本文選題：PtNPs + 導(dǎo)電水凝膠　； 參考：《北京科技大學(xué)》2017年博士論文

【摘要】：隨著低功耗微機(jī)電植入器件的發(fā)展,為植入微功耗器件提供長(zhǎng)期穩(wěn)定電能供應(yīng)又成了研究熱點(diǎn)。研究結(jié)構(gòu)簡(jiǎn)單、性能長(zhǎng)期穩(wěn)定、生物安全性高的非生物催化植入葡萄糖燃料電池是解決體內(nèi)供電問題的可行途徑。植入體表層葡萄糖燃料電池是非生物催化葡萄糖燃料電池中極具發(fā)展前途的一類電池,其主要的優(yōu)勢(shì)為:利用植入器件的表面作為電池電極,不需要再植入額外的電池殼體。然而這種燃料電池目前還存在電活性面積低、制備工藝復(fù)雜、植入免疫排斥以及燃料共混造成的電化學(xué)短路等問題,上述問題只有通過改造植入體表層葡萄糖燃料電池的電極膜材料設(shè)計(jì),才有可能會(huì)得到改善。有些多孔導(dǎo)電水凝膠除了具有離子導(dǎo)電和電子導(dǎo)電的雙重特性外,還擁有良好的生物相容性,設(shè)計(jì)制備具有選擇性催化功能的多孔導(dǎo)電水凝膠作為植入體表層葡萄糖燃料電池的電極膜極具探索價(jià)值。本文針對(duì)植入體表層葡萄糖燃料電池存在的問題,根據(jù)植入體表層葡萄糖燃料電池的原理和導(dǎo)電水凝膠的特性,設(shè)計(jì)制備了三種多孔導(dǎo)電水凝膠網(wǎng)絡(luò)結(jié)構(gòu)作為植入體表層葡萄糖燃料電池的電極膜,通過多種途徑對(duì)其結(jié)構(gòu)和組成進(jìn)行調(diào)整,以提升電極膜導(dǎo)電性和電化學(xué)活性,并最終實(shí)現(xiàn)其對(duì)富氧中性磷酸緩沖溶液(PBS)中的葡萄糖的選擇性催化功能,這為選擇性催化多孔導(dǎo)電水凝膠在植入體表層葡萄糖燃料電池中的應(yīng)用提供了實(shí)驗(yàn)基礎(chǔ)和理論依據(jù)。具體研究工作和結(jié)果如下:根據(jù)多壁碳納米管(MWCNTs)良好的導(dǎo)電性和電催化活性以及聚乙烯醇(PVA)的水凝膠特性,設(shè)計(jì)了 MWCNTs和PVA雙網(wǎng)絡(luò)多孔導(dǎo)電水凝膠,并通過電泳沉積(EPD)和冷凍解凍循環(huán)交聯(lián)工藝,制備了 MWCNTs/PVA導(dǎo)電水凝膠電極膜。通過對(duì)MWCNTs/PVA電極膜的電化學(xué)性能和微觀結(jié)構(gòu)的表征,表明了 MWCNTs/PVA水凝膠電極膜具有高親水性的多孔導(dǎo)電水凝膠網(wǎng)絡(luò)結(jié)構(gòu),雖然MWCNTs/PVA導(dǎo)電水凝膠電極膜對(duì)的PBS溶液中的葡萄糖沒有明顯的催化活性,但對(duì)多巴胺和pH9的堿性溶液中的葡萄糖有明顯的催化活性,該電極膜有可能用于植入在人體腸道的葡萄糖燃料電池�；诩{米鉑(PtNPs)的良好電催化活性,設(shè)計(jì)了 MWCNTs、PVA和PtNPs三元多孔導(dǎo)電水凝膠。并利用十六烷基溴化銨(CTAB)與氯鉑酸(CPA)的靜電吸附原理以及檸檬酸(VC)的溫和的化學(xué)還原性,在MWCNTs/PVA多孔導(dǎo)電水凝膠膜上實(shí)現(xiàn)了高載量的PtNPs負(fù)載。通過對(duì)PtNPs/MWCNTs/PVA電極膜的電化學(xué)性能測(cè)試以及微觀結(jié)構(gòu)的表征,PtNPs/MWCNTs/PVA導(dǎo)電水凝膠電極膜雖然不具有在富氧環(huán)境中對(duì)葡萄糖的選擇性催化能力,但該電極膜具有高電活性面積、低的表面電荷傳遞電阻以及良好的擴(kuò)散通透性等電化學(xué)特性基礎(chǔ)上,對(duì)中性的PBS溶液中葡萄糖的具有良好的電催化活性,該電極膜可用于陰極耗氧疊層植入葡萄糖燃料電池。利用細(xì)菌纖維素(BC)的天然納米網(wǎng)孔結(jié)構(gòu)、MWCNTs的良好導(dǎo)電性、PtNPs的良好電催化活性,設(shè)計(jì)了 PtNPs、MWCNTs、BC三元多孔疊層導(dǎo)電水凝膠。并利用超聲輔助的電泳沉積工藝,實(shí)現(xiàn)了 MWCNTs在BC薄膜上的滲入摻雜,從而保證了電極膜同時(shí)具有離子導(dǎo)電和電子導(dǎo)電的雙重特性;還利用BC對(duì)氯鉑酸的吸附能力和硼氫化鈉的強(qiáng)還原性,實(shí)現(xiàn)了在MWCNTs/BC多孔疊層導(dǎo)電水凝膠電極膜上的高載量PtNPs復(fù)合。通過對(duì)PtNPs/MWCNTs/BC導(dǎo)電水凝膠電極膜電化學(xué)性能的測(cè)試以及微觀結(jié)構(gòu)的表征,該電極膜不僅具有高電活性面積、低的表面電荷傳遞電阻以及良好的擴(kuò)散通透性等電化學(xué)特性,而且對(duì)PBS溶液中葡萄糖表現(xiàn)出了較高的催化活性的基礎(chǔ)上,最重要的發(fā)現(xiàn)是:該電極膜對(duì)富氧PBS溶液中的葡萄糖具有選擇催化性。PtNPs/MWCNTs/BC電極膜的多孔疊層結(jié)構(gòu)和PtNPs的高載量離散分布態(tài)是PtNPs/MWCNTs/BC導(dǎo)電水凝膠電極膜具有選擇性催化葡萄糖能力的原因,該電極膜可用于植入葡萄糖燃料表層電池。將PtNPs/MWCNTs/BC導(dǎo)電水凝膠電極膜作為陽(yáng)極膜和MWCNTs/BC導(dǎo)電水凝膠電極膜作為陰極膜構(gòu)建了植入體表層葡萄糖電池。在接近生理氧濃度和葡萄糖濃度的PBS溶液中,PtNPs/MWCNTs/BC-MWCNTs/BC葡萄糖燃料電池的最大功率密度達(dá)到了 2.75 ± 0.2 μWcm-2,該燃料電池還表現(xiàn)出了極好的溶解氧耐受度。利用浸提液細(xì)胞計(jì)數(shù)實(shí)驗(yàn)(CCK-8)和在材料表面培養(yǎng)骨髓間質(zhì)干細(xì)胞(MSC)的方法對(duì)PtNPs/MWCNTs/BC和MWCNTs/BC導(dǎo)電水凝膠電極膜的生物相容性進(jìn)行了評(píng)價(jià),該電極膜表現(xiàn)出了良好的生物相容性。上述研究表明:PtNPs/MWCNTs/BC選擇性催化導(dǎo)電水凝膠電極膜用于植入體表層葡萄糖電池的電極膜較為可行,該研究為長(zhǎng)期穩(wěn)定和生物安全性的體內(nèi)自供電器件的研究和應(yīng)用提供了新的材料體系和結(jié)構(gòu)設(shè)計(jì)。
