Sequestro de CO2 utilizando MOF-74-I : um estudo semiempírico

• Autor(a) principal: Daniel, Carlos Raphael Araújo
• Data de Publicação: 2016
• Tipo de documento: Tese
• Idioma: por
• Título da fonte: Repositório Institucional da UFS
• Texto Completo: https://ri.ufs.br/handle/riufs/3482
• topic: Engenharia de materiais; Materiais porosos; Dióxido de carbono; Gases (absorção e adsorção); Adsorção de CO2; MOF-74; Métodos semiempíricos; RMSD; CO2 adsorption; Semiempirical methods; ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA

A major problem of our time is the environmental impact and socio-economic consequences of greenhouse gases, caused mainly by burning fossil fuels. In this context, hybrid porous materials known as MOFs have been investigated both experimentally and computationally for CO2 adsorption, among many other applications. The large number of atoms, however, is an obstacle to computationally expensive methods. This work evaluates the performance of semi-empirical quantum methods (usually applied only to treat organic and biological compounds) in the description of CO2 adsorption process for IRMOF-74 series. The AM1, PM3 PM6 and PM7 methods were used in the description of 72 structures, and the impact of MOZYME algorithm in calculation was also evaluated. Chemical and geometrical properties of the system were estimated considering the presence or absence of water in the structure, variations in CO2 concentration in the unit cell, primary and secondary sites occupancy, and different metal ions in the structure. The results were compared with experimental data and computational estimates obtained by DFT, emphasizing the importance of correction for dispersion forces in energy calculations. The presence of open-shell metal ions affect the calculations, but PM6 and PM7 methods are able to reproduce the geometric structure of MOFs, found that the presence of water hinders CO2 adsorption, detected the primary and secondary adsorption sites, providing estimates for the binding energy comparable to that of the most widespread computational methods and in agreement with experimental data.