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.     

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.     

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。     

含氟无皂乳液P(CTFE-IBVE-SUA)的合成及性能研究

通过无皂乳液聚合法制备得到聚(三氟氯乙烯-乙烯基异丁基醚-十一烯酸钠)[P(CTFE-IBVE-SUA)]含氟乳液。考察了单体配比对聚合反应的影响,研究了SUA用量对乳液及聚合物性能的影响,并对聚合物的结构及乳胶粒的形貌进行了测定。结果表明:含氟无皂乳液P(CTFE-IBVE-SUA)的稳定性好、粒径分布均匀;改变单体配比中IBVE和CTFE的比例可以得到不同结构的含氟聚合物乳液;SUA用量对乳液的稳定性、乳胶粒的粒径大小及粒径分布、聚合物膜与水的接触角都有很大的影响;制得的乳液具有明显的核壳结构。     

Highly selective CuO/γ–Al2O3 catalyst promoted with hematite for efficient methanol dehydration to dimethyl ether

A recent alternative for replacing traditional hydrocarbons like gasoline, diesel, and natural gas, is the use of dimethyl ether (DME), which is more environmentally friendly. One of the ongoing challenges is to catalyze methanol dehydration for selectively producing the DME (2CH₃OH → CH₃OCH₃ + H₂O). It is established that the CuO catalyst over alumina performs the methanol dehydration, but the formation of by-products is the main drawback. For these reasons, we synthesized a CuO/γ–Al₂O₃ catalyst promoted with hematite aiming to enhance the activity toward DME at atmospheric conditions. The resulting bimetallic catalyst (CuO-Fe₂O₃/Al₂O₃) performed a 70% conversion at 290 °C, which is similar to other catalysts recently reported in the literature but done in harsh conditions. In addition, this bimetallic catalyst exhibited a 100% in selectivity toward the DME production. XPS spectra of the fresh and used catalyst suggested that the chemical oxidation states of Cu and Fe remain without change. After regenerating the catalyst at 600 °C for 2 h in air, it performed at a similar catalytic conversion, confirming the reusability of the as-synthesized material and reducing the environmental impact.     

Syngas production via partial oxidation of dimethyl ether over Rh/Ce0.75Zr0.25O2 catalyst and its application for SOFC feeding

Dimethyl ether (DME) partial oxidation (PO) was studied over 1 wt% Rh/Ce_0.75Zr_0.25O₂ catalyst at temperatures 300–700 °C, O₂:C molar ratio of 0.25 and GHSV 10000 h⁻¹. The catalyst was active and stable under reaction conditions. Complete conversion of DME was reached at 500 °C, but equilibrium product distribution was observed only at T ≥ 650 °C. High concentration of CH₄ and low contents of CO and H₂ were observed at 500–625 °C 75 cm³ of composite catalyst 0.24 wt% Rh/Ce_0.75Zr_0.25O₂/Al₂O₃/FeCrAl showed excellent catalytic performance in DME PO at O₂:C molar ratio of 0.29 and inlet temperature 840 °C which corresponded to carbon-free region. 100% DME conversion was reached at GHSV of 45,000 h⁻¹. The produced syngas contained (vol. %): 33.4 H₂, 34.8 N₂, 22.7 CO, 3.6 CO₂ and 1.6 CH₄. Composite catalyst demonstrated the specific syngas productivity (based on CO and H₂) in DME PO of 42.8 m³·L_cat⁻¹·h⁻¹ (STP) and the syngas productivity of more than 3 m³·h⁻¹ (STP) that was sufficient for 3 kW_e SOFC feeding. PO of natural gas and liquified petroleum gas can be carried out over the same catalyst with similar productivity, realizing the concept of multifuel hydrogen generation. The syngas composition obtained via DME PO was shown to be sufficient for YSZ-based SOFC feeding.     

Immobilized phosphotungstic acid for the construction of proton exchange nanocomposite membranes with excellent stability and fuel cell performance

Phosphotungstic acid (HPW) has a good potential as nanofillers in nanocomposite proton exchange membrane with the prerequisite of solving the leakage issue. It is immobilized onto mesoporous graphitic carbon nitride (mg-C₃N₄) nanosheets surface, and then incorporated into sulfonated poly (aryl ether sulfone) (SPAES) membrane. Structures of the HPW/mg-C₃N₄ nanocomposites and corresponding SPAES/HPW/mg-C₃N₄ membranes are characterized by spectroscopic techniques. Fundamental properties and fuel cell performance of the fabricated nanocomposite membranes, and the leakage of HPW are investigated. Along with the highly suppressed HPW leakage, the SPAES/HPW/mg-C₃N₄ membranes show improved dimensional stability, water affinity and physicochemical stability, as well as better proton conductivity and fuel cell performance. At 80 °C and 60–100% RH, the SPAES/HPW/mg–C₃N₄–1.5 membrane exhibits 2–3.6 times peak power densities (354.9–584.2 mW/cm²) of the pristine SPAES membrane, and proton conductivity of 203 mS/cm, dimensional change less than 7.5% and weight loss of 1.4% in Fenton oxidation test at 80 °C.     

Synthesis and evaluation of the thermal properties of biosourced poly(ether)ureas and copoly(ether)ureas from 1,4:3,6‐dianhydrohexitols

A new series of poly(ether)ureas were prepared by solution polyaddition of three diamines based on 1,4:3,6‐dianhydrohexitols with three types of diisocyanate. The corresponding poly(ether)ureas were obtained with high yields. They were characterized by various analytical techniques (NMR, TGA and differential thermal analysis, DSC). NMR spectroscopy allowed us to confirm structure type and to optimize reaction conditions and DSC proved the high thermal properties of the products obtained (T_g and T_m in the range 126 ? 158 °C and 235 ? 330 °C respectively). Then, copoly(ether)ureas partially based on commercial diamines were synthesized in order to reduce polymer cost and tune their thermal behaviour. The reactivity of both diamines was evaluated by their incorporation in the polymer by means of NMR spectra. Then their thermal properties were compared with fully commercial diamine based polyureas by DSC studies. © 2014 Society of Chemical Industry     

Robust proton exchange membrane for vanadium redox flow batteries reinforced by silica-encapsulated nanocellulose

High ion selectivity and mechanical strength are critical properties for proton exchange membranes in vanadium redox flow batteries. In this work, a novel sulfonated poly(ether sulfone) hybrid membrane reinforced by core-shell structured nanocellulose (CNC-SPES) is prepared to obtain a robust and high-performance proton exchange membrane for vanadium redox flow batteries. Membrane morphology, proton conductivity, vanadium permeability and tensile strength are investigated. Single cell tests at a range of 40–140 mA cm⁻² are carried out. The performance of the sulfonated poly(ether sulfone) membrane reinforced by pristine nanocellulose (NC-SPES) and Nafion® 212 membranes are also studied for comparison. The results show that, with the incorporation of silica-encapsulated nanocellulose, the membrane exhibits outstanding mechanical strength of 54.5 MPa and high energy efficiency above 82% at 100 mA cm⁻², which is stable during 200 charge-discharge cycles.