Investigation of dual atom doped single-layer MoS₂ for electrochemical reduction of carbon dioxide by first-principle calculations and machine-learning

Abstract

The exploration of efficient electrocatalysts for carbon dioxide reduction reaction (CO₂RR) with viable activity and superior selectivity remains a great challenge. The efficiency of CO₂RR over traditional transition metal-based catalysts is restricted by their inherent scaling relationships, so breaking this scaling relationship is the key to improving the catalytic performance. In this work, inspired by the recent experimental progress in the synthesis of dual atom catalysts (DACs), we reported a rational design of novel DACs with two transition metal atoms embedded in defective MoS₂ with S vacancies for CO₂ reduction; 21 metal dimer systems were selected, including six homonuclear catalysts (MoS₂-M₂, M = Cu, Fe, Ni, Mn, Cr, Co) and 15 heteronuclear catalysts (MoS₂-M₁M₂). First-principles calculations showed that the MoS₂-NiCr system not only breaks the linear relationship of key intermediates but also possesses a low overpotential of 0.58 V and superior selectivity in the process of methane generation, which can be used as a promising catalyst for methane formation from CO₂ electroreduction. Notably, by combining random forest regression machine learning study, we found that the CO₂RR activity of DACs is essentially controlled by some fundamental factors, such as the distance between metal centers and the number of outer electrons in the metal atoms. Our findings provide profound insights for the design of efficient DACs for CO₂RR.

Keywords

Electrocatalysis / CO₂RR / dual atom catalysts / random forest regression

References

[1] Goeppert A,Surya Prakash GK.Air as the renewable carbon source of the future: an overview of CO₂ capture from the atmosphere.Energy Environ Sci2012;5:7833-53

[2] Ding M,Jiang HL.Carbon capture and conversion using metal-organic frameworks and MOF-based materials.Chem Soc Rev2019;48:2783-828

[3] Zhu DD,Qiao SZ.Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide.Adv Mater2016;28:3423-52

[4] Fan Q,Choi C.Activation of Ni particles into single Ni–N atoms for efficient electrochemical reduction of CO₂.Adv Energy Mater2020;10:1903068

[5] Yue Y,Tang C.Ranking the relative CO₂ electrochemical reduction activity in carbon materials.Carbon2019;154:108-14

[6] Ling C,Du A.Computation-aided design of single-atom catalysts for one-pot CO₂ capture, activation, and conversion.ACS Appl Mater Interfaces2018;10:36866-72

[7] Zhang X,Zhang X.Highly selective and active CO₂ reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures.Nat Commun2017;8:14675 PMCID:PMC5344970

[8] Low J,Yu J.Surface modification and enhanced photocatalytic CO₂ reduction performance of TiO₂: a review.Appl Surf Sci2017;392:658-86

[9] Wang D,Liu W,Li Z.Fe-based MOFs for photocatalytic CO₂ reduction: role of coordination unsaturated sites and dual excitation pathways.ACS Catal2014;4:4254-60

[10] Jin S,Zhang K,Chen J.Advances and challenges for the electrochemical reduction of CO₂ to CO: from fundamentals to industrialization.Angew Chem Int Ed Engl2021;133:20795-816

[11] Zheng T,Wang H.Recent advances in electrochemical CO₂-to-CO conversion on heterogeneous catalysts.Adv Mater2018;30:1802066

[12] Zhou H,Wu X,Li J.Coordination engineering in cobalt-nitrogen-functionalized materials for CO₂ reduction.J Phys Chem Lett2019;10:6551-7

[13] Ren W,Yang W.Isolated diatomic Ni-Fe metal-nitrogen sites for synergistic electroreduction of CO₂.Angew Chem Int Ed Engl2019;58:6972-6

[14] Li H,Dai Y.Synergetic interaction between neighbouring platinum monomers in CO₂ hydrogenation.Nat Nanotechnol2018;13:411-7

[15] Liang Z,Xia D,Xu Q.Atomically dispersed metal sites in MOF-based materials for electrocatalytic and photocatalytic energy conversion.Angew Chem Int Ed Engl2018;57:9604-33

[16] Yuan CZ,Liu SJ.Semi-sacrificial template synthesis of single-atom Ni sites supported on hollow carbon nanospheres for efficient and stable electrochemical CO₂ reduction.Inorg Chem Front2020;7:1719-25

[17] Han L,Liu M.Stable and efficient single-atom Zn catalyst for CO₂ reduction to CH₄.J Am Chem Soc2020;142:12563-7

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

[19] Chen Y,Chen C,Wang D.Single-atom catalysts: synthetic strategies and electrochemical applications.Joule2018;2:1242-64

[20] Wang Y,Meng X,Deng D.Catalysis with two-dimensional materials confining single atoms: concept, design, and applications.Chem Rev2019;119:1806-54

