Oxidation of Polyisoprene Popcorn Polymer. IV. Effect of Polymer Purity on Carbon Dioxide and Water Yields

Abstract

Recent oxidation studies on polysisoprene popcorn polymer have shown that the yields of volatile products are a function of the presence or absence of residual isoprene dimers on the polymer. In contrast to previously reported data, no carbon dioxide is detected when highly purified polymer is used. Also, the yields of water drop to approximately half the previously reported values. Quantitative data are presented for the production of water during the early stages of autoxidation. The reported data emphasize the possible errors that can occur when oxidation reaction mechanisms are based on the stoichiometry of volatile products produced from impure polymer samples.     

Oxidation of Polyisoprene Popcorn Polymer. III. Further Studies on Water and Carbon Dioxide Production

The volatile products resulting from polyisoprene popcorn polymer oxidation were analyzed quantitatively for carbon dioxide and water, and semiquantitatively for formaldehyde. The production of these three products was a linear function of the amount of oxygen consumed in the reaction. For every mole of oxygen reacted, 0.098 mole of water, 0.038 mole of carbon dioxide, and > 0.016 mole of formaldehyde were formed. Twenty-four products were detected after extensive oxidation; the major ones being water, carbon dioxide, formaldehyde, formic acid, 2,5-hexanedione, and acetic acid. No levulin-aldehyde was identified in the products. A tentative oxidation mechanism is discussed.     

Initiation Reaction of the Alkali-Metal Catalyzed Polymerization of Dienes Bearing Allylic Protons

Initiation of the polymerization of dienes bearing allylic protons with metallic alkali metals were investigated. Addition of a tertiary amine into the solution resulted in the complete inhibition of the polymerization to give a mono- or dianionic dienylmetal compound and reduced dimers in quantitative yield. The planar conformations of the isolated dienyl alkali metal compounds, which are considered to be real active species toward the alkali-metal catalyzed polymerizations, were determined by PMR and ¹³C NMR spectroscopy. The catalytic activity toward polymerization as well as the chemical reactivity of those dienyl alkali metals was investigated.     

The Magnetic Field Effect on the Polymerization of Styrene in Supercritical Carbon Dioxide

Over the past decade there has been a growing interest in using supercritical fluids (SCFs) to promote reactions and to replace hazardous solvents with environmentally benign solvents, such as supercritical CO2 and H2O. Many reactions in SCFs have been studied1, including polymerization in scCO22. It is known that a small change in the pressure near critical point of a fluid causes a significant change in density-dependent properties such as the solubility parameter, viscosity, and dielect…     

The Effect of Neodymia on the Activity of Hydrocarbon Synthesis Catalysts from Carbon Dioxide

Inrecentyears,ironbasecatalystswereusedforcarbondioxidehydrogenationtolightolefinathighpressure'-'andatnormalpressure,Fe-Cobimetalliccatalystshowsgoodcarbondioxidehydrogenationactivitytolightolefins'6.Althoughhydrocarbonisthermodynamicfavoredthanthatofcarbonmonoxideatlowertemperature,thecatalysisactivityofFe-Cobimetalliccatalystisnothighenoughforhydrocarbonsynthesis.Inthispaper,neodymiawasaddedintothecatalysttoimproveitsactivityandlightolefinselectivity.TheFe-Cobimetalliccatalystswereprepare…     

碱性金属修饰金属有机骨架材料MOF-5吸附位点及其常态下分离二氧化碳/甲烷的应用

利用“一步法”合成并表征了4种碱性金属修饰的金属有机骨架材料MOF-5(记作M-MOF-5,M=Li,Na,K,Mg)。 并应用理想溶液吸附理论(IAST)对样品吸附选择性进行计算比较。 结果表明,碱性金属掺入可以降低MOF-5材料骨架结构的“互穿”程度,同时,在常温常压下,M-MOF-5对CO₂/CH₄的吸附选择性相对MOF-5(选择性为3.79)有着显著提高,尤其是Li-MOF-5(选择性为7.39)。 此外,Li-MOF-5的CO₂捕获能力相对MOF-5也有提高。     

