Computational design of spatially confined triatomic catalysts for nitrogen reduction reaction

Abstract

The electrocatalytic process of nitrogen reduction reactions (NRR) offers a promising approach towards achieving sustainable ammonia production, acting as an environmentally friendly replacement for the conventional Haber-Bosch method. Density functional theory calculations have been utilized to design and investigate a set of catalysts known as triple-atom catalysts (TACs) for electrochemical NRR, which are supported on graphite-C₃N₃ nanosheets. Herein, we have systematically evaluated these TACs using stringent screening to assess their catalytic performance. Among the candidates, supported Pt₃, Re₃, and Ru₃ trimers emerged as highly active with decent selectivity, involving a limiting potential range of -0.35~-0.11 V. According to analysis of electronic properties, we determined that high NRR activity stems from the d-π* electron-accepting and -donating mechanism. Significantly, the correlation between chemical activity of TACs and electronic structure was established as a pivotal physical parameter, which has led to the conclusion that we can precisely control the catalytic behavior of transition metal trimer clusters by selecting appropriate metal elements and designing moderate cluster-substrates interactions. In summary, these theoretical studies not only enhance our understanding of how catalytic properties are governed by metal-support interactions, regulating stability, activity, and selectivity, but also offer a useful method for screening and designing novel TACs for NRR.

Keywords

Density theory calculation / triple-atom catalysts / nitrogen reduction reaction / metal-support interactions

References

[1] Galloway JN,Erisman JW.Transformation of the nitrogen cycle: recent trends, questions, and potential solutions.Science2008;320:889-92

[2] Klerke A,Nørskov JK.Ammonia for hydrogen storage: challenges and opportunities.J Mater Chem2008;18:2304-10

[3] Guo J.Catalyst: NH₃ as an energy carrier.Chem2017;3:709-12

[4] Gao S,Wang Z.Spin regulation for efficient electrocatalytic N₂ reduction over diatomic Fe-Mo catalyst.J Colloid Interface Sci2023;630:215-23

[5] Zhang G,Meng Y,Ni Z.Layered double hydroxides-based photocatalysts and visible-light driven photodegradation of organic pollutants: a review.Chem Eng J2020;392:123684

[6] Chen JG,Seefeldt LC.Beyond fossil fuel-driven nitrogen transformations.Science2018;360:eaar6611 PMCID:PMC6088796

[7] Yang X,Anibal J.Mechanistic insights into electrochemical nitrogen reduction reaction on vanadium nitride nanoparticles.J Am Chem Soc2018;140:13387-91

[8] Gao Y,Cao Y.A theoretical study of electrocatalytic ammonia synthesis on single metal atom/MXene.Chinese J Catal2019;40:152-9

[9] Wu J,Yu YX.Single Nb or W atom-embedded BP monolayers as highly selective and stable electrocatalysts for nitrogen fixation with low-onset potentials.ACS Appl Mater Interfaces2021;13:10026-36

[10] Du P,Zhu G.Nitrogen reduction reaction on single cluster catalysts of defective PC₆-trimeric or tetrameric transition metal.Phys Chem Chem Phys2022;24:2219-26

[11] Andersen SZ,Yang S.A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements.Nature2019;570:504-8

[12] Zhang L,Shen H.High-efficiency photocatalytic ammonia synthesis by facet orientation-supported heterojunction Cu₂O@BiOCl[100] boosted by double built-in electric fields.Inorg Chem2022;61:6045-55

[13] Li L,Yao D,Qiao SZ.Electrochemical nitrogen reduction: identification and elimination of contamination in electrolyte.ACS Energy Lett2019;4:2111-6

[14] Hao YC,Chen LW.Promoting nitrogen electroreduction to ammonia with bismuth nanocrystals and potassium cations in water.Nat Catal2019;2:448-56

[15] Singh AR,Statt MJ,Cargnello M.Strategies toward selective electrochemical ammonia synthesis.ACS Catal2019;9:8316-24

[16] Martín AJ,Pérez-ramírez J.Electrocatalytic reduction of nitrogen: from haber-bosch to ammonia artificial leaf.Chem2019;5:263-83

[17] Han B,Li F.Fe₃ cluster anchored on the C₂N monolayer for efficient electrochemical nitrogen fixation.Catalysts2020;10:974

[18] Yu L.Pt₂ dimer anchored vertically in defective BN monolayer as an efficient catalyst for N₂ reduction: a DFT study.Catalysts2022;12:1387

[19] Geng Z,Kong X.Achieving a record-high yield rate of 120.9 $$ \mu \mathrm{g}_{\mathrm{NH}_{3}} \cdot \mathrm{mg}_{\text {cat.}}{}^{-1} \cdot \mathrm{h}^{-1} $$ for N₂ electrochemical reduction over Ru single-atom catalysts.Adv Mater2018;30:1803498

