Skip to main content
SpringerLink
Log in

Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis

  • Review Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Supported atomically dispersed metal catalysts (ADMCs) have received enormous attention due to their high atom utilization efficiency, mass activity and excellent selectivity. Single-atom site catalysts (SACs) with monometal-center as the quintessential ADMCs have been extensively studied in the catalysis-related fields. Beyond SACs, novel atomically dispersed metal catalysts (NADMCs) with flexible active sites featuring two or more catalytically centers including dual-atom and triple-atom catalysts have drawn ever-increasing attention recently. Owing to the presence of multiple neighboring active sites, NADMCs could exhibit much higher activity and selectivity compared with SACs, especially in those complicated reactions with multi-step intermediates. This review comprehensively outlines the recent exciting advances on the NADMCs with emphasis on the deeper understanding of the synergistic interactions among multiple metal atoms and underlying structure–performance relationships. It starts with the systematical introduction of principal synthetic approaches for NADMCs highlighting the key issues of each fabrication method including the atomically precise control in the design of metal nuclearity, and then the state-of-the-art characterizations for identifying and monitoring the atomic structure of NADMCs are explored. Thereafter, the recent development of NADMCs in energy-related applications is systematically discussed. Finally, we provide some new insights into the remaining challenges and opportunities for the development of NADMCs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Nørskov, J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 2017, 355, eaad4998.

    Article  Google Scholar 

  2. Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294–303.

    Article  CAS  Google Scholar 

  3. Zhong, M.; Tran, K.; Min, Y. M.; Wang, C. H.; Wang, Z. Y.; Dinh, C. T.; De Luna, P.; Yu, Z. Q.; Rasouli, A. S.; Brodersen, P. et al. Accelerated discovery of CO2 electrocatalysts using active machine learning. Nature 2020, 581, 178–183.

    Article  CAS  Google Scholar 

  4. García de Arquer, F. P.; Dinh, C. T.; Ozden, A.; Wicks, J.; McCallum, C.; Kirmani, A. R.; Nam, D. H.; Gabardo, C.; Seifitokaldani, A.; Wang, X. et al. CO2 electrolysis to multicarbon products at activities greater than 1 A·cm−2. Science 2020, 367, 661–666.

    Article  Google Scholar 

  5. Mistry, H.; Varela, A. S.; Kühl, S.; Strasser, P.; Cuenya, B. R. Nanostructured electrocatalysts with tunable activity and selectivity. Nat. Rev. Mater. 2016, 1, 16009.

    Article  CAS  Google Scholar 

  6. Anson, C. W.; Stahl, S. S. Mediated fuel cells: Soluble redox mediators and their applications to electrochemical reduction of O2 and oxidation of H2, alcohols, biomass, and complex fuels. Chem. Rev. 2020, 120, 3749–3786.

    Article  CAS  Google Scholar 

  7. Shao, M. H.; Chang, Q. W.; Dodelet, J. P.; Chenitz, R. Recent advances in electrocatalysts for oxygen reduction reaction. Chem. Rev. 2016, 116, 3594–3657.

    Article  CAS  Google Scholar 

  8. Maurer, F.; Jelic, J.; Wang, J. J.; Gänzler, A.; Dolcet, P.; Wöll, C.; Wang, Y. M.; Studt, F.; Casapu, M.; Grunwaldt, J. D. Tracking the formation, fate and consequence for catalytic activity of Pt single sites on CeO2. Nat. Catal. 2020, 3, 824–833.

    Article  CAS  Google Scholar 

  9. Zhang, J. Q.; Zhao, Y. F.; Guo, X.; Chen, C.; Dong, C. L.; Liu, R. S.; Han, C. P.; Li, Y. D.; Gogotsi, Y.; Wang, G. X. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction. Nat. Catal. 2018, 1, 985–992.

    Article  CAS  Google Scholar 

  10. Xie, X. H.; He, C.; Li, B. Y.; He, Y. H.; Cullen, D. A.; Wegener, E. C.; Kropf, A. J.; Martinez, U.; Cheng, Y. W.; Engelhard, M. H. et al. Performance enhancement and degradation mechanism identification of a single-atom Co-N-C catalyst for proton exchange membrane fuel cells. Nat. Catal. 2020, 3, 1044–1054.

    Article  CAS  Google Scholar 

  11. Wang, J.; Kim, S. J.; Liu, J. P.; Gao, Y.; Choi, S.; Han, J.; Shin, H.; Jo, S.; Kim, J.; Ciucci, F. et al. Redirecting dynamic surface restructuring of a layered transition metal oxide catalyst for superior water oxidation. Nat. Catal. 2021, 4, 212–222.

    Article  Google Scholar 

  12. Liu, C.; Qian, J.; Ye, Y. F.; Zhou, H.; Sun, C. J.; Sheehan, C.; Zhang, Z. Y.; Wan, G.; Liu, Y. S.; Guo, J. H. et al. Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO2 nanorod surface. Nat. Catal. 2021, 4, 36–45.

    Article  CAS  Google Scholar 

  13. Adabi, H.; Shakouri, A.; Ul Hassan, N.; Varcoe, J. R.; Zulevi, B.; Serov, A.; Regalbuto, J. R.; Mustain, W. E. High-performing commercial Fe-N-C cathode electrocatalyst for anion-exchange membrane fuel cells. Nat. Energy 2021, 6, 834–843.

    Article  CAS  Google Scholar 

  14. Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.

    Article  CAS  Google Scholar 

  15. Zhang, T. J.; Walsh, A. G.; Yu, J. H.; Zhang, P. Single-atom alloy catalysts: Structural analysis, electronic properties and catalytic activities. Chem. Soc. Rev. 2021, 50, 569–588.

    Article  CAS  Google Scholar 

  16. Zhao, D.; Zhuang, Z. W.; Cao, X.; Zhang, C.; Peng, Q.; Chen, C.; Li, Y. D. Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation. Chem. Soc. Rev. 2020, 49, 2215–2264.

    Article  CAS  Google Scholar 

  17. Zhuo, H. Y.; Zhang, X.; Liang, J. X.; Yu, Q.; Xiao, H.; Li, J. Theoretical understandings of graphene-based metal single-atom catalysts: Stability and catalytic performance. Chem. Rev. 2020, 120, 12315–12341.

    Article  CAS  Google Scholar 

  18. Qin, R. X.; Liu, K. L.; Wu, Q. Y.; Zheng, N. F. Surface coordination chemistry of atomically dispersed metal catalysts. Chem. Rev. 2020, 120, 11810–11899.

    Article  CAS  Google Scholar 

  19. Wang, Y. X.; Su, H. Y.; He, Y. H.; Li, L. G.; Zhu, S. Q.; Shen, H.; Xie, P. F.; Fu, X. B.; Zhou, G. Y.; Feng, C. et al. Advanced electrocatalysts with single-metal-atom active sites. Chem. Rev. 2020, 120, 12217–12314.

    Article  CAS  Google Scholar 

  20. Zhang, L. L.; Zhou, M. X.; Wang, A. Q.; Zhang, T. Selective hydrogenation over supported metal catalysts: From nanoparticles to single atoms. Chem. Rev. 2020, 120, 683–733.

    Article  CAS  Google Scholar 

  21. Zhang, J.; Wang, Z. J.; Chen, W. X.; Xiong, Y.; Cheong, W. C.; Zheng, L. R.; Yan, W. S.; Gu, L.; Chen, C.; Peng, Q. et al. Tuning polarity of Cu-O bond in heterogeneous Cu catalyst to promote additive-free hydroboration of alkynes. Chem 2020, 6, 725–737.

    Article  CAS  Google Scholar 

  22. Li, W. H.; Yang, J. R.; Wang, D. S.; Li, Y. D. Striding the threshold of an atom era of organic synthesis by single-atom catalysis. Chem 2022, 8, 119–140.

    Article  Google Scholar 

  23. Xiong, Y.; Li, H. C.; Liu, C. W.; Zheng, L. R.; Liu, C.; Wang, J. O.; Liu, S. J.; Han, Y. H.; Gu, L.; Qian, J. S. et al. Single-atom Fe catalysts for fenton-like reactions: Roles of different N species. Adv. Mater., in press, https://doi.org/10.1002/adma.202110653.

  24. Xu, Q.; Guo, C. X.; Li, B. B.; Zhang, Z. D.; Qiu, Y. J.; Tian, S. B.; Zheng, L. R.; Gu, L.; Yan, W. S.; Wang, D. S. et al. Al3+ dopants induced Mg2+ vacancies stabilizing single-atom Cu catalyst for efficient free-radical hydrophosphinylation of alkenes. J. Am. Chem. Soc. 2022, 144, 4321–4326.

    Article  CAS  Google Scholar 

  25. Chen, S. H.; Li, W. H.; Jiang, W. J.; Yang, J. R.; Zhu, J. X.; Wang, L. Q.; Ou, H. H.; Zhuang, Z. C.; Chen, M. Z.; Sun, X. H. et al. MOF encapsulating N-heterocyclic carbene-ligated copper single-atom site catalyst towards efficient methane electrosynthesis. Angew. Chem., Int. Ed. 2022, 61, e202114450.

    CAS  Google Scholar 

  26. Yang, J. R.; Li, W. H.; Tan, S. D.; Xu, K. N.; Wang, Y.; Wang, D. S.; Li, Y. D. The electronic metal-support interaction directing the design of single atomic site catalysts: Achieving high efficiency towards hydrogen evolution. Angew. Chem., Int. Ed. 2021, 60, 19085–19091.

    Article  CAS  Google Scholar 

  27. Xiong, Y.; Sun, W. M.; Han, Y. H.; Xin, P. Y.; Zheng, X. S.; Yan, W. S.; Dong, J. C.; Zhang, J.; Wang, D. S.; Li, Y. D. Cobalt single atom site catalysts with ultrahigh metal loading for enhanced aerobic oxidation of ethylbenzene. Nano Res. 2021, 14, 2418–2423.

    Article  CAS  Google Scholar 

  28. Zhang, Z. D.; Zhou, M.; Chen, Y. J.; Liu, S. J.; Wang, H. F.; Zhang, J.; Ji, S. F.; Wang, D. S.; Li, Y. D. Pd single-atom monolithic catalyst: Functional 3D structure and unique chemical selectivity in hydrogenation reaction. Sci. China Mater. 2021, 64, 1919–1929.

    Article  CAS  Google Scholar 

  29. Yang, J. R.; Li, W. H.; Wang, D. S.; Li, Y. D. Electronic metal-support interaction of single-atom catalysts and applications in electrocatalysis. Adv. Mater. 2020, 32, 2003300.

    Article  CAS  Google Scholar 

  30. Zhang, J.; Zheng, C. Y.; Zhang, M. L.; Qiu, Y. J.; Xu, Q.; Cheong, W. C.; Chen, W. X.; Zheng, L. R.; Gu, L.; Hu, Z. P. et al. Controlling N-doping type in carbon to boost single-atom site Cu catalyzed transfer hydrogenation of quinoline. Nano Res. 2020, 13, 3082–3087.

    Article  Google Scholar 

  31. Liu, Y. W.; Wu, X.; Li, Z.; Zhang, J.; Liu, S. X.; Liu, S. J.; Gu, L.; Zheng, L. R.; Li, J.; Wang, D. S. et al. Fabricating polyoxometalates-stabilized single-atom site catalysts in confined space with enhanced activity for alkynes diboration. Nat. Commun. 2021, 12, 4205.

    Article  CAS  Google Scholar 

  32. Jing, H. Y.; Liu, W.; Zhao, Z. Y.; Zhang, J. W.; Zhu, C.; Shi, Y. T.; Wang, D. S.; Li, Y. D. Electronics and coordination engineering of atomic cobalt trapped by oxygen-driven defects for efficient cathode in solar cells. Nano Energy 2021, 89, 106365.

