Skip to main content
SpringerLink
Log in

Supramolecular nano-assemblies with tailorable surfaces: recyclable hard templates for engineering hollow nanocatalysts

  • Letter
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Supramolecular assemblies are introduced here as new-concept hard templates for the synthesis of hollow nanostructures (exemplified with TiO2 hollow nanostructures in this work). Supramolecular templates with tunable morphology and rich surface functional groups facilitate the tight coating of other materials for the formation of hollow nanostructures. The weak interaction between the supramolecules or micromolecules benefits the facile removal of the templates for large-scale synthesis of hollow nanostructures and also affords excellent template reusability. This method allows for the incorporation of various metal dopants into the TiO2 lattice, as a typical example of nanocatalyst, by introducing the corresponding metal salt as a dopant source. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and UV-vis absorption spectroscopy investigations suggested substitution of Ti4+ sites by Co2+, which increased the activity of the catalytic sites in the doped materials, reducing the overpotential of TiO2 for the oxygen evolution reaction.

摘要

超分子自组装化合物具有可调控的形貌和丰富的表面官能团. 超分子或小分子单体之间的弱相互作用有利于除去模板, 作为硬模板合成空心纳米结构(以TiO2为例), 不仅能得到具有可调控形貌的空心纳米结构, 并且超分子模板可以回收和重复利用. 实验表明, 用三聚氰氨和三聚氰酸作为原料合成的超分子模板, 有利于在模板表面复合无机组分, 并且模板中的氢键在水中易断裂, 因此可以通过透析方法除去模板得到空心纳米结构. 这种超分子模板法也可以用于合成掺杂金属离子的空心结构纳米催化剂, 进一步调控电子结构增加析氧反应的活性位点, 降低超电势. 更重要的是, 此模板合成方法简单、 耗能低、 可重复利用, 可以用于合成大批量的空心结构纳米催化剂.

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

References

  1. Sieb NR, Wu NC, Majidi E, et al. Hollow metal nanorods with tunable dimensions, porosity, and photonic properties. ACS Nano, 2009, 3: 1365–1372

    Article  Google Scholar 

  2. Lou XW, Archer LA, Yang Z. Hollow micro-/nanostructures: synthesis and applications. Adv Mater, 2008, 20: 3987–4019

    Article  Google Scholar 

  3. Bai F, Sun Z, Wu H, et al. Templated photocatalytic synthesis of well-defined platinum hollow nanostructures with enhanced catalytic performance for methanol oxidation. Nano Lett, 2011, 11: 3759–3762

    Article  Google Scholar 

  4. Bao CX, Huang H, Yang J, et al. The maximum limiting performance improved counter electrode based on a porous fluorine doped tin oxide conductive framework for dye-sensitized solar cells. Nanoscale, 2013, 5: 4951–4957

    Article  Google Scholar 

  5. Wu X, Lu GQ, Wang L. Dual-functional upconverter-doped TiO2 hollow shells for light scattering and near-infrared sunlight harvesting in dye-sensitized solar cells. Adv Energy Mater, 2013, 3: 704–707

    Article  Google Scholar 

  6. Yao Y, McDowell MT, Ryu I, et al. Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. Nano Lett, 2011, 11: 2949–2954

    Article  Google Scholar 

  7. Wu H, Zhang S, Zhang J, et al. A hollow-core, magnetic, and mesoporous double-shell nanostructure: in situ decomposition/reduction synthesis, bioimaging, and drug-delivery properties. Adv Funct Mater, 2011, 21: 1850–1862

    Article  Google Scholar 

  8. Wei W, Ma GH, Hu G, et al. Preparation of hierarchical hollow CaCO3 particles and the application as anticancer drug carrier. J Am Chem Soc, 2008, 130: 15808–15810

    Article  Google Scholar 

  9. Wang D, Hisatomi T, Takata T, et al. Core/shell photocatalyst with spatially separated Co-catalysts for efficient reduction and oxidation of water. Angew Chem Int Ed, 2013, 52: 11252–11256

    Article  Google Scholar 

  10. Liu R, Mahurin SM, Li C, et al. Dopamine as a carbon source: the controlled synthesis of hollow carbon spheres and yolk-structured carbon nanocomposites. Angew Chem Int Ed, 2011, 50, 6799–6802

    Article  Google Scholar 

  11. Okada T, Miyamoto K, Sakai T, Mishima S. Encapsulation of a polyoxometalate into an organosilica microcapsule for highly active solid acid catalysis. ACS Catal, 2013, 4: 73–78

