Long-Chain Gemini Surfactant-Assisted Blade Coating Enables Large-Area Carbon-Based Perovskite Solar Modules with Record Performance

Carbon-based perovskite solar cells show great potential owing to their low-cost production and superior stability in ambient air.However,scaling up to high-efficiency carbon-based solar modules hinges on reliable deposition of uniform defect-free perovskite films over large areas,which is an unsettled but urgent issue.In this work,a long-chain gemini surfactant is introduced into perovskite precursor ink to enforce self-assembly into a network structure,considerably enhancing the coverage and smoothness of the perovskite films.The long gemini surfactant plays a distinctively synergistic role in perovskite film construction,crystallization kinetics modulation and defect passivation,leading to a certified record power conversion efficiency of 15.46%with Voc of 1.13 V and Jsc of 22.92 mA cm^(-2)for this type of modules.Importantly,all of the functional layers of the module are printed through a simple and high-speed(300 cm min^(-1))blade coating strategy in ambient atmosphere.These results mark a significant step toward the commercialization of all-printable carbon-based perovskite solar modules.

甜菜碱/AOS/Gemini季铵盐三元复合型泡排剂的研制与性能评价

泡沫排液技术是保障气井产量的重要手段,研发高性能的泡排剂极其关键。为适应高矿化度、高凝析油含量及高温等苛刻气井环境,以椰油酰胺丙基羟基磺基甜菜碱(CHSB)作为主剂,α-烯基磺酸钠(AOS)和合成的Gemini阳离子表面活性剂CAGB作为辅剂制备了一种高效环保的三元泡排体系。结果表明,三元复配体系AOS/CAGB/CHSB在摩尔比为12∶3∶35、总量为20 mmol/L时性能最优,泡沫体积和半衰期分别达到360 mL和30.27 min;在含有30%甲醇的泡排剂溶液中,测得的携液率最高可达31%,发泡率为95%;在含有0%~50%凝析油的泡排剂溶液中,三元泡沫体系表现出良好的性能,其中在凝析油含量为20%时,测得的携液率最高可达38%,发泡率为95%;优选的三元复配体系AOS/CAGB/CHSB对盐离子耐受性较差,加入螯合剂(氨三乙酸三钠(NTA))后,三元复配体系在矿化度为150 g/L的溶液中仍能稳定发泡和携液;温度大于50℃时,泡沫的携液率也逐渐增加,温度在90℃时,携液率在95%以上。此外,通过表面张力测试、泡沫微观结构观察也证实了该泡排剂体系存在的协同效应使其起泡、稳泡和泡沫携液能力得到有效提升。

Synthesis and Surface Activity of Novel Triazole-based Cationic Gemini Surfactants

The synthesis and surfactant activities of two new cationic gemini surfactants containing triazole compound as spacer were described. Their critical micelle concentrations (CMC), which are 1.8×10-4 mol/L and 3.9×10-4 mol/L respectively, are much lower than that of conventional surfactant cetyltrimethyl ammonium chloride (CTAC). In addition, compared with some gemini surfactants containing phenylene, xylylene and stilbenyl as spacer, this new kind of surfactants has good solubility in water at room temperature because of containing more hydrophilic groups or atoms in molecules.

Synthesis and Properties of Gemini Cationic Surfactants with Amide Spacers

Four gemini cationic surfactants {N,N′-di[2-(lauryldimethylamino)acetyl]polymethylenediamine dichloride, LAA-s-LAA, s=2,3,4,6} were synthesized by using four bis(α-chloroacetamide)s and N,N-dimethyllaurylamine, respectively. The molecular structures were characterized by means of IR, ~ 1H NMR, \{~ ~13 C NMR\} and MS, and the behavior of their aqueous solutions was studied. The critical micell concentrations(CMC) of LAA-s-LAA were one order of magnitude lower than that of dodecyltrimethyl ammonium chloride(DTAC). With the change of the length of spacer chain(s), their CMC values change, and CMC reaches the top value at s=4.

