Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, United States.
Nano Lett. 2011 May 11;11(5):2119-25. doi: 10.1021/nl200708y. Epub 2011 Apr 8.
We report on the synthesis and characterization of Sn-doped hematite nanowires and nanocorals as well as their implementation as photoanodes for photoelectrochemical water splitting. The hematite nanowires were prepared on a fluorine-doped tin oxide (FTO) substrate by a hydrothermal method, followed by high temperature sintering in air to incorporate Sn, diffused from the FTO substrate, as a dopant. Sn-doped hematite nanocorals were prepared by the same method, by adding tin(IV) chloride as the Sn precursor. X-ray photoelectron spectroscopy analysis confirms Sn(4+) substitution at Fe(3+) sites in hematite, and Sn-dopant levels increase with sintering temperature. Sn dopant serves as an electron donor and increases the carrier density of hematite nanostructures. The hematite nanowires sintered at 800 °C yielded a pronounced photocurrent density of 1.24 mA/cm(2) at 1.23 V vs RHE, which is the highest value observed for hematite nanowires. In comparison to nanowires, Sn-doped hematite nanocorals exhibit smaller feature sizes and increased surface areas. Significantly, they showed a remarkable photocurrent density of 1.86 mA/cm(2) at 1.23 V vs RHE, which is approximately 1.5 times higher than that of the nanowires. Ultrafast spectroscopy studies revealed that there is significant electron-hole recombination within the first few picoseconds, while Sn doping and the change of surface morphology have no major effect on the ultrafast dynamics of the charge carriers on the picosecond time scales. The enhanced photoactivity in Sn-doped hematite nanostructures should be due to the improved electrical conductivity and increased surface area.
我们报告了 Sn 掺杂赤铁矿纳米线和纳米珊瑚的合成与表征,以及它们作为光电化学水分解光阳极的应用。赤铁矿纳米线是通过水热法在掺氟氧化锡(FTO)衬底上制备的,然后在空气中进行高温烧结,使来自 FTO 衬底的 Sn 扩散并作为掺杂剂掺入。Sn 掺杂赤铁矿纳米珊瑚是通过相同的方法制备的,方法是添加四氯化锡作为 Sn 前体。X 射线光电子能谱分析证实 Sn(4+)取代了赤铁矿中的 Fe(3+)位,并且随着烧结温度的升高,Sn 掺杂剂的浓度增加。Sn 掺杂剂作为电子供体,增加了赤铁矿纳米结构的载流子密度。在 800°C 下烧结的赤铁矿纳米线在 1.23 V vs RHE 时产生了明显的光电流密度 1.24 mA/cm(2),这是赤铁矿纳米线中观察到的最高值。与纳米线相比,Sn 掺杂赤铁矿纳米珊瑚具有更小的特征尺寸和更大的表面积。值得注意的是,它们在 1.23 V vs RHE 时表现出显著的光电流密度 1.86 mA/cm(2),约为纳米线的 1.5 倍。超快光谱研究表明,在最初的几个皮秒内就存在显著的电子-空穴复合,而 Sn 掺杂和表面形貌的变化对皮秒时间尺度上载流子的超快动力学没有重大影响。Sn 掺杂赤铁矿纳米结构的增强光活性应归因于提高的电导率和增加的表面积。