本文選題：離子選擇膜技術(shù) + 全固態(tài)離子選擇電極��； 參考：《中國(guó)農(nóng)業(yè)大學(xué)》2016年博士論文

【摘要】：化肥是重要的農(nóng)業(yè)生產(chǎn)資料對(duì)糧食增產(chǎn)起到不可替代的作用。近年來(lái),因盲目追求高產(chǎn)、穩(wěn)產(chǎn)而導(dǎo)致的化肥尤其氮肥的過(guò)量施用造成了嚴(yán)重的農(nóng)業(yè)面源污染和經(jīng)濟(jì)效益下降。研究符合國(guó)情的土壤硝態(tài)氮前端感知技術(shù),為測(cè)土施肥提供技術(shù)保障具有重要意義�；诰酆衔锩舾心る姌O的硝態(tài)氮測(cè)量研究日益受到學(xué)界重視,通過(guò)國(guó)際合作攻關(guān)機(jī)制,研究課題組在全固態(tài)硝酸根摻雜聚吡咯膜電極的研究方面取得了階段性突破但電極的穩(wěn)定性及抗干擾性問(wèn)題成為了電極數(shù)據(jù)解譯與實(shí)際應(yīng)用的瓶頸。本文以離子選擇性敏感膜表面微形貌調(diào)控為切入點(diǎn),系統(tǒng)開展微形貌特征提取、量化、調(diào)控等制備技術(shù)研究,揭示離子敏感膜微形貌與其土壤硝態(tài)氮檢測(cè)性能間的作用機(jī)理及模型,進(jìn)一步加深了對(duì)聚合物選擇性敏感膜的響應(yīng)機(jī)理及過(guò)程的理解,對(duì)拓展基于全固態(tài)聚合膜電極的硝態(tài)氮快速低成本檢測(cè)技術(shù)研究具有重要的學(xué)術(shù)價(jià)值和現(xiàn)實(shí)意義。具體研究工作包括：1、研究了硝酸根摻雜聚吡咯膜的分形特征,探討了分形特征與傳感器性能之間的關(guān)系。通過(guò)改變聚合電流密度,在玻碳基底(GC)上制備不同形貌特征的NO3摻雜聚吡咯膜(PPy-NO3-),對(duì)膜進(jìn)行分形分析,探討了分形維數(shù)與電極電化學(xué)、傳質(zhì)動(dòng)力學(xué)性能的關(guān)系。研究結(jié)果表明：PPy-NO3膜具有分形特性,改變聚合電流密度能夠明顯改變膜的形貌；分形維數(shù)(Df)能更準(zhǔn)確地表征膜的微觀綜合復(fù)雜程度;在一定范圍內(nèi)分形維數(shù)與電極的線性范圍、響應(yīng)速率、檢測(cè)下限性能具有正相關(guān)關(guān)系,分形維數(shù)越大離子的膜相擴(kuò)散系數(shù)越高：1.2mA·cm-2聚合電流下膜的Df=2.58、擴(kuò)散系數(shù)D=7.48×10-11 crn2·s-1,相應(yīng)電極的線性范圍5.0×10-5-1.0×10-1M、響應(yīng)斜率-53.3mV·decade-1、響應(yīng)時(shí)間60 s,對(duì)主要干擾離子的選擇系數(shù)均達(dá)到10-2數(shù)量級(jí)。2、解析了水層形成導(dǎo)致響應(yīng)電勢(shì)漂移的機(jī)理,研制了以PPy-NO3-和石墨烯(GR)復(fù)合材料(PPy-NO3-/GR)為離子敏感膜的全固態(tài)離子選擇電極,有效抑制了電勢(shì)漂移。采用電化學(xué)還原法在GC表面直接修飾GR層,通過(guò)脈沖聚合法實(shí)現(xiàn)PPy-NO3-膜的聚合及與GR的復(fù)合并制備傳感器。研究結(jié)果表明：所制備的傳感器具備良好的電化學(xué)分析性能,包括：響應(yīng)斜率為-56.2mV·decade-1、線性范圍為10-5-1.0×10-1M、檢測(cè)下限為0.63×10-5M、響應(yīng)時(shí)間15 s及l(fā)ogKNO3-,Cl-=-2.5。響應(yīng)電勢(shì)穩(wěn)定性得到較大提升,ΔE·△t-1達(dá)到了0.67±0.05 mV·h-1。實(shí)際土樣測(cè)量結(jié)果顯示,該傳感器具有較高的準(zhǔn)確性且能在土壤泥漿直測(cè)方式下保持較好的穩(wěn)定性。3、理論解析了膜極化對(duì)電極響應(yīng)電勢(shì)穩(wěn)定性的影響,提出了抑制極化的微結(jié)構(gòu)調(diào)整方向,制備了具有納米管狀微形貌結(jié)構(gòu)的PPy-NO3--(T)膜,構(gòu)建了相應(yīng)的PPy-NO3-- (T) /GR/GC全固態(tài)離子選擇電極。利用直鏈淀粉分子模板誘導(dǎo)吡咯單體定向聚合生長(zhǎng),實(shí)現(xiàn)了納米管狀聚吡咯微結(jié)構(gòu)可控制備。實(shí)驗(yàn)結(jié)果表明：所制備的納米管狀微結(jié)構(gòu)能極大提高了離子敏感膜的離子傳輸速率,Rct到了95.7Ω,電化學(xué)電容Cem達(dá)到了0.98 mF、Cdl達(dá)到了4.5×10-6 mF,所制備的電極具備較高的穩(wěn)定性,ΔE·△t-1達(dá)到了80±6 μV·h-1。4、建立了適用于PPy-NO3-(T)/GR/GC電極在高濃度干擾離子存在、大范圍溫度變化情況下的干擾校正ANN模型。模型的輸入為氯電極、PPy-NO3--(T)/GR/GC電極的響應(yīng)電動(dòng)勢(shì)和測(cè)試溫度,輸出為NO3--N濃度,利用響應(yīng)面法解析模型參數(shù)及其交互作用對(duì)模型預(yù)測(cè)能力的影響并優(yōu)化計(jì)算相應(yīng)參數(shù)值。研究結(jié)果表明：ANN拓?fù)?-8-1、動(dòng)量系數(shù)0.73、學(xué)習(xí)率0.33所對(duì)應(yīng)的模型具有較好的預(yù)測(cè)能力(RMSET=2.75mg·kg-1, R2=0.97),對(duì)高Cl-干擾情況下的校正效果要優(yōu)于傳統(tǒng)能斯特方程標(biāo)定法,其有望用于農(nóng)田土壤硝態(tài)氮的實(shí)際測(cè)試。
