RESUMEN
WO3/BiVO4 heterojunction photoanodes can be efficiently employed in photoelectrochemical (PEC) cells for the conversion of water into molecular oxygen, the kinetic bottleneck of water splitting. Composite WO3/BiVO4 photoelectrodes possessing a nanoflake-like morphology have been synthesized through a multistep process and their PEC performance was investigated in comparison to that of WO3/BiVO4 photoelectrodes displaying a planar surface morphology and similar absorption properties and thickness. PEC tests, also in the presence of a sacrificial hole scavenger, electrochemical impedance analysis under simulated solar irradiation, and incident photon to current efficiency measurements highlighted that charge transport and charge recombination issues affecting the performance of the planar composite can be successfully overcome by nanostructuring the WO3 underlayer in nanoflake-like WO3/BiVO4 heterojunction electrodes.
RESUMEN
CuWO4 is a ternary semiconductor oxide with excellent visible light harvesting properties up to 550 nm and stability at high pH values, which make it a suitable material to build photoanodes for solar light conversion to hydrogen via water splitting. In this work, we studied the photoelectrochemical (PEC) performance of transparent CuWO4 electrodes with tunable light absorption and thickness, aiming at identifying the intrinsic bottlenecks of photogenerated charge carriers in this semiconductor. We found that electrodes with optimal CuWO4 thickness exhibit visible light activity due to the absorption of long-wavelength photons and a balanced electron and hole extraction from the oxide. The PEC performance of CuWO4 is light-intensity-dependent, with charge recombination increasing with light intensity and most photogenerated charge carriers recombining in bulk sites, as demonstrated by PEC tests performed in the presence of sacrificial agents or cocatalysts. The best-performing 580 nm thick CuWO4 electrode delivers a photocurrent of 0.37 mA cm-2 at 1.23 VSHE, with a 7% absorbed photon to current efficiency over the CuWO4 absorption spectrum.
RESUMEN
CuWO4 has emerged in the last years as a ternary metal oxide material for photoanodes application in photoelectrochemical cells, thanks to its relatively narrow band gap, high stability and selectivity toward the oxygen evolution reaction, though largely limited by its poor charge separation efficiency. Aiming at overcoming this limitation, we investigate here the effects that Cu(II) ion substitution has on the photoelectrocatalytic (PEC) performance of copper tungstate. Optically transparent CuWO4 thin-film photoanodes, prepared via spin coating and containing different amounts of Ni(II) ions, were fully characterized via UV-Vis spectroscopy, XRD and SEM analyses, and their PEC performance was tested via linear sweep voltammetry, incident photon to current efficiency and internal quantum efficiency analyses. From tests performed in the presence of a hole scavenger-containing electrolyte, the charge injection and separation efficiencies of the electrodes were also calculated. Pure-phase crystalline and/or heterojunction materials were obtained with higher PEC performance compared to pure CuWO4, mainly due to a significantly enhanced charge separation efficiency in the bulk of the material.
RESUMEN
Direct electrolysis of pH-neutral seawater to generate hydrogen is an attractive approach for storing renewable energy. However, due to the anodic competition between the chlorine evolution and the oxygen evolution reaction (OER), direct seawater splitting suffers from a low current density and limited operating stability. Exploration of catalysts enabling an OER overpotential below the hypochlorite formation overpotential (≈490 mV) is critical to suppress the chloride evolution and facilitate seawater splitting. Here, a proton-adsorption-promoting strategy to increase the OER rate is reported, resulting in a promoted and more stable neutral seawater splitting. The best catalysts herein are strong-proton-adsorption (SPA) materials such as palladium-doped cobalt oxide (Co3- x Pdx O4 ) catalysts. These achieve an OER overpotential of 370 mV at 10 mA cm-2 in pH-neutral simulated seawater, outperforming Co3 O4 by a margin of 70 mV. Co3- x Pdx O4 catalysts provide stable catalytic performance for 450 h at 200 mA cm-2 and 20 h at 1 A cm-2 in neutral seawater. Experimental studies and theoretical calculations suggest that the incorporation of SPA cations accelerates the rate-determining water dissociation step in neutral OER pathway, and control studies rule out the provision of additional OER sites as a main factor herein.
RESUMEN
Photoelectrochemical (PEC) water splitting converts solar light and water into oxygen and energy-rich hydrogen. WO3/BiVO4 heterojunction photoanodes perform much better than the separate oxide components, though internal charge recombination undermines their PEC performance when both oxides absorb light. Here we exploit the BiVO4 layer to sensitize WO3 to visible light and shield it from direct photoexcitation to overcome this efficiency loss. PEC experiments and ultrafast transient absorption spectroscopy performed by frontside (through BiVO4) or backside (through WO3) irradiating photoanodes with different BiVO4 layer thickness demonstrate that irradiation through BiVO4 is beneficial for charge separation. Optimized electrodes irradiated through BiVO4 show 40% higher photocurrent density compared to backside irradiation.
