Amine-functionalized low-cost industrial grade multi-walled carbon nanotubes for the capture of carbon dioxide

Industrial grade multi-walled carbon nanotubes (IG-MWCNTs) are a low-cost substitute for commercially purified multi-walled carbon nanotubes (P-MWCNTs). In this work, IG-MWCNTs were functionalized with tetraethylenepentamine (TEPA) for CO₂ capture. The TEPA impregnated IG-MWCNTs were characterized with various experimental methods including N₂ adsorption/desorption isotherms, elemental analysis, X-ray diffraction, Fourier transform infrared spectroscopy and thermogravimetric analysis. Both the adsorption isotherms of IG-MWCNTs-n and the isosteric heats of different adsorption capacities were obtained from experiments. TEPA impregnated IG-MWCNTs were also shown to have high CO₂ adsorption capacity comparable to that of TEPA impregnated P-MWCNTs. The adsorption capacity of IG-MWCNTs based adsorbents was in the range of 2.145 to 3.088 mmol/g, depending on adsorption temperatures. Having the advantages of low-cost and high adsorption capacity, TEPA impregnated IG-MWCNTs seem to be a promising adsorbent for CO₂ capture from flue gas.     

Palladium‐catalyzed carbonylation of primary amines in supercritical carbon dioxide

The chemoselectivity of the palladium‐catalyzed carbonylation of amines was affected by the addition of MeOH in supercritical carbon dioxide. The results show different selectivity in supercritical carbon dioxide CO₂(sc) from that in alcohol. Methyl carbamate and its derivatives were obtained in high yields in CO₂(sc).     

Lipase-catalyzed enantioselective transesterification of 3-hydroxy-3-(2-thienyl) propanenitrile in liquid carbon dioxide

The transesterification of 3-hydroxy-3-(2-thienyl) propanenitrile catalyzed by Pseudomonas fluorescens lipase (PFL) in liquid carbon dioxide (CO₂) was reported. Compared with that in organic solvent (n-hexane), the catalytic performance of PFL was dramatically enhanced in liquid CO₂. Under the optimal reaction conditions, PFL exhibited an excellent enantioselectivity (E-value: 92.9) with a high enzyme activity (82.5?μmol/g/min). Besides, the remained (S)-3-hydroxy-3-(2-thienyl) propanenitrile with high enantiomeric purity (ee?>?99%) was obtained in 4?h when the conversion was about 52%.

Lipase-catalyzed transesterification of 3-hydroxy-3-(2-thienyl) propanenitrile in liquid CO₂     

Facile preparation and synergy study of DMC/ZnGA composite catalyst for the synthesis of oligo (propylene‐carbonate) diols

To overcome the weak carbon dioxide (CO₂) conversion ability of Zn‐Co double metal cyanide (DMC) catalyst, zinc glutarate (ZnGA) catalyst was introduced into the DMC catalytic system and applied for the synthesis of oligo (propylene‐carbonate) diols. The DMC/ZnGA composite catalyst (mass ratio = 10:1) exhibited an excellent synergistic effect which had enhanced CO₂ activation ability, high yield and good selectivity. In copolymerization process, ZnGA catalyst not only provided activated CO₂ for DMC catalyst, but also transferred the propagating chain with more alternating structures to DMC catalyst. Both of the two effects increased the carbonate content in the final products. Overall, DMC catalyst dedicated to the polymer chain growth, while the increased CO₂ conversion mainly attributed to ZnGA catalyst. Oligo (propylene‐carbonate) diols with carbonate unit content of 45.1 mol%, Mn of 1228 g/mol, W_PC of 4.3 wt% and high yield of 1689 g/g _cat was obtained.     

