Design of efficient dual-atom catalysts for energy conversion

Abstract

Dual-atom catalysts (DACs) have triggered the burgeoning interest in the field of catalysis. The identification of coordination structures and the understanding of the catalytic role of dual-atom centers are of great significance to designing highly efficient DACs. This review summarizes the current synthesis methods for the construction of DACs. Then, we highlight the differences in geometric and electronic structures of DACs in terms of modulation strategies and engineering dual-metal interaction. In particular, the combination of various advanced characterizations and density functional theory (DFT) insights disclose the state of the dual-atom active center microenvironment. Moreover, the catalytic role of DACs in heterogeneous catalysis is discussed, involving the electronic effect of one metal as the main active center and the synergistic effect between dual metals. The structure-activity relationship and reaction mechanism based on experimental studies and theoretical exploration are discussed. Finally, the challenges and opportunities of DACs for the efficient valorization of energy-related small molecules are proposed. This review can offer new inspiration on developing DACs for energy conversion.

Keywords

Dual-atom catalysts / active structure / electronic interaction / synergistic effect / heterogeneous catalysis

References

[1] Zhang Q,Candelaria SL.Nanomaterials for energy conversion and storage.Chem Soc Rev2013;42:3127-71

[2] Falcone PM.Sustainable energy policies in developing countries: a review of challenges and opportunities.Energies2023;16:6682

[3] Chu S.Opportunities and challenges for a sustainable energy future.Nature2012;488:294-303

[4] Zhang F,Lin Q,Zhang X.Noble-metal single-atoms in thermocatalysis, electrocatalysis, and photocatalysis.Energy Environ Sci2021;14:2954-3009

[5] Ding S,Pérez-ramírez J.Transforming energy with single-atom catalysts.Joule2019;3:2897-929

[6] Liang J,Hwang S.Atomic arrangement engineering of metallic nanocrystals for energy-conversion electrocatalysis.Joule2019;3:956-91

[7] Luna P, Hahn C, Higgins D, Jaffer SA, Jaramillo TF, Sargent EH. What would it take for renewably powered electrosynthesis to displace petrochemical processes?.Science2019;364:eaav3506

[8] Dong C,Cheng D.Supported metal clusters: fabrication and application in heterogeneous catalysis.ACS Catal2020;10:11011-45

[9] Chen Y,Jia B,Jiang S.Isolating single and few atoms for enhanced catalysis.Adv Mater2022;34:e2201796

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

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

[12] Rong H,Zhang J,Li Y.Synthetic strategies of supported atomic clusters for heterogeneous catalysis.Nat Commun2020;11:5884 PMCID:PMC7674434

[13] Haruta M,Kobayashi T,Genet M.Low-temperature oxidation of CO over gold supported on TiO₂, α-Fe₂O₃, and Co₃O₄.J Catal1993;144:175-92

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

[15] Liu J.Catalysis by supported single metal atoms.ACS Catal2017;7:34-59

[16] Zhang H,Shi L.Single-atom catalysts: emerging multifunctional materials in heterogeneous catalysis.Adv Energy Mater2018;8:1701343

[17] Mitchell S,Pérez-Ramírez J.The multifaceted reactivity of single-atom heterogeneous catalysts.Angew Chem Int Ed2018;57:15316-29

[18] Kaiser SK,Faust Akl D,Pérez-Ramírez J.Single-atom catalysts across the periodic table.Chem Rev2020;120:11703-809

[19] Lang R,Huang Y.Single-atom catalysts based on the metal-oxide interaction.Chem Rev2020;120:11986-2043

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

[21] Mitchell S.Single atom catalysis: a decade of stunning progress and the promise for a bright future.Nat Commun2020;11:4302 PMCID:PMC7453014

[22] Wang A,Zhang T.Heterogeneous single-atom catalysis.Nat Rev Chem2018;2:65-81

[23] Liu P,Qin R.Photochemical route for synthesizing atomically dispersed palladium catalysts.Science2016;352:797-801

[24] Qiao B,Yang X.Single-atom catalysis of CO oxidation using Pt₁/FeO_x.Nat Chem2011;3:634-41

[25] Zhang J,Liu B.Coordination engineering of single-atom catalysts for the oxygen reduction reaction: a review.Adv Energy Mater2021;11:2002473

