基于金属有机配合物分解制备（光）电催化剂及其水分解性能研究
发布时间：2018-08-23 13:47
【摘要】：能源作为人类社会活动的物质基础,是可持续发展中重要的一部分,提高能源利用效率和开发新能源是解决当前社会能源危机的有效途径。氧析出反应由于在可充电燃料电池、水分解制氢和金属空气电池等各种能量转换和存储技术中起着重要作用,开发廉价、高效率、高选择性的析氧催化剂是十分必要的。本论文基于过渡金属(Ni、Co、Fe)有机配合物,分别构建了Ni(Co)Fe_2O_4/C,NiO-NiS/N-C,CoP/α-Fe_2O_3三种阳极析氧光电催化剂,并对三种催化剂的形貌、结构和组成进行了表征,通过三电极体系电化学工作站测试了催化剂的光电化学性能。主要内容如下:(1)采用化学共沉淀法合成了NiFe,CoFe普鲁士蓝类似物,在Ar气氛下高温热解后得到NiFe_2O_4/C和CoFe_2O_4/C纳米复合催化剂。表征结果表明:尖晶石立方相的CoFe_2O_4纳米颗粒均匀分散在原位生成的碳基底上。在1 M KOH电解液中,测试了NiFe_2O_4/C和CoFe_2O_4/C纳米复合材料的析氧活性及稳定性。实验结果表明NiFe_2O_4/C和CoFe_2O_4/C纳米复合催化剂具有良好的催化活性,起始电位分别为1.48 V,1.51 V vs.RHE。采用计时电位法在10 mA cm-2电流密度下经过8小时稳定性测试,NiFe_2O_4/C催化剂的析氧性能没有发生明显衰减。(2)设计合成了香草醛缩胺基硫脲合镍的席夫碱配合物,并混合硫脲作为前驱体,在Ar气氛下高温热解后得到NiO-NiS/N-C纳米复合催化剂。XRD,SEM和TEM等表征结果表明:原位生成的NiO,NiS纳米颗粒均匀分散在有机配合物分解的氮掺杂的碳基底上。在1 M KOH电解液中对NiO-NiS/N-C纳米复合催化剂的催化活性与稳定性进行了测试。实验结果表明NiO-NiS/N-C纳米复合催化剂表现出良好的催化活性,起始电位为1.56 V vs.RHE,达到10 mA cm-2电流密度所需的过电位为374 mV,塔菲尔斜率为44.7 mV dec-1。在10 mA cm-2电流密度下经过10小时稳定性测试之后,催化剂活性没有发生明显变化,表明该催化剂在碱性环境中其具有良好的稳定性。(3)以FTO为导电基底,采用水热法制备了α-Fe_2O_3纳米棒阵列薄膜。随后,将低温磷化法制备的CoP纳米颗粒沉积在α-Fe_2O_3纳米棒阵列表面(负载量为0.01 mg cm-2),制备了CoP/α-Fe_2O_3光阳极。光电化学测试结果显示:在1.23 V vs.RHE下,CoP/α-Fe_2O_3的光电流密度相比原始α-Fe_2O_3纳米棒阵列增大了44%,达到0.72 mA cm-2,电化学阻抗谱测试表明CoP纳米颗粒明显减小了α-Fe_2O_3表面的电荷转移电阻,莫特-肖特基曲线表明CoP/α-Fe_2O_3光阳极的载流子密度更高。CoP沉积在α-Fe_2O_3纳米棒阵列表面,有效减少了电子-空穴对的复合,加速了半导体/催化剂界面的析氧反应。
[Abstract]:As the material basis of human social activities, energy is an important part of sustainable development. To improve the efficiency of energy use and develop new energy is an effective way to solve the current social energy crisis. Oxygen precipitation reaction plays an important role in various energy conversion and storage technologies such as rechargeable fuel cells, hydrogen production by water decomposition and metal air batteries. It is necessary to develop cheap, high efficiency and high selectivity oxygen evolution catalysts. In this paper, based on the organic complexes of transition metal, three kinds of anodic oxide-evolution photocatalysts, Ni (Co) Fe2O4 / NiO-NiS / N-CnCoP / 伪 -Fe2O3, have been constructed, and the morphology, structure and composition of the three catalysts have been characterized. The photoelectrochemical properties of the catalyst were measured by a three electrode system electrochemical workstation. The main contents are as follows: (1) the nife-CoFe Prussian blue analogue was synthesized by chemical coprecipitation. NiFe_2O_4/C and CoFe_2O_4/C nanocomposite catalysts were prepared by pyrolysis in ar atmosphere at high temperature. The characterization results show that the spinel cubic CoFe_2O_4 nanoparticles are uniformly dispersed on the in-situ carbon substrate. The oxygen evolution activity and stability of NiFe_2O_4/C and CoFe_2O_4/C nanocomposites were measured in 1m KOH electrolyte. The experimental results show that NiFe_2O_4/C and CoFe_2O_4/C nanocomposite catalysts have good catalytic activity, and the initial potential is 1.48 V / V 1.51 V vs. RHE, respectively. The stability of NiFe2O4 / C catalyst was measured by chronopotentiometry at a current density of 10 Ma cm-2 for 8 hours. (2) the Schiff base complexes of vanillin acylamino thiourea and nickel were designed and synthesized. Using thiourea as the precursor, NiO-NiS/N-C nanocomposite catalyst. XRDX SEM and TEM were prepared after pyrolysis in ar atmosphere. The results showed that the in situ formed nio nis nanoparticles were uniformly dispersed on the nitrogen-doped carbon substrates of organic complex decomposition. The catalytic activity and stability of NiO-NiS/N-C nanocomposite catalyst were tested in 1m KOH electrolyte. The experimental results show that the NiO-NiS/N-C nanocomposite catalyst exhibits good catalytic activity. The initial potential is 1.56 V vs. RHE. the overpotential required to reach 10 Ma cm-2 current density is 374 MV, and the Taffel slope is 44.7 MV dec-1. After 10 hours stability test at 10 Ma cm-2 current density, the activity of the catalyst did not change obviously, which indicated that the catalyst had good stability in alkaline environment. (3) FTO was used as conductive substrate. 伪 -Fe _ S _ 2O _ 3 nanorod array films were prepared by hydrothermal method. Subsequently, the CoP nanoparticles prepared by low-temperature phosphating method were deposited on the surface of 伪 -FeTi2O3 nanorod array (loaded with 0.01mg cm-2), and the CoP/ 伪 -Fe2O3 photoanode was prepared. The photochemical results showed that the photocurrent density of CoP / 伪 -Fe _ 2O _ 3 at 1.23 V vs.RHE increased by 44% compared with the original 伪 -Fe _ 2O _ 3 nanorod array, and reached 0.72 Ma cm ~ (-2). The electrochemical impedance spectroscopy showed that the charge transfer resistance of 伪 -Fe _ (2) O _ (2) O _ (3) nanoparticles on the surface of 伪 -Fe _ (2) O _ (2) O _ (3) decreased obviously. The Mott-Schottky curve shows that the carrier density of the CoP/ 伪 -Fe _ 2O _ 3 photoanode is higher. Cop is deposited on the 伪 -Fe _ 2O _ 3 nanorod array surface, which effectively reduces the electron-hole pair recombination and accelerates the oxygen evolution reaction at the semiconductor / catalyst interface.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