[21] Chen W,He CT.Rational design of single molybdenum atoms anchored on N-doped carbon for effective hydrogen evolution reaction.Angew Chem Int Ed Engl2017;129:16302-6

[22] Zhang H,Zhou W.Dynamic traction of lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction.Sci Adv2018;4:eaao6657 PMCID:PMC5775028

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

[24] Luo Z,Zhang H.Chemically activating MoS₂ via spontaneous atomic palladium interfacial doping towards efficient hydrogen evolution.Nat Commun2018;9:2120 PMCID:PMC5974284

[25] Tian S,Tang Y.Effect of adatom doping on the electrochemical performance of 1T'-MoS₂ for oxygen reduction reactions.J Phys Chem C2020;124:24899-907

[26] Tian S.Activating transition metal dichalcogenide monolayers as efficient electrocatalysts for the oxygen reduction reaction via single atom doping.J Mater Chem C2021;9:6040-50

[27] Chen Y,Tang Q.First-principles studies on electrocatalytic activity of novel two-dimensional MA₂Z₄ monolayers toward oxygen reduction reaction.J Phys Chem C2021;125:22581-90

[28] Han Y,Chen W.Hollow N-doped carbon spheres with isolated cobalt single atomic sites: superior electrocatalysts for oxygen reduction.J Am Chem Soc2017;139:17269-72

[29] Yang HB,Liu S.Atomically dispersed Ni(I) as the active site for electrochemical CO₂ reduction.Nat Energy2018;3:140-7

[30] Ma M,Tang Q.Coordination environment engineering on nickel single-atom catalysts for CO₂ electroreduction.Nanoscale2021;13:19133-43

[31] Raciti D.Recent advances in CO₂ reduction electrocatalysis on copper.ACS Energy Lett2018;3:1545-56

[32] Qing G,Jackowski ST.Recent advances and challenges of electrocatalytic N₂ reduction to ammonia.Chem Rev2020;120:5437-516

[33] Wu T,Xing Z.Greatly improving electrochemical N₂ reduction over TiO₂ nanoparticles by iron doping.Angew Chem Int Ed Engl2019;58:18449-53

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

[35] Liu JC,Li J.Constructing high-loading single-atom/cluster catalysts via an electrochemical potential window strategy.J Am Chem Soc2020;142:3375-83

[36] Hansen HA,Peterson AA.Understanding trends in the electrocatalytic activity of metals and enzymes for CO₂ reduction to CO.J Phys Chem Lett2013;4:388-92

[37] Calle-Vallejo F,Koper MT.Introducing structural sensitivity into adsorption-energy scaling relations by means of coordination numbers.Nat Chem2015;7:403-10

[38] Abild-Pedersen F,Studt F.Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces.Phys Rev Lett2007;99:016105

[39] Nørskov JK,Rossmeisl J.Towards the computational design of solid catalysts.Nat Chem2009;1:37-46

[40] Man IC,Calle-Vallejo F.Universality in oxygen evolution electrocatalysis on oxide surfaces.ChemCatChem2011;3:1159-65

[41] Yang Y,Li H.O-coordinated W-Mo dual-atom catalyst for pH-universal electrocatalytic hydrogen evolution.Sci Adv2020;6:eaba6586 PMCID:PMC7274769

[42] Guo X,Lin S,Chen Z.Tackling the activity and selectivity challenges of electrocatalysts toward the nitrogen reduction reaction via atomically dispersed biatom catalysts.J Am Chem Soc2020;142:5709-21

[43] Deng C,Li F,Chen Z.Understanding activity origin for the oxygen reduction reaction on bi-atom catalysts by DFT studies and machine-learning.J Mater Chem A2020;8:24563-71

[44] 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

[45] Li X,Cui P,Jiang J.Design of efficient catalysts with double transition metal atoms on C₂N layer.J Phys Chem Lett2016;7:1750-5

[46] Jiao J,Liu S.Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO₂.Nat Chem2019;11:222-8

[47] Cao N,Zang K.Doping strain induced bi-Ti³⁺ pairs for efficient N² activation and electrocatalytic fixation.Nat Commun2019;10:2877 PMCID:PMC6599206

[48] Li X,Xu J.Selective visible-light-driven photocatalytic CO₂ reduction to CH₄ mediated by atomically thin CuIn₅S₈ layers.Nat Energy2019;4:690-9

[49] Fu J,Si R.Synergistic effects for enhanced catalysis in a dual single-atom catalyst.ACS Catal2021;11:1952-61

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

[51] Zhao J,Li F.Copper dimer supported on a C₂N layer as an efficient electrocatalyst for CO₂ reduction reaction: a computational study.J Phys Chem C2018;122:19712-21

[52] Hunter MA,Yuan Q,Searles DJ.Evaluating the catalytic efficiency of paired, single-atom catalysts for the oxygen reduction reaction.ACS Catal2019;9:7660-7

