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Carbon nanotubes anchored onto hollow carbon for efficient oxygen reduction

碳纳米管锚定在中空碳上用于高效氧还原反应

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Abstract

The rational design and facile construction of non-noble metal-based electrocatalysts for efficient oxygen reduction reaction (ORR) remain a challenge for the development of clean energy conversion devices. Herein, we synthesized a new type of hierarchical hollow carbon nanomaterials through one-step pyrolysis on bimetallic ZIF-Zn/Co precursors. The obtained hollow N-doped carbon composites, denoted as HNCT-CNTs, are enriched with Co-Nx sites and in-situ formed multi-walled carbon nanotubes (CNTs). Theoretical and experimental studies confirmed that the obtained HNCT-CNT exhibits excellent ORR catalytic activity with a reduced energy barrier for ORR intermediates. Owing to these advantages, the optimal catalyst shows an excellent half-wave potential of 0.85 V, a limiting current density up to 6.36 mA cm−2, a Tafel slope of 58.2 mV dec−1, and robust stability. Furthermore, the assembled Zn-air battery based on HNCT-CNT also displays an open circuit voltage of 1.49 V and a satisfactory power density of 116.56 mW cm−2. This template-directed preparation method opens up an interesting and efficient route to fabricate highly active non-noble metal-doped carbon nanomaterials for a wide range of electrochemical energy applications.

摘要

设计和制备用于高效氧还原反应(ORR)的非贵金属基电催化剂对于清洁能源转换装置的开发至关重要, 但又极具挑战性. 在本工作中,我们通过热解双金属前驱体ZIF-Zn/Co, 成功制备了一种新型的分级中空碳纳米复合材料HNCT-CNT. 该材料富含Co-N x 位点以及原位形成的多壁碳纳米管. 理论和实验表明, HNCT-CNT使ORR中间体的活化能垒降低, 因而表现出了优异的ORR性能. 最佳催化剂表现出较正的半波电位为0.85 V, 极限电流密度高达6.36 mA cm−2, Tafel斜率为58.2 mV dec−1, 且结构稳定性良好. 此外, 基于HNCT-CNT组装的锌空气电池还显示出1.49 V的开路电压和116.56 mW cm−2的功率密度. 综上, 这种无机物模板法为制备金属有机框架化合物衍生的非贵金属基碳纳米电催化剂用于高效的电化学能源领域提供了一种新的方法.

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References

  1. Chung HT, Cullen DA, Higgins D, et al. 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 

  2. Du D, Zhao S, Zhu Z, et al. Photo-excited oxygen reduction and oxygen evolution reactions enable a high-performance Zn-air battery. Angew Chem Int Ed, 2020, 59: 18140–18144

    Article  CAS  Google Scholar 

  3. Prabhu P, Jose V, Lee JM. Design strategies for development of TMD-based heterostructures in electrochemical energy systems. Matter, 2020, 2: 526–553

    Article  Google Scholar 

  4. Yang X, Zheng X, Li H, et al. Non-noble-metal catalyst and Zn/graphene film for low-cost and ultra-long-durability solid-state Zn-air batteries in harsh electrolytes. Adv Funct Mater, 2022, 32: 2200397

    Article  CAS  Google Scholar 

  5. Xu X, Pan Y, Zhong Y, et al. New undisputed evidence and strategy for enhanced lattice-oxygen participation of perovskite electrocatalyst through cation deficiency manipulation. Adv Sci, 2022, 9: 2200530

    Article  CAS  Google Scholar 

  6. Farahani FS, Rahmanifar MS, Noori A, et al. Trilayer metal-organic frameworks as multifunctional electrocatalysts for energy conversion and storage applications. J Am Chem Soc, 2022, 144: 3411–3428

    Article  Google Scholar 

  7. Chen K, Liu K, An P, et al. Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction. Nat Commun, 2020, 11: 4173

    Article  CAS  Google Scholar 

  8. Fan M, Yuan Q, Zhao Y, et al. A facile “double-catalysts” approach to directionally fabricate pyridinic N-B-pair-doped crystal graphene nanoribbons/amorphous carbon hybrid electrocatalysts for efficient oxygen reduction reaction. Adv Mater, 2022, 34: 2107040

