国外大学经典课件纳米材料在能源与生物医学的用途

1、Nanostructured Carbide-Derived Carbonsfor Energy-Related and Biomedical ApplicationsYury GogotsiDirector, A.J. Drexel Nanotechnology InstituteTrustee Chair Professor of Materials Science & EngineeringDrexel University, Philadelphia, PA 19104, USANanostructured Carbide-DerivedMajor R

2、esearch ActivitiesNanotubes, Nanocones, and Nanowires Y. G., J.A. Libera, N. Kalashnikov, M. Yoshimura, Science, v. 290, 317 (2000)Nanotube-Based Nanofluidic DevicesY. G., J. Libera, A. Yazicioglu, et al., Appl. Phys. Letters,v. 79, p.1021 (2001) N. Naguib, H. Ye, Y. G., et al. Nano Letters, v. 4, 2

3、237 (2004) Nanotube-Reinforced PolymersF. Ko, Y. G., A. Ali, et al., Advanced Materials, v. 15, 1161 (2003)Nanodiamond Powders and CompositesS. Osswald, G. Yushin, V. Mochalin, S. Kucheyev, Y. G., J. American Chemical Society, v. 128, 11635 (2006) Indentation Induced Phase Transformations Y. G., A.

4、Kailer, K.G. Nickel, Nature, v. 401, 663 (1999) Raman Spectroscopy and Electron MicroscopyP.H. Tan, S. Dimovski, Y.G., Phil. Trans. Royal Soc. Lond. A, v.362, 2289 (2004) Carbide-Derived Carbons for Energy-Related and Other ApplicationsY. G, M. Yoshimura, Nature, v. 367, 628-630 (1994) Y. G., S. Wel

5、z, D. Ersoy, M.J. McNallan, Nature, v. 411, 283 (2001) J. Chmiola, G. Yushin, Y.G., et al., Science, v. 313, 1760 (2006)Major Research ActivitiesNanotnucleusmitochondriaCarbon NanotubeNanotube-Tipped Multifunctional Cellular ProbesJ. R. Freedman, et al. Appl. Phys. Lett. 90, 103108 (2007)D. Staack,

6、et al, Angewandte Chemie Int. Ed., 47, 8020 (2008)M. G. Schrlau, et al, Nanotechnology 19, 325102 (2008) vElectrical. Fluorescence.Optical, SERS,Electrochemical measurements50% O. Hutchins, US Patent, 1271713 (1918)W.A. Mohun, US Patent, 3066099 (1962)S.K. Gordeev et al., J.Appl. Chem. (USSR) 64, 11

7、78 (1991)N.F. Fedorov, Russ. Chem. J. 39, 73 (1995)Y. Gogotsi, M. Yoshimura, Nature, 367, p. 628 (1994)A. Kravchik et al., Russ. J. Appl. Chem. 72, 2159 (1999)Y. Gogotsi, et al, Nature, 411, p. 283 (2001)J. Leis, et al. Carbon, 39, 2043 (2001)Carbide-Derived Carbon (CDC)SiPositions and spatial distr

8、ibution of carbon atoms in the carbide affect the structure and pore size/shape of CDC G. Yushin, A. Nikitin, Y. Gogotsi, Carbide Derived Carbon, in Nanomaterials Handbook, CRC Press (2006) Carbide Lattice Template for CDCPositions and spatial distribuG. Yushin, A. Nikitin, Y. Gogotsi, in Nanomateri

9、als Handbook, ed. by Y. Gogotsi (CRC Press, 2006) Carbide Lattice Template for CDCTi3SiC2-CDC (1200C)SiC-CDC (1200C)Pore-size distributions calculated using NL DFT modelAr sorption at 77 KAutosorb-1G. Yushin, A. Nikitin, Y. GogoGogotsi, Y., et al., Nature Materials, v. 2, 591 (2003) dD/dT 0.0005 nm/

10、oC,or: +/- 10o C temperature control - better than 0.1 pore control.Tunable Pore Size in CDCChoice of starting material and synthesis conditions gives an almost unlimited range of porosity distributions High surface area Uniform poresTi3SiC2 -CDCT=300CGogotsi, Y., et al., Nature MaSiCT=1700C, 10-6 v

11、acuumgraphitenanotubesFormation of Graphite and NanotubesZ. G. Cambaz, G. Yushin, S. Osswald, V. Mochalin, Y. Gogotsi, Carbon (2008) 46, 841 Vacuum decomposition of SiC produces ordered nanostructures:Graphene, graphite or CNTsFactors affectingCDC structure:TemperatureCrystal faceOxygen PSurface sta