[Abstract]:With the development of low power microelectromechanical implants, it has become a hot spot to provide long-term stable power supply for the implanted micro power devices. The study of simple structure, long-term stability and high biosafety non biocatalytic implantation of glucose fuel cell is a feasible way to solve the problem of power supply in the body. The pool is a very promising type of battery in the non biocatalytic glucose fuel cell. Its main advantage is that the surface of the implanted device is used as the battery electrode and no additional battery shell is needed. However, this fuel cell has a low electroactive area, complex preparation process, implanting immune rejection and co fuel. Only through the modification of the electrode membrane material of the glucose fuel cell on the surface of the implant, it is possible to improve it. Some porous conductive hydrogels have good biocompatibility besides the dual characteristics of ionic conduction and electronic conduction, and the design preparation has a choice. Porous conductive hydrogels with sexual catalytic function are of great value as the electrode membrane of the glucose fuel cell on the surface of the implant. In this paper, three kinds of porous conductive hydrogels are designed and prepared on the basis of the principle of the glucose fuel cell on the surface of the implant and the specificity of the conductive hydrogel. As the electrode membrane of the glucose fuel cell on the surface of the implant, the network structure adjusts its structure and composition through a variety of ways to improve the conductivity and electrochemical activity of the electrode membrane, and finally realize the selective catalytic function of the glucose in the oxygen rich neutral phosphate buffer solution (PBS). This is a selective catalysis for the porous conductive water. The gel has provided experimental basis and theoretical basis for the application of the glucose fuel cell on the surface of the implant. The specific research work and results are as follows: according to the good conductivity and electrocatalytic activity of MWCNTs and the hydrogel properties of polyvinyl alcohol (PVA), the MWCNTs and PVA double network porous conductive hydrogels are set up. MWCNTs/PVA conductive hydrogel electrode film was prepared by EPD and freezing thawing cyclic crosslinking process. The electrochemical performance and microstructure of the MWCNTs/PVA electrode film showed that the MWCNTs/PVA hydrogel electrode film has a high hydrophilic porous conductive water gel network structure, although MWCNTs/PVA electric hydrogel electricity is electric. The polar membrane has no obvious catalytic activity for glucose in the PBS solution, but it has obvious catalytic activity for the glucose in the alkaline solution of dopamine and pH9. The electrode membrane may be used to implant glucose fuel cells in the human intestine. Based on the good electrocatalytic activity of nano platinum (PtNPs), MWCNTs, PVA and PtNPs are designed for more than three yuan. With the electrostatic adsorption of sixteen alkyl ammonium bromide (CTAB) and chlorinated platinum acid (CPA) and the mild chemical reducibility of citric acid (VC), the PtNPs load of high load was realized on the MWCNTs/PVA porous conductive hydrogel membrane. The electrochemical properties of the PtNPs/MWCNTs/PVA electropolar membrane and the characterization of the microstructure were characterized. Although the PtNPs/MWCNTs/PVA conductive hydrogel electrode film does not have