Reduction of N2O by H2 Catalyzed by Keggin–Type Phosphotungstic Acid Supported Single-Atom Catalysts: An Insight from Density Functional Theory Calculations

In the present paper, the mechanisms of N2O reduction by H2 were systemically examined over various polyoxometalate-supported single-atom catalysts (SACs) M1/PTA (M = Fe, Co, Mn, Ru, Rh, Os, Ir, and Pt; PTA = [PW12O40]3-) by means of density functional theory calculations. Among these M1/PTA SACs, Os1/PTA SAC possesses high activity for N2O reduction by H2 with a relatively low rate-determining barrier. The favorable catalytic pathway involves the first and second N2O decomposition over the Os1/PTA SAC and hydrogenation of the key species after the second N2O decomposition. Molecular geometry and electronic structure analyses along the favorable reaction pathway indicate that a strong charge-transfer cooperative effect of metal and support effectively improves the catalytic activity of Os1/PTA SAC. The isolated Os atom not only plays the role of adsorption and activation of the N2O molecule but also works as an electron transfer medium in the whole reaction process. Meanwhile, the PTA support with very high redox stability has also been proven to be capable of transporting the electron to promote the whole reaction. We expect that our computation results can provide ideas for designing new SACs for N2O reduction by using H2 selective catalytic reduction technology.