Co(O)₄(N)-type single-atom-based catalysts and liganddriven modulation of electrocatalytic properties for reducing oxygen molecules

Abstract

Single-atom-based catalysts are intriguing electrocatalytic platforms that combine the advantages of molecular catalysts and conductive carbon-based materials. In this work, hybrids (Co-NrGO-1 and Co-NrGO-2) were generated by wet-reactions between organometallic complexes (Co(CH₃COO)₂ and Co[CH₃(CH₂)₃CH(C₂H₅)COO]₂, respectively) and N-doped reduced graphene oxide at 25°C. Various characterizations revealed the formation of atomically dispersed Co(O)₄(N) species in Co-NrGO-2. Density functional theory (DFT) calculations explained the effect of the aliphatic C7 group in Co2 on the formation processes. The Co-NrGO-2 hybrid showed excellent catalytic performance, such as onset (0.94 V) and half-wave (0.83 V) potentials, for electrochemical oxygen reduction reaction (ORR). Co-NrGO-2 outperformed Co-NrGO-1, which was explained by more back donation to the antibonding orbitals of O₂ from electron-rich aliphatic groups. DFT calculations support this feature, with mechanistic investigations showing favored ORR reactions and facile breakage of double bonds in O₂.

Keywords

electrocatalysts / electronic effect / graphenes / oxygen reduction reaction / single atom catalyst

References

[1] Li Y, Li Q, Wang H, Zhang L, Wilkinson DP, Zhang J. Recent progresses in oxygen reduction reaction electrocatalysts for electrochemical energy applications. Electrochem Energy Rev. 2019;2(4):518-538.

[2] Shao M, Chang Q, Dodelet J, Chenitz R. Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev. 2016;116(6):3594-3657.

[3] Wang X, Li Z, Qu Y, et al. Review of metal catalysts for oxygen reduction reaction: from nanoscale engineering to atomic design. Chem. 2019;5(6):1486-1511.

[4] Kwon IS, Kwak IH, Kang HS, Park J. Molecular intercalation of transition metal dichalcogenide nanosheets to enhance electrocatalytic activity toward hydrogen evolution reaction. Bull Kor Chem Soc. 2022;43(12):1352-1363.

[5] Chen M, Li X, Yang F, et al. Atomically dispersed MnN₄ catalysts via environmentally benign aqueous synthesis for oxygen reduction: mechanistic understanding of activity and stability improvements. ACS Catal. 2020;10(18):10523-10534.

[6] Zhang Y, Meng S, Ding J, Peng Q, Yu Y. Transition metal-coordinated graphitic carbon nitride dots as a sensitive and facile fluorescent probe for β-amyloid peptide detection. Analyst. 2019;144(2):504-511.

[7] Cheng Y, Zhao S, Johannessen B, et al. Single-atom catalysts: atomically dispersed transition metals on carbon nanotubes with ultrahigh loading for selective electrochemical carbon dioxide reduction. Adv Mater. 2018;30(13):1706287.

[8] Zhao Y, Yan L, Zhao X. Cover feature: development of carbonbased electrocatalysts for ambient nitrogen reduction reaction: challenges and perspectives. Chemelectrochem. 2022;9(3): e202101126.

[9] Nagappan S, Duraivel M, Hira SA, et al. Heteroatom-doped nanomaterials/core–shell nanostructure based electrocatalysts for the oxygen reduction reaction. J Mater Chem A. 2022;10(3):987-1021.

[10] Baskaran S, Jung J. Termolecular Eley–Rideal pathway for efficient CO oxidation on phosphorene-supported singleatom cobalt catalyst. Bull Kor Chem Soc. 2022;43(11):1254-1261.

[11] Lee DH, Lee WJ, Lee WJ, Kim SO, Kim Y-H. Theory, synthesis, and oxygen reduction catalysis of Fe-Porphyrin-like carbon nanotube. Phys Rev Lett. 2011;106(17):175502.

[12] Sa YJ, Seo DJ, Woo J, et al. A general approach to preferential formation of active Fe–N_x sites in Fe–N/C electrocatalysts for efficient oxygen reduction reaction. J Am Chem Soc. 2016;138(45):15046-15056.

[13] Wan X, Liu Q, Liu J, et al. Iron atom–cluster interactions increase activity and improve durability in Fe–N–C fuel cells. Nat Commun. 2022;13(1):2963.

[14] Woo J, Lim JS, Lim T, et al. Fe–N/C catalysts with tunable mesoporous structures and carbon layer numbers reveal the role of interlayer O₂ activation. EES Catal. 2023;1:62-73.

[15] Bates JS, Khamespanah F, Cullen DA, et al. Molecular catalyst synthesis strategies to prepare atomically dispersed Fe-N-C heterogeneous catalysts. J Am Chem Soc. 2022;144(41):18797-18802.

[16] Ahmed S, Rim HR, Sun HJ, Lee HK, Shim J, Park G. Fabrication of heteroatom doped cobalt catalyst for oxygen reduction and evolution reactions in alkaline medium. Bull Kor Chem Soc. 2022;43(5):745-749.

