures were developed. A premixed dough was leavened by 1% (feed basis) SC-CO 2 injection in a twin screw extruder at 37 °C. Specific mechanical energy input was 18 kW h/ton. SCFX leavened dough and bread density, moisture content, bake loss, texture profile analysis (TPA) and stress relaxation were evaluated and compared to conventional yeast leavened breads throughout 5-day storage. A combination of vacuum and conventional baking yielded the lowest SCFX leavened bread density of 0.19 g/cm 3 and crumb hardness comparable to conventional yeast leavened and commercial products. This approach could be beneficial for a continuous production of consistent ready-to-bake dough and breads having equivalent quality to commercial products but produced in shorter time and without ethanol emission issues. Industrial relevance The dough leavening process in conventional bread production is an industrial hurdle for a number of reasons. First, it is very time consuming. Dough leavening through yeast fermentation can take up to eight hours, which is not conducive to high production rates. This long waiting period also means a great deal of storage space is required to produce a large amount of dough. This storage environment must be carefully controlled in terms of temperature, humidity, and air conditions in order to maintain optimal yeast fermentation, which can also be very costly. Finally, the emission of ethanol, a significant byproduct of yeast fermentation, must be controlled according to the EPA clean air act. Expensive catalytic converters must be installed and maintained in commercial bread production facilities. Bread produced by super critical fluid extrusion (SCFX) overcomes these problems. Total dough production time is less than an hour, and with the proper baking equipment, the entire process can be made continuous. This means constant output, less downtime, and none of the costly storage space used for conventional dough proofing. Furthermore, since there is no yeast being used, there is no ethanol being produced. This means no harmful volatile organic emissions and no expensive catalytic converter. Coupled with vacuum baking, this process results in bread with qualities similar to commercially produced bread in significantly less time.

Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives

Abstract A silver/DBU catalyst system was developed for the effective synthesis of cyclic carbonate and oxazolidinone from the reaction of CO2 with propargylic alcohols and propargylic amines, respectively, in high yields under mild conditions. It was found that the [3,3]-sigmatropic Meyer–Schuster-type rearrangement of the propargylic alcohol was mediated by CO2 in DMF to afford the corresponding α,β-unsaturated carbonyl compounds in high yields. The silver salt combined with the chiral Schiff base ligand could be applied to enantioselective chemical CO2 incorporation into various bispropargylic alcohols to produce the corresponding cyclic carbonate in high yields with high enantioselectivity. The absolute configuration was determined by VCD spectroscopy as well as by X-ray analysis. These products were found to be active for the aminolysis reaction to afford the corresponding carbamate derivatives in high yields without any loss of optical purity.

ChemInform Abstract: Incorporation of Carbon Dioxide into Amines Under Mild Conditions Promoted by Triphenylstibine Oxide-Tetraphosphorus Decasulfide System.

ChemInform Abstract: Incorporation of Carbon Dioxide into Amines Under Mild Conditions Promoted by Triphenylstibine Oxide-Tetraphosphorus Decasulfide System.