Synthesis,characterization, rheological and thermal behavior of metallocene ethylene − norbornene copolymers with low norbornene content using pentafluorophenol modified methylaluminoxane

Ethylene ? norbornene copolymers were synthesized using rac‐ethylene bis(indenyl) zirconium dichloride/pentafluorophenol modified methylaluminoxane. First, the effect of using a modifier in combination with a low ratio of Al/Zr on the catalyst activity and co‐monomer incorporation was studied. The results of copolymerization reveal a 20% co‐monomer incorporation improvement and a rise of activity by 2‐fold in the presence of the modifier. Rheological measurements show a higher molecular weight in copolymers synthesized using modified methylaluminoxane. The alternative and dyad block microstructures of copolymers become possible in the case of a norbornene content of more than 14 mol%. Second, the effect of co‐monomer content on the rheological and thermal behavior of the synthesized copolymers was investigated. The results of the rheological study indicate a lower molecular weight in samples containing a higher norbornene content. Dynamic mechanical thermal analysis confirms the influence of different microstructures on the glass transition temperature. The crystal structure of copolymers having a higher molecular weight is emphasized using wide angle X‐ray scattering and DSC even with a greater incorporation of norbornene. © 2015 Society of Chemical Industry     

中空碳基材料在电解水中的研究进展

氢能所具有的清洁、高能量密度特点，使其成为一种未来的理想能源。相较于石油、天然气等的热解制氢技术，利用可再生清洁能源进行电催化分解水制氢具有高效和清洁无污染的特点，且获得氢气产物纯度高，具备大规模发展的潜力。而在大规模水电解过程中，电催化剂是不可或缺的元素之一。它能有效地加速电解水在阴阳两极反应的动力学过程。传统的贵金属基催化剂具有良好的电催化析氢、析氧活性，但成本高昂、储量稀缺，从而限制了其规模化地推广及应用。开发新型高效廉价的非贵金属基电催化剂已成为时下研究热点。中空碳基纳米材料集成了中空材料和碳基材料的优势，作为电催化剂，在电解水方面有着潜在的应用价值。本文总结了近年来微纳米结构碳基中空材料作为新型电解水催化剂的研究进展，介绍了高效碳基中空析氧/析氢催化剂的设计原则和相应的设计策略，并对开发持久高效的中空碳基电解水催化剂进行了总结和展望。     

阴离子种类及浓度对RCT催化剂催化湿式氧化处理头孢废水的影响

采用催化湿式氧化法处理头孢类废水,以RCT为催化剂,考察了阴离子对污染物降解效果的影响。结果表明,不加阴离子时,RCT催化剂能有效催化污染物的降解,TOC和TN去除率分别为78.3%和85.9%;投加不同阴离子对反应的影响不同。RCT催化剂可将头孢氨苄废水中的有机N转化为$N_{2}$,少部分以$NO_{3}-N$形式存在;阴离子F^-、Cl^-、Br^-、I-及$S^{2-}_{4}$对TN的降解影响不大,而$N^{-}_{3}$、$P^{3-}_4$、$CO^{2-}_{3}$、$Si^{2-}_{3}$及$B_{4}O^{2-}_{7}$则明显抑制了对TN的去除。投加F^-、Cl^-、Br^-、I-及$NO^{-}_{3}$对TOC的降解有促进作用(I^-> F^-> Cl^-> Br^-> $NO^{-}_{3}$),TOC的降解率提高了3.1~18.6个百分点;而投加$S^{2-}_{4}$、P,$P^{3-}_4$、$CO^{2-}_{3}$、$SiO^{2-}_{3}$及$B_{4}O^{2-}_{7}$对TOC的降解有抑制作用($SiO^{2-}_{3}$> ,$P^{3-}_4$> $CO^{2-}_{3}$> $B_{4}O^{2-}_{7}$> $S^{2-}_{4}$),TOC的降解率降低了2.0~46.9个百分点。研究Cl-浓度对RCT催化剂降解效果的影响,当Cl-为0.1 mol·L-1时,对TOC的去除有抑制作用,而较高的Cl-浓度(≥0.3 mol·L-1)对TOC的去除却有促进作用,投加Cl-对TN的去除有促进作用,但随着Cl-浓度的增加[(0.1~0.8) mol·L-1],TN的去除率变化不明显(约为88%)。     

Selective Hydrogenation of Biomass-Derived Succinic Acid: Reaction Network and Kinetics

The conversion of bio-based succinic acid (SA) to the value-added chemicals 1,4-butanediol (BDO), γ-butyrolactone (GBL), and tetrahydrofuran (THF) can replace the corresponding petrochemical production routes to achieve a sustainable process. The reaction network for aqueous-phase catalytic hydrogenation of succinic acid over a supported Re-Pd catalyst was identified and the reaction kinetics was determined. With the developed kinetic model, the composition of the product mixture regarding the desired products (BDO, GBL, THF) can be described as a function of educt concentration, temperature, and pressure. The maximum BDO yield was achieved at high pressure and low temperature, while low pressure and high temperature favored GBL and THF production.     