[17] Xue N, Zhang Y, Wang C, et al. Enhancing oxygen reduction reaction performance in acidic media via bimetal Fe and Cr synergistic effects. Int J Hydrogen Energy. 2022;47(80):33979-33987.

[18] Xu M, Ge J, Liu C, Xing W. Recent advances in active sites identification and new M−N−C catalysts development towards ORR. J Phys Mater. 2021;4:044008.

[19] Neyens E, Baeyens J. A review of classic Fenton’s peroxidation as an advanced oxidation technique. J Hazard Mater. 2003;98(1-3):33-50.

[20] Han J, Sa YJ, Shim Y, et al. Coordination chemistry of [Co (acac)₂] with N-doped graphene: implications for oxygen reduction reaction reactivity of organometallic Co-O₄-N species. Angew Chem Int Ed. 2015;54(43):12622-12626.

[21] Lisboa TP, Oliveria RS, de Oliveira WBV, et al. A 3D carbon black disposable electrochemical sensor modified with reduced graphene oxide used for the sensitive determination of levofloxacin. New J Chem. 2023;47(5):2240-2247.

[22] Choi S, Kim C, Suh JM, Jang HW. Reduced graphene oxidebased materials for electrochemical energy conversion reactions. Carbon Energy. 2019;1:85-108.

[23] Park S, Ruoff RS. Chemical methods for the production of graphenes. Nat Nanotechnol. 2009;4:217-224.

[24] Shin H-J, Kim SM, Yoon S-M, et al. Tailoring electronic structures of carbon nanotubes by solvent with electron-donating and -withdrawing groups. J Am Chem Soc. 2008;130(6):2062-2066.

[25] Kim S, Park G, Sennu P, et al. Effect of degree of reduction on the anode performance of reduced graphene oxide in Li-ion batteries. RSC Adv. 2015;5(105):86237-86241.

[26] Shin Y, Park S. Production of B-doped reduced graphene oxide using wet-process in tetrahydrofuran. Carbon Lett. 2021;31(5):887-893.

[27] Shin Y, Lee S, Park S, et al. Production of N-doped reduced graphene oxide/Fe₃O₄ hybrids and effect of order of production steps on electrocatalytic performances for oxygen reduction reaction. ChemistrySelect. 2018;3(44):12690-12695.

[28] Compton OC, Nguyen ST. Graphene oxide, highly reduced graphene oxide, and graphene: versatile building blocks for carbon-based materials. Small. 2010;6:711-723.

[29] Wu Y, Zhang N, Yuen G, de Lannoy CF. Cross-linked iron nanoparticle-doped reduced graphene oxide membranes for micropollutant removal from water. J Chem Eng. 2023;455:140624.

[30] Gupta B, Kumar N, Panda K, et al. Role of oxygen functional groups in reduced graphene oxide for lubrication. Sci Rep. 2017;7:1-14.

[31] Stobinski L, Lesiak B, Malolepszy A, et al. Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods. J Electron Spectrosc Relat Phenom. 2014;195:145-154.

[32] Bayatsarmadi B, Zheng Y, Vasileff A, Qiao SZ. Recent advances in atomic metal doping of carbon-based nanomaterials for energy conversion. Small. 2017;13(21):1700191.

[33] Kochubey D, Kaichev V, Saraev A, Tomyn S, Belov A, Voloshin Y. Combined X-ray absorption near-edge structure and X-ray photoelectron study of the electrocatalytically active cobalt(I) cage complexes and the clathrochelate cobalt(II)- and cobalt(III)-containing precursors and analogs. J Phys Chem C. 2013;117(6):2753-2759.

[34] Tang Y, Dong L, Mao S, Gu H, Malkoske T, Chen B. Enhanced photocatalytic removal of tetrabromobisphenol A by magnetic CoO@graphene nanocomposites under visible-light irradiation. ACS Appl Energy Mater. 2018;1(6):2698-2708.

[35] Indra A, Menezes PW, Zaharieva I, Dau H, Driess M. Detecting structural transformation of cobalt phosphonate to active bifunctional catalysts for electrochemical water-splitting. J Mater Chem A. 2020;8(5):2637-2643.

[36] Iqbal N, Khan I, Ali A, Qurashi A. A sustainable molybdenum oxysulphide-cobalt phosphate photocatalyst for effectual solardriven water splitting. J Adv Res. 2022;36:15-26.

[37] Fantauzzi M, Secci F, Angotzi MS, Passiu C, Cannas C, Rossi A. Nanostructured spinel cobalt ferrites: Fe and Co chemical state, cation distribution and size effects by X-ray photoelectron spectroscopy. RSC Adv. 2019;9(33):19171-19179.

[38] Xu S, Sun Z, Sun C, et al. Homogeneous and fast ion conduction of PEO-based solid-state electrolyte at low temperature. Adv Funct Mater. 2020;30(51):2007172.

[39] Oversteeg CH, Doan HQ, Groot FM, Cuk T. In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts. Chem Soc Rev. 2017;46(1):102-125.