12、te (roughness)Surface chemistryHeating rateM. Kusunoki at al. Applied Physics Letters 77, 424, 2000; Chemical Physics Letters, 366, 458, 2002SiT=1700C, 10-6 vacuumgraphitCDC: Powders, Films, Fibers, Bulk CDC coated SiC Tyranno fabricBulk CDCfrom sinteredSiCCDC coateddynamic sealsd=3 cmPowderCDC: Pow

13、ders, Films, Fibers, BEfficiency of Energy TechnologiesInputIdeal storage(no losses)OutputSupercapacitors: 109%0%100%Primaryrenewable energyU. Bossel - European Fuel Cell Forum - July 2008 Liquefied hydrogen: 400%Compressed hydrogen: 312%Compressed air: 156%Pumped water: 130%Lead acid batteries: 120

14、%Lithium-ion batteries: 116%Useful energyEnergy DistributionToday: 80% chemical, 20% physicalFuture: 20% chemical, 80% physicalChemical StorageCapacitive StorageCross-cutting panelP. Simon, Y. Gogotsi, Nature Materials, v.7, 845 (2008)Efficiency of Energy TechnologUnexpected capacitance increase as

15、pores decrease below 1nmChmiola, J.; Yushin, G.; Gogotsi, Y.; Portet, C.; Simon, P.; Taberna, P.-L., Science, 2006, v. 313, 1760Increase in Carbon Capacitance at pore size below 1 nmCation: (CH3CH2)4N+Anion: BF4-Unexpected capacitance increasIons MUST be desolvated!TiC-CDC ElectrochemistryJ. Chmiola

16、, C. Largeot, P.-L. Taberna, P. Simon, Y. Gogotsi, Angew. Chemie Int. Ed. v. 47, 3395 (2008)Ions MUST be desolvated!TiC-CDNeed to increase energy (100W-h kg-1) to directly compete with batteriesLarger voltage window that traditional electrolytes provides much greater energy densityStill need to unde

17、rstand capacitance mechanisms and possibly increase the voltage window even moreCarbon-Electrolyte CouplesQuestion: How to match a porous carbon (select from hundreds) with an electrolyte (select from thousands)?P. Simon, Y. Gogotsi, Nature Materials, v.7, 845 (2008)Need to increase energy (100WTiC-

18、CDC Ionic LiquidC. Largeot, et al, J. Am. Chem. Soc. v. 130, 2730 (2008) Specific gravimetric and volumetric capacitances change versus the chlorination temperature for CDC electrodes tested in EMI-TFSI electrolyte at 60C. A standard activated carbon (Kuraray) designed for organic electrolyte-based

19、supercapacitors reached 90 F/g and 45 F/cm3 under the same experimental conditions. TiC-CDC Ionic LiquidC. LargeCryo-adsorption of HydrogenWeak interaction between H2 and adsorbent (e.g. isosteric heat of H2 adsorption is 5 kJ/mole on plan graphite and 5-7 kJ/mole on MOF, which is too weak for RT ad

20、sorption)Challenges:MOF* Nanoporous CarbonCandidates:* O. Yaghi, et al. , J. Am. Chem. Soc., 128, 3494 (2006) Y. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005) Cryo-adsorption of HydrogenWea0.91.00.81.01.82.0 TiC-CDC ZrC-CDC SiC-CDC B4C-CDC H2 wt.

21、% per unit SSA,Pore size, nm.103m2wt%.gSmall pores are more efficient than large ones for a given SSASSA of 3000 m2/g will be needed at ambient pressure for 7wt% storage - FEASIBLE!Empty symbols: H2 treated samplesY. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005) CDC for H2 Storage: Cryo-ads

22、orption77K1 atm0.91.01.41.5CDC for H2 storage: Cryo-adsorption Large volume of pores $ 17 billion / year in the US Inflammatory response is driven by a complex network of cytokines, inflammatory mediators Cytokine removal from blood brings under control the unregulated pro- and ant

23、i-inflammatory processes driving sepsisHydrogenTNF-9.4 x 9.4 x 11.7 nmCDC for Protein AdsorptionGranCDC for Cytokine* Adsorption* cytokines are regulatory proteins that are released by cells of the immune system and need to be removed from the blood in case of an autoimmune disease.TNF-IL-6 CDC outp

24、erformed commercial carbons in the efficiency of cytokines removal G. Yushin, et al. Biomaterials, 27, 5755 , 2006CDC for Cytokine* Adsorption* CDC for Cytokine Adsorption Adsorption depends on the SSA of adsorbents accessible by cytokinesG. Yushin, et al. Biomaterials, 27, 5755 , 2006CDC for Cytokine Adsorption AdFurther reading:G. Yushin, Y. Gogotsi, and A. Nikitin, Carbide Derived Carbon, in Nanomaterials Handb