the ability to selectively catalyze glucose in the oxygen rich environment, the electrode film has a high electroactive area, low surface charge transfer resistance and good diffusion permeability and so on, it has good electrocatalysis for glucose in neutral PBS solution. The electrode membrane can be used for the implantation of the cathode oxygen depletion layer to the glucose fuel cell. Using the natural nano mesh structure of the bacterial cellulose (BC), the good electrical conductivity of MWCNTs and the good electrocatalytic activity of PtNPs, a PtNPs, MWCNTs, BC three element porous laminated conductive hydrogel is designed. And the ultrasonic assisted electrophoretic deposition technology is used to realize the MWCNT The infiltration and doping of s on the BC film guarantee the dual characteristics of both ionic conduction and electronic conduction, and the high load PtNPs recombination on the MWCNTs/BC porous conductive hydrogel electrode film is realized by using BC for the adsorption capacity of chloroplatinate and the strong reducibility of sodium borohydride. By conducting a conductive hydrocoagulation to PtNPs/MWCNTs/BC. The electrochemical properties of the colloid electrode film and the characterization of the microstructure are not only characterized by high electroactive area, low surface charge transfer resistance and good diffusion permeability, but also on the basis of high catalytic activity for glucose in PBS solution. The most important discovery is that the electrode membrane is used. The glucose in the oxygen rich PBS solution has the porous layer structure of the selective catalytic.PtNPs/MWCNTs/BC electrode membrane and the high load discrete distribution of the PtNPs, which is the reason for the selective catalytic glucose ability of the PtNPs/MWCNTs/BC conductive hydrogel electrode membrane. The electrode membrane can be used to implant the surface battery of the glucose fuel surface. PtNPs/MWCNTs/BC conduction is conductive. The water gel electrode membrane was used as the anode film and the MWCNTs/BC conductive hydrogel electrode membrane as the cathode membrane to construct the glucose battery on the surface of the implant. The maximum power density of the PtNPs/MWCNTs/BC-MWCNTs/BC glucose fuel cell reached 2.75 + 0.2 Wcm-2 in the PBS solution near the physiological oxygen concentration and the glucose concentration, and the fuel cell was also used. Excellent tolerance to dissolved oxygen was shown. The biocompatibility of PtNPs/MWCNTs/BC and MWCNTs/BC conductive hydrogel electrode membranes was evaluated by the method of extraction cell count (CCK-8) and bone marrow mesenchymal stem cell (MSC) culture on the surface of the material. The electrode membrane showed good biocompatibility. The above study showed that PtNP It is more feasible to use s/MWCNTs/BC to selectively catalyze the electrode film of the conductive hydrogel electrode for the implant surface glucose battery. This study provides a new material system and structure design for the research and application of the self powered devices in the body for long-term stability and biosafety.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ427.26;TM911.4

