EarlyDevelopmentsChemical modification of atitanium (rv) oxideelectrode to give stable dyesensitisation withouta supersensitiserofroeofonHOFig, 2Pbotocurrent-time characteristics for a derivatised TiOelectrode held at 1.2 V (versus SSE) and illuminated with lightfrom a 150-w Xe lamp passing through a 450-nm interferencefilter.Arrowsrepresent time of light switching gon and off.Steady-CO2Hstatecurrentwas70nAcmPhotocurrentsDyechemicallybindsto TiO,crystalSystemaimedatwateroxidationSurprisingly low Φini = 0.25%Goodenough,butnotgood enough(boomboom)J.B.Goodenough et alNature,1979.280.571
Early Developments J. B. Goodenough et al Nature, 1979, 280, 571 • Dye chemically binds to TiO2 crystal • System aimed at water oxidation • Surprisingly low Φinj = 0.25% • Goodenough, but not good enough (boom boom) Photocurrents 50
GratzelSmall changes can get big improvements!M.Gratzeletal,J.Am.Chem.Soc.1985,107,2988e3CO.HOHCO2HTiO2OHCO2HO0CO2H450500550400600[Ru(dcbpy)3]2+onTiO2colloids/nmPhotocurrentactionspectra中ini=60%(oxidationofaqueoushydroquinone)IPCEat460nm=44%(A) = [Ru(dcbpy)3J2+Compared to [Ru(bpy),]2+ IPCE =2.5%(B) = [Ru(bpy)3J2+IPCE=incidentphotontocurrentefficiency(C) = no sensitizer对苯二酚，Hydroquinone
Grätzel Small changes can get big improvements! M. Grätzel et al, J. Am. Chem. Soc.,1985, 107, 2988 Φinj = 60% IPCE at 460 nm = 44% Compared to [Ru(bpy)3] 2+ IPCE = 2.5% [Ru(dcbpy)3] 2+ on TiO2 colloids Photocurrent action spectra (oxidation of aqueous hydroquinone) (A) = [Ru(dcbpy)3] 2+ (B) = [Ru(bpy)3] 2+ (C) = no sensitizer IPCE = incident photon to current efficiency TTiO2 e- e- 对苯二酚 51 , Hydroquinone
GratzelPartllB.O'ReganandMichaelGratzelNature1991,353,737HO.0HO.CTiO,nanoparticles sinteredat450ConconductingglassDvewithbroadabsorptionprofile+ExRedoxelectrolyte(l-/l)inorganicsolvent (iodine)+Pt cathode4005006007008OCA-nn
Grätzel Part II B. O’Regan and Michael Grätzel Nature 1991, 353, 737 Dye with broad absorption profile TiO2 nanoparticles sintered at 450 °C on conducting glass + + Redox electrolyte (I- /I3 - ) in organic solvent (iodine) + Pt cathode 52
TheFirst DSSCDye-Sensitized SolarCell (DSSC)LUMOhCB3/ 15RedoxpotentialHOMOelectrolyteTiO2FTOPtDyeTiO2DyeOInGratzel'sfirstexample:IPCE(520nm)80to97%Overallefficiency-7.1to7.9%(simulated solarspectrum)12%indiffusedaylightDyeshighlystableundertheconditions
The First DSSC In Grätzel’s first example: IPCE (520 nm) 80 to 97% Overall efficiency – 7.1 to 7.9% (simulated solar spectrum) 12% in diffuse daylight Dyes highly stable under the conditions 53
OfficialRecord-2006to2012CO2HL.Y.Hanetal11.1%(simulatedsolarspectrum)HO2CN-C-SN749-theblackdyeOnTiO2,1-/l3redoxelectrolyteLightscatteringof TiO,electrodeoptimizedCNDeoxycholicacidcoabsorbentusedHO,CCOH=SHO"OHCO2HHO20CSimilarresultsobtainedwithN3/N719andarangeofotherdyesHOCO2H
Official Record – 2006 to 2012 11.1% (simulated solar spectrum) N749 – the black dye On TiO2, I- /I3 - redox electrolyte Light scattering of TiO2 electrode optimized Deoxycholic acid coabsorbent used Similar results obtained with N3/N719 and a range of other dyes L. Y. Han et al 54