丙烯酸酯基吸附树脂对水体中单宁酸和没食子酸的吸附研究

选用3种商品丙烯酸酯基吸附树脂作为吸附剂,研究单宁酸和没食子酸在树脂上的吸附行为和机理。吸附等温线表明,丙烯酸酯基吸附树脂对单宁酸的吸附量远高于没食子酸的吸附量,这归因于两种有机酸亲水性的差异;HP-2MG比其他两种树脂对单宁酸有更高的吸附容量,而XAD-7树脂对没食子酸的吸附量高于其它两种丙烯酸酯基吸附树脂,这归因于树脂比表面积和孔径的差异;吸附热力学研究表明,丙烯酸酯基吸附树脂对天然有机酸的吸附是自发的放热过程,疏水作用是主要吸附作用。     

新型吸附树脂对水中苯的吸附行为

研究表明,苯对人的毒性作用表现在中枢神经系统,65g／m^3的苯可引起广泛的出血导致死亡。反复暴露的低浓度苯主要对血液及造血组织产生毒性作用。根据苯吸入致白血病的流行病学研究数据,采用定量外推法计算出饮用水苯质量浓度为0．01mg/L时终身患癌的超额危险度为10^-5,因此饮用水中的苯的限值为0．01mg／L。因此,有效去除饮水中的苯具有重要的意义。     

氨基修饰超高交联树脂对没食子酸的吸附性能

以亲水性小分子有机酸没食子酸作为研究对象,研究了氨基修饰超高交联树脂对没食子酸的吸附行为和机理.结果表明,氨基修饰超高交联树脂WJN-10对没食子酸有较高的吸附容量和吸附作用力;π-π共轭作用是树脂WJN-10吸附没食子酸主要作用力;WJN-10吸附没食子酸是物理吸附主导;吸附速率主要受控于颗粒内扩散过程;WJN-10对没食子酸有较好的吸附-脱附性能.     

DFT方法研究酸性沸石上苯与乙烯烷基化反应的机理

采用B3LYP/6-31G*水平计算来研究酸性沸石上苯与乙烯的烷基化反应历程,从生成能和反应活化能角度分析并讨论了苯与乙烯的反应机理.选取4T簇模型模拟分子筛的酸性位,使用密度泛函理论对烷基化反应三种不同的反应机理(两个联合反应机理和一个分步反应机理)进行计算分析.结果表明,在联合反应机理中,乙烯的质子化和苯与乙烯间C-C键的形成同时发生;分步反应机理中,首先形成一个稳定的乙醇盐中间物种,然后与苯分子反应形成乙苯.联合机理速控步骤的活化能约为160kJ/mol,分步机理速控步骤的活化能为190.24kJ/mol,因此,酸性沸石上苯与乙烯烷基化反应机理主要以联合机理为主,但分步机理与其有一定程度的竞争。     

苯在CuCl（111）表面吸附的密度泛函理论研究

采用量子化学的密度泛函理论方法,探讨了苯分子在CuCl(111)表面上不同覆盖度下不同吸附位上的平行吸附行为. 计算结果表明,随覆盖度的减小,吸附作用增强, Cl位上的吸附是稳定的吸附模式,在低覆盖度下吸附能约为74 kJ/mol, 在顶位和穴位上的吸附属于较弱的物理吸附. 同时对吸附前后的电子布居和态密度进行了分析. 吸附过程中,苯分子的π电子向底物转移,同时Cu的 3d轨道的电子反馈给苯的反键π轨道.     

苯分子与Si_6O_18H_12和Al_6O_24H_30团簇模型相互作用的理论研究(英文)

粘土矿已经被广泛用来去除有机物,修复和净化被石油碳氢化合物污染的土壤和地下水.我们选择高岭石作为研究对象,构造了Si6O18H12和Al6O24H30两个团簇模型分别代表高岭石的硅氧层表面和铝氧层表面,在MP2/6-31G(d,p)//B3LYP/6-31G(d,p)的理论水平上系统地研究了气态下苯分子和高岭石团簇模型的相互作用.并进一步分析了苯分子和高岭石表面相互作用的各种气态性质,比如:优化的几何构型、结构参数、吸附能、自然键轨道电荷分布、振动频率变化、静电势、电子密度性质(次级氢键的电子密度和拉普拉斯算符值)和电子密度差分等.优化的几何构型表明苯分子吸附在高岭石表面的本质可能是次级氢键的形成.其他性质的结果进一步验证了次级氢键的存在,并指出苯更倾向于吸附在高岭石的铝氧层表面,且苯环和铝氧层表面形成近似90°的夹角.     

