Self-optimized and renewable Ni–Co alloy@Co–Co2C catalyst for higher alcohols synthesis from syngas

Higher alcohols synthesis (HAS) from syngas (CO/H₂) has attracted widespread attention, while the low selectivity and poor stability of the catalysts mainly stumbled its industrial application. In the work, Ni–Co alloy nanoparticles (NPs) derived from Co_1-xNi_xAl₂O₄ loaded on the SiO₂ with large specific surface area were prepared; and during reaction, the highly dispersed Ni–Co alloys were self-optimized to Ni–Co alloy@Co–Co₂C. Importantly, Ni–Co alloy@Co–Co₂C can be regenerated through oxidation - reduction - self-optimization process. Characteristic results indicated that the structural liberalization during the reaction process inhibited the loss of Ni, regulated and balanced the dual active sites of the catalyst and the Ni–Co alloys were regenerated after the re-oxidation and re-reduction process. The optimized catalyst exhibited excellent catalytic performance, including a high total selectivity to alcohols of 39.3% and an excellent catalytic stability at 250 °C, 3.5 MPa (H₂/CO = 2) and a space velocity of 6000 mL (g_cat h)^?1. In addition, the Ni–Co alloy@Co–Co₂C catalyst after stability test could recover its original catalytic performance after re-oxidation and re-reduction. The renewable characteristics and superior catalytic performance of Ni–Co alloy@Co–Co₂C made the catalyst to be one of the potential industrial catalysts for HAS.     

聚乙烯醇对芳纶复合纱聚苯胺导电层耐久性影响

为提高聚苯胺导电层与基材之间的黏结牢度,以聚乙烯醇为共混高聚物,通过连续原位聚合法在对位芳纶纱线表面形成聚乙烯醇/聚苯胺导电层,制备得到芳纶/聚苯胺/聚乙烯醇复合导电纱。分析了导电纱的结构与性能,并研究了聚乙烯醇对聚苯胺导电层耐水洗和耐磨性的影响。结果表明:适量添加聚乙烯醇有助于提高导电纱导电层的结构规整性及电导率,随着聚乙烯醇质量分数的提高,导电纱的电导率呈先上升后下降的趋势,当聚乙烯醇占苯胺的质量分数为4.30%时,制得的复合导电纱线的电导率最高,达到(1.120±0.198) S/cm;聚乙烯醇的添加和质量分数的提高,有助于聚苯胺导电层耐水洗性及在较小外力作用下的耐磨性的提高。     

Imidazolium functionalized poly(vinyl alcohol) membranes for direct methanol alkaline fuel cell applications

In this study, imidazolium functionalized poly(vinyl alcohol) (PVA) was synthesized by acetalization and direct quaternization reaction. Afterwards, composite anion exchange membranes based on imidazolium‐ and quaternary ammonium‐ functionalized PVA were used for direct methanol alkaline fuel cell applications. ¹H NMR and Fourier transform infrared spectroscopy data indicated that imidazole functionalized PVA was successfully synthesized. Inductively coupled plasma mass spectrometry data demonstrated that the imidazolium structure was efficiently obtained by direct quaternization of the imidazole group. Composite anion exchange membranes were fabricated by application of the functionalized PVA solution on the surface of porous polycarbonate (PC) membranes. Fuel cell related properties of all prepared membranes were investigated systematically. The imidazolium functionalized composite membrane (PVA‐Im/PC) exhibited higher ionic conductivity (7.8 mS cm^?1 at 30 °C) despite a lower water uptake and ion exchange capacity value compared to that of quaternary ammonium. In addition, PVA‐Im/PC showed the lowest methanol permeation rate and the highest membrane selectivity as well as high alkaline and oxidative stability. Dynamic mechanical analysis results reveal that both composite membranes were mechanically resistant up to 10⁷ Pa at 140 °C. The superior performance of imidazolium functionalized PVA composite membrane compared to quaternary ammonium functionalized membrane makes it a promising candidate for direct methanol alkaline fuel cell applications. © 2020 Society of Chemical Industry     

聚乙烯醇/牛I型胶原支架材料的制备及评价

研究了一种聚乙烯醇(PVA)和胶原(COL)复合支架材料的制备方法。采用氨基硅烷对PVA海绵表面进行了氨基化修饰后，通过戊二醛溶液交联牛Ⅰ型胶原(COL)，最后通过赖氨酸溶液封闭，获得一种PVA/COL复合支架材料。采用扫描电镜(SEM)、X光电子能谱仪(XPS)、傅里叶红外光谱(FT-IR)等手段对支架材料的理化性能进行表征，并通过细胞实验对支架材料的生物学性能进行评价。结果表明，经过COL修饰的PVA孔隙率为21.33%，平均孔径为168.68 ?m且均匀分布，支架材料接触角为20.03°。对支架材料的生物学评价结果表明C3A细胞在复合材料上黏附良好，优于PVA组；CCK-8增殖检测结果表明细胞在复合材料上呈增殖生长趋势，与对照组PVA相比差异显著(P?0.01)。将PVA和COL复合制备得到的支架材料具有良好的理化及生物学特性，具有广阔的应用前景。     

The Modification of Chrome Tanned Leather by Polyethylene Glycol-Linked Gemini Fatty Alcohol Phosphate

