Screening silica-confined single-atom catalysts for nonoxidative conversion of methane

The development of a single-atom iron catalyst (Fe©SiO₂) for the direct conversion of methane to olefins, aromatics, and hydrogen is a breakthrough in the field of nonoxidative conversion of methane (NCM). However, the optimization of the catalyst remains desirable for industrial applications. Herein, 25 transition metals, including Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, and Au, are selected to replace the central Fe atom for screening out better single-atom catalysts for the NCM. Using the performance on the activation of methane, such as the adsorption energy of methane, the dissociation energy, and the barrier of methane as the screening descriptors, Mn©SiO₂, Fe©SiO₂, W©SiO₂, and Re©SiO₂ are first screened out. The remarkable performance of the four catalysts on methane activation is attributed to the unique geometric structure and the d_z ² orbitals of the central metal crossing over the Fermi level, which can benefit the interaction between methane and the catalysts. By considering the catalytic performance on the whole pathway of methane to ethylene, W©SiO₂ is finally selected as the most active catalyst for the NCM, which has the lowest rate-determining barrier of 1.62 eV and the smallest free energy span (1.06 eV) of the overall catalytic cycle.