Gemini阳离子/含氟阴离子表面活性剂混合体系的界面润湿调控及解水锁机制研究

为有效解决低渗透致密砂岩气藏开采普遍存在的水锁伤害问题,研究了Gemini阳离子表面活性剂双季铵盐BQ-16和含氟阴离子表面活性剂全氟辛基磺酸钾(PPS)在降低表面张力和润湿调控方面的协同作用,并探究了BQ-16/PPS表面活性剂混合体系的润湿调控及解水锁机制。结果表明,当PPS的摩尔分数(α_(PPS))为0.7时,BQ-16/PPS表面活性剂混合体系的表面张力达到最低,低于任一纯组分,此时BQ-16/PPS表面活性剂混合体系接近电中性;BQ-16和PPS在岩心表面润湿调控方面表现出协同效应,当BQ-16/PPS表面活性剂混合体系总浓度为1×10^(-4)mol·L^(-1)、α_(PPS)为0.7时,盐水滴接触角最大,达到84.23°;BQ-16/PPS表面活性剂混合体系(α_(PPS)=0.7)在石英砂表面的吸附过程符合准二级动力学方程和Freundlich等温吸附模型,低浓度时为单分子层吸附,高浓度时为多分子层吸附;BQ-16/PPS表面活性剂混合体系(α_(PPS)=0.7)可将岩心的液体饱和度降至0.410,并将渗透率恢复值提高至0.78,说明BQ-16/PPS表面活性剂混合体系可有效解决水锁伤害,这主要与混合体系能够显著降低表面张力并通过在岩心表面的吸附改变岩心表面润湿性有关。

Molecular Dynamics Simulation for the Effect of Chain Length of Spacer and Tail of Cationic Gemini Surfactant on the Complex with Anionic Polyelectrolyte

Interaction of anionic polyelectrolyte with cationic gemini surfactant has been investigated by coarse-grained molecular dynamics simulation.Polyelectrolyte facilitates the oppositely charged ionic surfactants to aggregate by suppressing the electrostatic repulsion between ionic head groups leading to the formation of micellar complex.With addition of surfactant,the conformation of polyion chain changes from stretched to random coiled to spherical,and at the same time more free micelles are formed by surfactants in mixtures.Increasing the length of spacer or tail chain in gemini surfactant will weaken its interaction with polyelectrolyte and simultaneously strengthen its tendency to self-assemble.The simulation results are consistent with experimental observations and reveal that the electrostatic interaction plays an important role in the interaction of polyelectrolyte with gemini sur- factant.

新型三嗪基Gemini表面活性剂的合成与表面活性研究

本文以三聚氯氰、十二胺、乙二胺、1,4-丁二胺、1,6-己二胺、N,N-二甲基-1,3-丙二胺、溴乙烷为原料,合成了3种不同连接基长度的三嗪基Gemini表面活性剂C_(12)-m-C_(12)(m=2,4,6)。通过FT-IR、1H NMR、ESI-MS对其结构进行了表征。利用表面张力法、稳态荧光法、动态光散射法测定了所合成的三嗪基Gemini表面活性剂的表面活性。表面张力测试结果表明,随着连接基亚甲基数从2增加到6,C_(12)-m-C_(12)的临界胶束浓度(CMC)从0.013 mmol/L增加到0.050 mmol/L;动态光散射法测试结果表明,C_(12)-m-C_(12)的粒径随着连接基长度的增加而增加;稳态荧光法研究结果表明,随着连接基长度的增加,表面活性剂越容易形成较大的胶束,C_(12)-2-C_(12),C_(12)-4-C_(12),C_(12)-6-C_(12)在水溶液中的临界胶束聚集数分别为105,76和68。

Comparative studies on flotation of illite,pyrophyllite and kaolinite with Gemini and conventional cationic surfactants

