亲核氧化反应在可持续生产增值化学品中扮演着重要角色。电催化甘油氧化反应作为亲核氧化反应的一种重要类型,可以制得包括甲酸在内的C_(1)至C_(3)衍生产物。非贵金属氢氧化物/羟基氧化物被广泛应用于甘油氧化反应,但在中等电位下难以...亲核氧化反应在可持续生产增值化学品中扮演着重要角色。电催化甘油氧化反应作为亲核氧化反应的一种重要类型,可以制得包括甲酸在内的C_(1)至C_(3)衍生产物。非贵金属氢氧化物/羟基氧化物被广泛应用于甘油氧化反应,但在中等电位下难以达到工业级电流密度(大于300 mA·cm^(-2))。研究表明,氢氧化物/羟基氧化物催化的甘油氧化反应通过间接氧化机理进行,即通过电生成的含有亲电吸附氧的羟基氧化物氧化亲核试剂(甘油)。因此,理解甘油氧化反应中电催化剂的演变至关重要。在本文中,通过循环伏安法活化钼酸镍(NiMoO_(4)),开发了一种钼掺杂的羟基氧化镍(Mo-NiOOH)催化剂。通过多种表征方法对Mo-NiOOH进行了系统表征,结果显示,Mo-NiOOH继承了NiMoO_(4)前驱体的纳米片阵列形貌,但Mo含量降低,证明循环伏安法活化后实现了从氧化物到羟基氧化物的相重构。此外,Mo-NiOOH中Ni^(3+)/Ni^(2+)的比例高于循环伏安法活化制备的NiOOH。在活化过程中,Mo物种从NiMoO_(4)中浸出,制备得到的Mo-NiOOH保留了NiMoO_(4)前驱体的纳米片阵列形貌。与氢氧化镍(Ni(OH)_(2))经循环伏安法活化合成的NiOOH相比,Mo-NiOOH具有更高的Ni^(3+)/Ni^(2+)比例以及更高的电化学比表面积(ECSAs),且促进了Ni^(2+)氧化为Ni^(3+)。因此,Mo-NiOOH达到高电流密度(400mA·cm^(-2))的电位(1.51V vs.RHE)低于NiOOH(1.84 V vs.RHE)。此外,Mo-NiOOH表现出高于NiOOH的甲酸盐法拉第效率(84.7%vs.59.6%),表明钼掺杂加速了碳-碳键断裂。多电位阶跃实验显示,NiOOH和Mo-NiOOH催化的甘油电氧化通过类似的羟基氧化物介导的间接氧化机理进行。原位电化学阻抗谱和原位拉曼光谱证实,Mo掺杂促进了甘油氧化反应动力学以及Ni^(2+)氧化为Ni^(3+)的过程,导致Mo-NiOOH比NiOOH具有更高的活性和甲酸选择性。本研究通过可溶性阴离子浸出策略来调节羟基氧化物表面结构,为设计高性能亲核氧化反应电催化剂提供了指导。展开更多
The novel covalently modified glassy carbon electrode with poly(xylitol) was prepared using an electropolymerization technique for the simultaneous determination of uric acid(UA), xanthine(XA) and hypoxanthine(HX). Th...The novel covalently modified glassy carbon electrode with poly(xylitol) was prepared using an electropolymerization technique for the simultaneous determination of uric acid(UA), xanthine(XA) and hypoxanthine(HX). This new electrode presents an excellent electrocatalytic activity towards the oxidation of UA, XA and HX by cyclic voltammetry(CV) method. The oxidation peaks of the three compounds were well defined and had enhanced the peak currents. The separation potentials of the oxidation peak potentials for UA-XA and XA-HX were 380 and 370 mV in CV, respectively. Using differential pulse voltammetry(DPV) method, the calibration curves in the ranges of 5-55, 1.3-75.3 and 4-59 μmol/L were obtained for HX, XA and UA, respectively. The lowest detection limits(S/N=3) were 4.5, 0.75 and 3.75 μmol/L for HX, XA and UA, respectively. The practical application of the modified electrode was demonstrated by the determination of UA, XA, HX in human urine samples.展开更多
The electro-polymerization behavior of aniline in reverse(W/O) microemulsion was investigated. The experiment results show that the cyclic voltammetry polymerization behavior of aniline in W/O microemulsion is differe...The electro-polymerization behavior of aniline in reverse(W/O) microemulsion was investigated. The experiment results show that the cyclic voltammetry polymerization behavior of aniline in W/O microemulsion is different from that in aqueous solution remarkably. With the increase of scan cycle, the oxidation potential shifts positively and the reduction potential shifts negatively, i.e., the redox potential difference increases. H+ apparent concentration affects the aniline polymerization evidently. When H+ concentration is lower than 0.08 mol/L, the electro-polymerization of aniline is difficult. With the increase of H+ concentration, the polymerization current of aniline increases gradually. Only when H+ concentration is high enough(0.5 mol/L), aniline can be well electro-polymerized. Moreover, under the same condition, the aniline polymerization current in W/O microemulsion is higher than that in aqueous solution. The scanning electron microscopy image shows that the deposited polyaniline(PANI) has uniform fiber morphology with diameter of about 100 nm. Further study result suggests that the electrochemical activity of the PANI in HCl is similar to that of the PANI prepared in aqueous solution.展开更多
