Photocurrent of BiVO4 is limited by surface recombination, not surface catalysis.

نویسندگان

  • Carolin Zachäus
  • Fatwa F Abdi
  • Laurence M Peter
  • Roel van de Krol
چکیده

Bismuth vanadate is one of the most promising photoanode materials for photoelectrochemical water splitting. In order to achieve high photocurrents the surface of BiVO4 always has to be modified with water oxidation catalysts, such as cobalt phosphate (CoPi), FeOOH, or NiFeO x . While this has generally been attributed to the poor intrinsic catalytic activity of BiVO4, detailed insight into the fate of the photogenerated charge carriers at the surface is still lacking. We used intensity modulated photocurrent spectroscopy (IMPS) to investigate the surface carrier dynamics of bare and CoPi-modified spray-deposited BiVO4 films. Using a model developed by Peter et al., it was possible to distinguish the reaction rate constants for surface recombination and charge transfer to the electrolyte. We found that modification with CoPi reduced the surface recombination of BiVO4 with a factor of 10-20, without significantly influencing the charge transfer kinetics. Control experiments with RuO x , one of the best known OER electrocatalysts, did not affect surface recombination and led to an actual decrease of the photocurrent. These results show that the main role of the CoPi is to passivate the surface of BiVO4 and that, contrary to earlier assumptions, the photocurrent of BiVO4 is limited by surface recombination instead of charge transfer. The importance of surface recombination is well recognized for conventional semiconductors in the field of photovoltaics; these findings show that it may also play a crucial role in oxide-based semiconductors for photoelectrochemical energy conversion.

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منابع مشابه

Efficient suppression of back electron/hole recombination in cobalt phosphate surface-modified undoped bismuth vanadate photoanodes† †Electronic supplementary information (ESI) available: XRD characterization and SEM images of CoPi-modified and unmodified BiVO4, continuous illumination J–V curves, transient absorption fit results, and transient absorption decays measured as a function of excitation intensities. See DOI: 10.1039/c5ta05826k Click here for additional data file.

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عنوان ژورنال:
  • Chemical science

دوره 8 5  شماره 

صفحات  -

تاریخ انتشار 2017