[20] Tao H,Ding LX.Nitrogen fixation by Ru single-atom electrocatalytic reduction.Chem2019;5:204-14

[21] Han Z,Zhang J.Single Ru-N₄ site-embedded porous carbons for electrocatalytic nitrogen reduction.ACS Appl Mater Interfaces2023;15:13025-32

[22] Nørskov JK,Hvolbaek B,Chorkendorff I.The nature of the active site in heterogeneous metal catalysis.Chem Soc Rev2008;37:2163-71

[23] Azofra LM,MacFarlane DR.Promising prospects for 2D d²-d⁴ M₃C₂ transition metal carbides (MXenes) in N₂ capture and conversion into ammonia.Energy Environ Sci2016;9:2545-9

[24] Choi C,Kim NY,Kim YH.Suppression of hydrogen evolution reaction in electrochemical N₂ reduction using single-atom catalysts: a computational guideline.ACS Catal2018;8:7517-25

[25] Skúlason E,Gudmundsdóttir S.A theoretical evaluation of possible transition metal electro-catalysts for N₂ reduction.Phys Chem Chem Phys2012;14:1235-45

[26] Liu L.Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles.Chem Rev2018;118:4981-5079 PMCID:PMC6061779

[27] Su P,Wang X.Exceptional electrochemical HER performance with enhanced electron transfer between Ru nanoparticles and single atoms dispersed on a carbon substrate.Angew Chem Int Ed Engl2021;60:16044-50

[28] Yang XF,Qiao B,Liu J.Single-atom catalysts: a new frontier in heterogeneous catalysis.Acc Chem Res2013;46:1740-8

[29] Lv X,Wang H,Dai Y.Holey graphitic carbon nitride (g-CN) supported bifunctional single atom electrocatalysts for highly efficient overall water splitting.Appl Catal B Environ2020;264:118521

[30] Zhao J.Single Mo atom supported on defective boron nitride monolayer as an efficient electrocatalyst for nitrogen fixation: a computational study.J Am Chem Soc2017;139:12480-7

[31] Zhao J,Cai Q.Single transition metal atom embedded into a MoS₂ nanosheet as a promising catalyst for electrochemical ammonia synthesis.Phys Chem Chem Phys2018;20:9248-55

[32] Chen Z,Cabrera CR.Computational screening of efficient single-atom catalysts based on graphitic carbon nitride (g-C₃N₄) for nitrogen electroreduction.Small Methods2019;3:1800368

[33] He T,Will G.Transition-metal single atoms anchored on graphdiyne as high-efficiency electrocatalysts for water splitting and oxygen reduction.Small Methods2019;3:1800419

[34] Liu Y,Fan X.Electrochemical reduction of N₂ to ammonia on Co single atom embedded N-doped porous carbon under ambient conditions.J Mater Chem A2019;7:26358-63

[35] Wang S,Lv X,Dai Y.W supported on g-CN manifests high activity and selectivity for N₂ electroreduction to NH₃.J Mater Chem A2020;8:1378-85

[36] Yu X,Xu W,Su Y.Core-packing-related vibrational properties of thiol-protected gold nanoclusters and their excited-state behavior.Inorg Chem2023;62:20450-7

[37] Zhao J,Zhou S.Endohedrally doped cage clusters.Chem Rev2020;120:9021-163

[38] Yu X,Xu W.Tuning photoelectron dynamic behavior of thiolate-protected MAu₂₄ nanoclusters via heteroatom substitution.Nanoscale Horiz2022;7:1192-200

[39] Yan H,Wu H.Bottom-up precise synthesis of stable platinum dimers on graphene.Nat Commun2017;8:1070 PMCID:PMC5715161

[40] Li G,Liu H,Li Y.Architecture of graphdiyne nanoscale films.Chem Commun2010;46:3256-8

[41] Tian S,Chen W.Carbon nitride supported Fe₂ cluster catalysts with superior performance for alkene epoxidation.Nat Commun2018;9:2353 PMCID:PMC6003949

[42] Ji S,Fu Q.Confined pyrolysis within metal-organic frameworks to form uniform Ru₃ clusters for efficient oxidation of alcohols.J Am Chem Soc2017;139:9795-8

[43] Pei W,Yu X.Graphitic carbon nitride supported trimeric metal clusters as electrocatalysts for N₂ reduction reaction.J Catal2024;429:115232

[44] Li Y,Li C.Atomically dispersed metal dimer species with selective catalytic activity for nitrogen electrochemical reduction.J Mater Chem A2019;7:22242-7

[45] Li H,Cai Q,Zhao J.Nitrogen electroreduction performance of transition metal dimers embedded into N-doped graphene: a theoretical prediction.J Mater Chem A2020;8:4533-43

[46] Zheng G,Tian Z,Chen L.Heterogeneous single-cluster catalysts (Mn₃, Fe₃, Co₃, and Mo₃) supported on nitrogen-doped graphene for robust electrochemical nitrogen reduction.J Energy Chem2021;54:612-9

