Hollow microstructural regulation of single-atom catalysts for optimized electrocatalytic performance

Abstract

Single-atom catalysts (SACs) and hollow microstructured materials have recently undergone significant advancements in the field of catalysis. The combination of SACs and hollow microstructured materials can further endow them with extraordinary characteristics, such as high loadings, uniform active sites and unique metal-support interactions and electronic structures. In this review, we focus on the design and construction of SACs supported on hollow microstructured materials for enhancing electrocatalytic reactions. Due to these unique hollow microstructures, most of the active sites can be fully exposed in catalysis. Therefore, the atomic utilization rate is greatly improved. Furthermore, the synergistic effect of SACs and hollow microstructured supports can bring about unpredictable characteristics. The hollow microstructures not only adjust the geometry and electronic structure of the SACs to improve their activity but the SACs can also serve as an auxiliary stimulus to the intrinsic activity of the support to achieve better performance. Compared with the reported traditional dual atomic catalysts, hollow microstructures are conducive for the isolation of atomically dispersed binary atom active sites on both sides of the particle shell. Combined with the current development status, we summarize the challenges and prospects in this area. This review is conducive to the reasonable design and manufacture of advanced SACs supported on hollow materials and the promotion of their future industrial usage in energy applications.

Keywords

Microstructures / single-atom catalysts / hollow structures / electrocatalytic activity / energy conversion

References

[1] Chen Z,Liu W.Amination strategy to boost the CO₂ electroreduction current density of M-N/C single-atom catalysts to the industrial application level.Energy Environ Sci2021;14:2349-56

[2] Zhou A,Zhao C,Wu X.A leaf-branch TiO2/carbon@MOF composite for selective CO₂ photoreduction.Appl Catal B: Environ2020;264:118519

[3] Gao P,Bu X.Direct conversion of CO₂ into liquid fuels with high selectivity over a bifunctional catalyst.Nat Chem2017;9:1019-24

[4] Gabardo CM,Edwards JP.Continuous carbon dioxide electroreduction to concentrated multi-carbon products using a membrane electrode assembly.Joule2019;3:2777-91

[5] Dou Y,Yao Y,Li J.Suppressing hydrogen evolution for high selective CO₂ reduction through surface-reconstructed heterojunction photocatalyst.Appl Catal B: Environ2021;286:119876

[6] Zhao C,Dou Y,Bai J.Dual MOFs template-directed fabrication of hollow-structured heterojunction photocatalysts for efficient CO₂ reduction.Chem Eng J2021;416:129155

[7] Zhang N,Yan H.Single-atom site catalysts for environmental catalysis.Nano Res2020;13:3165-82

[8] Ou H,Lin L,Wang X.Biomimetic donor-acceptor motifs in conjugated polymers for promoting exciton splitting and charge separation.Angew Chem Int Ed Engl2018;57:8729-33

[9] Ou H,Chen X,Wang X.Solvated electrons for photochemistry syntheses using conjugated carbon nitride polymers.ACS Catal2019;9:2949-55

[10] Xu Q,Wang D.Single-atom site catalysts supported on two-dimensional materials for energy applications.Chin Chem Lett2021;

[11] Ou H,Li Y.How to select effective electrocatalysts: nano or single atom?.Nano Select2021;2:492-511

[12] Gu J,Bai L,Hu X.Atomically dispersed Fe³⁺ sites catalyze efficient CO₂ electroreduction to CO.Science2019;364:1091-4

[13] Askins EJ,Li M,Amine K.Toward a mechanistic understanding of electrocatalytic nanocarbon.Nat Commun2021;12:3288 PMCID:PMC8172927

[14] Zhu Y,Peng C,Mei Y.Carbon-supported single metal site catalysts for electrochemical CO₂ reduction to CO and beyond.Small2021;17:e2005148

[15] Zhang Y,Yang W,Jiang HL.Rational fabrication of low-coordinate single-atom Ni electrocatalysts by MOFs for highly selective CO₂ reduction.Angew Chem Int Ed Engl2021;60:7607-11

[16] Zhang H,Luan D.Atomically dispersed reactive centers for electrocatalytic CO₂ reduction and water splitting.Angew Chem Int Ed Engl2021;60:13177-96 PMCID:PMC8248387

[17] Chen S,Zhu J.Lewis acid site-promoted single-atomic Cu catalyzes electrochemical CO₂ methanation.Nano Lett2021;21:7325-31