Controlling the Product Platform of Carbon Dioxide Reduction: Adaptive Catalytic Hydrosilylation of CO2 Using a Molecular Cobalt(II) Triazine Complex

The catalytic reduction of carbon dioxide (CO₂) is considered a major pillar of future sustainable energy systems and chemical industries based on renewable energy and raw materials. Typically, catalysts and catalytic systems are transforming CO₂ preferentially or even exclusively to one of the possible reduction levels and are then optimized for this specific product. Here, we report a cobalt‐based catalytic system that enables the adaptive and highly selective transformation of carbon dioxide individually to either the formic acid, the formaldehyde, or the methanol level, demonstrating the possibility of molecular control over the desired product platform.     

Effective tri-metallic TiO2 supported catalyst for hydrocarbon production from carbon dioxide

The current socio-economic issues with concerns on environmental quality and global warming are attributed to high concentrations of atmospheric carbon dioxide due to extensive usage of fossil fuels. Thus, over the last two decades, comprehensive work has been reported on carbon capture and storage and catalytic conversion of carbon dioxide to hydrocarbons. Among these, the reactions with hydrocarbons to form value-added products have been in focus. In this work, an attempt was made to identify the feasibility of the reaction: carbon dioxide and steam to form hydrocarbons of fuel value. After reviewing the literature on the development of various catalysts and their mechanism, a multi-metallic catalyst supported by TiO₂ Nano-needles was explored. The reaction mechanism is expected to proceed with activated CO₂ complex and hydroxyl groups over the metal oxide catalyst. Current reported work on CO₂ and Hydrogen proceeds with activated CO₂ and protons over the catalyst. The characterization techniques mainly XPS, XRD, TGA, FESEM-EDAX, FTIR, and NMR were used to analyze the catalyst activity and to confirm the products formed. The reaction is found to yield methanol and oxygen only. However, the conversion is found to be 0.4% - 3.8% in the temperature range 350°C to 550°C. The reaction of CO₂ with hydroxyl groups from water vapor can be effective as an alternative to the reaction with protons from hydrogen.     

Synthesis of dimethyl carbonate from methanol and supercritical carbon dioxide

The synthesis of dimethyl carbonate (DMC) from methanol and supercritical carbon dioxide over various base catalysts has been studied. Compounds of group-I elements (Li, Na and K) were used as base catalysts. The promoter and the dehydrating agent were also used to enhance the yield of DMC. The effects of the catalysts, promoter and dehydrating agent on the yield of DMC were investigated. By-products such as dimethyl ether (DME) and C₁–C₂ hydrocarbons were formed with the DMC as a main product. The yield of DMC with different alkali metal catalysts ranked in the following order: K > Na > Li. The catalysts of the metal-CO₃ compounds were more effective than the metal-OH compounds in DMC synthesis. The maximum DMC yield reached up to about 12 mol% in the presence of K₂CO₃ (catalyst), CH₃I (promoter) and 2,2-dimethoxypropane (dehydrating agent) at 130–140°C and 200 bar. The reaction mechanism of DMC synthesis from methanol and supercritical carbon dioxide was proposed.     

Vapor–liquid equilibria of the carbon dioxide (CO2) + 2,2-dichloro-1,1,1-trifluoroethane (R123) system and carbon dioxide (CO2) + 1-chloro-1,2,2,2-tetrafluoroethane (R124) system

Binary vapor–liquid equilibrium data were measured for the carbon dioxide (CO₂) + 2,2-dichloro-1,1,1-trifluoroethane (R123) system and the carbon dioxide (CO₂) + 1-chloro-1,2,2,2-tetrafluoroethane (R124) system at temperature from 313.15 to 333.15 K. These experiments were carried out with a circulating-type apparatus with on-line gas chromatography. The experimental data were correlated well by Peng–Robinson equation of state using the Wong–Sandler mixing rules.     

Cu-Co-Fe oxide catalysts supported on carbon nanotubes for the oxidation of CO

The catalytic activity and adsorption characteristics of the surface of catalysts in the form of carbon nanotubes produced on nickel and cobalt oxides with the Cu-Co-Fe oxide system as supported active phase were studied. At carbon nanotubes produced on nickel oxide with (10 + 10) wt.% of the catalytically active phase total conversion of CO to CO₂ is realized at 47 °C. This sample has high specific surface area and a large volume of mesopores. It was shown that the increase in catalytic activity correlates with the increase in the amount of the α₂ form of CO₂. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 4, pp. 222–226, July–August, 2006.     

