浸渍—氧化法制备β-PbO_2-SPE复合膜电极的研究
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摘要
SPE(solid polymer electrolyte)复合膜电极以其电解质简单、电流效率高、能耗低、副反应少、操作弹性大和催化活性好已成为电化学材料研究领域热点之一。现有的制备PbO_2—SPE复合膜电极的方法有机械施压法(热压法)和电化学沉积法两种，但这两种方法各有特点，也各存在不足。为此，本文首次提出并采用浸渍—氧化法制备β-PbO_2—SPE复合膜电极，旨在将催化活性更好的β-PbO_2通过化学方法直接沉积到SPE基膜上。作为河南省杰出人才创新基金项目(项目编号：521001400)，本文以Nafion阳离子膜作为基膜，进行了基膜类型的选择与活化、制备技术与工艺条件优化、电极性能表征、电极改性和评价以及膜电极电催化降解苯酚研究，具有较高的学术理论意义和工程应用前景。
基膜是制备β-PbO_2—SPE复合膜电极的基础，依据Nafion膜的结构特征，通过净化实验和溶胀实验，以及SEM、EDS测试，表明Nafion324膜是较理想的基膜，确定出了基膜活化的方法及步骤，获得了基膜充分溶胀条件。在5种氧化实验方案基础上，获得浸渍-氧化法制备β-PbO_2—SPE复合膜电极的工艺路线。通过理论分析和较细致的单因素实验，首次优化出制备β-PbO_2—SPE复合膜电极最佳工艺条件为：浸渍过程中用超声波搅拌，温度50℃，浸渍液浓度配比为0.05 mol·L~(-1)Pb(NO_3)_2+1.0mol·L~(-1)NH_4Ac，浸渍时间2.0h；氧化过程中超声搅拌强度为40W，温度为40℃；氧化时间2.0h。在优化条件下经过8-11次重复浸渍—氧化过程，可制成完整的β-PbO_2—SPE复合膜电极。经过XRD、SEM、EDS测试，表明β-PbO_2—SPE复合膜电极沉积层主要成分为β-PbO_2，晶粒细小，致密且均匀分布在基膜上，与基膜结合牢固。稳态极化曲线显示，在1.0mol·L~(-1)H_2SO_4溶液中β-PbO_2—SPE复合膜电极析氧电位约为100mv(vs．SCE)，交换电流密度为i~0=7.182×10~(-3)A·cm~(-2)，电极的稳定性较好、耐腐蚀性强。循环伏安曲线证明膜电极具有电化学降解苯酚的能力，苯酚在膜电极上降解过程准可逆，受扩散控制。
根据化学沉积过程中添加剂的作用原理，从络合和缓冲型添加剂中选择F~-、从改性型添加剂中选择Fe~(2+)、从稳定镀液型添加剂中选择重金属离子Co~(2+)，分别制备出3种改性β-PbO_2—SPE复合膜电极。通过XRD、SEM、EDS、稳态极化曲线、循环伏安曲线等研究，表明改性的β-PbO_2—SPE复合膜电极表面沉积的β-PbO_2更加均匀、致密，增强了膜电极的活性和稳定性，更适合作为电化学降解过程中的阳极材料。初步探讨添加剂在β-PbO_2沉积过程中机理的结果显示，添加F~-只改变催化层的形貌，添加Fe~(2+)和CO~(2+)形成了α-Fe_2O_3和β-PbO_2共沉积以及CO_3O_4和β-PbO_2共沉积的电催化层，提高膜电极的电催化活性。
β-PbO_2—SPE及3种改性复合膜电极降解浓度为100mg·L~(-1)的苯酚溶液的结果证明：在1.0mol·L~(-1)H_2SO_4介质中4种膜电极显示出较强的苯酚降解能力，其降解能力大小顺序可归结为：β-PbO_2／Co—SPE＞β-PbO_2／Fe—SPE＞β-PbO_2—SPE≈β-PbO_2／F—SPE，且在电解过程中，槽电压均低于相近测试条件下其它β-PbO_2电极，有利于降低能耗、提高电能效率，体现了膜电极的优点。实验结果从另一方面也证明加入添加物制备出了性能更加优良的β-PbO_2—SPE复合膜电极。
SPE composite membrane electrode has been becoming the frontier of electrochemical material field due to its simple media condition, higher current efficiency, the lower energy consumption, the less side-reaction, the wider operation range and the outstanding electrocatalytic active. All now manners of making PbO_2—SPE composite membrane electrode can be calssified into two categories, One is the mechanical method, and another is electrochemical method. These two methods have their advantages and, simultaneously, have their shortness. So, a completely new plan, impregnation-oxidation method, was put forward to and was used to prepare PbO_2—SPE composite membrane electrode, the concept is to directly depositβ-PbO_2 in the basal membrane by the electroless method. As a new researching item, supported by He'nan Outstanding talent innovation fund (No: 521001400), this work has been done a lot, it included: to choose the types of basal membrane material, to research the activating method of basal membrane, to optimize the preparing technical and the technology conditions, to characterizes electrode performance, to modify and evaluate electrode performance and research the effect in degradation phenol. All the research will be valuable in the academic filed and is very useful in the industrial project.