    Article  CAS  Google Scholar 

  33. Li, W. H.; Yang, J. R.; Jing, H. Y.; Zhang, J.; Wang, Y.; Li, J.; Zhao, J.; Wang, D. S.; Li, Y. D. Creating high regioselectivity by electronic metal-support interaction of a single-atomic-site catalyst. J. Am. Chem. Soc. 2021, 143, 15453–15461.

    Article  CAS  Google Scholar 

  34. Zhao, C. M.; Dai, X. Y.; Yao, T.; Chen, W. X.; Wang, X. Q.; Wang, J.; Yang, J.; Wei, S. Q.; Wu, Y. E.; Li, Y. D. Ionic Exchange of metal-organic frameworks to access single nickel sites for efficient electroreduction of CO2. J. Am. Chem. Soc. 2017, 139, 8078–8081.

    Article  CAS  Google Scholar 

  35. Zhang, L. Z.; Fischer, J. M. T. A.; Jia, Y.; Yan, X. C.; Xu, W.; Wang, X. Y.; Chen, J.; Yang, D. J.; Liu, H. W.; Zhuang, L. Z. et al. Coordination of atomic Co-Pt coupling species at carbon defects as active sites for oxygen reduction reaction. J. Am. Chem. Soc. 2018, 140, 10757–10763.

    Article  CAS  Google Scholar 

  36. Wang, J.; Huang, Z. Q.; Liu, W.; Chang, C. R.; Tang, H. L.; Li, Z. J.; Chen, W. X.; Jia, C. J.; Yao, T.; Wei, S. Q. et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc. 2017, 139, 17281–17284.

    Article  CAS  Google Scholar 

  37. Wan, J. W.; Zhao, Z. H.; Shang, H. S.; Peng, B.; Chen, W. X.; Pei, J. J.; Zheng, L. R.; Dong, J. C.; Cao, R.; Sarangi, R. et al. In situ phosphatizing of triphenylphosphine encapsulated within metal-organic frameworks to design atomic Co1-P1N3 interfacial structure for promoting catalytic performance. J. Am. Chem. Soc. 2020, 142, 8431–8439.

    Article  CAS  Google Scholar 

  38. Jiang, W. J.; Gu, L.; Li, L.; Zhang, Y.; Zhang, X.; Zhang, L. J.; Wang, J. Q.; Hu, J. S.; Wei, Z. D.; Wan, L. J. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe-NxJ. Am. Chem. Soc. 2016, 138, 3570–3578.

    Article  CAS  Google Scholar 

  39. Zhang, E. H.; Tao, L.; An, J. K.; Zhang, J. W.; Meng, L. Z.; Zheng, X. B.; Wang, Y.; Li, N.; Du, S. X.; Zhang, J. T. et al. Engineering the local atomic environments of indium single-atom catalysts for efficient electrochemical production of hydrogen peroxide. Angew. Chem., Int. Ed. 2022, 61, e202117347.

    CAS  Google Scholar 

  40. Yang, J. R.; Li, W. H.; Xu, K. N.; Tan, S. D.; Wang, D. S.; Li, Y. D. Regulating the tip effect on single-atom and cluster catalysts: Forming reversible oxygen species with high efficiency in chlorine evolution reaction. Angew. Chem., Int. Ed. 2022, 134, e202200366.

    Google Scholar 

  41. Wang, Y.; Zheng, M.; Li, Y. R.; Ye, C. L.; Chen, J.; Ye, J. Y.; Zhang, Q. H.; Li, J.; Zhou, Z. Y.; Fu, X. Z. et al. p-d orbital hybridization induced by a monodispersed Ga site on a Pt3Mn nanocatalyst boosts ethanol electrooxidation. Angew. Chem., Int. Ed. 2022, 61, e202115735.

    CAS  Google Scholar 

  42. Zhao, Q.; Sun, J.; Li, S. C.; Huang, C. P.; Yao, W. F.; Chen, W.; Zeng, T.; Wu, Q.; Xu, Q. J. Single nickel atoms anchored on nitrogen-doped graphene as a highly active cocatalyst for photocatalytic H2 evolution. ACS Catal. 2018, 8, 11863–11874.

    Article  CAS  Google Scholar 

  43. Shi, R.; Tian, C. C.; Zhu, X.; Peng, C. Y.; Mei, B. B.; He, L.; Du, X. L.; Jiang, Z.; Chen, Y.; Dai, S. Achieving an exceptionally high loading of isolated cobalt single atoms on a porous carbon matrix for efficient visible-light-driven photocatalytic hydrogen production. Chem. Sci. 2019, 10, 2585–2591.

    Article  CAS  Google Scholar 

  44. Liang, Z. B.; Qu, C.; Xia, D. G.; Zou, R. Q.; Xu, Q. Atomically dispersed metal sites in MOF-based materials for electrocatalytic and photocatalytic energy conversion. Angew. Chem., Int. Ed. 2018, 57, 9604–9633.

    Article  CAS  Google Scholar 

  45. Ji, S. F.; Qu, Y.; Wang, T.; Chen, Y. J.; Wang, G. F.; Li, X.; Dong, J. C.; Chen, Q. Y.; Zhang, W. Y.; Zhang, Z. D. et al. Rare-earth single erbium atoms for enhanced photocatalytic CO2 reduction. Angew. Chem., Int. Ed. 2020, 59, 10651–10657.

    Article  CAS  Google Scholar 

  46. Wang, G.; He, C. T.; Huang, R.; Mao, J. J.; Wang, D. S.; Li, Y. D. Photoinduction of Cu single atoms decorated on UiO-66-NH2 for enhanced photocatalytic reduction of CO2 to liquid fuels. J. Am. Chem. Soc. 2020, 142, 19339–19345.

    Article  CAS  Google Scholar 

  47. Lu, C.; Fang, R. Y.; Chen, X. Single-atom catalytic materials for advanced battery systems. Adv. Mater. 2020, 32, 1906548.

    Article  CAS  Google Scholar 

  48. Zhuang, Z. C.; Kang, Q.; Wang, D. S.; Li, Y. D. Single-atom catalysis enables long-life, high-energy lithium-sulfur batteries. Nano Res. 2020, 13, 1856–1866.

    Article  CAS  Google Scholar 

  49. Lai, W. H.; Wang, H.; Zheng, L. R.; Jiang, Q.; Yan, Z. C.; Wang, L.; Yoshikawa, H.; Matsumura, D.; Sun, Q.; Wang, Y. X. et al. General synthesis of single-atom catalysts for hydrogen evolution reactions and room-temperature Na-S batteries. Angew. Chem., Int. Ed. 2020, 59, 22171–22178.

    Article  CAS  Google Scholar 

  50. Zhang, B. W.; Sheng, T.; Liu, Y. D.; Wang, Y. X.; Zhang, L.; Lai, W. H.; Wang, L.; Yang, J. P.; Gu, Q. F.; Chou, S. L. et al. Atomic cobalt as an efficient electrocatalyst in sulfur cathodes for superior room-temperature sodium-sulfur batteries. Nat. Commun. 2018, 9, 4082.

    Article  Google Scholar 

  51. Cui, T. T.; Wang, Y. P.; Ye, T.; Wu, J.; Chen, Z. Q.; Li, J.; Lei, Y. P.; Wang, D. S.; Li, Y. D. Engineering dual single-atom sites on 2D ultrathin N-doped carbon nanosheets attaining ultra-low-temperature zinc-air battery. Angew. Chem., Int. Ed. 2022, 61, e202115219.

    Article  CAS  Google Scholar 

  52. Jiao, L.; Yan, H. Y.; Wu, Y.; Gu, W. L.; Zhu, C. Z.; Du, D.; Lin, Y. H. When nanozymes meet single-atom catalysis. Angew. Chem., Int. Ed. 2020, 59, 2565–2576.

    Article  CAS  Google Scholar 

  53. Xiang, H. J.; Feng, W.; Chen, Y. Single-atom catalysts in catalytic biomedicine. Adv. Mater. 2020, 32, 1905994.

    Article  CAS  Google Scholar 

  54. Ji, S.; Jiang, B.; Hao, H.; Chen, Y.; Dong, J.; Mao, Y.; Zhang, Z.; Gao, R.; Chen, W.; Zhang, R. et al. Matching the kinetics of natural enzymes with a single-atom iron nanozyme. Nat. Catal. 2021, 4, 407–417.

    Article  CAS  Google Scholar 

  55. Zhang, N. Q.; Ye, C. L.; Yan, H.; Li, L. C.; He, H.; Wang, D. S.; Li, Y. D. Single-atom site catalysts for environmental catalysis. Nano Res. 2020, 13, 3165–3182.

    Article  CAS  Google Scholar 

  56. Shang, Y. N.; Xu, X.; Gao, B. Y.; Wang, S. B.; Duan, X. G. Singleatom catalysis in advanced oxidation processes for environmental remediation. Chem. Soc. Rev. 2021, 50, 5281–5322.

    Article  CAS  Google Scholar 

  57. Wan, J. W.; Chen, W. X.; Jia, C. Y.; Zheng, L. R.; Dong, J. C.; Zheng, X. S.; Wang, Y.; Yan, W. S.; Chen, C.; Peng, Q. et al. Defect effects on TiO2 nanosheets: Stabilizing single atomic site Au and promoting catalytic properties. Adv. Mater. 2018, 30, 1705369.

    Article  Google Scholar 

  58. Zhang, J.; Huang, Q. A.; Wang, J.; Wang, J.; Zhang, J. J.; Zhao, Y. F. Supported dual-atom catalysts: Preparation, characterization, and potential applications. Chin. J. Catal. 2020, 41, 783–798.

    Article  CAS  Google Scholar 

  59. Zhang, W. Y.; Chao, Y. G.; Zhang, W. S.; Zhou, J. H.; Lv, F.; Wang, K.; Lin, F. X.; Luo, H.; Li, J.; Tong, M. P. et al. Emerging dual-atomic-site catalysts for efficient energy catalysis. Adv. Mater. 2021, 33, 2102576.

    Article  CAS  Google Scholar 

  60. Pan, Y.; Zhang, C.; Liu, Z.; Chen, C.; Li, Y. D. Structural regulation with atomic-level precision: From single-atomic site to diatomic and atomic interface catalysis. Matter 2020, 2, 78–110.

    Article  Google Scholar 

  61. Rong, H. P.; Ji, S. F.; Zhang, J. T.; Wang, D. D.; Li, Y. D. Synthetic strategies of supported atomic clusters for heterogeneous catalysis. Nat. Commun. 2020, 11, 5884.

    Article  CAS  Google Scholar 

  62. Wang, J.; You, R.; Zhao, C.; Zhang, W.; Liu, W.; Fu, X. P.; Li, Y. Y.; Zhou, F. Y.; Zheng, X. S.; Xu, Q. et al. N-coordinated dual-metal single-site catalyst for low-temperature CO oxidation. ACS Catal. 2020, 10, 2754–2761.

    Article  CAS  Google Scholar 

  63. Chen, J. Y.; Li, H.; Fan, C.; Meng, Q. W.; Tang, Y. W.; Qiu, X. Y.; Fu, G. T.; Ma, T. Y. Dual single-atomic Ni-N4 and Fe-N4 sites constructing janus hollow graphene for selective oxygen electrocatalysis. Adv. Mater. 2020, 32, 2003134.

    Article  CAS  Google Scholar 

  64. Han, X. P.; Ling, X. F.; Yu, D. S.; Xie, D. Y.; Li, L. L.; Peng, S. J.; Zhong, C.; Zhao, N. Q.; Deng, Y. D.; Hu, W. B. Atomically dispersed binary Co-Ni sites in nitrogen-doped hollow carbon nanocubes for reversible oxygen reduction and evolution. Adv. Mater. 2019, 31, 1905622.

