IM-5分子筛在Ni-Cu催化剂甲烷热裂解制氢反应中的作用研究

甲烷热裂解制氢并生成高附加值的纳米碳材料,被认为是极具发展前景的氢气生产途径,但高性能催化剂的研发仍存在诸多挑战.我们选择多种载体(TS-1、 IM-5、 Y、介孔SiO₂、 γ-Al₂O₃、 CNTs),采用浸渍法制备Ni-Cu负载催化剂,通过低温N2吸附-脱附、 XRD、 SEM和H₂-TPR等系列表征方法对样品进行分析,考察不同载体对催化剂甲烷裂解制氢和纳米碳材料的影响.实验结果发现,分子筛载体独特的孔道结构有利于金属颗粒的分散,能有效避免反应中界面效应导致的催化剂失活,可提高催化剂反应活性并延长反应寿命,也显著提高了其碳产率.其中以IM-5分子筛为载体的催化剂表现最佳,在反应温度为700℃时, NiCu/IM-5催化剂甲烷转化率高达80%,氢气选择性达100%,反应400 min后活性未见明显降低. NiCu/IM-5催化剂碳产率高达1 446 g_C/g_cat,是NiCu/SiO₂催化剂的5.7倍, NiCu/γ-Al     

钾改性氧化铝基羰基硫水解催化剂及其失活机理

天然气、油田伴生气、高炉煤气等化工生产过程中伴生COS气体,不仅会腐蚀管道和毒害催化剂,还会严重污染环境并危害人类健康。COS催化水解反应可在温和条件下高效的将COS脱除,是最具应用前景的COS脱除技术之一。碱金属元素因其具有独特的电子供体性质、表面碱性和静电吸附等特性,常被用作助催化剂以提高Al₂O₃的COS催化水解性能。近年来,以钾为助剂改性的Al₂O₃催化剂(K₂CO₃/Al₂O₃)在COS催化水解反应中得到广泛的应用,但由于负载在Al₂O₃上的K物种的组成复杂,目前研究者对K₂CO₃/Al₂O₃催化剂上COS水解机理的理解仍存在一定的困惑和争议。本论文通过湿法浸渍法合成出一系列钾盐和钠盐改性的Al₂O₃催化剂,并利用各类先进的表征技术对这些催化剂进行分析。活性测试表明,以K₂CO₃、K₂C₂O₄、NaHCO₃、Na₂CO₃和NaC₂O₄改性Al₂O₃催化剂均有助于COS的水解。其中K₂CO₃/Al₂O₃拥有最佳的COS水解性能,连续运行20 h后其COS转化率仍高于~93%,远远优于未改性的Al₂O₃ (~58%)。我们利用原位红外光谱和X射线光电子能谱探明了反应过程中催化剂的化学结构特征,阐明了H₂O分子在K₂CO₃/Al₂O₃上的水解作用机制。原位红外表明COS在K₂CO₃/Al₂O₃上的水解过程中形成了硫代碳酸氢盐中间产物。X射线光电子能谱表征证明催化剂的失活主要是因为催化剂表面积累了硫酸盐和单质硫。此外,我们还研究了水蒸气含量对COS水解性能的影响,研究发现,由于H₂O和COS分子在催化剂表面存在竞争吸附,过量的H₂O会引起催化活性的下降。上述研究表明,K₂CO₃/Al₂O₃催化剂上COS水解性能的提高主要是形成了HO-Al-O-K界面活性位。更为重要的是,所制备的催化剂都是在模拟工业工况条件下进行的,这为后续的工业应用提供了宝贵理论指导。本工作为理解助剂钾在Al₂O₃催化剂上COS水解活性的增强提供了新的见解,这为未来设计稳定高效的COS水解催化剂打开了新的发展方向。     

A Tailored Versatile and Efficient NHC-Based NNC-Pincer Manganese Catalyst for Hydrogenation of Polar Unsaturated Compounds

The reactivity of metal-hydride complexes can be harnessed by the modification of ancillary ligands. With the aim of improving the hydride-donor ability of the key Mn−H intermediate and reducing steric hindrance, we herein report the rational design of a versatile and efficient NHC-based NNC-pincer Mn catalyst for hydrogenation reactions. This newly developed catalyst exhibited higher activity than the corresponding NNP-pincer Mn catalyst owing to its reduced steric hindrance and enhanced Mn−H σ-bonding orbital energy level through a π-antibonding interaction. Using this highly active NNC-pincer Mn catalyst, a rich array of polar unsaturated compounds (>80 examples) including esters, N-heteroarenes, amides, carbonates, and urea derivatives, were successfully hydrogenated under relatively mild conditions. This work represents a rare example of a general phosphine-free Mn-catalyzed hydrogenation system.     

Durable Electrocatalytic Reduction of Nitrate to Ammonia over Defective Pseudobrookite Fe2TiO5 Nanofibers with Abundant Oxygen Vacancies

We propose the pseudobrookite Fe₂TiO₅ nanofiber with abundant oxygen vacancies as a new electrocatalyst to ambiently reduce nitrate to ammonia. Such catalyst achieves a large NH₃ yield of 0.73 mmol h⁻¹ mg⁻¹_cat. and a high Faradaic Efficiency (FE) of 87.6 % in phosphate buffer saline solution with 0.1 M NaNO₃, which is lifted to 1.36 mmol h⁻¹ mg⁻¹_cat. and 96.06 % at −0.9 V vs. RHE for nitrite conversion to ammonia in 0.1 M NaNO₂. It also shows excellent electrochemical durability and structural stability. Theoretical calculation reveals the enhanced conductivity of this catalyst and an extremely low free energy of −0.28 eV for nitrate adsorption at the presence of vacant oxygen.     

