Probing the catalytic activity of M-N_4−xO_x embedded graphene for the oxygen reduction reaction by density functional theory

Abstract

In this work, the detailed oxygen reduction reaction (ORR) catalytic performance of M-N_4−xO_x (M= Fe, Co, and Ni; x = 1–4) has been explored via the detailed density functional theory method. The results suggest that the formation energy of M-N_4−xO_x shows a good linear relationship with the number of doped O atoms. The adsorption manner of O₂ on M-N_4−xO_x changed from end-on (x = 1 and 2) to side-on (x = 3 and 4), and the adsorption strength gradually increased. Based on the results for binding strength of ORR intermediates and the Gibbs free energy of ORR steps on the studied catalysts, we screened out two highly active ORR catalysts, namely Co-N₃O₁ and Ni-N₂O₂, which possess very small overpotentials of 0.27 and 0.32 V, respectively. Such activities are higher than the precious Pt catalyst. Electronic structure analysis reveals one of the reasons for the higher activity of Co-N₃O₁ and Ni-N₂O₂ is that they have small energy gaps and moderate highest occupied molecular orbital energy levels. Furthermore, the results of the density of states reveal that the O doping can improve the electronic structure of the original catalyst to tune the adsorption of the ORR intermediates.

Graphical abstract

Keywords

M-N-C catalyst / oxygen doping / oxygen reduction reaction / catalytic activity / density functional theory

References

[1] Kabir E, Kumar P, Kumar S, Adelodun A A, Kim K H. Solar energy: potential and future prospects. Renewable & Sustainable Energy Reviews, 2018, 82: 894–900

[2] Podjaski F, Kröger J, Lotsch B V. Toward an aqueous solar battery: direct electrochemical storage of solar energy in carbon nitrides. Advanced Materials, 2018, 30(9): 1705477

[3] Sorgulu F, Dincer I. A renewable source based hydrogen energy system for residential applications. International Journal of Hydrogen Energy, 2018, 43(11): 5842–5851

[4] Endo N, Shimoda E, Goshome K, Yamane T, Nozu T, Maeda T. Simulation of design and operation of hydrogen energy utilization system for a zero emission building. International Journal of Hydrogen Energy, 2019, 44(14): 7118–7124

[5] Zhang L, Shan B, Zhao Y, Guo Z. Review of micro seepage mechanisms in shale gas reservoirs. International Journal of Heat and Mass Transfer, 2019, 139: 144–179

[6] Feng G, An L, Li B, Zuo Y, Song J, Ning F, Jiang N, Cheng X, Zhang Y, Xia D. Atomically ordered non-precious Co₃Ta intermetallic nanoparticles as high-performance catalysts for hydrazine electrooxidation. Nature Communications, 2019, 10(1): 4514

[7] Chen X, Sun F, Bai F, Xie Z. DFT study of the two dimensional metal-organic frameworks X₃(HITP)₂ as the cathode electrocatalysts for fuel cell. Applied Surface Science, 2019, 471: 256–262

[8] Zhang D, Wu F, Peng M, Wang X, Xia D, Guo G. One-step, facile and ultrafast synthesis of phase- and size-controlled Pt-Bi intermetallic nanocatalysts through continuous-flow microfluidics. Journal of the American Chemical Society, 2015, 137(19): 6263–6269

[9] An L, Yan H, Chen X, Li B, Xia Z, Xia D. Catalytic performance and mechanism of N-CoTi@CoTiO₃ catalysts for oxygen reduction reaction. Nano Energy, 2016, 20: 134–143

[10] Lee J M, Han H, Jin S, Choi S M, Kim H J, Seo M H, Kim W B. A review on recent progress in the aspect of stability of oxygen reduction electrocatalysts for proton-exchange membrane fuel cell: quantum mechanics and experimental approaches. Energy Technology (Weinheim), 2019, 7(9): 1900312

[11] Kacprzak A. Hydroxide electrolyte direct carbon fuel cells— technology review. International Journal of Energy Research, 2019, 43(1): 65–85

[12] Dekel D R. Review of cell performance in anion exchange membrane fuel cells. Journal of Power Sources, 2018, 375: 158–169

[13] Chen X, Huang S, Sun F, Lai N. Modifications of metal and ligand to modulate the oxygen reduction reaction activity of two-dimensional MOF catalysts. Journal of Physical Chemistry C, 2020, 124(2): 1413–1420

[14] Song Y, Zhang X, Cui X, Shi J. The ORR kinetics of ZIF-derived Fe-N-C electrocatalysts. Journal of Catalysis, 2019, 372: 174–181

