Influence of mesoporous phosphotungstic acid on the physicochemical properties and performance of sulfonated poly ether ether ketone in proton exchange membrane fuel cell

This study demonstrates the successful development of hybrid mesoporous siliceous phosphotungstic acid (mPTA-Si) and sulfonated poly ether ether ketone (SPEEK) as a proton exchange membrane with a high performance in hydrogen proton exchange membrane fuel cells (PEMFC). SPEEK acts as a polymeric membrane matrix and mPTA-Si acts as the mechanical reinforcer and proton conducting enhancer. Interestingly, incorporating mPTA-Si did not affect the morphological aspect of SPEEK as dense membrane upon loading the amount of mPTA-Si up to 2.5 wt%. The water uptake reduced to 14% from 21.5% when mPTA-Si content increases from 0.5 to 2.5 wt% respectively. Meanwhile, the proton conductivity increased to 0.01 Scm^?1 with 1.0 wt% mPTA-Si and maximum power density of 180.87 mWcm^?2 which is 200% improvement as compared to pristine SPEEK membrane. The systematic study of hybrid SP-mPTA-Si membrane proved a substantial enhancement in the performance together with further improvement on physicochemical properties of parent SPEEK membrane desirable for the PEMFC application.     

烯丙基聚烷氧基环氧醚的制备及其性能

针对烯丙基聚烷氧基环氧醚中存在催化剂和钾钠离子含量高,导致制备的三元共聚嵌段硅油反应活性差的问题,研究了在无相转移催化剂的条件下制备烯丙基聚烷氧基环氧醚的方法,表征了产物的结构,分析了制备条件对产物pH值与环氧指数的影响;以其为原料制备了三元共聚嵌段硅油,并对棉织物进行柔软整理,分析了整理后织物的亲水性、手感及物理力学性能。结果表明:当原料烯丙基聚氧乙烯醚、环氧氯丙烷和氢氧化钠的量比为1∶2.5∶1.5,冰醋酸的添加量是过量氢氧化钠的1.1倍时,产物烯丙基聚烷氧基环氧醚的环氧指数为1.77 mol/kg,pH值小于7,精制后钾钠离子含量可降低到5 μg/g以下;织物经过硅油整理后具有较好的亲水性,当整理液质量浓度为30 g/L时,毛效达到7.3 cm,手感评级达到4.7级以上,织物整体性能有所提高。     

HT-PEMs based on nitrogen-heterocycle decorated poly (arylene ether ketone) with enhanced proton conductivity and excellent stability

The proton transport can be enhanced by properly controlling the chemical structure of side chains. In this work, polyelectrolytes supported on poly (arylene ether ketone), decorated with four kinds of nitrogen-heterocycles, were prepared as alternative materials for high-temperature proton exchange membrane (HT-PEM) applications. Particularly, the “prominent basic” alongside backbone makes positive imidazole group more effective than other three to promote phosphoric acid doping, enhance proton conductivity and avoid phosphoric acid leakage. The obtained BrPAEK-MeIm1.6 membranes (1.6 imidazole/unit), with PA doping level of 19.2 in 1 h acid absorption process, exhibited the conductivity of 0.091 S cm^?1 at 170 °C. Under harsh experimental conditions, membrane with higher imidazole exhibited relatively higher phosphoric acid retention ability (27% enhancement). The stability of proton conductivity has also been demonstrated, which indicates that the PA/BrPAEK-MeIm1.6 come to an equilibrium state with 77.7% of initial conductivity after 5 h. Then, there is almost negligible conductivity loss within 30 h. These results provide a basic understanding of nitrogen-heterocyclic addition and PA absorption and open up avenues for further research in this area.     

The direct,one-step process for synthesis of dimethyl ether from syngas. III. DME as a chemical feedstock

In Parts I & II of this Series, we illustrated the process research studies on a new, trendsetting indirect syngas conversion process, the direct, one-step LPDME^tm process, which is now a shining example of “dual catalysis” or “cooperative/adaptive” catalysis and also of thermodynamic/kinetic coupling in series-parallel reactions.

