Inverse Opal CuCrO2 Photocathodes for H2 Production Using Organic Dyes and a Molecular Ni Catalyst

Creissen, Charles E.; Warnan, Julien; Antón-García, Daniel; Farré, Yoann; Odobel, Fabrice; Reisner, Erwin

Abstract

Dye-sensitized photoelectrochemical (DSPEC) cells are an emerging approach to producing solar fuels. The recent development of delafossite CuCrO2 as a p-type semiconductor has enabled H2 generation through the coassembly of catalyst and dye components. Here, we present a CuCrO2 electrode based on a high-surface-area inverse opal (IO) architecture with benchmark performance in DSPEC H2 generation. Coimmobilization of a phosphonated diketopyrrolopyrrole (DPP-P) or perylene monoimide (PMI-P) dye with a phosphonated molecular Ni catalyst (NiP) demonstrates the ability of IO-CuCrO2 to photogenerate H2. A positive photocurrent onset potential of approximately +0.8 V vs RHE was achieved with these photocathodes. The DPP-P-based photoelectrodes delivered photocurrents of −18 μA cm–2 and generated 160 ± 24 nmol of H2 cm–2, whereas the PMI-P-based photocathodes displayed higher photocurrents of −25 μA cm–2 and produced 215 ± 10 nmol of H2 cm–2 at 0.0 V vs RHE over the course of 2 h under visible light illumination (100 mW cm–2, AM 1.5G, λ > 420 nm, 25 °C). The high performance of the PMI-constructed system is attributed to the well-suited molecular structure and photophysical properties for p-type sensitization. These precious-metal-free photocathodes highlight the benefits of using bespoke IO-CuCrO2 electrodes as well as the important role of the molecular dye structure in DSPEC fuel synthesis.

Citation

Creissen, C. E., Warnan, J., Antón-García, D., Farré, Y., Odobel, F., & Reisner, E. (2019). Inverse Opal CuCrO2 Photocathodes for H2 Production Using Organic Dyes and a Molecular Ni Catalyst. ACS catalysis, 9(10), 9530-9538. https://doi.org/10.1021/acscatal.9b02984

• Journal Article Type: Article
• Online Publication Date: Sep 9, 2019
• Publication Date: Oct 4, 2019
• Deposit Date: May 30, 2023
• Journal: ACS Catalysis
• Electronic ISSN: 2155-5435
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 9
• Issue: 10
• Pages: 9530-9538
• DOI: https://doi.org/10.1021/acscatal.9b02984
• Keywords: Catalysis; General Chemistry