摘要
第一章:主要综述了有机小分子(甲醇、甲醛和甲酸)在钯催化剂和镍催化剂上的电催化氧化研究进展及其氧化机理。
第二章:采用电化学沉积法制备了钯纳米修饰玻碳电极(Pd/GC/CV),利用扫描电子显微镜表征(SEM)对Pd/GC/CV电极进行了表征,钯纳米粒子分散均匀,粒径范围在100～200 nm。利用循环伏安法(CV)研究了Pd/GC/CV电极对甲醛的电催化氧化,发现该电极对甲醛具有较高的催化活性,并经优化实验条件,建立了用其测定甲醛的电化学分析方法,线性范围为1.0×10~(-4)～1.4×10~(-2) mol·L~(-1),检出限为3.0×10~(-5) mol·L~(-1),相对标准偏差为3.9%,对模拟样品进行了检测,回收率为94.7～104.0%。
第三章:利用恒电位法在玻碳电极上沉积钯纳米粒子,制成修饰电极(Pd/GC),采用循环伏安法研究其电化学行为。运用循环伏安法对比了Pd/GC/CV电极和Pd/GC电极对甲酸的电催化活性,结果表明后者的活性优于前者。运用线性扫描伏安法初步探讨了甲酸在Pd/GC电极上的氧化机理。
第四章:利用循环伏安法在镍电极表面电沉积氢氧化镍制得修饰电极(Ni(OH)_2/Ni),用其对甲醛和甲醇进行电催化氧化,发现该修饰电极对甲醛和甲醇具有较高的催化活性。经优化实验条件,建立了用其测定甲醛的电化学分析方法,线性范围为7.0×10~(-5)～1.6×10~(-2) mol·L~(-1),检出限为2.0×10~(-5) mol·L~(-1),相对标准偏差为4.3%,对模拟样品进行了检测,回收率为93.3～103.5%。同时研究发现甲醇浓度和循环伏安扫描速度均对甲醇在Ni(OH)_2/Ni电极上的电化学行为有所影响。
第五章:总结钯纳米粒子对甲醛和甲酸的电催化氧化作用,以及氢氧化镍修饰的镍电极对甲醛和甲醇的电催化氧化作用,并提出下一步的计划。
Chapter 1: This paper mainly reviews the recent development of electrocatalytic oxidation of small organic molecules (methanol, formaldehyde and formic acid) on the palladium catalysts and nickel catalysts as well as their oxidation mechanism.
Chapter 2: Using electrochemical deposition method, glassy carbon electrode modified with palladium nanoparticles (Pd/GC/CV) was prepared and it was characterized by scanning electron microscopy (SEM), which showed that they were well-dispersed and the size range of spherical particles was about 100～200 run. The electrocatalytic properties of Pd/GC/CV electrode for formaldehyde oxidation had been investigated by cyclic voltametry and high electrocatalytic activity was observed. The experimental parameters were optimized for establishing the method of formaldehyde determination. The oxidation peak current was linearly proportional to the concentration of formaldehyde over the range of 1.0×10~(-4)～1.4×10~(-2) mol·L~(-1) with the detection limit being 3.0×10~(-5) mol·L~(-1) and RSD being 3.9 %. And the artificial samples were determined with the recovery of 94.7～104.0 %.
Chapter 3: Palladium nanoparticles were prepared by potentiostatic technique on glassy carbon electrode (Pd/GC), whose electrochemical behavior was investigated by cyclic voltametry. After comparing the electrocatalytic activity, the result showed Pd/GC was more active to formic acid than Pd/GC/CV. The oxidation mechanism of formic acid on the Pd/GC electrode was discussed primely by linear sweep voltammetry (LSV).
Chapter 4: The nickel hydroxide-modified nickel electrode (Ni(OH)_2/Ni) was prepared by cyclic voltammetry and its electrocatalytic properties for methanol and formaldehyde oxidation had been investigated. And high electrocatalytic activity was observed. The experimental parameters were optimized for establishing the method of formaldehyde determination. The oxidation peak current was linearly proportional to the concentration of formaldehyde over the range of 7.0×10~(-5)～1.6×10~(-2) mol·L~(-1) with the detection limit being 2.0×10~(-5) mol·L~(-1) and RSD being 4.3 %. And the artificial samples were determined with the recovery of 93.3～103.5 %. The concentration of methanol and the scan rate also had an effect on the electrochemical behavior of methanol.
Chapter 5: The work mentioned above had been summarized and the further work was proposed.
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