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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,USA,Major Research Activities,Nanotubes,Nanocones,and Nanowires
2、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(
3、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.Roya
4、l 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),nucleus,mitochondria,Carbon Nanotube,Nanotube-Tipped
5、Multifunctional Cellular Probes,J.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),v,Electrical.Fluorescence.Optical,SERS,Electrochemical measurements,Glass pipette,Nanotube,Carbide-Derived Carbon(CD
6、C),SiC(s)+2Cl2(g)SiCl4(g)+C(s),Process Features Network of open poresPrecise control over structure and pore size Coating,free standing monolith or powder Numerous carbides can be used Linear kinetics,Vcarbide=VCDC,Etching Agent:,Cl2,F2,Br2,I2,HCl,HBr,HI,Supercritical H2O,200-1200oC,Temperature:,Car
7、bide,2 nm,CarbidePorosity=0%,Carbide Derived Carbon,Nanoporous CarbonPorosity 50%,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
8、.J.Appl.Chem.72,2159(1999)Y.Gogotsi,et al,Nature,411,p.283(2001)J.Leis,et al.Carbon,39,2043(2001),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(
9、2006),Carbide Lattice Template for CDC,G.Yushin,A.Nikitin,Y.Gogotsi,in Nanomaterials Handbook,ed.by Y.Gogotsi(CRC Press,2006),Carbide Lattice Template for CDC,Ti3SiC2-CDC(1200C),SiC-CDC(1200C),Pore-size distributions calculated using NL DFT model,Ar sorption at 77 KAutosorb-1,Gogotsi,Y.,et al.,Natur
10、e 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 CDC,Choice of starting material and synthesis conditions gives an almost unlimited range of porosity distributions,High surface area Uniform pores,Ti3SiC2-CDC,T=300C,Format
11、ion of Graphite and Nanotubes,Z.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 rate
12、,M.Kusunoki at al.Applied Physics Letters 77,424,2000;Chemical Physics Letters,366,458,2002,CDC:Powders,Films,Fibers,Bulk,CDC coated SiC Tyranno fabric,Bulk CDCfrom sinteredSiC,CDC coateddynamic seals,d=3 cm,Powder,Efficiency of Energy Technologies,Input,Ideal storage(no losses),Output,Supercapacito
13、rs:109%,0%,100%,Primaryrenewable energy,U.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 energy,Energy DistributionToday:80%chemical,20%physicalFuture:20%chemi
14、cal,80%physical,Chemical StorageCapacitive StorageCross-cutting panel,P.Simon,Y.Gogotsi,Nature Materials,v.7,845(2008),Unexpected capacitance increase as pores decrease below 1nm,Chmiola,J.;Yushin,G.;Gogotsi,Y.;Portet,C.;Simon,P.;Taberna,P.-L.,Science,2006,v.313,1760,Increase in Carbon Capacitance a
15、t pore size below 1 nm,Cation:(CH3CH2)4N+Anion:BF4-,Ions MUST be desolvated!,TiC-CDC Electrochemistry,J.Chmiola,C.Largeot,P.-L.Taberna,P.Simon,Y.Gogotsi,Angew.Chemie Int.Ed.v.47,3395(2008),Need to increase energy(100W-h kg-1)to directly compete with batteriesLarger voltage window that traditional el
16、ectrolytes provides much greater energy densityStill need to understand capacitance mechanisms and possibly increase the voltage window even more,Carbon-Electrolyte Couples,Question:How to match a porous carbon(select from hundreds)with an electrolyte(select from thousands)?,P.Simon,Y.Gogotsi,Nature
17、 Materials,v.7,845(2008),TiC-CDC Ionic Liquid,C.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 e
18、lectrolyte-based supercapacitors reached 90 F/g and 45 F/cm3 under the same experimental conditions.,Cryo-adsorption of Hydrogen,Weak 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),Cha
19、llenges:,MOF*Nanoporous Carbon,Candidates:,*O.Yaghi,et al.,J.Am.Chem.Soc.,128,3494(2006),Y.Gogotsi,et al.,J.Am.Chem.Soc.,127,16006(2005),0,.,6,0,.,7,0,.,8,0,.,9,1,.,0,1,.,1,1,.,2,1,.,3,1,.,4,1,.,5,1,.,6,0,.,8,1,.,0,1,.,2,1,.,4,1,.,6,1,.,8,2,.,0,2,.,2,2,.,4,2,.,6,T,i,C,-,C,D,C,Z,r,C,-,C,D,C,S,i,C,-,C
20、,D,C,B,4,C,-,C,D,C,P,o,r,e,s,i,z,e,n,m,Small 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 samples,Y.Gogotsi,et al.,J.Am.Chem.Soc.,127,16006(2005),CDC for H2 Storage:Cryo-adsorption,77K1
21、atm,CDC for H2 storage:Cryo-adsorption,Large volume of pores 1 nm needed for high storage capacityDensity of gaseous H2 innano-pores can be higherthan density of liquid H2 J.Jagiello et al.,J.Phys.Chem.B,in press(2006),Q.Wang et al.,J.Chem.Phys.110,577-586(1999),if all these poresfilled with liquid
22、H2,Small pores increase the interaction with H2 and thus result in higher H2 coverage of the sorbent surfaceCDC demonstrate stronger interaction with H2 than CNT and MOF,G.Yushin et al.,Advanced Functional Materials,16,p.2288-2293(2006),Overall,linear dependence of storage on BET SSA,similar to 1 at
23、m.,Similar to 1 atm.,small pores are overweighted in the SSA/normalized storage.,Correlation of 60 bar 77K storage with SSA and volume of small pores,Activation is effective if the increase in SSA comes mainlyfrom small pores.On this basis,CDCs can outperform ACs.,max,The best pore size,Useful pores
24、,Little or no contribution,Y.Gogotsi,et al,Importance of Pore Size in High Pressure Hydrogen Storage by Porous Carbons,Int.J.Hydrogen Energy(2008),CDC for Protein Adsorption,Grand challenge-Sepsis,Severe sepsis kills 1,500 people/day(comparable to lung and breast cancer(2,700 and 1,100 people/day,re
25、spectively)Sepsis$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 sepsis,Hydrogen,TNF-,9.4 x 9.4 x 11.7 nm,CDC for Cytokine*
26、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,27,5755,2006,CDC for
27、Cytokine Adsorption,Adsorption depends on the SSA of adsorbents accessible by cytokines,G.Yushin,et al.Biomaterials,27,5755,2006,Further reading:G.Yushin,Y.Gogotsi,and A.Nikitin,Carbide Derived Carbon,in Nanomaterials Handbook,Y.Gogotsi,Editor.2006,CRC Press.p.237-280.,Conclusions,CDC process enable
28、s 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 app
29、lications,Acknowledgements,Students 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,