[18] Zhou A,Dou Y,Han J.The fabrication of oriented organic-inorganic ultrathin films with enhanced electrochromic properties.J Mater Chem C2016;4:8284-90

[19] Sultan S,Singh AN.Single atoms and clusters based nanomaterials for hydrogen evolution, oxygen evolution reactions, and full water splitting.Adv Energy Mater2019;9:1900624

[20] Gusmão R,Sofer Z.Recent developments on the single atom supported at 2D materials beyond graphene as catalysts.ACS Catal2020;10:9634-48

[21] Harzandi AM,Nissimagoudar AS.Ruthenium core-shell engineering with nickel single atoms for selective oxygen evolution via nondestructive mechanism.Adv Energy Mater2021;11:2003448

[22] Wang Y,Li Y.Atom-level interfacial synergy of single-atom site catalysts for electrocatalysis.J Energy Chem2022;65:103-15

[23] Jing H,Zhao Z.Electronics and coordination engineering of atomic cobalt trapped by oxygen-driven defects for efficient cathode in solar cells.Nano Energy2021;89:106365

[24] Sun X,Ye C.Phosphorus induced electron localization of single iron sites for boosted CO₂ electroreduction reaction.Angew Chem Int Ed Engl2021;60:23614-8

[25] Zhou A,Zhou J.Rational localization of metal nanoparticles in yolk-shell MOFs for enhancing catalytic performance in selective hydrogenation of cinnamaldehyde.ChemSusChem2020;13:205-11

[26] Ryoo R,Jo C.Rare-earth-platinum alloy nanoparticles in mesoporous zeolite for catalysis.Nature2020;585:221-4

[27] Kim S,Choi KM.Single-atom Pd catalyst anchored on Zr-based metal-organic polyhedra for Suzuki-Miyaura cross coupling reactions in aqueous media.Nano Res2021;14:486-92

[28] He T,Zhou J.A practice of reticular chemistry: construction of a robust mesoporous palladium metal-organic framework via metal metathesis.J Am Chem Soc2021;143:9901-11

[29] Mao J,Pei J,Wang D.Structure regulation of noble-metal-based nanomaterials at an atomic level.Nano Today2019;26:164-75

[30] Zhuang Z,Wang D.Single-atom catalysis enables long-life, high-energy lithium-sulfur batteries.Nano Res2020;13:1856-66

[31] Zhou A,Zhou J,Chen Y.Pd@ZIF-67 derived recyclable Pd-based catalysts with hierarchical pores for high-performance heck reaction.ACS Sustainable Chem Eng2018;6:2103-11

[32] Wang X,Bai Y,Yin Y.Synthesis, properties, and applications of hollow micro-/nanostructures.Chem Rev2016;116:10983-1060

[33] Prieto G,Duyckaerts N,Wang GH.Hollow nano- and microstructures as catalysts.Chem Rev2016;116:14056-119

[34] Wang Z,Yang N,Wang D.Core-shell nano/microstructures for heterogeneous tandem catalysis.Mater Chem Front2021;5:1126-39

[35] Zhao Z,Li W,Wang G.Modulating the microstructure and surface chemistry of carbocatalysts for oxidative and direct dehydrogenation: a review.Chin J Catal2016;37:644-70

[36] Zhu C,Shi Q,Lin Y.Single-atom electrocatalysts.Angew Chem Int Ed Engl2017;56:13944-60

[37] Li Z,Liu Y.Well-defined materials for heterogeneous catalysis: from nanoparticles to isolated single-atom sites.Chem Rev2020;120:623-82

[38] Meng G,Li X,Li Y.Electronic structure regulations of single-atom site catalysts and their effects on the electrocatalytic performances.Appl Phys Rev2021;8:021321

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

[40] Zhuang Z,Li Y.Atomically dispersed nonmagnetic electron traps improve oxygen reduction activity of perovskite oxides.Energy Environ Sci2021;14:1016-28

[41] Xiong Y,Huang ZQ.Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation.Nat Nanotechnol2020;15:390-7

[42] Wu Y,Li Y.Nanocrystals from solutions: catalysts.Chem Soc Rev2014;43:2112-24

[43] Zhang J,Chen W.Tuning polarity of Cu-O bond in heterogeneous Cu catalyst to promote additive-free hydroboration of alkynes.Chem2020;6:725-37

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

[45] Duchesne PN,Deming CP.Golden single-atomic-site platinum electrocatalysts.Nat Mater2018;17:1033-9