To search a novel class of effective silicate mineral collectors,the Gemini quaternary ammonium salt surfactant(butane-α,ω-bis(dimethyl dodeculammonium bromide),12-4-12) and its corresponding conventional monomeric surfactant(dedecyl trimethyl ammonium bromide,DTAB) were adopted to comparatively study the flotation behaviors of illite,pyrophyllite and kaolinite. Three silicate minerals with the Gemini surfactant as collector reveal floatability far better than with the corresponding traditional one. At pH 6,the best recoveries of illite,pyrophyllite and kaolinite with 3.5×10-4 mol/L 12-4-12 are 99.2%,91.7% and 99.6%,respectively. The fluorescence and contact angle measurement were also conducted for the further investigation of surfactants aggregation behavior and silicate mineral surface hydrophobic properties. FTIR spectra analysis and electrokinetic analysis show that the mechanism of adsorption of collector molecules on mineral surfaces is almost identical for the electronic attraction and hydrogen bonds effect. The superior collecting power of dimeric collector may be attributed primarily to its special structure and its essential properties.

Novel Piperazine-based Gemini and Bola Surfactants

A series of piperazine-based Gemini and Bola surfactants were synthesized. Gemini 1 and 5 have well surface activities. Their critical micelle concentrations （cmc） is 6.47×10^-4 mol/L and 1.17×10^-3mol/L, respectively. Bola surfactants 2 and compound 3, possessing better water solubility, have lower surface activities. Calculation, carried out by MM2 energy minimization, showed that compound with more hydrophobic chains in a spacer of limited length is difficult to be synthesized.

Interaction of DNA with Cationic Gemini Surfactant Trimethylene-1, 3-bis （dodecyldimethyl-ammonium bromide） and Anionic Surfactant SDS Mixed System

有 cationic 双子座表面活化剂 trimethylene-1,3-bis (dodecyl dimethyl 铵溴化物)(12-3-12 ) 和 anionic 表面活化剂钠 dodecyl 硫酸盐(SDS ) 的 DNA 的相互作用混合了系统被测量荧光，希腊语的第六个字母潜力，紫外力的光谱，和圆形的二色性调查了。当 SDS 不在时，由于静电、恐水病的相互作用， 12-3-12 大批在 micellization 前在 DNA 链上形成象 micelle 一样结构阶段。为 12-3-12 和 SDS 的混合系统， SDS 上的否定费用能对 DNA 竞争因为在相对地控告的表面活化剂之间的更强壮的相互作用，与 cationic 绑 12-3-12，并且这样， catanionic 混合微粒在 DNA/12-3-12 建筑群的形成前被形成。此后，混合微粒上的正电荷与 DNA 绑，并且这样，希腊语的第六个字母潜力从的变化对否定积极没有 SDS，与系统显然不同。同时， SDS 的存在从 DNA/EB 建筑群推迟 ethidium 溴化物(EB ) 的排除。DNA 的符合构造与 12-3-12 过程作为有约束力从本国的 B 形式经历一个变化到 chiral 阶段。在把 SDS 加到 DNA/12-3-12 复杂答案之上，然而， DNA 被释放到体积，阶段再回到 B 形式。

Synthesis and Surface Activity of Biquaternary Ammonium Salt Gemini Surfactants with Ester Bond

The synthesis and surface activity of gemini surfactants with ester bond as spacer are described. Their critical micelle concentrations （CMC） are much lower than that of conventional surfactants, i.e., 1.62×10^-5, 1.38×10^-5, 1.28×10^-5 mol·L^-1 for gemini Ⅰ, Ⅱ and Ⅲ respectively. Surface tension at the CMC of gemini Ⅰ, Ⅱ and Ⅲ were 36.4, 38.5, 41.2 mN · m^-1. The physico-chemical properties such as Krafft points, foaming abilities and emulsifying power were also investigated. It is found that the title compounds have low Krafft points and show good solubility in water. The gemini surfactants synthesized also exhibit good foaming properties and excellent emulsifying power toward toluene. The foaming abilities and emulsifying power increase with the increase in carbon number of hydrophobic chain, and this might be caused by the sheer viscosity of different gemini surfactant solution.