    Article  Google Scholar 

  12. Ye TN, Xu M, Fu W, et al. The crystallinity effect of mesocrystalline BaZrO3 hollow nanospheres on charge separation for photocatalysis. Chem Commun, 2014, 50: 3021–3023

    Article  Google Scholar 

  13. Jana S, Chang JW, Rioux RM. Synthesis and modeling of hollow intermetallic Ni-Zn nanoparticles formed by the Kirkendall effect. Nano Lett, 2013, 13: 3618–3625

    Article  Google Scholar 

  14. Han FD, Bai YJ, Liu R, et al. Template-free synthesis of interconnected hollow carbon nanospheres for high-performance anode material in lithium-ion batteries. Adv Energy Mater, 2011, 1: 798–801

    Article  Google Scholar 

  15. Wang Z, Zhou L, Lou XW. Metal oxide hollow nanostructures for lithium-ion batteries. Adv Mater, 2012, 24: 1903–1911

    Article  Google Scholar 

  16. Li XH, Zhang DH, Chen, JS. Synthesis of amphiphilic superparamagnetic ferrite/block copolymer hollow submicrospheres. J Am Chem Soc, 2006, 128: 8382–8383

    Article  Google Scholar 

  17. Qiao ZA, Guo B, Binder AJ, et al. Controlled synthesis of mesoporous carbon nanostructures via a “silica-assisted” strategy. Nano Lett, 2012, 13: 207–213

    Article  Google Scholar 

  18. Choi SH, Ankonina G, Youn DY, et al. Hollow ZnO nanofibers fabricated using electrospun polymer templates and their electronic transport properties. ACS Nano, 2009, 3: 2623–2631

    Article  Google Scholar 

  19. Liu H, Qu J, Chen Y, et al. Hollow and cage-bell structured nanomaterials of noble metals. J Am Chem Soc, 2012, 134: 11602–11610

    Article  Google Scholar 

  20. Ha TL, Kim JG, Kim SM, Lee IS. Reversible and cyclical transformations between solid and hollow nanostructures in confined reactions of manganese oxide and silica within nanosized spheres. J Am Chem Soc, 2012, 135: 1378–1385

    Article  Google Scholar 

  21. Wang B, Chen JS, Wu HB, Wang Z, Lou XW. Quasiemulsion-templated formation of α-Fe2O3 hollow spheres with enhanced lithium storage properties. J Am Chem Soc, 2011, 133: 17146–17148

    Article  Google Scholar 

  22. White RJ, Tauer K, Antonietti M, Titirici MM. Functional hollow carbon nanospheres by latex templating. J Am Chem Soc, 2010, 132: 17360–17363

    Article  Google Scholar 

  23. Chen X, Wu Y, Su B, et al. Terminating marine methane bubbles by superhydrophobic sponges. Adv Mater, 2012, 24: 5884–5889

    Article  Google Scholar 

  24. Wang Y, Su X, Lu S. Sha pe-controlled synthesis of TiO2 hollow structures and their application in lithium batteries. J Mater Chem, 2012, 22: 1969–1976

    Article  Google Scholar 

  25. Fechler N, Fellinger TP, Antonietti M. “Salt templating”: a simple and sustainable pathway toward highly porous functional carbons from ionic liquids. Adv Mater, 2013, 25: 75–79

    Article  Google Scholar 

  26. Tian P, Ye J, Xu N, et al. A magnesium carbonate recyclable template to synthesize micro hollow structures at a large scale. Chem Commun, 2011, 47: 12008–12010

    Article  Google Scholar 

  27. Zhou Y, Yan D. Sup ramolecular self-assembly of amphiphilic hyperbranched polymers at all scales and dimensions: progress, characteristics and perspectives. Chem Commun, 2009, 1172–1188

    Google Scholar 

  28. Antonietti M. Silica nanocasting of lyotropic surfactant phases and organized organic matter: material science or an analytical tool? Philos Trans R Soc A-Math Phys Eng Sci, 2006, 364: 2817–2840

    Article  Google Scholar 

  29. Mathias JP, Simanek EE, Whitesides GM. Self-assembly through hydrogen bonding: peripheral crowding-a new strategy for the preparation of stable supramolecular aggregates based on parallel, connected CA3 · M3 rosettes. J Am Chem Soc, 1994, 116: 4326–4340