[26] Zhu Y,Song X,Mei Y.Single-atom catalysts: engineering local coordination environments of atomically dispersed and heteroatom-coordinated single metal site electrocatalysts for clean energy-conversion.Adv Energy Mater2020;10:1902844

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

[28] Sun T,Li J.Design of local atomic environments in single-atom electrocatalysts for renewable energy conversions.Adv Mater2021;33:e2003075

[29] Li X,Zhang J,Li Y.Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance.Nano Res2020;13:1842-55

[30] Lin J,Qiao B.Remarkable performance of Ir₁/FeO_x single-atom catalyst in water gas shift reaction.J Am Chem Soc2013;135:15314-7

[31] Resasco J,Dai S.Uniformity is key in defining structure-function relationships for atomically dispersed metal catalysts: the case of Pt/CeO₂.J Am Chem Soc2020;142:169-84

[32] Muravev V,Su Y.Interface dynamics of Pd-CeO₂ single-atom catalysts during CO oxidation.Nat Catal2021;4:469-78

[33] Peterson EJ,Lin S.Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina.Nat Commun2014;5:4885

[34] Wei H,Wang A.FeO_x-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes.Nat Commun2014;5:5634

[35] DeRita L,Dai S.Structural evolution of atomically dispersed Pt catalysts dictates reactivity.Nat Mater2019;18:746-51

[36] Li R.Superiority of dual-atom catalysts in electrocatalysis: one step further than single-atom catalysts.Adv Energy Mater2022;12:2103564

[37] Zhu P,Wang D.Advances and regulation strategies of the active moiety in dual-atom site catalysts for efficient electrocatalysis.Adv Energy Mater2023;13:2300884

[38] Lei L,Han X,Guo X.From synthesis to mechanisms: in-depth exploration of the dual-atom catalytic mechanisms toward oxygen electrocatalysis.Adv Mater2024;36:e2311434

[39] Zhang W,Zhang W.Emerging dual-atomic-site catalysts for efficient energy catalysis.Adv Mater2021;33:e2102576

[40] Chen Y,Pan Q,Ma T.Inter-metal interaction of dual-atom catalysts in heterogeneous catalysis.Angew Chem Int Ed2023;62:e202306469

[41] Yardimci D,Gates BC.Surface-mediated synthesis of dimeric rhodium catalysts on MgO: tracking changes in the nuclearity and ligand environment of the catalytically active sites by X-ray absorption and infrared spectroscopies.Chemistry2013;19:1235-45

[42] Wang J,Liu W.Design of N-coordinated dual-metal sites: a stable and active Pt-free catalyst for acidic oxygen reduction reaction.J Am Chem Soc2017;139:17281-4

[43] 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

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

[45] Gong YN,Shi WJ.Modulating the electronic structures of dual-atom catalysts via coordination environment engineering for boosting CO₂ electroreduction.Angew Chem Int Ed2022;61:e202215187

[46] Hai X,Yu Q.Geminal-atom catalysis for cross-coupling.Nature2023;622:754-60

[47] Dostagir NHM,Oshiro K.Mitigating the poisoning effect of formate during CO₂ hydrogenation to methanol over Co-containing dual-atom oxide catalysts.JACS Au2024;4:1048-58

[48] Zhang H,Lee JM.Tailoring of active sites from single to dual atom sites for highly efficient electrocatalysis.ACS Nano2022;16:17572-92 PMCID:PMC9706812

[49] Wong M,Loh JY.Leveraging dual-atom catalysts for electrocatalysis revitalization: exploring the structure-performance correlation.Adv Energy Mater2024;14:2303281

[50] Gao Y,Wang D.Microenvironment engineering of single/dual-atom catalysts for electrocatalytic application.Adv Mater2023;35:e2209654

[51] Li Y,Yang X,Wu G.Designing and engineering atomically dispersed metal catalysts for CO₂ to CO conversion: from single to dual metal sites.Angew Chem Int Ed2024;63:e202317884

[52] Pu T,Zhang F.Dual atom catalysts for energy and environmental applications.Angew Chem Int Ed2023;62:e202305964

[53] Tang T,Wang Z.Structural engineering of atomic catalysts for electrocatalysis.Chem Sci2024;15:5082-112 PMCID:PMC10988631