    Article  CAS  Google Scholar 

  65. Lin, L.; Li, H. B.; Yan, C. C.; Li, H. F.; Si, R.; Li, M. R.; Xiao, J. P.; Wang, G. X.; Bao, X. H. Synergistic catalysis over iron-nitrogen sites anchored with cobalt phthalocyanine for efficient CO2 electroreduction. Adv. Mater. 2019, 31, 1903470.

    Article  CAS  Google Scholar 

  66. Zhou, Y.; Song, E. H.; Chen, W.; Segre, C. U.; Zhou, J. D.; Lin, Y. C.; Zhu, C.; Ma, R. G.; Liu, P.; Chu, S. F. et al. Dual-metal interbonding as the chemical facilitator for single-atom dispersions. Adv. Mater. 2020, 32, 2003484.

    Article  CAS  Google Scholar 

  67. Tian, S. B.; Fu, Q.; Chen, W. X.; Feng, Q. C.; Chen, Z.; Zhang, J.; Cheong, W. C.; Yu, R.; Gu, L.; Dong, J. C. et al. Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation. Nat. Commun. 2018, 4, 2353.

    Article  Google Scholar 

  68. Li, H. L.; Wang, L. B.; Dai, Y. Z.; Pu, Z. T.; Lao, Z. H.; Chen, Y. W.; Wang, M. L.; Zheng, X. S.; Zhu, J. F.; Zhang, W. H. et al. Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation. Nat. Nanotechnol. 2018, 13, 411–417.

    Article  CAS  Google Scholar 

  69. Yang, Y.; Qian, Y. M.; Li, H. J.; Zhang, Z. H.; Mu, Y. W.; Do, D.; Zhou, B.; Dong, J.; Yan, W. J.; Qin, Y. et al. O-coordinated W-Mo dual-atom catalyst for pH-universal electrocatalytic hydrogen evolution. Sci. Adv. 2020, 6, eaba6586.

    Article  CAS  Google Scholar 

  70. Hou, C. C.; Wang, H. F.; Li, C. X.; Xu, Q. From metal-organic frameworks to single/dual-atom and cluster metal catalysts for energy applications. Energy Environ. Sci. 2020, 13, 1658–1693.

    Article  CAS  Google Scholar 

  71. Qi, K.; Chhowalla, M.; Voiry, D. Single atom is not alone: Metal-support interactions in single-atom catalysis. Mater. Today 2020, 40, 173–192.

    Article  CAS  Google Scholar 

  72. Fang, X. Z.; Jiao, L.; Yu, S. H.; Jiang, H. L. Metal-organic framework-derived FeCo-N-doped hollow porous carbon nanocubes for electrocatalysis in acidic and alkaline media. ChemSusChem 2017, 10, 3019–3024.

    Article  CAS  Google Scholar 

  73. Ji, S. F.; Chen, Y. J.; Fu, Q.; Chen, Y. F.; Dong, J. C.; Chen, W. X.; Li, Z.; Wang, Y.; Gu, L.; He, W. et al. Confined pyrolysis within metal-organic frameworks to form uniform Ru3 clusters for efficient oxidation of alcohols. J. Am. Chem. Soc. 2017, 134, 9795–9798.

    Article  Google Scholar 

  74. Zhu, Z. J.; Yin, H. J.; Wang, Y.; Chuang, C. H.; Xing, L.; Dong, M. Y.; Lu, Y. R.; Casillas-Garcia, G.; Zheng, Y. L.; Chen, S. et al. Coexisting single-atomic Fe and Ni sites on hierarchically ordered porous carbon as a highly efficient ORR electrocatalyst. Adv. Mater. 2020, 32, 2004670.

    Article  CAS  Google Scholar 

  75. Ji, S. F.; Chen, Y. J.; Wang, X. L.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Chemical synthesis of single atomic site catalysts. Chem. Rev. 2020, 120, 11900–11955.

    Article  CAS  Google Scholar 

  76. Xiong, Y.; Dong, J. C.; Huang, Z. Q.; Xin, P. Y.; Chen, W. X.; Wang, Y.; Li, Z.; Jin, Z.; Xing, W.; Zhuang, Z. B. et al. Singleatom Rh/N-doped carbon electrocatalyst for formic acid oxidation. Nat. Nanotechnol. 2020, 15, 390–397.

    Article  CAS  Google Scholar 

  77. Li, Z.; Chen, Y. J.; Ji, S. F.; Tang, Y.; Chen, W. X.; Li, A.; Zhao, J.; Xiong, Y.; Wu, Y. E.; Gong, Y. et al. Iridium single-atom catalyst on nitrogen-doped carbon for formic acid oxidation synthesized using a general host-guest strategy. Nat. Chem. 2020, 12, 764–772.

    Article  Google Scholar 

  78. Wang, J.; Liu, W.; Luo, G.; Li, Z. J.; Zhao, C.; Zhang, H. R.; Zhu, M. Z.; Xu, Q.; Wang, X. Q.; Zhao, C. M. et al. Synergistic effect of well-defined dual sites boosting the oxygen reduction reaction. Energy Environ. Sci. 2018, 11, 3375–3379.

    Article  CAS  Google Scholar 

  79. Wei, Y. S.; Sun, L. M.; Wang, M.; Hong, J. H.; Zou, L. L.; Liu, H. W.; Wang, Y.; Zhang, M.; Liu, Z.; Li, Y. W. et al. Fabricating dualatom iron catalysts for efficient oxygen evolution reaction: A heteroatom modulator approach. Angew. Chem., Int. Ed. 2020, 54, 16013–16022.

    Article  Google Scholar 

  80. Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Ptl/FeOx. Nat. Chem. 2011, 3, 634–641.

    Article  CAS  Google Scholar 

  81. Lu, J. L.; Elam, J. W.; Stair, P. C. Synthesis and stabilization of supported metal catalysts by atomic layer deposition. Acc. Chem. Res. 2013, 46, 1806–1815.

    Article  CAS  Google Scholar 

  82. Lu, J. L. A perspective on new opportunities in atom-by-atom synthesis of heterogeneous catalysts using atomic layer deposition. Catal. Lett. 2021, 151, 1535–1545.

    Article  CAS  Google Scholar 

  83. Zhang, L.; Banis, M. N.; Sun, X. L. Single-atom catalysts by the atomic layer deposition technique. Natl. Sci. Rev. 2018, 5, 628–630.

    Article  CAS  Google Scholar 

  84. Cheng, N. C.; Stambula, S.; Wang, D.; Banis, M. N.; Liu, J.; Riese, A.; Xiao, B. W.; Li, R. Y.; Sham, T. K.; Liu, L. M. et al. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nat. Commun. 2016, 7, 13638.

    Article  CAS  Google Scholar 

  85. Sun, S. H.; Zhang, G. X.; Gauquelin, N.; Chen, N.; Zhou, J. G.; Yang, S. L.; Chen, W. F.; Meng, X. B.; Geng, D. S.; Banis, M. N. et al. Single-atom catalysis using Pt/graphene achieved through atomic layer deposition. Sci. Rep. 2013, 3, 1775.

    Article  Google Scholar 

  86. Cao, Y. J.; Chen, S.; Luo, Q. Q.; Yan, H.; Lin, Y.; Liu, W.; Cao, L. L.; Lu, J. L.; Yang, J. L.; Yao, T. et al. Atomic-level insight into optimizing the hydrogen evolution pathway over a Co1-N4 single-site photocatalyst. Angew. Chem., Int. Ed. 2017, 56, 12191–12196.

    Article  CAS  Google Scholar 

  87. Yan, H.; Lin, Y.; Wu, H.; Zhang, W. H.; Sun, Z. H.; Cheng, H.; Liu, W.; Wang, C. L.; Li, J. J.; Huang, X. H. et al. Bottom-up precise synthesis of stable platinum dimers on graphene. Nat. Commun. 2017, 8, 1070.

    Article  Google Scholar 

  88. Zhang, L.; Si, R. T.; Liu, H. S.; Chen, N.; Wang, Q.; Adair, K.; Wang, Z. Q.; Chen, J. T.; Song, Z. X.; Li, J. J. et al. Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction. Nat. Commun. 2019, 10, 4936.

    Article  Google Scholar 

  89. Zhang, Z. R.; Feng, C.; Liu, C. X.; Zuo, M.; Qin, L.; Yan, X. P.; Xing, Y. L.; Li, H. L.; Si, R.; Zhou, S. M. et al. Electrochemical deposition as a universal route for fabricating single-atom catalysts. Nat. Commun. 2020, 11, 1215.

    Article  CAS  Google Scholar 

  90. Shi, Y.; Huang, W. M.; Li, J.; Zhou, Y.; Li, Z. Q.; Yin, Y. C.; Xia, X. H. Site-specific electrodeposition enables self-terminating growth of atomically dispersed metal catalysts. Nat. Commun. 2020, 11, 4558.

    Article  CAS  Google Scholar 

  91. Shi, Y.; Ma, Z. R.; Xiao, Y. Y.; Yin, Y. C.; Huang, W. M.; Huang, Z. C.; Zheng, Y. Z.; Mu, F. Y.; Huang, R.; Shi, G. Y. et al. Electronic metal-support interaction modulates single-atom platinum catalysis for hydrogen evolution reaction. Nat. Commun. 2021, 12, 3021.

    Article  Google Scholar 

  92. Bai, L. C.; Hsu, C. S.; Alexander, D. T. L.; Chen, H. M.; Hu, X. L. A cobalt-iron double-atom catalyst for the oxygen evolution reaction. J. Am. Chem. Soc. 2019, 141, 14190–14199.

    Article  CAS  Google Scholar 

  93. Zhao, Y. Y.; Yan, X. X.; Yang, K. R.; Cao, S. F.; Dong, Q.; Thorne, J. E.; Materna, K. L.; Zhu, S. S.; Pan, X. Q.; Flytzani-Stephanopoulos, M. et al. End-on bound iridium dinuclear heterogeneous catalysts on WO3 for solar water oxidation. ACS Cent. Sci. 2018, 4, 1166–1172.

    Article  CAS  Google Scholar 

  94. Zhao, Y. Y.; Yang, K. R.; Wang, Z. C.; Yan, X. X.; Cao, S. F.; Ye, Y. F.; Dong, Q.; Zhang, X. Z.; Thorne, J. E.; Jin, L. et al. Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation. Proc. Natl. Acad. Sci. USA 2018, 115, 2902–2907.

    Article  CAS  Google Scholar 

  95. Gao, R. J.; Wang, J.; Huang, Z. F.; Zhang, R. R.; Wang, W.; Pan, L.; Zhang, J. F.; Zhu, W. K.; Zhang, X. W.; Shi, C. X. et al. Pt/Fe2O3 with Pt-Fe pair sites as a catalyst for oxygen reduction with ultralow Pt loading. Nat. Energy 2021, 6, 614–623.

    Article  CAS  Google Scholar 

  96. Vorobyeva, E.; Fako, E.; Chen, Z. P.; Collins, S. M.; Johnstone, D.; Midgley, P. A.; Hauert, R.; Safonova, O. V.; Vilé, G.; López, N. et al. Atom-by-atom resolution of structure-function relations over low-nuclearity metal catalysts. Angew. Chem., Int. Ed. 2019, 58, 8724–8729.

    Article  CAS  Google Scholar 

  97. Wang, Y.; Mao, J.; Meng, X. G.; Yu, L.; Deng, D. H.; Bao, X. H. Catalysis with two-dimensional materials confining single atoms: Concept, design, and applications. Chem. Rev. 2019, 119, 1806–1854.

    Article  CAS  Google Scholar 

  98. Hannagan, R. T.; Giannakakis, G.; Flytzani-Stephanopoulos, M.; Sykes, E. C. H. Single-atom alloy catalysis. Chem. Rev. 2020, 120, 12044–12088.

