Alloyed single-atom catalysts for electro- and photo- catalytic water splitting

Abstract

Water splitting by using renewable energy to produce hydrogen and oxygen can be regarded as one of the most promising approaches for sustainable energy conversion. Developing cost-effective and high-performance water splitting catalysts plays an increasingly important role in enhancing overall efficiency. Alloyed single-atom catalysts (alloyed SACs, also known as single-atom alloy), with one of the metal atoms atomically dispersed in a host metal, combine the advantages of both SACs and traditional metal alloys. They show the maximum utilization of active metal atoms and uniquely geometric and electronic structures, offering great potential in reducing the cost of catalyst and boosting the performance in catalytic water splitting. This review aims to provide a comprehensive summary of the development of alloyed SACs for oxygen and hydrogen evolution reactions by water splitting. We start with a brief introduction of the mechanism for water splitting under electrocatalytic and photocatalytic conditions, followed by emphasizing the merits of the formation of alloyed SACs for water splitting. Then, the case studies of electro- and photo- catalytic hydrogen and oxygen evolution via water splitting are illustrated and discussed. Finally, challenges and prospects are provided, with further continued efforts expected for achieving future exciting progress in tailoring the active sites for designing high-performance catalysts.

Keywords

Alloyed single-atom catalyst / photocatalysis / electrocatalysis / water splitting / oxygen evolution reaction / hydrogen evolution reaction

References

[1] Miao L,Cao X.Computational chemistry for water-splitting electrocatalysis.Chem Soc Rev2024;53:2771-807

[2] Wei S,Tukker A,Steubing B.Future environmental impacts of global hydrogen production.Energy Environ Sci2024;17:2157-72

[3] Zhao L,Liang S,Fu J.Coordination anchoring synthesis of high-density single-metal-atom sites for electrocatalysis.Coord Chem Rev2022;466:214603

[4] Nakaya Y.Catalysis of alloys: classification, principles, and design for a variety of materials and reactions.Chem Rev2023;123:5859-947

[5] Liu L.Bimetallic sites for catalysis: from binuclear metal sites to bimetallic nanoclusters and nanoparticles.Chem Rev2023;123:4855-933 PMCID:PMC10141355

[6] Yun Q,Li C.Synthesis of PdM (M = Zn, Cd, ZnCd) nanosheets with an unconventional face-centered tetragonal phase as highly efficient electrocatalysts for ethanol oxidation.ACS Nano2019;13:14329-36

[7] Zhang Z,Cui X.Crystal phase and architecture engineering of lotus-thalamus-shaped Pt-Ni anisotropic superstructures for highly efficient electrochemical hydrogen evolution.Adv Mater2018;30:1801741

[8] Zhu J,Lyu Z.Facet-controlled Pt–Ir nanocrystals with substantially enhanced activity and durability towards oxygen reduction.Mater Today2020;35:69-77

[9] Kyriakou G,Jewell AD.Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations.Science2012;335:1209-12

[10] Hannagan RT,Flytzani-Stephanopoulos M.Single-atom alloy catalysis.Chem Rev2020;120:12044-88

[11] Mao J,Pei J,Li Y.Single atom alloy: an emerging atomic site material for catalytic applications.Nano Today2020;34:100917

[12] Zhang T,Yu J.Single-atom alloy catalysts: structural analysis, electronic properties and catalytic activities.Chem Soc Rev2021;50:569-88

[13] Sun X,Jiang G,Xu C.Fundamentals and catalytic applications of single-atom alloys.Sci China Mater2024;67:1-17

[14] Pei G,Chai M,Zhang T.Isolation of Pd atoms by Cu for semi-hydrogenation of acetylene: effects of Cu loading.Chin J Catal2017;38:1540-8

[15] Pei GX,Yang X.Performance of Cu-alloyed Pd single-atom catalyst for semihydrogenation of acetylene under simulated front-end conditions.ACS Catal2017;7:1491-500

[16] Pei GX,Wang A.Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene.ACS Catal2015;5:3717-25

[17] Pei GX,Wang A.Promotional effect of Pd single atoms on Au nanoparticles supported on silica for the selective hydrogenation of acetylene in excess ethylene.New J Chem2014;38:2043

[18] Shen T,Zhao T,Wang D.Recent advances of single-atom-alloy for energy electrocatalysis.Adv Energy Mater2022;12:2201823

