The formation and evolution of carbonate species in CO oxidation over mono-dispersed Fe on graphene.

Fe is not only the most abundant metal on the planet but is also the key component of many enzymes in organisms that are capable of catalyzing many chemical conversions. Mono-dispersed Fe atoms on carbonaceous materials are single atom catalysts (SACs) that function like enzymes. To take advantage of the outstanding catalytic performance of Fe-based SACs, we extended a CO oxidation reaction network over mono-dispersed Fe atoms on graphene (FeGR) by first-principles based calculations. FeGR-catalyzed CO oxidation is initiated with a revised Langmuir-Hinshelwood pathway through a CO-assisted scission of the O-O bond in peroxide species (OCOO). We showed that carbonate species (CO3), which were previously generally considered as a persistent species blocking reaction sites, may form from CO2 and negatively charged O species. This pathway competes with desorption of CO2 and reduction of the Fe center with gaseous CO, and it is exothermic and inevitable, especially at low temperatures and with high CO2 content. Although direct dissociation of CO3 is demanding on FeGR, further adsorption of CO on Fe in CO3 is plausible and takes place spontaneously. We then showed that adsorbed CO may react with CO3, forming a cyclic-carbonate-like species that dissociates easily to CO2. These findings highlight the reaction condition-dependent formation and evolution of CO3 as well as its contribution to CO conversion, and it may extend the understanding of the performance of SACs in low temperature CO oxidation.

Unique Reactivity of Transition Metal Atoms Embedded in Graphene to CO, NO, O2 and O Adsorption: A First-Principles Investigation.

Taking the adsorption of CO, NO, O2 and O as probes, we investigated the electronic structure of transition metal atoms (TM, TM = Fe, Co, Ni, Cu and Zn) embedded in graphene by first-principles-based calculations. We showed that these TM atoms can be effectively stabilized on monovacancy defects on graphene by forming plausible interactions with the C atoms associated with dangling bonds. These interactions not only give rise to high energy barriers for the diffusion and aggregation of the embedded TM atoms to withstand the interference of reaction environments, but also shift the energy levels of TM-d states and regulate the reactivity of the embedded TM atoms. The adsorption of CO, NO, O2 and O correlates well with the weight averaged energy level of TM-d states, showing the crucial role of interfacial TM-C interactions on manipulating the reactivity of embedded TM atoms. These findings pave the way for the developments of effective monodispersed atomic TM composites with high stability and desired performance for gas sensing and catalytic applications.

CO oxidation catalyzed by Pt-embedded graphene: a first-principles investigation.

We addressed the potential catalytic role of Pt-embedded graphene in CO oxidation by first-principles-based calculations. We showed that the combination of highly reactive Pt atoms and defects over graphene makes the Pt-embedded graphene a superior mono-dispersed atomic catalyst for CO oxidation. The binding energy of a single Pt atom onto monovacancy defects is up to -7.10 eV, which not only ensures the high stability of the embedded Pt atom, but also vigorously excludes the possibility of diffusion and aggregation of embedded Pt atoms. This strong interfacial interaction also tunes the energy level of Pt-d states for the activation of O2, and promotes the formation and dissociation of the peroxide-like intermediate. The catalytic cycle of CO oxidation is initiated through the Langmuir-Hinshelwood mechanism, with the formation of a peroxide-like intermediate by the coadsorbed CO and O2, by the dissociation of which the CO2 molecule and an adsorbed O atom are formed. Then, another gaseous CO will react with the remnant O atom and make the embedded Pt atom available for the subsequent reaction. The calculated energy barriers for the formation and dissociation of the peroxide-like intermediate are as low as 0.33 and 0.15 eV, respectively, while that for the regeneration of the embedded Pt atom is 0.46 eV, indicating the potential high catalytic performance of Pt-embedded graphene for low temperature CO oxidation.