[15] Kulkarni A, Siahrostami S, Patel A, Nørskov J K. Understanding catalytic activity trends in the oxygen reduction reaction. Chemical Reviews, 2018, 118(5): 2302–2312

[16] Dong Y, Deng Y, Zeng J, Song H, Liao S. A high-performance composite ORR catalyst based on the synergy between binary transition metal nitride and nitrogen-doped reduced graphene oxide. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(12): 5829–5837

[17] Jiang H, Gu J, Zhen X, Li M, Qiu X, Wang L, Li W, Chen Z, Ji X, Li J. Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER. Energy & Environmental Science, 2019, 12(1): 322–333

[18] Kreider M E, Gallo A, Back S, Liu Y, Siahrostami S, Nordlund D, Sinclair R, Nørskov J K, King L A, Jaramillo T F. Precious metal-free nickel nitride catalyst for the oxygen reduction reaction. ACS Applied Materials & Interfaces, 2019, 11(30): 26863–26871

[19] Zou X, Wang L, Yakobson B I. Mechanisms of the oxygen reduction reaction on B- and/or N-doped carbon nanomaterials with curvature and edge effects. Nanoscale, 2018, 10(3): 1129–1134

[20] Lin Y, Liu P, Velasco E, Yao G, Tian Z, Zhang L, Chen L. Fabricating single-atom catalysts from chelating metal in open frameworks. Advanced Materials, 2019, 31(18): 1808193

[21] Sun F, Chen X. Oxygen reduction reaction on Ni₃(HITP)₂: a catalytic site that leads to high activity. Electrochemistry Communications, 2017, 82: 89–92

[22] Zheng X, Wu J, Cao X, Abbott J, Jin C, Wang H, Strasser P, Yang R, Chen X, Wu G. N-, P-, and S-doped graphene-like carbon catalysts derived from onium salts with enhanced oxygen chemisorption for Zn-air battery cathodes. Applied Catalysis B: Environmental, 2019, 241: 442–451

[23] Zhu C, Shi Q, Xu B Z, Fu S, Wan G, Yang C, Yao S, Song J, Zhou H, Du D, Beckman S P, Su D, Lin Y. Hierarchically porous M-N-C (M= Co and Fe) single-atom electrocatalysts with robust MN_x active moieties enable enhanced ORR performance. Advanced Energy Materials, 2018, 8(29): 1801956

[24] Amiinu I S, Liu X, Pu Z, Li W, Li Q, Zhang J, Tang H, Zhang H, Mu S. From 3D ZIF nanocrystals to Co-N_x/C nanorod array electrocatalysts for ORR, OER, and Zn-Air batteries. Advanced Functional Materials, 2018, 28(5): 1704638

[25] Dong Y, Zhou M, Tu W, Zhu E, Chen Y, Zhao Y, Liao S, Huang Y, Chen Q, Li Y. Hollow loofah-like N, O-co-doped carbon tube for electrocatalysis of oxygen reduction. Advanced Functional Materials, 2019, 29(18): 1900015

[26] Chen X, Ge F, Lai N N. O co-doped graphene as a potential catalyst for the oxygen reduction reaction. Journal of the Electrochemical Society, 2019, 166(12): F847–F851

[27] Yang Y, Mao K, Gao S, Huang H, Xia G, Lin Z, Jiang P, Wang C, Wang H, Chen Q. O-, N-atoms-coordinated Mn cofactors within a graphene framework as bioinspired oxygen reduction reaction electrocatalysts. Advanced Materials, 2018, 30(28): 1801732

[28] Peng H, Liu F, Liu X, Liao S, You C, Tian X, Nan H, Luo F, Song H, Fu Z, Huang P. Effect of transition metals on the structure and performance of the doped carbon catalysts derived from polyaniline and melamine for ORR application. ACS Catalysis, 2014, 4(10): 3797–3805

[29] Masa J, Zhao A, Xia W, Muhler M, Schuhmann W. Metal-free catalysts for oxygen reduction in alkaline electrolytes: influence of the presence of Co, Fe, Mn and Ni inclusions. Electrochimica Acta, 2014, 128: 271–278

[30] Wang X, Cullen D A, Pan Y T, Hwang S, Wang M, Feng Z, Wang J, Engelhard M H, Zhang H, He Y, Shao Y, Su D, More K L, Spendelow J S, Wu G. Nitrogen-coordinated single cobalt atom catalysts for oxygen reduction in proton exchange membrane fuel cells. Advanced Materials, 2018, 30(11): 1706758

[31] Delley B. From molecules to solids with the DMol³ approach. Journal of Chemical Physics, 2000, 113(18): 7756–7764

[32] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

[33] Delley B. An all-electron numerical method for solving the local density functional for polyatomic molecules. Journal of Chemical Physics, 1990, 92(1): 508–517