    Article  CAS  Google Scholar 

  9. Al-Zoubi T, Zhou Y, Yin X, et al. Preparation of nonprecious metal electrocatalysts for the reduction of oxygen using a low-temperature sacrificial metal. J Am Chem Soc, 2020, 142: 5477–5481

    Article  CAS  Google Scholar 

  10. Wang X, Jia Y, Mao X, et al. Edge-rich Fe-N4 active sites in defective carbon for oxygen reduction catalysis. Adv Mater, 2020, 32: 2000966

    Article  CAS  Google Scholar 

  11. Zhao KM, Liu S, Li YY, et al. Insight into the mechanism of axial ligands regulating the catalytic activity of Fe-N4 sites for oxygen reduction reaction. Adv Energy Mater, 2022, 12: 2103588

    Article  CAS  Google Scholar 

  12. He Y, Shi Q, Shan W, et al. Dynamically unveiling metal-nitrogen coordination during thermal activation to design high-efficient atomically dispersed CoN4 active sites. Angew Chem Int Ed, 2021, 60: 9516–9526

    Article  CAS  Google Scholar 

  13. Zhang J, Zhang J, He F, et al. Defect and doping co-engineered non-metal nanocarbon ORR electrocatalyst. Nano-Micro Lett, 2021, 13: 65

    Article  CAS  Google Scholar 

  14. Lin L, Miao N, Wallace GG, et al. Engineering carbon materials for electrochemical oxygen reduction reactions. Adv Energy Mater, 2021, 11: 2100695

    Article  CAS  Google Scholar 

  15. Hong Y, Li L, Huang B, et al. Molecular control of carbon-based oxygen reduction electrocatalysts through metal macrocyclic complexes functionalization. Adv Energy Mater, 2021, 11: 2100866

    Article  CAS  Google Scholar 

  16. Jiang H, Gu J, Zheng X, et al. Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER. Energy Environ Sci, 2019, 12: 322–333

    Article  CAS  Google Scholar 

  17. Feng X, Bai Y, Liu M, et al. Untangling the respective effects of heteroatom-doped carbon materials in batteries, supercapacitors and the ORR to design high performance materials. Energy Environ Sci, 2021, 14: 2036–2089

    Article  CAS  Google Scholar 

  18. Liu R, von Malotki C, Arnold L, et al. Triangular trinuclear metal-N4 complexes with high electrocatalytic activity for oxygen reduction. J Am Chem Soc, 2011, 133: 10372–10375

    Article  CAS  Google Scholar 

  19. Li Y, Zhang P, Wan L, et al. A general carboxylate-assisted approach to boost the ORR performance of ZIF-derived Fe/N/C catalysts for proton exchange membrane fuel cells. Adv Funct Mater, 2021, 31: 2009645

    Article  CAS  Google Scholar 

  20. Yang M, Zhang CH, Li NW, et al. Design and synthesis of hollow nanostructures for electrochemical water splitting. Adv Sci, 2022, 9: 2105135

    Article  CAS  Google Scholar 

  21. Ding H, Wang P, Su C, et al. Epitaxial growth of ultrathin highly crystalline Pt-Ni nanostructure on a metal carbide template for efficient oxygen reduction reaction. Adv Mater, 2022, 34: 2109188

    Article  CAS  Google Scholar 

  22. Wang X, Chen Z, Han Z, et al. Manipulation of new married edge-adjacent Fe2N5 catalysts and identification of active species for oxygen reduction in wide pH range. Adv Funct Mater, 2022, 32: 2111835

    Article  CAS  Google Scholar 

  23. Chai L, Hu Z, Wang X, et al. Fe7C3 nanoparticles with in situ grown CNT on nitrogen doped hollow carbon cube with greatly enhanced conductivity and ORR performance for alkaline fuel cell. Carbon, 2021, 174: 531–539

    Article  CAS  Google Scholar 

  24. Liang Z, Guo H, Zhou G, et al. Metal-organic-framework-supported molecular electrocatalysis for the oxygen reduction reaction. Angew Chem Int Ed, 2021, 60: 8472–8476

