Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2020 Jul 27;10(46):27856-27863.
doi: 10.1039/d0ra05287f. eCollection 2020 Jul 21.

Density functional study on the CO oxidation reaction mechanism on MnN2-doped graphene

Mingming Luo  1 , Zhao Liang  1 , Chao Liu  1 , Xiaopeng Qi  1 , Mingwei Chen  1 , Hui Yang  1 , Tongxiang Liang  1
Affiliations

Density functional study on the CO oxidation reaction mechanism on MnN2-doped graphene

Mingming Luo et al. RSC Adv. .

Abstract

The CO oxidation mechanisms over three different MnN2-doped graphene (MnN2C2: MnN2C2-hex, MnN2C2-opp, MnN2C2-pen) structures were investigated through first-principles calculations. The vacancy in graphene can strongly stabilize Mn atoms and make them positively charged, which promotes O2 activation and weakens CO adsorption. Hence, CO oxidation activity is enhanced and the catalyst is prevented from being poisoned. CO oxidation reaction (COOR) on MnN2C2 along the Eley-Rideal (ER) mechanism and the Langmuir-Hinshelwood (LH) mechanism will leave one O atom on the Mn atom, which is difficult to react with isolated CO. COOR on MnN2C2-opp along the ER mechanism and termolecular Eley-Rideal (TER) mechanism need overcome low energy barriers in the rate limiting step (RLS), which are 0.544 and 0.342 eV, respectively. The oxidation of CO along TER mechanism on MnN2C2-opp is the best reaction pathway with smallest energy barrier. Therefore, the MnN2C2-opp is an efficient catalysis and this study has a guiding role in designing effective catalyst for CO oxidation.

PubMed Disclaimer

Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Views of the optimized three configurations and deformation density: (a) MnN2C2-hex, (b) MnN2C2-opp, (c) MnN2C2-pen. ΔEf and ΔEb represent formation energy and binding energy. Where gray, blue and purple represent C, N and Mn atom, respectively. PDOS of MnN2C2, Fermi levels are indicated by dotted lines.
Fig. 2
Fig. 2. Molecular dynamics trajectory of MnN2C2 at 1000 K with snapshots of intermediates at different times.
Fig. 3
Fig. 3. Structure of single molecule adsorption (O2, CO, CO2) and bimolecular co-adsorption (CO + O2, 2CO) on MnN2C2.
Fig. 4
Fig. 4. The adsorption energy of gas on MnN2C2.
Fig. 5
Fig. 5. (a) Relative energy of O2 molecule dissociation and (b) the CO + *O2 → *CO + *O2 reaction on MnN2C2. (c) Structure of O2 molecule dissociation and (d) CO + *O2 → *CO + *O2 reaction on MnN2C2-opp.
Fig. 6
Fig. 6. (a) COOR via the LH mechanisms on MnN2C2, (b) COOR via the TER mechanisms on MnN2C2. (c) Structure of the COOR on MnN2C2-opp via the LH and (d) TER mechanisms.
Fig. 7
Fig. 7. Relative energy (a) and structure of CO and O react to form CO2 on (b) MnN2C2-hex, (c) MnN2C2-opp and (d) MnN2C2-pen.
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

References

    1. Zibrak J. D. Ernst A. N. Engl. J. Med. 1998;339:1603–1608. doi: 10.1056/NEJM199811263392206. - DOI - PubMed
    1. Townsend C. L. Maynard R. L. Occup. Environ. Med. 2002;59:708–711. doi: 10.1136/oem.59.10.708. - DOI - PMC - PubMed
    1. Freund H. J. Meijer G. Scheffler M. Schlçgl R. Wolf M. Angew. Chem. 2011;50:10064–10094. doi: 10.1002/anie.201101378. - DOI - PubMed
    1. Alavi A. Hu P. Deutsch T. Silvestrelli P. L. Hutter J. Phys. Rev. Lett. 1998;80:3650–3653. doi: 10.1103/PhysRevLett.80.3650. - DOI
    1. Kalita B. Deka R. C. J. Am. Chem. Soc. 2009;131:13252–13254. doi: 10.1021/ja904119b. - DOI - PubMed