The basal membrane is the basement to prepare good composite membrane electrode material. According to the special structure of Nation basal membrane, based on the clearing and swelling processes, and by means of the analyses of SEM and EDS, the experimental results declared that Nafion324 positive ionic membrane was the ideal basal membrane material in preparingβ-PbO_2—SPE composite membrane electrodes. The methods and steps to active basal membrane were decided and the conditions to swell cleared Nation324 well were obtained too. Based on the conclusions of the five impregnation-oxidation programs, the technical sheet to prepareβ-PbO_2—SPE composite membrane electrodes was determined. Through the detailed processes analyses to depositingβ-PbO_2 in basal membrane and entirely single factor experiments, the author firstly optimizes the conditions in preparingβ-PbO_2—SPE composite membrane electrodes. The impregnating conditions are: stirring is proceeded in ultrasonic wave, the impregnating temperature is kept at 50℃, the better impregnating solution component is 0.05 mol·L~(-1) Pb(NO_3)_2+1.0 mol·L~(-1) NH_4Ac, and the impregnating time is 2.0 h; the oxidation conditions are: the stirring strength of ultrasonic wave is 40W, the oxidation temperature is 40℃and the oxidation time is 2.0 h. Under all the conditions, a completeβ-PbO_2—SPE composite membrane electrode can be prepared out by repeating the impregnating-oxidation processes for 8-11 times, the characterization results ofβ-PbO_2—SPE composite membrane electrode are as follows: The X-ray diffraction result shows that the main composition of plating layer isβ-PbO_2. Theβ-PbO_2 crystal particle is fine and tightly deposited in Nation324 basal membrane. The SEM diagram and the EDS analysis declare that the plating layer ofβ-PbO_2 is compact and uniform in basic membrane. The polarization curve demonstrated, in 1.0 mol·L~(-1) H2SO_4 solution, thatβ-PbO_2—SPE composite membrane electrode oxygen evolution voltage is 100mv (vs. SCE), and the exchange current density i~0=7.182×10~(-3)A·cm~(-2), and theβ-PbO_2 layer has good stability and anti-corrosion. The cyclic voltammogram (CV)curves of phenol solution onβ-PbO_2—SPE composite membrane electrode demonstrated that the electrode has capability in degradation phenol, and the degradation processes of phenol on membrane electrodes were quasi-reversibility and were controlled by diffuse processes.
According to the roles of additive agents in electroless plating technical, the inorganic additives F~-、Fe~(2+) and Co~(2+) were introduced in impregnation process and to obtained three kinds of modificationβ-PbO_2—SPE composite membrane electrodes. Though the tests by XRD、SEM、EDS、the polarization curves and CV curves, the results showed thatβ-PbO_2 layers in modifiedβ-PbO_2—SPE composite membrane electrodes are more uniform and compact than normalβ-PbO_2—SPE composite membrane electrodes, and the active and stable of composite membrane electrodes are improved so that the modifiedβ-PbO_2—SPE composite membrane electrodes are more suitable for anodic materials. The roles of the three additive agents in depositing processes ofβ-PbO_2 were preliminary discussed, the conclusions are: the F~- is only to change the depositing form of plating layer, Fe~(2+) and Co~(2+) can be oxide intoα-Fe_2O_3 and Co_3O_4 and commonly deposited withβ-PbO_2 in Nation324 membrane, so that, the modifiedβ-PbO_2—SPE composite membrane electrodes have better the electrocatalytic active than normal electrode.
