Be 12 O 12 Nano-cage as a Promising Catalyst for CO 2 Hydrogenation.

An efficient conversion of CO2 into valuable fuels and chemicals has been hotly pursued recently. Here, for the first time, we have explored a series of M12 x12 nano-cages (M = B, Al, Be, Mg; X = N, P, O) for catalysis of CO2 to HCOOH. Two steps are identified in the hydrogenation process, namely, H2 activation to 2H*, and then 2H* transfer to CO2 forming HCOOH, where the barriers of two H* transfer are lower than that of the H2 activation reaction. Among the studied cages, Be12 O12 is found to have the lowest barrier in the whole reaction process, showing two kinds of reaction mechanisms for 2H* (simultaneous transfer and a step-wise transfer with a quite low barrier). Moreover, the H2 activation energy barrier can be further reduced by introducing Al, Ga, Li, and Na to B12 N12 cage. This study would provide some new ideas for the design of efficient cluster catalysts for CO2 reduction.