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Size effects of platinum particles@CNT on HER and ORR performance

Pt@CNT中铂晶粒尺寸对HER和ORR的影响

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Abstract

Platinum (Pt) is an efficient catalyst for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), but the debate of the relevance between the Pt particle size and its electrocatalytic activity still exist. The strong metal-support interaction (SMSI) between the metal and carrier causes the charge transfer and mass transport from the support to the metal. Herein, Pt species (0.5 wt.%) with various particle sizes supported on carbon nanotubes (CNTs) have been synthesized by a photo-reduction method. The ~1.5 nm-sized Pt catalyst shows much higher HER performance than the counterparts in all pH solutions, and the mass activity of it is even 23–36 times that of Pt/C. While for ORR, the ~3 nm-sized Pt catalyst exhibits the optimal performance, and the mass activity is 3 times and even 16 times that of Pt/C in acidic and alkaline media, respectively. The high HER and ORR performances of the ~1.5 nm- and ~3 nm-sized Pt catalysts benefit from the SMSI between Pt and the CNTs matrix and the higher ratio of face sites to edge sites, which is meaningful for the design of efficient electrocatalysts for renewable energy application.

摘要

铂(Pt)是析氢反应(HER)和氧还原反应(ORR)的高效催化剂, 然而, 关于铂颗粒粒径大小与其电催化活性之间相关性的争论仍然存在. 金属-载体强相互作用(SMSI)是导致金属与载体之间电荷转移和质量转移的相互作用. 本文采用光还原法合成了碳纳米管负载的不同粒径的Pt粒子(0.5 wt.%). 在所有pH溶液中, 尺寸约为1.5 nm的Pt催化剂的HER催化性能都明显高于同类催化剂, 其质量活性甚至是Pt/C的23–36倍. 而对于ORR, 约3 nm的Pt催化剂表现出最佳的催化性能, 在酸性和碱性条件下, 其质量活性分别是Pt/C的3 倍和16倍. ~1.5和~3 nm大小的Pt催化剂分别表现出的较优异的HER和ORR性能, 主要与铂和碳纳米管之间的相互作用有关, 这为可再生能源电催化剂的设计提供了参考.

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References

  1. Shao M, Chang Q, Dodelet JP, et al. Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev, 2016, 116: 3594–3657

    CAS  Google Scholar 

  2. Bashyam R, Zelenay P. A class of non-precious metal composite catalysts for fuel cells. Nature, 2006, 443: 63–66

    CAS  Google Scholar 

  3. Lin H, Chen L, Lu X, et al. Two-dimensional titanium carbide MXenes as efficient non-noble metal electrocatalysts for oxygen reduction reaction. Sci China Mater, 2019, 62: 662–670

    CAS  Google Scholar 

  4. Zhang W, Lai W, Cao R. Energy-related small molecule activation reactions: Oxygen reduction and hydrogen and oxygen evolution reactions catalyzed by porphyrin- and corrole-based systems. Chem Rev, 2017, 117: 3717–3797

    CAS  Google Scholar 

  5. Nie Y, Li L, Wei Z. Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction. Chem Soc Rev, 2015, 44: 2168–2201

    CAS  Google Scholar 

  6. Wu J, Yang H. Platinum-based oxygen reduction electrocatalysts. Acc Chem Res, 2013, 46: 1848–1857

    CAS  Google Scholar 

  7. Cheng H, Liu S, Hao Z, et al. Optimal coordination-site exposure engineering in porous platinum for outstanding oxygen reduction performance. Chem Sci, 2019, 10: 5589–5595

    CAS  Google Scholar 

  8. Wu Y, Tao X, Qing Y, et al. Cr-doped FeNi-P nanoparticles encapsulated into N-doped carbon nanotube as a robust bifunctional catalyst for efficient overall water splitting. Adv Mater, 2019, 31: 1900178

    Google Scholar 

  9. Yin J, Jin J, Zhang H, et al. Atomic arrangement in metal-doped NiS2 boosts the hydrogen evolution reaction in alkaline media. Angew Chem, 2019, 131: 18849–18855

    Google Scholar 

  10. Tan Y, Xu C, Chen G, et al. Facile synthesis of manganese-oxidecontaining mesoporous nitrogen-doped carbon for efficient oxygen reduction. Adv Funct Mater, 2012, 22: 4584–4591

    CAS  Google Scholar 

  11. Choi Y, Lim D, Oh E, et al. Effect of proton irradiation on electrocatalytic properties of MnO2 for oxygen reduction reaction. J Mater Chem A, 2019, 7: 11659–11664