[47] Cui C,Luo Z.Nitrogen reduction reaction on small iron clusters supported by N-doped graphene: a theoretical study of the atomically precise active-site mechanism.Nano Res2020;13:2280-8

[48] Li L.Design of a graphene nitrene two-dimensional catalyst providing a well-defined site accommodating up to three metals, with application to N₂ reduction electrocatalysis.Chem Commun2020;56:8960-3

[49] Kresse G.Ab initio molecular dynamics for liquid metals.Phys Rev B Condens Matter1993;47:558-61

[50] Kresse G.Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium.Phys Rev B Condens Matter1994;49:14251-69

[51] Kresse G.From ultrasoft pseudopotentials to the projector augmented-wave method.Phys Rev B1999;59:1758

[52] Blöchl PE.Projector augmented-wave method.Phys Rev B Condens Matter1994;50:17953-79

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

[54] Tian J,Xia W.Solar driven CO₂ hydrogenation to HCOOH on (TiO₂)_n (n = 1-6) atomic clusters.Phys Chem Chem Phys2023;25:28533-40

[55] 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

[56] Grimme S,Goerigk L.Effect of the damping function in dispersion corrected density functional theory.J Comput Chem2011;32:1456-65

[57] Monkhorst HJ.Special points for Brillouin-zone integrations.Phys Rev B1976;13:5188

[58] Peterson AA,Studt F,Nørskov JK.How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels.Energy Environ Sci2010;3:1311-5

[59] Peterson AA.Activity descriptors for CO₂ electroreduction to methane on transition-metal catalysts.J Phys Chem Lett2012;3:251-8

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

[61] Lv X,Huang B,Frauenheim T.High-throughput screening of synergistic transition metal dual-atom catalysts for efficient nitrogen fixation.Nano Lett2021;21:1871-8

[62] Zhou Y,Liang L.Unraveling the size-dependent effect of Ru-based catalysts on ammonia synthesis at mild conditions.J Catal2021;404:501-11

[63] Wang S,Bai X,Ling C.Highly efficient photo-/electrocatalytic reduction of nitrogen into ammonia by dual-metal sites.ACS Cent Sci2020;6:1762-71 PMCID:PMC7596869

[64] Ling C,Li Q,Wang J.Metal-free single atom catalyst for N₂ fixation driven by visible light.J Am Chem Soc2018;140:14161-8

[65] Hu R,Zeng Q,Shang J.Bimetallic pairs supported on graphene as efficient electrocatalysts for nitrogen fixation: search for the optimal coordination atoms.ChemSusChem2020;13:3636-44

[66] Pei W,Zhao J,Dou SX.Optimization of photocarrier dynamics and activity in phosphorene with intrinsic defects for nitrogen fixation.J Mater Chem A2020;8:20570-80

[67] Janesko BG.Replacing hybrid density functional theory: motivation and recent advances.Chem Soc Rev2021;50:8470-95

[68] Shinde R,Wong BM.Improved band gaps and structural properties from Wannier-Fermi-Löwdin self-interaction corrections for periodic systems.J Phys Condens Matter2021;33:115501

[69] Back S,Kim NY,Jung Y.Single-atom catalysts for CO₂ electroreduction with significant activity and selectivity improvements.Chem Sci2017;8:1090-6 PMCID:PMC5369399

[70] Li H,Yang X,Zhao J.Pt overlayer for direct oxidation of CH₄ to CH₃OH.Chinese Chem Lett2023;34:108292

[71] Zhou S,Du Q.Foreign atom encapsulated Au₁₂ golden cages for catalysis of CO oxidation.Phys Chem Chem Phys2019;21:10587-93

[72] Pei W,Yu X,Zhao J.Atomically precise gold nanoclusters for CO oxidation: balancing activity and stability by ligand shedding.J Phys D Appl Phys2023;56:445304

[73] Han B.Regulating the electrocatalytic performance for nitrogen reduction reaction by tuning the N contents in Fe₃@N_xC_20-x (x = 0~4): a DFT exploration.J Mater Inf2023;3:24

[74] Gu YT,Tao Q,Zhu Q.Machine learning for prediction of CO₂/N₂/H₂O selective adsorption and separation in metal-zeolites.J Mater Inf2023;3:19

[75] Hu Y,Wei Z,Zhao Y.Recent advances and applications of machine learning in electrocatalysis.J Mater Inf2023;3:18

[76] Sun Y,Xie M.Excitonic Au₄Ru₂(PPh₃)₂(SC₂H₄Ph)₈ cluster for light-driven dinitrogen fixation.Chem Sci2020;11:2440-7 PMCID:PMC8157179

[77] Zhou S,Zhao Y,Liu N.Low-dimensional non-metal catalysts: principles for regulating p-orbital-dominated reactivity.npj Comput Mater2021;7:186