Exclusion effect of carbon dioxide on the crystallization of polypropylene

We investigated the crystallization growth of isotactic polypropylene under carbon dioxide (CO₂) at various CO₂ pressures and temperatures by in situ observation with a digital high‐fidelity microscope and a specially designed high‐pressure visualized cell. The fibrils within the spherulite were distorted and branched by crystallization under CO₂ at pressures higher than 2 MPa, and this suggested the exclusion of CO₂ from the growth front of the fibrils. The spherulite growth rate (G) at 140 °C increased with the CO₂ pressure, attained a maximum value around 0.3 MPa, and then decreased. Above 6 MPa, it became slower than that under air at the ambient pressure. An analysis of the crystallization kinetics by the Hoffman–Lauritzen theory revealed that the pressure dependence of G could be ascribed to the change in the transportation rate of crystallizable molecules (β_g) with pressure; that is, β_g increased and then decreased with pressure. The increase in β_g at a low pressure was caused by the plasticizing effect of CO₂, whereas the decrease in β_g at a high pressure was due to the exclusion of CO₂ from the crystal growth front. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1565–1572, 2004     

Direct incorporation of carbon dioxide in poly(glycidyl methacrylate) and its application to the synthesis of hydrogel

This study is related to an integrated process for the application of CO₂ to poly(hydroxy urethane) and hydrogel viapoly(1,3-dioxolane-2-oxo-4-yl)methyl methacrylate [poly (DOMA)]. Quaternary ammonium salts showed good catalytic activity in the synthesis of poly(DOMA) by the direct incorporation of CO₂ into poly(glycidyl methacrylate) [poly(GMA)]. Poly[3-(N-butylcarbamoyloxy)-2-hydroxypropyl methacrylate] [poly(CHPMA)] was successfully synthesized from poly(DOMA) and n-butylamine. Hydrogels were also prepared from the poly(CHPMA), using several diisocyanates as crosslinkers, and their swelling degrees were studied by measuring water content in the hydrogels.     

Carbon Dioxide Destruction with Methane Reforming by a Novel Plasma-Catalytic Converter

A novel plasma-catalyst converter (NPCC) was engineered in applying the carbon capture utilization technology for the destruction of carbon dioxide (CO₂), which is a cause of global warming and is generated from the combustion of fossil fuels. The NPCC has an orifice-type baffle to improve an amount of gas feed with the higher CO₂ destruction for a stationary point sources application . To examine its ability for the CO₂ destruction, the performance analysis was conducted on the effects of methane additive, nozzle injection velocity, total gas feed, and catalyst type. The product gas from the NPCC was combustible components like CO, H₂, CH₄, THCs. The CO₂ destruction and the CH₄ conversion at a 1.29 CH₄/CO₂ ratio were 37 and 47 %, respectively, and the energy decomposition efficiency was 0.0036 L/min W. The nickel oxide catalyst among other catalysts showed the most effectiveness for the CO₂ destruction and CH₄ conversion at a lower temperature. The carbon-black produced without the catalytic bed has carbon nanoparticles with diverse shapes, such as spherical carbon particles and carbon nanotubes; and its high conductivity and specific surface area were suitable for special electronic materials, fuel cells, and nanocomponents.     