    CAS  Google Scholar 

  12. Yao N, Li P, Zhou Z, et al. Synergistically tuning water and hydrogen binding abilities over Co4N by Cr doping for exceptional alkaline hydrogen evolution electrocatalysis. Adv Energy Mater, 2019, 9: 1902449

    CAS  Google Scholar 

  13. Qiao Z, Hwang S, Li X, et al. 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: A balance between graphitization and hierarchical porosity. Energy Environ Sci, 2019, 12: 2830–2841

    CAS  Google Scholar 

  14. Gan J, Luo W, Chen W, et al. Mechanistic understanding of size-dependent oxygen reduction activity and selectivity over Pt/CNT nanocatalysts. Eur J Inorg Chem, 2019, 2019(27): 3210–3217

    CAS  Google Scholar 

  15. Zeng L, Cui X, Shi J. A facile strategy for ultrasmall Pt NPs being partially-embedded in N-doped carbon nanosheet structure for efficient electrocatalysis. Sci China Mater, 2018, 61: 1557–1566

    CAS  Google Scholar 

  16. Dong C, Lian C, Hu S, et al. Size-dependent activity and selectivity of carbon dioxide photocatalytic reduction over platinum nanoparticles. Nat Commun, 2018, 9: 1252

    Google Scholar 

  17. Yan QQ, Wu DX, Chu SQ, et al. Reversing the charge transfer between platinum and sulfur-doped carbon support for electrocatalytic hydrogen evolution. Nat Commun, 2019, 10: 4977

    Google Scholar 

  18. Garlyyev B, Kratzl K, Rück M, et al. Optimizing the size of platinum nanoparticles for enhanced mass activity in the electrochemical oxygen reduction reaction. Angew Chem Int Ed, 2019, 58: 9596–9600

    CAS  Google Scholar 

  19. van Deelen TW, Hernández Mejía C, de Jong KP. Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity. Nat Catal, 2019, 2: 955–970

    CAS  Google Scholar 

  20. Selvaraj V, Alagar M. Ethylene glycol oxidation on Pt and Pt-Ru nanoparticle decorated polythiophene/multiwalled carbon nanotube composites for fuel cell applications. Nanotechnology, 2008, 19: 045504

    Google Scholar 

  21. Selvaraj V, Vinoba M, Alagar M. Electrocatalytic oxidation of ethylene glycol on Pt and Pt-Ru nanoparticles modified multi-walled carbon nanotubes. J Colloid Interface Sci, 2008, 322: 537–544

    CAS  Google Scholar 

  22. Johansson AC, Larsen JV, Verheijen MA, et al. Electrocatalytic activity of atomic layer deposited Pt-Ru catalysts onto N-doped carbon nanotubes. J Catal, 2014, 311: 481–486

    CAS  Google Scholar 

  23. Matsubu JC, Zhang S, Derita L, et al. Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts. Nat Chem, 2017, 9: 120–127

    CAS  Google Scholar 

  24. Tabassum H, Mahmood A, Zhu B, et al. Recent advances in confining metal-based nanoparticles into carbon nanotubes for electrochemical energy conversion and storage devices. Energy Environ Sci, 2019, 12: 2924–2956

    CAS  Google Scholar 

  25. Srejic I, Rakocevic Z, Nenadovic M, et al. Oxygen reduction on polycrystalline palladium in acid and alkaline solutions: Topographical and chemical Pd surface changes. Electrochim Acta, 2015, 169: 22–31

    CAS  Google Scholar 

  26. Wu X, Scott K. A non-precious metal bifunctional oxygen electrode for alkaline anion exchange membrane cells. J Power Sources, 2012, 206: 14–19

    CAS  Google Scholar 

  27. Wang YF, Zhao SX, Yu L, et al. Design of multiple electrode structures based on nano Ni3S2 and carbon nanotubes for high performance supercapacitors. J Mater Chem A, 2019, 7: 7406–7414

    Google Scholar 

  28. Ji J, Zhang Y, Tang L, et al. Platinum single-atom and cluster anchored on functionalized MWCNTs with ultrahigh mass efficiency for electrocatalytic hydrogen evolution. Nano Energy, 2019, 63: 103849

    CAS  Google Scholar 

  29. He Y, Xu H, Shi J, et al. Polydopamine coating layer modified current collector for dendrite-free Li metal anode. Energy Storage Mater, 2019, 23: 418–426

    Google Scholar 

  30. Seok S, Choi I, Lee KG, et al. Dopamine-induced Pt and N-doped carbon@silica hybrids as high-performance anode catalysts for polymer electrolyte membrane fuel cells. RSC Adv, 2014, 4: 42582–42584

