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Comparison of photoelectrochemical water oxidation activity of a synthetic photocatalyst system with photosystem II.


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Type

Article

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Authors

Lai, Yi-Hsuan 
Kato, Masaru 
Mersch, Dirk 

Abstract

This discussion describes a direct comparison of photoelectrochemical (PEC) water oxidation activity between a photosystem II (PSII)-functionalised photoanode and a synthetic nanocomposite photoanode. The semi-biological photoanode is composed of PSII from the thermophilic cyanobacterium Thermosynechococcus elongatus on a mesoporous indium tin oxide electrode (mesoITO|PSII). PSII embeds all of the required functionalities for light absorption, charge separation and water oxidation and ITO serves solely as the electron collector. The synthetic photoanode consists of a TiO(2) and NiO(x) coated nanosheet-structured WO(3) electrode (nanoWO(3)|TiO(2)|NiO(x)). The composite structure of the synthetic electrode allows mimicry of the functional key features in PSII: visible light is absorbed by WO(3), TiO(2) serves as a protection and charge separation layer and NiO(x) serves as the water oxidation electrocatalyst. MesoITO|PSII uses low energy red light, whereas nanoWO(3)|TiO(2)|NiO(x) requires high energy photons of blue-end visible and UV regions to oxidise water. The electrodes have a comparable onset potential at approximately 0.6 V vs. reversible hydrogen electrode (RHE). MesoITO|PSII reaches its saturation photocurrent at 0.84 V vs. RHE, whereas nanoWO(3)|TiO(2)NiO(x) requires more than 1.34 V vs. RHE. This suggests that mesoITO|PSII suffers from fewer limitations from charge recombination and slow water oxidation catalysis than the synthetic electrode. MesoITO|PSII displays a higher 'per active' site activity, but is less photostable and displays a much lower photocurrent per geometrical surface area and incident photon to current conversion efficiency (IPCE) than nanoWO(3)|TiO(2)|NiO(x_.

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Keywords

0306 Physical Chemistry (incl. Structural), 0302 Inorganic Chemistry

Journal Title

Faraday Discuss

Conference Name

Journal ISSN

1359-6640
1364-5498

Volume Title

176

Publisher

Royal Society of Chemistry (RSC)
Sponsorship
Engineering and Physical Sciences Research Council (EP/H00338X/2)
Financial support from EPSRC (EP/H00338X/2 to E. R. and nanoDTC to D. M.), the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and National Foundation for Research, Technology and Development), the OMV Group (to E. R.) and Cambridge Trust (to Y.-H. L.) are gratefully acknowledged.