基于外电场作用氟氯碳酰的光谱特性和解离特性

采用密度泛函方法(DFT)在B3LYP/6-31G(d)水平上优化计算了在不同外电场作用下氟氯碳酰分子的物理性质,包括键长、键角、分子体系总能量、偶极矩、能隙、红外光谱、拉曼光谱以及解离特性.研究表明在外电场(-0.02—0.07 a.u.)作用下,氟氯碳酰分子结构有明显的变化,随着外电场的增强,分子C-O键长、C-Cl键长逐渐增大,C-F键长逐渐减小,分子体系总能量、能隙先增大后减小,偶极矩先减小后增大;分子红外光谱的O p-deform、CCl stretch(str)、CF str振动发生了蓝移,CO str振动发生了红移,CO deform振动先红移后蓝移,分子拉曼光谱的O p-deform、CCl str、CF str、CO str振动移动情况与红外光谱相同,当外电场强度为0.03 a.u.时,分子C-Cl势垒消失,分子发生解离,当外电场强度为-0.005 a.u.时,分子两个键断裂,发生逐步解离.研究工作为进一步研究氟氯碳酰分子的解离特性及臭氧层的保护提供理论依据.     

杂多酸催化分解氟里昂-12

Chlorine atoms from chlorofluorocarbons (CFCs) deplete stratospheric ozone and CFCs are green-house gases too. Owing to these environmental problems, many kinds of CFCs have been banned since the Montreal Protocol and two kinds of cleaning techniques have been developed. One is the synthesis of CFCs alternatives[1,2] and the other is the decomposition of banned CFCs in existing equipments[3,4].     

气相催化异构化氟氯烯烃的方法及机理解释

气相催化是一种绿色环保的化工方法.氟氯烯烃是一种重要的化工原料,其中顺式和反式结构的氟氯烯烃具有较大的物理属性差异.我们旨在研发一种气相催化异构化氟氯烯烃的方法.首先以CF_3CCl=CClCF_3为原料,讨论了不同催化剂的气相异构化效率.其次,采用XRD、 TPD、 BET、 XPS、 GC、 GC-MS等手段讨论了催化剂的组成、酸性强度、催化剂表面酸性种类、催化剂活性组分、异构化产物的组成情况.在此基础之上,提出了异构化的机理解释.最后,采用4种不同原料,验证了上述机理解释.为工业化生产提供了重要的理论依据.     

Characteristics and nature of the halogen-bonding interactions between CCl3F and ozone: a supermolecular and SAPT study

The strength and nature of the halogen-bond interactions in CCl₃F···O₃ complexes were examined by means of ab initio quantum-chemical calculations and symmetry-adapted perturbation theory (SAPT). Our calculations predict a trifurcated C–Cl···O interaction for the global minimum of CCl₃F···O₃ complex and several local minima, differing slightly in energy, separated by very low barriers. The calculations, which include a rigorous decomposition of the interaction energies, also indicate that the interaction of CCl₃F molecule with O₃ is characterised by contributions from both electrostatic and dispersion energies, with the contribution of the latter being dominant. The evaluated SAPT interaction energies for the CCl₃F···O₃ complexes are generally in good agreement with those obtained using the supermolecule CCSD(T) method, suggesting that SAPT is a proper method to study the intermolecular interactions in these complexes.     

Plasma Destruction of Ozone Depleting Substances

The literature on the plasma destruction of ozone depleting substances (ODS) such as CCl₂F₂ and CBrF₃ is reviewed, and compared with more recent work on the decomposition of CCl₂F₂ and CBrClF₂ in oxygen and steam. A comprehensive kinetic scheme for the decomposition of CBrClF₂, which includes the decomposition of CCl₂F₂ and CBrF₃, is presented. Simulations performed with this scheme, and experimental results, demonstrate the importance of allowing for the interconversion of ODS in the assessment of plasma destruction devices.Both experimental and modeling results show that the efficiency of operation of a practical plasma ODS destruction device can be quantified in terms of a throughput parameter, the feed to plasma power ratio (units mol (kWh)^-1), or in terms of the thermochemical mixing temperature, T_m, of the plasma, ODS and oxidant. At low throughputs and high T_m, essentially complete destruction may be achieved, with below-ppm quantities of ODS remaining in the plasma exhaust gases. As throughput rises and Tm falls, a threshold is reached above which the ODS residual rises steeply towards the practical working limit set for ODS destruction by the Montreal Protocol (a destruction level of 99.99%). The assessment of this limit must include all ODS in the exhaust gases, weighted for ozone depleting potential. The use of steam, rather than oxygen, as the oxidizing gas gives superior destruction performance.     

Thermal plasma decomposition of chlorofluorocarbons

Dichlorodifluoromethane was decomposed by a thermal argon plasma generated by a DC are discharge. The experiments and the kinetic calculations showed that the complete decomposition of the chlorofluorocarbon proceeded with the simultaneous additions of hydrogen and oxygen. Both the expertimental and calculated results confirmed that it is favorable, for the decomposition, not to quench the products but to add an excess of hydrogen over the stoichiometric amount, which leads to a reduction in chlorine formation.