    Article  CAS  Google Scholar 

  99. He, Z. Y.; He, K.; Robertson, A. W.; Kirkland, A. I.; Kim, D.; Ihm, J.; Yoon, E.; Lee, G. D.; Warner, J. H. Atomic structure and dynamics of metal dopant pairs in graphene. Nano Lett. 2014, 14, 3766–3772.

    Article  CAS  Google Scholar 

  100. Gu, J.; Jian, M. Z.; Huang, L.; Sun, Z. H.; Li, A. W.; Pan, Y.; Yang, J. Z.; Wen, W.; Zhou, W.; Lin, Y. et al. Synergizing metal-support interactions and spatial confinement boosts dynamics of atomic nickel for hydrogenations. Nat. Nanotechnol. 2021, 16, 1141–1149.

    Article  CAS  Google Scholar 

  101. Timoshenko, J.; Roldan Cuenya, B. In situ/operando electrocatalyst characterization by X-ray absorption spectroscopy. Chem. Rev. 2021, 121, 882–961.

    Article  CAS  Google Scholar 

  102. Frati, F.; Hunault, M. O. J. Y.; de Groot, F. M. F. Oxygen K-edge X-ray absorption spectra. Chem. Rev. 2020, 120, 4056–4110.

    Article  CAS  Google Scholar 

  103. Zhao, J.; Ji, S. F.; Guo, C. X.; Li, H. J.; Dong, J. C.; Guo, P.; Wang, D. S.; Li, Y. D.; Toste, F. D. A heterogeneous iridium single-atomsite catalyst for highly regioselective carbenoid O-H bond insertion. Nat. Catal. 2021, 4, 523–531.

    Article  CAS  Google Scholar 

  104. Fei, H. L.; Dong, J. C.; Chen, D. L.; Hu, T. D.; Duan, X. D.; Shakir, I.; Huang, Y.; Duan, X. F. Single atom electrocatalysts supported on graphene or graphene-like carbons. Chem. Soc. Rev. 2019, 48, 5207–5241.

    Article  CAS  Google Scholar 

  105. Xia, Z. M.; Zhang, H.; Shen, K. C.; Qu, Y. Q.; Jiang, Z. Wavelet analysis of extended X-ray absorption fine structure data: Theory, application. Phys. B:Condens. Matter 2018, 542, 12–19.

    Article  CAS  Google Scholar 

  106. Tian, S. B.; Wang, B. X.; Gong, W. B.; He, Z. Z.; Xu, Q.; Chen, W. X.; Zhang, Q. H.; Zhu, Y. Q.; Yang, J. R.; Fu, Q. et al. Dual-atom Pt heterogeneous catalyst with excellent catalytic performances for the selective hydrogenation and epoxidation. Nat. Commun. 2021, 12, 3181.

    Article  CAS  Google Scholar 

  107. Zhang, N.; Zhou, T. P.; Ge, J. K.; Lin, Y.; Du, Z. Y.; Zhong, C. A.; Wang, W. J.; Jiao, Q. Y.; Yuan, R. L.; Tian, Y. C. et al. High-density planar-like Fe2N6 structure catalyzes efficient oxygen reduction. Matter 2020, 3, 509–521.

    Article  Google Scholar 

  108. Xiao, M. L.; Chen, Y. T.; Zhu, J. B.; Zhang, H.; Zhao, X.; Gao, L. Q.; Wang, X.; Zhao, J.; Ge, J. J.; Jiang, Z. et al. Climbing the apex of the ORR volcano plot via binuclear site construction: Electronic and geometric engineering. J. Am. Chem. Soc. 2019, 141, 17763–17770.

    Article  CAS  Google Scholar 

  109. Bai, L. C.; Hsu, C. S.; Alexander, D. T. L.; Chen, H. M.; Hu, X. L. Double-atom catalysts as a molecular platform for heterogeneous oxygen evolution electrocatalysis. Nat. Energy 2021, 6, 1054–1066.

    Article  CAS  Google Scholar 

  110. Ding, T.; Liu, X. K.; Tao, Z. N.; Liu, T. Y.; Chen, T.; Zhang, W.; Shen, X. Y.; Liu, D.; Wang, S. C.; Pang, B. B. et al. Atomically precise dinuclear site active toward electrocatalytic CO2 reduction. J. Am. Chem. Soc. 2021, 143, 11317–11324.

    Article  CAS  Google Scholar 

  111. Li, Y. W.; Su, H. B.; Chan, S. H.; Sun, Q. CO2 electroreduction performance of transition metal dimers supported on graphene: A theoretical study. ACS Catal. 2015, 5, 6658–6664.

    Article  CAS  Google Scholar 

  112. Shen, H. M.; Li, Y. W.; Sun, Q. CO2 electroreduction performance of phthalocyanine sheet with Mn dimer:A theoretical study. J. Phys. Chem. C 2017, 121, 3963–3969.

    Article  CAS  Google Scholar 

  113. Cui, T. T.; Ma, L. N.; Wang, S. B.; Ye, C. L.; Liang, X.; Zhang, Z. D.; Meng, G.; Zheng, L. R.; Hu, H. S.; Zhang, J. W. et al. Atomically dispersed Pt-N3C1 sites enabling efficient and selective electrocatalytic C-C bond cleavage in lignin models under ambient conditions. J. Am. Chem. Soc. 2021, 143, 9429–9439.

    Article  CAS  Google Scholar 

  114. Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2022, 1, 100013.

    Article  Google Scholar 

  115. Liang, Z.; Song, L. P.; Sun, M. Z.; Huang, B. L.; Du, Y. P. Tunable CO/H2 ratios of electrochemical reduction of CO2 through the Zn-Ln dual atomic catalysts. Sci. Adv. 2021, 7, eabl4915.

    Article  CAS  Google Scholar 

  116. Sun, M. Z.; Wong, H. H.; Wu, T.; Dougherty, A. W.; Huang, B. L. Stepping out of transition metals: Activating the dual atomic catalyst through main group elements. Adv. Energy Mater. 2021, 11, 2101404.

    Article  CAS  Google Scholar 

  117. Sun, M. Z.; Wong, H. H.; Wu, T.; Dougherty, A. W.; Huang, B. L. Entanglement of spatial and energy segmentation for C1 pathways in CO2 reduction on carbon skeleton supported atomic catalysts. Adv. Energy Mater. 2022, 12, 2103781.

    Article  CAS  Google Scholar 

  118. Sun, M. Z.; Wu, T.; Dougherty, A. W.; Lam, M.; Huang, B. L.; Li, Y. L.; Yan, C. H. Self-validated machine learning study of graphdiyne-based dual atomic catalyst. Adv. Energy Mater. 2021, 11, 2003796.

    Article  CAS  Google Scholar 

  119. Luo, G.; Jing, Y.; Li, Y. F. Rational design of dual-metal-site catalysts for electroreduction of carbon dioxide. J. Mater. Chem. A 2020, 8, 15809–15815.

    Article  CAS  Google Scholar 

  120. Yao, Y. C.; Hu, S. L.; Chen, W. X.; Huang, Z. Q.; Wei, W. C.; Yao, T.; Liu, R. R.; Zang, K. T.; Wang, X. Q.; Wu, G. et al. Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis. Nat. Catal. 2019, 2, 304–313.

    Article  CAS  Google Scholar 

  121. Greiner, M. T.; Jones, T. E.; Beeg, S.; Zwiener, L.; Scherzer, M.; Girgsdies, F.; Piccinin, S.; Armbrüster, M.; Knop-Gericke, A.; Schlögl, R. Free-atom-like d states in single-atom alloy catalysts. Nat. Chem. 2018, 10, 1008–1015.

    Article  CAS  Google Scholar 

  122. Lee, J.; Kumar, A.; Yang, T.; Liu, X. H.; Jadhav, A. R.; Park, G. H.; Hwang, Y.; Yu, J. M.; Nguyen, C. T. K.; Liu, Y. et al. Stabilizing the OOH* intermediate via pre-adsorbed surface oxygen of a single Ru atom-bimetallic alloy for ultralow overpotential oxygen generation. Energy Environ. Sci. 2020, 13, 5152–5164.

    Article  CAS  Google Scholar 

  123. Hwang, J.; Noh, S. H.; Han, B. Design of active bifunctional electrocatalysts using single atom doped transition metal dichalcogenides. Appl. Surf. Sci. 2019, 471, 545–552.

    Article  CAS  Google Scholar 

  124. Yang, T.; Song, T. T.; Zhou, J.; Wang, S. J.; Chi, D. Z.; Shen, L.; Yang, M.; Feng, Y. P. High-throughput screening of transition metal single atom catalysts anchored on molybdenum disulfide for nitrogen fixation. Nano Energy 2020, 68, 104304.

    Article  CAS  Google Scholar 

  125. Lv, X. S.; Wei, W.; Huang, B. B.; Dai, Y.; Frauenheim, T. High-throughput screening of synergistic transition metal dual-atom catalysts for efficient nitrogen fixation. Nano Lett. 2021, 21, 1871–1878.

    Article  CAS  Google Scholar 

  126. Ulissi, Z. W.; Tang, M. T.; Xiao, J. P.; Liu, X. Y.; Torelli, D. A.; Karamad, M.; Cummins, K.; Hahn, C.; Lewis, N. S.; Jaramillo, T. F. et al. Machine-learning methods enable exhaustive searches for active bimetallic facets and reveal active site motifs for CO2 reduction. ACS Catal. 2017, 7, 6600–6608.

    Article  CAS  Google Scholar 

  127. Jinnouchi, R.; Hirata, H.; Asahi, R. Extrapolating energetics on clusters and single-crystal surfaces to nanoparticles by machine-learning scheme. J. Phys. Chem. C 2017, 121, 26397–26405.

    Article  CAS  Google Scholar 

  128. Sun, M. Z.; Dougherty, A. W.; Huang, B. L.; Li, Y. L.; Yan, C. H. Accelerating atomic catalyst discovery by theoretical calculations-machine learning strategy. Adv. Energy Mater. 2020, 10, 1903949.

    Article  CAS  Google Scholar 

  129. Zhu, X. R.; Yan, J. X.; Gu, M.; Liu, T. Y.; Dai, Y. F.; Gu, Y. H.; Li, Y. F. Activity origin and design principles for oxygen reduction on dual-metal-site catalysts: A combined density functional theory and machine learning study. J. Phys. Chem. Lett. 2019, 10, 7760–7766.

    Article  CAS  Google Scholar 

  130. Liu, M. M.; Wang, L. L.; Zhao, K. N.; Shi, S. S.; Shao, Q. S.; Zhang, L.; Sun, X. L.; Zhao, Y. F.; Zhang, J. J. Atomically dispersed metal catalysts for the oxygen reduction reaction: Synthesis, characterization, reaction mechanisms and electrochemical energy applications. Energy Environ. Sci. 2019, 12, 2890–2923.

    Article  CAS  Google Scholar 

  131. Zheng, X. B.; Li, P.; Dou, S. X.; Sun, W. P.; Pan, H. G.; Wang, D. S.; Li, Y. D. Non-carbon-supported single-atom site catalysts for electrocatalysis. Energy Environ. Sci. 2021, 14, 2809–2858.

    Article  CAS  Google Scholar 

  132. Li, S.; Chen, B. B.; Wang, Y.; Ye, M. Y.; van Aken, P. A.; Cheng, C.; Thomas, A. Oxygen-evolving catalytic atoms on metal carbides. Nat. Mater. 2021, 20, 1240–1247.

    Article  CAS  Google Scholar 

  133. Zheng, X. B.; Cui, P. X.; Qian, Y. M.; Zhao, G. Q.; Zheng, X. S.; Xu, X.; Cheng, Z. X.; Liu, Y. Y.; Dou, S. X.; Sun, W. P. Multifunctional active-center-transferable platinum/lithium cobalt oxide heterostructured electrocatalysts towards superior water splitting. Angew. Chem., Int. Ed. 2020, 54, 14533–14540.

