Insights into the mechanism and aging of a noble-metal free H2-evolving dye-sensitized photocathode

Nicolas Kaeffer; Christopher Windle; Romain Brisse; Corinne Gablin; Didier Léonard; Bruno Jousselme; Murielle Chavarot-Kerlidou; Vincent Artero

Insights into the mechanism and aging of a noble-metal free H2-evolving dye-sensitized photocathode

Nicolas Kaeffer ¹ Christopher Windle ¹ Romain Brisse ² Corinne Gablin ³ Didier Léonard ³ Bruno Jousselme ² Murielle Chavarot-Kerlidou ¹ Vincent Artero ^{1, *}

* Corresponding author

1 LCBM - UMR 5249 - Laboratoire de Chimie et Biologie des Métaux

2 LICSEN - Laboratoire Innovation en Chimie des Surfaces et NanoSciences

NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)

3 Surfaces

ISA - Institut des Sciences Analytiques

Abstract : Dye-sensitized photo-electrochemical cells (DS-PECs) form an emerging technology for the large-scale storage of solar energy in the form of (solar) fuels because of the low cost and ease of processing of their constitutive photoelectrode materials. Preparing such molecular photocathodes requires a well-controlled co-immobilization of molecular dyes and catalysts onto transparent semiconducting materials. Here we used a series of surface analysis techniques to describe the molecular assembly of a push-pull organic dye and a cobalt diimine-dioxime catalyst co-grafted on a p-type NiO electrode substrate. (Photo) electrochemical measurements allowed characterization of electron transfer processes within such an assembly and to demonstrate for the first time that a Co$^I$ species is formed as the entry into the light-driven H$_2$ evolution mechanism of a dye-sensitized photocathode. This co-grafted noble-metal free H$_2$-evolving photocathode architecture displays similar performances to its covalent dye-catalyst counterpart based on the same catalytic moiety. Post-operando time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of these photoelectrodes after extensive photoelectrochemical operation suggested decomposition pathways of the dye and triazole linkage used to graft the catalyst onto NiO, providing grounds for the design of optimized molecular DS-PEC components with increased robustness upon turnover.

Document type :

Journal articles

Domain :

Chemical Sciences / Material chemistry

Chemical Sciences / Catalysis

Complete list of metadatas

Cited literature [40 references] Display Hide Download

https://hal-cea.archives-ouvertes.fr/cea-01884495
Contributor : Serge Palacin <>
Submitted on : Monday, October 1, 2018 - 10:00:28 AM
Last modification on : Monday, June 3, 2019 - 3:46:34 PM

c8sc00899j.pdf

Publisher files allowed on an open archive

Insights into the mechanism and aging of a noble-metal free H2-evolving dye-sensitized photocathode

File

Identifiers

Collections

Citation

Export

Metrics

101

72

Contact

Insights into the mechanism and aging of a noble-metal free H2-evolving dye-sensitized photocathode

File

Identifiers

Collections

Citation

Export

Share

Metrics

101

72

Contact