Adsorption of Carbon Dioxide on Activated Carbon

The adsorption of CO2 on a raw activated carbon A and three modified activated carbon samples B, C, and D at temperatures ranging from 303 to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus in order to obtain more information about the effect of CO2 on removal of organic sulfur-containing compounds in industrial gases. The active ingredients impregnated in the carbon samples show significant influence on the adsorption for CO2 and its volumes adsorbed on modified carbon samples B, C, and D are all larger than that on the raw carbon sample A. On the other hand, the physical parameters such as surface area, pore volume, and micropore volume of carbon samples show no influence on the adsorbed amount of CO2. The Dubinin-Radushkevich (D-R) equation was the best model for fitting the adsorption data on carbon samples A and B, while the Preundlich equation was the best fit for the adsorption on carbon samples C and D. The isosteric heats of adsorption on carbon samples A, B, C, and D derived from the adsorption isotherms using the Clapeyron equation decreased slightly increasing surface loading. The heat of adsorption lay between 10.5 and 28.4 kJ/mol, with the carbon sample D having the highest value at all surface coverages that were studied. The observed entropy change associated with the adsorption for the carbon samples A, B, and C (above the surface coverage of 7 ml/g) was lower than the theoretical value for mobile adsorption. However, it was higher than the theoretical value for mobile adsorption but lower than the theoretical value for localized adsorption for carbon sample D.     

The Effect of Branching Structure on the Properties of Entangled or Non-covalently Crosslinked Polyisoprene

The branching structures in natural rubber(NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the complexity of the system. Herein, polyisoprene-(polyisoprene-g-polylactide)(PI-PLA) as model compound containing branching structure was designed and synthesized, which can improve the modulus, strength and viscoelasticity activation energy compared to those of the pristine polyisoprene(PI). The reason is that the branching structure contributes to the entanglement between polyisoprene chains. In order to probe the effect of branching structure on noncovalently crosslinked system, the polyisoprene block of PI-PLA was epoxidized and mixed with Fe~(3+) ions to introduce coordination bonds. Compared with the linear counterpart, the branching structure obviously enhanced activation energy of coordinated polyisoprenes, remarkably improving the mechanical properies of elastomer.     

添加物对光促进下环己烯与二氧化碳羰基化反应的影响

Owing to the greenhouse effect, the rise of carbon dioxide concentration in the atmosphere is a global environmental issue.     

不同Cu-Ni比对二氧化碳加氢反应的影响

Ｃｕ基和Ｎｉ基触媒都是优良的加氢催化剂，广泛地用于费托合成和其它加氢工业。以ＣＯ２加氢合成甲醇和烃类为背景，在较低温度下对Ｃｕ－Ｎｉ双金属催化剂的性能已有所研究［１，２］。然而，对Ｃｕ－Ｎｉ催化剂在较高温度下的催化性能的研究尚未见报道。本文在文献的基...     

The Carbonylations of Cyclohexene with Carbon Dioxide

Carb0ndi0xide,anaturalandinexpensivesourceoffunctionalcarbonunits,showspotentialabilitiesf0rthefunctionalization0f0rganicsubstrate.ThehighstabilityofCO=,however,andthelack0freliablemeth0ds0factivation,considerablyrestrictitsappIications'.Inrecentyearstransiti0nmetalcatalyzedreacti0ns0fcarb0ndi0xideaimedattheutilizationofCO2asbuildingblockinorganicsynthesishaveattractedc0nsiderableattentions,becausecarbondi0xideisthebiggestcarbonsourceonearchandthebasisofallbiochemicalorganicsynthesispr0cesse…     

Wetting of a Charged Surface of Glassy Carbon by Molten Alkali-Metal Chlorides

Values of the contact angle of wetting of a surface of glassy carbon by molten chlorides of lithium, sodium, potassium, and cesium are measured by the meniscus weight method to determine the common factors of wettability of solid surfaces by ionic melts upon a change in the salt phase composition and a jump in electric potential. It is found that with a potential shift in the positive direction the shape of the curve of the contact angle’s dependence on the potential varies upon substitution of one salt by another: the angle of wetting shrinks monotonously in lithium chloride but remains constant in molten cesium chloride. This phenomenon is explained by the hypothesis that the nature of the halide anion adsorption on the positively charged surface of an electrode is chemical and not electrostatic. It is shown that the adsorption process is accompanied by charge transfer through the interface, with covalent bonding between the adsorbent and adsorbate.

