1、石墨相氮化碳(g-C3N4)HFJ材料簡介UniYcrsilyorScienceandTGC-hnolcgyofChina>引言> g-C3N4的合成制備> g-C3N4的材料改性> g-C3N4的應用領域>展望UniYcrshy©rScicntcandTGC-hnologyofChina1. 引言1967TiO2光解水示意圖¥FujishimaVacuumOrE(NHE)"1申10得謬我朮大孝UniversityofScienceandTc(;hiiologyofChina常見半導體在pH=O時的禁帶寬度以及與標準氫電極電位、真空能

2、級的相對位置帶隙較寬一一對可見光響應弱或無響應（如TiO2.ZnO）帶隙較窄一一部分光腐蝕現象嚴重（如CdS）均含有過渡金屬元素UniYcrshy©rScicntcandTGC-hnologyofChina1-引言2008年ARTICLESPUBLISHEDONLINE：9NOVEMBCR2006(DOtiai038/NMAT23nnaturematerialsAmetal-freepolymericphotocatalystforhydrogenproductionfromwaterundervisiblelightXinchenWang1,2*,KazuhikoMaeda3,Ar

3、neThomas1,KazuhiroTakanabe3,GangXin3,JohanM.Carlsson4,KazunariDomen3*andMarkusAntonietti1王心晨Theproductionofhydrogenfromwaterusingacatalystandsolarenergyisanidealfutureenergysource,independentoffossilreserves.Foraneconomicaluseofwaterandsolarenergy,catalyststhataresufficientlyefficient,stable,inexpen

4、siveandcapableofharvestinglightarerequiredHere,weshowthatanabundantmaterial,polymerkcarbonnitride,canproducehydrogenfromwaterundervisiblelightirradiationinthepresenceofasacrificialdonor.Contrarytootherconductingpolymersemiconductors,carbonnrtndoischemicallyandthermallystableanddo«snotrolyoncomp

5、licateddevicemanufacturing.Theresultsrepresentanimportantfirststeptowardsphotosynthesisingeneralwhereartificialconjugatedpolymersemiconductorscanbeusedasenergytransducers.1.引言UniYcrshy©rScicntcandTGC-hnologyofChina優點：非金屬半導體、原料豐富價格低、帶隙合適、化學穩定且無毒缺點：比表面積比較低、有限的可見光吸收、光生載流子易復合UniYcrshy©rScicntc

6、andTGC-hnologyofChina2g-C3N4W合成制備ChemSocRev主流方法：熱聚合一一簡單、快捷、大批量其他方法：CVD、溶劑熱一一復雜、耗時、產量低UniYentityofScicneeandTcchnolcgyofChina2. g-C3N4的合成制備1.nnh22NNh2nnh2CyanamideDicyanamideCyanamideDicyanamideMelamineHnAnn人人Tri-s-triazine,r人人人人人人”N人丄1NNNMelem十NXNH2Polymericg-C3N4UniYcrsity©rScienceandTGG.hnolv

7、gyofChina2. 0£叫的合成制備4.0iih2n*c'nh2Urea5.sAh2nnh2Thioureaiiiiii000.20.40.60.81.0P/P°UniYcrshy©rScicntcandTGC-hnologyofChinaNH】o/nhvsh：oHOCNnh2N入N迪Ji1H2NNNH2異原子/NNN人N入N"NNN入NN次N人NN上N人kNNNNNNHa"S=C=NHIIHS-C=Nnh2N入N型mNNN*N入N（、nFnW»NNN入NN次N入NN戈N入N上診rAUrea:58m2/gThiourea:

8、18m2/gDicyanamide:10m2/ghollownanospheresnanorod2. g-C3N4M合成制備Templates:SiO2AAOCaCO3ionicliquidssurfactantsmesoporousnanoflowerUniYcrsityorScienceandTGC-hnologyofChina3. g-C3N4料改性目的：增加比表面積增加可見光吸收范圍抑制光生電子-空穴的簡單復合UniYcrshy©rScicntcandTGC-hnologyofChina3. g-C3N4*t料改性g-Cg叫的剝離0.335nm石墨石墨烯0.326nmBulk

9、g-C3N4.OHh3ccarbonnitrogenU-butancdiolExfoliationaAS120.Ad»orp<io«ADcsorptQfiQraph®r»a4.k«C3N4BET-32.54m%0.40.6RototlvoProssuro(P/Po|pmd/uniEC一ssauzo-ln0.9-2.1nm3-6layersII.元素摻雜UniYcrsityorScienceandTechnologyofChina3. g-C3N4*t料改性金屬元素：Fe、Cu、Zn、Ni等非金屬元素：0、P、S、B、I、F等P-NP2po

10、fPCN-Sme)Mlsualu-133.1eV130131132133134135136Bindingenergy(eV)300400500600700800Wavelength(nm)921(ne)aoueqosq<0.0CBMidgapstates2.68eV2.2eVVB申®糾琢我水'大孝UniYcrsityorScienceandTechnologyofChina3.g-C3N4*t料改性in.有機分子共聚NNNNHjN人N尹沽N人節N.土兒人m人人人入：入NNNNNnN*""*Nnh/n人人丄00吧CN,network»、XNn

11、h22入N/n入NElNH3heatnh2AN人NAANNNH2NH?1NNjlTNNNAAAh2nannnh2s11吩400500600700800A/nmUniYcrshy©rScicntcandTGC-hnologyofChina3.g-C3N4材料改性IV.構建異質結與其他半導體InterfaceInterfaceInterfaceConductor與金屬phenolproductSchottkyJunctionCuTCPPg-C3N4UniYcrshy©rScicntcandTGC-hnologyofChina4. g-C3N4的應用領域I.光解水200&

12、100|imol/h/g2019:>10mmol/h/g水相中NO、N02»no3-Cr(VI)Cr(lll)BacterialDisinfection申®樹謬我水'大孝UniYcrsilyorScicnccandTGGhnolcgyofChina4. gCs叫的應用領域II. 光降解污染物/殺菌CO2+2H+2eTHCOOH(E角ox=0.61VvsNHEatpH7)UniYcrshy©rScicntcandTGC-hnologyofChina4. g-C3N4的應用領域III. CO2還原MultielectronreductionCBEfSolarfuels(CH4,CO,CH3OH,etc.)CO2+4H+4eHCHO+H2O(E爲ox=一048VvsNHEatpH7)CO2+2H+2e"TCO+H2O(E：應=-0.53VvsNHEatpH7)VBCO2十6H+十6e"-CH3OH十H2O=-0.38VvsNHEatpH力h+g-C3N4CO2+8H+8e"TCH4+2H2O(Eredox=-0.24VvsNHEatpH