[54] Li Y,Sun H.Current status and perspectives of dual-atom catalysts towards sustainable energy utilization.Nano-Micro Lett2024;16:139 PMCID:PMC10904713

[55] Li H,Liu G,Yu J.Noble-metal-free single - and dual-atom catalysts for artificial photosynthesis.Adv Mater2024;36:e2301307

[56] Liu H,Zhang J.Synergetic dual-atom catalysts: the next boom of atomic catalysts.ChemSusChem2022;15:e202200498

[57] Zhang J,Wang J,Zhang JJ.Supported dual-atom catalysts: preparation, characterization, and potential applications.Chin J Catal2020;41:783-98

[58] Tang T,Guan J.Structural optimization of carbon-based diatomic catalysts towards advanced electrocatalysis.Coor Chem Rev2023;492:215288

[59] Zhang T,Xue L,Xiong P.Engineering of geometrical configurations in dual-atom catalysts for electrocatalytic applications.J Energy Chem2024;94:273-87

[60] Zhang S,Zhang Y.Dual-atom catalysts: controllable synthesis and electrocatalytic applications.Sci China Chem2021;64:1908-22

[61] George SM.Atomic layer deposition: an overview.Chem Rev2010;110:111-31

[62] O’neill BJ,Lee J.Catalyst design with atomic layer deposition.ACS Catal2015;5:1804-25

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

[64] Chen S,Gu J.Dehydrogenation of ammonia borane by platinum-nickel dimers: regulation of heteroatom interspace boosts bifunctional synergetic catalysis.Angew Chem Int Ed2022;61:e202211919

[65] Li Y,Cao R,He H.Dual-atom Ag₂/graphene catalyst for efficient electroreduction of CO₂ to CO.Appl Catal B: Environ2020;268:118747

[66] Xie P,Yao Z.Oxo dicopper anchored on carbon nitride for selective oxidation of methane.Nat Commun2022;13:1375 PMCID:PMC8927601

[67] Ding T,Tao Z.Atomically precise dinuclear site active toward electrocatalytic CO₂ reduction.J Am Chem Soc2021;143:11317-24

[68] Liang X,Zhang C,Lu T.Controlled synthesis of a Ni₂ dual-atom catalyst for synergistic CO₂ electroreduction.Appl Catal B: Environ2023;322:122073

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

[70] Zhang N,Kang Y.A supported Pd₂ dual-atom site catalyst for efficient electrochemical CO₂ reduction.Angew Chem Int Ed2021;60:13388-93

[71] Yu Z,Diaconescu VM.Atomically dispersed dinuclear iridium active sites for efficient and stable electrocatalytic chlorine evolution reaction.Chem Sci2024;15:9216-23 PMCID:PMC11186302

[72] Guan E,Vasiliu M,Dixon DA.MgO-supported iridium metal pair-site catalysts are more active and resistant to CO poisoning than analogous single-site catalysts for ethylene hydrogenation and hydrogen-deuterium exchange.ACS Catal2019;9:9545-53

[73] Gong Q,Ren X,Liu J.Ultra-low-loaded Ni-Fe dimer anchored to nitrogen/oxygen sites for boosting electroreduction of carbon dioxide.ChemSusChem2021;14:4499-506

[74] Wang Y,Liu J.Catalysis stability enhancement of Fe/Co dual-atom site via phosphorus coordination for proton exchange membrane fuel cell.Nano Res2022;15:3082-9

[75] Wang C,Feng Y.Co and Pt dual-single-atoms with oxygen-coordinated Co-O-Pt dimer sites for ultrahigh photocatalytic hydrogen evolution efficiency.Adv Mater2021;33:e2003327

[76] Hou C,Li C.From metal-organic frameworks to single/dual-atom and cluster metal catalysts for energy applications.Energy Environ Sci2020;13:1658-93

[77] Liu J,Guo C,Qiao S.Design strategies toward advanced MOF-derived electrocatalysts for energy-conversion reactions.Adv Energy Mater2017;7:1700518

[78] Zhu Z,Chen S.Metal-organic framework (MOF)-based clean energy conversion: recent advances in unlocking its underlying mechanisms.Small2024;20:e2309119