[34] Chen X, Ge F, Chen T, Lai N. The effect of GGA functionals on the oxygen reduction reaction catalyzed by Pt(111) and FeN₄ doped graphene. Journal of Molecular Modeling, 2019, 25(7): 180

[35] Chen X. Graphyne nanotubes as electrocatalysts for oxygen reduction reaction: the effect of doping elements on the catalytic mechanisms. Physical Chemistry Chemical Physics, 2015, 17(43): 29340–29343

[36] Modak B, Srinivasu K, Ghosh S K. Exploring metal decorated porphyrin-like porous fullerene as catalyst for oxygen reduction reaction: a DFT study. International Journal of Hydrogen Energy, 2017, 42(4): 2278–2287

[37] Chen X, Qiao Q, An L, Xia D. Why do boron and nitrogen doped α- and g-graphyne exhibit different oxygen reduction mechanism? a first-principles study. Journal of Physical Chemistry C, 2015, 119(21): 11493–11498

[38] Zhang X, Yang Z, Lu Z, Wang W. Bifunctional CoN_x embedded graphene electrocatalysts for OER and ORR: a theoretical evaluation. Carbon, 2018, 130: 112–119

[39] Calle-Vallejo F, Martinez J I, Rossmeisl J. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions. Physical Chemistry Chemical Physics, 2011, 13(34): 15639–15643

[40] Vayner E, Anderson A B. Theoretical predictions concerning oxygen reduction on nitrided graphite edges and a cobalt center bonded to them. Journal of Physical Chemistry C, 2007, 111(26): 9330–9336

[41] Wang S, Zhang L, Xia Z, Roy A, Chang D W, Baek J B, Dai L. BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. Angewandte Chemie International Edition, 2012, 51(17): 4209–4212

[42] Bhatt M D, Lee G, Lee J S. Oxygen reduction reaction mechanisms on Al-doped X-graphene (X= N, P, and S) catalysts in acidic medium: a comparative DFT study. Journal of Physical Chemistry C, 2016, 120(46): 26435–26441

[43] Xue L, Li Y, Liu X, Liu Q, Shang J, Duan H, Dai L, Shui J. Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells. Nature Communications, 2018, 9(1): 3819

[44] Chen X, Li F, Zhang N, An L, Xia D. Mechanism of oxygen reduction reaction catalyzed by Fe(Co)-N_x/C. Physical Chemistry Chemical Physics, 2013, 15(44): 19330–19336

[45] Chen X, Sun F, Chang J. Cobalt or nickel doped SiC nanocages as efficient electrocatalyst for oxygen reduction reaction: a computational prediction. Journal of the Electrochemical Society, 2017, 164(6): F616–F619

[46] Chen X, Chang J, Ke Q. Probing the activity of pure and N-doped fullerenes towards oxygen reduction reaction by density functional theory. Carbon, 2018, 126: 53–57

[47] Zhang X, Lu Z, Yang Z. The mechanism of oxygen reduction reaction on CoN₄ embedded graphene: a combined kinetic and atomistic thermodynamic study. International Journal of Hydrogen Energy, 2016, 41(46): 21212–21220

[48] Zhang J, Wang Z, Zhu Z. The inherent kinetic electrochemical reduction of oxygen into H₂O on FeN₄-carbon: a density functional theory study. Journal of Power Sources, 2014, 255: 65–69

[49] Chen X, Hu R. DFT-based study of single transition metal atom doped g-C₃N₄ as alternative oxygen reduction reaction catalysts. International Journal of Hydrogen Energy, 2019, 44(29): 15409–15416

[50] Nørskov J K, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin J R, Bligaard T, Jónsson H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. Journal of Physical Chemistry B, 2004, 108(46): 17886–17892

[51] Tripković V, Skúlason E, Siahrostami S, Nørskov J K, Rossmeisl J. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations. Electrochimica Acta, 2010, 55(27): 7975–7981

[52] Aihara J. Reduced HOMO-LUMO gap as an index of kinetic stability for polycyclic aromatic hydrocarbons. Journal of Physical Chemistry A, 1999, 103(37): 7487–7495

Acknowledgements

This work was supported by the Applied Basic Research Project of Science and Technology Department of Sichuan Province (Grant No. 2020YJ0418), the Youth Science and Technology Innovation Team of Southwest Petroleum University (Grant No. 2018CXTD05), the Open Fund of State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation of Southwest Petroleum University (Grant No. PLN201925), and the Postgraduate Research and Innovation Fund of Southwest Petroleum University (Grant No. 2019cxzd027).

RIGHTS & PERMISSIONS

2021 Higher Education Press