Interaction in Binary Mixtures of Gemini Surfactant G12-6-12 and CTAB by NMR

在 N， N 二度(dimethyldodecyl )-1,6-hexanediammoniumdibromide (G12-6-12 ) 和在 D2O 水的媒介的 cetyltrimethylammonium 溴化物(CTAB ) 之间的相互作用被 NMR 在 298 K 调查了。G12-6-12 和 CTAB 的测量批评 micelle 集中(cmc ) 分别地是大约 0.773 和 0.668 mmol/L。 cmc *(混合的 cmc )值是不到 CMC *(理想地混合的答案的 cmc )在混合系统，和相互作用参数 M < 0 在在混合系统的 G12-6-12 的不同臼齿的部分，但是就 0.3 ， cmc *值比 CMC 小得多*，并且 M 满足 M 的关系> ln ( cmc1/cmc2 )( cmc1 ：纯 G12-6-12 和 cmc2 的 cmc：纯 CTAB 的 cmc ) 。结果显示那在那里存在在 G12-6-12 和 CTAB 之间的协同，并且他们能形成混合微粒，它被 2D NOESY 和自我散开系数 D 实验进一步证明。在 2D NOESY 在 G12-6-12 和 CTAB 之间有分子间的生气山峰，并且在混合答案的微粒的半径在在 D 实验的 G12-6-12 纯答案比那大，显示有混合微粒。不管多么 > 0.3，我们发现那 cmc CMC， M0，显然二表面活化剂是几乎理想的混合适合伪阶段分离模型和常规答案理论。

Phase Separation and Microstructure of Mixed Surfactants Solution Containing Cationic Geminis and Traditional Anionic Surfactant

The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-l,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodium dodecyl sulfate (SDS) with or without added salt have been studied. An ATPS is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In ATPS region, the lowest total concentration of surfactants varies with the mixing ratio of geminis to SDS. Photographs obtained from freeze-etching, negative-staining and transmission electron microscopy show that the microstructures of two phases are different from each other. Micelles and vesicles can coexist in a single phase. The addition of salts can change the phase diagram of ATPS. Furthermore, the added salts promote the aggregation of rod-like micelles to form coarse network structure that increase the viscosity of solutions. The negative ions of the added salts are the determining factor.

Synthesis of Cardanol Sulfonate Gemini Surfactant and Enthalpy-Entropy Compensation of Micellization in Aqueous Solutions

A novel cardanol sulfonate Gemini surfactant with high surface properties was synthesized by cashew phenol, 1,3-dibromopropane and chlorosulfonic acid through three steps procedure of etherification, sulfonation and neutralization. A surface tension method was employed to investigate the thermo-dynamic properties of micellization in aqueous solution for cardanol sulfonate Gemini surfactant synthesized in laboratory. As a result, the micellization of cardanol sulfonate Gemini surfactant in aqueous solutions is spontaneous and entropy-driven. The micellization process is enthalpy-entropy compensated with the compensation temperature (Tc) of 308 ± 1 K.

Biphasic Catalytic Hydroformylation of 1-Dodecene in Micellar System with Cationic Gemini Surfactants

The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.

Innovative surfactant of Gemini-type for dissolution mitigation of steel in pickling HCl medium

A new surfactant of Gemini-type,N,N'-((phthylbis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethyldodecan-1-aminium bromide)is prepped&confirmed.The dissolution suppression impact of the new compound on steel is performed in 1 mol·L^(-1)HCl environment by means of chemical and electrochemical methods.The prepared surfactant is an agreeable dissolution inhibitor for steel.The mitigation efficacy rises with the quantity of the compound.The surfactant belongs to inhibitors of mixed-type.The adsorption of the synthesized compound followed the Langmuir's model.The negative magnitudes of bothΔG_(ads)^(θ) andΔH^(adsθ)indicate that the adsorption process proceeds from its own accord and exothermic.The mechanism of adsorption is elucidated by scanning microscopy.It is established that the transfer resistance(R_(ct))value rose,where the value of the phase element(CPE)reduced with the amount of synthesized inhibitor.According to the experimental data arrived by surface tension measurements,the prepared compound is a powerful active agent at the air/water boundary.

