Self-assembly of an organic–inorganic block copolymer for nano-ordered ceramics
Source abstract
Abstract
Self-assembly is a promising approach for achieving controlled nanoscale architectures in ceramics. The addition of ceramic-forming precursors to templating agents such as self-assembled surfactants or organic block copolymers (BCPs) has thus far been the primary route to forming ordered nanoporous oxides1,2,3,4,5 and nanostructured non-oxide ceramics6,7,8,9. In spite of its viability, however, this approach has several intrinsic shortcomings, including: (1) stringent requirements for amphiphilicity between template and precursor, lack of which may lead to macro-phase separation and loss of nano-scale order; (2) morphologies that can change uncontrollably with varying amounts of added ceramic precursor. Here we report a novel single-source ceramic precursor, based on a hybrid organic–inorganic BCP of polynorbornene–decaborane, that enables the formation of ordered ceramic nanostructures with tunable morphology and composition. In particular, we describe the synthesis of nanostructured boron carbonitride and mesoporous boron nitride, the latter of which exhibits the highest reported surface area for this material to date.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Block Copolymer Self-Assembly · Covalent Organic Framework Applications · Mesoporous Materials and Catalysis
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (29)
Show source-provided references
1. Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. & Beck, J. S. Ordered mesoporous molecular sieves synthesized by a liquid crystal template mechanism. Nature 359, 710–712 (1992).10.1038/359710a0 ↗
2. Templin, M. et al. Organically modified aluminosilicate microstructures from block copolymer phases. Science 278, 1795–1798 (1997).10.1126/science.278.5344.1795 ↗
3. Pai, R. A. et al. Mesoporous silicates prepared using preorganized templates in supercritical fluids. Science 303, 507–510 (2004).10.1126/science.1092627 ↗
4. Chan, V. Z.-H. et al. Ordered bicontinuous nanoporous and nanorelief ceramic films from self-assembling polymer precursors. Science 286, 1716–1719 (1999).10.1126/science.286.5445.1716 ↗
5. Ulrich, R., Du Chesne, A., Templin, M. & Wiesner, U. Nano-objects with controlled shape, size and composition form block copolymer mesophases. Adv. Mater. 11, 141–146, (1999).10.1002/(SICI)1521-4095(199902)11:2<141::AID-ADMA141>3.0.CO;2-R ↗
6. Kamperman, M., Garcia, C. B. W., Du, P., Ow, H. & Wiesner, U. Ordered mesoporous ceramics stable up to 1500 °C from diblock copolymer mesophase. J. Am. Chem. Soc. 126, 14708–14709 (2004).10.1021/ja046795h ↗
7. Wan, J. et al. Nanostructured non-oxide ceramics templated via block copolymer self-assembly. Chem. Mater. 17, 5613–5617 (2005).10.1021/cm051124j ↗
8. Armatas, G. S. & Knatzidis, M. G. Mesostructured germanium with cubic pore symmetry. Nature 441, 1122–1125 (2006).10.1038/nature04833 ↗
9. Sun, D. et al. Hexagonal nanoporous germanium through surfactant-driven self-assembly of zintl clusters. Nature 441, 1126–1130 (2006).10.1038/nature04891 ↗
10. Galloro, J. et al. Replicating the structure of a crosslinked polyferrocenylsilane inverse opal in the form of a magnetic ceramic. Adv. Funct. Mater. 12, 382–388 (2002).10.1002/1616-3028(20020517)12:5<382::AID-ADFM382>3.0.CO;2-X ↗
11. Temple, K. et al. Spontaneous vertical ordering and pyrolytic formation of nanoscopic ceramic patterns from poly(styrene-b-ferrocenylsilane). Adv. Mater. 15, 297–300 (2003).10.1002/adma.200390071 ↗