    Article  Google Scholar 

  134. Zheng, X. B.; Chen, Y. P.; Zheng, X. S.; Zhao, G. Q.; Rui, K.; Li, P.; Xu, X.; Cheng, Z. X.; Dou, S. X.; Sun, W. P. Electronic structure engineering of LiCoO2 toward enhanced oxygen electrocatalysis. Adv. Energy Mater. 2019, 4, 1803482.

    Article  Google Scholar 

  135. Jiang, K.; Liu, B. Y.; Luo, M.; Ning, S. C.; Peng, M.; Zhao, Y.; Lu, Y. R.; Chan, T. S.; de Groot, F. M. F.; Tan, Y. W. Single platinum atoms embedded in nanoporous cobalt selenide as electrocatalyst for accelerating hydrogen evolution reaction. Nat. Commun. 2019, 10, 1743.

    Article  Google Scholar 

  136. Wu, J. B.; Xiong, L. K.; Zhao, B. T.; Liu, M. L.; Huang, L. Densely populated single atom catalysts. Small Methods 2020, 4, 1900540.

    Article  CAS  Google Scholar 

  137. Zhu, J.; Hu, L. S.; Zhao, P. X.; Lee, L. Y. S.; Wong, K. Y. Recent advances in electrocatalytic hydrogen evolution using nanoparticles. Chem. Rev. 2020, 120, 851–918.

    Article  CAS  Google Scholar 

  138. Rui, K.; Zhao, G. Q.; Lao, M. M.; Cui, P. X.; Zheng, X. S.; Zheng, X. B.; Zhu, J. X.; Huang, W.; Dou, S. X.; Sun, W. P. Direct hybridization of noble metal nanostructures on 2D metal-organic framework nanosheets to catalyze hydrogen evolution. Nano Lett. 2019, 14, 8447–8453.

    Article  Google Scholar 

  139. Kibsgaard, J.; Chorkendorff, I. Considerations for the scaling-up of water splitting catalysts. Nat. Energy 2019, 4, 430–433.

    Article  Google Scholar 

  140. Lu, K.; Liu, Y. Z.; Lin, F.; Cordova, I. A.; Gao, S. Y.; Li, B. M.; Peng, B.; Xu, H. P.; Kaelin, J.; Coliz, D. et al. LixNiO/Ni heterostructure with strong basic lattice oxygen enables electrocatalytic hydrogen evolution with Pt-like activity. J. Am. Chem. Soc. 2020, 142, 12613–12619.

    Article  CAS  Google Scholar 

  141. Podjaski, F.; Weber, D.; Zhang, S. Y.; Diehl, L.; Eger, R.; Duppel, V.; Alarcón-Lladó, E.; Richter, G.; Haase, F.; Morral, A. F. I. et al. Rational strain engineering in delafossite oxides for highly efficient hydrogen evolution catalysis in acidic media. Nat. Catal. 2020, 3, 55–63.

    Article  CAS  Google Scholar 

  142. Zhu, C. Z.; Shi, Q. R.; Feng, S.; Du, D.; Lin, Y. H. Single-atom catalysts for electrochemical water splitting. ACS Energy Lett. 2018, 3, 1713–1721.

    Article  CAS  Google Scholar 

  143. Chen, Y.; Rao, Y.; Wang, R. Z.; Yu, Y. N.; Li, Q. L.; Bao, S. J.; Xu, M. W.; Yue, Q.; Zhang, Y. N.; Kang, Y. J. Interfacial engineering of Ni/V2O3 for hydrogen evolution reaction. Nano Res. 2020, 13, 2407–2412.

    Article  CAS  Google Scholar 

  144. Gong, M.; Wang, D. Y.; Chen, C. C.; Hwang, B. J.; Dai, H. J. A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Res. 2016, 4, 28–46.

    Article  Google Scholar 

  145. Lao, M. M.; Rui, K.; Zhao, G. Q.; Cui, P. X.; Zheng, X. S.; Dou, S. X.; Sun, W. P. Platinum/nickel bicarbonate heterostructures towards accelerated hydrogen evolution under alkaline conditions. Angew. Chem., Int. Ed. 2019, 58, 5432–5437.

    Article  CAS  Google Scholar 

  146. Li, P.; Zhao, G. Q.; Cui, P. X.; Cheng, N. Y.; Lao, M. M.; Xu, X.; Dou, S. X.; Sun, W. P. Nickel single atom-decorated carbon nanosheets as multifunctional electrocatalyst supports toward efficient alkaline hydrogen evolution. Nano Energy 2021, 83, 105850.

    Article  CAS  Google Scholar 

  147. Chao, T. T.; Luo, X.; Chen, W. X.; Jiang, B.; Ge, J. J.; Lin, Y.; Wu, G.; Wang, X. Q.; Hu, Y. M.; Zhuang, Z. B. et al. Atomically dispersed copper-platinum dual sites alloyed with palladium nanorings catalyze the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2017, 56, 16047–16051.

    Article  CAS  Google Scholar 

  148. Kuang, P. Y.; Wang, Y. R.; Zhu, B. C.; Xia, F. J.; Tung, C. W.; Wu, J. S.; Chen, H. M.; Yu, J. G. Pt single atoms supported on N-doped mesoporous hollow carbon spheres with enhanced electrocatalytic H2-evolution activity. Adv. Mater. 2021, 33, 2008599.

    Article  CAS  Google Scholar 

  149. Cao, L. L.; Luo, Q. Q.; Liu, W.; Lin, Y.; Liu, X. K.; Cao, Y. J.; Zhang, W.; Wu, Y. E.; Yang, J. L.; Yao, T. et al. Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution. Nat. Catal. 2019, 2, 134–141.

    Article  CAS  Google Scholar 

  150. Liu, X.; Jiao, Y.; Zheng, Y.; Davey, K.; Qiao, S. Z. A computational study on Pt and Ru dimers supported on graphene for the hydrogen evolution reaction: New insight into the alkaline mechanism. J. Mater. Chem. A 2019, 7, 3648–3654.

    Article  CAS  Google Scholar 

  151. Zhang, L. Z.; Jia, Y.; Liu, H. L.; Zhuang, L. Z.; Yan, X. C.; Lang, C. G.; Wang, X.; Yang, D. J.; Huang, K. K.; Feng, S. H. et al. Charge polarization from atomic metals on adjacent graphitic layers for enhancing the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2019, 58, 9404–9408.

    Article  CAS  Google Scholar 

  152. Cao, L. J.; Wang, X. L.; Yang, C.; Lu, J. J.; Shi, X. Y.; Zhu, H. W.; Liang, H. P. Highly active Fe/Pt single-atom bifunctional electrocatalysts on biomass-derived carbon. ACS Sustainable Chem. Eng. 2020, 4, 189–196.

    Google Scholar 

  153. Zeng, X. J.; Shui, J. L.; Liu, X. F.; Liu, Q. T.; Li, Y. C.; Shang, J. X.; Zheng, L. R.; Yu, R. H. Single-atom to single-atom grafting of Pt1 onto Fe-N4 center: Pt1@Fe-N-C multifunctional electrocatalyst with significantly enhanced properties. Adv. Energy Mater. 2018, 8, 1701345.

    Article  Google Scholar 

  154. Kumar, A.; Bui, V. Q.; Lee, J.; Wang, L. L.; Jadhav, A. R.; Liu, X. H.; Shao, X. D.; Liu, Y.; Yu, J. M.; Hwang, Y. et al. Moving beyond bimetallic-alloy to single-atom dimer atomic-interface for all-pH hydrogen evolution. Nat. Commun. 2021, 12, 6766.

    Article  CAS  Google Scholar 

  155. Li, Q.; Wu, J. B.; Wu, T.; Jin, H. R.; Zhang, N.; Li, J.; Liang, W. X.; Liu, M. L.; Huang, L.; Zhou, J. Phase engineering of atomically thin perovskite oxide for highly active oxygen evolution. Adv. Funct. Mater. 2021, 31, 2102002.

    Article  CAS  Google Scholar 

  156. Zhao, G. Q.; Li, P.; Cheng, N. Y.; Dou, S. X.; Sun, W. P. An Ir/Ni(OH)2 heterostructured electrocatalyst for the oxygen evolution reaction: Breaking the scaling relation, stabilizing iridium(V), and beyond. Adv. Mater. 2020, 32, 2000872.

    Article  CAS  Google Scholar 

  157. Chen, J. Y.; Cui, P. X.; Zhao, G. Q.; Rui, K.; Lao, M. M.; Chen, Y. P.; Zheng, X. S.; Jiang, Y. Z.; Pan, H. G.; Dou, S. X. et al. Low-coordinate iridium oxide confined on graphitic carbon nitride for highly efficient oxygen evolution. Angew. Chem., Int. Ed. 2019, 58, 12540–12544.

    Article  CAS  Google Scholar 

  158. Seitz, L. C.; Dickens, C. F.; Nishio, K.; Hikita, Y.; Montoya, J.; Doyle, A.; Kirk, C.; Vojvodic, A.; Hwang, H. Y.; Norskov, J. K. et al. A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction. Science 2016, 353, 1011–1014.

    Article  CAS  Google Scholar 

  159. Nong, H. N.; Falling, L. J.; Bergmann, A.; Klingenhof, M.; Tran, H. P.; Spöri, C.; Mom, R.; Timoshenko, J.; Zichittella, G.; Knop-Gericke, A. et al. Key role of chemistry versus bias in electrocatalytic oxygen evolution. Nature 2020, 587, 408–413.

    Article  CAS  Google Scholar 

  160. Song, J. J.; Wei, C.; Huang, Z. F.; Liu, C. T.; Zeng, L.; Wang, X.; Xu, Z. J. A review on fundamentals for designing oxygen evolution electrocatalysts. Chem. Soc. Rev. 2020, 49, 2196–2214.

    Article  CAS  Google Scholar 

  161. Huang, L. A.; He, Z. S.; Guo, J. F.; Pei, S. E.; Shao, H. B.; Wang, J. M. Photodeposition fabrication of hierarchical layered Co-doped Ni oxyhydroxide (NixCo1−xOOH) catalysts with enhanced electrocatalytic performance for oxygen evolution reaction. Nano Res. 2020, 13, 246–254.

    Article  CAS  Google Scholar 

  162. Wang, T. J.; Liu, X. Y.; Li, Y.; Li, F. M.; Deng, Z. W.; Chen, Y. Ultrasonication-assisted and gram-scale synthesis of Co-LDH nanosheet aggregates for oxygen evolution reaction. Nano Res. 2019, 13, 79–85.

    Article  Google Scholar 

  163. Zhang, B.; Zheng, X. L.; Voznyy, O.; Comin, R.; Bajdich, M.; Garcia-Melchor, M.; Han, L. L.; Xu, J. X.; Liu, M.; Zheng, L. R. et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science 2016, 352, 333–337.

    Article  CAS  Google Scholar 

  164. Mefford, J. T.; Akbashev, A. R.; Kang, M.; Bentley, C. L.; Gent, W. E.; Deng, H. D.; Alsem, D. H.; Yu, Y. S.; Salmon, N. J.; Shapiro, D. A. et al. Correlative operando microscopy of oxygen evolution electrocatalysts. Nature 2021, 593, 67–73.

    Article  CAS  Google Scholar 

  165. Chen, Y. J.; Gao, R.; Ji, S. F.; Li, H. J.; Tang, K.; Jiang, P.; Hu, H. B.; Zhang, Z. D.; Hao, H. G.; Qu, Q. Y. et al. Atomic-level modulation of electronic density at cobalt single-atom sites derived from metal-organic frameworks: Enhanced oxygen reduction performance. Angew. Chem., Int. Ed. 2021, 60, 3212–3221.

