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Science China Materials

, Volume 62, Issue 3, pp 341–350 | Cite as

Highly porous Pt-Pb nanostructures as active and ultrastable catalysts for polyhydric alcohol electrooxidations

  • Lingzheng Bu (卜令正)
  • Qi Shao (邵琪)
  • Xiaoqing Huang (黄小青)Email author
Articles
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Abstract

Highly porous materials have attracted intensive attention in the past decades due to their unique geometrical configuration, unusual structural features, and outstanding physicochemical properties, but the facile creation of porous metal nanomaterias remains a formidable challenge. Most reports focused on using hard templates to create porous metal nanomaterials via sacrificing the templates. Herein, we have created a new class of porous PtPb/Pt nanocrystals (NCs) with well-defined morphology, composition and porosity through a facile chemical etching approach. Due to the highly open three-dimensional (3D) structure and alloy effect, the porous PtPb/Pt NCs exhibit enhanced performances towards polyhydric alcohol electrooxidations with the optimized porous Pt3Pb nanoplates exhibiting superior activities of 1.75 mA cm−2 and 1.19 A mg−1Pt for ethylene glycol oxidation reaction (EGOR) and of 1.46 mA cm−2 and 1.00 A mg−1Pt for glycerol oxidation reaction (GOR) that are much higher than the commercial Pt/C (0.34 mA cm−2 and 0.22 A mg−1Pt for EGOR, 0.30 mA cm−2 and 0.20 A mg−1Pt for GOR). In addition, the porous Pt3Pb nanoplates can endure the long-term stability in EG and glycerol oxidation reactions with limited activity and structure change after 20,000 and 5,000 cycles, respectively, showing a highly promising class of porous Ptbased electrocatalysts for direct polyhydric alcohol fuel cells and beyond.

Keywords

nanoporous Pt-Pb nanoplate Pt-Pb octahedron ethylene glycol oxidation glycerol oxidation 

高度多孔的铂铅纳米晶用作高效的多元醇电氧化催化剂

摘要

本论文采用简便的湿化学刻蚀法首次成功合成了具有明确形貌、 组分和多孔性的PtPb/Pt多孔纳米晶. 由于具有高度开放的三维立体结构和合金效应, PtPb/Pt多孔纳米晶的多元醇电催化性能良好. 其中, 最优化的Pt3Pb多孔纳米片在乙二醇氧化反应中的催化活性为1.75 mA cm−2和1.19 A mg−1Pt, 在丙三醇氧化反应中的催化活性为1.46 mA cm−2和1.00 A mg−1Pt, 均远远高于商业Pt/C催化剂的催化活性. 另外, Pt3Pb多孔纳米片在乙二醇和丙三醇氧化反应中均表现出优异的电催化稳定性, 分别经过20000个循环和5000个循环后, 其催化活性 没有发生明显衰减且纳米结构没有发生改变. 因此, Pt3Pb多孔纳米片可作为一种非常有发展前景的铂基电催化剂应用于多元醇燃料电池 及相关领域中.

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Notes

Acknowledgements

This work was financially supported by the Ministry of Science and Technology (2016YFA0204100, 2017YFA0208200), the National Natural Science Foundation of China (21571135), Young Thousand Talented Program, Natural Science Foundation of Jiangsu Higher Education Institutions (17KJB150032), the project of scientific and technologic infrastructure of Suzhou (SZS201708), start-up support from Soochow University, and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

Supplementary material

40843_2018_9321_MOESM1_ESM.pdf (4.5 mb)
Highly Porous Pt-Pb Nanostructures as Active and Ultrastable Catalysts for Polyhydric Alcohol Electrooxidation