催化光度法时间程序测定土壤中痕量碘

碘是评价环境的重要元素之一,是地球化学勘察样品常测元素。本实验建立了艾斯卡试剂分解-热水提取样品,催化分光光度法时间程序测定碘的方法。详细讨论了艾斯卡试剂手工制作与行星球磨机制作的利弊;;参比液的选择;17℃-25℃不同环境温度条件对实验结果的影响;全程序空白溶液,与36g/L的碳酸钠溶液两种方法制作标准曲线及标准曲线线性范围;样品烧结时间及温度;乙酸用量对样品测试吸光度的影响。结果表明：利用行星球磨机制作艾斯卡试剂,选择试剂空白为参比液,在19℃的恒温环境下,采用36g/L的碳酸钠溶液制作0-8ug/mL标准曲线,样品采用0-300℃、300-500℃、500-750℃三阶段升温,750℃保持30min的烧结程序,乙酸用量为5mL时可以得到可靠的结果。该方法克服了艾斯卡试剂制作困难、样品烧结结块及实验反应速率过快等困难。通过方法学考察表明：基于所建方法碘元素校准曲线系数＞0.999;方法检出限为0.2 mg/kg;测定GSS36、GSS37、GSS38、GSS40、GSS47、GSS48、GSS49等9种国家一级标准物质,结果均在参考值范围内,相对标准偏差RSD＜5%。该方法测定的结果准确度及精密度高、 检出限低、减少碘记忆效应的存在,适用于地球化学勘察土壤样品中碘的测定。     

Modeling of biomass-based hydrogen production via catalytic sorption-enhanced reformer integrated with a gasifier

The sorption enhanced reformer concept breaks the thermodynamic limits of steam methane reforming and water-gas shift reactions with selective CO₂ removal to produce more H₂. In this paper, we propose a dynamic kinetic model for sorption-enhanced steam reformers (SERs) integrated with biomass gasifiers. An analysis of operating conditions was conducted to examine high purity hydrogen production. The kinetic model was validated with published literature results at different reactor pressures (5-20 bar), steam/carbon ratios (2-5), and reactor temperatures (673K–1023K). This study shows that biomass gasifiers can be integrated with SER reactors to produce high purity H₂.     

Comparative study of Co3O4-ZSM-5 catalysts synthesized by different hydrothermal methods for the catalytic oxidation of dichloromethane

In this work, various Co₃O₄-ZSM-5 catalysts were prepared by the microwave hydrothermal method (MH-Co₃O₄@ZSM-5), dynamic hydrothermal method (DH-Co₃O₄@ZSM-5), and conventional hydrothermal method (CH-Co₃O₄/ZSM-5). Their catalytic oxidation of dichloromethane (DCM) was analyzed. Detailed characterizations such as X-ray diffractometer (XRD), scanning microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), H₂ temperature-programmed reduction (H₂-TPR), temperature-programmed desorption of O₂ (O₂-TPD), temperature-programmed desorption of NH₃ (NH₃-TPD), diffuse reflectance infrared Fourier-transform spectra with NH₃ molecules (NH₃-DRIFT), and temperature-programmed surface reaction (TPSR) were performed. Results showed that with the assistance of microwave, MH-Co₃O₄@ZSM-5 formed a uniform core-shell structure, while the other two samples did not. MH-Co₃O₄@ZSM-5 possessed rich surface adsorbed oxygen species, higher ratio of Co³⁺/Co²⁺, strong acidity, high reducibility, and oxygen mobility among the three Co₃O₄-ZSM-5 catalysts, which was beneficial for the improvement of DCM oxidation. In the oxidation of dichloromethane, MH-Co₃O₄@ZSM-5 presented the best activity and mineralization, which was consistent with the characterizations results. Meanwhile, according to the TPSR test, HCl or Cl₂ removal from the catalyst surface was also promoted in MH-Co₃O₄@ZSM-5 by their abundant Brønsted acid sites and the promotion of Deacon reaction by Co₃O₄ or the synergistic effect of Co₃O₄ and ZSM-5. According to the results of in situ DRIFT studies, a possible reaction pathway of DCM oxidation was proposed over the MH-Co₃O₄@ZSM-5 catalysts.     

“功能涂料”课程的教学改革:打造趣味性、互动性和挑战性的课堂*

本着培养涂料行业精英人才的宗旨,针对涂料行业对人才需求的特点,结合多年教学经验,从教材的选择、教学内容设置、教学方法改进以及考核方法改革等4个方面探索了“功能涂料”课程的教学方法改革与课程实践。通过自编教材,精心设置授课内容,将科研成果、前沿知识、生活场景、新闻事件与书本知识相结合,提高课堂的趣味性;通过讨论法和交换式互动上课来加强课堂的互动性;通过过程性评价提高课程的学业挑战度。通过教学改革,本课程的选课率和出勤率得到了大幅提高,学生对涂料的兴趣明显增加,毕业后选择进入涂料领域工作的学生也越来越多。     

Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol with formic acid as hydrogen donor over CuCs-MCM catalyst

Catalytic transfer hydroge nation(CTH) of furfural(FF) to furfu ryl alcohol(FFA) has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6% FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.     

分子筛膜反应器的研究进展

分子筛膜具有规整的微孔结构(<1 nm), 耐高温高压、 抗有机溶剂, 在液相和气相小分子分离中受到广泛关注. 分子筛膜可以与催化反应耦合于一体构成膜反应器, 使反应过程与组分分离同时进行, 促进反应平衡移动, 达到反应强化的效果. 本文概述了近十年不同类型分子筛膜反应器在催化反应中的应用研究进展, 并对分子筛膜反应器未来的发展趋势进行了展望.