This study elucidates how nitrogen functionalities influence the transition and transfer of photogenerated electrons in graphene‐based materials. Graphene oxide dots (GODs) and Nitrogen‐doped GODs (NGODs) are synthesized by thermally treating graphene oxide (GO) sheets in argon and ammonia, respectively, and then ultrasonically exfoliating the sheets in nitric acid. The nitrogen functionalities of NGODs are mainly quaternary/pyridinic/pyrrolic, and the nitrogen atoms in these functionalities are planar to the GO sheets and repair the vacancy defects on the sheets. Hydrothermal treatment of NGODs in ammonia yields ammonia‐treated NGODs (A‐NGODs), with some pyridinic/pyrrolic groups being converted to amino/amide groups. The nitrogen atoms in the amino/amide groups are not planar to the GO sheets and are prone to donate their lone pair electrons to resonantly conjugate with the aromatic π electrons. The promoted conjugation facilitates the relaxation of photogenerated electrons to the triplet states and prolongs the electron lifetime. When deposited with Pt as the co‐catalyst, the samples catalyze H2 production from an aqueous triethanolamine solution under 420 nm monochromatic irradiation at quantum yields of 7.3% (GODs), 9.7% (NGODs), and 21% (A‐NGODs). The high activity of A‐NGODs demonstrates that architecting nitrogen functionalities effectively mediate charge motion in carbon‐based materials for application to photoenergy conversion.

An electrophoretic deposition (EPD) method, consisting of repetitive short-term depositions with intermediate drying, was developed to prepare nanocrystalline TiO2 films for dye-sensitized solar cells (DSSCs). After calcination, the EPD TiO2 films exhibited a more compact TiO2 network than films derived from the conventional paste-coating (PC) method. X-ray absorption fine structure spectroscopic analysis showed that the EPD films had a higher density of defect states than the PC films because of the higher number of interparticle necking regions created in the EPD films. However, the DSSCs assembled with the EPD films outperformed those with the PC films by 20% in photocurrent and 15% in solar energy conversion efficiency. Intensity-modulated photocurrent spectroscopic analysis showed that the EPD films had a shorter electron transit time than the PC films. Under one-sun illumination on the cells at open-circuit, impedance analysis showed that the EPD films had a constant charge collection efficiency of 95% for thicknesses ranging from 4 to 13 μm, whereas the efficiency of the PC films was not greater than 90% and showed a decreasing trend with increasing film thickness. Concerning the porosity dependence of the electron transport dynamics, the electron diffusivity had much weaker dependence than one would expect from the percolation model with hard spheres. This may result from the fact that interparticle necking causes greater lattice distortion for more compact TiO2 films. The present study demonstrates that an optimized EPD process can construct a nanocrystalline TiO2 architecture with a minimized void fraction to shorten the electron traveling distance and to effectively collect photogenerated charges, even for films with large thicknesses.

Graphene oxide nanomaterials with tunable electronic properties act as efficient photoenergy-conversion media in photoluminescence, photovoltaics, and photocatalytic water splitting.

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