Metal–Organic Framework-Based Catalysts: Chemical Fixation of CO2 with Epoxides Leading to Cyclic Organic Carbonates

Abstract

As a C1 feedstock, CO 2 has the potential to be uniquely highly economical in both a chemical and a financial sense. In particular, the highly atom-economical acid-catalyzed cycloaddition of CO 2 to epoxides to yield cyclic organic carbonates (OCs), a functionality having many important industrial applications, is an attractive reaction for the utilization of CO 2 as a chemical feedstock. Metal-organic frameworks (MOFs) are promising candidates in catalysis as they are a class of crystalline, porous, and functional materials with remarkable properties including great surface area, high stability, open channels, and permanent porosity. MOFs structure tunability and their affinity for CO 2 , makes them great catalysts for the formation of OCs using CO 2 and epoxides. In this review, we examine MOF-based catalytic materials for the cycloaddition of carbon dioxide to epoxides. Catalysts are grouped based on the location of catalytic sites, i.e., at the struts, nodes, defect sites, or some combination thereof. Additionally, important features of each catalyst system are critically discussed.

CO2 Cycloaddition to Epoxides by using M‐DABCO Metal–Organic Frameworks and the Influence of the Synthetic Method on Catalytic Reactivity

“…As mentioned earlier, the most effective catalysts have both Lewis acid and Lewis base sites. For example, previous studies have shown that catalysts such as zeolites or mesoporous silicate with acid–base pairs are more active . The catalytic sites of MOFs for the CO 2 /epoxides coupling reaction may be the nodes/secondary building units (SBU), the functional linkers, or both .…”

Metal–organic frameworks containing N-heterocyclic carbenes and their precursors

“…MOFs combine the benefits of both heterogeneous and homogeneous catalysis [35]. It is possible to prepare MOFs in which the catalytic functions are efficient at their three major components: the metal nodes, the organic linker, and the porous system.…”

APLICAÇÕES CATALÍTICAS DE MOFs DE Zr, Al, Ni, Co e Cu: CICLOADIÇÃO DE CO2 E SÍNTESE DE GLICÓIS

“…Constituindo-se como a forma mais oxidada do carbono, o CO2 apresenta natureza inerte, dessa forma, a síntese de carbonatos cíclicos via cicloadição necessita do uso de catalisadores (Zalomaeva et al, 2013;Beyzavi et al, 2015;Kim et al, 2013). De modo a evitar o inconveniente da separação dos catalisadores homogêneos convencionais, diversos catalisadores heterogêneos têm sido investigados, dentre eles, os materiais que compõem a classe das Metal-Organic Frameworks (MOFs) (Zalomaeva et al, 2013;Kim et al, 2013).…”

“…Muito importante na escolha da MOF é verificar a presença de sítios ácidos ou básicos na estrutura (Beyzavi et al, 2015;Kim et al, 2013). Em seus trabalhos, J.…”

“…Por ser um gás do efeito estufa, um dos causadores do aquecimento global, o interesse em explorá-lo, especificamente, para a produção de carbonatos cíclicos, vem crescendo nos últimos anos, isso porque os carbonatos apresentam-se como substitutos promissores dos óxidos nas reações de síntese de policarbonatos e glicóis (Zalomaeva et al, 2013;Beyzavi et al, 2015). Essa reação específica pode ser promovida via cicloadição de CO2 a óxidos de hidrocarbonetos caracterizados por um grupo funcional epóxido (Zalomaeva et al, 2013;Beyzavi et al, 2015;Zhu et al, 2013).…”