Commandeur Daniel, McGuckin Joshua, Chen Qiao
Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, BN1 9QJ, United Kingdom.
Nanotechnology. 2020 Apr 9;31(26):265403. doi: 10.1088/1361-6528/ab776c. Epub 2020 Feb 18.
For the first time, hematite (α-FeO) crystals were electrochemically deposited over vertically aligned conductive zinc oxide nanorods (NR) to form a specially designed 3D heterostructure with a unique triple layer structure. The structure formed with a thin layer of ZnFeO sandwiched between the hematite and the ZnO, which forms a barrier to reduce the back migration of holes. Hence, the charge separation is significantly improved. The small unequal bandgaps of α-FeO and ZnFeO help to enhance and broaden visible light absorption. The electron transportation was further improved by yttrium doping in the ZnO (YZnO) NRs, resulting in increased conductivity. This allowed the vertically aligned NRs to perform as electron highways, which also behave as effective optical waveguides for improved light trapping and absorption, since ZnO absorbs little visible light. All these benefits made the unique structures suitable for high performance photoelectrochemical (PEC) water splitting. Optimisation of α-FeO thickness led to a photocurrent density improvement from 0.66 to 0.95 mA cm at 1.23 V. This was further improved to 1.59 mA cm by annealing at 550 °C for 3 h, representing a record-breaking photocurrent for α-FeO/ZnO systems. Finally IPCE confirmed the successful generation and transfer of photoelectrons under visible light excitation in the specifically designed heterostructure photoanode, with 5% efficiency for blue light, and 15% for violet light.
首次通过电化学方法将赤铁矿(α-Fe₂O₃)晶体沉积在垂直排列的导电氧化锌纳米棒(NR)上,形成具有独特三层结构的特殊设计的三维异质结构。该结构由夹在赤铁矿和氧化锌之间的一层薄薄的ZnFe₂O₄构成,形成一个势垒以减少空穴的反向迁移。因此,电荷分离得到显著改善。α-Fe₂O₃和ZnFe₂O₄的小且不相等的带隙有助于增强和拓宽可见光吸收。通过在ZnO(YZnO)纳米棒中掺杂钇进一步改善了电子传输,从而提高了导电性。这使得垂直排列的纳米棒能够充当电子高速公路,由于ZnO几乎不吸收可见光,它们还充当有效的光波导以改善光捕获和吸收。所有这些优点使得这种独特结构适用于高性能光电化学(PEC)水分解。α-Fe₂O₃厚度的优化使光电流密度在1.23 V时从0.66提高到0.95 mA/cm²。通过在550°C下退火3小时,光电流密度进一步提高到1.59 mA/cm²,这代表了α-Fe₂O₃/ZnO体系的破纪录光电流。最后,IPCE证实了在专门设计的异质结构光阳极中,在可见光激发下光电子的成功产生和转移,蓝光效率为5%,紫光效率为15%。