A Theoretical Study of Single-Atom Catalysis of CO Oxidation Using Au Embedded 2D h-BN Monolayer: A CO-Promoted O2 Activation

Abstract

The CO oxidation behaviors on single Au atom embedded in two-dimensional h-BN monolayer are investigated on the basis of first-principles calculations, quantum Born-Oppenheim molecular dynamic simulations (BOMD) and micro-kinetic analysis. We show that CO oxidation on h-BN monolayer support single gold atom prefers an unreported tri-molecular Eley-Rideal (E-R) reaction, where O2 molecule is activated by two pre-adsorbed CO molecules. The formed OCOAuOCO intermediate dissociates into two CO2 molecules synchronously, which is the rate-limiting step with an energy barrier of 0.47 eV. By using the micro-kinetic analysis, the CO oxidation following the tri-molecular E-R reaction pathway entails much higher reaction rate (1.43 × 105 s−1) than that of bimolecular Langmuir-Hinshelwood (L-H) pathway (4.29 s−1). Further, the quantum BOMD simulation at the temperature of 300 K demonstrates the complete reaction process in real time.

The Power of Single‐Atom Catalysis

“…Hollow sites, each missing three carbon atoms, on graphene were thought to be ideal anchoring sites for single Ni atoms after calculation 11b. Recently, theoretical screening with the aim of finding robust anchoring sites for SACs have been reported intensively, for example, for graphene,22e TiN,22c BN,32 θ ‐Al 2 O 3 ,22b TiO 2 ,9b and various metal nanoparticles 10. In fact, robust anchoring of the single atom to the support is not enough to achieve the potential of SACs.…”

Probing the Reactivity of Functionalized Surfaces by Porphyrin Metalation

“…All these parameters strongly depend on the physicochemistry of the surface as well as on temperature. Recent studies focused also on single‐atom catalysis, and the modification of spin‐states in surface‐supported paramagnetic molecules . Limited research, however, has been performed on the role of adsorbate‐induced surface superstructures as they influence on‐surface chemical reactions.…”

Pd1/BN as a promising single atom catalyst of CO oxidation: a dispersion-corrected density functional theory study

“…O 2 molecule is activated by CO molecules directly 11 . In the TER mechanism, a free O 2 molecule is activated by two co-adsorbed CO molecules to form an OCO-metal-OCO intermediate.…”

“…Fortunately, the practical Pt single atom catalyst supported by iron oxide was experimentally prepared for the first time by Qiao et al (named as Pt 1 /FeO x ), and the excellent performance of the Pt 1 /FeO x demonstrates that heterogeneous catalysis with single atom catalyst is no longer a dream 10 . For example, single atomic Au on h-BN with boron vacancy exhibits great thermally stability even during the CO oxidation process 11 . For example, single atomic Au on h-BN with boron vacancy exhibits great thermally stability even during the CO oxidation process 11 .…”