文摘亲核氧化反应在可持续生产增值化学品中扮演着重要角色。电催化甘油氧化反应作为亲核氧化反应的一种重要类型,可以制得包括甲酸在内的C_(1)至C_(3)衍生产物。非贵金属氢氧化物/羟基氧化物被广泛应用于甘油氧化反应,但在中等电位下难以达到工业级电流密度(大于300 mA·cm^(-2))。研究表明,氢氧化物/羟基氧化物催化的甘油氧化反应通过间接氧化机理进行,即通过电生成的含有亲电吸附氧的羟基氧化物氧化亲核试剂(甘油)。因此,理解甘油氧化反应中电催化剂的演变至关重要。在本文中,通过循环伏安法活化钼酸镍(NiMoO_(4)),开发了一种钼掺杂的羟基氧化镍(Mo-NiOOH)催化剂。通过多种表征方法对Mo-NiOOH进行了系统表征,结果显示,Mo-NiOOH继承了NiMoO_(4)前驱体的纳米片阵列形貌,但Mo含量降低,证明循环伏安法活化后实现了从氧化物到羟基氧化物的相重构。此外,Mo-NiOOH中Ni^(3+)/Ni^(2+)的比例高于循环伏安法活化制备的NiOOH。在活化过程中,Mo物种从NiMoO_(4)中浸出,制备得到的Mo-NiOOH保留了NiMoO_(4)前驱体的纳米片阵列形貌。与氢氧化镍(Ni(OH)_(2))经循环伏安法活化合成的NiOOH相比,Mo-NiOOH具有更高的Ni^(3+)/Ni^(2+)比例以及更高的电化学比表面积(ECSAs),且促进了Ni^(2+)氧化为Ni^(3+)。因此,Mo-NiOOH达到高电流密度(400mA·cm^(-2))的电位(1.51V vs.RHE)低于NiOOH(1.84 V vs.RHE)。此外,Mo-NiOOH表现出高于NiOOH的甲酸盐法拉第效率(84.7%vs.59.6%),表明钼掺杂加速了碳-碳键断裂。多电位阶跃实验显示,NiOOH和Mo-NiOOH催化的甘油电氧化通过类似的羟基氧化物介导的间接氧化机理进行。原位电化学阻抗谱和原位拉曼光谱证实,Mo掺杂促进了甘油氧化反应动力学以及Ni^(2+)氧化为Ni^(3+)的过程,导致Mo-NiOOH比NiOOH具有更高的活性和甲酸选择性。本研究通过可溶性阴离子浸出策略来调节羟基氧化物表面结构,为设计高性能亲核氧化反应电催化剂提供了指导。
基金Project(201215135) supported by the Natural Science Foundation of Jilin Province,China
文摘The novel covalently modified glassy carbon electrode with poly(xylitol) was prepared using an electropolymerization technique for the simultaneous determination of uric acid(UA), xanthine(XA) and hypoxanthine(HX). This new electrode presents an excellent electrocatalytic activity towards the oxidation of UA, XA and HX by cyclic voltammetry(CV) method. The oxidation peaks of the three compounds were well defined and had enhanced the peak currents. The separation potentials of the oxidation peak potentials for UA-XA and XA-HX were 380 and 370 mV in CV, respectively. Using differential pulse voltammetry(DPV) method, the calibration curves in the ranges of 5-55, 1.3-75.3 and 4-59 μmol/L were obtained for HX, XA and UA, respectively. The lowest detection limits(S/N=3) were 4.5, 0.75 and 3.75 μmol/L for HX, XA and UA, respectively. The practical application of the modified electrode was demonstrated by the determination of UA, XA, HX in human urine samples.
基金Projects(51071067,21271069,20673036,J1210040,50473022) supported by National Natural Science Foundation of ChinaProject(2013GK3015) supported by the Science and Technology Program of Hunan Province,China
文摘The electro-polymerization behavior of aniline in reverse(W/O) microemulsion was investigated. The experiment results show that the cyclic voltammetry polymerization behavior of aniline in W/O microemulsion is different from that in aqueous solution remarkably. With the increase of scan cycle, the oxidation potential shifts positively and the reduction potential shifts negatively, i.e., the redox potential difference increases. H+ apparent concentration affects the aniline polymerization evidently. When H+ concentration is lower than 0.08 mol/L, the electro-polymerization of aniline is difficult. With the increase of H+ concentration, the polymerization current of aniline increases gradually. Only when H+ concentration is high enough(0.5 mol/L), aniline can be well electro-polymerized. Moreover, under the same condition, the aniline polymerization current in W/O microemulsion is higher than that in aqueous solution. The scanning electron microscopy image shows that the deposited polyaniline(PANI) has uniform fiber morphology with diameter of about 100 nm. Further study result suggests that the electrochemical activity of the PANI in HCl is similar to that of the PANI prepared in aqueous solution.