12. Bates, F. S. & Fredrickson, G. H. Block copolymers – designer soft materials. Physics Today 52, 32–38 (1999).10.1063/1.882522 ↗
13. Shen, Q. H. & Interrante, L. V. Structural characterization of poly(silylenemethylene). Macromolecules 29, 5788–5796 (1996).10.1021/ma960199t ↗
14. Seyferth, D., Strohmann, C., Dando, N. R. & Perrotta, A. J. Poly(ureidosilazanes): preceramic polymeric precursors for silicon carbonitride and silicon nitride. Synthesis, characterization, and pyrolytic conversion to Si3N4/SiC ceramics. Chem. Mater. 7, 2058–2066 (1995).10.1021/cm00059a012 ↗
15. Wei, X., Carroll, P. J. & Sneddon, L. G. New routes to organodecaborane polymers via ruthenium-catalyzed ring-opening metathesis polymerization. Organometallics 23, 163–165 (2004).10.1021/om0342107 ↗
16. Welna, D. T., Bender, J. D., Wei, X., Sneddon, L. G. & Allcock, H. R. Preparation of boron-carbide/carbon nanofibers from a poly(norbornenedecaborane) single-source precursor via electrostatic spinning. Adv. Mater. 17, 859–862 (2005).10.1002/adma.200401257 ↗
17. Wei, X., Carroll, P. J., Sneddon, L. G. Ruthenium-catalyzed ring-opening polymerization syntheses of poly(organodecaboranes): New single-source boron-carbide precursors. Chem. Mater. 18, 1113–1123 (2006).10.1021/cm0524603 ↗
18. Choi, T.-L. & Grubbs, R. H. Controlled living ring-opening-metathesis polymerization by a fast-initiating ruthenium catalyst. Angew. Chem. Int. Edn. 42, 1743–1746 (2003).10.1002/anie.200250632 ↗
19. Lodge, T. P., Pudil, B. & Hanley, K. J. The full phase behavior for block copolymer in solvents of varying selectivity. Macromolecules 35, 4707–4717 (2002).10.1021/ma0200975 ↗
20. Funaki, Y. et al. Influence of casting solvents on microphase-separated structures of poly(2-vinylpyridine)-block-polyisoprene. Polymer 40, 7147–7156 (1999).10.1016/S0032-3861(99)00112-3 ↗
21. Mirabelli, M. G. L. & Sneddon, L. G. Synthesis of boron nitride via a polymeric vinylpentaborane precursor. Inorg. Chem. 27, 3271–3272 (1988).10.1021/ic00292a004 ↗
22. Rees, W. S. Jr & Seyferth, D. High-yield synthesis of boron carbide (B4C)/boron nitride ceramic materials by pyrolysis of polymeric Lewis base adducts of decarborane(14). J. Am. Ceram. Soc. 71, C194–C196 (1988).10.1111/j.1151-2916.1988.tb05873.x ↗
23. Dibandjo, P., Chassagneux, F., Bois, L., Sigala, C. & Miele, P. Comparison between SBA-15 silica and CMK-3 carbon nanocasting for mesoporous boron nitride synthesis. J. Mater. Chem. 15, 1917–1923 (2005).10.1039/b417891b ↗
24. Dibandjo, P. et al. Synthesis of boron nitride with ordered mesostructure. Adv. Mater. 17, 571–574 (2005).10.1002/adma.200401501 ↗
25. Vinu, A. et al. Synthesis of mesoporous BN and BCN exhibiting large surface areas via templating methods. Chem. Mater. 17, 5887–5890 (2005).10.1021/cm051780j ↗
26. Han, W. Q., Brutchey, R., Tilley, T. D. & Zettl, A. Activated boron nitride derived from activated carbon. Nano Lett. 4, 173–176 (2004).10.1021/nl034843a ↗
27. Hagio, T., Nonaka, K. & Sato, T. Microstructural development with crystallization of hexagonal boron nitride. J. Mater. Sci. Lett. 16, 795–798 (1997).10.1023/A:1018518222594 ↗
28. Jacobsen, C. J. H. Boron nitride: a novel support for ruthenium-based ammonia synthesis catalysts. J. Catal. 200, 1–3 (2001).10.1006/jcat.2001.3200 ↗
29. Hansen, T. W. et al. Atomic-resolution in situ transmission electron microscopy of a promoter of a heterogeneous catalyst. Science 294, 1508–1510 (2001).10.1126/science.1064399 ↗