Foaming Properties of CO2-Triggered Surfactants for Switchable Foam Control

Switchable surfactants, particularly those triggered by CO₂ used for switchable foam control, are relatively less documented. In this article, the foaming performance of 2-alkyl-1-hydroxyethylimidazolinium bicarbonate cationic surfactants (HEAIBs) was investigated for the first time. The foaming properties of these surfactants demonstrate that HEAIBs can generate foam with moderate stability, on demand, can be rapidly yet reversibly dissipated upon exposure to air. The results illustrated such a facile trigger, and the foam on/off transition would have huge potential to form a new class of stimuli-response foaming agents.      

A CO2-Switchable Polymer Surfactant Copolymerized with DMAEMA and AM as a Heavy Oil Emulsifier

A CO₂-switchable polymer surfactant was synthesized with acrylamide (AM) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The changes in conductivity, particle size, and ζ-potential were adopted to illustrate its switchability. The CMC of the surfactant was determined by the break point of the curve of surface tension versus concentration. An oil emulsion with 8 g/L surfactant almost reached the highest stability. The thermodynamic stability of the emulsion decreased sharply upon increase of the temperature. Adding an inorganic salt was hard to affect the emulsion stability because the surfactant is non-ionic. The emulsion could maintain its stability even if the concentration of NaCl was as high as 10 g/L. The emulsion could easily be broken by bubbling CO₂. Its dehydration rate was 155 times faster than that without the presence of CO₂, and the amount of residual oil in water was only 32.22 ppm, which displayed brilliant performance of de-emulsification.     

Soybean-Oil-Based CO2-Switchable Surfactants with Multiple Heads

Oligomeric surfactants display the novel properties of low surface activity, low critical micellar concentration and enhanced viscosity, but no CO₂ switchable oligomeric surfactants have been developed so far. The introduction of CO₂ can convert tertiary amine reversibly to quaternary ammonium salt, which causes switchable surface activity. In this study, epoxidized soybean oil was selected as a raw material to synthesize a CO₂-responsive oligomeric surfactant. After addition and removal of CO₂, the conductivity analyzing proves that the oligomeric surfactant had a good response to CO₂ stimulation. The viscosity of the oligomeric surfactant solution increased obviously after sparging CO₂, but returned to its initial low viscosity in the absence of CO₂. This work is expected to open a new window for the study of bio-based CO₂-stimulated oligomeric surfactants.     

CO2/N2-switchable viscoelastic fluids based on a pseudogemini surfactant system

We prepared a CO₂/N₂-switchable pseudogemini surfactant system composed of sodium oleate (NaOA) and N, N, N’, N’-tetramethyl-1, 6-hexanediamine (TMHDA) at a mole ratio of 2:1. The two tertiary amine groups of the TMHDA can be protonated into quaternary ammonium salt when the system was bubbled with CO₂, which can ‘‘bridge’’ two NaOA molecules via electrostatic attraction to form a pseudogemini surfactant. The formed pseudogemini surfactant can further self-assemble to wormlike micelles, causing a sharp increase in viscosity. The viscoelastic property and structure transitions of the pseudogemini surfactant system were investigated before and after bubbling of CO₂. The pseudogemini surfactant system transformed from water-like to gel-like fluid with the bubbling of CO₂, followed by white precipitate. The cryo-transmission electron microscope (cryo-TEM) characterization and rheological measurements exhibited that the sol–gel transition was attributed to a spherical-wormlike micelle transition. Moreover, this transition was switchable at least in three cycles. Finally, a reasonable mechanism of aggregate behavior transition was proposed from the viewpoint of the molecular states, micelle structures, and intermolecular interactions.     

