本文關(guān)鍵詞： ZIF-67模板 鈷基氧化物 核殼結(jié)構(gòu) 葡萄糖檢測 電催化析氧 超級電容器　出處：《哈爾濱工業(yè)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：金屬有機(jī)骨架材料(MOFs)具有較大的比表面積、高孔隙率、可調(diào)諧的孔徑和功能等特性,成為多孔材料中具有代表性的材料。以MOFs為模板制備的多孔半導(dǎo)體金屬氧化物由于其在結(jié)構(gòu)上繼承了MOFs的特點(diǎn),具有獨(dú)特的機(jī)械性能、光學(xué)性能以及優(yōu)異電化學(xué)性能,一直被大量研究,并被廣泛應(yīng)用在催化、能量存儲、藥物釋放、生物傳感器等方面。因此,本論文以ZIF-67為前驅(qū)體,通過共沉淀法及相應(yīng)熱處理成功引入鋅和碳元素合成了雙金屬氧化物Zn0.35Co2.65O4及具有核殼結(jié)構(gòu)的CoO@Co3O4/C復(fù)合物,用于電化學(xué)葡萄糖傳感器、電催化產(chǎn)氧及超級電容器電極材料。研究內(nèi)容如下:(1)以ZIF-67為模板,通過共沉淀法合成雙金屬氧化物Zn0.35Co2.65O4,利用掃描電子顯微鏡(Scanning Electron Microscope,SEM)及透射電子顯微鏡(Transmission Electron Microscope,TEM)、X射線衍射(X-Ray Diffraction,XRD)、X射線光電子能譜(X-Ray Photoelectron Spectroscopy,XPS)和Mapping等測試手段對雙金屬氧化物的形貌、晶型、化學(xué)組成進(jìn)行表征,結(jié)合時(shí)間電流曲線測試考查雙金屬氧化物在pH為7.4緩沖溶液及堿性環(huán)境中無酶葡萄糖檢測方面的性能。當(dāng)電解液為pH=7.4的PBS溶液時(shí),電極檢測窗口為13.28μM-13 mM,檢測限為1.3μM(S/N=3),靈敏度為47.71μA m M-1 cm-2,響應(yīng)時(shí)間少于3 s,當(dāng)電解液為0.1M的NaOH溶液時(shí),電極檢測窗口為5μM-13 mM,檢測限為1.41μM(S/N=3),靈敏度為41.8μA mM-1 cm-2,響應(yīng)時(shí)間少于2 s。與Co3O4進(jìn)行對比,Zn離子的引入使得樣品在檢測葡萄糖時(shí),具有更好的檢測限及擬合效果,響應(yīng)時(shí)間更短,但是靈敏度有所下降。(2)以ZIF-67為前驅(qū)體,通過浸泡葡萄糖溶液進(jìn)行表面修飾及退火處理,得到具有核殼結(jié)構(gòu)的CoO@Co3O4/C復(fù)合材料。利用SEM、高倍透射電子顯微鏡(High Transmission Electron Microscope,HTEM)、XRD和XPS等測試手段對復(fù)合材料的形貌、晶型及化學(xué)組成進(jìn)行表征,結(jié)合循環(huán)伏安、恒電流充放電、交流阻抗譜、線性伏安掃描等測量方法考查復(fù)合材料在電容和電催化析氧等方面的性能。通過對比復(fù)合材料與Co3O4的比電容和過電位,分析樣品表面碳元素的存在及核殼結(jié)構(gòu)對樣品在電化學(xué)方面的影響。測試結(jié)果顯示,在電流密度為1 mA cm-1,樣品比電容能達(dá)到184 F g-1,在電流密度為10 mA cm-1下,CoO@Co3O4/C的過電位值為386 m V,經(jīng)過6 h的穩(wěn)定性測試,催化劑仍保持原有電流密度的83.1%。證明CoO@Co3O4/C無論是在電容還是電催化析氧方面性能都得到了明顯增強(qiáng)。同時(shí)結(jié)合表面光伏和瞬態(tài)光伏技術(shù),研究核殼結(jié)構(gòu)復(fù)合材料的光生電荷遷移行為,結(jié)果表明樣品中的碳具有良好的電子輸運(yùn)及接受能力,鈷基氧化物與碳的協(xié)同二元結(jié)構(gòu),加快光生載流子的有效傳輸和分離,核殼結(jié)構(gòu)復(fù)合材料具有更長的光生壽命用于參與光電反應(yīng),具有較好光電性能。
[Abstract]:The metal-organic framework material (MOFs) has large specific surface area, high porosity, tunable pore size and function, etc. Porous semiconductor metal oxides prepared by using MOFs as template have unique mechanical properties, optical properties and excellent electrochemical properties due to their structural inheritance of MOFs. It has been widely studied and widely used in catalysis, energy storage, drug release, biosensor and so on. Bimetallic oxide Zn0.35Co2.65O4 and CoO@Co3O4/C complex with core-shell structure were successfully synthesized by introducing zinc and carbon elements through coprecipitation and heat treatment. Electrode materials for electrocatalytic oxygen generation and supercapacitors. The research contents are as follows: ZIF-67 as a template. Bimetallic oxide Zn0.35Co2.65O4 was synthesized by coprecipitation method. The morphology, crystal type and morphology of bimetallic oxides were measured by scanning electron microscopy (SEM) and transmission electron microscope (TEM), transmission Electron microscopesimetry (TEM) and X-ray diffraction (X-Ray DiffractionXRDX) X-ray photoelectron spectroscopy (X-Ray Photoelectron