四氢呋喃对M-1催化剂性能的影响

结合乙烯气相流化床反应工艺的特点,深入探讨分析四氢呋喃对M-1催化剂的作用和影响,结果表明,四氢呋喃的含量直接影响M-1催化剂的活性和催化乙烯与丁烯-1共聚生产的树脂产品性能。为了生产性能优良的乙烯与丁烯-1共聚产品,需要将四氢呋喃的含量严格控制在较窄的范围。     

Effects of molecular modifications for water splitting enhancement of BiVO4

Combined organic (molecular adsorption) and inorganic (TiO₂ passivation) modifications for enhancing water splitting efficiency of porous bismuth vanadate electrodes are tested. The catalytic activity of BiVO₄ is increased after adsorption of a newly prepared ruthenium catalyst. TiO₂ passivation and sensitization with RuP dye does not show straightforward improvements to the complex photocatalytic behaviour depending on the configuration of the (two- or three-electrode) photoelectrochemical cell, type of the experiment and sample aging. The time constant for electron transport in BiVO₄ electrodes (in the range of seconds, revealed by electrochemical impedance measurements) was found to correlate with the stable photocurrent of the cells. The femtosecond transient absorption studies confirm the negligible effects of RuP on the population of the photoexcited carriers in BiVO₄. The transient absorption studies also show that the processes responsible for the differences in photocurrents of the modified BiVO₄ samples occur on a time scale longer than the first nanoseconds.     

Facile synthesis of PdAu/C by cold plasma for efficient dehydrogenation of formic acid

Decomposition of formic acid biomass to generate hydrogen is vital for coping with fossil energy depletion, environmental pollution, and developing clean, efficient, safe, and sustainable modern energy system. In this study, a PdAu/C−C bimetallic catalyst was prepared by the co-impregnation method followed by an atmospheric pressure (AP) cold plasma treatment to synthesize PdAu/C−P catalysts. The resulting PdAu/C−P showed excellent catalytic activity for the formic acid dehydrogenation (FAD) reaction. The total volume of H₂ and CO₂ released from the FAD reaction was about 375 mL after 4 h at 50 °C, and the initial turnover frequency (TOF_initial) was 808.6 h⁻¹. We used X−ray diffractometry (XRD), temperature programmed reduction (TPR) and high-resolution transmission electron microscopy (HRTEM) to show that plasma can effectively promote the redispersion of Pd−Au particles on the surface of the support. The average particle size of PdAu/C−P (3.5 ± 1.5 nm) was less than PdAu/C−C (4.4 ± 1.9 nm) and uniformly distributed. X-ray photoelectron spectroscopy (XPS), TPR, and HRTEM showed that PdAu/C−P has a higher degree of alloying. In addition, the strong electric field in the plasma facilitated more metal sites located on the outer surface of the support in PdAu/C−P, and the atomic ratio of M/C (M = Pd and Au) (0.0134) was much larger than that of PdAu/C−C (0.0060). The apparent activation energy (E_a) of PdAu/C−P for the FAD reaction was only 27.25 kJ mol⁻¹, and it had much higher activity and stability than the commercial Pd/C (Sigma−Aldrich). The total volume of H₂ and CO₂ produced over the PdAu/C−P for three cycles was 1.33, 5.87, and 8.56 times that of commercial Pd/C. Overall, the cold plasma enhanced the degree of alloying, promoted the redispersion of agglomerated particles, and regulated the surface enrichment of the active metal components. This is of great significance for guiding the preparation of high−performance multi-metal catalysts by cold plasma.     

铁碳微电解填料（Fe/C-MEF）活化过硫酸盐降解活性黑5

采用高温微孔活化技术制备了铁碳微电解填料（Fe/C-MEF），用于活化过硫酸盐（PDS）降解高浓度活性黑5（RB5）染料废水。使用扫描电镜和能谱仪对Fe/C-MEF进行了表征。对比了不同工艺对RB5的降解性能，结果表明Fe/C-MEF/PDS体系表现出更加高效的去除率，且Fe/C-MEF反应前后结构稳定易回收重复利用。探究了PDS浓度、Fe/C-MEF浓度、pH、无机阴离子对体系降解RB5的影响，得到优化的反应条件，PDS浓度、Fe/C-MEF浓度分别为1.5×10^-2mol/L、24g/L；表明PDS水解能调节pH至3附近，使体系保持较高的去除率；无机阴离子的存在会影响体系对RB5的降解，且根本原因为影响体系pH限制催化剂释放和消耗·SO{}_{\mathrm{4}}^{-}生成更低活性的自由基。自由基淬灭实验表明，在反应中Fe/C-MEF同时作为微电解反应主体和PDS的非均相催化剂，在两者协同作用下高效降解RB5。Fe/C-MEF经过6次循环利用，体系对RB5依然保持高的脱色率，具有很好的稳定性。     

电催化氮气还原合成氨催化材料研究进展

氨是纺织、制药、化肥等领域重要的化工原料，也是一种清洁的能源载体，需求量大。目前氨的工业生产主要为Haber-Bosch法，反应条件严苛，能源消耗大且碳排放较高。电催化氮气还原(NRR)合成氨是一种在常温常压下进行的反应，工作电位低，且电能可通过清洁能源提供，是一种很有潜力的合成氨新工艺。但目前电催化NRR材料的产氨速率和法拉第效率低、工作稳定性不够高、溶液中痕量氨的定量检测困难及检测标准不统一等都为其发展带来了巨大挑战。本文首先介绍了电催化NRR的反应机理和常用研究方法，然后重点梳理了2019年以来NRR催化材料的最新研究进展，最后对该领域研究面临的挑战和机遇进行了展望。