Be₁₂O₁₂ Nano-cage as a Promising Catalyst for CO₂ 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 M₁₂x₁₂ 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, Be₁₂O₁₂ 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 B₁₂N₁₂ cage. This study would provide some new ideas for the design of efficient cluster catalysts for CO₂ reduction.