Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.     

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.     

二氧化碳加氢直接合成二甲醚催化剂的研究——沉淀次序对复合催化剂结构和性能的影响

以草酸乙醇溶液为沉淀剂,采用不同的沉淀次序(并流、反加和正加)制备了CuO-ZnO-Al2O3/HZSM-5复合型催化剂,对CO2加氢直接合成二甲醚反应的催化活性顺序为:并流法催化剂>反加法催化剂>正加法催化剂。3种复合催化剂的还原温度由低到高的顺序为:并流法催化剂<反加法催化剂<正加法催化剂。在沉淀过程中,反加法和正加法均形成类胶体沉淀,相应催化剂的比表面积也较大。IR研究发现,催化剂在1101cm-1处表现Cu/Zn/Al氧化物与HZSM-5分子筛之间相互作用的IR吸收峰强度与其催化活性间存在对应关系。XRD结果表明,并流法得到的催化剂前驱体中有铜锌同形取代现象,有利于催化剂活性的发挥。     

分子筛绿色化合成技术的开发

对现有分子筛合成废液中氨氮及还原性物质的来源进行分析，确定降低排放废水中氨氮浓度及COD的方案。对现有ZRP-5分子筛制备流程进行优化，增加母液及赶胺水回用工序；建立母液浓缩装置，将钛硅分子筛及Β分子筛的合成母液及重排母液应用于ZSM-5分子筛的合成，实现废液的梯级利用。上述措施既解决了因分子筛生产废液的排放造成的环境污染，亦因废物资源化降低了ZSM-5分子筛的生产成本。     

外源乙烯对黄瓜幼苗根系生长及内源多胺含量的影响

精确控制营养液溶氧浓度和外源乙烯浓度,研究了黄瓜幼苗根系在低氧水培时的生长情况以及PAs含量的变化。结果表明,外源乙烯对根际低氧逆境下黄瓜幼苗根系的生长有抑制作用,虽然根径增粗,含水量增加,但根系的总根数、总表面积、总体积、干重和鲜重都有所减少,随着乙烯浓度的增加,抑制作用增强;外源乙烯对根际低氧逆境下黄瓜幼苗根系PAs含量有着明显的拮抗作用,外源乙烯使根际低氧逆境下黄瓜幼苗根系的伤害症状加重。     

Staining of poly(ethylene terephthalate) by ruthenium tetroxide

The staining of poly(ethylene terephthalate) (PET) by ruthenium tetroxide (RuO₄) is used to obtain a contrast at the crystalline lamellar scale in transmission electron microscopy. This paper demonstrates the efficiency of this technique conducted in vapor phase on ultracut bulk samples. Advantages of this method against other contrast enhancing techniques and the parameters of staining are discussed. The depth of attack is measured and is shown to be limited by a crosslinking process. The chemical mechanisms are investigated by grazing infrared spectroscopy and involve the oxidation of the aliphatic moeities of PET.     

载体比表面积及孔径对Nb_2O_5/α-Al_2O_3催化剂酸性及反应性能的影响

采用浸渍法制备了Nb2O5/α-A l2O3催化剂(简称催化剂)并用于环氧乙烷水合制乙二醇的反应,通过控制α-A l2O3载体中致孔剂的含量来调变载体的孔径、孔分布及比表面积;采用吡啶吸附红外光谱、氨程序升温脱附法研究了载体的比表面积及孔径对催化剂酸性及反应性能的影响。实验结果表明,产物的选择性受扩散因素及催化剂酸性的影响,而催化剂的酸量、酸密度可以通过载体的孔径及比表面积的变化加以调控。比表面积较小及孔径较大的载体对催化剂催化环氧乙烷水合制乙二醇的反应较为有利。当载体的比表面积小于0.80m2/g、孔径为4.00~8.00μm时,在反应温度160℃、反应压力1.5M Pa、n(H2O)∶n(EO)=22、液态空速25h-1的条件下,环氧乙烷的转化率大于99.8%,乙二醇的选择性超过89.9%。     

溶剂对环氧乙烷催化水合制乙二醇的影响

研究了NY催化剂催化环氧乙烷水合制乙二醇(EG)过程中,溶剂、催化剂添加量和水与环氧乙烷的摩尔比(简称水比)对EG选择性的影响。实验结果表明,以丙三醇作为溶剂使催化剂进行循环,能提高EG的选择性,效果好于以生成的EG作为溶剂循环催化剂。催化剂添加量、水比和溶剂添加量对EG选择性具有较大影响,其中溶剂添加量对EG选择性的影响最显著。在低水比(1.0~4.0)条件下,EG质量分数小于30%、催化剂质量分数大于7.2%时,EG选择性稳定在95.63%~97.92%,平均值为96.80%,此结果对于进一步降低EG合成工艺的能耗具有指导意义。     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.