    CAS  Google Scholar 

  31. Qu K, Zheng Y, Jiao Y, et al. Polydopamine-inspired, dual heteroatom-doped carbon nanotubes for highly efficient overall water splitting. Adv Energy Mater, 2017, 7: 1602068

    Google Scholar 

  32. Yang Y, Zhang X, Wang H, et al. Preparation of nanoscrolls by rolling up graphene oxide-polydopamine-Au sheets using lyophilization method. Chem Asian J, 2016, 11: 1821–1827

    CAS  Google Scholar 

  33. Wang J, Ciucci F. In-situ synthesis of bimetallic phosphide with carbon tubes as an active electrocatalyst for oxygen evolution reaction. Appl Catal B-Environ, 2019, 254: 292–299

    CAS  Google Scholar 

  34. Xu Y, Deng P, Chen G, et al. 2D nitrogen-doped carbon nanotubes/graphene hybrid as bifunctional oxygen electrocatalyst for long-life rechargeable Zn-air batteries. Adv Funct Mater, 2020, 30: 1906081

    CAS  Google Scholar 

  35. Lu Z, Wang J, Huang S, et al. N,B-codoped defect-rich graphitic carbon nanocages as high performance multifunctional electrocatalysts. Nano Energy, 2017, 42: 334–340

    CAS  Google Scholar 

  36. Zhao D, Sun K, Cheong WC, et al. Synergistically interactive pyridinic-N-MoP sites: Identified active centers for enhanced hydrogen evolution in alkaline solution. Angew Chem, 2020, 132: 9067–9075

    Google Scholar 

  37. Pu Z, Zhao J, Amiinu IS, et al. A universal synthesis strategy for P-rich noble metal diphosphide-based electrocatalysts for the hydrogen evolution reaction. Energy Environ Sci, 2019, 12: 952–957

    CAS  Google Scholar 

  38. Zheng X, Cao Y, Han X, et al. Pt embedded Ni3Se2@NiOOH core-shell dendrite-like nanoarrays on nickel as bifunctional electrocatalysts for overall water splitting. Sci China Mater, 2019, 62: 1096–1104

    CAS  Google Scholar 

  39. Morales-Guio CG, Stern LA, Hu X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem Soc Rev, 2014, 43: 6555–6569

    CAS  Google Scholar 

  40. Lin H, Shi Z, He S, et al. Heteronanowires of MoC-Mo2C as efficient electrocatalysts for hydrogen evolution reaction. Chem Sci, 2016, 7: 3399–3405

    CAS  Google Scholar 

  41. Bockris JOM, Potter EC. The mechanism of the cathodic hydrogen evolution reaction. J Electrochem Soc, 1952, 99: 169–186

    CAS  Google Scholar 

  42. Ye S, Luo F, Zhang Q, et al. Highly stable single Pt atomic sites anchored on aniline-stacked graphene for hydrogen evolution reaction. Energy Environ Sci, 2019, 12: 1000–1007

    CAS  Google Scholar 

  43. Lu XF, Yu L, Lou XWD. Highly crystalline Ni-doped FeP/carbon hollow nanorods as all-pH efficient and durable hydrogen evolving electrocatalysts. Sci Adv, 2019, 5: eaav6009

    CAS  Google Scholar 

  44. Zhao Y, Ling T, Chen S, et al. Non-metal single-iodine-atom electrocatalysts for the hydrogen evolution reaction. Angew Chem Int Ed, 2019, 58: 12252–12257

    CAS  Google Scholar 

  45. Wan X, Wu HB, Guan BY, et al. Confining sub-nanometer Pt clusters in hollow mesoporous carbon spheres for boosting hydrogen evolution activity. Adv Mater, 2020, 32: 1901349

    CAS  Google Scholar 

  46. Zhang L, Han L, Liu H, et al. Potential-cycling synthesis of single platinum atoms for efficient hydrogen evolution in neutral media. Angew Chem Int Ed, 2017, 56: 13694–13698

    CAS  Google Scholar 

  47. McCrory CCL, Jung S, Peters JC, et al. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J Am Chem Soc, 2013, 135: 16977–16987

    CAS  Google Scholar 

  48. Guo L, Jiang WJ, Zhang Y, et al. Embedding Pt nanocrystals in N-doped porous carbon/carbon nanotubes toward highly stable electrocatalysts for the oxygen reduction reaction. ACS Catal, 2015, 5: 2903–2909

    CAS  Google Scholar 

  49. Karuppannan M, Kim Y, Gok S, et al. A highly durable carbonnanofiber-supported Pt-C core-shell cathode catalyst for ultra-low Pt loading proton exchange membrane fuel cells: facile carbon encapsulation. Energy Environ Sci, 2019, 12: 2820–2829

