High-tech systems and materials

1. November 15, 2011 High-tech systems and materials Andrey Yaroslavtsev Kurnakov Institute of General and Inorganic Chemistry RAS Topchiev Institute of Petroleum Synthesis RAS

2. Positions of Russia in R&D: ratio of needs and capacities Transducers and sensors Liquid mediums Catalysts Ceramic materials Composites Crystalline structures Индекс технологического уровня российских разработок (опережение/отставание России в области НИОКР) Index of R&D results readiness Devices Metals and alloys Coatings and films Polymers Sorbents, membranes and filters Life systems Electronics Индекс рыночной перспективности (динамика рынка и конкурентные преимущества продуктов) Index of demand perspective

3. 2.1. Sensor materials • nanomaterials for miniature highly sensitive sensors with high selectivity; • 2.2. Materials for Energetics •  hybrid membranes and bimetallic catalysts for fuel cells; •  nanomaterials for new generation of electrochemical power sources; •  catalysts for the processing of high quality fuel. 2.3. Optical materials and materials for light production •  nano-structured optical fibers.

4. Hierarchical optical chemosensory materials PHOTOCHEMISTRY CENTER OF RAS Scheme of hierarchical sensory material structure 50ppm 10ppm ASM, 20×20 m ASM, 3×3 m Electron microscopy, 220×160 m TEM, 0,4×0,4 m benzene • п-Xylol n-xylene 2,5ppm 10ppm 5ppm 50ppm 10ppm 25 ppm 50 ppm Intensity change of 420 nm wavelength in the presence of various concentrations of n-xylene Intensity change of 420 nm wavelength in the presence of various concentrations of benzene

5. Multi - electrode system (including special membrane electrode) based on biocompatible nanosensors to measure the freshness of beer Diagram of beer responses ? A1A2…An В multivariate analysis algorithm V Similar systems can be used for the analysis of proteins, drugs, blood etc. sour X1 X2 X3 … Xn stale Voronezh State University, IGIC RAS fresh

6. MSU, Department of material science 3D thermocatalytic Gas Sensors (pellistors) Determination of methane concentration in coal mines Characteristics: • Т = 360 ÷ 590 °С • С = 0 ÷ 5 % vol. СН4 • Sensitivity 15 - 50 mV/% vol. СН4 • Power consumption 75 - 200 mW

7. Hybrid membranes for fuel cells Electron microscopy of MF-4SC membrane (Russian analog of Nafion ), modified by silica (in situ synthesis), particle size 2-5 nm Temperature dependence of conductivity forMF-4SC membrane modified by acid zirconium phosphate (a-e).Comparison sample (f). Ion conductivity as a function of RH for MF-4SC (1);MF-4SC+SiO2 (2);MF-4SC+SiO2+HPW (3) and MF-4SC+SiO2+CsHPW (4). Kurnakov Institute of General and Inorganic Chemistry RAS 7

8. Cathode materials for lithium ion accumulators Comparison of cathode materials Discharge capacity, mA/h Traditional material Charge process LiCoO2 Li1-XCoO2 (CoO2) Charge Discharge Rate of discharge/charge Electron microscopy of LiFePO4 composite with carbon. Charge-discharge curves(4-th cycle) Kurnakov Institute of General and Inorganic Chemistry RAS

9. Fiber Optics Research Center of RAS Bismuth-doped fibers for lasers and optical amplifiers The broad band of luminescence in Bi-doped fibers enables one to develop fiber lasers and amplifiers in the wavelength region uncovered by effective rare-earth active media. Recently developed Bismuth-doped fiber lasers: spectral lasing region and maximal CW output power.

10. 2.6. Nanoscale catalysts for deep processing of raw materials  nanostructured and nanoscale catalysts for petrochemical processes;  catalytic conversion processes of natural gas and oil associated gas into liquid fuels, hydrogen and valuable organic products;  catalytic methods for processing of renewable raw materials (biogas and biomass) into valuable organic products.

11. Nanoheterogeneous and nanostructurated catalysts for hydrocarbon feeds transformation Topchiev Institute of Petroleum Synthesis RAS Catalytic processes for natural/ associated gas conversion Heavy oils, bitumens, heavy residues conversion HYDROGEN SYNTHETIC FUELS CHEMICAL PRODUCTS HYDROGEN FUELS LIGHT OIL Hierarchic oxides systems Metal – organic frameworks Nanoheterogeneous catalysts

12. Catalytic cracking of vacuum gasoil Topchiev Institute of Petroleum Synthesis RAS The advantages of new technology : • Flexible processing of vacuum gasoil • Processing using gasoline mode: • Gasoline (<205оС) yield – 56% mass. • Overall yield of propane-propylene and butane-butylene fractions, gasoline and light gasoil – 87,5% mass. • Research octane number – 94,2 • Consumption of fresh catalyst - lower than 0,5 kg/t of feed

13. Production of the low molecular weight olefins or high-octane gasoline from natural gas via dimethyl ether  Natural gas Traditional route Perspective route Syngas Methanol DME DME Gasoline,Olefins Process schemes of conversion of natural gas to olefins • Stage of “syngas to DME” is more effective and cheaper that stage “syngas to methanol” • Stage “DME to hydrocarbons” is simpler and more effective than stage “methanolto hydrocarbons”

