Probing the catalytic activity of M-N4−xOx embedded graphene for the oxygen reduction reaction by density functional theory
Fan Ge1,3, Qingan Qiao2, Xin Chen1,3,4(), You Wu1
1. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China 2. School of Chemistry and Materials Science, Ludong University, Yantai 264025, China 3. Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China 4. Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
In this work, the detailed oxygen reduction reaction (ORR) catalytic performance of M-N4−xOx (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-N4−xOx shows a good linear relationship with the number of doped O atoms. The adsorption manner of O2 on M-N4−xOx 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.
. [J]. Frontiers of Chemical Science and Engineering, 2021, 15(5): 1206-1216.
Fan Ge, Qingan Qiao, Xin Chen, You Wu. Probing the catalytic activity of M-N4−xOx embedded graphene for the oxygen reduction reaction by density functional theory. Front. Chem. Sci. Eng., 2021, 15(5): 1206-1216.
E Kabir, P Kumar, S Kumar, A A Adelodun, K H Kim. Solar energy: potential and future prospects. Renewable & Sustainable Energy Reviews, 2018, 82: 894–900 https://doi.org/10.1016/j.rser.2017.09.094
2
F Podjaski, J Kröger, B V Lotsch. Toward an aqueous solar battery: direct electrochemical storage of solar energy in carbon nitrides. Advanced Materials, 2018, 30(9): 1705477 https://doi.org/10.1002/adma.201705477
3
F Sorgulu, I Dincer. A renewable source based hydrogen energy system for residential applications. International Journal of Hydrogen Energy, 2018, 43(11): 5842–5851 https://doi.org/10.1016/j.ijhydene.2017.10.101
4
N Endo, E Shimoda, K Goshome, T Yamane, T Nozu, T Maeda. 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 https://doi.org/10.1016/j.ijhydene.2019.01.232
G Feng, L An, B Li, Y Zuo, J Song, F Ning, N Jiang, X Cheng, Y Zhang, D Xia. Atomically ordered non-precious Co3Ta intermetallic nanoparticles as high-performance catalysts for hydrazine electrooxidation. Nature Communications, 2019, 10(1): 4514 https://doi.org/10.1038/s41467-019-12509-7
7
X Chen, F Sun, F Bai, Z Xie. 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 https://doi.org/10.1016/j.apsusc.2018.12.014
8
D Zhang, F Wu, M Peng, X Wang, D Xia, G Guo. 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 https://doi.org/10.1021/jacs.5b01088
9
L An, H Yan, X Chen, B Li, Z Xia, D Xia. Catalytic performance and mechanism of N-CoTi@CoTiO3 catalysts for oxygen reduction reaction. Nano Energy, 2016, 20: 134–143 https://doi.org/10.1016/j.nanoen.2015.12.002
10
J M Lee, H Han, S Jin, S M Choi, H J Kim, M H Seo, W B Kim. 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 https://doi.org/10.1002/ente.201900312
11
A Kacprzak. Hydroxide electrolyte direct carbon fuel cells— technology review. International Journal of Energy Research, 2019, 43(1): 65–85 https://doi.org/10.1002/er.4197
X Chen, S Huang, F Sun, N Lai. 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 https://doi.org/10.1021/acs.jpcc.9b09647
14
Y Song, X Zhang, X Cui, J Shi. The ORR kinetics of ZIF-derived Fe-N-C electrocatalysts. Journal of Catalysis, 2019, 372: 174–181 https://doi.org/10.1016/j.jcat.2019.02.023
15
A Kulkarni, S Siahrostami, A Patel, J K Nørskov. Understanding catalytic activity trends in the oxygen reduction reaction. Chemical Reviews, 2018, 118(5): 2302–2312 https://doi.org/10.1021/acs.chemrev.7b00488
16