The experimental results showed that, in 1.0 mol·L~(-1) H_2SO_4 solution, and the content of phenol is 100mg·L~(-1), normal and modifiedβ-PbO_2—SPE composite membrane electrodes have stronger degradation power. The order of degradation power is:β-PbO_2/ Co—SPE＞β-PbO_2/Fe—SPE＞β-PbO_2—SPE≈β-PbO_2/F—SPE. The tank voltages, at above processes, are lower than other PbO_2 electrodes in nearly same operating conditions. This result is benefitial in decreasing electricity consumption and increasing current efficiency, and it is the reason to prepareβ-PbO_2—SPE composite membrane electrode. The order also demonstrates that the goodβ-PbO_2—SPE composite membrane electrodes can be obtained when the additive agents were introduced in impregnation-oxidation processes.
基膜是制备β-PbO_2—SPE复合膜电极的基础，依据Nafion膜的结构特征，通过净化实验和溶胀实验，以及SEM、EDS测试，表明Nafion324膜是较理想的基膜，确定出了基膜活化的方法及步骤，获得了基膜充分溶胀条件。在5种氧化实验方案基础上，获得浸渍-氧化法制备β-PbO_2—SPE复合膜电极的工艺路线。通过理论分析和较细致的单因素实验，首次优化出制备β-PbO_2—SPE复合膜电极最佳工艺条件为：浸渍过程中用超声波搅拌，温度50℃，浸渍液浓度配比为0.05 mol·L~(-1)Pb(NO_3)_2+1.0mol·L~(-1)NH_4Ac，浸渍时间2.0h；氧化过程中超声搅拌强度为40W，温度为40℃；氧化时间2.0h。在优化条件下经过8-11次重复浸渍—氧化过程，可制成完整的β-PbO_2—SPE复合膜电极。经过XRD、SEM、EDS测试，表明β-PbO_2—SPE复合膜电极沉积层主要成分为β-PbO_2，晶粒细小，致密且均匀分布在基膜上，与基膜结合牢固。稳态极化曲线显示，在1.0mol·L~(-1)H_2SO_4溶液中β-PbO_2—SPE复合膜电极析氧电位约为100mv(vs．SCE)，交换电流密度为i~0=7.182×10~(-3)A·cm~(-2)，电极的稳定性较好、耐腐蚀性强。循环伏安曲线证明膜电极具有电化学降解苯酚的能力，苯酚在膜电极上降解过程准可逆，受扩散控制。
根据化学沉积过程中添加剂的作用原理，从络合和缓冲型添加剂中选择F~-、从改性型添加剂中选择Fe~(2+)、从稳定镀液型添加剂中选择重金属离子Co~(2+)，分别制备出3种改性β-PbO_2—SPE复合膜电极。通过XRD、SEM、EDS、稳态极化曲线、循环伏安曲线等研究，表明改性的β-PbO_2—SPE复合膜电极表面沉积的β-PbO_2更加均匀、致密，增强了膜电极的活性和稳定性，更适合作为电化学降解过程中的阳极材料。初步探讨添加剂在β-PbO_2沉积过程中机理的结果显示，添加F~-只改变催化层的形貌，添加Fe~(2+)和CO~(2+)形成了α-Fe_2O_3和β-PbO_2共沉积以及CO_3O_4和β-PbO_2共沉积的电催化层，提高膜电极的电催化活性。
β-PbO_2—SPE及3种改性复合膜电极降解浓度为100mg·L~(-1)的苯酚溶液的结果证明：在1.0mol·L~(-1)H_2SO_4介质中4种膜电极显示出较强的苯酚降解能力，其降解能力大小顺序可归结为：β-PbO_2／Co—SPE＞β-PbO_2／Fe—SPE＞β-PbO_2—SPE≈β-PbO_2／F—SPE，且在电解过程中，槽电压均低于相近测试条件下其它β-PbO_2电极，有利于降低能耗、提高电能效率，体现了膜电极的优点。实验结果从另一方面也证明加入添加物制备出了性能更加优良的β-PbO_2—SPE复合膜电极。
SPE composite membrane electrode has been becoming the frontier of electrochemical material field due to its simple media condition, higher current efficiency, the lower energy consumption, the less side-reaction, the wider operation range and the outstanding electrocatalytic active. All now manners of making PbO_2—SPE composite membrane electrode can be calssified into two categories, One is the mechanical method, and another is electrochemical method. These two methods have their advantages and, simultaneously, have their shortness. So, a completely new plan, impregnation-oxidation method, was put forward to and was used to prepare PbO_2—SPE composite membrane electrode, the concept is to directly depositβ-PbO_2 in the basal membrane by the electroless method. As a new researching item, supported by He'nan Outstanding talent innovation fund (No: 521001400), this work has been done a lot, it included: to choose the types of basal membrane material, to research the activating method of basal membrane, to optimize the preparing technical and the technology conditions, to characterizes electrode performance, to modify and evaluate electrode performance and research the effect in degradation phenol. All the research will be valuable in the academic filed and is very useful in the industrial project.