References

  1. 1.
    Davis ME. Ordered porous materials for emerging applications. Nature, 2002, 417: 813–821CrossRefGoogle Scholar
  2. 2.
    Zhang J, Li CM. Nanoporous metals: fabrication strategies and advanced electrochemical applications in catalysis, sensing and energy systems. Chem Soc Rev, 2012, 41: 7016–7031CrossRefGoogle Scholar
  3. 3.
    Parlett CMA, Wilson K, Lee AF. Hierarchical porous materials: catalytic applications. Chem Soc Rev, 2013, 42: 3876–3893CrossRefGoogle Scholar
  4. 4.
    Slater AG, Cooper AI. Function-led design of new porous materials. Science, 2015, 348: aaa8075CrossRefGoogle Scholar
  5. 5.
    Kitagawa S. Future porous materials. Acc Chem Res, 2017, 50: 514–516CrossRefGoogle Scholar
  6. 6.
    Eddaoudi M, Kim J, Rosi N, et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science, 2002, 295: 469–472CrossRefGoogle Scholar
  7. 7.
    Li Y, Fu ZY, Su BL. Hierarchically structured porous materials for energy conversion and storage. Adv Funct Mater, 2012, 22: 4634–4667CrossRefGoogle Scholar
  8. 8.
    Valtchev V, Tosheva L. Porous nanosized particles: preparation, properties, and applications. Chem Rev, 2013, 113: 6734–6760CrossRefGoogle Scholar
  9. 9.
    Perego C, Millini R. Porous materials in catalysis: challenges for mesoporous materials. Chem Soc Rev, 2013, 42: 3956–3976CrossRefGoogle Scholar
  10. 10.
    Saint Remi JC, Lauerer A, Chmelik C, et al. The role of crystal diversity in understanding mass transfer in nanoporous materials. Nat Mater, 2016, 15: 401–406CrossRefGoogle Scholar
  11. 11.
    Kumar KV, Preuss K, Titirici MM, et al. Nanoporous materials for the onboard storage of natural gas. Chem Rev, 2017, 117: 1796–1825CrossRefGoogle Scholar
  12. 12.
    Wei J, Sun Z, Luo W, et al. New insight into the synthesis of largepore ordered mesoporous materials. J Am Chem Soc, 2017, 139: 1706–1713CrossRefGoogle Scholar
  13. 13.
    Braun PV, Wiltzius P. Electrochemical fabrication of 3D microperiodic porous materials. Adv Mater, 2001, 13: 482–485CrossRefGoogle Scholar
  14. 14.
    Choi M, Cho HS, Srivastava R, et al. Amphiphilic organosilanedirected synthesis of crystalline zeolite with tunable mesoporosity. Nat Mater, 2006, 5: 718–723CrossRefGoogle Scholar
  15. 15.
    Fan W, Snyder MA, Kumar S, et al. Hierarchical nanofabrication of microporous crystals with ordered mesoporosity. Nat Mater, 2008, 7: 984–991CrossRefGoogle Scholar
  16. 16.
    Zhang J, Bu JT, Chen S, et al. Urothermal synthesis of crystalline porous materials. Angew Chem Int Ed, 2010, 49: 8876–8879CrossRefGoogle Scholar
  17. 17.
    Kloke A, von Stetten F, Zengerle R, et al. Strategies for the fabrication of porous platinum electrodes. Adv Mater, 2011, 23: 4976–5008CrossRefGoogle Scholar
  18. 18.
    Côté AP, Benin AI, Ockwig NW, et al. Porous, crystalline, covalent organic frameworks. Science, 2005, 310: 1166–1170CrossRefGoogle Scholar
  19. 19.
    Pérez-Ramírez J, Christensen CH, Egeblad K, et al. Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design. Chem Soc Rev, 2008, 37: 2530CrossRefGoogle Scholar
  20. 20.
    Wu D, Xu F, Sun B, et al. Design and preparation of porous polymers. Chem Rev, 2012, 112: 3959–4015CrossRefGoogle Scholar
  21. 21.
    Furukawa H, Cordova KE, O'Keeffe M, et al. The chemistry and applications of metal-organic frameworks. Science, 2013, 341: 1230444CrossRefGoogle Scholar
  22. 22.
    Lang X, Hirata A, Fujita T, et al. Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors. Nat Nanotech, 2011, 6: 232–236CrossRefGoogle Scholar
  23. 23.
    He W, Jiang C, Wang J, et al. High-rate oxygen electroreduction over graphitic-n species exposed on 3D hierarchically porous nitrogen-doped carbons. Angew Chem Int Ed, 2014, 53: 9503–9507CrossRefGoogle Scholar
  24. 24.
    Xu Y, Zhang B. Recent advances in porous Pt-based nanostructures: synthesis and electrochemical applications. Chem Soc Rev, 2014, 43: 2439–2450CrossRefGoogle Scholar
  25. 25.
    Zhu C, Du D, Eychmüller A, et al. Engineering ordered and nonordered porous noble metal nanostructures: synthesis, assembly, and their applications in electrochemistry. Chem Rev, 2015, 115: 8896–8943CrossRefGoogle Scholar
  26. 26.
    Bing Y, Liu H, Zhang L, et al. Nanostructured Pt-alloy electrocatalysts for PEM fuel cell oxygen reduction reaction. Chem Soc Rev, 2010, 39: 2184–2202CrossRefGoogle Scholar
  27. 27.
    Chen C, Kang Y, Huo Z, et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science, 2014, 343: 1339–1343CrossRefGoogle Scholar
  28. 28.
    Xiong Y, Xia Y. Shape-controlled synthesis of metal nanostructures: the case of palladium. Adv Mater, 2007, 19: 3385–3391CrossRefGoogle Scholar