Experimental Study of Surface and Solution Properties of Gemini -conventional Surfactant Mixtures on Solubilization of Polycyclic Aromatic Hydrocarbon

Experimental data are presented on the enhanced solubilities of fluorene (FLR) resulting from solubilization in aqueous solutions of two conventional surfactants: cationic cetyltrimethylammonium bromide (CTAB) , anionic sodium dodecyl sulfate (SDS), nonioinic polyethylene glycol dodecyl ether (Brij35) and a cationic gemini bis (hexadecyldimethylammonium) pentane dibromide (G5). The critical micellar concentration of surfactants was determined by surface tension measurements and aqueous solubilities of fluorene compound in surfactant solutions were measured spectrophotometrically. Solubilization of PAH compound commenced at the surfactant critical micelle concentration and was proportional to the concentration of surfactant in micelle. The results of the mixed systems were analyzed with the help of regular solution theory, in which the deviation of CMCexp values for mixed surfactant systems from CMCideal was measured by evaluating the interaction parameter, βm. Negative values of βm were observed in all equimolar binary systems which show synergism in the mixed micelle. Attraction force between two oppositely charged head groups lead the strongest synergism effect between cationic gemini and anionic conventional surfactant. In addition to molar solubilization ratio (MSR) solubilization efficiency is also quantified in terms of micelle-water partition coefficient (Km).

<i>N</i>-Acetylated Gemini Surfactants: Synthesis, Surface-Active Properties, Antifungal Activity, and Ecotoxicity Bioassays

A series of N-acetylated cationic gemini surfactants (3a-e) having dimeric structures derived from tertiary amines were synthesized. Their antifungal potency and surface properties were determined. It also studied the acute toxicity of the molecule with the best performance and the best water solubility (3e) through Chlorella vulgaris and Daphnia magna bioassays. The results were compared to those obtained for a commercially available reference compound 2-(thiocyanomethylthio) benzothiazole (TCMTB). Parameters such as surface tension (&#978CMC), critical micelle concentration (CMC), surface excess concentration (Γ), and area per molecule (A) were determined. The resulting values indicated that the five gemini surfactants are characterized by good surface-active and self-aggregation properties. All surfactants were tested to evaluate their antifungal activity. Six fungal strains were used to conduct the study. The minimum inhibitory concentration (MIC) value was measured by the fungal growth inhibition. The results of the MICs were compared with two commercially available reference compounds (Fluconazole and TCMTB). The least active molecule was 3e, but 3b and 3d were found to be the most potent compounds with a similar activity for all strains. Candida albicans was the most sensitive one. In contrast, Aspergillus niger was resistant. Ecotoxicity of gemini 3e was assessed: the commercial formulation (TCMTB) was between three and four orders of magnitude more toxic than the gemini one for the biological species tested.

Triphase Catalysis Based on Gemini Surfactant-Clay Intercalates

A series of novel catalysts was developed using cationic Gemini surfactants intercalated in natural montmorillonite (MMT) clay. These Gemini surfactant-MMT intercalates were used to study the kinetics of a nucleophilic displacement reactions converting n-butyl bromide to n-butyl chloride in a triphase catalytic (TC) system. Most reaction rates compared favorably to those of biphase catalytic reactions where Gemini surfactants were used in the absence of MMT. Catalytic activity varied with Gemini surfactant structure, specifically with carbon spacer group and side chain length. In addition to the ease of catalyst separation that a triphase system affords, Gemini-MMT catalysts are stable and can be recycled and re-used several times.