The basal membrane is the basement to prepare good composite membrane electrode material. According to the special structure of Nation basal membrane, based on the clearing and swelling processes, and by means of the analyses of SEM and EDS, the experimental results declared that Nafion324 positive ionic membrane was the ideal basal membrane material in preparingβ-PbO_2—SPE composite membrane electrodes. The methods and steps to active basal membrane were decided and the conditions to swell cleared Nation324 well were obtained too. Based on the conclusions of the five impregnation-oxidation programs, the technical sheet to prepareβ-PbO_2—SPE composite membrane electrodes was determined. Through the detailed processes analyses to depositingβ-PbO_2 in basal membrane and entirely single factor experiments, the author firstly optimizes the conditions in preparingβ-PbO_2—SPE composite membrane electrodes. The impregnating conditions are: stirring is proceeded in ultrasonic wave, the impregnating temperature is kept at 50℃, the better impregnating solution component is 0.05 mol·L~(-1) Pb(NO_3)_2+1.0 mol·L~(-1) NH_4Ac, and the impregnating time is 2.0 h; the oxidation conditions are: the stirring strength of ultrasonic wave is 40W, the oxidation temperature is 40℃and the oxidation time is 2.0 h. Under all the conditions, a completeβ-PbO_2—SPE composite membrane electrode can be prepared out by repeating the impregnating-oxidation processes for 8-11 times, the characterization results ofβ-PbO_2—SPE composite membrane electrode are as follows: The X-ray diffraction result shows that the main composition of plating layer isβ-PbO_2. Theβ-PbO_2 crystal particle is fine and tightly deposited in Nation324 basal membrane. The SEM diagram and the EDS analysis declare that the plating layer ofβ-PbO_2 is compact and uniform in basic membrane. The polarization curve demonstrated, in 1.0 mol·L~(-1) H2SO_4 solution, thatβ-PbO_2—SPE composite membrane electrode oxygen evolution voltage is 100mv (vs. SCE), and the exchange current density i~0=7.182×10~(-3)A·cm~(-2), and theβ-PbO_2 layer has good stability and anti-corrosion. The cyclic voltammogram (CV)curves of phenol solution onβ-PbO_2—SPE composite membrane electrode demonstrated that the electrode has capability in degradation phenol, and the degradation processes of phenol on membrane electrodes were quasi-reversibility and were controlled by diffuse processes.
According to the roles of additive agents in electroless plating technical, the inorganic additives F~-、Fe~(2+) and Co~(2+) were introduced in impregnation process and to obtained three kinds of modificationβ-PbO_2—SPE composite membrane electrodes. Though the tests by XRD、SEM、EDS、the polarization curves and CV curves, the results showed thatβ-PbO_2 layers in modifiedβ-PbO_2—SPE composite membrane electrodes are more uniform and compact than normalβ-PbO_2—SPE composite membrane electrodes, and the active and stable of composite membrane electrodes are improved so that the modifiedβ-PbO_2—SPE composite membrane electrodes are more suitable for anodic materials. The roles of the three additive agents in depositing processes ofβ-PbO_2 were preliminary discussed, the conclusions are: the F~- is only to change the depositing form of plating layer, Fe~(2+) and Co~(2+) can be oxide intoα-Fe_2O_3 and Co_3O_4 and commonly deposited withβ-PbO_2 in Nation324 membrane, so that, the modifiedβ-PbO_2—SPE composite membrane electrodes have better the electrocatalytic active than normal electrode.
The experimental results showed that, in 1.0 mol·L~(-1) H_2SO_4 solution, and the content of phenol is 100mg·L~(-1), normal and modifiedβ-PbO_2—SPE composite membrane electrodes have stronger degradation power. The order of degradation power is:β-PbO_2/ Co—SPE＞β-PbO_2/Fe—SPE＞β-PbO_2—SPE≈β-PbO_2/F—SPE. The tank voltages, at above processes, are lower than other PbO_2 electrodes in nearly same operating conditions. This result is benefitial in decreasing electricity consumption and increasing current efficiency, and it is the reason to prepareβ-PbO_2—SPE composite membrane electrode. The order also demonstrates that the goodβ-PbO_2—SPE composite membrane electrodes can be obtained when the additive agents were introduced in impregnation-oxidation processes.
引文
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