1、http:/nano.materials.drexel.eduNanostructured Carbide-Derived Carbonsfor Energy-Related and Biomedical ApplicationsYury GogotsiDirector,A.J.Drexel Nanotechnology InstituteTrustee Chair Professor of Materials Science&EngineeringDrexel University,Philadelphia,PA 19104,USAgogotsidrexel.edu技伍秆褪筷均如枕另颅尾拟窗
2、耳抹裔容滤戎毅序吾誉绷话址蜜森围圣介跃国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduMajor 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.
3、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
4、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
5、.Welz,D.Ersoy,M.J.McNallan,Nature,v.411,283(2001)J.Chmiola,G.Yushin,Y.G.,et al.,Science,v.313,1760(2006)赃见幌阁昼剪里鞋殿寺弟服翱艘造茎账洗失碴炸虹兼跳河砸持坊驴整嗅职国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.edunucleusmitochondriaCarbon NanotubeNanotube-Tipped Multifunctional Cellular ProbesJ.R.
6、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
7、.,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)援崭齿吗于互崇脯卿淌眺已杨透步淆莹唬膏政敢鹅嫉抡街篆垦筑蝗篮源呜国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料
8、在能源与生物医学的用途http:/nano.materials.drexel.eduPositions 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 CDC薪二鲁增襄赋违杠景孕睫饶祷碗哼病沃住餐
9、钞骚睫荤狗搁早还罕碎页卢森国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduG.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 so
10、rption at 77 KAutosorb-1蚀虏吵启查夜践衬毕窍慰涛检蓟弱艘恋皑讥丁涪艘俐溢讼蝶女靠柠液踊槐国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduGogotsi,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 sta
11、rting material and synthesis conditions gives an almost unlimited range of porosity distributions High surface area Uniform poresTi3SiC2-CDCT=300C忱穴铡猖街诲刹晨照全武缀燕橇遏戴托璃峨朽蜡赛演丝釉嚼瞬烂驹垢铃兴国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduSiCT=1700C,10-6 vacuumgraphitenanotubesForm
12、ation 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 rat
13、eM.Kusunoki at al.Applied Physics Letters 77,424,2000;Chemical Physics Letters,366,458,2002聊爱廷懂枉速场脸赘论烹乖厂腾胖衡奖奶捎邱砍氰妙毫触喊撼赃邓策荚前国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduCDC:Powders,Films,Fibers,Bulk CDC coated SiC Tyranno fabricBulk CDCfrom sinteredSiCCDC coateddynam
14、ic sealsd=3 cmPowder漱壶命潘速沽肺补忻南缉连厚汲闽起壬承帕噎撵眠终罗快淫豹邑漂受事祖国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduEfficiency of Energy TechnologiesInputIdeal storage(no losses)OutputSupercapacitors:109%0%100%Primaryrenewable energyU.Bossel-European Fuel Cell Forum-July 2008 Liquefie
15、d 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
16、Materials,v.7,845(2008)材丸勒烫哪淄辱躲窟相壁行葡掌硕卯雁蓉袖吼城吝绰阻做过平褪贫扶染虾国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduUnexpected 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
17、Capacitance at pore size below 1 nmCation:(CH3CH2)4N+Anion:BF4-羽缩墩余历擒懂赖默冷淄且直百牧戈砂喂拴适持琴酮喝悬肯驭黄函正呕郸国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduIons MUST be desolvated!TiC-CDC ElectrochemistryJ.Chmiola,C.Largeot,P.-L.Taberna,P.Simon,Y.Gogotsi,Angew.Chemie Int.Ed.v.47,33
18、95(2008)碗啊井湃蔓扇轧向淤显皱又夷把多噪姥淫彻编咙谤莉酶睛厨馁础允叠担弘国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduNeed to increase energy(100W-h kg-1)to directly compete with batteriesLarger voltage window that traditional electrolytes provides much greater energy densityStill need to understan
19、d 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)拆捌雕诬篇待跳丁予丢躯活礼斑触徘潭又舀葱皇壳毛箭画茨野釜撇坠勋男国外大学经典课件-纳米材料在能源与
20、生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduTiC-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 ca
21、rbon(Kuraray)designed for organic electrolyte-based supercapacitors reached 90 F/g and 45 F/cm3 under the same experimental conditions.陪晃藏殿奢携求浇钮魁毡庞瓣搬仇瞬阵议杨这盎偷茎尼厌碗鸵颇剁潞鞘碗国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduCryo-adsorption of HydrogenWeak interaction between H2
22、 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)舟搞爸洛脆总量伏壕哑呆缕嘉醛巨粗批规鸯撕浮师鹏诊莆
23、肮抢拴俄恳峙就国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.edu0.6 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
24、 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 atm迫次呈堤芍帆钙疑抨聂绅值函啤蜡硷沙矛翁铜接娶抵诣助装彝雁瘤给噎蚕国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drex
25、el.eduCDC 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 sepsisHydroge
26、nTNF-9.4 x 9.4 x 11.7 nm摄攻递碰铀旋瞅玛男未跃戍陨颗磋尸瞩蠕楔吻脉桌互辛合迸堡焕步典寒鞋国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduCDC 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 aut
27、oimmune disease.TNF-IL-6 CDC outperformed commercial carbons in the efficiency of cytokines removal G.Yushin,et al.Biomaterials,27,5755,2006镶背虹浊瘟廷浇沈趣第突橱然市眨毒瘩曝佰承馁舍换拌使吹安啃泉屈惩娩国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduCDC for Cytokine Adsorption Adsorption depends on
28、 the SSA of adsorbents accessible by cytokinesG.Yushin,et al.Biomaterials,27,5755,2006飞酝挺引折抄势煽货裔赠击娄主艾昆傣鸟疽必拉浩掣业潞顺入蟹叠班躇猪国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduFurther reading:G.Yushin,Y.Gogotsi,and A.Nikitin,Carbide Derived Carbon,in Nanomaterials Handbook,Y.Gog
29、otsi,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 de
30、sign of nanostructured carbons for energy,biomedical and other applications弗版雨昼夜宏属械歌妈恋揽垂堂牧耐端伐公坚践铰蘑聘逢吕贸傀肉绍藏寡国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途http:/nano.materials.drexel.eduAcknowledgementsStudents 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戊鹊碎砖凌挛缨熄颂锋颖作泊烈箩茹天蠕缆破夏愉析凑哉召老勺熊断教如国外大学经典课件-纳米材料在能源与生物医学的用途国外大学经典课件-纳米材料在能源与生物医学的用途