Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 123, Issue 35, Pages 21403-21414Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.9b06401
Keywords
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Funding
- NWO Physical Sciences
- Netherlands Organization for Scientific Research (NWO)
- NWO Solar to Products program [733.000.007]
- China Scholarship Council [201606450019]
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A dye-sensitized photoelectrochemical cell (DS-PEC) is a promising device for direct conversion of solar energy into fuel. The basic idea, inspired by natural photosynthesis, is to couple the photoinduced charge separation process to catalytic water splitting. The photo-oxidized dye coupled to a water oxidation catalyst (WOC) should exert a thermodynamic driving force for the catalytic cycle, while water provides the electrons for regenerating the oxidized dye. These conditions impose specific energetic constraints on the molecular components of the photoanode in the DS-PEC. Here, we consider a supramolecular complex integrating a mononuclear Ru-based WOC with a fully organic naphthalene-diimide (NDI) dye that is able to perform fast photo-induced electron injection into the conduction band of the titanium-dioxide semiconductor anode. By means of constrained ab initio molecular dynamics simulations in explicit water solvent, it is shown that the oxidized NDI provides enough driving force for the whole photocatalytic water splitting cycle. The results provide strong evidence for the significant role of spin alignment and solvent rearrangement in facilitating the proton-coupled electron transfer processes. The predicted activation free energy barriers confirm that the O-O bond formation is the rate-limiting step. Our results expand the current understanding of the photocatalytic water oxidation mechanism and provide guidelines for the optimization of high-performance DS-PEC devices.
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