没食子酸修饰的超高交联吸附树脂对2,4-二氯苯氧乙酸的吸附性能研究

通过后交联反应和化学修饰反应制备了没食子酸修饰的超高交联吸附树脂(GAMR),以大孔吸附树脂XAD-4树脂为对照,研究了GAMR对水中2,4-二氯苯氧乙酸(2,4-D)的吸附性能.实验结果表明:GAMR具有较丰富的微孔,比表面积和微孔面积分别为1 232.3和899.5 m²·g^-1.GAMR对2,4-D的吸附动力学过程符合准一级动力学方程,吸附过程同时存在物理吸附和化学吸附.Freundlich等温方程能较好地拟合GAMR对2,4-D的吸附等温线.GAMR对2,4-D吸附过程的ΔG为负值,ΔH和ΔS均大于0,表明吸附是自发、吸热和熵增加的过程.与XAD-4相比,所制备的GAMR对2,4-D的吸附去除率显著提高.     

苯分子与Si6O18H12和Al6O24H30团簇模型相互作用的理论研究

粘土矿已经被广泛用来去除有机物,修复和净化被石油碳氢化合物污染的土壤和地下水. 我们选择高岭石作为研究对象,构造了Si₆O₁₈H₁₂和Al₆O₂₄H₃₀两个团簇模型分别代表高岭石的硅氧层表面和铝氧层表面,在MP2/6-31G(d,p)//B3LYP/6-31G(d,p)的理论水平上系统地研究了气态下苯分子和高岭石团簇模型的相互作用. 并进一步分析了苯分子和高岭石表面相互作用的各种气态性质,比如：优化的几何构型、结构参数、吸附能、自然键轨道电荷分布、振动频率变化、静电势、电子密度性质(次级氢键的电子密度和拉普拉斯算符值)和电子密度差分等. 优化的几何构型表明苯分子吸附在高岭石表面的本质可能是次级氢键的形成. 其他性质的结果进一步验证了次级氢键的存在,并指出苯更倾向于吸附在高岭石的铝氧层表面,且苯环和铝氧层表面形成近似90°的夹角.     

没食子酸修饰树脂对对氯苯胺和对硝基苯胺的吸附行为

通过Friedel-Crafts后交联及化学修饰反应,制备了没食子酸修饰的超高交联吸附树脂(GAMR),并通过傅里叶变换红外光谱仪、元素分析仪和比表面及孔径分析仪对其理化性质进行了表征。通过等温吸附实验和吸附动力学实验,研究了GAMR树脂对不同温度下水溶液中的对氯苯胺和对硝基苯胺的吸附行为。结果表明,GAMR树脂具有较高的比表面积(1227.1m2/g)和较丰富的微孔(888.5m2/g),树脂表面修饰了较丰富的羟基和羰基。GAMR树脂对对氯苯胺和对硝基苯胺均具有良好的吸附性能,吸附量随着温度的升高而下降。Freundlich等温吸附方程能够更好地拟合吸附等温线数据,GAMR树脂对对氯苯胺和对硝基苯胺的吸附机理较复杂。吸附焓变ΔH0,表示吸附过程为放热反应,且以物理吸附为主;吸附自由能变ΔG0,说明吸附过程可自发进行;吸附熵变ΔS0,表明吸附质分子在树脂表面上的运动受到了限制。动力学实验结果表明,吸附过程符合一级动力学方程,颗粒内扩散是吸附过程的主要控制步骤。     

DFT和热力学研究氢键协同效应及对关联1H NMR的影响

用DFT方法在B3LYP／6—311 G(d,p)水平下研究了甲醇线性和环状分子簇．对于不同大小的分子簇之间定义了协同因子,计算得到的协同因子可以验证氢键的强协同效应,环状分子簇之间的协同效应远远大于线性分子簇,做为理论验证和比较,热力学模型分别采用含氢键缔合的格子流体状态方程(LFHB),以及含氢键协同效应的LFHB,关联醇一惰性体系的^1H核磁共振化学位移．考虑协同效应的关联结果优于原始的LFHB,比较量子化学计算的和热力学模型中采用的协同因子,认为甲醇和乙醇在溶液中更可能大部分以线性缔合形式存在。     

Interfacial thermodynamics of gallic acid adsorption on a chargeable hydrophobic surface