    Article  CAS  Google Scholar 

  25. Li Z, Song M, Zhu W, et al. MOF-derived hollow heterostructures for advanced electrocatalysis. Coord Chem Rev, 2021, 439: 213946

    Article  CAS  Google Scholar 

  26. Daglar H, Gulbalkan HC, Avci G, et al. Effect of metal-organic framework (MOF) database selection on the assessment of gas storage and separation potentials of MOFs. Angew Chem Int Ed, 2021, 60: 7828–7837

    Article  CAS  Google Scholar 

  27. Gao D, Chen JH, Fang S, et al. Simultaneous quantitative recognition of all purines including N6-methyladenine via the host-guest interactions on a Mn-MOF. Matter, 2021, 4: 1001–1016

    Article  CAS  Google Scholar 

  28. Mallakpour S, Nikkhoo E, Hussain CM. Application of MOF materials as drug delivery systems for cancer therapy and dermal treatment. Coord Chem Rev, 2022, 451: 214262

    Article  CAS  Google Scholar 

  29. Sun Q, Zhu K, Ji X, et al. MOF-derived three-dimensional ordered porous carbon nanomaterial for efficient alkaline zinc-air batteries. Sci China Mater, 2022, 65: 1453–1462

    Article  CAS  Google Scholar 

  30. Lin SY, Xia LX, Cao Y, et al. Electronic regulation of ZnCo dual-atomic active sites entrapped in 1D@2D hierarchical N-doped carbon for efficient synergistic catalysis of oxygen reduction in Zn-air battery. Small, 2022, 18: 2107141

    Article  CAS  Google Scholar 

  31. Yuan S, Zhang J, Hu L, et al. Decarboxylation-induced defects in MOF-derived single cobalt atom@carbon electrocatalysts for efficient oxygen reduction. Angew Chem Int Ed, 2021, 60: 21685–21690

    Article  CAS  Google Scholar 

  32. Wang W, Yan H, Anand U, et al. Visualizing the conversion of metal-organic framework nanoparticles into hollow layered double hydroxide nanocages. J Am Chem Soc, 2021, 143: 1854–1862

    Article  CAS  Google Scholar 

  33. Liu P, Gao S, Zhang G, et al. Hollow engineering to Co@N-doped carbon nanocages via synergistic protecting-etching strategy for ultrahigh microwave absorption. Adv Funct Mater, 2021, 31: 2102812

    Article  CAS  Google Scholar 

  34. Wang Y, Deng Z, Huang J, et al. 2D Zr-Fc metal-organic frameworks with highly efficient anchoring and catalytic conversion ability towards polysulfides for advanced Li-S battery. Energy Storage Mater, 2021, 36: 466–477

    Article  Google Scholar 

  35. Guo Y, Huang Q, Ding J, et al. Ultrasmall Mo2C in N-doped carbon material from bimetallic ZnMo-MOF for efficient hydrogen evolution. Int J Hydrogen Energy, 2021, 46: 2182–2190

    Article  CAS  Google Scholar 

  36. Huang Q, Xu Y, Guo Y, et al. Highly graphitized N-doped carbon nanosheets from 2-dimensional coordination polymers for efficient metal-air batteries. Carbon, 2022, 188: 135–145

    Article  CAS  Google Scholar 

  37. Lee MJ, Kwon HT, Jeong HK. High-flux zeolitic imidazolate framework membranes for propylene/propane separation by postsynthetic linker exchange. Angew Chem Int Ed, 2018, 57: 156–161

    Article  CAS  Google Scholar 

  38. Yun Y, Sheng H, Bao K, et al. Design and remarkable efficiency of the robust sandwich cluster composite nanocatalysts ZIF-8@Au25@ZIF-67. J Am Chem Soc, 2020, 142: 4126–4130

    Article  CAS  Google Scholar 

  39. Arafat Y, Azhar MR, Zhong Y, et al. Advances in zeolite imidazolate frameworks (ZIFs) derived bifunctional oxygen electrocatalysts and their application in zinc-air batteries. Adv Energy Mater, 2021, 11: 2100514

    Article  CAS  Google Scholar 

  40. Wang X, Chai L, Ding J, et al. Chemical and morphological transformation of MOF-derived bimetallic phosphide for efficient oxygen evolution. Nano Energy, 2019, 62: 745–753