Y Dong, Y Deng, J Zeng, H Song, S Liao. 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 https://doi.org/10.1039/C6TA10496G
17
H Jiang, J Gu, X Zhen, M Li, X Qiu, L Wang, W Li, Z Chen, X Ji, J Li. 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 https://doi.org/10.1039/C8EE03276A
18
M E Kreider, A Gallo, S Back, Y Liu, S Siahrostami, D Nordlund, R Sinclair, J K Nørskov, L A King, T F Jaramillo. Precious metal-free nickel nitride catalyst for the oxygen reduction reaction. ACS Applied Materials & Interfaces, 2019, 11(30): 26863–26871 https://doi.org/10.1021/acsami.9b07116
19
X Zou, L Wang, B I Yakobson. 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 https://doi.org/10.1039/C7NR08061A
20
Y Lin, P Liu, E Velasco, G Yao, Z Tian, L Zhang, L Chen. Fabricating single-atom catalysts from chelating metal in open frameworks. Advanced Materials, 2019, 31(18): 1808193 https://doi.org/10.1002/adma.201808193
21
F Sun, X Chen. Oxygen reduction reaction on Ni3(HITP)2: a catalytic site that leads to high activity. Electrochemistry Communications, 2017, 82: 89–92 https://doi.org/10.1016/j.elecom.2017.07.028
22
X Zheng, J Wu, X Cao, J Abbott, C Jin, H Wang, P Strasser, R Yang, X Chen, G Wu. 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 https://doi.org/10.1016/j.apcatb.2018.09.054
23
C Zhu, Q Shi, B Z Xu, S Fu, G Wan, C Yang, S Yao, J Song, H Zhou, D Du, S P Beckman, D Su, Y Lin. Hierarchically porous M-N-C (M= Co and Fe) single-atom electrocatalysts with robust MNx active moieties enable enhanced ORR performance. Advanced Energy Materials, 2018, 8(29): 1801956 https://doi.org/10.1002/aenm.201801956
24
I S Amiinu, X Liu, Z Pu, W Li, Q Li, J Zhang, H Tang, H Zhang, S Mu. From 3D ZIF nanocrystals to Co-Nx/C nanorod array electrocatalysts for ORR, OER, and Zn-Air batteries. Advanced Functional Materials, 2018, 28(5): 1704638 https://doi.org/10.1002/adfm.201704638
25
Y Dong, M Zhou, W Tu, E Zhu, Y Chen, Y Zhao, S Liao, Y Huang, Q Chen, Y Li. Hollow loofah-like N, O-co-doped carbon tube for electrocatalysis of oxygen reduction. Advanced Functional Materials, 2019, 29(18): 1900015 https://doi.org/10.1002/adfm.201900015
26
X Chen, F Ge, N N Lai. O co-doped graphene as a potential catalyst for the oxygen reduction reaction. Journal of the Electrochemical Society, 2019, 166(12): F847–F851 https://doi.org/10.1149/2.1551912jes
27
Y Yang, K Mao, S Gao, H Huang, G Xia, Z Lin, P Jiang, C Wang, H Wang, Q Chen. O-, N-atoms-coordinated Mn cofactors within a graphene framework as bioinspired oxygen reduction reaction electrocatalysts. Advanced Materials, 2018, 30(28): 1801732 https://doi.org/10.1002/adma.201801732
28
H Peng, F Liu, X Liu, S Liao, C You, X Tian, H Nan, F Luo, H Song, Z Fu, P Huang. 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 https://doi.org/10.1021/cs500744x
29
J Masa, A Zhao, W Xia, M Muhler, W Schuhmann. 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 https://doi.org/10.1016/j.electacta.2013.11.026
30
X Wang, D A Cullen, Y T Pan, S Hwang, M Wang, Z Feng, J Wang, M H Engelhard, H Zhang, Y He, Y Shao, D Su, K L More, J S Spendelow, G Wu. Nitrogen-coordinated single cobalt atom catalysts for oxygen reduction in proton exchange membrane fuel cells. Advanced Materials, 2018, 30(11): 1706758 https://doi.org/10.1002/adma.201706758
31
B Delley. From molecules to solids with the DMol3 approach. Journal of Chemical Physics, 2000, 113(18): 7756–7764 https://doi.org/10.1063/1.1316015
32