    Article  CAS  Google Scholar 

  166. Wei, B.; Fu, Z. H.; Legut, D.; Germann, T. C.; Du, S. Y.; Zhang, H. J.; Francisco, J. S.; Zhang, R. F. Rational design of highly stable and active MXene-based bifunctional ORR/OER double-atom catalysts. Adv. Mater. 2021, 33, 2102595.

    Article  CAS  Google Scholar 

  167. Wu, C. C.; Zhang, X. M.; Xia, Z. X.; Shu, M.; Li, H. Q.; Xu, X. L.; Si, R.; Rykov, A. I.; Wang, J. H.; Yu, S. S. et al. Insight into the role of Ni-Fe dual sites in the oxygen evolution reaction based on atomically metal-doped polymeric carbon nitride. J. Mater. Chem. A 2019, 7, 14001–14010.

    Article  CAS  Google Scholar 

  168. Xiao, M. L.; Zhu, J. B.; Li, S.; Li, G. R.; Liu, W. W.; Deng, Y. P.; Bai, Z. Y.; Ma, L.; Feng, M.; Wu, T. P. et al. 3D-orbital occupancy regulated Ir-Co atomic pair toward superior bifunctional oxygen electrocatalysis. ACS Catal. 2021, 11, 8837–8846.

    Article  CAS  Google Scholar 

  169. Zhu, X. F.; Zhang, D. T.; Chen, C. J.; Zhang, Q. R.; Liu, R. S.; Xia, Z. H.; Dai, L. M.; Amal, R.; Lu, X. Y. Harnessing the interplay of Fe-Ni atom pairs embedded in nitrogen-doped carbon for bifunctional oxygen electrocatalysis. Nano Energy 2020, 71, 104597.

    Article  CAS  Google Scholar 

  170. Wan, W. C.; Zhao, Y. G.; Wei, S. Q.; Triana, C. A.; Li, J. G.; Arcifa, A.; Allen, C. S.; Cao, R.; Patzke, G. R. Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts. Nat. Commun. 2021, 12, 5589.

    Article  CAS  Google Scholar 

  171. Zhao, C. X.; Li, B. Q.; Liu, J. N.; Zhang, Q. Intrinsic electrocatalytic activity regulation of M-N-C single-atom catalysts for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2021, 60, 4448–4463.

    Article  CAS  Google Scholar 

  172. Bu, L. Z.; Zhang, N.; Guo, S. J.; Zhang, X.; Li, J.; Yao, J. L.; Wu, T.; Lu, G.; Ma, J. Y.; Su, D. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 2016, 354, 1410–1414.

    Article  CAS  Google Scholar 

  173. Escudero-Escribano, M.; Malacrida, P.; Hansen, M. H.; Vej-Hansen, U. G.; Velázquez-Palenzuela, A.; Tripkovic, V.; Schiøitz, J.; Rossmeisl, J.; Stephens, I. E. L.; Chorkendorff, I. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 2016, 352, 73–76.

    Article  CAS  Google Scholar 

  174. Li, M. F.; Zhao, Z. P.; Cheng, T.; Fortunelli, A.; Chen, C. Y.; Yu, R.; Zhang, Q. H.; Gu, L.; Merinov, B. V.; Lin, Z. Y. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 2016, 354, 1414–1419.

    Article  CAS  Google Scholar 

  175. Wang, H. T.; Xu, S. C.; Tsai, C.; Li, Y. Z.; Liu, C.; Zhao, J.; Liu, Y. Y.; Yuan, H. Y.; Abild-Pedersen, F.; Prinz, F. B. et al. Direct and continuous strain control of catalysts with tunable battery electrode materials. Science 2016, 354, 1031–1036.

    Article  CAS  Google Scholar 

  176. Luo, M. C.; Zhao, Z. L.; Zhang, Y. L.; Sun, Y. J.; Xing, Y.; Lv, F.; Yang, Y.; Zhang, X.; Hwang, S.; Qin, Y. N. et al. PdMo bimetallene for oxygen reduction catalysis. Nature 2019, 574, 81–85.

    Article  CAS  Google Scholar 

  177. Tian, X. L.; Zhao, X.; Su, Y. Q.; Wang, L. J.; Wang, H. M.; Dang, D.; Chi, B.; Liu, H. F.; Hensen, E. J. M.; Lou, X. W. et al. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 2019, 366, 850–856.

    Article  CAS  Google Scholar 

  178. Wang, L.; Zeng, Z. H.; Gao, W. P.; Maxson, T.; Raciti, D.; Giroux, M.; Pan, X. Q.; Wang, C.; Greeley, J. Tunable intrinsic strain in two-dimensional transition metal electrocatalysts. Science 2019, 363, 870–874.

    Article  CAS  Google Scholar 

  179. Chen, Y. P.; Cai, J. Y.; Li, P.; Zhao, G. Q.; Wang, G. M.; Jiang, Y. Z.; Chen, J.; Dou, S. X.; Pan, H. G.; Sun, W. P. Hexagonal boron nitride as a multifunctional support for engineering efficient electrocatalysts toward the oxygen reduction reaction. Nano Lett. 2020, 20, 6807–6814.

    Article  CAS  Google Scholar 

  180. Wang, Y.; Wang, D. S.; Li, Y. D. Rational design of single-atom site electrocatalysts: From theoretical understandings to practical applications. Adv. Mater. 2021, 33, 2008151.

    Article  CAS  Google Scholar 

  181. Zhang, Q.; Zhang, X. X.; Wang, J. Z.; Wang, C. W. Graphene-supported single-atom catalysts and applications in electrocatalysis. Nanotechnology 2021, 32, 032001.

    Article  CAS  Google Scholar 

  182. Zhuang, Z. C.; Li, Y.; Li, Y. H.; Huang, J. Z.; Wei, B.; Sun, R.; Ren, Y. J.; Ding, J.; Zhu, J. X.; Lang, Z. Q. et al. Atomically dispersed nonmagnetic electron traps improve oxygen reduction activity of perovskite oxides. Energy Environ. Sci. 2021, 14, 1016–1028.

    Article  CAS  Google Scholar 

  183. Wang, Y.; Wang, D. S.; Li, Y. D. Atom-level interfacial synergy of single-atom site catalysts for electrocatalysis. J. Energy Chem. 2022, 65, 103–115.

    Article  CAS  Google Scholar 

  184. Yang, J. R.; Li, W. H.; Wang, D. S.; Li, Y. D. Single-atom materials: Small structures determine macroproperties. Small Struct. 2021, 2, 2000051.

    Article  CAS  Google Scholar 

  185. Gong, S. P.; Wang, C. L.; Jiang, P.; Hu, L.; Lei, H.; Chen, Q. W. Designing highly efficient dual-metal single-atom electrocatalysts for the oxygen reduction reaction inspired by biological enzyme systems. J. Mater. Chem. A 2018, 6, 13254–13262.

    Article  CAS  Google Scholar 

  186. Zhou, Y. D.; Yang, W.; Utetiwabo, W.; Lian, Y. M.; Yin, X.; Zhou, L.; Yu, P. W.; Chen, R. J.; Sun, S. R. 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. Lett. 2020, 11, 1404–1410.

    Article  CAS  Google Scholar 

  187. Du, C.; Gao, Y. J.; Chen, H. Q.; Li, P.; Zhu, S. Y.; Wang, J. G.; He, Q. G.; Chen, W. A Cu and Fe dual-atom nanozyme mimicking cytochrome c oxidase to boost the oxygen reduction reaction. J. Mater. Chem. A 2020, 8, 16994–17001.

    Article  CAS  Google Scholar 

  188. Wang, B. W.; Zou, J. X.; Shen, X. C.; Yang, Y. C.; Hu, G. Z.; Li, W.; Peng, Z. M.; Banham, D.; Dong, A. G.; Zhao, D. Y. Nanocrystal supracrystal-derived atomically dispersed Mn-Fe catalysts with enhanced oxygen reduction activity. Nano Energy 2019, 63, 103851.

    Article  CAS  Google Scholar 

  189. Liu, D. X.; Wang, B.; Li, H. G.; Huang, S. F.; Liu, M. M.; Wang, J.; Wang, Q. J.; Zhang, J. J.; Zhao, Y. F. Distinguished Zn, Co-Nx-C-Sy active sites confined in dentric carbon for highly efficient oxygen reduction reaction and flexible Zn-air Batteries. Nano Energy 2019, 58, 277–283.

    Article  CAS  Google Scholar 

  190. Zhang, D. Y.; Chen, W. X.; Li, Z.; Chen, Y. J.; Zheng, L. R.; Gong, Y.; Li, Q. H.; Shen, R. G.; Han, Y. H.; Cheong, W. C. et al. Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction. Chem. Commun. 2018, 54, 4274–4277.

    Article  CAS  Google Scholar 

  191. Xiao, M. L.; Zhang, H.; Chen, Y. T.; Zhu, J. B.; Gao, L. Q.; Jin, Z.; Ge, J. J.; Jiang, Z.; Chen, S. L.; Liu, C. P. et al. Identification of binuclear Co2N5 active sites for oxygen reduction reaction with more than one magnitude higher activity than single atom CoN4 site. Nano Energy 2018, 46, 396–403.

    Article  CAS  Google Scholar 

  192. Yang, G. G.; Zhu, J. W.; Yuan, P. F.; Hu, Y. F.; Qu, G.; Lu, B. A.; Xue, X. Y.; Yin, H. B.; Cheng, W. Z.; Cheng, J. Q. et al. Regulating Fe-spin state by atomically dispersed Mn-N in Fe-N-C catalysts with high oxygen reduction activity. Nat. Commun. 2021, 12, 1734.

    Article  CAS  Google Scholar 

  193. Liu, M.; Li, N.; Cao, S. F.; Wang, X. M.; Lu, X. Q.; Kong, L. J.; Xu, Y. H.; Bu, X. H. A “pre-constrained metal twins” strategy to prepare efficient dual-metal-atom catalysts for cooperative oxygen electrocatalysis. Adv. Mater. 2022, 34, 2107421.

    Article  CAS  Google Scholar 

  194. Zhao, R.; Liang, Z. B.; Gao, S.; Yang, C.; Zhu, B. J.; Zhao, J. L.; Qu, C.; Zou, R. Q.; Xu, Q. Puffing up energetic metal-organic frameworks to large carbon networks with hierarchical porosity and atomically dispersed metal sites. Angew. Chem., Int. Ed. 2019, 58, 1975–1979.

    Article  CAS  Google Scholar 

  195. Ye, W.; Chen, S. M.; Lin, Y.; Yang, L.; Chen, S. J.; Zheng, X. S.; Qi, Z. M.; Wang, C. M.; Long, R.; Chen, M. et al. Precisely tuning the number of fe atoms in clusters on N-doped carbon toward acidic oxygen reduction reaction. Chem 2019, 5, 2865–2878.

    Article  CAS  Google Scholar 

  196. Han, A.; Wang, X. J.; Tang, K.; Zhang, Z. D.; Ye, C. L.; Kong, K. J.; Hu, H. B.; Zheng, L. R.; Jiang, P.; Zhao, C. X. et al. An adjacent atomic platinum site enables single-atom iron with high oxygen reduction reaction performance. Angew. Chem., Int. Ed. 2021, 60, 19262–19271.

    Article  CAS  Google Scholar 

  197. Lu, Z. Y.; Wang, B.; Hu, Y. F.; Liu, W.; Zhao, Y. F.; Yang, R. O.; Li, Z. P.; Luo, J.; Chi, B.; Jiang, Z. et al. An isolated zinc-cobalt atomic pair for highly active and durable oxygen reduction. Angew. Chem., Int. Ed. 2019, 58, 2622–2626.

