Abnormal Effects of Cations (Li+, Na+, and K+) on Photoelectrochemical and Electrocatalytic Water Splitting

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State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian 116023, China
*E-mail: [email protected]. Tel: 86-411-84379070. Fax: 86-411-84694447. Homepage: http://www.canli.dicp.ac.cn.
Cite this: J. Phys. Chem. B 2015, 119, 8, 3560–3566
Publication Date (Web):February 2, 2015
Copyright © 2015 American Chemical Society
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The electrode–electrolyte interface chemistry is highly important for photoelectrochemical (PEC) and electrocatalytic water splitting where cations in the electrolyte are often crucial. However, the roles of cations in an electrolyte are much debated and not well-understood. This work reports that the PEC and electrocatalytic water oxidation (WO) activities in basic electrolytes with different cations follow an unexpected trend (Li+ > K+ > Na+) especially for long-term reaction. Such an abnormal order of activity is found to be the balance effect of two factors: the distinct extents of the weakening of O–H bond on electrode surface after interacting with cations in different electrolytes and the different rates of oxygen reduction reaction (ORR) which turns out to be dominant. Li+ not only brings the most significant decrease of O–H bond strength but also is most effective for avoiding back reaction, while Na+ shows the most detrimental effect on WO because of ORR. Our results provide important insight into the roles of cations in WO and demonstrate a new strategy of tailoring the electrode–electrolyte interface via judicious choice of cations in electrolyte for more efficient PEC and electrocatalytic water splitting.

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Details about chemicals and materials, preparation of the electrolytes, fabrication of electrodes, (photo)electrochemical characterizations, characterizations and electrochemical measurements, computational methods, It curves (Figures S1 and S3), linear sweep voltammetric curves (Figures S2 and S4), XRD patterns (Figure S5), and the activities of photoanode before and after loading cocatalyst (Figures S6 and S7). This material is available free of charge via the Internet at http://pubs.acs.org.

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