J P Perdew, K Burke, M Ernzerhof. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868 https://doi.org/10.1103/PhysRevLett.77.3865
33
B Delley. An all-electron numerical method for solving the local density functional for polyatomic molecules. Journal of Chemical Physics, 1990, 92(1): 508–517 https://doi.org/10.1063/1.458452
34
X Chen, F Ge, T Chen, N Lai. 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 https://doi.org/10.1007/s00894-019-4071-y
35
X Chen. 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 https://doi.org/10.1039/C5CP05350A
36
B Modak, K Srinivasu, S K Ghosh. 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 https://doi.org/10.1016/j.ijhydene.2016.12.017
37
X Chen, Q Qiao, L An, D Xia. 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 https://doi.org/10.1021/acs.jpcc.5b02505
38
X Zhang, Z Yang, Z Lu, W Wang. Bifunctional CoNx embedded graphene electrocatalysts for OER and ORR: a theoretical evaluation. Carbon, 2018, 130: 112–119 https://doi.org/10.1016/j.carbon.2017.12.121
39
F Calle-Vallejo, J I Martinez, J Rossmeisl. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions. Physical Chemistry Chemical Physics, 2011, 13(34): 15639–15643 https://doi.org/10.1039/c1cp21228a
40
E Vayner, A B Anderson. 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 https://doi.org/10.1021/jp071576e
41
S Wang, L Zhang, Z Xia, A Roy, D W Chang, J B Baek, L Dai. BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. Angewandte Chemie International Edition, 2012, 51(17): 4209–4212 https://doi.org/10.1002/anie.201109257
42
M D Bhatt, G Lee, J S Lee. 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 https://doi.org/10.1021/acs.jpcc.6b09674
43
L Xue, Y Li, X Liu, Q Liu, J Shang, H Duan, L Dai, J Shui. Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells. Nature Communications, 2018, 9(1): 3819 https://doi.org/10.1038/s41467-018-06279-x
44
X Chen, F Li, N Zhang, L An, D Xia. Mechanism of oxygen reduction reaction catalyzed by Fe(Co)-Nx/C. Physical Chemistry Chemical Physics, 2013, 15(44): 19330–19336 https://doi.org/10.1039/c3cp52802b
45
X Chen, F Sun, J Chang. 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 https://doi.org/10.1149/2.1211706jes
46
X Chen, J Chang, Q Ke. Probing the activity of pure and N-doped fullerenes towards oxygen reduction reaction by density functional theory. Carbon, 2018, 126: 53–57 https://doi.org/10.1016/j.carbon.2017.10.007
47
X Zhang, Z Lu, Z Yang. 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 https://doi.org/10.1016/j.ijhydene.2016.08.011
48
J Zhang, Z Wang, Z Zhu. 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 https://doi.org/10.1016/j.jpowsour.2014.01.008
49
X Chen, R Hu. 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 https://doi.org/10.1016/j.ijhydene.2019.04.057
50
J K Nørskov, J Rossmeisl, A Logadottir, L Lindqvist, J R Kitchin, T Bligaard, H Jónsson. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. Journal of Physical Chemistry B, 2004, 108(46): 17886–17892 https://doi.org/10.1021/jp047349j
51
V Tripković, E Skúlason, S Siahrostami, J K Nørskov, J Rossmeisl. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations. Electrochimica Acta, 2010, 55(27): 7975–7981 https://doi.org/10.1016/j.electacta.2010.02.056
52
J Aihara. Reduced HOMO-LUMO gap as an index of kinetic stability for polycyclic aromatic hydrocarbons. Journal of Physical Chemistry A, 1999, 103(37): 7487–7495 https://doi.org/10.1021/jp990092i