    CAS  Google Scholar 

  50. Liu X, Zhu H, Yang X. One-step synthesis of dopamine-derived micro/mesoporous nitrogen-doped carbon materials for highly efficient oxygen-reduction catalysts. J Power Sources, 2014, 262: 414–420

    CAS  Google Scholar 

  51. Lao M, Rui K, Zhao G, et al. Platinum/nickel bicarbonate heterostructures towards accelerated hydrogen evolution under alkaline conditions. Angew Chem Int Ed, 2019, 58: 5432–5437

    CAS  Google Scholar 

  52. Yu FY, Lang ZL, Yin LY, et al. Pt-O bond as an active site superior to Pt0 in hydrogen evolution reaction. Nat Commun, 2020, 11: 490

    CAS  Google Scholar 

  53. Fu J, Lym J, Zheng W, et al. C-O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides. Nat Catal, 2020, 3: 446–453

    CAS  Google Scholar 

  54. Tian X, Lu XF, Xia BY, et al. Advanced electrocatalysts for the oxygen reduction reaction in energy conversion technologies. Joule, 2020, 4: 45–68

    CAS  Google Scholar 

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Acknowledgements

The authors acknowledge the support from the Natural Science Foundation of Shanghai (19ZR1479400), the State Key Laboratory for Modication of Chemical Fibers and Polymer Materials, Donghua University (KF1818), and the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology).

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Authors and Affiliations

  1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials & College of Materials Science and Engineering, Donghua University, Shanghai, 201620, China

    Zhonghua Ma  (马忠华), Lianjun Wang  (王连军) & Wan Jiang  (江莞)

  2. State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China

    Han Tian  (田汉), Ge Meng  (孟歌), Lingxin Peng  (彭凌欣), Yafeng Chen  (陈亚丰), Chang Chen  (陈昶), Ziwei Chang  (畅紫薇), Xiangzhi Cui  (崔香枝) & Jianlin Shi  (施剑林)

  3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Han Tian  (田汉), Ge Meng  (孟歌), Lingxin Peng  (彭凌欣), Chang Chen  (陈昶), Xiangzhi Cui  (崔香枝) & Jianlin Shi  (施剑林)

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  1. Zhonghua Ma  (马忠华)
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  2. Han Tian  (田汉)
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  5. Yafeng Chen  (陈亚丰)
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  6. Chang Chen  (陈昶)
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  7. Ziwei Chang  (畅紫薇)
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  8. Xiangzhi Cui  (崔香枝)
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  10. Wan Jiang  (江莞)
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  11. Jianlin Shi  (施剑林)
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Contributions

Author contributions Ma Z designed and engineered the samples; Ma Z performed the experiments; Ma Z wrote the paper with support from Cui X, Wang L and Jiang W. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Xiangzhi Cui  (崔香枝), Lianjun Wang  (王连军) or Wan Jiang  (江莞).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Zhonghua Ma received her BSc degree in materials science and engineering in 2018 from Donghua University. Currently, she is pursuing her MSc degree at Donghua University. Her research topic is the application of nanomaterials in electrocatalysis.

Xiangzhi Cui received her PhD degree in 2009 at Shanghai Institute of Ceramics, Chinese Academy of Sciences. She has been working at the institute since then, and now she is a full professor. Her main research interest includes the structural design and synthesis of nanostructured composites, and the electrochemical catalysis in clean energy.

Lianjun Wang is a full professor in the College of Material Science and Engineering at Donghua University. Dr. Wang received his PhD in chemical engineering from Dalian University of Technology in 2002. He did postdoctoral research at Shanghai Institute of Ceramics, Chinese Academy of Sciences (2002–2004) and Stockholm University (2007–2008). His research interests focus on the design and controlled fabrication of bulk nanocomposites with all-scale hierarchical architectures and their application in energy-related areas and LED.

Wan Jiang is a professor in the College of Materials Science and Engineering at Donghua University. Dr. Jiang received his master (1988) and PhD degrees (1994) from Tohoku University. He has been engaged in scientific research at R&D Department of RIKEN (Japan) and Shanghai Institute of Ceramics, Chinese Academy of Sciences. His research interests focus on the powder engineering and sintering technology, including rapid preparation of functional ceramic materials with controllable microstructure, fabrication of thermoelectric and photoelectric devices with high performance.

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Ma, Z., Tian, H., Meng, G. et al. Size effects of platinum particles@CNT on HER and ORR performance. Sci. China Mater. 63, 2517–2529 (2020). https://doi.org/10.1007/s40843-020-1449-2

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