Article pubs.acs.org/cm Tantalum Cobalt Nitride Photocatalysts for Water Oxidation under Visible Light † Yanqing Cong, Hyun S. Park, Hoang X. Dang, Fu-Ren F. Fan, Allen J. Bard,* and C. Buddie Mullins Center for Electrochemistry, Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, Texas 78712, United States Department of Chemical Engineering, Texas Materials Institute, Center for Nano- and Molecular Science, The University of Texas at Austin, 1 University Station C0400, Austin, Texas 78712, United States *S Supporting Information ABSTRACT: Tantalum cobalt nitride photocatalysts were prepared using a simple drop coating method on a Ta foil substrate followed by thermal ammonia treatment, and their photoelectrochemical (PEC) properties for water oxidation under visible light were studied. The resulting Ta0.9Co0.1Nx films showed a photocurrent 2 of ca. 1.5 mA/cm (12 times higher than that of Ta3N5)under 100 mW/cm2 visible light irradiation at 0.7 V vs Ag/AgCl in a 0.1 M Na2SO4 aqueous solution (pH 11). The good PEC performance was attributed to the introduction of cobalt and the formation of cobalt nitride, which efficiently facilitates electron transfer and suppresses the recombination of photogenerated electron−hole pairs. Some cobalt nitride could further be oxidized to generate cobalt oxide, which serves as an efficient electrocatalyst for water oxidation. The enhanced visible light activity and film stability under light irradiation make tantalum cobalt nitride a promising semiconductor for PEC water oxidation. KEYWORDS: tantalum cobalt nitride photocatalysts, photo-oxidation of water, photoelectrochemistry ■ INTRODUCTION heating Ta2O5 powder under a NH3 flow at high temperature, achieving a 34% quantum efficiency (QE) for TaON and 10% Photoelectrochemical (PEC) water splitting is a promising 14−17 for Ta3N5 for water oxidation under visible light irradiation. method for generating H2 from solar energy and has attracted much attention as a result of the increasing renewable energy Ta3N5 thin films have also been prepared by the nitridation of a − demand.1 3 It is especially important to develop a stable Ta2O5 film generated on Ta foil. An anodic photocurrent for semiconductor, which can perform effectively under visible light water oxidation was obtained under visible light irradiation, but 4 some oxidation of Ta3N5 itself was also observed. If a solution because 43% of solar energy is in the visible light region. Much 3− 4− work has been carried out to find band gaps and band positions of Fe(CN)6 /Fe(CN)6 was used as a redox relay instead of consistent with high efficiency and water splitting. To utilize water oxidation, Ta3N5 was much more stable, with no notice- visible light, the semiconductor band gap should be smaller than able surface oxidation. Under monochromatic (wavelength = 3 eV (420 nm). In addition, the band energy positions should be 450 nm) visible light irradiation, the incident monochromatic photon-to-current conversion efficiency (IPCE) could reach suitable for water splitting; the conduction band should be − + 1.2% in 0.1 M K2SO4 solution at pH 11 with a 0.1 V bias vs sufficiently negative for H reduction and the valence band 18 sufficiently positive for water oxidation.5 However, clearly, other Ag/AgCl. To further improve the photocatalytic activity, factors are important in gaining good efficiency, for example, Ta3N5 nanoparticles (NPs) were prepared by nitridation of a establishing conditions for good electron−hole separation, Ta2O5 NPs precursor. Compared to bulk Ta3N5 particles, Ta3N5 improving carrier mobility, passivating traps, and using electro- NPs showed enhanced photocatalytic activity, presumably catalysts. Although many photocatalysts have been developed associated with the higher number of surface active sites for − 19 6 10 hydrogen evolution. Ta3N5 NPs synthesized by other methods in the past decades, efficient and stable photocatalysts 20 responsive to visible light in aqueous solution are still few. have been attempted, but the synthetic yield was very low. Crystalline mesoporous Ta N was prepared from an Tantalum nitride (Ta3N5) is a good candidate for a PEC 3 5 catalyst under visible light irradiation and satisfies many of the amorphous mesoporous Ta2O5 by nitridation. The crystallized requirements mentioned: (1) Its band gap is 2.1 eV (absorption pore thickness of mesoporous Ta3N5 was ca. 2 nm, which edge at 600 nm). (2) At pH 0, its conduction band edge and improved charge transfer of electrons and holes so that the valence band edge is ca. −0.4 and 1.7 V vs NHE, respectively, well placed for water splitting. (3) It has a theoretical maximum Received: November 1, 2011 − solar spectrum photoconversion efficiency of 15.9%.11 13 Revised: January 9, 2012 ’ Domen s group has developed TaON and Ta3N5 powders by Published: January 9, 2012 © 2012 American Chemical Society 579 dx.doi.org/10.1021/cm203269n | Chem. Mater. 