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Fundamental insights in photoelectrocatalytic hydrogen production with a hole-transport bismuth metal-organic framework

DOI: 10.1021/jacs.9b10261 DOI Help

Authors: Alba García-sánchez (IMDEA Energy Institute) , Miguel Gomez-mendoza (IMDEA Energy Institute) , Mariam Barawi (IMDEA Energy Institute) , Ignacio Jose Villar-garcia (IMDEA Energy Institute) , Marta Liras (IMDEA Energy Institute) , Felipe Gandara (Instituto de Ciencia de Materiales de Madrid, CSIC) , Víctor A. De La Pena O'shea (IMDEA Energy Institute)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: December 2019

Abstract: Solar fuels production is a cornerstone in the development of emerging sustainable energy conversion and storage technologies. Light-induced H2 production from water represents one of the most crucial challenges to produce renewable fuel. Metal-organic frameworks (MOFs) are being investigated, due to the ability to assemble new structures with the use of suitable photoactive building blocks. However, the identification of the reaction intermediates remains elusive, which negatively impacts in the design of more efficient materials. Here, we report the synthesis and characterization of a new MOF prepared with the use of bismuth and dithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxylic acid (DTTDC), an electron-rich linker with hole transport ability. By combining theoretical studies and time-resolved spectroscopies, such as core hole clock and laser flash photolysis measurements, we have completed a comprehensive study at different time scales (fs to-ms) to determine the effect of competitive reactions on the overall H2 production. We found that an intermediate radical anion is formed upon reaction of photogenerated holes with an electron donor, which play a key role in the photoelectrocatalytic processes. These results shed new light on the use of MOFs for solar fuel production.

Journal Keywords: Metal-organic framework; photoelectrochemistry; charge transfer; hydrogen production

Subject Areas: Materials, Chemistry, Energy


Instruments: B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS