Preparation of Fe, Co, Ni-based single atom catalysts and the progress of their application in electrocatalysis

Abstract

Single-atom catalysts (SACs) have garnered considerable attention owing to their profound potential in promoting the efficient utilization of metal resources and attaining atomic-level economy. Fe, Co, Ni SACs have demonstrated broad application prospects in electrocatalysis due to their tunable composition and structure, as well as their unique electronic properties. Firstly, the various preparation methods for Fe, Co, Ni SACs are outlined in this review, including high-temperature pyrolysis, impregnation, chemical vapor deposition, and atomic layer deposition. These methods not only enhance the utilization efficiency of metal atoms but also ensure the stability of the catalysts. Subsequently, this review summarizes the recent progress in the applications of Fe, Co, Ni SACs for electrocatalysis, with a particular focus on their efficacy in hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction. Despite remarkable advancements, Fe, Co, Ni SACs still face challenges related to large-scale production, stability enhancement, comprehensive characterization, and mechanistic exploration. Finally, this review discusses these challenges and proposes strategies to address them in order to fully realize the potential of Fe, Co, Ni SACs as high-performance catalysts.

Keywords

Single-atom catalyst / heterogeneous catalyst / atomic utilization rate / electrocatalysis / energy conversion

References

[1] Zhou A,Li Y.Hollow microstructural regulation of single-atom catalysts for optimized electrocatalytic performance.Microstructures2022;2:2022005

[2] Kendall M.Fuel cell development for new energy vehicles (NEVs) and clean air in China.Prog Nat Sci Mater Int2018;28:113-20

[3] Tarhan C.A study on hydrogen, the clean energy of the future: hydrogen storage methods.J Energy Storage2021;40:102676

[4] Zhao Y,Huang C.Oxygen evolution/reduction reaction catalysts: from in situ monitoring and reaction mechanisms to rational design.Chem Rev2023;123:6257-358

[5] Wu K,Cheng J.Defect engineering in transition-metal (Fe, Co, and Ni)-based electrocatalysts for water splitting.Carbon Energy2024;6:e485

[6] Verma J.Cost-effective electrocatalysts for hydrogen evolution reactions (HER): challenges and prospects.Int J Hydrogen Energy2022;47:38964-82

[7] Jin S,Zhang K,Chen J.Advances and challenges for the electrochemical reduction of CO₂ to CO: from fundamentals to industrialization.Angew Chem Int Ed2021;133:20795-816

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

[9] Zhang Y,Duan T.Interfacial engineering of heterogeneous catalysts for electrocatalysis.Mater Today2021;48:115-34

[10] Long X,Gao G.Graphitic phosphorus coordinated single Fe atoms for hydrogenative transformations.Nat Commun2020;11:4074 PMCID:PMC7426939

[11] Wu T,Xu ZJ.Size effects of electrocatalysts: more than a variation of surface area.ACS Nano2022;16:8531-9

[12] Wang H.A review on particle size effect in metal-catalyzed heterogeneous reactions.Chin J Chem2020;38:1422-44

[13] Yu X,Tao S.Single-atom Fe catalyst for catalytic ethane dehydrogenation to ethylene.ChemCatChem2023;15:e202201612

[14] Tong M,Xing G,Wang L.Potential dominates structural recombination of single atom Mn sites for promoting oxygen reduction reaction.Angew Chem Int Ed2023;62:e202314933

[15] Jia C,Zhao Y.Nitrogen vacancy induced coordinative reconstruction of single-atom Ni catalyst for efficient electrochemical CO₂ reduction.Adv Funct Materials2021;31:2107072

[16] Xu H,Cao D.Revisiting the universal principle for the rational design of single-atom electrocatalysts.Nat Catal2024;7:207-18

[17] Wu X,Zuo S.Engineering the coordination sphere of isolated active sites to explore the intrinsic activity in single-atom catalysts.Nanomicro Lett2021;13:136 PMCID:PMC8184907

[18] Liu H,Zhang Z.Atomic-level asymmetric tuning of the Co₁-N₃P₁ catalyst for highly efficient N-alkylation of amines with alcohols.J Am Chem Soc2024;146:20518-29

[19] Deng Z,Lin J.Rational design and energy catalytic application of high-loading single-atom catalysts.Rare Met2024;43:4844-66

[20] Guo W,Wang X.General design concept for single-atom catalysts toward heterogeneous catalysis.Adv Mater2021;33:e2004287

[21] Liang J,Yang X.Theoretical and experimental investigations on single-atom catalysis: Ir₁/FeO_x for CO oxidation.J Phys Chem C2014;118:21945-51

[22] Tian J,Yao X.Chemical vapor deposition towards atomically dispersed iron catalysts for efficient oxygen reduction.J Mater Chem A2023;11:5288-95

[23] Yan H,Wang D.Highly efficient CeO₂-supported noble-metal catalysts: from single atoms to nanoclusters.Chem Catalysis2022;2:1594-623

[24] Park SJ,Tran DT,Lee JH.Delaminated MBene sheets beyond usual 2D transition metal materials for securing Pt single atoms to boost hydrogen evolution.Energy Environ Sci2023;16:4093-104

[25] Tan H,Lin S,Chen HM.Dynamic coordination structure evolutions of atomically dispersed metal catalysts for electrocatalytic reactions.Adv Mater Inter2023;10:2202050

[26] Liu Y,Liu Y.Shear-strained Pd single-atom electrocatalysts for nitrate reduction to ammonia.Angew Chem Int Ed2024;63:e202411396

[27] Zhu Y,Koketsu T.Author correction: iridium single atoms incorporated in Co₃O₄ efficiently catalyze the oxygen evolution in acidic conditions.Nat Commun2024;15:1395 PMCID:PMC10869774

[28] Mochizuki C,Yasumura S.Defective NiO as a stabilizer for Au single-atom catalysts.ACS Catal2022;12:6149-58

[29] Shah K,Mateen M.Cobalt single atom incorporated in ruthenium oxide sphere: a robust bifunctional electrocatalyst for HER and OER.Angew Chem2022;61:e202114951

[30] Wang Y,Shang L.High-efficiency oxygen reduction to hydrogen peroxide catalyzed by nickel single-atom catalysts with tetradentate N₂O₂ coordination in a three-phase flow cell.Angew Chem Int Ed2020;59:13057-62

[31] Mosrati J,Vuong TH.Tiny species with big impact: high activity of Cu single atoms on CeO₂-TiO₂ deciphered by operando spectroscopy.ACS Catal2021;11:10933-49

[32] Wu Y,Zhai P.Triggering lattice oxygen activation of single-atomic Mo sites anchored on Ni-Fe oxyhydroxides nanoarrays for electrochemical water oxidation.Adv Mater2022;34:e2202523

[33] Zheng Y,Huang N,Xu Q.Recent advances in metal-organic framework-derived materials for electrocatalytic and photocatalytic CO₂ reduction.Coord Chem Rev2024;510:215858

[34] Gloag L,Gooding JJ.Co-catalytic metal-support interactions in single-atom electrocatalysts.Nat Rev Mater2024;9:173-89

[35] Chen Z,Zhao J.Stabilizing Pt single atoms through Pt-Se electron bridges on vacancy-enriched nickel selenide for efficient electrocatalytic hydrogen evolution.Angew Chem Int Ed2023;62:e202308686

[36] Jia C,Song S.Highly ordered hierarchical porous single-atom Fe catalyst with promoted mass transfer for efficient electroreduction of CO₂.Adv Energy Mater2023;13:2302007

[37] Liu J,Liu X.Direct observation of metal oxide nanoparticles being transformed into metal single atoms with oxygen-coordinated structure and high-loadings.Angew Chem Int Ed2021;60:15248-53

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

[39] Wang M,Li X.Atomically dispersed Fe-heteroatom (N, S) bridge sites anchored on carbon nanosheets for promoting oxygen reduction reaction.ACS Energy Lett2021;6:379-86

[40] Hao Y,Zeng WJ.Switching the oxygen evolution mechanism on atomically dispersed Ru for enhanced acidic reaction kinetics.J Am Chem Soc2023;145:23659-69

[41] Zhao L,Zhang X.Construction of ultrathin s-scheme heterojunctions of single Ni atom immobilized Ti-MOF and BiVO₄ for CO₂ photoconversion of nearly 100% to CO by pure water.Adv Mater2022;34:e2205303

[42] Cheng Y,Lai G.Edge-site Co-N_x model single-atom catalysts for CO₂ electroreduction.ACS Catal2024;14:8446-55

[43] Li Y,Xi S,Wang X.Synthesis of N-doped highly graphitic carbon urchin-like hollow structures loaded with single-Ni atoms towards efficient CO₂ electroreduction.Angew Chem Int Ed2022;61:e202201491

[44] Li BQ,Chen S.Framework-porphyrin-derived single-atom bifunctional oxygen electrocatalysts and their applications in Zn-air batteries.Adv Mater2019;31:e1900592

[45] Li Q,Xiao H.Fe isolated single atoms on S, N codoped carbon by copolymer pyrolysis strategy for highly efficient oxygen reduction reaction.Adv Mater2018;30:e1800588

[46] Lim JW,Cho JH.A MOF-derived pyrrolic N-stabilized Ni single atom catalyst for selective electrochemical reduction of CO₂ to CO at high current density.J Mater Chem A2024;12:11090-100

[47] Yang H,Yi X.Constructing highly utilizable Fe-N₄ single-atom sites by one-step gradient pyrolysis for electroreduction of O₂ and CO₂.Chem Eng J2022;440:135749

[48] Pan Y,Wu K.Regulating the coordination structure of single-atom Fe-N_xC_y catalytic sites for benzene oxidation.Nat Commun2019;10:4290 PMCID:PMC6753116

[49] Koshy DM,Lee DU.Understanding the origin of highly selective CO₂ electroreduction to CO on Ni,N-doped carbon catalysts.Angew Chem Int Ed2020;59:4043-50

[50] Lei J,Yin D.Boosting the loading of metal single atoms via a bioconcentration strategy.Small2020;16:e1905920

[51] Wei S,Zhang Q.Isolated iron single-atom sites for oxygen reduction derived from a porphyrin-based carbon sphere by a polymerization-coordination-pyrolysis strategy.J Mater Chem A2023;11:16314-20

[52] Wang J,Wang Y.Atomically dispersed metal-nitrogen-carbon catalysts with d-orbital electronic configuration-dependent selectivity for electrochemical CO₂-to-CO reduction.ACS Catal2023;13:2374-85

[53] Noh WY,Lee Y.Molecularly engineered carbon platform to anchor edge-hosted single-atomic M-N/C (M = Fe, Co, Ni, Cu) electrocatalysts of outstanding durability.ACS Catal2022;12:7994-8006

[54] Xu H,Zhang X.Atomically dispersed iron regulating electronic structure of iron atom clusters for electrocatalytic H₂O₂ Production and biomass upgrading.Angew Chem Int Ed2023;62:e202314414

[55] Shi B,Fu X.Fe Single-atom catalyst for cost-effective yet highly efficient heterogeneous fenton catalysis.ACS Appl Mater Interfaces2022;14:53767-76

[56] Tan H,Henzie J.Assembly of hollow carbon nanospheres on graphene nanosheets and greation of iron-nitrogen-doped porous carbon for oxygen reduction.ACS Nano2018;12:5674-83

[57] Min S,Xu X.Transition metal (Fe, Co, Ni)-doped cuprous oxide nanowire arrays as self-supporting catalysts for electrocatalytic CO₂ reduction reaction to ethylene.Appl Surf Sci2024;663:160150

[58] Wang J,Li Y.Facile synthesis of atomic Fe-N-C materials and dual roles investigation of Fe-N₄ sites in fenton-like reactions.Adv Sci2021;8:e2101824