[Abstract]:Chemical fertilizer is an important agricultural production material which plays an irreplaceable role in increasing grain yield. In recent years, the excessive application of chemical fertilizer, especially nitrogen fertilizer, caused by blind pursuit of high yield and stable yield, has caused serious agricultural non-point source pollution and economic benefit decline. The study on the measurement of nitrate nitrogen based on the polymer sensitive membrane electrode has attracted more and more attention. Through the international cooperation mechanism, the research group has made a breakthrough in the research of all solid state nitrate doped polypyrrole membrane electrode, but the electrode stability and anti-interference problems have become the number of electrodes. According to the bottleneck of the interpretation and practical application, this paper takes the surface micromorphology of the ion selective sensitive membrane as the breakthrough point, and studies the preparation technology of the micro morphology feature extraction, quantification and regulation, and reveals the mechanism and model of the micromorphology of the ion sensitive membrane and the detection performance of soil nitrate nitrogen, and further deepens the selection of the polymer. The understanding of the response mechanism and process of the sensitive membrane is of great academic and practical significance for expanding the rapid and low cost detection technology of nitrate nitrogen based on all solid state polymeric membrane electrodes. The specific research work includes: 1, the fractal characteristics of the nitrate doped polypyrrole film are studied, and the fractal characteristics are discussed between the properties of the sensor and the performance of the sensor. By changing the polymerization current density, the NO3 doped polypyrrole film (PPy-NO3-) with different morphologies was prepared on the glass carbon substrate (GC). The fractal analysis of the membrane was carried out. The relationship between the fractal dimension and the electrode electrochemistry and the mass transfer kinetics was discussed. The results show that the PPy-NO3 film has the fractal characteristics and the polymerization current density can be changed. The morphology of the membrane is obviously changed, and the fractal dimension (Df) can more accurately characterize the micro comprehensive complexity of the membrane. In a certain range, the fractal dimension has a positive correlation with the linear range of the electrode, the response rate and the lower limit performance. The larger the fractal dimension is, the higher the membrane diffusion coefficient of the ions is: the Df=2.58 of the film under the polymerization current of 1.2mA. Cm-2. The diffusion coefficient is D=7.48 x 10-11 crn2. S-1, the linear range of the corresponding electrode is 5 x 10-5-1.0 x 10-1M, the response slope -53.3mV decade-1 and the response time 60 s, the selection coefficients of the main interfering ions are all 10-2 orders of magnitude.2, and the mechanism of the water layer formation in response to the drift of the response potential is analyzed, and the PPy-NO3- and the GR (PPy) composite material (PPy) is developed. -NO3-/GR) is an all solid ion selective electrode for the ion sensitive membrane, which effectively inhibits the drift of the potential. The electrochemical reduction method is used to modify the GR layer on the surface of the GC directly. The polymerization of the PPy-NO3- film and the composite of the GR with the GR are realized by the pulse polymerization. The results show that the prepared sensor has good electrochemical analysis. The results are as follows: the response slope is -56.2mV decade-1, the linear range is 10-5-1.0 x 10-1M, the detection limit is 0.63 x 10-5M, the response time is 15 s and logKNO3-, the Cl-=-2.5. response potential stability is greatly improved. The delta E / delta T-1 reaches 0.67 + 0.05 mV. The actual soil sample measurement of the h-1. is high accuracy and can be in the soil. A good stability.3 was maintained under the direct measurement of soil mud. The effect of membrane polarization on the stability of electrode response potential was theoretically analyzed. The direction of microstructural adjustment was proposed. The PPy-NO3-- (T) membrane with nanotubular micromorphology was prepared, and a corresponding PPy-NO3-- (T) /GR/GC all solid state ion selective electrode was constructed. The amylose molecular template induced the directional polymerization of pyrrole monomer and realized the controlled preparation of the nanotubular polypyrrole microstructure. The experimental results show that the nano tubular microstructures can greatly improve the ion transmission rate of the ion sensitive membrane, Rct to 95.7 Omega, the electrochemical capacitance of Cem reached 0.98 mF, and the Cdl reached 4.5 * 10-6 mF. The prepared electrode has high stability, and the delta E. Delta T-1 reaches 80 + 6 V. H-1.4. The interference correction ANN model is established for the PPy-NO3- (T) /GR/GC electrode under the presence of high concentration interfering ions and large range of temperature changes. The input of the model is the chlorine electrode, the PPy-NO3-- (T) /GR/GC electrode is the response electromotive force and the test temperature, the output is NO3--N concentration, the response surface method is used to analyze the influence of model parameters and their interaction on the model prediction ability and to optimize the calculation of the corresponding parameters. The results show that the ANN topology 3-8-1, the momentum coefficient 0.73, the learning rate 0.33 corresponding models have good prediction ability (RMSET= 2.75mg. Kg-1, R2=0.97), and the high Cl- interference condition correction. The positive effect is better than the traditional Nernst equation calibration method, which is expected to be applied to the practical test of nitrate nitrogen in farmland soil.

【學(xué)位授予單位】：中國(guó)農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：S151.9
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本文編號(hào)：1801498