Highly Efficient, Noble-Metal-Free, Fully Aqueous CO<sub>2</sub> Photoreduction Sensitized by a Robust Organic Dye
Fan Ma, Zhi‐Mei Luo, Jia‐Wei Wang, Gangfeng Ouyang
Abstract
The development of efficient, selective, and durable CO 2 photoreduction systems presents a long-standing challenge in full aqueous solutions owing to the presence of scarce CO 2 and the fierce competition against H 2 evolution, which is even more challenging when noble metals are not utilized. Herein, we present the facile decorations of four phosphonic acid groups on a donor–acceptor-type organic dye to obtain a water-soluble photosensitizer ( 4P-DPAIPN ), which succeeds the excellent photophysical and photoredox properties of its prototype, exhibiting long-lived delayed fluorescence (>10 μs) in aqueous solutions. Combining 4P-DPAIPN with a cationic cobalt porphyrin catalyst has accomplished record-high apparent quantum yields of 9.4–17.4% at 450 nm for CO 2 -to-CO photoconversion among the precedented systems (maximum 13%) in fully aqueous solutions. Remarkable selectivity of 82–93% and turnover number of 2700 for CO production can also be achieved with this noble-metal-free system, outperforming a benchmarking ruthenium photosensitizer and a commercial organic dye under parallel conditions. Such high performances of 4P-DPAIPN can be well maintained under real sunlight. More impressively, no significant decomposition of 4P-DPAIPN was detected during the long-term photocatalysis. Eventually, the photoinduced electron transfer pathways were proposed.