[19] Da Y,Tian Z,Chen W.The applications of single-atom alloys in electrocatalysis: progress and challenges.SmartMat2023;4:e1136

[20] Zhuang J.Recent advances of single-atom alloy catalyst: properties, synthetic methods and electrocatalytic applications.Mater Today Catal2023;2:100009

[21] Gao Q,Liu Y.Electrifying energy and chemical transformations with single-atom alloy nanoparticle catalysts.ACS Catal2024;14:6045-61 PMCID:PMC11036398

[22] Ahmed M,Zhao Y.Bridging together theoretical and experimental perspectives in single-atom alloys for electrochemical ammonia production.Small2024;20:2308084

[23] Gao Q,Pillai HS.Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia.Nat Synth2023;2:624-34

[24] Cao Y,Bo S.Single atom Bi decorated copper alloy enables C-C coupling for electrocatalytic reduction of CO₂ into C₂₊ products.Angew Chem Int Ed Engl2023;62:202303048

[25] Wang J,Xiao Y.Manipulating the water dissociation electrocatalytic sites of bimetallic nickel-based alloys for highly efficient alkaline hydrogen evolution.Angew Chem Int Ed Engl2022;61:202202518

[26] Wang H,Hofmann JP,Oropeza FE.The electronic structure of transition metal oxides for oxygen evolution reaction.J Mater Chem A2021;9:19465-88

[27] Hansen JN,Toudahl KK.Is there anything better than Pt for HER?.ACS Energy Lett2021;6:1175-80 PMCID:PMC8155388

[28] Zhu J,Zhao P,Wong KY.Recent advances in electrocatalytic hydrogen evolution using nanoparticles.Chem Rev2020;120:851-918

[29] Zhang, Z.; Yates, J. T. Jr. Band bending in semiconductors: chemical and physical consequences at surfaces and interfaces.Chem Rev2012;112:5520-51

[30] Ding C,Wang Z.Photoelectrocatalytic water splitting: significance of cocatalysts, electrolyte, and interfaces.ACS Catal2017;7:675-88

[31] 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

[32] Mao J,Pei J.Accelerating water dissociation kinetics by isolating cobalt atoms into ruthenium lattice.Nat Commun2018;9:4958 PMCID:PMC6251903

[33] Greiner MT,Beeg S.Free-atom-like d states in single-atom alloy catalysts.Nat Chem2018;10:1008-15

[34] Lee J,Yang T.Stabilizing the OOH^* intermediate via pre-adsorbed surface oxygen of a single Ru atom-bimetallic alloy for ultralow overpotential oxygen generation.Energy Environ Sci2020;13:5152-64

[35] Li M,Wan C.Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional electrocatalysis.Nat Catal2019;2:495-503

[36] Zhu Y,Bu L.Single-atom in-doped subnanometer Pt nanowires for simultaneous hydrogen generation and biomass upgrading.Adv Funct Mater2020;30:2004310

[37] Zeng L,Huang Q.Single-atom Cr-N₄ sites with high oxophilicity interfaced with Pt atomic clusters for practical alkaline hydrogen evolution catalysis.J Am Chem Soc2023;145:21432-41

[38] Ding J,Li Y.Monoatomic platinum-embedded hexagonal close-packed nickel anisotropic superstructures as highly efficient hydrogen evolution catalyst.Nano Lett2021;21:9381-7

[39] Huo L,Tang J.Ultrathin NiPt single-atom alloy for synergistically accelerating alkaline hydrogen evolution.ACS Appl Energy Mater2022;5:15136-45

[40] Luo M,Zou J,Wang G.Promoted alkaline hydrogen evolution by an N-doped Pt–Ru single atom alloy.J Mater Chem A2021;9:14941-7

[41] Zhang L,Liu S.Pt/Pd single-atom alloys as highly active electrochemical catalysts and the origin of enhanced activity.ACS Catal2019;9:9350-8

[42] Chen C,Li Z.Ruthenium-based single-atom alloy with high electrocatalytic activity for hydrogen evolution.Adv Energy Mater2019;9:1803913

[43] Tong Y,Wang L.Carbon-shielded single-atom alloy material family for multi-functional electrocatalysis.Adv Funct Mater2022;32:2205654

