基于金屬有機配合物分解制備（光）電催化劑及其水分解性能研究
發(fā)布時間：2018-08-23 13:47
【摘要】：能源作為人類社會活動的物質(zhì)基礎(chǔ),是可持續(xù)發(fā)展中重要的一部分,提高能源利用效率和開發(fā)新能源是解決當前社會能源危機的有效途徑。氧析出反應(yīng)由于在可充電燃料電池、水分解制氫和金屬空氣電池等各種能量轉(zhuǎn)換和存儲技術(shù)中起著重要作用,開發(fā)廉價、高效率、高選擇性的析氧催化劑是十分必要的。本論文基于過渡金屬(Ni、Co、Fe)有機配合物,分別構(gòu)建了Ni(Co)Fe_2O_4/C,NiO-NiS/N-C,CoP/α-Fe_2O_3三種陽極析氧光電催化劑,并對三種催化劑的形貌、結(jié)構(gòu)和組成進行了表征,通過三電極體系電化學(xué)工作站測試了催化劑的光電化學(xué)性能。主要內(nèi)容如下:(1)采用化學(xué)共沉淀法合成了NiFe,CoFe普魯士藍類似物,在Ar氣氛下高溫熱解后得到NiFe_2O_4/C和CoFe_2O_4/C納米復(fù)合催化劑。表征結(jié)果表明:尖晶石立方相的CoFe_2O_4納米顆粒均勻分散在原位生成的碳基底上。在1 M KOH電解液中,測試了NiFe_2O_4/C和CoFe_2O_4/C納米復(fù)合材料的析氧活性及穩(wěn)定性。實驗結(jié)果表明NiFe_2O_4/C和CoFe_2O_4/C納米復(fù)合催化劑具有良好的催化活性,起始電位分別為1.48 V,1.51 V vs.RHE。采用計時電位法在10 mA cm-2電流密度下經(jīng)過8小時穩(wěn)定性測試,NiFe_2O_4/C催化劑的析氧性能沒有發(fā)生明顯衰減。(2)設(shè)計合成了香草醛縮胺基硫脲合鎳的席夫堿配合物,并混合硫脲作為前驅(qū)體,在Ar氣氛下高溫熱解后得到NiO-NiS/N-C納米復(fù)合催化劑。XRD,SEM和TEM等表征結(jié)果表明:原位生成的NiO,NiS納米顆粒均勻分散在有機配合物分解的氮摻雜的碳基底上。在1 M KOH電解液中對NiO-NiS/N-C納米復(fù)合催化劑的催化活性與穩(wěn)定性進行了測試。實驗結(jié)果表明NiO-NiS/N-C納米復(fù)合催化劑表現(xiàn)出良好的催化活性,起始電位為1.56 V vs.RHE,達到10 mA cm-2電流密度所需的過電位為374 mV,塔菲爾斜率為44.7 mV dec-1。在10 mA cm-2電流密度下經(jīng)過10小時穩(wěn)定性測試之后,催化劑活性沒有發(fā)生明顯變化,表明該催化劑在堿性環(huán)境中其具有良好的穩(wěn)定性。(3)以FTO為導(dǎo)電基底,采用水熱法制備了α-Fe_2O_3納米棒陣列薄膜。隨后,將低溫磷化法制備的CoP納米顆粒沉積在α-Fe_2O_3納米棒陣列表面(負載量為0.01 mg cm-2),制備了CoP/α-Fe_2O_3光陽極。光電化學(xué)測試結(jié)果顯示:在1.23 V vs.RHE下,CoP/α-Fe_2O_3的光電流密度相比原始α-Fe_2O_3納米棒陣列增大了44%,達到0.72 mA cm-2,電化學(xué)阻抗譜測試表明CoP納米顆粒明顯減小了α-Fe_2O_3表面的電荷轉(zhuǎn)移電阻,莫特-肖特基曲線表明CoP/α-Fe_2O_3光陽極的載流子密度更高。CoP沉積在α-Fe_2O_3納米棒陣列表面,有效減少了電子-空穴對的復(fù)合,加速了半導(dǎo)體/催化劑界面的析氧反應(yīng)。
[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 / 偽 -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. 偽 -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 偽 -FeTi2O3 nanorod array (loaded with 0.01mg cm-2), and the CoP/ 偽 -Fe2O3 photoanode was prepared. The photochemical results showed that the photocurrent density of CoP / 偽 -Fe _ 2O _ 3 at 1.23 V vs.RHE increased by 44% compared with the original 偽 -Fe _ 2O _ 3 nanorod array, and reached 0.72 Ma cm ~ (-2). The electrochemical impedance spectroscopy showed that the charge transfer resistance of 偽 -Fe _ (2) O _ (2) O _ (3) nanoparticles on the surface of 偽 -Fe _ (2) O _ (2) O _ (3) decreased obviously. The Mott-Schottky curve shows that the carrier density of the CoP/ 偽 -Fe _ 2O _ 3 photoanode is higher. Cop is deposited on the 偽 -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.
【學(xué)位授予單位】：石河子大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36
本文編號：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 / 偽 -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. 偽 -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 偽 -FeTi2O3 nanorod array (loaded with 0.01mg cm-2), and the CoP/ 偽 -Fe2O3 photoanode was prepared. The photochemical results showed that the photocurrent density of CoP / 偽 -Fe _ 2O _ 3 at 1.23 V vs.RHE increased by 44% compared with the original 偽 -Fe _ 2O _ 3 nanorod array, and reached 0.72 Ma cm ~ (-2). The electrochemical impedance spectroscopy showed that the charge transfer resistance of 偽 -Fe _ (2) O _ (2) O _ (3) nanoparticles on the surface of 偽 -Fe _ (2) O _ (2) O _ (3) decreased obviously. The Mott-Schottky curve shows that the carrier density of the CoP/ 偽 -Fe _ 2O _ 3 photoanode is higher. Cop is deposited on the 偽 -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.
【學(xué)位授予單位】：石河子大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36
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