[59] Yin S,Li G.Seizing gaseous Fe²⁺ to densify O₂-accessible Fe-N₄ sites for high-performance proton exchange membrane fuel cells.Energy Environ Sci2022;15:3033-40

[60] Yuan S,Hu L.Decarboxylation-induced defects in MOF-derived single cobalt atom@carbon electrocatalysts for efficient oxygen reduction.Angew Chem Int Ed2021;60:21685-90

[61] Zhao Y,Fan G,Gu X.Surface-exposed single-Ni atoms with potential-driven dynamic behaviors for highly efficient electrocatalytic oxygen evolution.Angew Chem Int Ed2022;61:e202212542

[62] Wang C,Soldemo M,Weissenrieder J.Inverse single-site Fe₁(OH)_x/Pt(111) model catalyst for preferential oxidation of CO in H₂.Nano Res2022;15:709-15

[63] Chaipornchalerm P,Mano P.Rational design of Fe single sites supported on hierarchical zeolites via atomic layer deposition for few-walled carbon nanotube production.ACS Appl Mater Interfaces2024;16:33590-600

[64] Zhang L,Li L.Single atom surface engineering: a new strategy to boost electrochemical activities of Pt catalysts.Nano Energy2022;93:106813

[65] Cao Y,Luo Q.Atomic-level insight into optimizing the hydrogen evolution pathway over a Co₁-N₄ single-site photocatalyst.Angew Chem Int Ed2017;56:12191-6

[66] Wang X,Zhou W.Iron single-atom catalysts confined in covalent organic frameworks for efficient oxygen evolution reaction.Cell Rep Phys Sci2022;3:100804

[67] Wang X,Jin Y,Ma L.Supported single Fe atoms prepared via atomic layer deposition for catalytic reactions.ACS Appl Nano Mater2020;3:2867-74

[68] Yan H,Guo N.Atomic engineering of high-density isolated Co atoms on graphene with proximal-atom controlled reaction selectivity.Nat Commun2018;9:3197 PMCID:PMC6107637

[69] Bu F,Yu Y.Boosting benzene oxidation with a spin-state-controlled nuclearity effect on iron sub-nanocatalysts.Angew Chem2023;62:e202216062

[70] Jin T,Gao Q.Pyrolysis-free, facile mechanochemical strategy toward cobalt single-atom/nitrogen-doped carbon for highly efficient water splitting.Chem Eng J2022;433:134089

[71] Zhao X,Lu Q.Electrocatalytic enhancement mechanism of cobalt single atoms anchored on different MXene substrates in oxygen and hydrogen evolution reactions.EcoMat2023;5:e12293

[72] Yang H,Zhang C.Carbon dioxide electroreduction on single-atom nickel decorated carbon membranes with industry compatible current densities.Nat Commun2020;11:593 PMCID:PMC6992760

[73] Gong F,Zhao Y.Back cover: universal sub-nanoreactor strategy for synthesis of yolk-shell MoS₂ supported single atom electrocatalysts toward robust hydrogen evolution reaction.Angew Chem Int Ed2023;62:e202308091

[74] Liu JC,Li J.Toward rational design of oxide-supported single-atom catalysts: atomic dispersion of gold on ceria.J Am Chem Soc2017;139:6190-9

[75] Lin L,Gao R.Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts.Nature2017;544:80-3

[76] Zhao Y,Lu XF,Gu X.Exposing single Ni atoms in hollow S/N-doped carbon macroporous fibers for highly efficient electrochemical oxygen evolution.Adv Mater2022;34:e2203442

[77] Kumar P,Zeraati AS.High-density cobalt single-atom catalysts for enhanced oxygen evolution reaction.J Am Chem Soc2023;145:8052-63

[78] Hou M,Zhao D.Microenvironment reconstitution of highly active Ni single atoms on oxygen-incorporated Mo₂C for water splitting.Nat Commun2024;15:1342 PMCID:PMC10864306