本文编号：2199254
[Abstract]:As the material basis of human social activities, energy is an important part of sustainable development. To improve the efficiency of energy use and develop new energy is an effective way to solve the current social energy crisis. Oxygen precipitation reaction plays an important role in various energy conversion and storage technologies such as rechargeable fuel cells, hydrogen production by water decomposition and metal air batteries. It is necessary to develop cheap, high efficiency and high selectivity oxygen evolution catalysts. In this paper, based on the organic complexes of transition metal, three kinds of anodic oxide-evolution photocatalysts, Ni (Co) Fe2O4 / NiO-NiS / N-CnCoP / 伪 -Fe2O3, have been constructed, and the morphology, structure and composition of the three catalysts have been characterized. The photoelectrochemical properties of the catalyst were measured by a three electrode system electrochemical workstation. The main contents are as follows: (1) the nife-CoFe Prussian blue analogue was synthesized by chemical coprecipitation. NiFe_2O_4/C and CoFe_2O_4/C nanocomposite catalysts were prepared by pyrolysis in ar atmosphere at high temperature. The characterization results show that the spinel cubic CoFe_2O_4 nanoparticles are uniformly dispersed on the in-situ carbon substrate. The oxygen evolution activity and stability of NiFe_2O_4/C and CoFe_2O_4/C nanocomposites were measured in 1m KOH electrolyte. The experimental results show that NiFe_2O_4/C and CoFe_2O_4/C nanocomposite catalysts have good catalytic activity, and the initial potential is 1.48 V / V 1.51 V vs. RHE, respectively. The stability of NiFe2O4 / C catalyst was measured by chronopotentiometry at a current density of 10 Ma cm-2 for 8 hours. (2) the Schiff base complexes of vanillin acylamino thiourea and nickel were designed and synthesized. Using thiourea as the precursor, NiO-NiS/N-C nanocomposite catalyst. XRDX SEM and TEM were prepared after pyrolysis in ar atmosphere. The results showed that the in situ formed nio nis nanoparticles were uniformly dispersed on the nitrogen-doped carbon substrates of organic complex decomposition. The catalytic activity and stability of NiO-NiS/N-C nanocomposite catalyst were tested in 1m KOH electrolyte. The experimental results show that the NiO-NiS/N-C nanocomposite catalyst exhibits good catalytic activity. The initial potential is 1.56 V vs. RHE. the overpotential required to reach 10 Ma cm-2 current density is 374 MV, and the Taffel slope is 44.7 MV dec-1. After 10 hours stability test at 10 Ma cm-2 current density, the activity of the catalyst did not change obviously, which indicated that the catalyst had good stability in alkaline environment. (3) FTO was used as conductive substrate. 伪 -Fe _ S _ 2O _ 3 nanorod array films were prepared by hydrothermal method. Subsequently, the CoP nanoparticles prepared by low-temperature phosphating method were deposited on the surface of 伪 -FeTi2O3 nanorod array (loaded with 0.01mg cm-2), and the CoP/ 伪 -Fe2O3 photoanode was prepared. The photochemical results showed that the photocurrent density of CoP / 伪 -Fe _ 2O _ 3 at 1.23 V vs.RHE increased by 44% compared with the original 伪 -Fe _ 2O _ 3 nanorod array, and reached 0.72 Ma cm ~ (-2). The electrochemical impedance spectroscopy showed that the charge transfer resistance of 伪 -Fe _ (2) O _ (2) O _ (3) nanoparticles on the surface of 伪 -Fe _ (2) O _ (2) O _ (3) decreased obviously. The Mott-Schottky curve shows that the carrier density of the CoP/ 伪 -Fe _ 2O _ 3 photoanode is higher. Cop is deposited on the 伪 -Fe _ 2O _ 3 nanorod array surface, which effectively reduces the electron-hole pair recombination and accelerates the oxygen evolution reaction at the semiconductor / catalyst interface.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
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