[79] Lu Z,Hu Y.An isolated zinc-cobalt atomic pair for highly active and durable oxygen reduction.Angew Chem Int Ed2019;58:2622-6

[80] Li R,Liang X.Polystyrene waste thermochemical hydrogenation to ethylbenzene by a N-bridged Co, Ni dual-atom catalyst.J Am Chem Soc2023;145:16218-27

[81] Li M,Yuan Q.Proximity electronic effect of Ni/Co diatomic sites for synergistic promotion of electrocatalytic oxygen reduction and hydrogen evolution.Adv Funct Mater2023;33:2210867

[82] Ren W,Yang W.Isolated diatomic Ni-Fe metal-nitrogen sites for synergistic electroreduction of CO₂.Angew Chem Int Ed2019;58:6972-6

[83] Li Y,Zachman MJ.Atomically dispersed dual-metal site catalysts for enhanced CO₂ reduction: mechanistic insight into active site structures.Angew Chem Int Ed2022;61:e202205632

[84] Liu M,Cao S.A “pre-constrained metal twins” strategy to prepare efficient dual-metal-atom catalysts for cooperative oxygen electrocatalysis.Adv Mater2022;34:e2107421

[85] Yang X,Liu M,Xu Q.Confined synthesis of dual-atoms within pores of covalent organic frameworks for oxygen reduction reaction.Small2024;20:e2306295

[86] Yao Y,Yang Y.Mn-Co dual sites relay activation of peroxymonosulfate for accelerated decontamination.Appl Catal B: Environ2023;330:122656

[87] Zhang YX,Huang H.General synthesis of a diatomic catalyst library via a macrocyclic precursor-mediated approach.J Am Chem Soc2023;145:4819-27

[88] Leng K,Wang Y.Interfacial cladding engineering suppresses atomic thermal migration to fabricate well-defined dual-atom electrocatalysts.Adv Funct Mater2022;32:2205637

[89] Jones J,DeLaRiva AT.Thermally stable single-atom platinum-on-ceria catalysts via atom trapping.Science2016;353:150-4

[90] Zhou X,Li K.Dual-site single-atom catalysts with high performance for three-way catalysis.Adv Mater2022;34:e2201859

[91] Pu T,Tang X.Rational design of precious-metal single-atom catalysts for methane combustion.ACS Appl Mater Interfaces2022;14:43141-50

[92] Meier M,Jakub Z.CO oxidation by Pt₂/Fe₃O₄: metastable dimer and support configurations facilitate lattice oxygen extraction.Sci Adv2022;8:eabn4580

[93] Moges EA,Huang W.Sustainable synthesis of dual single-atom catalyst of Pd-N₄/Cu-N₄ for partial oxidation of ethylene glycol.Adv Funct Mater2022;32:2206887

[94] Han A,Tang K.An adjacent atomic platinum site enables single-atom iron with high oxygen reduction reaction performance.Angew Chem Int Ed2021;60:19262-71

[95] Jiao L,Zhang Y.Non-bonding interaction of neighboring Fe and Ni single-atom pairs on MOF-derived N-doped carbon for enhanced CO₂ electroreduction.J Am Chem Soc2021;143:19417-24

[96] Zhao X,Kong XP,Li Y.Dual-metal hetero-single-atoms with different coordination for efficient synergistic catalysis.J Am Chem Soc2021;143:16068-77

[97] Chen Y,Zhou C.Hierarchical dual single-atom catalysts with coupled CoN₄ and NiN₄ moieties for industrial-level CO₂ electroreduction to syngas.ACS Nano2023;17:22095-105

[98] Cui T,Ye T.Engineering dual single-atom sites on 2D ultrathin N-doped carbon nanosheets attaining ultra-low-temperature zinc-air battery.Angew Chem Int Ed2022;61:e202115219

[99] Chen Y,Pan X.Tuning the inter-metal interaction between Ni and Fe atoms in dual-atom catalysts to boost CO₂ electroreduction.Angew Chem Int Ed2024;63:e202411543

[100] Zhao C,Yang Y.Development of synergistically efficient Ni-Co pair catalytic sites for enhanced polysulfide conversion in lithium-sulfur batteries.Adv Funct Mater2024;34:2402175

