Establishing stability in organic semiconductor photocathodes for solar hydrogen production

Research output: Contribution to journalArticlepeer-review

  • External authors:
  • Liang Yao
  • Nestor Guijarro
  • Florent Boudoire
  • Yongpeng Liu
  • Rebekah A. Wells
  • Arvindh Sekar
  • Han-Hee Cho
  • Jun-Ho Yum
  • Florian Le Formal
  • Kevin Sivula

Abstract

As organic semiconductors attract increasing attention to application in the fields of bioelectronics and artificial photosynthesis, understanding the factors that determine their robust operation in direct contact with aqueous electrolytes becomes a critical task. Herein we uncover critical factors that influence the operational stability of donor:acceptor bulk heterojunction photocathodes for solar hydrogen production and significantly advance their performance under operational conditions. First, using the direct photoelectrochemical reduction of aqueous Eu3+ and impedance spectroscopy, we determine that replacing the commonly used fullerene-based electron acceptor with a perylene diimide-based polymer drastically increases operational stability and identify that limiting the photogenerated electron accumulation at the organic/water interface to values of ca. 100 nC cm–2 is required for stable operation (>12 h). These insights are extended to solar-driven hydrogen production using MoS3, MoP, or RuO2 water reduction catalyst overlayers where it is found that the catalyst morphology strongly affects performance due to differences in charge extraction. Optimized performance of bulk heterojunction photocathodes coated with a MoS3:MoP composite gave 1 Sun photocurrent density up to 8.7 mA cm–2 at 0 V vs RHE (pH 1). However, increased stability was gained with RuO2 where initial photocurrent density (>8 mA cm–2) deceased only 15% or 33% during continuous operation for 8 or 20 h, respectively, thus demonstrating unprecedented robustness without a protection layer. This performance represents a new benchmark for organic semiconductor photocathodes for solar fuel production and advances the understanding of stability criteria for organic semiconductor/water-junction-based devices.

Bibliographical metadata

Original languageEnglish
JournalJournal of the American Chemical Society
Early online date9 Apr 2020
DOIs
Publication statusPublished - 29 Apr 2020