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Spinel Structural Disorder Influences Solar-Water-Splitting Performance of ZnFe 2 O 4 Nanorod Photoanodes

Spinel Structural Disorder Influences Solar-Water-Splitting Performance of ZnFe 2 O 4 Nanorod Photoanodes

Xiaodi Zhu, Néstor Guijarro, Yongpeng Liu, Pascal Schouwink, Rebekah A Wells, Florian Le Formal, Song Sun, Chen Gao, Kevin Sivula

Adv Mater. 2018 Jul 5;e1801612.

PMID: 29975805

Abstract:

Zinc spinel ferrite, ZnFe2 O4 (ZFO), is an emerging photoanode material for photoelectrochemical (PEC) solar fuel production. However, a lack of fundamental insight into the factors limiting the photocurrent has prevented substantial advance in its performance. Herein, it is found that ZFO nanorod array photoelectrodes with varying crystallinity exhibit vastly different PEC properties. Using a sacrificial hole scavenger (H2 O2 ), spatially defined carrier generation, and electrochemical impedance spectroscopy, it is shown that ZFO with a relatively poor crystallinity but a higher spinel inversion degree (due to cation disorder) exhibits superior photogenerated charge separation efficiency and improved majority charge carrier transport compared to ZFO with higher crystallinity and a lower inversion degree. Conversely, the latter condition leads to better charge injection efficiency. Optimization of these factors, and the addition of a nickel-iron oxide cocatalyst overlayer, leads to a new benchmark solar photocurrent for ZFO of 1.0 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE) and 1.7 mA cm-2 at 1.6 V versus RHE. Importantly, the observed correlation between the cation disorder and the PEC performance represents a new insight into the factors important to the PEC performance of the spinel ferrites and suggests a path to further improvement.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP12645500	Nickel zinc iron oxide		12645-50-0	Price

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