     

二氧化碳电还原反应的理论研究

Converting CO₂ into value-added products via sustainable energy, such as electrical energy, has several advantages. First, it is one of the most promising routes to close the carbon loop and plays a crucial role in significantly reducing the CO₂ concentration in the atmosphere. Second, it can utilize CO₂ as a valuable industry reactant that can store energy by converting electrical energy to chemical energy. Although the CO₂ reduction reaction has been studied for more than three decades, the sluggish kinetics remain a bottleneck, which requires a highly efficient catalyst. However, none of the reported catalysts meets the requirements for any practical application due to low activity and poor selectivity. To rationally design a more efficient CO₂ reduction catalyst, understanding the reaction mechanism is crucial. Although it is challenging to experimentally capture and characterize the reactive intermediates, atomic modeling serves as an alternative for providing an understanding of the elementary reactions on a microscale. Significant progress has been made in understanding the reaction mechanism using multiscale simulations. In this study, important progress in revealing the reaction mechanism of CO₂ reduction using computational simulation in recent years is summarized. First, the advances in simulation methods for electrochemical reactions are introduced, and the advantages and disadvantages of various methods are compared. Second, the detailed reaction mechanism of CO₂ reduction to various major products, such as CO, CH₄, and C₂H₄, and minor products, such as ethanol and acetate, are disused. Different results obtained from different approximations are compared, while a mechanism that can better explain the existing experimental results is recommended. Third, the operando technique, such as ambient pressure X-ray photoelectron spectroscopy, is disused. The operando analysis results are direct evidence to validate the theoretically proposed reaction pathway. In turn, the theoretical predictions can help resolve the experimental spectrum, which is usually too complex to refer to a reference system. The combination of theory and operando experiments should be one of the most promising directions in determining the reaction mechanism. Fourth, novel synthesis strategies are discussed. These new ideas are beneficial for simplifying the synthesis process or increasing the diversity of products. Finally, the recent progress in the application of machine learning to big data for CO₂ reduction is discussed. These new powerful tools may play a crucial role in reaction mechanism studies. Overall, in the study of electrochemical reaction mechanism, theoretical simulation can provide the reaction details and energy information of elementary reactions at the atomic level. Therefore, in the study of electrochemical reaction mechanism of carbon dioxide, the microscopic mechanism that the experiment cannot provide is supplemented. On the one hand, it explains the existing experimental phenomena; however, on the other hand, it provides new insights for the study of reaction mechanism. On this basis, the use of new research paradigms, such as high-throughput computing and machine learning, provides new ideas for a rational design for accelerating material development.     

Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation

Homoleptic ceric pyrazolates (pz) Ce(RR’pz)₄ (R = R’ = tBu; R = R’ = Ph; R = tBu, R’ = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe₂)₂]₄ with the corresponding pyrazole derivative. The resulting complexes were investigated in their reactivity toward CO₂, revealing a significant influence of the bulkiness of the substituents on the pyrazolato ligands. The efficiency of the CO₂ insertion was found to increase in the order of tBu₂pz < Ph₂pz < tBuMepz < Me₂pz. For comparison, the pyrrole-based ate complexes [Ce₂(pyr)₆(µ-pyr)₂(thf)₂][Li(thf)₄]₂ (pyr = pyrrolato) and [Ce(cbz)₄(thf)₂][Li(thf)₄] (cbz = carbazolato) were obtained via protonolysis of the cerous ate complex Ce[N(SiHMe₂)₂]₄Li(thf) with pyrrole and carbazole, respectively. Treatment of the pyrrolate/carbazolate complexes with CO₂ seemed promising, but any reversibility could not be observed.     

Effect of Elevated Carbon Dioxide Exposure on Nutrition-Health Properties of Micro-Tom Tomatoes

(1) Background: The anthropogenically induced rise in atmospheric carbon dioxide (CO₂) and associated climate change are considered a potential threat to human nutrition. Indeed, an elevated CO₂ concentration was associated with significant alterations in macronutrient and micronutrient content in various dietary crops. (2) Method: In order to explore the impact of elevated CO₂ on the nutritional-health properties of tomato, we used the dwarf tomato variety Micro-Tom plant model. Micro-Toms were grown in culture chambers under 400 ppm (ambient) or 900 ppm (elevated) carbon dioxide. Macronutrients, carotenoids, and mineral contents were analyzed. Biological anti-oxidant and anti-inflammatory bioactivities were assessed in vitro on activated macrophages. (3) Results: Micro-Tom exposure to 900 ppm carbon dioxide was associated with an increased carbohydrate content whereas protein, minerals, and total carotenoids content were decreased. These modifications of composition were associated with an altered bioactivity profile. Indeed, antioxidant anti-inflammatory potential were altered by 900 ppm CO₂ exposure. (4) Conclusions: Taken together, our results suggest that (i) the Micro-Tom is a laboratory model of interest to study elevated CO₂ effects on crops and (ii) exposure to 900 ppm CO₂ led to the decrease of nutritional potential and an increase of health beneficial properties of tomatoes for human health.     