[101] Chai Y,Chen Y.Dual-atom catalyst with N-colligated Zn₁Co₁ species as dominant active sites for propane dehydrogenation.J Am Chem Soc2024;146:263-73

[102] Wang D,Tu X.Oxygen-bridged copper-iron atomic pair as dual-metal active sites for boosting electrocatalytic NO reduction.Adv Mater2023;35:e2304646

[103] Sun Z,Wei Z.Sulfur-bridged asymmetric CuNi bimetallic atom sites for CO₂ reduction with high efficiency.Adv Mater2024;36:e2404665

[104] Han X,Yu D.Atomically dispersed binary Co-Ni sites in nitrogen-doped hollow carbon nanocubes for reversible oxygen reduction and evolution.Adv Mater2019;31:e1905622

[105] Liu W,Ou P.Isolated Cu-Sn diatomic sites for enhanced electroreduction of CO₂ to CO.Nano Res2023;16:8729-36

[106] Yue Y,Jin C.Tailoring Cu-Zn dual-atom sites with reordering d-orbital splitting manner for highly efficient acetylene semihydrogenation.ACS Catal2024;14:3900-11

[107] Zhu J,Ren D.Quasi-covalently coupled Ni-Cu atomic pair for synergistic electroreduction of CO₂.J Am Chem Soc2022;144:9661-71

[108] Wang X,Guo S.p-d Orbital hybridization induced by asymmetrical FeSn dual atom sites promotes the oxygen reduction reaction.J Am Chem Soc2024;146:21357-66

[109] Wang D,Yang P.Fe-N₄ and Co-N₄ dual sites for boosting oxygen electroreduction in Zn-air batteries.J Mater Chem A2021;9:13678-87

[110] Yang H,Wang Q,Zhang T.Fe, Cu dual-metal single atom catalyst on commercial carbon black for efficient oxygen reduction reaction.J Mater Chem A2023;11:6191-7

[111] Tamtaji M,Liu T.Non-bonding interaction of dual atom catalysts for enhanced oxygen reduction reaction.Nano Energy2023;108:108218

[112] Tong M,Xie Y.Operando cooperated catalytic mechanism of atomically dispersed Cu-N₄ and Zn-N₄ for promoting oxygen reduction reaction.Angew Chem Int Ed2021;60:14005-12

[113] Meng L,Peng H.Bi/Zn dual single-atom catalysts for electroreduction of CO₂ to syngas.ChemCatChem2022;14:e202101801

[114] Chen C,Zhang F.Adjacent Fe Site boosts electrocatalytic oxygen evolution at Co site in single-atom-catalyst through a dual-metal-site design.Energy Environ Sci2023;16:1685-96

[115] Zhang Y,Zhang P,Ran J.Reversed electron transfer in dual single atom catalyst for boosted photoreduction of CO₂.Adv Mater2023;35:e2306923

[116] Yang G,Yuan P.Regulating Fe-spin state by atomically dispersed Mn-N in Fe-N-C catalysts with high oxygen reduction activity.Nat Commun2021;12:1734 PMCID:PMC7979714

[117] Zhou Y,Utetiwabo W.Revealing of active sites and catalytic mechanism in N-coordinated Fe, Ni dual-doped carbon with superior acidic oxygen reduction than single-atom catalyst.J Phys Chem Lett2020;11:1404-10

[118] Wang Y,Yan Y.Tailoring the d-band center of Ni on a dual-single-atom Ni-ZnNC catalyst for efficient H₂O₂ production.Mater Today Energy2023;38:101459

[119] Cheng H,Feng M.Atomically dispersed Ni/Cu dual sites for boosting the CO₂ reduction reaction.ACS Catal2021;11:12673-81

[120] Wang Y,Dong F.N-coordinated Cu-Ni dual-single-atom catalyst for highly selective electrocatalytic reduction of nitrate to ammonia.Small2023;19:e2207695

[121] Qiao J,Kong L.Precisely constructing orbital-coupled Fe-Co dual-atom sites for high-energy-efficiency Zn-Air/iodide hybrid batteries.Adv Mater2024;36:e2405533

[122] Chen Y,Zhou H.Coordination shell dependent activity of CuCo diatomic catalysts for oxygen reduction, oxygen evolution, and hydrogen evolution reaction.Adv Funct Mater2024;34:2311664