Application of CO2-Switchable Oleic-Acid-Based Surfactant for Reducing Viscosity of Heavy Oil

CO₂-switchable oligomeric surfactants have good viscosity-reducing properties; however, the complex synthesis of surfactants limits their application. In this study, a CO₂-switchable “pseudo”-tetrameric surfactant oleic acid (OA)/cyclic polyamine (cyclen) was prepared by simple mixing and subsequently used to reduce the viscosity of heavy oil. The surface activity of OA/cyclen was explored by a surface tensiometer and a potential for viscosity reduction was revealed. The CO₂ switchability of OA/cyclen was investigated by alternately introducing CO₂ and N₂, and OA/cyclen was confirmed to exhibit a reversible CO₂-switching performance. The emulsification and viscosity reduction analyses elucidated that a molar ratio of OA/cyclen of 4:1 formed the “pseudo”-tetrameric surfactants, and the emulsions of water and heavy oil with OA/cyclen have good stability and low viscosity and can be destabilized quickly by introducing CO₂. The findings reported in this study reveal that it is feasible to prepare CO₂-switchable pseudo-tetrameric surfactants with viscosity-reducing properties by simple mixing, thus providing a pathway for the emulsification and demulsification of heavy oil by using the CO₂-switchable “pseudo”-oligomeric surfactants.     

CO2开关型溶剂、溶质及表面活性剂

CO₂诱导的开关型溶剂、溶质及表面活性剂是指在通入和排出CO₂后,其溶液性质能发生可逆变化的新型溶剂、溶质及表面活性剂,是典型的环境刺激响应型智能化合物。本文综述了CO₂诱导的开关型溶剂、溶质及表面活性剂的结构、性能及研究进展,并指出了这些开关型溶剂、溶质及表面活性剂的发展方向及应用前景等。     

CO2-triggered switchable Pickering emulsion stabilized by guanidine-functionalized silica particles

The guanidine group-modified silica particles were used as emulsifier to obtain a CO₂-responsive Pickering emulsion. To compare the wettability effect of the particles on the stability of the emulsion, both guanidine and alkyl chain were attached on the surface of silica particles. The influences of tension, particles concentration, oil-water fraction, NaCl concentration, and CO₂ on Pickering emulsion properties were investigated. Although the particles did not decrease the surface and interfacial tensions of the air/oil-water interfaces, they attached on the oil–water interfaces and stabilized the emulsions at room temperature for at least 4 weeks. Addition of salt increased the emulsion stability and induced phase inversion at high salt concentration. The stabilization–destabilization cycles of the emulsion could be successively controlled by alternative CO₂/heating triggers due to the protonation-deprotonation of guanidine groups on the particle surfaces.     

CO2-Switchable Nanoemulsion Based on N,N-dimethyl Oleoaminde-Propylamine (DOAPA) and Sodium Dodecyl Sulphate (SDS)

This research reported a CO₂-switchable nanoemulsion that was formulated by dilution of water in oil microemulsion, which was formed by mixture of N,N-dimethyl oleoaminde-propylamine (DOAPA), sodium dodecyl sulphate (SDS), n-hexane, n-butanol, and water. A reversible switch process was observed between a monophasic nanoemulsion and complete phase separation at R = 1:1 with the CO₂ and N₂ bubbling alternately. The phase separation was not found, but the reversible switch between single phase nanoemulsion was detected by zeta potential, electrical conductivity, and dynamic light scattering at R = 1:1.5 and 1.5:1.     

Effects of CO2 Injection on Phase Behavior of Crude Oil

CO₂ flooding is a win-win technology, sequestrating greenhouse CO₂ while producing a significant amount of crude oil to help defray the cost of CO₂ sequestrating and enhancing oil recovery. However, due to the difference of sedimentary environment and poor properties of formations, physical properties of the crude oil and the effect of CO₂ flooding are not always satisfactory in most oilfields of China. Therefore, in this article, to improve the understanding of the oil recovery mechanisms and feasibility of CO₂ flooding in China, based on the oil and gas of Mao-3 oilfields, phase behavior of the CO₂ and crude oil system was investigated. Parameters like saturated pressure, volume factor, gas oil ratio, and viscosity were measured and their relationships analyzed. Results show that crude oil of Mao-3 reservoir and CO₂ has good mutual dissolution under reservoir conditions, and CO₂ could expand the oil and reduce the oil viscosity greatly. As a result, formation energy could be enhanced and flow characteristics of the oil could be improved by CO₂ flooding.     

