Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, Santa Cruz, CA 95064 (USA).
ChemSusChem. 2014 Mar;7(3):848-53. doi: 10.1002/cssc.201301013. Epub 2014 Feb 3.
Hematite (α-Fe2 O3 ) nanostructures have been extensively studied as photoanode materials for photoelectrochemical (PEC) water oxidation. However, the photoactivity of pristine hematite nanostructures is fairly low and typically requires thermal activation at temperature of 650 °C or above. Here, we report a new method for enhancing the photocurrent of hematite nanowires at a substantially lower temperature of 350 °C by means of a two-step annealing process (activation process). Hydrothermally grown β-FeOOH nanowires were first annealed in a pure N2 environment at 350 °C to form magnetite, followed by partial oxidation in air to convert magnetite to hematite. During this process, Fe(2+) sites (oxygen vacancies) were intentionally created to increase the donor density and therefore the electrical conductivity of hematite. The oxygen-deficient hematite nanowire photoanode created at low temperature (350 °C) show considerably enhanced photoactivity compared to pristine hematite sample that prepared by thermal annealing of β-FeOOH nanowires at 550 °C in air. Moreover, this low-temperature annealing method can be coupled with an element doping method to further increase the photoactivity of hematite nanowire. Sn-doped hematite nanowires prepared by the same low-temperature annealing method show at least three fold enhanced photocurrent compared to the undoped sample. Significantly, the highest temperature in the entire annealing process was 350 °C, which is the lowest activation temperature ever reported for hematite nanowire photoanodes.
赤铁矿 (α-Fe2O3) 纳米结构作为光电化学 (PEC) 水氧化的光阳极材料得到了广泛的研究。然而,原始赤铁矿纳米结构的光活性相当低,通常需要在 650°C 或更高的温度下进行热激活。在这里,我们报告了一种新的方法,可以通过两步退火过程(激活过程)在低得多的 350°C 温度下提高赤铁矿纳米线的光电流。首先,将水热生长的β-FeOOH 纳米线在纯 N2 环境中于 350°C 退火以形成磁铁矿,然后在空气中部分氧化以将磁铁矿转化为赤铁矿。在此过程中,故意创建 Fe(2+) 位(氧空位)以增加施主密度,从而提高赤铁矿的电导率。与在空气中通过β-FeOOH 纳米线的热退火在 550°C 制备的原始赤铁矿样品相比,在低温(350°C)下制备的缺氧气赤铁矿纳米线光阳极表现出相当大的增强的光活性。此外,这种低温退火方法可以与元素掺杂方法相结合,进一步提高赤铁矿纳米线的光活性。通过相同的低温退火方法制备的 Sn 掺杂赤铁矿纳米线的光电流比未掺杂样品至少提高了三倍。重要的是,整个退火过程中的最高温度为 350°C,这是赤铁矿纳米线光阳极报道的最低激活温度。