[46] Fu N,Li Z.Fabricating Pd isolated single atom sites on C3N4/rGO for heterogenization of homogeneous catalysis.Nano Res2020;13:947-51

[47] Sun T,Wang D.Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion.Nano Res2019;12:2067-80

[48] Wei S,Liu JC.Direct observation of noble metal nanoparticles transforming to thermally stable single atoms.Nat Nanotechnol2018;13:856-61

[49] Xu Q,Tian S.Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes.Sci China Mater2020;63:972-81

[50] Wang Y,Shen R.Pd-dispersed CuS hetero-nanoplates for selective hydrogenation of phenylacetylene.Nano Res2016;9:1209-19

[51] Zhang J,Zhang M.Controlling N-doping type in carbon to boost single-atom site Cu catalyzed transfer hydrogenation of quinoline.Nano Res2020;13:3082-7

[52] Xiong Y,Han Y.Cobalt single atom site catalysts with ultrahigh metal loading for enhanced aerobic oxidation of ethylbenzene.Nano Res2021;14:2418-23

[53] Cui T,Wang S.Atomically dispersed Pt-N₃C₁ sites enabling efficient and selective electrocatalytic C-C bond cleavage in lignin models under ambient conditions.J Am Chem Soc2021;143:9429-39

[54] Han Y,Xu R.Notched-polyoxometalate strategy to fabricate atomically dispersed Ru catalysts for biomass conversion.ACS Catal2021;11:2669-75

[55] Maschmeyer T,Sankar G.Heterogeneous catalysts obtained by grafting metallocene complexes onto mesoporous silica.Nature1995;378:159-62

[56] Fu Q,Flytzani-Stephanopoulos M.Active nonmetallic Au and Pt species on ceria-based water-gas shift catalysts.Science2003;301:935-8

[57] Hackett SF,Gass MH.High-activity, single-site mesoporous Pd/Al2O3 catalysts for selective aerobic oxidation of allylic alcohols.Angew Chem Int Ed Engl2007;46:8593-6

[58] Yin P,Wu Y.Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts.Angew Chem Int Ed Engl2016;55:10800-5

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

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

[61] Ji S,Wang T.Rare-earth single erbium atoms for enhanced photocatalytic CO₂ reduction.Angew Chem Int Ed Engl2020;59:10651-7

[62] Wang G,Zhang J,Wang D.Synergistic modulation of the separation of photo-generated carries via engineering of dual atomic sites for promoting photocatalytic performance.Adv Mater2021;:e2105904

[63] Li WH,Jing H.Creating high regioselectivity by electronic metal-support interaction of a single-atomic-site catalyst.J Am Chem Soc2021;143:15453-61

[64] Liu Z,Zhang P,Wang D.Bringing catalytic order out of chaos with nitrogen-doped ordered mesoporous carbon.Matter2021;4:3161-94

[65] Yang T,Zhang Y.Coordination tailoring of Cu single sites on C₃N₄ realizes selective CO₂ hydrogenation at low temperature.Nat Commun2021;12:6022 PMCID:PMC8519910

[66] Tang C,Shi B.Coordination tunes selectivity: two-electron oxygen reduction on high-loading molybdenum single-atom catalysts.Angew Chem Int Ed Engl2020;59:9171-6

[67] Wu K,Liu S.Porphyrin-like Fe-N₄ sites with sulfur adjustment on hierarchical porous carbon for different rate-determining steps in oxygen reduction reaction.Nano Res2018;11:6260-9

[68] 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

[69] Han A,Li X,Li Y.Atomic thickness catalysts: synthesis and applications.Small Methods2020;4:2000248

[70] Wang Y,Li Y.Rational design of single-atom site electrocatalysts: from theoretical understandings to practical applications.Adv Mater2021;33:e2008151

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

[72] Qi K,Voiry D.Single atom is not alone: metal-support interactions in single-atom catalysis.Mater Today2020;40:173-92

[73] Yang J,Wang D.Electronic metal-support interaction of single-atom catalysts and applications in electrocatalysis.Adv Mater2020;32:e2003300

[74] Wang GH,Richter FH.Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural.Nat Mater2014;13:293-300

[75] Yang J,Wang D.Single-atom materials: small structures determine macroproperties.Small Structures2021;2:2000051

[76] Zhang Z,Chen Y.Pd single-atom monolithic catalyst: functional 3D structure and unique chemical selectivity in hydrogenation reaction.Sci China Mater2021;64:1919-29

