Strain in Silica-Supported Ga(III) Sites : Neither Too Much nor Too Little for Propane Dehydrogenation Catalytic Activity

Altres ajuts: Acord transformatiu CRUE-CSICWell-defined Ga(III) sites on SiO are highly active, selective, and stable catalysts in the propane dehydrogenation (PDH) reaction. In this contribution, we evaluate the catalytic activity toward PDH of tricoordinated and tetracoordinated Ga(III) sites on SiO by means of first-principles calculations using realistic amorphous periodic SiO models. We evaluated the three reaction steps in PDH, namely, the C-H activation of propane to form propyl, the β-hydride (β-H) transfer to form propene and a gallium hydride, and the H-H coupling to release H, regenerating the initial Ga-O bond and closing the catalytic cycle. Our work shows how Brønsted-Evans-Polanyi relationships are followed to a certain extent for these three reaction steps on Ga(III) sites on SiO and highlights the role of the strain of the reactive Ga-O pairs on such sites of realistic amorphous SiO models. It also shows how transition-state scaling holds very well for the β-H transfer step. While highly strained sites are very reactive sites for the initial C-H activation, they are more difficult to regenerate. The corresponding less strained sites are not reactive enough, pointing to the need for the right balance in strain to be an effective site for PDH. Overall, our work provides an understanding of the intrinsic activity of acidic Ga single sites toward the PDH reaction and paves the way toward the design and prediction of better single-site catalysts on SiO for the PDH reaction. We performed computational calculations of Ga(III) single sites on realistic amorphous models of SiO to evaluate their catalytic activity toward the propane dehydrogenation reaction. Our results show that a balance in strain is key, in which neither too stiff nor too loose Ga−O bonding is needed to obtain the highest catalytic activity

Strain in Silica-Supported Ga (III) Sites: Neither Too Much nor Too Little for Propane Dehydrogenation Catalytic Activity

Well-defined Ga(III) sites on SiO2 are highly active, selective, and stable catalysts in the propane dehydrogenation reaction. In this contribution, we evaluate the catalytic activity towards propane dehydrogenation of tri-coordinated and tetra-coordinated Ga(III) sites on SiO2 by means of first principles calculations using realistic amorphous periodic SiO2models. We evaluated the three reaction steps in propane dehydrogenation, namely the C-H activation of propane to form propyl, the beta-hydride elimination transfer to form propene, and a Ga-hydride, and the H-H coupling to release H2, regenerating the initial Ga-O bond and closing the catalytic cycle. Our work shows how Brønsted-Evans-Polanyi relationships are followed for these three reaction steps on Ga(III) sites on SiO2 and highlights the role of the strain of the reactive Ga-O pairs on such sites of realistic amorphous SiO2 models. While highly strained sites are very reactive sites for the initial C-H activation, they are more difficult to regenerate. The corresponding less strained sites are not reactive enough, pointing to the need of a right balance in strain to be an effective site for propane dehydrogenation. Overall, our work provides an understanding of the intrinsic activity of acidic Ga single sites towards the propane dehydrogenation reaction and paves the road towards the design and prediction of better single-site catalysts on SiO2 for the propane dehydrogenation reaction.</p

Development of pharmacophores for inhibitors of the rapid component of the cardiac delayed rectifier potassium current

Blockade of cardiac-delayed rectifier potassium current (IKr) is an important mechanism for Class III antiarrhythmic effect. We developed pharmacophores for IKr inhibitors starting from structures of known blockers. To obtain the pharmacophores, DISCO module of SYBYL was used. Conformations required for DISCO computations were provided by Multisearch type conformational analyses. A common five-point three-dimensional relationship was identified for the most active compounds, whereas a four-point pharmacophore forming a subset of the former one, could be developed for less potent agents

Efeito do tempo de exposição a uma atmosfera coqueificante na microestrutura e nas propriedades de um concreto refratário usado na indústria petroquímica Effect of the exposure time in cokemaking atmosphere on the microstructure and properties of a refractory castable used in the petrochemical industry

Os concretos refratários usados em unidades de craqueamento catalítico fluidizado (UFCC) podem sofrer deterioração pela deposição de coque durante o processo de produção de hidrocarbonetos leves, ocasionando a diminuição do tempo de funcionamento do reator e conseqüente perda financeira para as petroquímicas. Diversos estudos foram feitos, porém nenhum deles aponta conclusivamente para a parcela que esta deposição tem na deterioração do concreto, permanecendo a dúvida se ele é o responsável pelos danos observados macroscopicamente no riser de uma UFCC. Este trabalho visou estudar o efeito do tempo de exposição a uma atmosfera coqueificante sobre um concreto refratário anti-erosivo, classe C, buscando identificar mudanças nas propriedades físicas e microestruturais que evidenciem o mecanismo de degradação e que possam fornecer subsídios para análises conclusivas acerca do entendimento do fenômeno. Para isso, prepararam-se amostras de um concreto usado industrialmente em UFCC, submetidas a um processo de coqueificação forçado em reator piloto. Fixou-se a temperatura e a taxa de aquecimento em 540 ºC e 50 ºC/h, respectivamente, variando-se os tempos de exposição ao gás propeno em 10, 60, 120, 240 e 480 h. Os corpos de prova tiveram suas microestruturas caracterizadas via microscopia ótica e eletrônica de varredura e suas fases por difração de raios X. Outros ensaios complementares foram necessários para o entendimento do fenômeno. Os resultados mostraram que a superfície e a microestrutura do material gradativamente se impregnam de coque, que preenche os poros, as microtrincas e as trincas. Não foram encontradas evidências de microtrincamento em torno dos poros da matriz do concreto preenchidos com coque, porém os agregados apresentam algum tipo de deterioração com o tempo de exposição ao propeno, não necessariamente causados diretamente pelo coque.<br>Refractory castables used in Fluidized Catalytic Cracking Units (FCCU) are said to deteriorate due coke formation during the production of light hydrocarbons, causing a shortening in the operating time of the reactor. Consequently, a significant financial loss for the petrochemical will occur. Several studies have been carried out, but none of them showed clearly how much is the contribution of the coke for the concrete final deterioration. It still remains the doubt if the coke is the responsible for the damage observed macroscopically in a FCCU's riser. In this way, this work aimed to study the effect of the time in a cokemaking atmosphere on an anti-erosive class-C refractory castable, seeking for microstructural changes or on physical properties that indicate degradation mechanisms and give support to the understanding of the phenomenon. Samples of an industrial refractory castable used in petrochemical units were prepared and subjected to a forced cokemaking process in a simulation reactor. The temperature and the heating rate were kept constant at 540 ºC and 50 ºC/h, respectively. The values of 10, 60, 120, 240 and 480 h were used for the time of exposition to the propene gas. The microstructure of the samples was characterized through optical and scanning electron microscopy and its mineralogical phases through X-ray diffraction. Complementary analyses were necessary to a better understanding of the phenomenon. The results show that the surface and the microstructure are gradually impregnated by coke, which fills up pores, microcracks and cracks. Evidences of microcracking around the coke filled pores were not found. However, many aggregates present some type of deterioration related to the time of exposition to propene. Those damages are not necessarily caused by coke directly