A series of polyethylene glycol-linked Gemini fatty alcohol phosphate surfactants (GFAP) were prepared with long chain n-alkanol (C = 8, 12, 16, 18), polyethylene glycol (PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000) and phosphorus oxychloride (POCl₃). The structure of the prepared surfactants was characterized by Fourier transform infrared spectrometer (FT-IR). The surfactants were employed for the modification of chrome-tanned leather. The morphological changes of chrome-tanned leather and modified chrome-tanned leather were observed by scanning electron microscopy (SEM). The relationship between the alkyl chain length and molecular weight of the PEG and the hydrophobicity, softness, mechanical strength of modified chrome-tanned leather was also discussed. The experimental results showed that the mechanical strength and softness of modified chrome-tanned leather were enhanced with an increase of alkyl chain length, while the hydrophobicity, mechanical strength and softness were decreased with an increase of molecular weight of the PEG. The hydrophobicity, mechanical strength and softness of modified chrome-tanned leather were optimized for an alkyl chain length of 16. Therefore, 16–200 Gemini phosphate surfactants with an alkyl chain length of 16 and a PEG molecular weight of 200 have a good comprehensive modification effect on Chrome-tanned leather, the tensile strength, tear strength and softness of modified chrome-tanned leather are 57.07 N mm⁻², 79.49 N mm⁻¹, 9.73 mm, respectively.     

不同醇沉竹荪多糖组分对青春双歧杆菌体外增殖作用的影响

本文以竹荪为原料提取多糖成分并以乙醇分级制备竹荪多糖(DPs)不同组分,通过青春双歧杆菌体外增殖试验初步评价竹荪多糖及其分级醇沉组分的益生元功效。结果显示在α-淀粉酶溶液中水解4 h后,20%、40%、50%、60%竹荪多糖醇沉组分水解度分别为9.10%、8.02%、8.88%、11.67%,与对照组菊粉(水解度13.15%)相比差异显著(P<0.05);80%竹荪多糖醇沉组分、未分级醇沉组分与菊粉对照组相比差异不显著(P>0.05)。在模拟胃液中水解6 h后,20%、40%、50%竹荪多糖醇沉组分水解度分别为17.30%、14.52%、9.61%,与对照组菊粉(水解度5.72%)相比差异显著(P<0.05);60%竹荪多糖醇沉组分、80%竹荪多糖醇沉组分、未分级醇沉组分水解度与对照组相比无显著差异(P>0.05)。随着竹荪多糖添加量的增加,青春双歧杆菌的菌体浓度呈现先增大而后不断减小的趋势。分级醇沉浓度达到80%的竹荪多糖组分和未分级的多糖组分,青春双歧杆菌体外增殖作用与pH下降显著且效果优于菊粉(P<0.05),并在20 h的发酵时间内两者表现出相似的效果。不同竹荪多糖醇沉组分对青春双歧杆菌均有增殖效果,且不同竹荪多糖醇沉组分的增殖效果和抗水解能力随乙醇浓度的增加而增强,未分级的多糖组分同样可以加强青春双歧杆菌增殖能力,具有益生元潜力。     

五粮浓香型白酒掺杂食用酒精的鉴别研究——基于碳稳定同位素技术

目的研究五粮浓香型白酒(原酒和成品酒)掺杂玉米及大米食用酒精后的乙醇碳同位素组成的变化规律,从而为白酒掺假鉴别服务。方法利用高温氧化还原稳定同位素比值质谱仪(isotoperatiomass spectrometer,IRMS)联用仪,对五粮浓香型白酒(原酒和成品酒)掺杂玉米及大米食用酒精后的乙醇碳同位素进行测试分析。结果宜宾地区所产不同年份和不同酒精度的原酒和成品酒,δ13C乙醇值范围分别为-21.42‰～-23.57‰和-21.01‰～-23.15‰,原酒和成品酒δ13C乙醇值分布范围基本一致,随年份和酒精度的不同其乙醇同位素组成无明显的变化规律。添加玉米酒精的原酒和成品酒的δ13C乙醇值明显增加,其值与添加量表现为正相关,当成品酒中酒精添加量为10%时,其δ13C乙醇差值为1.85‰,单样本t检验时差异性显著(双尾)0.0000.05。添加大米酒精的原酒和成品酒的δ13C乙醇值明显减小,其值与添加量表现为负相关,当原酒中酒精添加量为10%时,其δ13C乙醇差值为0.50‰,单样本t检验时差异性显著(双尾)0.0220.05。结论利用乙醇碳同位素组成判断宜宾产五粮浓香型白酒掺杂单一原料食用酒精,当掺杂食用酒精体积达到一定比例时,具有一定的应用前景。     

辛烯基琥珀酸淀粉酯的醇相法制备及其理化性质

以木薯淀粉为原料，在醇水相中进行预处理，在醇相中进行预处理淀粉与辛烯基琥珀酸酐（OSA）的酯化反应，制备了不同取代度的OSAS，研究了淀粉乳浓度、反应温度、反应pH、OSA用量及反应时间对产物取代度（DS）和反应效率（RE）的影响，并通过正交实验优化制备工艺，得出醇相法制备辛烯基琥珀酸淀粉酯（OSAS）的最佳工艺条件为反应时间4 h，反应温度为35 ℃，OSA用量为30%，pH为8.5，淀粉乳浓度为35%，此时产物DS为0.0889，RE为38.47%。以原木薯淀粉为原料，在该条件下制备的酯化淀粉DS为0.0323，RE为13.98%，表明该预处理能显著提高RE。FT-IR分析表明淀粉分子上成功引入辛烯基琥珀酸基团；XRD测试表明原木薯淀粉经过预处理后结晶度由21.48%下降至8.61%，A型结晶结构部分转化成V型，酯化反应首先发生在淀粉的表面及无定形区，其次进攻淀粉内部及结晶区进而导致结晶度有所下降；淀粉经酯化改性后，糊液粘度、抗凝沉性和透明度明显提高。