Tunable Viscoelastic Properties of Sodium Polyacrylate Solution via CO2-Responsive Switchable Water

Upon stimulus by CO₂, CO₂-switchable viscoelastic fluids experience a deliberate transition between non-viscous and highly viscous solution states. Despite attracting considerable recent attention, most such fluids have not been applied at a large- scale due to their high costs and/or complex synthesis processes. Here, we report the development of CO₂-switchable viscoelastic fluids using commercially available sodium polyacrylate (NaPAA) and N,N-dimethyl ethanol amine (DMEA)-based switchable water. Upon bubbling CO₂, into the solutions under study, DMEA molecules are protonated to generate quaternary ammonium salts, resulting in pronounced decreases in solutions viscosity and elasticity due to the influence of increased ionic strength on NaPAA molecular conformations. Upon removal of CO₂ via introduction of N₂, quaternary salts are deprotonated to tertiary amines, allowing recovery of fluid viscosity and elasticity to near the initial state. This work provides a simple approach to fabricating CO₂-switchable viscoelastic fluids, widening the potential use of CO₂ in stimuli-responsive applications.     

Determination of Minimum Miscibility Pressure of CO2–Oil System: A Molecular Dynamics Study

CO₂ enhanced oil recovery (CO₂-EOR) has become significantly crucial to the petroleum industry, in particular, CO₂ miscible flooding can greatly improve the efficiency of EOR. Minimum miscibility pressure (MMP) is a vital factor affecting CO₂ flooding, which determines the yield and economic benefit of oil recovery. Therefore, it is important to predict this property for a successful field development plan. In this study, a novel model based on molecular dynamics to determine MMP was developed. The model characterized a miscible state by calculating the ratio of CO₂ and crude oil atoms that pass through the initial interface. The whole process was not affected by other external objective factors. We compared our model with several famous empirical correlations, and obtained satisfactory results—the relative errors were 8.53% and 13.71% for the two equations derived from our model. Furthermore, we found the MMPs predicted by different reference materials (i.e., CO₂/crude oil) were approximately linear (R² = 0.955). We also confirmed the linear relationship between MMP and reservoir temperature (T_R). The correlation coefficient was about 0.15 MPa/K in the present study.     

Trends on CO2 Capture with Microalgae: A Bibliometric Analysis

The alarming levels of carbon dioxide (CO₂) are an environmental problem that affects the economic growth of the world. CO₂ emissions represent penalties and restrictions due to the high carbon footprint. Therefore, sustainable strategies are required to reduce the negative impact that occurs. Among the potential systems for CO₂ capture are microalgae. These are defined as photosynthetic microorganisms that use CO₂ and sunlight to obtain oxygen (O₂) and generate value-added products such as biofuels, among others. Despite the advantages that microalgae may present, there are still technical–economic challenges that limit industrial-scale commercialization and the use of biomass in the production of added-value compounds. Therefore, this study reviews the current state of research on CO₂ capture with microalgae, for which bibliometric analysis was used to establish the trends of the subject in terms of scientometric parameters. Technological advances in the use of microalgal biomass were also identified. Additionally, it was possible to establish the different cooperation networks between countries, which showed interactions in the search to reduce CO₂ concentrations through microalgae.     