    Article  Google Scholar 

  30. Jun YS, Lee EZ, Wang X, et al. From melamine-cyanuric acid supramolecular aggregates to carbon nitride hollow spheres. Adv Funct Mater, 2013, 23: 3661–3667

    Article  Google Scholar 

  31. Shalom M, Inal S, Fettkenhauer C, Neher D, Antonietti M. Improving carbon nitride photocatalysis by supramolecular preorganization of monomers. J Am Chem Soc, 2013, 135: 7118

    Article  Google Scholar 

  32. Zou XX, Li GD, Guo MY, et al. Heterometal alkoxides as precursors for the preparation of porous Fe- and Mn-TiO2 photocatalysts with high efficieccies. Chem Eur J, 2008, 14: 11123–11131

    Article  Google Scholar 

  33. Kong M, Li Y, Chen X, et al. Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency. J Am Chem Soc, 2011, 133: 16414–16417

    Article  Google Scholar 

  34. Li YF, Selloni A. Mechanism and activity of water oxidation on selected surfaces of pure and Fe-doped NiOx. ACS Catal, 2014, 4: 1148–1153

    Article  Google Scholar 

  35. Chen S, Duan J, Jaroniec M, Qiao SZ. Three-dimensional N-doped graphene hydrogel/NiCo double hydroxide electrocatalysts for highly efficient oxygen evolution. Angew Chem, 2013, 125: 13812–13815

    Article  Google Scholar 

  36. Li YF, Liu ZP, Liu L, Gao W. Mechanism and activity of photocatalytic oxygen evolution on titania anatase in aqueous surroundings. J Am Chem Soc, 2010, 132: 13008–13015

    Article  Google Scholar 

  37. Sun J, Zhang J, Zhang M, et al. Bioinspired hollow semiconductor nanospheres as photosynthetic nanoparticles. Nat Commun, 2012, 1139

    Google Scholar 

  38. Li YF, Liu ZP. Particle size, shape and activity for photocatalysis on titania anatase nanoparticles in aqueous surroundings. J Am Chem Soc, 2011, 133: 15743–15752

    Article  Google Scholar 

  39. Pfrommer LJ, Lublow M, Azarpira A, et al. A molecular approach to self-supported cobalt-substituted ZnO materials as remarkably stable electrocatalysts for water oxidation. Angew Chem Int Ed, 2014, 53: 5183–5187

    Google Scholar 

  40. Liu B, Chen HM, Liu C, et al. Large-scale synthesis of transition-metal-doped TiO2 nanowires with controllable overpotential. J Am Chem Soc, 2013, 135: 9995–9998

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

    Li-Na Han, Tian-Nan Ye, Li-Bing Lv, Kai-Xue Wang, Xiao Wei, Xin-Hao Li & Jie-Sheng Chen

Authors
  1. Li-Na Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tian-Nan Ye
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Li-Bing Lv
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kai-Xue Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xiao Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xin-Hao Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jie-Sheng Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xin-Hao Li or Jie-Sheng Chen.

Additional information

Li-Na Han received her bachelor’s degree in chemistry from Jilin University in 2012. She is currently studying for a PhD at Shanghai Jiao Tong University. Her research interests are based in the study of catalysis using TiO2 nanostructures.

Xin-Hao Li completed each of his academic degrees at the Department of Chemistry of Jilin University from 1999 to 2009, receiving his PhD in 2009 with Professor Jie-Sheng Chen. He then joined Prof. Markus Antonietti’s group as an Alexander von Humboldt Research Fellow at the Max-Planck Institute of Colloids and Interfaces from 2009 to 2012. Since 2013, he has been a professor at the School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University. His current scientific interests are mainly focused on the synthesis of carbon nitride and graphene based functional materials for energy and environmental science applications.

Jie-Sheng Chen received his PhD degree from Jilin University in 1989 and worked as a postdoctoral fellow in the Royal Institution of Great Britain, the United Kingdom, from 1990 to 1994, and as a professor at the Department of Chemistry, Jilin University from 1994 to 2008. Since 2008, he has been a professor at the School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University. His research interests are based in the synthesis of solid compounds and composite materials with new structures and functions.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Han, LN., Ye, TN., Lv, LB. et al. Supramolecular nano-assemblies with tailorable surfaces: recyclable hard templates for engineering hollow nanocatalysts. Sci. China Mater. 57, 7–12 (2014). https://doi.org/10.1007/s40843-014-0011-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-014-0011-4

Keywords

Search

Navigation