14. Catalyst — NiO+Co3O4/Al2O3 Pilot unit scheme with circulating fluidized catalyst bed

15. Topchiev Institute of Petroleum Synthesis RAS Pilot plant: DME and gasoline production • New technology and catalyst of oxidizing conversion of methane to syngas have been developed • New technology and catalyst of direct DME production from syngas have been developed • New technology and catalyst of gasoline production from DME have been developed • New technology and catalyst of lower olefins production from DME have been developed

16. Functional Materials • 2.7. Nanostructured membrane materials •  membrane materials, membrane reactors and membrane catalysis for the production of valuable chemical products; • nanostructured membranes with improved transport properties and devices for gases and liquids purification and separation. • 2.8. Biomimetic materials and materials for medicine •  bioresorbable materials for bone and dental implants; •  biodegradable and transdermal systems with controlled drugs release; •  systems with high adhesion to various substrates, including biological, for use as protective coatings, packaging, etc.

17. Membranes from anodic aluminum oxide MSU, Department of material science

18. The possibility of membrane reactors use for non-oxidizing methane dimerization under the UV irradiation to yield compounds C2 and more • Excitation of CH4 molecules by ultraviolet radiation allows to activate methane at 500-600 K. The use of membrane reactor allows to shift the thermodynamic balance dew to the removal of hydrogen from the reaction zone. Topchiev Institute of Petroleum Synthesis RAS Laboratory membrane catalyst setting for ethane oxidative dehydrogenation to ethylene (ODE) allows to carry out the process at ratios of ethane and oxygen, unacceptable in conventional reactors Scheme of membrane reactor ODE was carried out at 320-460 C in a flow reactor. Reactants conversion in membrane reactor Topchiev Institute of Petroleum Synthesis RAS Zelinskii Institute of Organic Chemistry RAS Increase in ethane conversion up to 70% with 95% selectivity.

19. Gas Gas Water Water Catalytic membrane contactor/reactor for O2 remove from water Principle • Single-stage process • Deposition of Pd onto hydrophobic polymeric porous membranes Liquid-Cell contactor Catalytic membranes synthesized Pd Hydrodechlorination of trichlorethylene (TCE) at room temperature Topchiev Institute of Petroleum Synthesis RAS porous membranes, TNO, Holst center

20. Hydroxylapatite material for implants and its coatings TEM image of amorphous HA 1 - nanocrystalline HA coating on titanium (1mkm) after TiO2 - nanocrystalline HA coating on silicon (1mkm)3 - nanocrystalline HA coating on titanium (1mkm)4 - nanostructured ceramics5 - amorphous HA coating on titanium (1mkm)6 - nanocrystalline Cu film (1mkm) on Si SEM image of the cross-cleaved HA coating on the Ti surface (a) and AFM-iso-ping cross-cleavage of the covering thickness of 3.0 mm HA (b) Voronezh State University Institute of Metallurgyof RAS

21. Polymer adhesives for medical applications • New family of hydrophilic pressure-sensitive adhesives based on interpolymeric complexes: • Adhesion to hydrophilic and wet surfaces; • Obtained from non-adhesive materials by simple mixing • Control of dissolution rate is possible; • Opportunity for preparation of PSAs with adhesive properties triggerred by external factors: temperature, pH, humidity. • Application in transdermal and transmucosal drug delivery systems: • Extension of the number of drugs that can be successfully delivered transdermally; • Suitable for delivery of hydrophilic drugs via transdermal route; • Excellent for transmucosal delivery due to good adhesion to wet surfaces and wide range of solubility rates: from rapidly soluble to insoluble in water. • Other applications: • Medical patches; • Wound dressings; • Teeth whitening and oral care products Topchiev Institute of Petroleum Synthesis RAS

22. Smart pressure-sensitive adhesives Wound dressings with temperature-assisted painless removal Phase II: Wound protection by dressing (<39oC) Phase I: Wound (<39oC) Phase III: Healing (<39oC) Wound Phase VI: Isolation of biomaterials bysimple folding Phase V: Painless dressing removal Phase IV: Heating of dressing (~40-50°C) Topchiev Institute of Petroleum Synthesis RAS

23. Carbohydrates. Novel pharmaagents under development and target diseases Drugs and materials with biological activity Inflammation: - Blockers of P-, E-, and L-selectins (synthetic compounds) Cancer: - Blockers of estrogen receptor (natural lignan from Siberian larch; pre-clinical); - Inhibitors of metastasis development (synthetic compounds) - Antiangiogenic agents (synthetic compounds) - Sensitizer for photodynamic therapy (synthetic compound, EMA approved) - Glycoconjugate oncovaccines (synthetic compound) Neural diseases: - Blockers of auto-antibodies which cause neuropathies (synthetic carbohydrate HNK-1 antigens and ganglioside ligands and their mimetics) - Stimulators of neurith outgrowth (synthetic compounds) Infection diseases: - Oligodentate blockers of bacterial toxins (synthetic compounds) - Glycoconjugate bacterial and fungal vaccines (synthetic compounds) Zelinskii Institute of Organic Chemistry RAS

24. T h a n k y o u f o r a t t e n t i o n