Petrolini Davi D, Cassinelli Wellington H, Pereira Cristiane A, Urquieta-González Ernesto A, Santilli Celso V, Martins Leandro
Instituto de Química, UNESP - Universidade Estadual Paulista R. Prof. Francisco Degni 55 14800-900 Araraquara SP Brazil
Instituto Federal de São Paulo - Campus Avaré Av. Prof. Celso Ferreira da Silva, 1333, Jardim Europa 18707-150 Avaré SP Brazil.
RSC Adv. 2019 Jan 24;9(6):3294-3302. doi: 10.1039/c8ra10076d. eCollection 2019 Jan 22.
Mixed aluminum and magnesium oxides (AlMgO) prepared by means of an emulsion-mediated sol-gel method was impregnated with copper nitrate solution and used in the ethanol dehydrogenative reactions to produce acetaldehyde and ethyl acetate. The emulsified system allowed to obtain a macro-mesoporous support that resulted in an outstanding dispersion of copper. The porous catalyst was about 3 times more active than the non-porous counterpart, due to the formation on the support's surface of Cu together with the more active Cu species. In fact, the simultaneous presence of Cu and Cu were advantageous for the catalytic performance, as the turnover frequencies, were 122 and 166 h for the non-porous reference catalyst and for the porous one, respectively. Both catalysts deactivated due to copper particles sintering, however the porous one deactivated less, as a consequence of the better dispersion of the Cu species on the macro and mesoporous support. Acetaldehyde was the main product, however by increasing the contact time by 6.6 times, the conversion of ethanol on the non-porous catalyst reached about 90% with a selectivity to ethyl acetate of 20% by means of the coupling reaction of ethanol and acetaldehyde. The selectivity to ethyl acetate was favoured on an increased support/copper interface that is given by larger copper particles.
通过乳液介导的溶胶 - 凝胶法制备的混合铝镁氧化物(AlMgO)用硝酸铜溶液浸渍,并用于乙醇脱氢反应以生产乙醛和乙酸乙酯。乳化体系使得能够获得大孔 - 介孔载体,从而实现了铜的优异分散。由于在载体表面形成了铜以及更具活性的铜物种,多孔催化剂的活性比无孔催化剂高约3倍。实际上,铜和铜的同时存在有利于催化性能,因为无孔参比催化剂和多孔催化剂的周转频率分别为122 h⁻¹和166 h⁻¹。两种催化剂都因铜颗粒烧结而失活,然而,由于铜物种在大孔和介孔载体上的分散性更好,多孔催化剂失活程度较小。乙醛是主要产物,然而,通过将接触时间增加6.6倍,通过乙醇和乙醛的偶联反应,无孔催化剂上乙醇的转化率达到约90%,乙酸乙酯的选择性为20%。较大的铜颗粒提供了更大的载体/铜界面,有利于提高乙酸乙酯的选择性。