An organic polymer nano-photocatalyst has been developed for highly efficient light driven proton reduction.

For the first time, organic semiconducting polymer dots (Pdots) based on poly[(9,9'-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3} thiadiazole)] (PFBT) and polystyrene grafting with carboxyl-group-functionalized ethylene oxide (PS-PEG-COOH) are introduced as a photocatalyst towards visible-light-driven hydrogen generation in a completely organic solvent-free system. With these organic Pdots as the photocatalyst, an impressive initial rate constant of 8.3 mmol h(-1)  g(-1) was obtained for visible-light-driven hydrogen production, which is 5-orders of magnitude higher than that of pristine PFBT polymer under the same catalytic conditions. Detailed kinetics studies suggest that the productive electron transfer quench of the excited state of Pdots by an electron donor is about 40 %. More importantly, we also found that the Pdots can tolerate oxygen during catalysis, which is crucial for further application of this material for light-driven water splitting.

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Developing low-temperature deNOx catalysts with high catalytic activity, SO2-tolerance and stability is highly desirable but remains challenging. Herein, by coating the mesoporous TiO2 layers on carbon nanotubes (CNTs)-supported MnOx and CeOx nanoparticles (NPs), we obtained a core-shell structural deNOx catalyst with high catalytic activity, good SO2-tolerance and enhanced stability. Transmission electron microscopy, X-ray diffraction, N2 sorption, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction and NH3 temperature-programmed desorption have been used to elucidate the structure and surface properties of the obtained catalysts. Both the specific surface area and chemisorbed oxygen species are enhanced by the coating of meso-TiO2 sheaths. The meso-TiO2 sheaths not only enhance the acid strength but also raise acid amounts. Moreover, there is a strong interaction among the manganese oxide, cerium oxide and meso-TiO2 sheaths. Based on these favorable properties, the meso-TiO2 coated catalyst exhibits a higher activity and more extensive operating-temperature window, compared to the uncoated catalyst. In addition, the meso-TiO2 sheaths can serve as an effective barrier to prevent the aggregation of metal oxide NPs during stability testing. As a result, the meso-TiO2 overcoated catalyst exhibits a much better stability than the uncoated one. More importantly, the meso-TiO2 sheaths can not only prevent the generation of ammonium sulfate species from blocking the active sites but also inhibit the formation of manganese sulfate, resulting in a higher SO2-tolerance. These results indicate that the design of a core-shell structure is effective to promote the performance of deNOx catalysts.

Solid state p-type dye-sensitized solar cells (p-ssDSCs) have been proposed and fabricated for the first time, using the organic dye P1 as the sensitizer on mesoporous NiO and phenyl-C61-butyric acid methyl ester (PCBM) as the electron conductor. The p-ssDSC has shown an impressive open circuit photovoltage of 620 mV. Femtosecond and nanosecond transient absorption spectroscopy has given evidence for sub-ps hole injection from the excited P1 to NiO, followed by electron transfer from P1˙(-) to PCBM.

In this study, four new diketopyrrolopyrrole (DPP) sensitizers, with a dicarboxylated triphenylamine anchoring group for attachment to NiO, were prepared and their electronic absorption, emission and electrochemical properties were recorded. The nature of the electronic excited-states was also modeled with Time-Dependent Density Functional Theory (TD-DFT) quantum chemistry calculations. The photovoltaic performances of these new dyes were characterized in NiO-based dye-sensitized solar cells (DSCs) with the classical iodide/triiodide and cobalt­(II/III)–polypyridine electrolytes, in which they proved to be quite active. Laser spectroscopy on dye/NiO/electrolyte films gave evidence for ultrafast hole injection into NiO (0.2–10 ps time scales). For the dyes with an appended naphtalenediimide (NDI) acceptor unit, ultrafast electron transfer to the NDI dramatically prolonged the lifetime of the charge separated state NiO+/dye–, from the ps time scale to an average lifetime ≈0.25 ms, which is among the slowest charge recombinations ever reported for dye/NiO systems. This allowed for efficient regeneration by CoIII–polypyridine electrolytes, which translated into much improved PV-performance compared to the DPP dyes without appended NDI. Overall, these results underscore the suitability of DPP as sensitizers for NiO-based photoelectrochemical devices for photovoltaic and photocatalysis.

Photoelectrochemical approach to solar energy conversion demands a kinetic optimization of various light-induced electron transfer processes. Of great importance are the redox mediator systems accomplishing the electron transfer processes at the semiconductor/electrolyte interface, therefore affecting profoundly the performance of various photoelectrochemical cells. Here, we develop a strategy—by addition of a small organic electron donor, tris(4-methoxyphenyl)amine, into state-of-art cobalt tris(bipyridine) redox electrolyte—to significantly improve the efficiency of dye-sensitized solar cells. The developed solar cells exhibit efficiency of 11.7 and 10.5%, at 0.46 and one-sun illumination, respectively, corresponding to a 26% efficiency improvement compared with the standard electrolyte. Preliminary stability tests showed the solar cell retained 90% of its initial efficiency after 250 h continuous one-sun light soaking. Detailed mechanistic studies reveal the crucial role of the electron transfer cascade processes within the new redox system.

A covalently linked organic dye–cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye‐sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time‐resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye–catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye–catalyst system on the photocathode is proposed on the basis of this study.