[123] Bi Z,Xu M,Zhou Y.Nitrogen-bridged Fe-Cu atomic pair sites for efficient electrochemical ammonia production and electricity generation with Zn-NO₂ batteries.Angew Chem Int Ed2024;63:e202313434

[124] Fan Z,Zhang Y.Oxygen-bridged indium-nickel atomic pair as dual-metal active sites enabling synergistic electrocatalytic CO₂ reduction.Angew Chem Int Ed2023;62:e202216326

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

[126] Mun Y,Kim K.Versatile strategy for tuning ORR activity of a single Fe-N₄ site by controlling electron-withdrawing/donating properties of a carbon plane.J Am Chem Soc2019;141:6254-62

[127] Zhou X,Huang GX.Identification of fenton-like active Cu sites by heteroatom modulation of electronic density.Proc Natl Acad Sci USA2022;119 PMCID:PMC8872710

[128] Yang Q,Li G.Chlorine bridge bond-enabled binuclear copper complex for electrocatalyzing lithium-sulfur reactions.Nat Commun2024;15:3231

[129] Wang JM,Lee JH.Asymmetric gradient orbital interaction of hetero-diatomic active sites for promoting C - C coupling.Nat Commun2023;14:3808

[130] Zhai S,Sun L.Heteronuclear dual single-atom catalysts for ambient conversion of CO₂ from air to formate.ACS Catal2023;13:3915-24

[131] Xiao M,Li S.3d-Orbital occupancy regulated Ir-Co atomic pair toward superior bifunctional oxygen electrocatalysis.ACS Catal2021;11:8837-46

[132] Zhang L,Li L,Su J.Enhanced oxygen reduction activity and stability of double-layer nitrogen-doped carbon catalyst with abundant Fe-Co dual-atom sites.Nano Energy2023;117:108854

[133] Shu Z,Liu X,Yan H.High-throughput screening of heterogeneous transition metal dual-atom catalysts by synergistic effect for nitrate reduction to ammonia.Adv Funct Mater2023;33:2301493

[134] Yu D,Hu F.Dual-sites coordination engineering of single atom catalysts for flexible metal-air batteries.Adv Energy Mater2021;11:2101242

[135] Song C,Zeng Z.Isolated diatomic Zn-Co metal-nitrogen/oxygen sites with synergistic effect on fast catalytic kinetics of sulfur species in Li-S battery.J Energy Chem2023;79:505-14

[136] Zhang Y,Fan L.Dual-atoms iron sites boost the kinetics of reversible conversion of polysulfide for high-performance lithium-sulfur batteries.Energy Storage Mater2023;63:103026

[137] Zhang S,Ma L.Constructing orbital coupling-modulated homogeneous dual-atom Fe-Fe sites for boosting bidirectional conversion of polysulfides.ACS Appl Mater Inter2024;16:33527-38

[138] Cao X,Wulan B.Atomic bridging structure of nickel-nitrogen-carbon for highly efficient electrocatalytic reduction of CO₂.Angew Chem Int Ed2022;61:e202113918

[139] Xu W,Zhang C.Insights into the electronic structure coupling effect of dual-metal atomic electrocatalytic platform for efficient clean energy conversion.Chem Eng J2023;461:141911

[140] Norskov JK.Electronic factors in catalysis.Prog Surf Sci1991;38:103-44

[141] Hao J,Hao J.Interatomic electronegativity offset dictates selectivity when catalyzing the CO₂ reduction reaction.Adv Energy Mater2022;12:2200579

[142] Yao D,Zhi X.Inter-metal interaction with a threshold effect in NiCu dual-atom catalysts for CO₂ electroreduction.Adv Mater2023;35:e2209386

[143] Zhang L,Liu S.Atomically dispersed Ni-Cu catalysts for pH-universal CO₂ electroreduction.Adv Mater2023;35:e2209590

[144] Li Z,Wang J.Asymmetric coordination of heterogeneous Fe-Se dual-atom sites boosts CO₂ electroreduction.Adv Funct Mater

[145] Xie W,Cui G.NiSn atomic pair on an integrated electrode for synergistic electrocatalytic CO₂ reduction.Angew Chem Int Ed2021;60:7382-8