In this part III, we take a look at several processes on the research and pilot scale that employ methanol and DME as chemical feedstocks for further conversion to value-added chemicals. A most rational and cogent argument for the use of DME as a feedstock is that the unit production cost of DME from the direct, one-step DME processes, most notably the LPDME^tm process, can be lower than methanol (from LPMeOH^tm), on a methanol-equivalent basis. DME also has inherently more benign physical and chemical properties, contains 1 less mole of water, and results in a substantially similar product distribution, as methanol, for the methanol-to-gasoline (MTG) and methanol-to-olefins (MTO) process. DME can also be converted to several other important chemicals; some of these include dimethoxymethane, dimethoxyethane, methylal, formaldehyde, acetic acid, methyl acetate, and polyoxymethylene ethers. In this report, we offer a critical assessment of the current status of these processes and a projected path to commercialization. Considering the trendsetting and impactful nature of DME as a chemical entity and as a chemical feedstock, along with its “free” cost, we are of the opinion that the future of DME, and of its chemical conversions, as so-called “DME economy”, is very bright.     

盖子环替换及定点突变提高菜豆环氧化物水解酶对邻甲基苯基缩水甘油醚的催化性能

菜豆环氧化物水解酶1和2（PvEH1、PvEH2）能够动力学拆分外消旋邻甲基苯基缩水甘油醚（rac-oMGE），从而保留(R)-oMGE。基于对PvEH1和PvEH2结构的同源模拟和分析，发现二者分子中的盖子环差异较大，故本文选择盖子环作为研究目标。经融合聚合酶链式反应（FPCR），获得了PvEH2的盖子环区域被PvEH1对应区域替换的杂合酶Pv2Pv1。用全细胞酶E. coli/pv2pv1催化rac-oMGE，当(S)-oMGE刚好水解完全时，产物(S)-3-邻甲苯基-1,2-丙二醇（(S)-oTPD）的ee_p由PvEH2的58.3%提高至75.5%。为进一步提高酶的性质，在Pv2Pv1中选取11个氨基酸位点进行丙氨酸(A)突变，获得最优突变子E. coli/pv2pv1^K176A，活性为E. coli/pv2pv1（4.2U/g）的2.1倍，且当S构型的底物刚好完全水解时，(S)-oTPD的ee_p进一步提高为80.3%。分子对接分析发现，盖子环替换和K176位点突变为A，均使(R)-oMGE环氧环中的C_α更易受到酶中D101位点的攻击。利用E. coli/pv2pv1^K176A催化150mmol/L rac-oMGE水解制备(R)-oMGE（ee_s＞99%）和(S)-oTPD（ee_p=80.4%），二者的产率Y_S和Y_P分别为32.7%和60.1%，时空产率STY_S和STY_P为1.6g/(L·h)和3.3g/(L·h)。本实验为改善EH的催化性质提供了一种有效策略。     

In-situ molecular-level hybridization enabling high-sulfonation-degree sulfonated poly(ether ether ketone) membrane with excellent anti-swelling ability and proton conduction

Sulfonated poly(ether ether ketone) (SPEEK) membrane with high sulfonation degree (SD) is a promising substitute of Nafion as proton exchange membrane (PEM), due to the excellent proton conductivity and low cost. However, its widespread application is limited by the inferior structural stability. Here, we report the fabrication of high SD SPEEK membrane with outstanding structural stability through an in-situ molecular-level hybridization method. Concretely, the ionic nanophase of SPEEK membrane is filled with precursors, which are then in-situ converted into polymer quantum dots (PQDs) by a microwave-assisted polycondensation process. In this manner, the micro-phase separation structure of SPEEK membrane is well maintained. PQDs with abundant hydrophilic functional groups together with the inherent –SO₃H groups impart hybrid membrane highly enhanced proton conductivity of 138.2 mS cm⁻¹ at 80 °C, which is comparable to Nafion. This then offers a 116.3% enhancement in device output power. Meanwhile, PQDs act as cross-linkers via generated electrostatic interactions with SPEEK, affording hybrid membrane with SD of 94.1% an ultralow swelling ratio of 1.35% at 25 °C, about 35 times lower than control membrane. More importantly, the in-situ molecular-level hybridization method is versatile, which can also boost the performances of chitosan (CS)-based membranes.     