Effect of TMB/P123 ratios on physicochemical properties of mesocellular foam carbon (MCF-C) as catalyst for ethanol dehydrogenation

The preparation of mesocellular foam carbon catalysts with different ratios of 1,3,5-trimethyl benzene (TMB)/P123 is represented for investigation in catalytic activity via ethanol dehydrogenation to acetaldehyde. The TMB was used as a swelling agent and P123 acted as template-structuring. The physicochemical properties of synthesized catalysts were determined using Brunauer-Emmett-Teller (BET) surface area analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM)–energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), ammonia temperature-programmed desorption (NH₃-TPD), and carbon dioxide temperature-programmed desorption (CO₂-TPD). The evidence suggested that various ratios of TMB/P123 can differently control the mesostructure including the pore size, specific surface area, and pore volume. Particularly, MCF-C 3.5 catalyst (TMB/P123 of 3.5) enhanced the catalytic via ethanol dehydrogenation. Interestingly, effectively controllable pore structure of catalysts is beneficial for the desorption of selective product such as acetaldehyde leading to remarkably increased yield of acetaldehyde. Furthermore, the MCF-C 3.5 evidently exhibited outstanding stability at temperature of 400 °C for 12 h. Thus, it can be reasonably selected the ratio of TMB/P123 as 3.5, which is dominantly facilitated either high diffusion of reactant or high stability without losing of the traditional structure compared with other ratios of TMB/P123.     

Alternating copolymerization of carbon dioxide and epoxide catalyzed by an aluminum Schiff base–ammonium salt system

The alternating copolymerization of carbon dioxide (CO₂) and cyclohexene oxide (CHO) with an aluminum Schiff base complex in conjunction with an appropriate additive as a novel initiator is demonstrated. A typical example is the copolymerization of CO₂ and CHO with the (Salophen)AlMe ( 1a )–tetraethylammonium acetate (Et₄NOAc) system. When a mixture of the 1a –Et₄NOAc system and CHO was pressurized by CO₂ (50 atm) at 80 °C in CH₂Cl₂, the copolymerization of CO₂ and CHO took place smoothly and produced a high polymer yield in 24 h. From the IR and NMR spectra, the product was characterized to be a copolymer of CO₂ and CHO with an almost perfect alternating structure. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis indicated that an unfavorable reaction between Et₄NOAc and CH₂Cl₂ and a possible chain‐transfer reaction with concomitant water occurred, and this resulted in the bimodal distribution of the obtained copolymer. With carefully predried reagents and apparatus, the alternating copolymerization in toluene gave a copolymer with a unimodal and narrower molecular weight distribution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4172–4186, 2005     

A new copolymerization process leading to poly(propylene carbonate) with a highly enhanced yield from carbon dioxide and propylene oxide

Using excessively loaded propylene oxide (PO) as a solvent, the copolymerization of carbon dioxide (CO₂) and PO was carried out with zinc glutarate catalyst, consequently producing poly(propylene carbonate) of high molecular weight in a high yield (64–70 g polymer per gram of catalyst) never achieved before. Both the PO used as solvent and the excessively loaded CO₂ were fully recoverable, respectively, and reusable for their copolymerization, indicating that this is a clean, green polymerization process to convert CO₂ to its polycarbonate. The polymer yield was further improved by scaling up the copolymerization process. Among zinc glutarate catalysts prepared through several synthetic routes, one from zinc oxide delivered the highest yield in the copolymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1863–1876, 1999     

Reversible isopentane-induced depression of carbon dioxide permeation through polycarbonate

Permeability data are reported for carbon dioxide in Lexan polycarbonate at 35°C. Measurements were made for both pure carbon dioxide and for a mixed feed consisting of carbon dioxide with a 117.8-torr (0.155-atm) Partial pressure of isopentane. The effects of varying upstream CO₂ driving pressure from 1 up to 20 atm were studied. The permeability to CO₂ is reduced significantly in the presence of isopentane; however, the fractional depression of the CO₂ permeability due to the isopentane at low driving pressures is much more significant than at high CO₂ driving pressures. The well-known pressure dependence of carbon dioxide permeabilities in glassy polymers, therefore, is largely diminished by introducing isopentane to the pure carbon dioxide feed. These observations are consistent with a model for transport in glassy polymers which explains the observed trends in terms of competition between the two penetrants for microvoid sorption sites existing in the non-equilibrium glassy polymer. Exclusion of carbon dioxide from microvoid sorption sites by the more condensable isopentane preempts transport through the microvoid regions, resulting in the observed depression of the CO₂ permeability.     