    Article  CAS  Google Scholar 

  198. Kong, F. P.; Si, R. T.; Chen, N.; Wang, Q.; Li, J. J.; Yin, G. P.; Gu, M.; Wang, J. J.; Liu, L. M.; Sun, X. L. Origin of hetero-nuclear Au- Co dual atoms for efficient acidic oxygen reduction. Appl. Catal. B:Environ. 2022, 301, 120782.

    Article  CAS  Google Scholar 

  199. Lin, S.; Diercks, C. S.; Zhang, Y. B.; Kornienko, N.; Nichols, E. M.; Zhao, Y. B.; Paris, A. R.; Kim, D.; Yang, P. D.; Yaghi, O. M. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 2015, 349, 1208–1213.

    Article  CAS  Google Scholar 

  200. Nitopi, S.; Bertheussen, E.; Scott, S. B.; Liu, X. Y.; Engstfeld, A. K.; Horch, S.; Seger, B.; Stephens, I. E. L.; Chan, K.; Hahn, C. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 2019, 119, 7610–7672.

    Article  CAS  Google Scholar 

  201. De Luna, P.; Hahn, C.; Higgins, D.; Jaffer, S. A.; Jaramillo, T. F.; Sargent, E. H. What would it take for renewably powered electrosynthesis to displace petrochemical processes. Science 2019, 364, eaav3506.

    Article  CAS  Google Scholar 

  202. Trindell, J. A.; Duan, Z. Y.; Henkelman, G.; Crooks, R. M. Well-defined nanoparticle electrocatalysts for the refinement of theory. Chem. Rev. 2020, 120, 814–850.

    Article  CAS  Google Scholar 

  203. Mori, K.; Taga, T.; Yamashita, H. Isolated single-atomic Ru catalyst bound on a layered double hydroxide for hydrogenation of CO2 to formic acid. ACS Catal. 2017, 7, 3147–3151.

    Article  CAS  Google Scholar 

  204. Cheng, N. C.; Zhang, L.; Doyle-Davis, K.; Sun, X. L. Single-atom catalysts: From design to application. Electrochem. Energy Rev. 2019, 2, 539–573.

    Article  Google Scholar 

  205. Chen, S. H.; Wang, B. Q.; Zhu, J. X.; Wang, L. Q.; Ou, H. H.; Zhang, Z. D.; Liang, X.; Zheng, L. R.; Zhou, L.; Su, Y. Q. et al. Lewis acid site-promoted single-atomic Cu catalyzes electrochemical CO2 methanation. Nano Lett. 2021, 21, 7325–7331.

    Article  CAS  Google Scholar 

  206. Jiang, Z. L.; Wang, T.; Pei, J. J.; Shang, H. S.; Zhou, D. N.; Li, H. J.; Dong, J. C.; Wang, Y.; Cao, R.; Zhuang, Z. B. et al. Discovery of main group single Sb-N4 active sites for CO2 electroreduction to formate with high efficiency. Energy Environ. Sci. 2020, 13, 2856–2863.

    Article  CAS  Google Scholar 

  207. Sun, X. H.; Tuo, Y. X.; Ye, C. L.; Chen, C.; Lu, Q.; Li, G. N.; Jiang, P.; Chen, S. H.; Zhu, P.; Ma, M. et al. Phosphorus induced electron localization of single iron sites for boosted CO2 electroreduction reaction. Angew. Chem., Int. Ed. 2021, 60, 23614–23618.

    Article  CAS  Google Scholar 

  208. Zhao, J.; Zhao, J. X.; Li, F. Y.; Chen, Z. F. Copper dimer supported on a C2N layer as an efficient electrocatalyst for CO2 reduction reaction: A computational study. J. Phys. Chem. C 2018, 122, 19712–19721.

    Article  CAS  Google Scholar 

  209. Ouyang, Y. X.; Shi, L.; Bai, X. W.; Li, Q.; Wang, J. L. Breaking scaling relations for efficient CO2 electrochemical reduction through dual-atom catalysts. Chem. Sci. 2020, 11, 1807–1813.

    Article  CAS  Google Scholar 

  210. Li, Y. Z.; Wei, B.; Zhu, M. H.; Chen, J. C.; Jiang, Q. K.; Yang, B.; Hou, Y.; Lei, L. C.; Li, Z. J.; Zhang, R. F. et al. Synergistic effect of atomically dispersed Ni-Zn pair sites for enhanced CO2 electroreduction. Adv. Mater. 2021, 33, 2102212.

    Article  CAS  Google Scholar 

  211. Zhu, W. J.; Zhang, L.; Liu, S. H.; Li, A.; Yuan, X. T.; Hu, C. L.; Zhang, G.; Deng, W. Y.; Zang, K. T.; Luo, J. et al. Enhanced CO2 electroreduction on neighboring Zn/Co monomers by electronic effect. Angew. Chem., Int. Ed. 2020, 54, 12664–12668.

    Article  Google Scholar 

  212. Pei, J. J.; Wang, T.; Sui, R.; Zhang, X. J.; Zhou, D. N.; Qin, F. J.; Zhao, X.; Liu, Q. H.; Yan, W. S.; Dong, J. C. et al. N-Bridged Co-N-Ni: New bimetallic sites for promoting electrochemical CO2 reduction. Energy Environ. Sci. 2021, 14, 3019–3028.

    Article  CAS  Google Scholar 

  213. Wei, X. F.; Wei, S. X.; Cao, S. F.; Hu, Y. Y.; Zhou, S. N.; Liu, S. Y.; Wang, Z. J.; Lu, X. Q. Cu acting as Fe activity promoter in dualatom Cu/Fe-NC catalyst in CO2RR to C1 products. Appl. Surf. Sci. 2021, 564, 150423.

    Article  CAS  Google Scholar 

  214. Xie, W. F.; Li, H.; Cui, G. Q.; Li, J. B.; Song, Y. K.; Li, S. J.; Zhang, X.; Lee, J. Y.; Shao, M. F.; Wei, M. NiSn atomic pair on an integrated electrode for synergistic electrocatalytic CO2 reduction. Angew. Chem., Int. Ed. 2021, 60, 7382–7388.

    Article  CAS  Google Scholar 

  215. Sun, M. J.; Gong, Z. W.; Yi, J. D.; Zhang, T.; Chen, X. D.; Cao, R. A highly efficient diatomic nickel electrocatalyst for CO2 reduction. Chem. Commun. 2020, 56, 8798–8801.

    Article  CAS  Google Scholar 

  216. Li, Y. F.; Chen, C.; Cao, R.; Pan, Z. W.; He, H.; Zhou, K. B. Dualatom Ag2/graphene catalyst for efficient electroreduction of CO2 to CO. Appl. Catal. B:Environ. 2020, 268, 118747.

    Article  CAS  Google Scholar 

  217. Jiao, J. Q.; Lin, R.; Liu, S. J.; Cheong, W. C.; Zhang, C.; Chen, Z.; Pan, Y.; Tang, J. G.; Wu, K. L.; Hung, S. F. et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2. Nat. Chem. 2019, 11, 222–228.

    Article  CAS  Google Scholar 

  218. Yang, J. R.; Zeng, D. Q.; Li, J.; Dong, L. Q.; Ong, W. J.; He, Y. L. A highly efficient Fenton-like catalyst based on isolated diatomic Fe-Co anchored on N-doped porous carbon. Chem. Eng. J. 2021, 404, 126376.

    Article  CAS  Google Scholar 

  219. Wang, Y.; Park, B. J.; Paidi, V. K.; Huang, R.; Lee, Y.; Noh, K. J.; Lee, K. S.; Han, J. W. Precisely constructing orbital coupling-modulated dual-atom fe pair sites for synergistic CO2 electroreduction. ACS Energy Lett. 2022, 7, 640–649.

    Article  CAS  Google Scholar 

  220. Cheng, H. Y.; Wu, X. M.; Feng, M. M.; Li, X. C.; Lei, G. P.; Fan, Z. H.; Pan, D. W.; Cui, F. J.; He, G. H. Atomically dispersed Ni/Cu dual sites for boosting the CO2 reduction reaction. ACS Catal. 2021, 11, 12673–12681.

    Article  CAS  Google Scholar 

  221. Jiao, L.; Zhu, J. T.; Zhang, Y.; Yang, W. J.; Zhou, S. Y.; Li, A. W.; Xie, C. F.; Zheng, X. S.; Zhou, W.; Yu, S. H. et al. Non-bonding interaction of neighboring Fe and Ni single-atom pairs on MOF-derived N-doped carbon for enhanced CO2 electroreduction. J. Am. Chem. Soc. 2021, 143, 19417–19424.

    Article  CAS  Google Scholar 

  222. Bao, D.; Zhang, Q.; Meng, F. L.; Zhong, H. X.; Shi, M. M.; Zhang, Y.; Yan, J. M.; Jiang, Q.; Zhang, X. B. Electrochemical reduction of N2 under ambient conditions for artificial N2 fixation and renewable energy storage using N2/NH3 cycle. Adv. Mater. 2017, 29, 1604799.

    Article  Google Scholar 

  223. van der Ham, C. J. M.; Koper, M. T. M.; Hetterscheid, D. G. H. Challenges in reduction of dinitrogen by proton and electron transfer. Chem. Soc. Rev. 2014, 43, 5183–5191.

    Article  CAS  Google Scholar 

  224. Liu, J. C.; Ma, X. L.; Li, Y.; Wang, Y. G.; Xiao, H.; Li, J. Heterogeneous Fe3 single-cluster catalyst for ammonia synthesis via an associative mechanism. Nat. Commun. 2018, 4, 1610.

    Article  Google Scholar 

  225. Liu, J. Y.; Kong, X.; Zheng, L. R.; Guo, X.; Liu, X. F.; Shui, J. L. Rare earth single-atom catalysts for nitrogen and carbon dioxide reduction. ACS Nano 2020, 14, 1093–1101.

    Article  CAS  Google Scholar 

  226. Qiu, Y.; Peng, X. Y.; Lü, F.; Mi, Y. Y.; Zhuo, L. C.; Ren, J. Q.; Liu, X. J.; Luo, J. Single-atom catalysts for the electrocatalytic reduction of nitrogen to ammonia under ambient conditions. Chem. Asian J. 2019, 14, 2770–2779.

    Article  CAS  Google Scholar 

  227. Liu, S. S.; Qian, T.; Wang, M. F.; Ji, H. Q.; Shen, X. W.; Wang, C.; Yan, C. L. Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis. Nat. Catal. 2021, 4, 322–331.

    Article  CAS  Google Scholar 

  228. Chen, Z.; Zhao, J. X.; Cabrera, C. R.; Chen, Z. F. Computational screening of efficient single-atom catalysts based on graphitic carbon nitride (g-C3N4) for nitrogen electroreduction. Small Methods 2019, 3, 1800368.

    Article  Google Scholar 

  229. Tao, H. C.; Choi, C.; Ding, L. X.; Jiang, Z.; Han, Z. S.; Jia, M. W.; Fan, Q.; Gao, Y. N.; Wang, H. H.; Robertson, A. W. et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem 2019, 5, 204–214.

    Article  CAS  Google Scholar 

  230. Liu, X.; Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Building up a picture of the electrocatalytic nitrogen reduction activity of transition metal single-atom catalysts. J. Am. Chem. Soc. 2019, 141, 9664–9672.

    Article  CAS  Google Scholar 

  231. Qian, Y. M.; Liu, Y. Y.; Zhao, Y.; Zhang, X. H.; Yu, G. H. Single vs. double atom catalyst for N2 activation in nitrogen reduction reaction: A DFT perspective. EcoMat 2020, 2, e12014.

    Article  CAS  Google Scholar 

  232. Yang, L.; Ma, X.; Xu, Y. Y.; Xu, J. Y.; Song, Y. D. A DFT study on application of dual-atom Fe2/phthalocyanine catalyst for N2 reduction reaction. Int. J. Electrochem. Sci. 2020, 15, 9698–9706.

