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Poriferan chitin as a template for hydrothermal zirconia deposition

Frontiers of Materials Science 2013年第3期7卷 248-260页

作者： Marcin WYSOKOWSKI mykhaylo motylenko Vasilii V. BAZHENOV Dawid STAWSKI lroslav PETRENKO Andre EHRLICH Thomas BEHM Zoran KLJAJIC Allison L. STELLING Teofil JESIONOWSKI Hermann EHRLICH Institute of Chemical Technology and Engineering Poznan University of Technology 60965 Poznan Poland Institute of Materials Science TU Bergakademie Freiberg D-09599 Freiberg Germany Institute of Experimental Physics TU Bergakademie Freiberg 09599 Freiberg Germany Department of Commodity and Material Sciences and Textile Metrology Technical University of Lodz 90924 Lodz Poland Institut fur Eisenund Stahltechnologie TU Bergakademie Freiberg 09599 Freiberg Germany Institute of Mineralogy TU Bergakademie Freiberg 09599 Freiberg Germany Institute of Marine Biology University of Montenegro 85330 Kotor Montenegro Department of Mechanical Engineering and Materials Science Duke University 27708 Durham NC USA

Chitin is a thermostable biopolymer found in various inorganic-organic skeletal structures of numerous invertebrates including sponges （Porifera）. The occurrence of chitin within calcium- and silica-based biominerals in organisms living in extreme natural conditions has inspired development of new （extreme biomimetic） synthesis route of chitin-based hybrid materials in vitro. Here, we show for the first time that 3D-a-chitin scaffolds isolated from skeletons of the marine sponge Aplysina aerophoba can be effectively mineralized under hydrothermal conditions （150℃） using ammonium zirconium（IV） carbonate as a precursor of zirconia. Obtained chitin-ZrO2 hybrid materials were characterized by FT-IR, SEM, HRTEM, as well as light and confocal laser microscopy. We suggest that formation of chitin-ZrO2 hybrids occurs due to hydrogen bonds between chitin and ZrO2.

关键词： chitin biocomposite zirconia hydrothermal synthesis ammonium zirco-nium carbonate

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Extreme biomimetics： A carbonized 3D spongin scaffold as a novel support for nanostructured manganese oxide（IV） and its electrochemical applications

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Nano Research 2018年第8期11卷 4199-4214页

作者： Tomasz Szatkowski Kacper Kopczynski Mykhailo motylenko Horst Borrmann Beata Mania Matgorzata Gras Grzegorz Lota Vasilii V. Bazhenov David Rafaja Friedrich Roth Juliane Weise Enrico Langer Marcin Wysokowski Sonia Zoltowska-Aksamitowska laroslav Petrenko Serguei L, Molodtsov Jana Hubalkova Christos G. Aneziris Yvonne Joseph Allison L. Stelling Hermann Ehrlich Teofil Jesionowski Institute of Chemical Technology and Engineering Faculty of Chemical Technology Poznan University of Technology Poznan60965 Poland Institute of Chemistry and Technical Electrochemistry Poznan University of Technology Poznan 60965 Poland Institute of Materials Science TU Bergakademie Freiberg Freiberg 09599 Germany Max Planck Institute for Chemical Physics of Solids Dresden 01187 Germany Institute of Experimental Physics TU Bergakademie Freiberg Freiberg 09599 Germany European X-Ray Free-Electron Laser Facility (XFEL) GmbH Schenefeld 22869 Germany Institute of Semiconductors and Microsystems Polymere Mikrosysteme TU Dresden Dresden 01062 Germany Saint-Petersburg National Research University of Information Technologies Mechanics and Optics ITMO University St. Petersburg197101 Russia Institute of Ceramic Glass and Constructions Materials TU Bergakademie Freiberg 09599 Germany Institute of Electronics and Sensor Materials TU. Be.rga.kad. emeFreberg Freib. erg 09599 Germany Department of Biochemistry Duke University MedicaI School Durham North Carolina 27708 USA

