Synthesis and Morphogenesis of Organic Polymer Materials with Hierarchical Structures in Biominerals

Abstract

Synthesis and morphogenesis of polypyrrole (PPy) with hierarchical structures from nanoscopic to macroscopic scales have been achieved by using hierarchically organized architectures of biominerals. We adopted biominerals, such as a sea urchin spine and nacreous layer, having hierarchical architectures based on mesocrystals as model materials used for synthesis of an organic polymer. A sea urchin spine led to the formation of PPy macroscopic sponge structures consisting of nanosheets less than 100 nm in thickness with the mosaic interior of the nanoparticles. The morphologies of the resultant PPy hierarchical architectures can be tuned by the structural modification of the original biomineral with chemical and thermal treatments. In another case, a nacreous layer provided PPy porous nanosheets consisting of the nanoparticles. Conductive pathways were formed in these PPy hierarchical architectures. The nanoscale interspaces in the mesocrystal structures of biominerals are used for introduction and polymerization of the monomers, leading to the formation of hierarchically organized polymer architectures. These results show that functional organic materials with complex and nanoscale morphologies can be synthesized by using hierarchically organized architectures as observed in biominerals.

Mesocrystals and Their Related Structures as intermediates between single crystals and polycrystals

“…22). 141) After the introduction and polymerization of the pyrrole monomer, the composite of polypyrrole and biomineral was formed. The dissolution of the biomineral led to the formation of hierarchical architectures of the polymer.…”

“…SEM (a, b, d, e) and TEM (c, f ) images of the original sea urchin spine (ac) and its hierarchical replication to polypyrrole (df ). 141) Reprinted with permission (Copyright 2014, American Chemical Society).…”

Multistage redox reactions of conductive-polymer nanostructures with lithium ions: potential for high-performance organic anodes

“…The theoretical capacity is determined by the doping level, such as 136 mAh g -1 for polypyrrole (PPy) with a maximum 33 mol% anion doping and 82 mAh g -1 for polythiophene (PTp) with 25 mol% anion doping 13,16,19,21 . The improved electrochemical properties were achieved by the design of the molecules and morphologies 17,[21][22][23][24][25][26][27][28] . Our group reported new methods for the simultaneous synthesis and morphology control of conductive polymers using solid-state oxidant crystals [24][25][26][27][28] .…”

Phase separation of composite materials through simultaneous polymerization and crystallization

“…11 Molecular and porous templates facilitate the formation of composites through the casting and coating of guest molecules. [12][13][14][15] In general, it is not easy to prepare composites based on polymers with low solubility and processability, such as conductive polymers with rigid π-conjugated systems.…”

“…In previous reports, [12][13][14][15][16][17][18][19] composites based on conductive polymers were synthesized by templating and coating coupled with polymerization. However, complex morphologies, such as phase-segregated sea-island structures on the submicrometer scale, are not easily obtained by typical methods.…”