    Article  CAS  Google Scholar 

  41. Chen N, Xiao TH, Luo Z, et al. Porous carbon nanowire array for surface-enhanced Raman spectroscopy. Nat Commun, 2020, 11: 4772

    Article  CAS  Google Scholar 

  42. Zhao M, Liu H, Zhang H, et al. A pH-universal ORR catalyst with single-atom iron sites derived from a double-layer MOF for superior flexible quasi-solid-state rechargeable Zn-air batteries. Energy Environ Sci, 2021, 14: 6455–6463

    Article  CAS  Google Scholar 

  43. Cheng Q, Yang L, Zou L, et al. Single cobalt atom and N codoped carbon nanofibers as highly durable electrocatalyst for oxygen reduction reaction. ACS Catal, 2017, 7: 6864–6871

    Article  CAS  Google Scholar 

  44. Xu H, Jia H, Li H, et al. Dual carbon-hosted Co-N3 enabling unusual reaction pathway for efficient oxygen reduction reaction. Appl Catal B-Environ, 2021, 297: 120390

    Article  CAS  Google Scholar 

  45. Jia Y, Xue Z, Yang J, et al. Tailoring the electronic structure of an atomically dispersed zinc electrocatalyst: Coordination environment regulation for high selectivity oxygen reduction. Angew Chem Intl Edit, 2022, 61: e202110838

    Article  CAS  Google Scholar 

  46. Shi H, Dai TY, Wan WB, et al. Mo-/Co-N-C hybrid nanosheets oriented on hierarchical nanoporous Cu as versatile electrocatalysts for efficient water splitting. Adv Funct Mater, 2021, 31: 2102285

    Article  CAS  Google Scholar 

  47. Liu X, Zhang G, Wang L, et al. Structural design strategy and active site regulation of high-efficient bifunctional oxygen reaction electrocatalysts for Zn-air battery. Small, 2021, 17: 2006766

    Article  CAS  Google Scholar 

  48. Xiao MJ, Ma B, Zhang ZQ, et al. Carbon nano-onion encapsulated cobalt nanoparticles for oxygen reduction and lithium-ion batteries. J Mater Chem A, 2021, 9: 7227–7237

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21601137), the Natural Science Foundation of Zhejiang Province (LQ16B010003), and the Basic Science and Technology Research Project of Wenzhou, Zhejiang Province (G20190007).

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Authors and Affiliations

  1. Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035, China

    Qiuhong Sun  (孙秋红), Dandan Chen  (陈丹丹), Qi Huang  (黄淇) & Jinjie Qian  (钱金杰)

  2. School of Materials and Energy, Guangdong University of Technology, Guangzhou, 510006, China

    Shaoming Huang  (黄少铭)

Authors
  1. Qiuhong Sun  (孙秋红)
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  2. Dandan Chen  (陈丹丹)
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  3. Qi Huang  (黄淇)
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  4. Shaoming Huang  (黄少铭)
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  5. Jinjie Qian  (钱金杰)
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Contributions

Qian J conceived the idea and supervised the project. Sun Q contributed to the experiments. Chen D conducted the DFT calculations. The paper was primarily written by Qian J and Sun Q. All authors contributed to the general discussion.

Corresponding author

Correspondence to Jinjie Qian  (钱金杰).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Qiuhong Sun received her bachelor’s degree from Wenzhou University in 2020, and now she is a graduate student at Wenzhou University. Her current research focuses on the design and synthesis of MOF-derived hierarchically porous materials with silica and oxide templates for electrochemical applications.

Jinjie Qian is an associate professor at the College of Chemistry and Materials Engineering, Wenzhou University. He received his PhD degree from Fujian Institute of Research on the Structure, Chinese Academy of Sciences, under the guidance of Prof. Maochun Hong. His current research is mainly involved in the electrochemical research on the carbon nanomaterials from metal-organic frameworks for energy storage and conversion.

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Sun, Q., Chen, D., Huang, Q. et al. Carbon nanotubes anchored onto hollow carbon for efficient oxygen reduction. Sci. China Mater. 66, 641–650 (2023). https://doi.org/10.1007/s40843-022-2173-3

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