ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia.
ACS Appl Mater Interfaces. 2013 Jun 12;5(11):5269-75. doi: 10.1021/am401112q. Epub 2013 Jun 3.
The current work demonstrates the importance of WO3 crystallinity in governing both photoenergy conversion efficiency and storage capacity of the flower structured WO3 electrode. The degree of crystallinity of the WO3 electrodes was varied by altering the calcination temperature from 200 to 600 °C. For the self-photochargeability phenomenon, the prevailing flexibility of the short-range order structure at low calcination temperature of 200 °C favors the intercalation of the positive cations, enabling more photoexcited electrons to be stored within WO3 framework. This leads to a larger amount of stored charges that can be discharged in an on-demand manner under the absence of irradiation for H2 generation. The stability of the electrodes calcined at 200 °C, however, is compromised because of the structural instability caused by the abundance insertion of cations. On the other hand, films that were calcined at 400 °C displayed the highest stability toward both intercalation of the cations and photoelectrochemical water splitting performance. Although crystallinty of WO3 was furthered improved at 600 °C heat treatment, the worsened contact between the WO3 platelets and the conducting substrate as induced by the significant sintering has been more detrimental toward the charge transport.
本工作证明了 WO3 结晶度在控制花状 WO3 电极的光电能量转换效率和存储容量方面的重要性。通过将煅烧温度从 200°C 改变到 600°C 来改变 WO3 电极的结晶度。对于自充电现象,在 200°C 的低温煅烧下,短程有序结构的灵活性有利于正离子的嵌入,从而使更多的光激发电子存储在 WO3 骨架内。这导致在没有光照的情况下,可以按需释放出更多的可放电电荷量,用于 H2 的生成。然而,由于阳离子大量插入引起的结构不稳定性,在 200°C 下煅烧的电极的稳定性受到了影响。另一方面,在 400°C 下煅烧的薄膜在阳离子的嵌入和光电化学水分解性能方面表现出最高的稳定性。尽管在 600°C 的热处理下 WO3 的结晶度进一步提高,但由于显著的烧结导致 WO3 薄片与导电基底之间的接触恶化,这对电荷输运更为不利。