Increased solar-driven chemical transformations through surface-induced benzoperylene aggregation in dye-sensitized photoanodes

The impact of benzo[ghi]perylenetriimide (BPTI ) dye aggregation on the performance of photoelectrochemical devices was explored, through imide-substitution with either alkyl ( BPTI-A , 2-ethylpropyl) or bulky aryl ( BPTI-B , 2,6-diisopropylphenyl) moieties, to, respectively, enable or suppress aggregation. While both dyes demonstrated similar monomeric optoelectronic properties in solution, adsorption onto mesoporous SnO 2 revealed different behavior, with BPTI-A forming aggregates via π-stacking and BPTI-B demonstrating reduced aggregation in the solid state. BPTI photoanodes were tested in dye-sensitized solar cells (DSSCs) before application to dye-sensitized photoelectrochemical cells (DSPECs) for Br 2 production (a strong oxidant) coupled to H 2 generation (a solar fuel). BPTI-A demonstrated a twofold higher dye loading of the SnO 2 surface than BPTI-B , resulting in a fivefold enhancement to both photocurrent and Br 2 production. The enhanced output of the photoelectrochemical systems (with respect to dye loading) was attributed to both J - and H- aggregation phenomena in BPTI-A photoanodes that lead to improved light harvesting. Our investigation provides a strategy to exploit self-assembly via aggregation to improve molecular light-harvesting and charge separation properties that can be directly applied to dye-sensitized photoelectrochemical devices. Graphical Abstract Increased Solar-Driven Chemical Transformations through Surface-Induced Benzoperylene Aggregation in Dye-Sensitized Photoanodes. Benzo[ghi]perylenetriimide ( BPTI ) dyes are investigated to reveal the effect of aggregation by π-stacking on photovoltaic parameters in dye-sensitized devices. Photoanodes with aggregating BPTIs show both J- and H- aggregation phenomena leading to enlarged visible light absorbance and increased electron injection. The use of aggregating BPTI outperforms a non-aggregation BPTI with fivefold in terms of photocurrent and product generation.