1、十四 拉曼光譜的主要應(yīng)用,從拉曼光譜獲取的信息,不同的物質(zhì)，其拉曼譜是不同的，就象人的指紋一樣，因此拉曼光譜可用于物相的分析與表征。,Fig.1 The picture of the Ming Yongle Blue and White porcelain.,永樂(lè)青花瓷,唐壽州窯黃釉瓷,Fig.2 The Raman Spectrum of glaze,SiO4四面體的 Si-O彎曲振動(dòng),SiO4四面體的 Si-O拉伸振動(dòng),這兩個(gè)峰的面積比（Ip=A500/A1000）與陶瓷的燒成溫度相關(guān)聯(lián) Ip越大，燒成溫度越高,Ip0.9,Ip=0.8,Fig.3 The Raman spectrum o

2、f black reticulation spot on the blue colour of Blue and white porcelain.,662,302 Fe3O4,Fig.4 The Raman spectrum of yellow spot on the blue colour of Blue and White porcelain.,224,291,407 Fe2O3 662, Fe3O4,Fig.5 The Raman spectrum of black spot on the blue colour of Blue and white porcelain.,584,628

3、Mn2O3 547 MnO,在還原氣氛下，青花料中的錳應(yīng)趨向于形成Mn3O4,Fig.6 The Raman spectrum of wirelike black spot on the blue colour of Blue and White porcelain.,692，522，488 Co3O4,鈷是青花料的主要顯色元素，但在青花彩中發(fā)現(xiàn)氧化鈷的結(jié)晶尚屬首次,Fig.7 The Raman spectrum of white crystal grain in the glaze,位于970 和953 cm-1的峰分別屬于磷酸鈣和硅酸鈣，說(shuō)明該釉是以CaO為主要助熔劑，屬于石灰釉類(lèi),而磷

4、酸鈣的形成則可能是在釉料中加有草木灰之類(lèi)的植物灰料,拉曼光譜在催化中的應(yīng)用, 拉曼光譜能提供催化劑本身以及表面上物種的結(jié)構(gòu)信息，這是認(rèn)識(shí)催化劑和催化反應(yīng)最為重要的信息。, 拉曼光譜較容易實(shí)現(xiàn)原位條件下 (高溫、高壓，復(fù)雜體系) 的催化研究。, 拉曼光譜可以用于催化劑制備的研究，特別是可以對(duì)催化劑制備過(guò)程從水相到固相的實(shí)時(shí)研究。, 拉曼光譜可以實(shí)現(xiàn)時(shí)間分辨動(dòng)力學(xué)和動(dòng)態(tài)學(xué)的研究。, No active sites; less shape selectivity Possible effect in regioselectivity and enantioselectivity,介孔材料是目前材料領(lǐng)

5、域發(fā)展極為迅速的一個(gè)方向，但介孔材料很少應(yīng)用于催化，因?yàn)槿狈Υ呋钚灾行?在介孔材料中引入活性中心和表征活性中心是目前催化領(lǐng)域的前沿研究方向,Micropore, 20 ,Mesopore, 20150 , Acidic sites; shape selectivity Less active sites for oxidation and hydrogenation,催化劑中過(guò)渡金屬中心的電荷轉(zhuǎn)移躍遷吸收,/nm,200,300,400,500,(MOx)n,Bulk oxide,Absorbance,Reference: MoxOyn-,TS-1 催化劑和選擇氧化,SiO2,Ti,TS-1

6、 H2O2,+,+,NH3,+,Framework Ti 2%,TiO2,TS-1 的紫外共振拉曼光譜,ex=244 nm,TS-1 的紫外共振拉曼光譜,紫外拉曼譜峰的歸屬,Ti-SBA-15的紫外共振拉曼光譜,Si/Ti=400,Si/Ti=50,Si/Ti=200,Si/Ti=100,Si/Ti=20,SBA-15,ex=244 nm,Framework site in TS-1 1125 cm-1,Isolated site in mesoporous materials 1100-1110 cm-1,Isolated site on SiO2 1085 cm-1,SiO2,1125 c

7、m-1 譜峰的位置對(duì)Ti的配位環(huán)境非常敏感,Fe/ZSM-5 催化劑中的多種活性物種,Fe Species: 1) Framework Fe, 2) Extraframework Fe a) Isolated Fe b) Oligomer Fe 3) Nanoparticle FeOx,物種極其復(fù)雜結(jié)構(gòu)鑒定困難,ex= 244 nm,ex= 325 nm,UV Raman spectre of Fe-silicalite (Si/Fe=100) with different excitation lines,利用拉曼共振效應(yīng)檢測(cè)Fe-ZSM-5中的骨架鐵物種,From 1110 cm-1 ba

8、nd,From 516 cm-1 band,0.006(Fe/Si),0.02,0.01,0.05,0.025,Fe/Si molar ratio,分子篩中骨架位鐵物種的最大含量為0.010(鐵硅摩爾比),紫外拉曼光譜對(duì)Fe-silicalite骨架鐵物種的半定量分析,Framework species are formed first, then the extraframework species appear.,Fe/Si=0.025,ex=325 nm,Fe/Si=0.02,Fe/Si=0.01,Fe/Si=0.005,Fe/Si=0.0025,利用拉曼共振效應(yīng)檢測(cè)Fe-ZSM-5中骨

9、架外鐵物種,400,600,800,1000,1200,1400,1115,1010,510,516,1065,1155,1067,975,1100,511,380,290,1008,800,1065,Raman Shift /cm-1,18O2 同位素交換,16O2 treated at 550 oC,H2 treated at 550 oC,16O2 treated again at 550 oC,1165 cm-1 1155 cm-1, =10 cm-1 1115 cm-1 1067 cm-1 , =48 cm-1 1010 cm-1 975 cm-1 , =35 cm-1 516 cm

10、-1 510 cm-1 , =6 cm-1,lex=325 nm,18O2 exchanged at 550 oC,Fe-silicalite 紫外拉曼譜峰的歸屬,ex = 244 nm 516, 1110 cm-1,ex = 325 nm 520, 1005, 1115, 1165 cm-1,Framework,Extraframework,1110 cm-1 Framework iron in Fe-ZSM-5,1080-1100 cm-1 Framework iron in Fe-SBA-15,紫外拉曼譜峰的歸屬,Assignment of UV Raman bands for extr

11、aframework iron species formed at low iron concentration,Fe-silicalite: 520, 1005, 1165 cm-1,Fe-Al-SBA-15: 510, 1140 cm-1,Raman band around 1140 cm-1 exited by 325 nm laser is attributed to the extraframework iron species associated with framework Al, Ga or Fe atoms,Fe-SBA-15 Fe-AlSBA-15 Fe-GaSBA-15,ZrO2 的晶相結(jié)構(gòu),m-ZrO2 and t-ZrO2 的特征拉曼光譜,monoclinic,tetragonal, 對(duì)于單斜相 (m)，譜峰474 cm-1強(qiáng)于634 cm 1，而四方相(t) 恰好相反。 單斜相的拉曼譜圖中，在472 和 6