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

An efficient conversion of CO(2) into valuable fuels and chemicals has been hotly pursued recently. Here, for the first time, we have explored a series of M(12)x(12) nano-cages (M = B, Al, Be, Mg; X = N, P, O) for catalysis of CO(2) to HCOOH. Two steps are identified in the hydrogenation process, namely, H(2) activation to 2H*, and then 2H* transfer to CO(2) forming HCOOH, where the barriers of two H* transfer are lower than that of the H(2) activation reaction. Among the studied cages, Be(12)O(12) 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 H(2) activation energy barrier can be further reduced by introducing Al, Ga, Li, and Na to B(12)N(12) cage. This study would provide some new ideas for the design of efficient cluster catalysts for CO(2) reduction.