硫酸化SnO2/SPPESK复合质子交换膜的制备及燃料电池性能

非氟聚合物磺化聚芳醚砜酮（SPPESK）具有甲醇渗透率低、化学、热稳定性高等优点，但其高的电导率需通过提高磺化度获得，导致膜因过度溶胀而失去尺寸稳定性。添加无机纳米颗粒可以有效提高膜性能，但因其表面缺少功能化基团，导致颗粒有机相容性差，阻醇性能和质子传导率不易同时提高。硫酸化改性的纳米颗粒因其表面具有酸性位点和硫酸基团，能够有效克服这一问题。本文制备表面硫酸化改性的SnO₂（SSnO₂）纳米颗粒并引入SPPESK基质制备有机无机复合质子交换膜。当SSnO₂含量不大于7.5%时，纳米颗粒具有良好的有机相容性，可均匀分散于聚合物基质。SSnO₂含量为7.5%时，80℃下复合膜吸水率（19.6%）比SPPESK原膜提高19%，接近Nafion115。颗粒诱导膜内离子簇的聚集扩大，降低了质子的传导阻力，质子传导率分别比SPPESK原膜和Nafion115膜提高48%和30%。同时，纳米颗粒增大了甲醇传递空间位阻，甲醇渗透率较SPPESK原膜和Nafion115膜分别降低46%和71%。直接甲醇燃料电池0.5V处功率密度分别比SPPESK原膜和Nafion115膜高205%和50%。     

煤基液体产物中酚类化合物的组成研究

以5种不同煤加工转化过程得到的液体产物煤衍生油为原料，研究了其中酚类化合物的组成与分布特征。首先将不同煤衍生油蒸馏切取富含酚170～210 ℃酚油馏分，采用酸碱抽提法提取其富集酚类组分，其次对富集酚类组分进行硅醚衍生化预处理，最后利用GC/MS详细分析了酚油馏分中酚类化合物的组成与分布。结果表明:不同煤衍生油的酚油馏分中酚类化合物主要由烷基苯酚、茚满醇、苯二酚3种类型组成，其中烷基苯酚均占90%以上。4号CDO其酚类类型包括烷基苯酚、茚满醇、苯二酚3部分，其中烷基苯酚占92.4%。低级酚占全部酚类的86.1%，高级酚占13.9%;2号CDO其酚类类型由烷基苯酚、苯二酚2部分组成，其中烷基苯酚占99.89%。低级酚占全部酚类的99.5%，高级酚仅占0.5%;1号CDO和3号CDO其酚类类型只包含烷基苯酚类，高温炼焦产生的1号CDO全部以低级酚为主。3号CDO低级酚占全部酚类的98.4%，高级酚占1.6%;5号CDO其酚类类型包括烷基苯酚、茚满醇2部分，其中烷基苯酚占94.8%。低级酚占全部酚类的91.6%，高级酚含量占8.4%。因此，应足够重视不同煤衍生油中低级酚的提取利用。     

离子液体催化合成双烷基二苯醚

以盐酸三乙胺/三氯化铝(Et_3NHCl-AlCl_3)离子液体为催化剂,二苯醚和1-十二烯烃为原料合成了双烷基二苯醚。通过正交试验,得到烷基化反应的较优工艺条件为:n(二苯醚):n(1-十二烯烃)=1:3,二苯醚用量0.3 mol,催化剂用量0.045 mol,反应温度70℃,反应时间1 h。在此条件下,烷基化转化率为98.1%,双烷基二苯醚选择性为33.7%。改变离子液体的阳离子和阴离子部分结构,研究了催化剂结构对其催化性能的影响。结果表明,该类催化剂的催化活性主要由阴离子部分的结构决定,较优的阴阳离子组合为Et_3NHCl-AlCl_3。     

直喷二甲醚对稀汽油混合气燃烧过程影响的研究

在一台四冲程单缸汽油机上,通过缸内直喷二甲醚(DME)实现了空气稀释汽油混合气的稳定燃烧。研究结果表明:在1 500r/min下,固定循环燃油热值时,直喷DME可以降低汽油机稀燃下的循环变动,加速初期火焰发展速度,缩短燃烧持续期,提高汽油稀燃稳定燃烧的过量空气系数上限。稀燃和直喷DME相结合可以改善发动机在稀燃下的燃油经济性。与理论空燃比混合气相比,稀燃能使指示燃油消耗率最多降低11.7%。改变点火时刻和直喷DME比例能实现不同过量空气系数下的最佳燃烧相位。随着过量空气系数的增加,最佳放热中心相位提前。