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。     

LITTLEWOOD-PALEY THEOREM FOR SCHR(O)DINGER OPERATORS

Let H be a Schr(o)dinger operator on Rn. Under a polynomial decay condition for the kernel of its spectral operator, we show that the Besov spaces and Triebel-Lizorkin spaces associated with H are well defined. We further give a Littlewood-Paley characterization of Lp spaces in terms of dyadic functions of H. This generalizes and strengthens the previous result when the heat kernel of H satisfies certain upper Gaussian bound.     

基于曲线问题情境的信息化教学尝试*——以“沉淀溶解平衡”为例

基于高中生对实验曲线理解困难的现状,为挖掘实验曲线的教学价值,以沉淀溶解平衡为例,结合课堂演示实验和教学软件,设计了“宏观微观符号曲线”多重表征教学为一体的实验探究课。根据沉淀溶解平衡实验证据,绘制实验曲线,构建微观模型和图像,从而培养学生的证据收集与应用意识,提高学生对曲线的分析和理解能力,领会各种变化曲线的来源。在曲线理解的基础上建立“溶解平衡转化”思维模型,以此为开展“曲线融入式”的问题引导型实验教学提供参考案例。     

Solvent-free 1,6-conjugate arylation of para-quinone methides: A greener approach to unsymmetrical triarylmethanes

A highly efficient arylation of para-quinone methides (p-QMs) with N,N-dimethylaniline under solvent free condition has been developed, which proceeded via a para-toluenesulfonic acid (TsOH)-promoted 1,6-conjugated addition pathway. This methodology provided a green and sustainable methodology to construct various novel unsymmetrical triarylmethanes (TAMs) with the advantages of good functional group tolerance, scalability, and regioselectivity.     

Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions

We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone^® in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.     

Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s

We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols. Four poly(dithioacetal)s(P1-P4) were prepared via the base-catalyzed thiol-yne "click" polyaddition of two dithiols(1,4-butanedithiol(4 S) and 1,5-pentanedithiol(5 S)) and two alkynones(3-butyn-2-one(Y1) and 1-phenyl-2-propyn-1-one(Y2)) at high concentrations. We systematically investigated the base-catalyzed polymerization of 4 S and Y1(for polymer P1) under different conditions, and found that this polymerization was a highly concentration-dependent dynamic system: polymer P1 was formed at high concentration, while seven-membered dithioacetal, 1-(1,3-dithiepan-2-yl) propan-2-one(C1), was obtained at low concentration. The polymerization of 4 S and Y2(for polymer P4)displayed similar polymerization behavior, generating 2-(1,3-dithiepan-2-yl)-1-phenylethanone(C4) at low concentration. On the contrary,polymer P2(from Y1 and 5 S) was exclusively obtained with no formation of eight-membered dithioacetal. The polymerizations of Y1 with 1,2-ethanedithiol(2 S) and 1,3-dimercaptopropane(3 S) only afforded corresponding five-and six-membered dithioacetals, 1-(1,3-dithiolan-2-yl)propan-2-one(C2) and 1-(1,3-dithian-2-yl) propan-2-one(C3). This dynamic behavior of P1 and P4 was attributed to the concentrationdependent retro-Michael addition reaction between a thiol and a β-sulfido-α,β-unsaturated carbonyl compound catalyzed by bases.Furthermore, polymers P1 and P4 could be depolymerized into C1 and C4 in yields of 58% and 95%, respectively. The ring-opening polymerization of C1 at high concentration could successfully regenerate polymer P1. Thus, a new type of closed-loop recyclable poly(dithioacetal)s was developed.     

Extremely Low Vapor-Pressure Data as Access to PC-SAFT Parameter Estimation for Ionic Liquids and Modeling of Precursor Solubility in Ionic Liquids