[77] Yang J,Tan S.The electronic metal-support interaction directing the design of single atomic site catalysts: achieving high efficiency towards hydrogen evolution.Angew Chem Int Ed Engl2021;60:19085-91

[78] Zhao J,Guo C.A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O-H bond insertion.Nat Catal2021;4:523-31

[79] Zhao Y,Zhu X.Simultaneous oxidative and reductive reactions in one system by atomic design.Nat Catal2021;4:134-43

[80] Zhang T,Yang H.Atomically dispersed nickel(I) on an alloy-encapsulated nitrogen-doped carbon nanotube array for high-performance electrochemical CO₂ reduction reaction.Angew Chem Int Ed Engl2020;59:12055-61

[81] Li Z,(David) Lou XW.Rational designs and engineering of hollow micro-/nanostructures as sulfur hosts for advanced lithium-sulfur batteries.Energy Environ Sci2016;9:3061-70

[82] Kumar R.NiCo₂O₄ nano-/microstructures as high-performance biosensors: a review.Nanomicro Lett2020;12:122 PMCID:PMC7770908

[83] Yu J,Tang L.Metal-free carbon materials for persulfate-based advanced oxidation process: microstructure, property and tailoring.Prog Mater Sci2020;111:100654

[84] Yu L,Lou XWD.The design and synthesis of hollow micro-/nanostructures: present and future trends.Adv Mater2018;30:e1800939

[85] Wang Z,Jiang M,Li Y.One-step accurate synthesis of shell controllable CoFe₂O₄ hollow microspheres as high-performance electrode materials in supercapacitor.Nano Res2016;9:2026-33

[86] Song X,Guo L.General dimension-controlled synthesis of hollow carbon embedded with metal singe atoms or core-shell nanoparticles for energy storage applications.Adv Energy Mater2018;8:1801101

[87] Liu C,Han J,Liu Q.A Perspective on the relationship between microstructure and performance of Cu-based zeolites for the selective catalytic reduction of NO_x.Catal Surv Asia2020;24:179-95

[88] Kong W,Zhang J,Anpo M.Microstructure and hydrogen production activity of Pt-TiO2 prepared by precipitation-photodeposition.Res Chem Intermed2013;39:1701-10

[89] Shojaeefard M,Nazemian M.A review on microstructure reconstruction of PEM fuel cells porous electrodes for pore scale simulation.Int J Hydrogen Energy2016;41:20276-93

[90] Yang D,He T.Visible-light-switched electron transfer over single porphyrin-metal atom center for highly selective electroreduction of carbon dioxide.Nat Commun2019;10:3844 PMCID:PMC6710284

[91] Wang Z,Hu Y.Simultaneous diffusion of cation and anion to access N, S co-coordinated Bi-sites for enhanced CO₂ electroreduction.Nano Res2021;14:2790-6

[92] Yuan C,Liu S.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

[93] Kim S,Sasmaz E.Yolk-shell Pt-NiCe@SiO₂ single-atom-alloy catalysts for low-temperature dry reforming of methane.ACS Catal2021;11:8247-60

[94] Chen Y,Zhao S.Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell.Nat Commun2018;9:5422 PMCID:PMC6303331

[95] Wei YS,Zou R.Metal-organic framework-based catalysts with single metal sites.Chem Rev2020;120:12089-174

[96] 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

[97] Song Z,Doyle-davis K,Luo J.Recent advances in MOF-derived single atom catalysts for electrochemical applications.Adv Energy Mater2020;10:2001561

[98] He T,Yuan S.Kinetically controlled reticular assembly of a chemically stable mesoporous Ni(II)-pyrazolate metal-organic framework.J Am Chem Soc2020;142:13491-9

[99] Gong YN,Qian Y.Regulating the coordination environment of MOF-templated single-atom nickel electrocatalysts for boosting CO₂ reduction.Angew Chem Int Ed Engl2020;59:2705-9

[100] 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

[101] Chen Y,Ji S.Atomic-level modulation of electronic density at cobalt single-atom sites derived from metal-organic frameworks: enhanced oxygen reduction performance.Angew Chem Int Ed Engl2021;60:3212-21

[102] He T,Ni B.Zirconium-porphyrin-based metal-organic framework hollow nanotubes for immobilization of noble-metal single atoms.Angew Chem Int Ed Engl2018;57:3493-8

[103] Yang Z,Zhu M.Structural revolution of atomically dispersed Mn sites dictates oxygen reduction performance.Nano Res2021;14:4512-9