[79] Jasinski R.A new fuel cell cathode catalyst.Nature1964;201:1212-3

[80] Lin Y,Velasco E.Fabricating single-atom catalysts from chelating metal in open frameworks.Adv Mater2019;31:e1808193

[81] 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

[82] Jiang H,Jiao L.Ni single atoms anchored on N-doped carbon nanosheets as bifunctional electrocatalysts for urea-assisted rechargeable Zn-air batteries.Appl Catal B: Environ2022;310:121352

[83] Wroblowa HS,Razumney G.Electroreduction of oxygen: a new mechanistic criterion.J Electroanal Chem Interfacial Electrochem1976;69:195-201

[84] Ye C.Recent advances in the design of a high performance metal-nitrogen-carbon catalyst for the oxygen reduction reaction.J Mater Chem A2021;9:22218-47

[85] Kang Z,Wang D.Carbon-based single-atom catalysts: impacts of atomic coordination on the oxygen reduction reaction.Nanoscale2023;15:9605-34

[86] Jun S, Choi S, Kim J, Kwon KC, Park SH, Jang HW. Non-noble metal single atom catalysts for electrochemical energy conversion reactions.Chinese J Catal2023;50:195-214

[87] Liang Z,Cao R.Recent advances in Co-based electrocatalysts for the oxygen reduction reaction.Sustain Energy Fuels2020;4:3848-70

[88] Garba MD,Khan S.CO₂ towards fuels: a review of catalytic conversion of carbon dioxide to hydrocarbons.J Environ Chem Eng2021;9:104756

[89] Goyal N,Hu Y.Tailoring single-metal atom catalysts: a strategic defect engineering approach for electrochemical reduction reactions.J Mater Chem A2024;12:19685-719

[90] Tang T,Guan J.Optimizing the electrocatalytic selectivity of carbon dioxide reduction reaction by regulating the electronic structure of single-atom M-N-C materials.Adv Funct Mater2022;32:2111504

[91] Pei J,Mao J.A replacement strategy for regulating local environment of single-atom Co-S_xN_4-x catalysts to facilitate CO₂ electroreduction.Nat Commun2024;15:416

[92] Chen S,Kao CW.Unveiling the proton-feeding effect in sulfur-doped Fe-N-C single-atom catalyst for enhanced CO₂ electroreduction.Angew Chem Int Ed2022;61:e202206233

[93] Wen M,Jiao L,Jiang HL.Microwave-assisted rapid synthesis of MOF-based single-atom Ni catalyst for CO₂ electroreduction at ampere-level current.Angew Chem2024;63:e202318338

[94] Fan B,Liu Z,Yuan H.Recent progress in single atomic catalysts for electrochemical N₂ fixation.Microstructures2024;4:2024025

[95] Wang Q,Wang D.Defect engineering in earth-abundant electrocatalysts for CO₂ and N₂ reduction.Energy Environ Sci2019;12:1730-50

[96] Zhang R,Yang W,Jiang H.Single-atom catalysts templated by metal-organic frameworks for electrochemical nitrogen reduction.J Mater Chem A2019;7:26371-7

[97] Wu ZY,Yong X.Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst.Nat Commun2021;12:2870 PMCID:PMC8128876

[98] Langevelde PH, Katsounaros I, Koper MT. Electrocatalytic nitrate reduction for sustainable ammonia production.Joule2021;5:290-4

[99] Sathishkumar N,Chen H.Mechanistic exploring the catalytic activity of single-atom catalysts anchored in graphitic carbon nitride toward electroreduction of nitrate-to-ammonia.Appl Surf Sci2022;598:153829

[100] Zhang S,Shi T.Electrocatalytically active Fe-(O-C₂)₄ single-atom sites for efficient reduction of nitrogen to ammonia.Angew Chem Int Ed2020;59:13423-9

[101] Xu J,Liu H.Breaking local charge symmetry of iron single atoms for efficient electrocatalytic nitrate reduction to ammonia.Angew Chem Int Ed2023;62:e202308044