Effect of Supercritical Carbon Dioxide Conditions on PVDF/PVP Microcellular Foams

Supercritical carbon dioxide (ScCO₂) was used as a physical foaming agent to prepare poly(vinylidene f luoride)/poly(N-vinyl pyrrolidone) (PVDF/PVP) microstructure material. The effects of foaming conditions including saturation pressure, foaming temperature and foaming time on PVDF/PVP foams morphology, thermal and electrical behavior were systematically investigated by scanning electron microscope, differential scanning calorimeter and broadband dielectric spectrometer. Small cell and low cell density were achieved at low pressure of 12 MPa, as increasing saturation pressure, the average cell size increased first, and then decreased. The competition between the cell growth and cell nucleation played an important role in average cell size, which was directly related to ScCO₂ processing conditions. With increasing foaming temperature, cell size was increased and cell density was decreased, in a nearly linear manner. The variation of foaming time was considered to be closely related to the time for cells to grow. Thus, the results revealed that the average cell size enhanced with extending foaming time. The thermal properties of PVDF/PVP composites are slightly inf luenced by foaming parameters, and the dielectric constant of PVDF/PVP composite foams decreased with increasing volume expansion ratio.     

Promoter Effect of Potassium on an Iron Catalyst in the Carbon Dioxide Hydrogenation Reaction

Catalysts containing copper, zinc and aluminium oxides are used extensively in hydrogenation reactions, low temperature water-gas shift and low pressure methanol synthesis processes. In the present study, the effects of certain pertinent preparation parameters on catalysts' activity have been studied, applying the saturated fractional factorial experimental design method. The influence of time and temperature of calcination, aging time, the method of mixing of reactant solutions, the nature of the precipitant and the molar ratio of the latter to metal nitrates have been investigated. The catalysts prepared, using sodium carbonate showed higher activities relative to those synthesized by applying sodium hydrogen carbonate. Higher temperatures and longer time of calcination have profound effects on the activity of catalysts prepared, using sodium hydrogen carbonate. Shorter aging times and higher molar ratios of precipitant to metal nitrates promoted the activity of catalysts prepared by sodium carbonate. In case of catalysts synthesized, using sodium hydrogen carbonate as the precipitant, the aging time should be maintained as short as possible in order the catalysts to acquire higher activities.     

The Effect of Functional Groups on the Phase Behavior of Carbon Dioxide Binaries and Their Role in CCS

In recent years we have focused our efforts on investigating various binary mixtures containing carbon dioxide to find the best candidate for CO₂ capture and, therefore, for applications in the field of CCS and CCUS technologies. Continuing this project, the present study investigates the phase behavior of three binary systems containing carbon dioxide and different oxygenated compounds. Two thermodynamic models are examined for their ability to predict the phase behavior of these systems. The selected models are the well-known Peng–Robinson (PR) equation of state and the General Equation of State (GEOS), which is a generalization for all cubic equations of state with two, three, and four parameters, coupled with classical van der Waals mixing rules (two-parameter conventional mixing rule, 2PCMR). The carbon dioxide + ethyl acetate, carbon dioxide + 1,4-dioxane, and carbon dioxide + 1,2-dimethoxyethane binary systems were analyzed based on GEOS and PR equation of state models. The modeling approach is entirely predictive. Previously, it was proved that this approach was successful for members of the same homologous series. Unique sets of binary interaction parameters for each equation of state, determined for the carbon dioxide + 2-butanol binary model system, based on k₁₂–l₁₂ method, were used to examine the three systems. It was shown that the models predict that CO₂ solubility in the three substances increases globally in the order 1,4-dioxane, 1,2-dimethoxyethane, and ethyl acetate. CO₂ solubility in 1,2-dimethoxyethane, 1.4-dioxane, and ethyl acetate reduces with increasing temperature for the same pressure, and increases with lowering temperature for the same pressure, indicating a physical dissolving process of CO₂ in all three substances. However, CO₂ solubility for the carbon dioxide + ether systems (1,4-dioxane, 1,2-dimethoxyethane) is better at low temperatures and pressures, and decreases with increasing pressures, leading to higher critical points for the mixtures. By contrast, the solubility of ethyl acetate in carbon dioxide is less dependent on temperatures and pressures, and the mixture has lower pressures critical points. In other words, the ethers offer better solubilization at low pressures; however, the ester has better overall miscibility in terms of lower critical pressures. Among the binary systems investigated, the 1,2-dimethoxyethane is the best solvent for CO₂ absorption.