Stadler Daniel, Brede Thomas, Schwarzbach Danny, Maccari Fernando, Fischer Thomas, Gutfleisch Oliver, Volkert Cynthia A, Mathur Sanjay
Institute of Inorganic Chemistry, Department of Chemistry, University of Cologne Greinstr. 6 D-50939 Cologne Germany
Institute of Materials Physics, University of Goettingen Friedrich-Hund-Platz 1 D-37077 Goettingen Germany.
Nanoscale Adv. 2019 Oct 17;1(11):4290-4295. doi: 10.1039/c9na00467j. eCollection 2019 Nov 5.
Chemical vapor deposition of iron pentacarbonyl (Fe(CO)) in an external magnetic field ( = 1.00 T) was found to significantly affect the microstructure and anisotropy of as-deposited iron crystallites that could be transformed into anisotropic hematite (α-FeO) nanorods by aerobic oxidation. The deterministic influence of external magnetic fields on CVD deposits was found to be substrate-independent as demonstrated by the growth of anisotropic α-Fe columns on FTO (F:SnO) and Si (100), whereas the films deposited in the absence of the magnetic field were constituted by isotropic grains. TEM images revealed gradual increase in average crystallite size in correlation to the increasing field strength and orientation, which indicates the potential of magnetic field-assisted chemical vapor deposition (mfCVD) in controlling the texture of the CVD grown thin films. Given the facet-dependent activity of hematite in forming surface-oxygenated intermediates, exposure of crystalline facets and planes with high atomic density and electron mobilities is crucial for oxygen evolution reactions. The field-induced anisotropy in iron nanocolumns acting as templates for growing textured hematite pillars resulted in two-fold higher photoelectrochemical efficiency for hematite films grown under external magnetic fields ( = 0.050 mA cm), when compared to films grown in zero field ( = 0.027 mA cm). The dark current measurements indicated faster surface kinetics as the origin of the increased catalytic activity.
发现在外部磁场(= 1.00 T)中五羰基铁(Fe(CO)₅)的化学气相沉积会显著影响沉积态铁微晶的微观结构和各向异性,这些微晶通过有氧氧化可转变为各向异性的赤铁矿(α-Fe₂O₃)纳米棒。如在FTO(F:SnO₂)和Si(100)上生长各向异性的α-Fe柱所证明的,外部磁场对化学气相沉积沉积物的决定性影响与基底无关,而在无磁场情况下沉积的薄膜由各向同性晶粒构成。透射电子显微镜图像显示,平均微晶尺寸随着场强和取向的增加而逐渐增大,这表明磁场辅助化学气相沉积(mfCVD)在控制化学气相沉积生长的薄膜织构方面具有潜力。鉴于赤铁矿在形成表面氧化中间体方面的晶面依赖性活性,暴露具有高原子密度和电子迁移率的晶面和平面对于析氧反应至关重要。作为生长织构化赤铁矿柱模板的铁纳米柱中的场诱导各向异性,使得在外部磁场(= 0.050 mA cm⁻²)下生长的赤铁矿薄膜的光电化学效率比在零磁场(= 0.027 mA cm⁻²)下生长的薄膜高出两倍。暗电流测量表明,更快的表面动力学是催化活性增加的原因。