High hydrogen evolution activities of dual-metal atoms incorporated N-doped graphenes achieved by coordination regulation

Abstract

Electrolysis of water to produce hydrogen (H) can solve the current energy crisis and environmental problems. However, efficient hydrogen evolution reaction (HER) catalysts are still limited to a few noble metals, thus prohibiting their broad applications. Herein, first-principles calculations were carried out to investigate the theoretical HER performances of a series of N-doped graphenes containing inexpensive single- and dual-metal atoms. Among them, MN₄-gra (M = Fe, Co, Ni), homonuclear MMN₆-gra, and heteronuclear M1M2N₆-gra mostly exhibit low HER activities due to the weak H adsorption, and only CoN₄-gra, NiNiN₆-gra, and CoNiN₆-gra show better ΔG_*H values of 0.19, 0.15 and 0.27 eV, respectively. In contrast, low-coordinated MMN₅-gra and M1M2N₅-gra both have rather high HER activities. In particular, the ΔG_*H values of FeNiN₅-gra and CoNiN₅-gra are as low as -0.04 and -0.06 eV, respectively, very close to the ideal 0 eV. Detailed analyses reveal that such high activity mainly stems from the reduced metal coordination and the synergistic effect between the two metals, which greatly enhance the adsorption ability of the active center. More interestingly, the strong H adsorption of MMN₅-gra/M1M2N₅-gra could enable them to further adsorb a second H atom and generate a stable HMH intermediate to yield the final product H₂. Under this novel mechanism, the two-step |ΔG_*H| values of FeNiN₅-gra and CoNiN₅-gra are all no more than 0.10 eV. Our work not only discloses the important effect of coordination regulation and site synergy on enhancing the catalytic activity but also finds a new HER path on the metal-embedded N-doped graphenes.

Keywords

Hydrogen evolution reaction / density functional calculations / N-doped graphene / dual-atom catalyst / coordination regulation

References

[1] Li L,Shao Q.Metallic nanostructures with low dimensionality for electrochemical water splitting.Chem Soc Rev2020;49:3072-106

[2] Jiao Y,Jaroniec M.Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions.Chem Soc Rev2015;44:2060-86

[3] Huang J,An T.Increasing the active sites and intrinsic activity of transition metal chalcogenide electrocatalysts for enhanced water splitting.J Mater Chem A2020;8:25465-98

[4] Kim HJ,Joo J.Recent advances in non-precious group metal-based catalysts for water electrolysis and beyond.J Mater Chem A2022;10:50-88

[5] Gray HB.Powering the planet with solar fuel.Nat Chem2009;1:7

[6] Liu M,Chen W.Graphene-supported nanoelectrocatalysts for fuel cells: synthesis, properties, and applications.Chem Rev2014;114:5117-60

[7] Majlan E,Daud W,Haque M.Electrode for proton exchange membrane fuel cells: a review.Renew Sust Energ Rev2018;89:117-34

[8] Nørskov JK,Logadottir A.Trends in the exchange current for hydrogen evolution.J Electrochem Soc2005;152:J23

[9] Seh ZW,Dickens CF,Nørskov JK.Combining theory and experiment in electrocatalysis: insights into materials design.Science2017;355:eaad4998

[10] Xu H,Cao D.A universal principle for a rational design of single-atom electrocatalysts.Nat Catal2018;1:339-48

[11] Benck JD,Kibsgaard J,Jaramillo TF.Catalyzing the hydrogen evolution reaction (HER) with molybdenum sulfide nanomaterials.ACS Catal2014;4:3957-71

[12] Du H,Guo X,Li J.Recent progress in transition metal phosphides with enhanced electrocatalysis for hydrogen evolution.Nanoscale2018;10:21617-24

[13] Sun J,Yu L.Highly efficient hydrogen evolution from a mesoporous hybrid of nickel phosphide nanoparticles anchored on cobalt phosphosulfide/phosphide nanosheet arrays.Small2019;15:e1804272