spectroscopyXPS4) and Mapping. The chemical composition was characterized, and the performance of bimetallic oxide in detecting enzyme free glucose in pH 7.4 buffer solution and alkaline environment was examined by time-current curve test. When the electrolyte was PBS solution with pH=7.4, The detection window of electrode is 13.28 渭 M-13 mm, the detection limit is 1.3 渭 M / s, the sensitivity is 47.71 渭 A m M -1 cm -2, the response time is less than 3 s, when the electrolyte is 0.1 M NaOH solution, The detection window of electrode is 5 渭 M-13 mm, the detection limit is 1.41 渭 M ~ (-1) S / N ~ (-1), the sensitivity is 41.8 渭 A mM-1 / cm ~ (-2), the response time is less than 2 s. Compared with Co3O4, the introduction of Zn ion makes the sample have better detection limit and fitting effect, and the response time is shorter. However, the sensitivity has decreased. 2) with ZIF-67 as the precursor, the surface was modified and annealed by soaking glucose solution. CoO@Co3O4/C composites with core-shell structure were obtained. The morphology, crystal form and chemical composition of the composites were characterized by means of SEM, high power transmission electron microscopy (HTEM), high power transmission electron microscopy (HTEM), high power transmission electron microscopy (HTEM), high power transmission electron microscopy (HTEM), high power transmission electron microscopy (HTEM), high power transmission electron microscopy (HTEM) and high power transmission electron microscopy (TEM). Ac impedance spectroscopy and linear voltammetry were used to examine the properties of the composite in capacitance and electrocatalytic oxygen evolution. The specific capacitance and overpotential of the composite and Co3O4 were compared. The presence of carbon elements on the surface of the sample and the effect of core-shell structure on the electrochemistry of the sample were analyzed. When the current density is 1 Ma cm-1, the specific capacitance of the sample can reach 184F g-1, and the overpotential value of CoOr Co3O4 / C is 386mV at the current density of 10mA cm-1. The stability of the sample has been tested after 6 hours. The catalyst still maintains the current density of 83.1. It is proved that the performance of CoO@Co3O4/C in both capacitance and electrocatalytic oxygen evolution has been significantly enhanced, and combined with surface photovoltaic and transient photovoltaic technology, The photoinduced charge transfer behavior of core-shell structure composites is studied. The results show that the carbon in the samples has good electron transport and receptivity, and the Co-base oxides and carbon have a synergistic binary structure, which speeds up the effective transport and separation of photogenerated carriers. The core-shell composite has longer photoinduced life to participate in photoelectric reaction and has better photoelectric properties.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB383.4;O646
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本文編號：1542038