Synthesis and Photocatalytic Properties of Tantalum Nitride with an Inverse Opal Structure
Authors: Moriga Toshihiro , Fujisaka Ai , Hirayama Natsumi , Furukawa Yusuke , Richardo Lewi Peter , Murai Kei-ichiro , Chen Wan-Ting , Waterhouse Geoffrey I N 
Published: February 2020

Certain oxynitrides (LaTiO2N and TaON) and nitrides (Ta3N5) demonstrate potential as visible-light-driven photocatalysts1. These materials are typically synthesized from oxide precursors by thermal ammonolysis at temperatures up to 950 oC. Accordingly, these oxynitrides and nitrides intrinsically possess an abundance of anion vacancies or defects which act as electron-hole pair recombination centers, thereby limiting photocatalytic performance.
In this work, we introduce photonic band gap engineering as a strategy for suppressing electron-hole pair recombination in tantalum nitride thin films, thereby achieving improved photocatalytic performance. Briefly, a series of inverse opal (IO) Ta3N5 thin films with different macropore sizes were fabricated by the colloidal crystal template approach. This kind of approach has been successfully made on TiO2 photocatalysts2. Three batches of monodisperse polymethylmethacrylate (PMMA) colloids of diameters ranging from 230 to 430 nm were first synthesized by the surfactant-free emulsion polymerization of methyl methacrylate. PMMA colloidal crystal thin films were then grown on silica glass slides using a flow-controlled vertical deposition technique. As the meniscus of the suspension moved down the glass slide by pumping up a peristaltic pump, colloidal crystal layer of several microns were deposited. Several drops of TaCl5 solution were placed softly on the edge of the colloidal crystal and immersed into the crystal by capillary phenomena. Subsequently, the interstitial voids in the colloidal crystal films (synthetic opals) were filled with a tantalum hydroxide sol. Ammonolysis of the resulting composite films under an ammonia stream of 200 ml/min at 700ºC yielded IO Ta3N5 thin films, shown in Fig.1. The IO Ta3N5 films possess a 3-dimensionally ordered macroporous structure with periodicity on the scale of visible-light wavelengths, resulting in pseudo photonic band gaps at visible wavelengths. By matching the red-edge of the PBG location with the absorption edge of Ta3N5, electron-hole pair recombination is suppressed and the photocatalytic activity dramatically improved.
In this experiment, strong reflection due to [111] photonic bandgap was clearly observed at 543nm for the IO amorphous Ta2O5 film and at 581nm for the IO Ta3N5 film, respectively. Appearance of the IO Ta3N5 film was reddish orange in color but it gave a strong yellow reflection in a certain angle, seen in Fig. 2. Since the optical bandgap of Ta3N5 was estimated to be 2.1eV (=590nm), the IO tantalum nitrides with both optical and bandgaps properly matched could be fabricated. Photocatalystic H2 evolution activity of the IO Ta3N5 under UV or visible ray irradiation will be appeared at the presentation, togather with a comparison with that of Ta3N5 powder.

References

Tsuyoshi Takata, Chengsi Pan and Kazunari Domen; Sci. Technol. Adv. Mater., 16 (2015) 033506 (18pp).

Waterhouse et al., Sci. Rep., 3 (2013) 2849 (5pp).

Figure 1