[44] Wang B,Li D.Single atom iridium decorated nickel alloys supported on segregated MoO₂ for alkaline water electrolysis.Adv Mater2024;36:e2305437

[45] Zhou C,Liu PF.Towards the object-oriented design of active hydrogen evolution catalysts on single-atom alloys.Chem Sci2021;12:10634-42 PMCID:PMC8356813

[46] Yang S,Li G.Single cobalt atoms immobilized on palladium-based nanosheets as 2D single-atom alloy for efficient hydrogen evolution reaction.Small2023;19:e2207651

[47] Jin R,Sharma S,Du X.Toward active-site tailoring in heterogeneous catalysis by atomically precise metal nanoclusters with crystallographic structures.Chem Rev2021;121:567-648

[48] Walsh AG.Thiolate-protected single-atom alloy nanoclusters: correlation between electronic properties and catalytic activities.Adv Mater Inter2021;8:2001342

[49] Kumar B,Shimizu N.Gold nanoclusters as electrocatalysts: size, ligands, heteroatom doping, and charge dependences.Nanoscale2020;12:9969-79

[50] Kwak K,Tang Q.A molecule-like PtAu₂₄(SC₆H₁₃)₁₈ nanocluster as an electrocatalyst for hydrogen production.Nat Commun2017;8:14723 PMCID:PMC5353570

[51] Kwak K,Tang Q,Lee D.Rationally designed metal nanocluster for electrocatalytic hydrogen production from water.J Mater Chem A2018;6:19495-501

[52] Li X,Tsukuda T.Ligand effects on the hydrogen evolution reaction catalyzed by Au₁₃ and Pt@Au₁₂: alkynyl vs thiolate.J Phys Chem C2021;125:23226-30

[53] Hu G,Lee D,Jiang D.Metallic hydrogen in atomically precise gold nanoclusters.Chem Mater2017;29:4840-7

[54] Choi W,Kwak K.Effects of metal-doping on hydrogen evolution reaction catalyzed by MAu₂₄ and M₂Au₃₆ nanoclusters (M = Pt, Pd).ACS Appl Mater Interfaces2018;10:44645-53

[55] Jo Y,Kim M,Choi W.Promotion of alkaline hydrogen production via Ni-doping of atomically precise Ag nanoclusters.Bulletin Korean Chem Soc2021;42:1672-7

[56] Ding H,Chu W,Xie Y.Structural transformation of heterogeneous materials for electrocatalytic oxygen evolution reaction.Chem Rev2021;121:13174-212

[57] Luo X,Zhong H.Single-atom Ir-anchored 3D amorphous NiFe nanowire@nanosheets for boosted oxygen evolution reaction.ACS Appl Mater Interfaces2020;12:3539-46

[58] Babu DD,Anandhababu G.Atomic iridium@cobalt nanosheets for dinuclear tandem water oxidation.J Mater Chem A2019;7:8376-83

[59] Mu X,Liu X.High-entropy ultrathin amorphous metal–organic framework-stabilized Ru(Mo) dual-atom sites for water oxidation.ACS Energy Lett2024;9:5763-70

[60] Su L,Wang J.Pt–Cu interaction induced construction of single Pt sites for synchronous electron capture and transfer in photocatalysis.Adv Funct Mater2021;31:2104343

[61] Pan Y,Zheng X.Precise fabrication of single-atom alloy co-catalyst with optimal charge state for enhanced photocatalysis.Natl Sci Rev2021;8:nwaa224 PMCID:PMC8288370

[62] Du XL,Li YH.Isolation of single Pt atoms in a silver cluster: forming highly efficient silver-based cocatalysts for photocatalytic hydrogen evolution.Chem Commun2017;53:9402-5

[63] Zhang Y,Meng W,Meng S.Plasmon-induced water splitting on Ag-alloyed Pt single-atom catalysts.Front Chem2021;9:742794 PMCID:PMC8573343

[64] Kurashige W,Wakamatsu K.Atomic-level understanding of the effect of heteroatom doping of the cocatalyst on water-splitting activity in AuPd or AuPt alloy cluster-loaded BaLa₄Ti₄O₁₅.ACS Appl Energy Mater2019;2:4175-87

[65] Liu Y,Springer A.Correlating heteroatoms doping, electronic structures, and photocatalytic activities of single-atom-doped Ag₂₅(SR)₁₈ nanoclusters.Solar RRL2023;7:2201057