This review will be centered around the work that has been reported on the development of metal–organic frameworks (MOFs) serving as catalysts for the conversion of carbon dioxide into short-chain hydrocarbons and the generation of clean energies starting from biomass. MOFs have mainly been used as support for catalysts or to prepare catalysts derived from MOFs (as sacrifice template), obtaining interesting results in the hydrogenation or oxidation of biomass. They have presented a good performance in the hydrogenation of CO2 into light hydrocarbon fuels. The common patterns to be considered in the performance of the catalysts are the acidity of MOFs, metal nodes, surface area and the dispersion of the active sites, and these parameters will be discussed in this review.

The aerobic oxidation of cyclohexene was done using the heterometallic metal organic frameworks (MOFs) {[La2Cu3(μ-H2O)(ODA)6(H2O)3]⋅3H2O}n (LaCuODA)) (1) and {[La2Co3(ODA)6(H2O)6]∙12H2O}n (LaCoODA) (2) as catalysts, in solvent free conditions (ODA, oxydiacetic acid). After 24 h of reaction, the catalytic system showed that LaCoODA had a better catalytic performance than that of LaCuODA (conversion 85% and 67%). The structures of both catalysts were very similar, showing channels running along the c axis. The physicochemical properties of both MOFs were determined to understand the catalytic performance. The Langmuir surface area of LaCoODA was shown to be greater than that of LaCuODA, while the acid strength and acid sites were greater for LaCuODA. On the other hand, the redox potential of the active sites was related to CoII/CoIII in LaCoODA and CuII/CuI in LaCuODA. Therefore, it is concluded that the Langmuir surface area and the redox potentials were more important than the acid strength and acid sites of the studied MOFs, in terms of the referred catalytic performance. Finally, the reaction conditions were also shown to play an important role in the catalytic performance of the studied systems. Especially, the type of oxidant and the way to supply it to the reaction medium influenced the catalytic results.

The present work reports a new group of heterogeneous catalysts with a 3D structure, CuLnIDA, {[Cu3Ln2(IDA)6]·8H2O} (Ln: LaIII, GdIII or YbIII), with an organic linker (H2IDA: iminodiacetic acid).

Heterometallic 3d-4f inorganic polymers were prepared using 3,5 pyridinedicarboxylic acid (H2PDC), {[CuLn2(PDC)2(SO4)2(H2O)6]·H2O}n (Ln: SmIII, CuSmPDC, EuIII, CuEuPDC, GdIII, and CuGdPDC). These catalysts are active in the aerobic oxidation of cycloalkenes under solvent-free conditions, with a conversion for the oxidation of cyclohexene of 71% after one hour of the reaction, and a TOF value of 1438 h-1 for CuSmPDC. On the other hand, the oxidation of cycloheptene and cyclooctene exhibited slightly lower conversions of 52% and 47%, and TOF values of 1053 and 159 h-1 after 1 and 6 hours of the reaction, respectively. The radical mechanism for the oxidation reaction of cyclohexene was assessed by Raman and EPR spectroscopy. The first evidenced the formation of Cu-O2 adducts and the second permitted is to observe the presence of the oxygen centered radical species, which act as initiators of the reaction chain to generate the products. An increase in the temperature of the reaction correlates with the adduct formation, and with the enhancement of the oxidation reaction.