Theoretical estimation of dielectric loss of oxide glasses using nonequilibrium molecular dynamics simulations

To theoretically explore amorphous materials with a sufficiently low dielectric loss, which are essential for next-generation communication devices, the applicability of a nonequilibrium molecular dynamics simulation employing an external alternating electric field was examined using alkaline silicate glass models. In this method, the dielectric loss is directly evaluated as the phase shift of the dipole moment from the applied electric field. This method enabled us to evaluate the dielectric loss in a wide frequency range from 1 GHz to 10 THz. It was observed that the dielectric loss reaches its maximum at a few THz. The simulation method was found to qualitatively reproduce the effects of alkaline content and alkaline type on the dielectric loss. Furthermore, it reasonably reproduced the effect of mixed alkalines on the dielectric loss, which was observed in our experiments on sodium and/or potassium silicate glasses. Alkaline mixing was thus found to reduce the dielectric loss.     

Novel silicon-contained lignin-based carbon fibers derived from bamboo pulping black liquor with improved electrochemical performance for supercapacitors

Carbon fibers (CFs) are a promising candidate as electrode materials for flexible supercapacitors given its light weight and moderate cost. In this study, the lignin used was partially separated from kraft bamboo pulping black liquor and the higher molecular weight fraction, unavoidably contains a small amount of silicon compounds, so named silicon-contained lignin. Novel CFs were prepared using commercial polyacrylonitrile (PAN) and the lignin by electrospinning and further carbonization. Even in the presence of silicon compounds, the fibrous morphology of precursor fibers was significantly good, and the CFs with uniform fiber diameter and high specific surface area up to 182 m²/g were obtained with an increase in silicon-contained lignin. The CFs fabricated from silicon-contained lignin and commercial PAN had higher specific capacitance (22.20 mF/cm² at 10 mA/cm²) and superb cycling stability (94.21%) than that from silicon-free lignin or pure PAN separately.     

Comb-shaped diblock copolystyrene for anion exchange membranes

To improve the properties of diblock copolystyrene-based anion exchange membranes (AEMs), a series of AEMs with comb-shaped quaternary ammonium (QA) architecture (QA-PS_m-b-PDVPPA_n-xC where x denotes the number of carbon atoms in different alkyl tail chains and has values of 1, 4, 8, and 10 and C denotes carbon) were designed and synthesized via subsequent quaternization reactions with three different alkyl halogens (methyl iodide and N-alkane bromines (CH₃[CH₂] _x-1Br where x = 4, 8, and 10). Compared with triblock analogues quaternized with methyl iodide in our previous research, QA-PS_m-b-PDVPPA_n-xC (x = 4, 8, and 10) AEMs are more flexible with the introduction of a long alkyl tail chain; this probably impedes crystallization of the rigid polystyrene-based main chain and induces sterically adjustable ionic association. An increase in the pendant alkyl tail chain length generally led to enhanced microphase separation of the obtained AEMs, and this was confirmed using small-angle X-ray scattering and atomic force microscopy. The highest conductivity (25.5 mS cm⁻¹) was observed for QA-PS₁₂₀-b-PDVPPA₈₀-10C (IEC = 1.94 meq g^–1) at 20 °C. Furthermore, the water uptake (<30%) and swelling ratio (<13.1%) of QA-PS_m-b-PDVPPA_n-xC AEMs are less than half of these corresponding values for their triblock counterparts. The QA-PS₁₂₀-b-PDVPPA₈₀-10C membrane retained a maximum stability that was as high as 86.8% of its initial conductivity after a 40-day test (10 M NaOH, 80 °C), and this was probably because of the steric shielding of the cationic domains that were surrounded by the longest alkyl tail chains. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47370.     

有色冶炼二次含砷物料碱法脱砷工艺现状

分析了典型二次含砷物料化学成分特点,概括了当前有色冶炼工业中产生的二次含砷物料碱法脱砷工艺及原理,主要包括湿法脱砷工艺和火法—湿法联合脱砷工艺。其中,碱法脱砷工艺常用NaOH单碱浸出、NaOH-Na_2S混合碱浸出和NaOH+Na_2S混合碱两段浸出三种体系,并采用双氧水、加压、曝气、微波、球磨等氧化手段强化砷的浸出;火法—湿法联合脱砷工艺主要有低温碱性熔炼—水浸、焙烧预氧化—碱性浸出以及低温碱性焙烧—热水浸出工艺,低温碱性焙烧—热水浸出工艺选择性脱砷效果好,物料普适性广。最后,结合现有研究指出了碱法脱砷工艺存在的问题及二次含砷物料无害化、资源化研究方向。     