2012, 24, 579−586 Chemistry of Materials Article photocatalytic activity of mesoporous Ta3N5 was 3 times that of films, which were prepared by the same method on a Co foil substrate 21 conventional bulk Ta N . Domen’s group prepared a Ta N (Alfa Aesar, 99.9% purity). A 10 mM precursor solution of Co(NO3)2 3 5 3 5 μ × thin-film using a reactive sputtering technique. The Ta N film in methanol (30 L) was dropped onto a Co foil (15 mm 15 mm) 3 5 and then dried in air. After repeating this process 10 times, the samples showed an anodic photoresponse for water oxidation, but self- were annealed under an NH flow (100 mL/min) at 850 °Cfor2hto oxidation of Ta N occurred and the photocurrent decreased 3 3 5 produce films denoted as CoxNy. rapidly with illumination time. IrO2 modification was used to Characterization. Glancing incidence angle X-ray diffraction suppress the self-oxidation of the Ta3N5 film and improve the (GIXRD) was performed with a Bruker-Norius D8 advanced diffracto- α efficiency of water oxidation. Ta3N5 films modified with IrO2 meter, using a Cu K radiation source operated at 40 kV and 40 mA, had 30 times higher photocurrent than that of an unmodified with an incidence angle of 0.5°. Scanning electron microscopy (SEM) sample at 1.0 V bias vs Ag/AgCl.22 Grimes’ group fabricated images were obtained on a Zeiss Supra 40 VP field emission SEM. X-ray photoelectron spectroscopy (XPS) was performed with a Kratos highly oriented Ta3N5 nanotube array films by anodization of Axis Ultra DLD instrument (Manchester, UK) with a monochromatic tantalum foil followed by nitridation. An IPCE as high as 5.3% at Al X-ray source. 450 nm was achieved for 240 nm long Ta3N5 nanotube arrays in Photoelectrochemical Experiments. The PEC properties of 1 M KOH solution with 0.5 V bias.12 each sample were detected by using a three-electrode borosilicate glass Although many efforts have been made to optimize the cell equipped with a Pt-gauze counter electrode and an Ag/AgCl structure and properties of Ta3N5, the promotion of photo- reference electrode. A potentiostat (CH Instruments, model 630D, Austin, TX) was used to perform electrochemical measurements. All conversion efficiency with good stability of the Ta3N5 semi- PEC tests were performed at room temperature. The prepared films conductor is still challenging. Self-oxidation of Ta3N5 needs to be suppressed for water oxidation and novel stable materials are were used as working electrodes and were clamped into the glass cell via an O-ring with a 0.2 cm2 geometric area exposed to the electrolyte needed overcome these challenges. solution and to light irradiation. The PEC water oxidation experiments In this work, a new tantalum cobalt nitride (Ta Co − N ) y 1 y x were carried out in 0.1 M Na2SO4 solution with pH adjusted to 11 by photocatalyst was fabricated on a Ta substrate for water oxida- adding NaOH. Irradiation was achieved through the electrolyte tion for the first time. To the best of our knowledge, no previous solution by a Xe lamp (XBO 150 W, Osram, Munich, Germany) with work regarding the tantalum cobalt nitride or cobalt-doped an incident UV−visible light intensity of about 110 mW/cm2.AUV λ Ta3N5 has been reported. The structural and PEC performance cutoff filter ( > 420 nm) was used for visible light irradiation, and the resulting visible light intensity was ca. 100 mW/cm2. A mono- of TayCo1−yNx electrodes were systematically studied. The chromator (Photon Technology International, Birmingham, NJ) was photocurrent of Ta0.9Co0.1Nx films increased by 12 times relative to that of Ta N films under visible light irradiation. Stability used in combination with a power meter (Newport Model 1830-C, 3 5 Irvine, CA) and a silicon detector (Newport Model 818-UV, Irvine, under light illumination was also improved due to the presence CA) to measure incident photon to current conversion efficiencies of cobalt. Cobalt nitride (CoxNy) was found in the TayCo1−yNx (IPCE). Electrochemical impedance spectroscopy (EIS) was per- samples, and its role was also investigated. formed using an Autolab instrument (PGSTAT30/FRA2) to obtain the Mott−Schottky plot at frequencies of 200, 500, and 1000 Hz and a ■ EXPERIMENTAL SECTION peak-to-peak amplitude of 5 mV at each potential. Preparation of TayCo1−yNx Films. The TayCo1−yNx films were prepared by a drop coating method on a Ta foil substrate (Alfa Aesar, ■ RESULTS AND DISCUSSION 99.95% purity). A 10 mM precursor solution of TaCl5 (Sigma-Aldrich, 99.99% purity) in methanol (Fisher Scientific, 99.9% purity) was Characterization of TayCo1−yNx Films. GIXRD analyses μ prepared, and 30 L of the precursor solution was pipetted onto a Ta were used to identify the crystal phase of TayCo1−yNx films. To foil (15 mm ×15 mm) and then dried in air at room temperature.