Be12O12 Nano-cage as a Promising Catalyst for CO2 Hydrogenation

Abstract

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.

Adsorption of sarin and chlorosarin onto the Al12N12 and Al12P12 nanoclusters: DFT and TDDFT calculations

“…Subsequently, all the structures have been optimized using the M06‐2X functional 36,37 in conjunction with the 6‐311++G** standard basis set. The M06‐2X density functional has been previously reported to calculate interaction energies, metallic and nonmetallic compounds, kinetics, and stability of noncovalent interactions on the different nanostructures 38–42 . Natural bond orbital analysis, vibration frequencies, and thermodynamic parameters were also calculated at the same level.…”

Rational Design of Main Group Metal-Embedded Nitrogen-Doped Carbon Materials as Frustrated Lewis Pair Catalysts for CO2 Hydrogenation to Formic Acid

“…As the most abundant metallic element in the earth’s crust, aluminum (Al) has been embedded in low-dimensional nanomaterials, which have been widely used in catalytic reactions including oxygen reduction and CO oxidation. − In addition, frustrated Lewis pairs (FLPs) based on main group elements also show high catalytic activity. − Recently, based on the synergistic effect of Lewis acid and base, a series of FLPs such as Al/P, B/C, B/N, P/N, and B/P have been developed in homogeneous catalysis − ,− and heterogeneous systems − for the hydrogenation of unsaturated molecules such as C 2 H 2 and CO 2 . For example, Ye et al , demonstrated that FLP-functionalized metal–organic frameworks (MOFs) can activate H 2 dissociation and further realize CO 2 hydrogenation.…”

Activation of CO2 by Alkaline-Earth Metal Hydrides: Matrix Infrared Spectra and DFT Calculations of HM(O2CH) and (MH2)(HCOOH) Complexes (M = Sr, Ba)

“…We performed CO 2 reactions with MnH 2 in solid parahydrogen and the transformation of CO 2 into formate has been achieved via hydride ion transfer . Recently, there have been few experimental studies on CO 2 activation by the main group metal hydrides as promoters, − and the enhanced CO 2 conversion to methanol has been investigated by strontium, magnesium, or calcium as basic promoters doped on coprecipitation of copper, zinc, and aluminum nitrates. Higher alcohols have been synthesized from selective CO 2 hydrogenation by potassium- or cesium-promoted CuFeZn catalysts .…”