[14] Yan Q,Wei T.Hierarchical edge-rich nickel phosphide nanosheet arrays as efficient electrocatalysts toward hydrogen evolution in both alkaline and acidic conditions.ACS Sustainable Chem Eng2019;7:7804-11

[15] Gao Q,Shi Z,Tang Y.Structural design and electronic modulation of transition-metal-carbide electrocatalysts toward efficient hydrogen evolution.Adv Mater2019;31:1802880

[16] Han N,Lu Z.Nitrogen-doped tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water splitting in acid.Nat Commun2018;9:924 PMCID:PMC5834627

[17] Zhou S,Jiang S,Hou H.Flexible and refractory tantalum carbide-carbon electrospun nanofibers with high modulus and electric conductivity.Mater Lett2017;200:97-100

[18] Zhang B,Wang J.Interface engineering: The Ni(OH)₂/MoS₂ heterostructure for highly efficient alkaline hydrogen evolution.Nano Energy2017;37:74-80

[19] Ling Y,Zhang Q,Cai W.A self-template synthesis of defect-rich WS₂ as a highly efficient electrocatalyst for the hydrogen evolution reaction.Chem Commun2018;54:2631-4

[20] Pan Y,Sun K.A bimetallic Zn/Fe polyphthalocyanine-derived single-atom Fe-N₄ catalytic site:a superior trifunctional catalyst for overall water splitting and Zn-air batteries.Angew Chem Int Ed Engl2018;57:8614-8

[21] Cao L,Chen J.Dynamic oxygen adsorption on single-atomic Ruthenium catalyst with high performance for acidic oxygen evolution reaction.Nat Commun2019;10:4849 PMCID:PMC6813412

[22] Varela AS,Strasser P.Molecular nitrogen-carbon catalysts, solid metal organic framework catalysts, and solid metal/nitrogen-doped carbon (MNC) catalysts for the electrochemical CO₂ reduction.Adv Energy Mater2018;8:1703614

[23] Yao Y,Chen W.Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis.Nat Catal2019;2:304-13

[24] Wang X,Qu Y.Review of metal catalysts for oxygen reduction reaction: from nanoscale engineering to atomic design.Chem2019;5:1486-511

[25] Zhao Y,Chen W.Two-step carbothermal welding to access atomically dispersed Pd₁ on three-dimensional zirconia nanonet for direct indole synthesis.J Am Chem Soc2019;141:10590-4

[26] Lei Y,Liu Y.Designing atomic active centers for hydrogen evolution electrocatalysts.Angew Chem Int Ed Engl2020;59:20794-812

[27] Wang Y,He Y.Advanced electrocatalysts with single-metal-atom active sites.Chem Rev2020;120:12217-314

[28] Zhuo HY,Liang JX,Xiao H.Theoretical understandings of graphene-based metal single-atom catalysts: stability and catalytic performance.Chem Rev2020;120:12315-41

[29] Khalid M,Honorato AMB.Metallic single-atoms confined in carbon nanomaterials for the electrocatalysis of oxygen reduction, oxygen evolution, and hydrogen evolution reactions.Catal Sci Technol2020;10:6420-48

[30] Fei H,Arellano-Jiménez MJ.Atomic cobalt on nitrogen-doped graphene for hydrogen generation.Nat Commun2015;6:8668 PMCID:PMC4639894

[31] Qu Y,Li Z.Thermal emitting strategy to synthesize atomically dispersed Pt metal sites from bulk Pt metal.J Am Chem Soc2019;141:4505-9

[32] Xue Y,Yi Y.Anchoring zero valence single atoms of nickel and iron on graphdiyne for hydrogen evolution.Nat Commun2018;9:1460 PMCID:PMC5899097

[33] Lu B,Wu F.Ruthenium atomically dispersed in carbon outperforms platinum toward hydrogen evolution in alkaline media.Nat Commun2019;10:631 PMCID:PMC6367462

[34] Zhang L,Liu H.Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction.Nat Commun2019;10:4936 PMCID:PMC6821730