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     

羟甲基化木质素/纤维素气凝胶粒子的制备、表征及吸附性能

以羟甲基化木质素和纤维素为原料，NaOH/尿素水溶液为溶解体系，采用冷冻干燥法制备羟甲基化木质素/纤维素气凝胶粒子。采用扫描电子显微镜（SEM）、傅里叶变换红外光谱（FT-IR）仪、X射线衍射（XRD）仪、比表面积及孔径分析仪等对其结构进行了表征。研究结果表明：羟甲基化木质素分子通过氢键作用附着在纤维素骨架上，气凝胶内部仍保持三维网状结构，羟甲基化木质素的引入使得气凝胶表面出现明显收缩，网状结构的致密度随着羟甲基化木质素用量提高而逐渐降低；同时气凝胶粒子具有纤维素Ⅱ型红外吸收峰和XRD衍射峰；粒子表现出Ⅱ型吸附/脱附等温线，孔径均在15 nm以下，且随着羟甲基化木质素用量不断提高，比表面积、孔容均有所减小，HKL-4的比表面积为105.3m²/g，孔容为0.336 6cm³/g，孔径为13.67nm。吸附性能分析表明在25℃下吸附5 h，HKL-4气凝胶粒子对金胺O、亚甲基蓝和罗丹明B的吸附量分别为33.06、96.06和43.26mg/g，对亚甲基蓝的饱和吸附量可达208.7 mg/g，吸附过程更符合Langmuir等温吸附模型，主要为单分子层吸附。     

Ni-P/HZSM-5催化木质素降解制备酚类化学品

采用Ni-P复合改性HZSM-5催化剂催化木质素降解制备高附加值的单酚类化学品，探讨了催化剂种类、金属负载量、反应温度、反应时间以及溶剂种类对木质素催化降解制备酚类化合物的影响。同时采用X射线衍射仪（XRD）、比表面积和孔径分析仪（BET）、化学吸附仪（NH₃-TPD）、热重分析仪（TG）以及气相色谱质谱联用仪（GC/MS）对催化剂以及液相产物进行分析表征，同时探讨其催化失活以及再生机制。结果表明：Ni、P高度分散在HZSM-5催化剂的表面，Ni的添加有效地弱化了C－C键，致使β-O-4和α-O-4发生断裂，有效地提高了木质素加氢解聚的活性，减少了焦炭的生成，但催化剂的再生水热稳定性较差，重复使用性较低。当采用甲醇为供氢试剂，在反应温度为220℃，氢气压力为2MPa，反应时间为8h，催化剂负载量为10%，NaOH为共催化剂时，其木质素的转化率为98.6%，酚类化合物的含量达到74.97%。产物以苯酚、愈创木酚和紫丁香酚为主，低温促进了紫丁香酚的产生。     

木质素基表面活性剂研究现状

木质素作为一种天然高分子化合物，其来源丰富，可以用来代替石油资源制备表面活性剂，缓解当前石油资源枯竭的问题。常见的木质素基表面活性剂有阳离子表面活性剂、阴离子表面活性剂、两性离子表面活性剂以及非离子表面活性剂。木质素基表面活性剂在工业领域具有广泛的应用范围，可以作为染料分散剂、混凝土减水剂、沥青乳化剂以及原油采集过程中的驱油剂等。木质素基表面活性剂的开发利用为生物质产品的高值化利用开辟了一条新的路径。     

甘油预处理蔗渣的木质素分离提取及结构表征

以甘油分别对甘蔗渣进行常压甘油自催化（AGO）预处理和常压甘油碱催化（al-AGO）预处理。利用酸沉法分别从预处理液中得到自催化甘油木质素（AGOL）和碱催化甘油木质素（al-AGOL）。利用单因素实验和正交实验得到最佳木质素提取工艺为转速8000r/min、离心时间15min、甘油混合液pH为3、甘油混合液浓度10%，在该条件下木质素AGOL和al-AGOL提取率分别达到72%和76%。采用扫描电镜（SEM）、元素分析、紫外光谱（UV）、凝胶色谱（GPC）、核磁共振¹H谱、热重分析以及抗氧化活性分析等技术手段对提取得到的木质素进行结构表征。结果表明：从甘蔗渣中提取的球磨甘蔗木质素（MBL）、AGOL和al-AGOL主要呈现出球形特征；AGOL和al-AGOL具有相似的活性特点，与MBL相比，AGOL和al-AGOL的分子量更小、分布更窄、均一性更好，热稳定性和抗氧化活性更高，有望成为重要的工业原料。     

木质素与高密度聚乙烯共热解特性研究

生物质与塑料共热解是一种非常有效的生物质利用方法之一,但由于生物质结构的复杂性,共热解过程的机理尚不明晰。木质素是生物质的主要组分之一,本文通过热重-质谱联用仪和裂解器-气相色谱质谱仪研究其与高密度聚乙烯共热解过程,获取共热解特性及热解产物分布特性,以揭示共热解过程机制。结果显示,木质素与高密度聚乙烯共热解过程存在协同效应,使得热解失重速率加快,热解固体残渣含量减少。共热解过程有利于CH₄、H₂O、CO和C₂H₄的生成,抑制CO₂的生成。同时,酚类、醇类和糖类等含氧化合物产量减少,烷烃和烯烃类化合物产量增加。结果表明,共热解过程会发生氢转移现象,氢与木质素衍生热解产物结合发生反应,从而抑制含氧化合物的生成,促进烷烃类和烯烃类化合物生成。