[40] de Lima AEP, de Oliveira DC. In situ XANES study of cobalt in Co-Ce-Al catalyst applied to steam reforming of ethanol reaction. Catal Today. 2017;283:104-109.

[41] Dahéron L, Dedryvère R, Martinez H, et al. Electron transfer mechanisms upon lithium deintercalation from LiCoO₂ to CoO₂ investigated by XPS. Chem Mater. 2008;20(2):583-590.

[42] Pu Z, Amiinu IS, Cheng R, et al. Single-atom catalysts for electrochemical hydrogen evolution reaction: recent advances and future perspectives. Nano-Micro Lett. 2020;12:1-29.

[43] Ahmmad B, Nishi M, Hirose F, Ohkubo T, Kuroda Y. Structure of hydrated cobalt ions confined in the nanospace of single-walled carbon nanotubes. Phys Chem Chem Phys. 2013;15(21):8264-8270.

[44] Tong Y, Chen P, Zhou T, et al. A bifunctional hybrid electrocatalyst for oxygen reduction and evolution: cobalt oxide nanoparticles strongly coupled to B, N-decorated graphene. Angew Chem Int Ed. 2017;56(25):7121-7125.

[45] Miller TE, Davies V, Li J, et al. Actualizing in situ X-ray absorption spectroscopy characterization of PEMFC-cycled Ptelectrodes. J Electrochem Soc. 2018;165(9):F597-F603.

[46] Sa YJ, Park SO, Jung GY, et al. Heterogeneous Co–N/C electrocatalysts with controlled cobalt site densities for the hydrogen evolution reaction: structure–activity correlations and kinetic insights. ACS Catal. 2018;9(1):83-97.

[47] Li Z, Ji S, Liu Y, et al. Well-defined materials for heterogeneous catalysis: from nanoparticles to isolated single-atom sites. Chem Rev. 2019;120(2):623-682.

[48] Cai W, Piner RD, Stadermann FJ, et al. Synthesis and solidstate NMR structural characterization of ¹³C-labeled graphite oxide. Science. 2008;321(5897):1815-1817.

[49] Gao W, Alemany LB, Ci L, Ajayan M. New insights into the structure and reduction of graphite oxide. Nat Chem. 2009;1(5):403-408.

[50] Park S, Hu Y, Hwang JO, et al. Chemical structures of hydrazine-treated graphene oxide and generation of aromatic nitrogen doping. Nat Commun. 2012;3(1):638.

[51] Jang D, Lee Y, Shin Y, et al. Coordination structure of Jacobsen catalyst with N-modified graphene and their electrocatalytic properties for reducing oxygen molecules. Appl Catal B Environ. 2020;263:118337.

[52] Jang D, Lee S, Kim S, et al. Production of P, N Co-doped graphene-based materials by a solution process and their electrocatalytic performance for oxygen reduction reaction. ChemNanoMat. 2018;4(1):118-123.

[53] Zhong X, Jiang Y, Chen X, et al. Integrating cobalt phosphide and cobalt nitride-embedded nitrogen-rich nanocarbons: high-performance bifunctional electrocatalysts for oxygen reduction and evolution. J Mater Chem A. 2016;4(27):10575-10584.

[54] Chen C, Li H, Chen J, et al. Surface molecular encapsulation with cyclodextrin in promoting the activity and stability of Fe single-atom catalyst for oxygen reduction reaction. Energy Environ Mater. 2022;6(2):e12346.

[55] Yang F, Mao J, Li S, Yin J, Zhou J, Liu W. Cobalt–graphene nanomaterial as an efficient catalyst for selective hydrogenation of 5-hydroxymethylfurfural into 2, 5-dimethylfuran. Catal Sci Technol. 2019;9(6):1329-1333.

[56] Li C, Wong L, Tang L, et al. Kinetic modelling of temperatureprogrammed reduction of cobalt oxide by hydrogen. Appl Catal A Gen. 2017;537:1-11.

[57] Hajjar Z, Kazemeini M, Rashidi A, Bazmi M. In situ and simultaneous synthesis of a novel graphene-based catalyst for deep hydrodesulfurization of naphtha. Catal Lett. 2015;145(9):1660-1672.

[58] Miessler GL, Fischer PJ, Tarr DA. Inorganic Chemistry. 5th ed. Miessler, Pearson, 420-425.

[59] Nørskov JK, Rossmeisl J, Logadottir A, et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J Phys Chem B. 2004;108(46):17886-17892.

[60] Zhou Y, Li Z, Xia X. Engineering the electronic structure of active centers in metalloporphyrins to boost oxygen reduction reaction activity. Chemelectrochem. 2022;9(19):e202200900.

[61] Ge X, Sumboja A, Wuu D, et al. Oxygen reduction in alkaline media: from mechanisms to recent advances of catalysts. ACS Catal. 2015;5(8):4643-4667.

[62] Jiang K, Back S, Akey AJ, et al. Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination. Nat Commun. 2019;10(1):3997.

RIGHTS & PERMISSIONS

2024 The Authors. EcoEnergy published by John Wiley & Sons Australia, Ltd on behalf of China Chemical Safety Association.