Actinyl-Modified g-CN as CO Activation Materials for Chemical Conversion and Environmental Remedy via an Artificial Photosynthetic Route.

With the reported CO activation for the oxidation of benzene to phenol (-ENE → -OL) by the graphitic carbon nitride g-CN () via an artificial photosynthetic route as inspiration, -valent actinyls (AnO) (An = U, Np, Pu; m = VI, V; = 2, 1) have been introduced for its further modification. Our calculations indicate thermodynamic spontaneity in the feasibility of g-CN-(AnO) () formation. The magnificent structural and electronic properties of are utilized for CO activation in terms of the rarely studied -ENE → -OL conversion. The calculated free energies show that most steps of the catalytic cycle are favored by complexes. The first step (carbamate formation) is slightly endothermic in all cases, where is 0.51 eV higher than and is -0.01 eV lower. All benzene addition reactions release energy, with that for being the lowest. The phenolate formation is favored by some actinyl complexes over , and is only 0.23 eV higher. The phenol release (resulting in formamide complexes) and CO desorption are exothermic for all . The overall process suggests the improved catalytic performance of actinyl-modified materials, and the slightly depleted uranyl-carbon nitride could be one of the promising catalysts.