One-dimensional 3d-TM–solophene polymers as high-activity single‐atom catalysts for CO oxidation

Abstract

Inspired by the successful synthesized one-dimensional (1D) 3d-transition metal solophene polymer (TM-SP), we systematically investigate CO oxidation reactions on TM-SP as single atom catalysts (SACs) by density functional theory (DFT). The stabilities, adsorptive profiles of reactants and chemical kinetics as three descriptors are taken into account to efficiently select promising SACs among nine candidates (TM-SP, TM = Sc-Cu). Our calculations reveal that Sc-SP shows the highest catalytic activity for CO oxidation. After considering the Langmuir Hinshelwood (LH), Eley Rideal (ER) and tri-molecular Eley-Rideal (TER) mechanisms, we found the rate-determining step of CO oxidation on Sc-SP prefers to follow the LH mechanism whose energy barrier is 0.58 eV. The second CO2 generated fast via either LH or ER mechanisms with no activation barrier. Moreover, our results verify that the catalytic behavior of transition metals is intrinsic, because the kinetic characteristic is independent by changes in the different macrocyclic ligands (N2O2, N3O and N4) of the active sites in the kinetically-controlled CO oxidation reaction. The high catalytic performance of Sc-SP may be attributed to the proper strengths of adsorbates, high stabities and fast kinetics. These results provide atomic-level insights into CO oxidation which opens up a novel strategy for rational design of efficient SACs.