Extraction of Camphor Tree Essential Oil by Steam Distillation and Supercritical CO2 Extraction

The essential oil extracted from Cinnamomum camphora leaves is a mixture of volatile compounds, mainly terpenes, and is widely used in medicine, perfume and chemical industries. In this study, the extraction processes of essential oil from Cinnamomum camphora leaves by steam distillation and supercritical CO₂ extraction were summarized and compared, and the camphor tree essential oil was detected by GC/MS. The extraction rate of essential oil extracted by steam distillation is less than 0.5%, while that of supercritical CO₂ extraction is 4.63% at 25 MPa, 45 °C and 2.5 h. GC/MS identified 21 and 42 compounds, respectively. The content of alcohols in the essential oil is more than 35%, and that of terpenoids is more than 80%. The steam extraction method can extract volatile substances with a low boiling point and more esters and epoxides; The supercritical method is suitable for extracting weak polar substances with a high alcohol content. Supercritical CO₂ extraction can selectively extract essential oil components and effectively prevent oxidation and the escape of heat sensitive substances.     

碳氢表面活性剂在超临界CO2中形成微乳液的研究进展

在超临界CO₂中形成微乳液可以克服CO₂对高分子量和亲水性物质溶解能力差的缺点。碳氢表面活性剂成本低,对环境友好,利用碳氢表面活性剂形成超临界CO₂微乳液有利于工业应用,但绝大部分碳氢表面活性剂不能形成微乳液,所以需要对碳氢表面活性剂进行选择和设计。本文介绍了微乳液的形成、表征和评价,从表面活性剂的亲CO₂性能和界面活性两方面,综述了碳氢表面活性剂的设计思想和进展。另外介绍了助表面活性剂对形成超临界CO₂微乳液的作用,并对常规碳氢表面活性剂在助表面活性剂的作用下形成超临界CO₂微乳液的体系进行了综述。最后,介绍了含碳氢表面活性剂的混合表面活性剂在形成超临界CO₂微乳液方面的研究情况。     

Switchable Adhesion of Superhydrophobic ZnO Nanorod Film

We have fabricated superhydrophobic zinc surface with reversible transformation between sliding state and adhesion by a simple hydrothermal method. Uniformly ZnO₂ nanorod was obtained at 120°C. After self-assembling of a film of n-octadecanethiol, the surface with a water contact angle (CA) of 153 ± 2°, exhibited a nonwetting property. The surface showed switchable adhesion just upon introducing UV illumination and heating treatment in turn.     

CO2 Hydrogenation Catalyzed by Graphene-Based Materials

In the context of an increased interest in the abatement of CO₂ emissions generated by industrial activities, CO₂ hydrogenation processes show an important potential to be used for the production of valuable compounds (methane, methanol, formic acid, light olefins, aromatics, syngas and/or synthetic fuels), with important benefits for the decarbonization of the energy sector. However, in order to increase the efficiency of the CO₂ hydrogenation processes, the selection of active and selective catalysts is of utmost importance. In this context, the interest in graphene-based materials as catalysts for CO₂ hydrogenation has significantly increased in the last years. The aim of the present paper is to review and discuss the results published until now on graphene-based materials (graphene oxide, reduced graphene oxide, or N-dopped graphenes) used as metal-free catalysts or as catalytic support for the thermocatalytic hydrogenation of CO₂. The reactions discussed in this paper are CO₂ methanation, CO₂ hydrogenation to methanol, CO₂ transformation into formic acid, CO₂ hydrogenation to high hydrocarbons, and syngas production from CO₂. The discussions will focus on the effect of the support on the catalytic process, the involvement of the graphene-based support in the reaction mechanism, or the explanation of the graphene intervention in the hydrogenation process. Most of the papers emphasized the graphene’s role in dispersing and stabilizing the metal and/or oxide nanoparticles or in preventing the metal oxidation, but further investigations are needed to elucidate the actual role of graphenes and to propose reaction mechanisms.     