Selective and Efficient Reduction of Carbon Dioxide to Carbon Monoxide on Oxide‐Derived Nanostructured Silver Electrocatalysts

In this work, the selective electrocatalytic reduction of carbon dioxide to carbon monoxide on oxide‐derived silver electrocatalysts is presented. By a simple synthesis technique, the overall high faradaic efficiency for CO production on the oxide‐derived Ag was shifted by more than 400 mV towards a lower overpotential compared to that of untreated Ag. Notably, the Ag resulting from Ag oxide is capable of electrochemically reducing CO₂ to CO with approximately 80 % catalytic selectivity at a moderate overpotential of 0.49 V, which is much higher than that (ca. 4 %) of untreated Ag under identical conditions. Electrokinetic studies show that the improved catalytic activity is ascribed to the enhanced stabilization of COOH^. intermediate. Furthermore, highly nanostructured Ag is likely able to create a high local pH near the catalyst surface, which may also facilitate the catalytic activity for the reduction of CO₂ with suppressed H₂ evolution.     

Equilibrium solubility of carbon dioxide in 2(methylamino)ethanol

In this paper the equilibrium solubility of carbon dioxide in 1.0 M, 2.0 M and 4.0 M 2(methylamino)ethanol (MAE) is measured at 303, 313 and 333 K, and at CO₂ partial pressures ranging from 1 to 100 kPa using stirred cell reactor. The Kent-Eisenberg model was used to predict the solubility of carbon dioxide in MAE solutions. The equilibrium constant representing hydrolysis of carbamate ion is correlated with temperature, CO₂ partial pressure and amine concentration by non-linear regression, using experimental results of carbamate ion concentrations. The model predicted results showed good agreement with the experimental solubility results. The solubility profile of CO₂ in MAE showed better performance when compared with other commercial amines.     

(n‐Bu2Sn)2O(CO3): An active,robust and recyclable organotin(IV) for the direct synthesis of linear organic carbonates from carbon dioxide and alcohols

Organotin(IV) compounds are known to promote the direct synthesis of organic carbonates from carbon dioxide and alcohols. In the past, structural studies have highlighted that the carbonato moiety is a recurring ligand of tin species collected during CO₂ pressurized reactions. In a mimetic approach and in order to achieve an available and recyclable precursor, the title compound (n ‐Bu₂Sn)₂O(CO₃) ( 1 ) was prepared in a single step by reacting commercial di‐n ‐butyltin dichloride with an aqueous solution of sodium carbonate. Compound 1 was characterized using infrared spectroscopy and thermogravimetric and elemental analyses. Multinuclear NMR investigations in solution were also conducted. Compound 1 was then evaluated for the direct carbonation of alcohols (methanol, ethanol, n ‐butanol and isopropanol) under CO₂ pressure. Recycling experiments were performed showing the efficient reuse of 1 without loss of activity. Furthermore, the infrared fingerprint of 1 was preserved even after several runs demonstrating a good stability. The effects of pressure and of reaction time on dimethyl carbonate formation were also studied.     

New Device for Adding Polar Modifiers to Carbon Dioxide Mobile Phase for Supercritical Fluid Chromatography

Abstract

Adding additional components to supercritical carbon dioxide in supercritical fluid chromatography can extend or significantly alter the fluid solvating properties. Polar samples which are difficult to be analyzed with pure supercritical CO₂ because of their high polarity can be separated by adding polar modifiers to supercritical CO₂. In this paper, a new mixing device using a teflon high capacity filter for adding polar modifiers to carbon dioxide mobile phase is introduced. This new mixing device could keep the amount of modifier in the mobile phase constant for a much longer time than a saturator column. The amount of water or methanol dissolved in supercritical CO₂ was measured by amperometric microsensor which is made of thin film of perfluorosulfonate ionomer(PFSI).