[146] Hu C,Chen J.Main-group metal single-atomic regulators in dual-metal catalysts for enhanced electrochemical CO₂ reduction.Small2022;18:e2201391

[147] Wei X,Cao S.Cu acting as Fe activity promoter in dual-atom Cu/Fe-NC catalyst in CO₂RR to C1 products.Appl Surf Sci2021;564:150423

[148] Xiao Z,Qiao Z.Atomically dispersed Fe-Cu dual-site catalysts synergistically boosting oxygen reduction for hydrogen fuel cells.Chem Eng J2022;446:137112

[149] Wang J,Yang J.Tuning the atomic configuration environment of MnN4 sites by Co cooperation for efficient oxygen reduction.J Energy Chem2023;82:547-59

[150] Rong C,Wang Y.Electronic structure engineering of single-atom Ru sites via Co-N₄ sites for bifunctional pH-universal water splitting.Adv Mater2022;34:e2110103

[151] Zeng Y,Wang S.Unraveling the electronic structure and dynamics of the atomically dispersed iron sites in electrochemical CO₂ reduction.J Am Chem Soc2023;145:15600-10

[152] Yang J,Xu M.Dynamic behavior of single-atom catalysts in electrocatalysis: identification of Cu-N₃ as an active site for the oxygen reduction reaction.J Am Chem Soc2021;143:14530-9

[153] Xu S.Theoretical insights into heterogeneous photo.electrochemical CO₂ reduction.Chem Rev2019;119:6631-69

[154] Li L,Lin X,Gong J.Theoretical insights into single-atom catalysts.Chem Soc Rev2020;49:8156-78

[155] Tian D,Li K,Kattel S.Density functional theory studies of transition metal carbides and nitrides as electrocatalysts.Chem Soc Rev2021;50:12338-76

[156] Li Y,Zhu M.Synergistic effect of atomically dispersed Ni-Zn pair sites for enhanced CO₂ electroreduction.Adv Mater2021;33:e2102212

[157] Zeng Z,Bin Yang H.Orbital coupling of hetero-diatomic nickel-iron site for bifunctional electrocatalysis of CO₂ reduction and oxygen evolution.Nat Commun2021;12:4088 PMCID:PMC8253796

[158] Guo Z,Yang G.Synergistic engineering of heteronuclear Ni-Ag dual-atom catalysts for high-efficiency CO₂ electroreduction with nearly 100% CO selectivity.Chem Eng J2023;476:146556

[159] Pei J,Lin J.Integrating host design and tailored electronic effects of yolk-shell Zn-Mn diatomic sites for efficient CO₂ electroreduction.Angew Chem Int Ed2024;63:e202316123

[160] Yi JD,Zhou H,Wu Y.Design of Co-Cu diatomic site catalysts for high-efficiency synergistic CO₂ electroreduction at industrial-level current density.Angew Chem Int Ed2022;61:e202212329

[161] Sun H,Qiu Y.Atomic metal-support interaction enables reconstruction-free dual-site electrocatalyst.J Am Chem Soc2022;144:1174-86

[162] Yu Z,Lagrow AP.Iridium-iron diatomic active sites for efficient bifunctional oxygen electrocatalysis.ACS Catal2022;12:9397-409

[163] Pei Z,Zhang H,Luan D.Highly efficient electrocatalytic oxygen evolution over atomically dispersed synergistic Ni/Co dual sites.Angew Chem Int Ed2022;61:e202207537

[164] Deng D,Liu X.Non-covalent interaction of atomically dispersed Cu and Zn pair sites for efficient oxygen reduction reaction.Adv Funct Mater2022;32:2203471

[165] Zhao S,Qu Z.Cascade synthesis of Fe-N₂-Fe dual-atom catalysts for superior oxygen catalysis.Angew Chem Int Ed2024;63:e202408914

[166] Huang S,Sun P.The strain induced synergistic catalysis of FeN₄ and MnN₃ dual-site catalysts for oxygen reduction in proton-/anion-exchange membrane fuel cells.Appl Catal B: Environ2022;317:121770

[167] Pan L,Lu F.Single-atom or dual-atom in TiO₂ nanosheet: which is the better choice for electrocatalytic urea synthesis?.Angew Chem Int Ed2023;62:e202216835