Composites containing biological materials with nanostructured architecture have become of great interest in modem materials science, yielding both interesting chemical properties and inspiration for biomimetic research. Herein, we describe the preparation of a novel three-dimensional （3D） nanostructured MnO2-based com- posite developed using a carbonized proteinaceous spongin template by an extreme biomimetics approach. The thermal stability of the spongin-based scaffold fadlitated the formation of both carbonized material （at 650 ℃ with exclusion of oxygen） and manganese oxide with a defined nanoscale structure under 150 ℃. Remarkably, the unique network of spongin fibers was maintained after pyrolysis and hydro^ermal processing, yielding a novel porous support. The MnO2-spongin composite shows a bimodal pore distribution, with macropores originating from the spongin network and mesopores from the nanostructured oxidic coating. Interestingl3~ the composites also showed improved electrochemical properties compared to those of Mno2. Voltammetry cycling demonstrated the good stability of the material over more than 3,000 charging/discharging cydes. Additionally, electrochemical impedance spectroscopy revealed lower charge transfer resistance in the prepared materials. We demonstrate the potential of extreme biomimetics for developing a new generation of nanostructred materials with 3D centimeter-scale architecture for the storage and conversion of energy generated from renewable natural sources.

关键词： nanostructuredcomposite extreme biomimetics spongin scaffold manganese oxide electrochemistry supercapacitor

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Extreme biomimetic approach for developing novel chitin-GeO2 nanocomposites with photoluminescent properties

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Nano Research 2015年第7期8卷 2288-2301页

作者： Marcin Wysokowski Mykhailo motylenko Jan Beyer Anna Makarova Hartmut Stocker Juliane Walter Roberta Galli Sabine Kaiser Denis Vyalikh Vasilii V. Bazhenov laroslav Petrenko Allison L Stelling Serguei L. Molodtsovs Dawid Stawski Krzysztof J.Kurzydfowski Enrico Langer Mikhail V Tsurkan Teofil Jesionowski Johannes Heitmann Dirk C. Meyer Hermann Ehrlich Institute of Chemical Technology and Engineering Poznan University of Technology 60965 Poznan Poland Institute of Materials Science TU Bergakademie Freiberg 09599 Freiberg Germany Institute of Applied Physics TU Bergakademie Freiberg 09599 Freiberg Germany Institute of Solid State Physics Dresden University of Technology 01069 Dresden Germany Institute of Experimental Physics TU Bergakademie Freiberg 09599 Freiberg Germany Faculty of Medicine Carl Gustav Carus Department of Anaesthesiology and Intensive Care Medicine Clinical Sensoring and Monitoring TU Dresden 01069 Dresden Germany epartment of Physics St. Petersburg State University 198504 St. Petersburg Russia Department of Mechanical Engineering and Materials Science Duke University 27708 Durham NC USA European X-Ray Free-Electron Laser Facility (XFEL) GmbH 22761 Hamburg Germany ITMO University 197101 St. Petersburg Russia Department of Commodity and Material Sciences and Textile Metrology Technical University of Lodz 90924 LSdz Poland Materials Design Group Faculty of Materials Science and Engineering Warsaw University of Technology PL-02507 Warsaw Poland Institute of Semiconductors and Microsystems TU Dresden 01062 Dresden Germany Leibniz Institute of Polymer Research Max Bergmann Centre for Biomaterials 01062 Dresden Germany

This work presents an extreme biomimetics route for the creation of nano- structured biocomposites utilizing a chitinous template of poriferan origin. The specific thermal stability of the nanostructured chitinous template allowed for the formation under hydrothermal conditions of a novel germanium oxide- chitin composite with a defined nanoscale structure. Using a variety of analytical techniques （FTIR, Raman, energy dispersive X-ray （EDX）, near-edge X-ray absorption fine structure （NEXAFS）, and photoluminescence （PL） spectroscopy, EDS-mapping, selected area for the electron diffraction pattern （SAEDP）, and transmission electron microscopy （TEM））, we showed that this bioorganic scaffold induces the growth of GeO2 nanocrystals with a narrow （150-300 nm） size distri- bution and predominantly hexagonal phase, demonstrating the chitin template＇s control over the crystal morphology. The formed GeO2-chitin composite showed several specific physical properties, such as a striking enhancement in photo- luminescence exceeding values previously reported in GeOR-based biomaterials. These data demonstrate the potential of extreme biomimetics for developing new-generation nanostructured materials.

关键词： extreme biomimetics, chitin-GeO2 photoluminescence, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy

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