RESUMEN
Photoelectrochemical solar energy conversion offers a way to directly store light into energy-rich chemicals. Photoanodes based on the WO3/BiVO4 heterojunction are most effective mainly thanks to the efficient separation of photogenerated charges. The WO3/BiVO4 interfacial space region in the heterojunction is investigated here with the increasing thickness of the BiVO4 layer over a WO3 scaffold. On the basis of X-ray diffraction analysis results, density functional theory simulations show a BiVO4 growth over the WO3 layer along the BiVO4 {010} face, driven by the formation of a stable interface with new covalent bonds, with a favorable band alignment and band bending between the two oxides. This crystal facet phase matching allows a smooth transition between the electronic states of the two oxides and may be a key factor ensuring the high efficiency attained with this heterojunction. The photoelectrochemical activity of the WO3/BiVO4 photoanodes depends on both the irradiation wavelength and the thickness of the visible-light-absorbing BiVO4 layer, a 75 nm thick BiVO4 layer on WO3 being best performing.
RESUMEN
CuWO4 is a ternary metal oxide semiconductor with promising properties for photoelectrochemical (PEC) water splitting and solar light conversion, due to its quite low band gap (2.3 eV) and high stability in an alkaline environment. Aiming at understanding the origin of the relatively low PEC efficiency attained with CuWO4 photoanodes, we here investigate transparent CuWO4 electrodes prepared by a simple solution-based method through the combination of femtosecond transient absorption spectroscopy with electrochemical, PEC, and photochromic characterizations. The very fast recombination dynamics of the charge carriers photogenerated in CuWO4, which is the reason for its low efficiency, is discussed in relation with its PEC performance and with the recently calculated band structure of this material, also in comparison with the behavior of other semiconductor oxides employed in PEC applications, in particular Fe2O3.
RESUMEN
The need for stable oxide-based semiconductors with a narrow band gap, able to maximize the exploitation of the visible light portion of the solar spectrum, is a challenging issue for photoelectrocatalytic (PEC) applications. In the present work, CuW1-x Mo x O4 (E g = 2.0 eV for x = 0.5), which exhibits a significantly reduced optical band gap E g compared with isostructural CuWO4 (E g = 2.3 eV), was investigated as a photoactive material for the preparation of photoanodes. CuW0.5Mo0.5O4 electrodes with different thicknesses (80-530 nm), prepared by a simple solution-based process in the form of multilayer films, effectively exhibit visible light photoactivity up to 650 nm (i.e., extended compared with CuWO4 photoanodes prepared by the same way). Furthermore, the systematic investigation on the effects on photoactivity of the CuW0.5Mo0.5O4 layer thickness evidenced that long-wavelength photons can better be exploited by thicker electrodes. PEC measurements in the presence of NaNO2, acting as a suitable hole scavenger ensuring enhanced photocurrent generation compared with that of water oxidation while minimizing dark currents, allowed us to elucidate the role that molybdenum incorporation plays on the charge separation efficiency in the bulk and on the charge injection efficiency at the photoanode surface. The adopted Mo for W substitution increases the visible light photoactivity of copper tungstate toward improved exploitation and storage of visible light into chemical energy via photoelectrocatalysis.
RESUMEN
The PEC performance of WO3/BiVO4 heterojunction photoanodes with a fixed BiVO4 thick top layer and different WO3 layer thicknesses was investigated under backside irradiation, in comparison with the performance of the same electrodes without a top BiVO4 layer. While the performance of these latter increase with increasing WO3 thickness, the presence of a BiVO4 layer, besides leading to an effective sensitization up to 520 nm, leads to a decrease of incident photon to current efficiency in the short wavelength's range. After having excluded major WO3 filter effects, this has been attributed to charge carrier recombination effects occurring when both oxides get excited and becoming more relevant with increasing WO3 thickness and decreasing excitation wavelength.
RESUMEN
The dynamics of photopromoted electrons in BiVO4, WO3, and WO3/BiVO4 heterojunction electrodes has been directly probed by transient absorption (TA) midinfrared (mid-IR) spectroscopy in the picosecond to microsecond time range. By comparison of the dynamics recorded with the two individual oxides at 2050 cm-1 with that of the heterojunction system after excitation at different wavelengths, electron-transfer processes between selectively excited BiVO4 and WO3 have been directly tracked for the first time. These results support the charge carrier interactions which were previously hypothesized by probing the BiVO4 hole dynamics through TA spectroscopy in the visible range. Nanosecond mid-IR TA experiments confirmed that charge carrier separation occurs in WO3/BiVO4 electrodes under visible-light excitation, persisting up to the microsecond time scale.