The thermodynamics of adsorption of gallic acid (GA, 3,4,5-trihydroxylbenzoic acid) on the hanging mercury drop electrode (HMDE) surface was studied by temperature-dependent stripping voltammetry (TD-SV), at physiological pH 7.4. The thermodynamic parameters, e.g., Gibbs free energy, ΔG(ADS), enthalpy, ΔΗ(ADS) and entropy, ΔS(ADS), of adsorption have been determined at physiological temperatures 2-40 °C. Chemisorption of the radical species ≡[GA(OH)(2)(O(-))]* is the energetically important reaction. The thermodynamic data show a complex mechanism of adsorption of GA on the electrode surface, which is strongly dependent on temperature. At low-temperatures T<12 °C, adsorption is controlled by enthalpy, while at T>22 °C, adsorption is entropy driven. In the temperature range 12 °C and 22 °C, a combined enthalpy-entropy stabilization occurs. A mechanism is proposed which analyses the implication of thermodynamics to the interfacial adsorption of polyphenols with cell membranes under physiological conditions.     

Olefin adsorption on silica-supported silver salts--a DFT study

Recent experiments have shown that silver salts supported on mesoporous silicas display excellent adsorption selectivities of ethylene over ethane and propylene over propane. Employing the techniques of density functional theory, we have investigated the fundamental bases of this separation process by examining silver salts dispersed on model silica surfaces. Our model system includes Ag+ cations, their counteranions, silica supports, and surface silanols. Both adsorption geometries and energetics of ethylene and propylene were explored. Our results indicate that the nature of the Ag-olefin interaction is predominantly hybridization between Ag d and olefin pi states, which is supported by analyses of electron density difference plots and density of states. The counteranions, such as NO3- were found to interact strongly with surface silanols through multiple hydrogen bonds but have limited effect on the adsorption energy of olefins on the Ag+ cations. The current work supports recent experiments, which indicate that Ag-salt/silica may be a very promising adsorbent for olefin/paraffin separation.     

金镍六原子团簇吸附CO的密度泛函研究

在UBP86/LAN2DZ水平上计算了金镍二元团簇(AunNi6-n,n=0～6)吸附CO的稳定构型和相关性质.计算结果表明,AunNi6-nCO团簇的最低能量结构是在AunNi6-n团簇最低能量结构或亚稳态结构基础上吸附CO分子而形成.优化结构中C-O键长表明,吸附后的CO没有解离,即CO分子在AunNi6-n团簇表...     

Nitrogen substitution effect on hydrogen adsorption properties of Ti-decorated benzene

Structural Chemistry - Ab initio calculations are performed to study hydrogen storage properties of Ti-doped benzene and Ti-doped nitrogen-substituted benzene complexes. Two of the carbon atoms in...     

Experimental and DFT study of the partial oxidation of benzene by N2O over H-ZSM-5: acid catalyzed mechanism

The reaction mechanism for hydroxylation of benzene by N(2)O has been studied on chemically modified ZSM-5 catalysts. A maximum in catalytic activity and selectivity was reached for steamed samples under mild conditions (about 30% conversion with 94% selectivity). Chemical modifications, through ion exchange (H(+) versus Na(+)), have demonstrated the importance of the presence of Br?nsted acid sites. The results obtained suggest a Langmuir-Hinshelwood mechanism between benzene and N(2)O adsorbed on two distinct active sites. A density functional theory study considering the possible reaction intermediates also confirmed the possible formation of protonated nitrous oxide, leading to a Wheland-type intermediate, thus supporting an electrophilic aromatic substitution assisted by the confined environment provided by the active zeolite framework.     

DFT study of oxygen adsorption on modified nanostructured gold pyramids

Periodic DFT calculations are used to predict and investigate the adsorption behavior of molecular oxygen on Au, Au/Pt, and Pt surfaces. To obtain an array of pyramids containing surface atoms with the lowest possible coordination number, a nano-modified surface consisting of a symmetrically "modified" (100) surface was used. The effect of atom substitution (organized alloying) is investigated. The adsorption of molecular oxygen on a pure gold pyramid is exothermic by 0.77 eV for the end-on adsorption mode. In the case of a pure platinum pyramid, the end-on adsorption mode was found to dissociate; however, a side-on geometry was encountered with an energy of adsorption of 2.3 eV. This value is in line with the fact that the adsorption energy of small molecules does not vary much on Pt surfaces with different indices. Additionally, some geometrically related trends of the surface deformation in relation to its composition and after adsorption of molecular oxygen are highlighted.