国外大学经典课件-纳米材料在能源与生物医学的用途.ppt

http:/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,USAhttp:/Major Research 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.4,2237(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.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.Welz,D.Ersoy,M.J.McNallan,Nature,v.411,283(2001)J.Chmiola,G.Yushin,Y.G.,et al.,Science,v.313,1760(2006)http:/nucleusmitochondriaCarbon NanotubeNanotube-Tipped Multifunctional Cellular ProbesJ.R.Freedman,et al.Appl.Phys.Lett.90,103108(2007)D.Staack,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)64,1178(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)http:/Positions and spatial distribution 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 CDChttp:/G.Yushin,A.Nikitin,Y.Gogotsi,in Nanomaterials 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-1http:/Gogotsi,Y.,et al.,Nature Materials,v.2,591(2003)dD/dT 0.0005 nm/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=300Chttp:/SiCT=1700C,10-6 vacuumgraphitenanotubesFormation 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 state(roughness)Surface chemistryHeating rateM.Kusunoki at al.Applied Physics Letters 77,424,2000;Chemical Physics Letters,366,458,2002http:/CDC:Powders,Films,Fibers,Bulk CDC coated SiC Tyranno fabricBulk CDCfrom sinteredSiCCDC coateddynamic sealsd=3 cmPowderhttp:/Efficiency 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%Lithium-ion batteries:116%Useful energyEnergy DistributionToday:80%chemical,20%physicalFuture:20%chemical,80%physical1.Chemical Storage2.Capacitive Storage3.Cross-cutting panelP.Simon,Y.Gogotsi,Nature Materials,v.7,845(2008)http:/Unexpected capacitance increase as 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-http:/Ions MUST be desolvated!TiC-CDC ElectrochemistryJ.Chmiola,C.Largeot,P.-L.Taberna,P.Simon,Y.Gogotsi,Angew.Chemie Int.Ed.v.47,3395(2008)http:/Need to increase energy(100W-h kg-1)to directly compete with batteriesLarger voltage window that traditional electrolytes provides much greater energy densityStill need to understand 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)http:/TiC-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 supercapacitors reached 90 F/g and 45 F/cm3 under the same experimental conditions.http:/Cryo-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 adsorption)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)http:/0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.60.81.01.21.41.61.82.02.22.42.6 TiC-CDC ZrC-CDC SiC-CDC B4C-CDC H2 wt.%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-adsorption77K1 atmhttp:/CDC 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 anti-inflammatory processes driving sepsisHydrogenTNF-9.4 x 9.4 x 11.7 nmhttp:/CDC 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 outperformed commercial carbons in the efficiency of cytokines removal G.Yushin,et al.Biomaterials,27,5755,2006http:/CDC for Cytokine Adsorption Adsorption depends on the SSA of adsorbents accessible by cytokinesG.Yushin,et al.Biomaterials,27,5755,2006http:/Further reading:G.Yushin,Y.Gogotsi,and A.Nikitin,Carbide Derived Carbon,in Nanomaterials Handbook,Y.Gogotsi,Editor.2006,CRC Press.p.237-280.ConclusionsCDC process enables design and fine tuning of porous carbons for improved performance in energy applications:electrochemical capacitors,hydrogen storage,methane storage,fuel cell catalyst support,etc.Move from trial-and-error tests to science-driven design of nanostructured carbons for energy,biomedical and other applicationshttp:/AcknowledgementsStudents and post-docs at Drexel University Drexel University:J.Chmiola,G.Yushin,C.Portet,E.Hoffman,R.Dash,G.Cambaz and otherCollaborators:Prof.P.Simon,Paul Sabatier University,Toulouse,FranceProf.J.E.Fischer,University of PennsylvaniaProf.M.Barsoum,Drexel University,Prof.M.J.McNallan,UICFunding:DOE,NSF,Arkema