  29. 29.
    Malgras V, Ataee-Esfahani H, Wang H, et al. Nanoarchitectures for mesoporous metals. Adv Mater, 2016, 28: 993–1010CrossRefGoogle Scholar
  30. 30.
    Maksimuk S, Yang S, Peng Z, et al. Synthesis and characterization of ordered intermetallic PtPb nanorods. J Am Chem Soc, 2007, 129: 8684–8685CrossRefGoogle Scholar
  31. 31.
    Kang Y, Pyo JB, Ye X, et al. Synthesis, shape control, and methanol electro-oxidation properties of Pt–Zn alloy and Pt3Zn intermetallic nanocrystals. ACS Nano, 2012, 6: 5642–5647CrossRefGoogle Scholar
  32. 32.
    Zhang D, Wu F, Peng M, et al. One-step, facile and ultrafast synthesis of phase-and size-controlled Pt–Bi intermetallic nanocatalysts through continuous-flow microfluidics. J Am Chem Soc, 2015, 137: 6263–6269CrossRefGoogle Scholar
  33. 33.
    Cui Z, Chen H, Zhao M, et al. Synthesis of structurally ordered Pt3Ti and Pt3V nanoparticles as methanol oxidation catalysts. J Am Chem Soc, 2014, 136: 10206–10209CrossRefGoogle Scholar
  34. 34.
    Cui Z, Chen H, Zhou W, et al. Structurally ordered Pt3Cr as oxygen reduction electrocatalyst: ordering control and origin of enhanced stability. Chem Mater, 2015, 27: 7538–7545CrossRefGoogle Scholar
  35. 35.
    Niu Z, Becknell N, Yu Y, et al. Anisotropic phase segregation and migration of Pt in nanocrystals en route to nanoframe catalysts. Nat Mater, 2016, 15: 1188–1194CrossRefGoogle Scholar
  36. 36.
    Wang C, Zhang L, Yang H, et al. High-indexed Pt3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching. Nano Lett, 2017, 17: 2204–2210CrossRefGoogle Scholar
  37. 37.
    Wang L, Yamauchi Y. Metallic nanocages: synthesis of bimetallic Pt–Pd hollow nanoparticles with dendritic shells by selective chemical etching. J Am Chem Soc, 2013, 135: 16762–16765CrossRefGoogle Scholar
  38. 38.
    He DS, He D, Wang J, et al. Ultrathin icosahedral Pt-enriched nanocage with excellent oxygen reduction reaction activity. J Am Chem Soc, 2016, 138: 1494–1497CrossRefGoogle Scholar
  39. 39.
    Xiao C, Wang LL, Maligal-Ganesh RV, et al. Intermetallic NaAu2 as a heterogeneous catalyst for low-temperature CO oxidation. J Am Chem Soc, 2013, 135: 9592–9595CrossRefGoogle Scholar
  40. 40.
    Kim D, Resasco J, Yu Y, et al. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nat Commun, 2014, 5: 4948CrossRefGoogle Scholar
  41. 41.
    Cui Z, Li L, Manthiram A, et al. Enhanced cycling stability of hybrid Li–air batteries enabled by ordered Pd3Fe intermetallic electrocatalyst. J Am Chem Soc, 2015, 137: 7278–7281CrossRefGoogle Scholar
  42. 42.
    Bu L, Zhang N, Guo S, et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science, 2016, 354: 1410–1414CrossRefGoogle Scholar
  43. 43.
    Bu L, Shao Q, E B, et al. PtPb/PtNi intermetallic core/atomic layer shell octahedra for efficient oxygen reduction electrocatalysis. J Am Chem Soc, 2017, 139: 9576–9582CrossRefGoogle Scholar
  44. 44.
    Yao Y, He DS, Lin Y, et al. Modulating fcc and hcp ruthenium on the surface of palladium-copper alloy through tunable lattice mismatch. Angew Chem Int Ed, 2016, 55: 5501–5505CrossRefGoogle Scholar
  45. 45.
    Bambagioni V, Bianchini C, Marchionni A, et al. Pd and Pt–Ru anode electrocatalysts supported on multi-walled carbon nanotubes and their use in passive and active direct alcohol fuel cells with an anion-exchange membrane (alcohol=methanol, ethanol, glycerol). J Power Sources, 2009, 190: 241–251CrossRefGoogle Scholar
  46. 46.
    Hong W, Shang C, Wang J, et al. Bimetallic PdPt nanowire networks with enhanced electrocatalytic activity for ethylene glycol and glycerol oxidation. Energy Environ Sci, 2015, 8: 2910–2915CrossRefGoogle Scholar
  47. 47.
    Yang S, Peng Z, Yang H. Platinum lead nanostructures: formation, phase behavior, and electrocatalytic properties. Adv Funct Mater, 2008, 18: 2745–2753CrossRefGoogle Scholar
  48. 48.
    Xia BY, Ng WT, Wu HB, et al. Self-supported interconnected Pt nanoassemblies as highly stable electrocatalysts for low-temperature fuel cells. Angew Chem Int Ed, 2012, 51: 7213–7216CrossRefGoogle Scholar
  49. 49.
    Wu Y, Wang D, Niu Z, et al. A strategy for designing a concave Pt-Ni alloy through controllable chemical etching. Angew Chem Int Ed, 2012, 51: 12524–12528CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Lingzheng Bu (卜令正)
    • 1
  • Qi Shao (邵琪)
    • 1
  • Xiaoqing Huang (黄小青)
    • 1
    Email author
  1. 1.College of Chemistry, Chemical Engineering and Materials ScienceSoochow UniversitySuzhouChina

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