Interfacial band alignment and photoelectrochemical properties of all-sputtered BiVO₄/FeNiO<i>_x</i> and BiVO₄/FeMnO<i>_x</i>p–n heterojunctions

BiVO4 is a well-known n-type semiconductor with great potential for photoelectrochemical (PEC) conversion of solar energy into chemical fuels. Nevertheless, photocurrent densities achieved for bare BiVO4 photoanodes are still far from their theoretical maximum due to the sluggish water oxidation kinetics and limitation in electron-hole recombination. In this work, magnetron sputtering deposition was used for depositing FeMOx (M = Ni, Mn) as cocatalyst layers to induce p–n heterojunctions and suppress charge recombination on BiVO4 photoanodes. The all-sputtered p–n heterojunction BiVO4/FeMnOx exhibited the highest photocurrent density (1.25 mA cm−2 at 1.23 V vs. RHE) and excellent chemical stability, indicating that the combination of Mn sites on Fe-based oxides provides promising cocatalytic materials for PEC applications. Experimental and theoretical techniques were used to investigate the interfacial band alignment and charge transport properties of BiVO4/FeMOx (M = Ni, Mn) heterojunctions. Our results show that type II heterojunctions arise in the BiVO4/FeMOx (M = Ni, Mn) interface after equilibrium, thereby providing potential barriers to inhibit electron flow from the BiVO4 to the FeMOx layers. Furthermore, the BiVO4/FeMnOx film showed a larger space charge region (SCR) characterized by a more intense built-in electric field than BiVO4/FeNiOx, explaining its higher PEC performance. In summary, this work provides a viable technique for producing photocatalytic heterojunction systems based on metal oxide semiconductors and introduces simple tools for investigating interface effects on photoinduced charge carrier pathways for PEC applications

Ionic liquid based dopant-free band edge shift in BiVO4 particles for photocatalysis under simulated sunlight irradiation

Foreign elemental doping is a widely utilized strategy to modify the electronic structure of semiconductors. Herein, we present a dopant-free novel synthesis approach to control the electronic structure of a semiconductor. Utilizing butyl methyl imidazolium ([BMIM]Cl) and methoxyethyl methyl imidazolium ([M(MOE)Im][Cl]) chloride ILs, we prepared four different Bi and V based ILs: 3-butyl-1-methyl-1H-imidazol 3-ium vanadate [BMIm][VO3], 3-(2-methoxyethyl)-1-methyl-1H-imidazol-3-ium vanadate [M(MOE)Im][VO3], 3-butyl-1-methyl-1H-imidazol-3-ium tetrachlorobismate [BMIm][BiCl4] and 3-(2-methoxyethyl)-1-methyl 1H-imidazol-3-ium tetrachlorobismate [M(MOE)Im][BiCl4]. Owing to the bimetallic oxide nature of BiVO4, these gels were mixed either with each other or with Bi/V commercial salts and simply heat-treated to obtain monoclinic BiVO4. Depending on the IL, the bandgap energy of pure BiVO4 will be redshifted (2.44 to 2.25 eV). The IL based synthesis induced oxygen vacancies and uplifted the BiVO4 valence band edge as observed in the X-ray photoelectron spectroscopy (XPS). These effects were profound for IL anchored Bi; however, the side effects of this synthesis were chemisorption of a higher oxygen content and low reactivity of Bi with V to form an additional V2O5 phase. ILs acted as templates to form smooth spherical particles with improved crystallinity. [M(MOE)Im] based synthesis resulted in lower-order crystallinity and a large V–O bonding length of BiVO4 compared to [BMIm] which may be ascribed to its lower-order cationic–anionic electrostatic attraction associated with the presence of oxygen in the ether-group for [M(MOE)Im]. [BMIm] cation-based synthesis suppressed photogenerated charge-recombination and resulted in a five-fold O2 evolution of B30 mmol for 3 h (AM 1.5G illumination) compared to pure BiVO4 which was better compared to the sample prepared by the conventional hydrothermal process. It also improved the photocurrent, and the MS plots have shown that the conduction band was not much affected; however, the defect density was larger for IL based synthesi

Revealing the true impact of interstitial and substitutional nitrogen doping in TiO2 on photoelectrochemical applications

Application of photocatalysts that strongly absorb within the visible range is a common strategy to improve the efficiency of photoelectrochemical (PEC) systems; this may translate to high photocurrents, but it is not always the case. Here, we show that nitrogen doping enhances visible light absorption of TiO2; however, it does not necessarily result in improved PEC performance. Depending on the applied external potential, N-doping can improve, or degrade, PEC performance either under water oxidation conditions or via hole scavenging (Na2S/Na2SO3). In this work, we developed a holistic approach to evaluate the true impact of N doping in TiO2 on PEC performance. Interstitial and substitutional N doping are experimentally explored for the first time through a simple and novel PEC approach which complemented X-ray photoelectron analyses. Using this approach, we show that interstitial N doping of anatase TiO2 dominates up to 400 °C and substitutional doping up to ca. 600 °C, without rutile formation. This reveals that the bottleneck for doping higher N-concentrations in TiO2 is the direct transformation to thermodynamically favorable N-rich phases, such as TiN/Ti2N at 700 °C, inhibiting the formation of rutile phase. Transmission electron microscopy revealed that N doping proceeds mainly from the inner to the outer tube walls via nitridation and follows a preferential pathway from interstitial to substitutional doping. Direct PEC experimental evidence on visible light activation of N doped TiO2, and the location of interband states, showed acceptor levels of 1.0 eV for substitutional and 0.7 eV for interstitial doping above the TiO2 valence band maximum. In addition, due to O vacancies and Ti3+ species, donor levels below the conduction band minimum were also created. These levels act as trapping/recombination centers for charge carriers and, therefore, the gain in the visible range due to N doping does not translate to an improved PEC performance by these structural defects. Ultimately, we show that whilst there is a benefit of visible light absorption through N doping in TiO2, the PEC performance of the samples only surpasses pristine TiO2 at relatively high biasing (>0.3 V vs. Ag/AgCl)