[35] Bai L,Alexander DTL,Hu X.A cobalt-iron double-atom catalyst for the oxygen evolution reaction.J Am Chem Soc2019;141:14190-9

[36] He T,Du A.Atomically embedded asymmetrical dual-metal dimers on N-doped graphene for ultra-efficient nitrogen reduction reaction.J Catal2020;388:77-83

[37] Zheng X,Ye W,Liu Y.Building up bimetallic active sites for electrocatalyzing hydrogen evolution reaction under acidic and alkaline conditions.Chem Eng J2021;413:128027

[38] Zhou Y,Chen W.Dual-metal interbonding as the chemical facilitator for single-atom dispersions.Adv Mater2020;32:e2003484

[39] Zhao W,Lin Y.Pt-Ru dimer electrocatalyst with electron redistribution for hydrogen evolution reaction.ACS Catal2022;12:5540-8

[40] Lu B,Chen S.Electrocatalysis of single-atom sites: impacts of atomic coordination.ACS Catal2020;10:7584-618

[41] Perdew JP,Ernzerhof M.Generalized gradient approximation made simple.Phys Rev Lett1996;77:3865-8

[42] Kresse G.Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Phys Rev B Condens Matter1996;54:11169-86

[43] Grimme S,Ehrlich S.A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu.J Chem Phys2010;132:154104

[44] Zhang C,Li B.Dual-metal atom incorporated N-doped graphenes as oxygen evolution reaction electrocatalysts: high activities achieved by site synergies.J Mater Chem A2022;10:8309-23

[45] Momma K.VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data.J Appl Cryst2011;44:1272-6

[46] Yang TT,House SD,Lee JK.Computationally guided design to accelerate discovery of doped β-Mo₂C catalysts toward hydrogen evolution reaction.ACS Catal2022;12:11791-800

[47] Nørskov JK,Logadottir A.Origin of the overpotential for oxygen reduction at a fuel-cell cathode.J Phys Chem B2004;108:17886-92

[48] Hossain MD,Zhuang M.Rational design of graphene-supported single atom catalysts for hydrogen evolution reaction.Adv Energy Mater2019;9:1803689

[49] Hammer B.Why gold is the noblest of all the metals.Nature1995;376:238-40

[50] Lim J,Choi C.Ultralow overpotential of hydrogen evolution reaction using Fe-doped defective graphene: a density functional study.ChemCatChem2018;10:4450-5

[51] Yang Y,Liang Z.Role of local coordination in bimetallic sites for oxygen reduction: a theoretical analysis.J Energy Chem2020;44:131-7

[52] Crabtree RH.Dihydrogen complexes: some structural and chemical studies.Acc Chem Res1990;23:95-101

[53] Heinekey DM,Lluch JM.Elongated dihydrogen complexes: what remains of the H-H bond?.Chem Soc Rev2004;33:175-82

[54] Kubas GJ.Fundamentals of H₂ binding and reactivity on transition metals underlying hydrogenase function and H₂ production and storage.Chem Rev2007;107:4152-205

[55] Kubas GJ.Molecular hydrogen complexes: coordination of a .sigma. bond to transition metals.Acc Chem Res1988;21:120-8

[56] Crabtree RH.Dihydrogen complexation.Chem Rev2016;116:8750-69

[57] Alcaraz G,Sabo-Etienne S.Bis sigma-bond dihydrogen and borane ruthenium complexes: bonding nature, catalytic applications, and reversible hydrogen release.Acc Chem Res2009;42:1640-9

[58] Di Liberto G, Cipriano LA, Pacchioni G. Role of dihydride and dihydrogen complexes in hydrogen evolution reaction on single-atom catalysts.J Am Chem Soc2021;143:20431-41 PMCID:PMC8662730

[59] Di Liberto G, Cipriano LA, Pacchioni G. Single atom catalysts: what matters most, the active site or the surrounding?.ChemCatChem2022;14:e202200611

[60] Wang J,Song H.Water dissociation kinetic-oriented design of nickel sulfides via tailored dual sites for efficient alkaline hydrogen evolution.Adv Funct Mater2021;31:2008578