Long-Term Antibacterial Film Nanocomposite Incorporated with Patchouli Essential Oil Prepared by Supercritical CO2 Cyclic Impregnation for Wound Dressing

Biocompatible skin wound dressing materials with long-term therapeutic windows and anti-infection properties have attracted great attention all over the world. The cooperation between essential oil and non-toxic or bio-based polymers was a promising strategy. However, the inherent volatility and chemical instability of most ingredients in essential oils make the sustained pharmacological activity of essential oil-based biomaterials a challenge. In this study, a kind of film nanocomposite loaded with patchouli essential oil (PEO-FNC) was fabricated. PEO-loaded mesoporous silica nanoparticles (PEO-MSNs) with drug load higher than 40 wt% were firstly prepared using supercritical CO₂ cyclic impregnation (SCCI), and then combined with the film matrix consisting of polyvinyl alcohol and chitosan. The morphology of PEO-MSNs and PEO-FNC was observed by transmission and scanning electron microscope. The mechanical properties, including hygroscopicity, tensile strength and elongation at break (%), were tested. The release behavior of PEO from the film nanocomposite showed that PEO could keep releasing for more than five days. PEO-FNC exhibited good long-term (>48 h) antibacterial effect on Staphylococcus aureus and non-toxicity on mouse fibroblast (L929 cells), making it a promising wound dressing material.     

CO2-Responsive Wormlike Micelles Based on Pseudo-Tetrameric Surfactant

Wormlike micelles, which are linear aggregates created by the self-assembly of surfactants, may entangle to form dynamic three-dimensional network-like structures, endowing solutions with considerable macroscopic viscoelasticity. Recently, a pressing need has arisen to research a novel stimuli-responsive worm-like micelle that is efficient and environmentally friendly. CO₂ is an inexpensive, abundant, non-toxic, biocompatible, and non-combustible gas, and it is anticipated that CO₂ may serve as the trigger for stimuli-responsive worm-like micelles. In this paper, the formation of CO₂-switchable pseudo-tetrameric surfactants, which subsequently self-assemble into CO₂-switched wormlike micelles, is accomplished using a simple mixing of two commercial reagents, such as stearic acids and cyclen. The rheological characteristics switched by the use of CO₂ are cycled between that of a low-viscosity (1.2 mPa·s) fluid and a viscoelastic fluid (worm-like micelles, 3000 mPa·s). This article expands the field of study on stimuli-responsive worm-like micelles.     

CO2 responsive wormlike micelles based on sodium oleate,potassium chloride and N,N-dimethylethanolamine

The anionic surfactant sodium oleate (NaOA) can self-assemble in aqueous solution in the presence of counter-ion inorganic salts to form wormlike micelles (WLMs), which exhibited viscoelastic behavior. In this paper, KCl was used to induce the formation of wormlike micelles with sodium oleate. In this process, we found that the addition of N, N-dimethylethanolamine (DMEA) can destroy the structure of WLMs leading significant decrease of viscosity. However, after introducing CO₂ into the ternary solution (KCl-NaOA-DMEA), the WLMs can be regenerated due to the electrostatic interaction between the protonated DMEA and the anionic surfactants. The addition of sodium hydroxide (NaOH) causes the electrostatic interaction between OA^- and DMEAH⁺ be destroyed, which results in the wormlike micelles becoming spherical micelles of lower viscosity. The transition of WLMs with high viscosity and low viscosity spherical micelles can be repeated several times by using CO₂ and NaOH.     

表面活性剂控制合成不同形貌的纳米硫化铋

采用硝酸铋和硫脲为反应物,通过添加不同的表面活性剂如Triton X-100+OP-10、TX-10、Triton X-100,用回流法合成了硫化铋纳米花。所得产物用XRD、EDS、TEM、SAED、SEM以及UV-Vis进行了表征。结果表明,经85～110 ℃回流反应3 h,可以得到结晶良好、具有各种形貌的正交晶相的硫化铋纳米花。经计算,其晶胞参数为a=0.439 34 nm, b=0.965 64 nm, c=1.118 5 nm。UV-Vis分析表明,硫化铋