【參考文獻(xiàn)】

相關(guān)期刊論文 前7條

1 劉樹敏;鄭裕東;李偉;孫乙;岳麗娜;趙振江;;聚乙烯醇/酸化碳納米管高親水性三維孔電極膜的制備與電化學(xué)性能[J];高等學(xué)�；瘜W(xué)學(xué)報(bào);2016年02期

2 邵亮;柳明珠;邱建輝;高春梅;張國(guó)宏;秦利軍;;導(dǎo)電水凝膠的制備[J];化學(xué)進(jìn)展;2011年05期

3 林德盟;車劍飛;;水凝膠修飾生物兼容性電極[J];化學(xué)進(jìn)展;2010年06期

4 ;Synthesis, characterization and swelling properties of a chemically cross-linked poly(vinyl alcohol) hydrogel[J];Frontiers of Chemistry in China;2007年02期

5 楊連利;梁國(guó)正;;水凝膠在醫(yī)學(xué)領(lǐng)域的熱點(diǎn)研究及應(yīng)用[J];材料導(dǎo)報(bào);2007年02期

6 武旭業(yè),黃世文,張建濤,卓仁禧;物理交聯(lián)聚乙烯醇/羥基末端聚酰胺-胺樹型高分子水凝膠的制備與性質(zhì)研究[J];高等學(xué)�；瘜W(xué)學(xué)報(bào);2004年02期

7 王宗花,劉軍,顏流水,王義明,羅國(guó)安;羧基化碳納米管嵌入石墨修飾電極對(duì)多巴胺和抗壞血酸的電催化[J];分析化學(xué);2002年09期

相關(guān)碩士學(xué)位論文 前1條

1 韋曉娟;植入式微型醫(yī)療器械供電方法研究[D];中國(guó)科學(xué)院研究生院（理化技術(shù)研究所）;2008年

，

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