本文選題：海水提鈾 + 功能膜電極�。� 參考：《青島科技大學(xué)》2017年碩士論文

【摘要】：本實(shí)驗(yàn)采用鎳片作為基體材料,在鎳片表面進(jìn)行修飾改性并組裝功能高分子復(fù)合膜,制備出功能高分子膜電極。首先合成出丙烯腈-乙酸乙烯酯共聚物(P(AN-VAc)),并對(duì)其使用醇的堿性溶液進(jìn)行酯交換反應(yīng)及羧基化反應(yīng)制備出帶有羥基、羧基的改性共聚物P(AN-VAc-VA-AA)。然后合成出具有一定導(dǎo)電性與強(qiáng)制還原性能的二茂鐵基團(tuán)改性聚氨酯預(yù)聚體,通過(guò)傅里葉變換紅外光譜測(cè)試(FT-IR)、核磁共振氫譜測(cè)試(1H-NMR)、熱重分析測(cè)試(TGA)、差示掃描量熱法(DSC)對(duì)各步驟產(chǎn)物進(jìn)行分析表征。依次將KH-550、改性聚氨酯預(yù)聚體及P(AN-VAc-VA-AA)組裝至經(jīng)預(yù)處理的鎳片上,然后進(jìn)行偕胺肟化獲得表面帶有羧基及偕胺肟基的功能膜電極。使用掃描電子顯微鏡(SEM)觀察膜電極組裝過(guò)程中各步的表面形貌;使用熒光分光光度法測(cè)定了功能膜電極對(duì)鈾離子的吸附量,并探究了時(shí)間、pH條件、吸附溫度等條件對(duì)功能膜電極吸附性能的影響;使用循環(huán)伏安法探究了功能膜電極的電化學(xué)行為。(1)合成制備帶有羧基的功能高分子,與二茂鐵基團(tuán)改性聚氨酯預(yù)聚物同溶于二甲基亞砜(DMSO)中進(jìn)行組裝,最佳組裝時(shí)間為10 min,在0.01 mol L-1的鹽酸羥胺中性溶液中偕胺肟化,最佳反應(yīng)時(shí)間為50 min,可制得功能高分子膜電極。(2)合成具有二茂鐵功能基的PU預(yù)聚體。二茂鐵基團(tuán)通過(guò)α-羥乙基二茂鐵(Fc-CHOHCH3)的形式向異氰酸酯中引入:用料量為Fc-CHOHCH3:六亞甲基二異氰酸酯(HDI):三羥甲基丙烷(TMP)=1:3:1(摩爾比),其中α-羥乙基二茂鐵由乙酰基二茂鐵還原制備最佳條件是0℃下,以FcCOCH3:CuSO4:NaBH4=1:3:3(摩爾比)反應(yīng)1.6 h;PU預(yù)聚體以DMSO做溶劑。(3)使用熒光分光光度法檢測(cè)吸脫附溶液中鈾酰濃度,熒光增強(qiáng)劑用量為2.4%、pH=7時(shí)是最佳檢測(cè)條件。(4)功能電極在常溫的中性1μg mL-1的硝酸鈾酰標(biāo)準(zhǔn)液中,在8 h左右可以達(dá)到平衡吸附量為1.67 mgU g-1的吸附平衡狀態(tài),且在室溫至35℃區(qū)間,隨溫度升高,吸附達(dá)到平衡的速度越快。(5)使用循環(huán)伏安法對(duì)功能電極進(jìn)行電化學(xué)表征,該功能電極在pH=6.8的磷酸鹽緩沖電解質(zhì)溶液中電化學(xué)脫附電壓為-1.13 V。(6)功能膜電極在天然海水中進(jìn)行吸附測(cè)試,室溫狀態(tài)下,吸附時(shí)間為8h時(shí),吸附容量為1.1 mgU g-1。
[Abstract]:In this experiment, the functional polymer film electrode was prepared by modifying and assembling the functional polymer composite film on the nickel surface. Firstly, acrylonitrile-vinyl acetate copolymers were synthesized, and the modified copolymers with hydroxyl and carboxyl groups were prepared by transesterification and carboxylation of the basic solution of alcohols to prepare the modified copolymers with hydroxyl and carboxyl groups. Then a ferrocene group modified polyurethane prepolymer with certain electrical conductivity and reducibility was synthesized. The products were characterized by Fourier transform infrared spectroscopy (FTIR), 1H-NMR-1H-NMR, TGA and DSC-DSC. KH-550, modified polyurethane prepolymer and P AN-VAc-VA-AA were assembled on the pretreated nickel wafer, and then the functional membrane electrode with carboxyl group and amidoxime group on the surface was obtained by amidoximation. Scanning electron microscopy (SEM) was used to observe the surface morphology of each step in the process of assembling the membrane electrode, and the adsorption amount of uranium ion on the functional membrane electrode was determined by fluorescence spectrophotometry, and the time and pH conditions were investigated. The effect of adsorption temperature on the adsorption performance of functional membrane electrode was studied by cyclic voltammetry. The electrochemical behavior of functional membrane electrode was investigated by using cyclic voltammetry to synthesize functional polymer with carboxyl group. The modified polyurethane prepolymer with ferrocene group was assembled in DMSO (dimethyl sulfoxide). The best assembly time was 10 minutes, and the amidoxime was formed in 0.01 mol L-1 hydroxylamine hydrochloride neutral solution. The pu prepolymer with ferrocene functional group can be synthesized by the best reaction time of 50 min. The ferrocene group is introduced into the isocyanate in the form of 偽 -hydroxyethyl ferrocene (Fc-CHOHCH3): Fc-CHOHCH3: Hexamethyldiisocyanate (HDI): trimethylol propane (TMPP) 1: 3: 1 (mole ratio, where 偽 -hydroxyethyl ferrocene is added by acetyl ferrocene) The optimum preparation condition is 0 鈩，

本文編號(hào)：1974679