Precursor solubility is a crucial factor in industrial applications, dominating the outcome of reactions and purification steps. The outcome and success of thermodynamic modelling of this industrially important property with equations of states, such as Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), vastly depends on the quality of the pure-component parameters. The pure-component parameters for low-volatile compounds such as ionic liquids (ILs) have been commonly estimated using mixture properties, e. g. the osmotic pressure of aqueous solutions. This leads to parameters that depend on the solvent, and transferability to other mixtures often causes poor modeling results. Mixture-independent experimental properties would be a more suitable basis for the parameter estimation offering a way to universal parameter sets. Model parameters for ILs are available in the literature [10.1016/j.fluid.2012.05.029], but they were estimated using pure-IL density data. The present work focuses on a step towards a more universal estimation strategy that includes new experimental vapor-pressure data of the pure IL. ILs exhibit an almost negligible vapor pressure in magnitude of usually 10⁻⁵ Pa even at elevated temperatures. In this work, such vapor-pressure data of a series of 1-ethyl-3-methyl-imidazolium-based [C₂mim]-ILs with various IL-anions (e. g. tetrafluoroborate [BF₄]⁻, hexafluorophosphate [PF₆]⁻, bis(trifluoromethylsulfonyl)imide [NTf₂]⁻) were experimentally determined and subsequently used for PC-SAFT parameter estimation. The so-determined parameters were used to predict experimental molecular precursor solubility in ILs and infinitely diluted activity coefficients of various solvents in ILs. The parameters were further compared to modeling results using classical parametrization methods (use of liquid-density data only for the molecular PC-SAFT and the ion-based electrolyte PC-SAFT). As a result, the modeled precursor solubilities using the new approach are much more precise than using the classical parametrization methods, and required binary parameters were found to be much smaller (if needed). In sum, including the pure-component vapor-pressure data of ILs opens the door towards parameter estimation that is not biased by mixture data. This procedure might be suitable also for polymers and for all kind of ionic species but needs extension to ion-specific parametrization in the long term.     

制备条件对稀土掺杂TiO2物理性质和光催化降解吡唑草胺性能的影响

多相光催化是一种非常有效的降解各种水污染物的方法.本文以稀土(镝和镨)掺杂的TiO2为光催化剂,考察了制备条件对其物理性质和光催化性能的影响.采用溶胶-凝胶法和不同条件(反应温度450,550,650oC;反应时间4,8,12 h)的固态反应法制备了TiO2样品.运用X射线衍射分析了该样品的晶相,发现只存在锐钛矿相,并得到Raman光谱的证实.同时采用扫描电镜观察了样品的结构和粒径;以BET法计算了其比表面积;运用紫外-可见光漫反射光谱测得了样品的带隙能量.通过测量紫外光照射下常用除草剂吡唑草胺的降解速率评价了样品的光催化活性,反应过程中吡唑草胺的浓度用高效液相色谱分析.结果表明,稀土掺杂使得TiO2吸收边红移,并提高了其光催化活性;制备时最优的固态反应条件为550oC反应8 h.     

30℃时MgCl2-MgSO4-CH3CH2OH-H2O四元体系液固相平衡的研究

采用等温法测定了30℃时Mg Cl2-Mg SO4-CH3CH2OH-H2O四元体系及边界三元体系Mg Cl2-CH3CH2OH-H2O和Mg SO4-CH3CH2OH-H2O的相平衡数据,绘制了相图并划分了相应的结晶区。实验结果表明,随着乙醇-水体积比不同,四元体系Mg Cl2-Mg SO4-CH3CH2OH-H2O出现了不同的结晶区,随着乙醇含量的增加,Mg Cl2和Mg SO4的溶解度越来越小,不饱和区越来越小,体系中平衡固相的结晶水含量越来越低,说明乙醇具有一定的盐析作用和脱水作用。当乙醇-水体积比为5∶5时,是获得镁盐的最佳比例。这为芒硝和白钠镁矾共生矿中镁盐的分离和提纯提供基础的理论数据。     

温和条件下金属双氮杂环卡宾配合物催化CO2直接转化为炔酸的高效均相羧化反应

近年来,催化CO2合成精细化学品的研究备受关注。本研究在温和条件下利用金属双氮杂环卡宾催化剂实现CO2与末端炔烃的直接羧化反应,并提出合理的催化机理。首先,合成制备了铜基、银基两种金属双氮杂环卡宾催化剂,实验证明银双氮杂环卡宾配合物具有较好催化活性。通过改变环境条件和底物种类,对反应条件及催化剂底物适应性进行了探究,利用核磁共振谱仪表征产物分子结构并计算直接羧化反应的催化产率。结果表明,适宜催化条件为:1.2eq Cs2CO3作为添加剂、1大气压、室温、无水溶剂和1(mmol)%催化剂用量。银基金属催化剂活性较铜基催化剂高并具有广泛的底物适应性,对苯乙炔的催化产率高达93%;对乙炔气体同样具有良好的催化活性。此类催化剂具有优良的催化活性,能催化合成丙炔酸等重要医药中间体,在工业应用上具有极大潜力和广阔前景。