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Direct Deposition of Amorphous Cobalt–VanadiumMixed Oxide Films for Electrocatalytic Water Oxidation

机译:非晶态钴-钒的直接沉积用于电催化水氧化的混合氧化物薄膜

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摘要

Efficiency of water oxidation catalysts in terms of overpotential, current density, and voltage stability over time with facile methods of their fabrication remains a key challenge in developing competent mechanisms of storing energy in the form of green hydrogen fuels. In this work, a rapid one-step aerosol-assisted chemical vapor deposition (AACVD) method is employed to synthesize amorphous and highly active cobalt–vanadium mixed oxide catalysts (CoVOx) directly over fluorine-doped tin oxide (FTO) substrates. Morphological and structural characterizations made by field emission scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy techniques revealed the formation of pure-phase amorphous films with a gradual variation of topography as a function of deposition time. Of these films, the most active film (CoVOx-20) was obtained in 20 min deposition, showing a spongy networking of interwoven nanofibers with a homogeneous distribution of 3–4 nm pores, achieving an overpotential of 308 mV at 10mA/cm2 current density. A much higher current density of175 mA/cm2 could be achieved just at 380 mV of overpotentialwith Tafel slope as low as 62 mV/dec for this whole range while exhibitinglong-term stability. Mass activity, electrochemical impedance spectroscopydata, and the estimation of electrochemically active surface areaall endorsed this high catalytic performance of CoVOx-20,which is unprecedented for a low-cost, upscalable, and relativelyless conductive substrate such as FTO used here. Our findings, thus,not only highlight the benefits of using AACVD in preparing two-dimensionalamorphous catalysts but also prove the high efficiency of CoVOx materials thus obtained, as outlined in a plausible reactionmechanism.
机译:利用易于制造的方法,水氧化催化剂在过电位,电流密度和随时间变化的电压稳定性方面的效率,仍然是开发以绿色氢燃料形式储存能量的有效机制中的关键挑战。在这项工作中,一种快速的一步式气溶胶辅助化学气相沉积(AACVD)方法被用来直接在掺氟氧化锡(FTO)衬底上合成非晶态和高活性钴-钒混合氧化物催化剂(CoVOx)。通过场发射扫描电子显微镜,X射线衍射,能量色散X射线光谱学和X射线光电子能谱技术进行的形态和结构表征揭示了纯相非晶膜的形成,其形貌随功能逐渐变化沉积时间。在这些薄膜中,活性最高的薄膜(CoVOx-20)在20分钟的沉积过程中获得,显示出交织的纳米纤维海绵状网络,具有均匀分布的3-4 nm孔,在10时可达到308 mV的过电势mA / cm 2 电流密度。更高的电流密度仅在380 mV的超电势下即可达到175 mA / cm 2 在整个范围内,Tafel斜率低至62 mV / dec长期稳定。质量活度,电化学阻抗谱数据,以及电化学活性表面积的估计所有人都认可CoVOx-20的这种高催化性能,对于低成本,可升级和相对而言这是前所未有的导电性较低的基材,例如此处使用的FTO。因此,我们的发现不仅突出了使用AACVD制备二维电极的好处无定形催化剂,但也证明了如此获得的CoVOx材料的高效率,如合理的反应所述机制。

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