[53] Chen X,Backes C,Mcdonald AR.Functionalization of two-dimensional MoS₂: on the reaction between MoS₂ and organic thiols.Angewandte Chemie2016;128:5897-902

[54] Kim IS,Jariwala D.Influence of stoichiometry on the optical and electrical properties of chemical vapor deposition derived MoS₂.ACS Nano2014;8:10551-8 PMCID:PMC4212723

[55] Tsai C,Park S.Electrochemical generation of sulfur vacancies in the basal plane of MoS₂ for hydrogen evolution.Nat Commun2017;8:15113 PMCID:PMC5530599

[56] Patra TK,Schulman DS.Defect dynamics in 2-D MoS₂ probed by using machine learning, atomistic simulations, and high-resolution microscopy.ACS Nano2018;12:8006-16

[57] Liu G,Li MM.MoS₂ monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction.Nat Chem2017;9:810-6

[58] Li H,Sawada H.Atomic structure and dynamics of single platinum atom interactions with monolayer MoS₂.ACS Nano2017;11:3392-403

[59] Li F.A di-boron pair doped MoS₂ (B2@MoS₂) single-layer shows superior catalytic performance for electrochemical nitrogen activation and reduction.Nanoscale2019;11:18769-78

[60] Delley B.An all-electron numerical method for solving the local density functional for polyatomic molecules.J Chem Phys1990;92:508-17

[61] Delley B.From molecules to solids with the DMol³ approach.J Chem Phys2000;113:7756-64

[62] Ernzerhof M.Assessment of the Perdew-Burke-Ernzerhof exchange-correlation functional.J Chem Phys1999;110:5029-36

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

[64] Keith JA,Jacob T.Theoretical investigations of the oxygen reduction reaction on Pt(111).Chemphyschem2010;11:2779-94

[65] Zhang P,Hou XL,Jiang Q.Layered SiC sheets: a potential catalyst for oxygen reduction reaction.Sci Rep2014;4:3821 PMCID:PMC3898266

[66] Klamt A.Conductor-like screening model for real solvents: a new approach to the quantitative calculation of solvation phenomena.J Phys Chem1995;99:2224-35

[67] Verma AM,Melander MM.Computational screening of doped graphene electrodes for alkaline CO₂ reduction.Front Energy Res2021;8:606742

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

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

[70] Shi C,Lausche AC.Trends in electrochemical CO₂ reduction activity for open and close-packed metal surfaces.Phys Chem Chem Phys2014;16:4720-7

[71] Ouyang Y,Bai X,Wang J.Breaking scaling relations for efficient CO₂ electrochemical reduction through dual-atom catalysts.Chem Sci2020;11:1807-13 PMCID:PMC8148381

[72] Wang S,Li J.High-throughput screening of nitrogen-coordinated bimetal catalysts for multielectron reduction of CO₂ to CH₄ with high selectivity and low limiting potential.J Phys Chem C2021;125:7155-65

[73] Zhang YJ,Michalsky R.Competition between CO₂ reduction and H₂ evolution on transition-metal electrocatalysts.ACS Catal2014;4:3742-8

[74] Chang X,Gong J.CO₂ photo-reduction: insights into CO₂ activation and reaction on surfaces of photocatalysts.Energy Environ Sci2016;9:2177-96

[75] Chen S,Morozov SI.Design of a graphene nitrene two-dimensional catalyst heterostructure providing a well-defined site accommodating one to three metals, with application to CO₂ reduction electrocatalysis for the two-metal case.J Phys Chem Lett2020;11:2541-9

[76] Breiman L.Random forests.Mach Learn2001;45:5-32

[77] Jiang Z,Hu C.Interlayer-confined nife dual atoms within MoS₂ electrocatalyst for ultra-efficient acidic overall water splitting (Adv. Mater. 32/2023).Adv Mater2023;35:2370227

[78] Zhao Z.Computational screening of near-surface alloys for CO₂ electroreduction.ACS Catal2018;8:3885-94

[79] Li H.Active-site computational screening: role of structural and compositional diversity for the electrochemical CO₂ reduction at Mo carbide catalysts.ACS Catal2020;10:11814-21

[80] Kour G,Du A.Computational screening of single-atom alloys TM@Ru(0001) for enhanced electrochemical nitrogen reduction reaction.J Mater Chem A2022;10:6204-15

[81] Liu S,Liu J.Computational screening of single-atom catalysts for direct electrochemical NH₃ synthesis from NO on defective boron phosphide monolayer.Appl Surf Sci2023;611:155764

[82] 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

[83] Zhao Z,Lu G.Computational discovery of nickel-based catalysts for CO₂ reduction to formic acid.J Phys Chem C2017;121:20865-70