[104] Wang C,Zhong M.Hollow mesoporous carbon nanocages with Fe isolated single atomic site derived from a MOF/polymer for highly efficient electrocatalytic oxygen reduction.J Mater Chem A2021;9:22095-101

[105] Li Y,Cheng W.Loading single-Ni atoms on assembled hollow N-rich carbon plates for efficient CO₂ Electroreduction.Adv Mater2021;e2105204

[106] Han A,Tang K.An adjacent atomic platinum site enables single-atom iron with high oxygen reduction reaction performance.Angew Chem Int Ed Engl2021;60:19262-71

[107] 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

[108] Deng Y,Tian X.g-C₃N₄ promoted MOF derived hollow carbon nanopolyhedra doped with high density/fraction of single Fe atoms as an ultra-high performance non-precious catalyst towards acidic ORR and PEM fuel cells.J Mater Chem A2019;7:5020-30

[109] Su P,Zhang J.Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction.Nano Res2021;14:1069-77

[110] Kuang P,Zhu B.Pt single atoms supported on N-doped mesoporous hollow carbon spheres with enhanced electrocatalytic H₂-evolution activity.Adv Mater2021;33:e2008599

[111] Chen J,Fan C.Dual single-atomic Ni-N₄ and Fe-N₄ sites constructing janus hollow graphene for selective oxygen electrocatalysis.Adv Mater2020;32:e2003134

[112] Chen Y,Zhu Y.Atomic Fe dispersed on N-doped carbon hollow nanospheres for high-efficiency electrocatalytic oxygen reduction.Adv Mater2019;31:e1806312

[113] Zhang H,Chen T,Zhang J.unveiling the activity origin of electrocatalytic oxygen evolution over isolated Ni atoms supported on a N-doped carbon matrix.Adv Mater2019;31:e1904548

[114] Xiong W,Wang H.Hollow mesoporous carbon sphere loaded Ni-N₄ single-atom: support structure study for CO₂ electrocatalytic reduction catalyst.Small2020;16:e2003943

[115] Qiu X,Pang H.Isolated Fe single atomic sites anchored on highly steady hollow graphene nanospheres as an efficient electrocatalyst for the oxygen reduction reaction.Adv Sci (Weinh)2019;6:1801103 PMCID:PMC6343057

[116] Li D,Zhu M.Synergistic catalysis by single-atom catalysts and redox mediator to improve lithium-oxygen batteries performance.Small2021;17:e2101620

[117] Liang K,Zhou X.Osmotic pressure-induced pocket-like spheres with Fe single-atom sites for the oxygen reduction reaction.J Mater Chem A2021;9:13908-15

[118] Zhang M,Chen W.Metal (Hydr)oxides@Polymer core-shell strategy to metal single-atom materials.J Am Chem Soc2017;139:10976-9

[119] Zhao J,Liu R.Urea-bridging synthesis of nitrogen-doped carbon tube supported single metallic atoms as bifunctional oxygen electrocatalyst for zinc-air battery.Appl Catal B Environ2019;256:117778

[120] Wei X,Zhao M.Cross-linked polyphosphazene hollow nanosphere-derived N/P-doped porous carbon with single nonprecious metal atoms for the oxygen reduction reaction.Angew Chem Int Ed Engl2020;59:14639-46

[121] Hai X,Guo N.Engineering local and global structures of single Co atoms for a superior oxygen reduction reaction.ACS Catal2020;10:5862-70

[122] He Y,Zhang J.Low-temperature strategy toward Ni-NC@Ni core-shell nanostructure with single-Ni sites for efficient CO₂ electroreduction.Nano Energy2020;77:105010

[123] Lai W,Hu Z.The quasi-Pt-allotrope catalyst: hollow PtCo@single-atom Pt₁ on nitrogen-doped carbon toward superior oxygen reduction.Adv Funct Mater2019;29:1807340

[124] Cheng Q,Mao K.Co nanoparticle embedded in atomically-dispersed Co-N-C nanofibers for oxygen reduction with high activity and remarkable durability.Nano Energy2018;52:485-93

[125] Cai C,Wang Q.Direct observation of yolk-shell transforming to gold single atoms and clusters with superior oxygen evolution reaction efficiency.ACS Nano2019;13:8865-71

[126] Gao R,Zheng L.Enhancing the catalytic activity of Co₃O₄ for Li-O₂ batteries through the synergy of surface/interface/doping engineering.ACS Catal2018;8:1955-63