    Article  Google Scholar 

  233. Chen, Z. W.; Yan, J. M.; Jiang, Q. Single or double: Which is the altar of atomic catalysts for nitrogen reduction reaction. Small Methods 2019, 3, 1800291.

    Article  Google Scholar 

  234. He, T. W.; Puente Santiago, A. R.; Du, A. J. Atomically embedded asymmetrical dual-metal dimers on N-doped graphene for ultraefficient nitrogen reduction reaction. J. Catal. 2020, 388, 77–83.

    Article  CAS  Google Scholar 

  235. Zheng, X. B.; Li, P.; Zhu, H. J.; Rui, K.; Zhao, G. Q.; Shu, J.; Xu, X.; Sun, W. P.; Dou, S. X. New insights into understanding the exceptional electrochemical performance of P2-type manganese-based layered oxide cathode for sodium ion batteries. Energy Stor. Mater. 2018, 15, 257–265.

    Google Scholar 

  236. Van der Ven, A.; Deng, Z.; Banerjee, S.; Ong, S. P. Rechargeable alkali-ion battery materials: Theory and computation. Chem. Rev. 2020, 120, 6977–7019.

    Article  CAS  Google Scholar 

  237. Zheng, X. B.; Li, P.; Zhu, H. J.; Zhao, G. Q.; Rui, K.; Shu, J.; Xu, X.; Wang, X. L.; Sun, W. P.; Dou, S. X. Understanding the structural and chemical evolution of layered potassium titanates for sodium ion batteries. Energy Stor. Mater. 2020, 25, 502–509.

    Google Scholar 

  238. Service, R. F. Zinc aims to beat lithium batteries at storing energy. Science 2021, 372, 890–891.

    Article  CAS  Google Scholar 

  239. Sun, W.; Wang, F.; Zhang, B.; Zhang, M. Y.; Küpers, V.; Ji, X.; Theile, C.; Bieker, P.; Xu, K.; Wang, C. S. et al. A rechargeable zinc-air battery based on zinc peroxide chemistry. Science 2021, 371, 46–51.

    Article  CAS  Google Scholar 

  240. Zhou, J. W.; Cheng, J. L.; Wang, B.; Peng, H. S.; Lu, J. Flexible metal-gas batteries: A potential option for next-generation power accessories for wearable electronics. Energy Environ. Sci. 2020, 13, 1933–1970.

    Article  CAS  Google Scholar 

  241. Zhou, T. P.; Zhang, N.; Wu, C. Z.; Xie, Y. Surface/interface nanoengineering for rechargeable Zn-air batteries. Energy Environ. Sci. 2020, 13, 1132–1153.

    Article  CAS  Google Scholar 

  242. Wu, J. B.; Zhou, H.; Li, Q.; Chen, M.; Wan, J.; Zhang, N.; Xiong, L. K.; Li, S.; Xia, B. Y.; Feng, G. et al. Densely populated isolated single Co-N site for efficient oxygen electrocatalysis. Adv. Energy Mater. 2019, 9, 1900149.

    Article  Google Scholar 

  243. Zhao, C. X.; Liu, J. N.; Wang, J.; Ren, D.; Yu, J.; Chen, X.; Li, B. Q.; Zhang, Q. A AE = 0.63 V bifunctional oxygen electrocatalyst enables high-rate and long-cycling zinc-air batteries. Adv. Mater. 2021, 33, 2008606.

    Article  CAS  Google Scholar 

  244. Xiao, M. L.; Xing, Z. H.; Jin, Z.; Liu, C. P.; Ge, J. J.; Zhu, J. B.; Wang, Y.; Zhao, X.; Chen, Z. W. Preferentially engineering FeN4 edge sites onto graphitic nanosheets for highly active and durable oxygen electrocatalysis in rechargeable Zn-air batteries. Adv. Mater. 2020, 32, 2004900.

    Article  CAS  Google Scholar 

  245. Zhang, W. M.; Liu, Y. Q.; Zhang, L. P.; Chen, J. Recent advances in isolated single-atom catalysts for zinc air batteries: A focus review. Nanomaterials 2019, 9, 1402.

    Article  CAS  Google Scholar 

  246. Peng, L. S.; Shang, L.; Zhang, T. R.; Waterhouse, G. I. N. Recent advances in the development of single-atom catalysts for oxygen electrocatalysis and zinc-air batteries. Adv. Energy Mater. 2020, 10, 2003018.

    Article  CAS  Google Scholar 

  247. Li, Z. H.; He, H. Y.; Cao, H. B.; Sun, S. M.; Diao, W. L.; Gao, D. L.; Lu, P. L.; Zhang, S. S.; Guo, Z.; Li, M. J. et al. Atomic Co/Ni dual sites and Co/Ni alloy nanoparticles in N-doped porous Januslike carbon frameworks for bifunctional oxygen electrocatalysis. Appl. Catal. B:Environ 2019, 240, 112–121.

    Article  CAS  Google Scholar 

  248. Chong, L. N.; Wen, J. G.; Kubal, J.; Sen, F. G.; Zou, J. X.; Greeley, J.; Chan, M.; Barkholtz, H.; Ding, W. J.; Liu, D. J. Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks. Science 2018, 362, 1276–1281.

    Article  CAS  Google Scholar 

  249. Chung, H. T.; Cullen, D. A.; Higgins, D.; Sneed, B. T.; Holby, E. F.; More, K. L.; Zelenay, P. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 2017, 357, 479–484.

    Article  CAS  Google Scholar 

  250. He, Y. H.; Liu, S. W.; Priest, C.; Shi, Q. R.; Wu, G. Atomically dispersed metal-nitrogen-carbon catalysts for fuel cells: Advances in catalyst design, electrode performance, and durability improvement. Chem. Soc. Rev. 2020, 49, 3484–3524.

    Article  CAS  Google Scholar 

  251. Gao, C.; Low, J.; Long, R.; Kong, T. T.; Zhu, J. F.; Xiong, Y. J. Heterogeneous single-atom photocatalysts: Fundamentals and applications. Chem. Rev. 2020, 120, 12175–12216.

    Article  CAS  Google Scholar 

  252. Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981–5079.

    Article  CAS  Google Scholar 

  253. Li, F. Y.; Chen, Z. F. Cu dimer anchored on C2N monolayer: Low-cost and efficient Bi-atom catalyst for CO oxidation. Nanoscale 2018, 10, 15696–15705.

    Article  CAS  Google Scholar 

  254. Wang, Q.; Jin, B. J.; Hu, M.; Jia, C. Y.; Li, X.; Sharman, E.; Jiang, J. N-doped graphene-supported diatomic Ni-Fe catalyst for synergistic oxidation of CO. J. Phys. Chem. C 2021, 125, 5616–5622.

    Article  CAS  Google Scholar 

  255. Li, F. Y.; Liu, X. Y.; Chen, Z. F. 1 + 1’ > 2: Heteronuclear biatom catalyst outperforms its homonuclear counterparts for CO oxidation. Small Methods 2019, 3, 1800480.

    Article  Google Scholar 

  256. Zhou, P.; Hou, X. G.; Chao, Y. G.; Yang, W. X.; Zhang, W. Y.; Mu, Z. J.; Lai, J. P.; Lv, F.; Yang, K.; Liu, Y. X. et al. Synergetic interaction between neighboring platinum and ruthenium monomers boosts CO oxidation. Chem. Sci. 2019, 10, 5898–5905.

    Article  CAS  Google Scholar 

  257. Fu, J. H.; Dong, J. H.; Si, R.; Sun, K. J.; Zhang, J. Y.; Li, M. R.; Yu, N. N.; Zhang, B. S.; Humphrey, M. G.; Fu, Q. et al. Synergistic effects for enhanced catalysis in a dual single-atom catalyst. ACS Catal. 2021, 11, 1952–1961.

    Article  CAS  Google Scholar 

  258. Ji, S. F.; Chen, Y. J.; Zhao, S.; Chen, W. X.; Shi, L. J.; Wang, Y.; Dong, J. C.; Li, Z.; Li, F. W.; Chen, C. et al. Atomically dispersed ruthenium species inside metal-organic frameworks: Combining the high activity of atomic sites and the molecular sieving effect of MOFs. Angew. Chem., Int. Ed. 2019, 58, 4271–4275.

    Article  CAS  Google Scholar 

  259. Liang, J. X.; Lin, J.; Liu, J. Y.; Wang, X. D.; Zhang, T.; Li, J. Dual metal active sites in an Ir1/FeOx single-atom catalyst: A redox mechanism for the water-gas shift reaction. Angew. Chem., Int. Ed. 2020, 59, 12968–12975.

    Article  Google Scholar 

  260. Ni, W. P.; Liu, Z. X.; Guo, X. G.; Zhang, Y.; Ma, C.; Deng, Y. J.; Zhang, S. G. Dual single-cobalt atom-based carbon electrocatalysts for efficient CO2-to-syngas conversion with industrial current densities. Appl. Catal. B:Environ. 2021, 291, 120092.

    Article  CAS  Google Scholar 

  261. Ao, X.; Zhang, W.; Zhao, B. T.; Ding, Y.; Nam, G.; Soule, L.; Abdelhafiz, A.; Wang, C. D.; Liu, M. L. Atomically dispersed Fe-N-C decorated with Pt-alloy core-shell nanoparticles for improved activity and durability towards oxygen reduction. Energy Environ. Sci. 2020, 13, 3032–3040.

    Article  CAS  Google Scholar 

  262. Li, X. Y.; Rong, H. P.; Zhang, J. T.; Wang, D. S.; Li, Y. D. Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance. Nano Res. 2020, 13, 1842–1855.

    Article  CAS  Google Scholar 

  263. Hai, X.; Xi, S. B.; Mitchell, S.; Harrath, K.; Xu, H. M.; Akl, D. F.; Kong, D. B.; Li, J.; Li, Z. J.; Sun, T. et al. Scalable two-step annealing method for preparing ultra-high-density single-atom catalyst libraries. Nat. Nanotechnol. 2022, 17, 174–181.

    Article  CAS  Google Scholar 

  264. Lai, W. H.; Zhang, L. F.; Hua, W. B.; Indris, S.; Yan, Z. C.; Hu, Z.; Zhang, B. W.; Liu, Y. N.; Wang, L.; Liu, M. et al. Generaln-electron-assisted strategy for Ir, Pt, Ru, Pd, Fe, Ni single-atom electrocatalysts with bifunctional active sites for highly efficient water splitting. Angew. Chem., Int. Ed. 2019, 58, 11868–11873.

    Article  CAS  Google Scholar 

  265. Zheng, T. T.; Liu, C. X.; Guo, C. X.; Zhang, M. L.; Li, X.; Jiang, Q.; Xue, W. Q.; Li, H. L.; Li, A. W.; Pao, C. W. et al. Copper-catalysed exclusive CO2 to pure formic acid conversion via singleatom alloying. Nat. Nanotechnol. 2021, 16, 1386–1393.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was partially supported by the Beijing Natural Science Foundation (No. 2224096), the National Key R&D Program of China (No. 2018YFA0702003), the Science and Technology Key Project of Guangdong Province, China (No. 2020B010188002), and the China Postdoctoral Science Foundation (Nos. 2021M690086 and 2021TQ0170). X. B. Z. acknowledges funding support from the Office of China Postdoctoral Council (No. YJ20200277) and the “Shuimu Tsinghua Scholar Program” (No. 2020SM109) of Tsinghua University, China.

Author information

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Xiaobo Zheng, Beibei Li, Qishun Wang, Dingsheng Wang & Yadong Li

Authors
  1. Xiaobo Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Beibei Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qishun Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Dingsheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yadong Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Dingsheng Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zheng, X., Li, B., Wang, Q. et al. Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis. Nano Res. 15, 7806–7839 (2022). https://doi.org/10.1007/s12274-022-4429-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-022-4429-9

Keywords

Search

Navigation