RESUMO
Tin(II) compounds are versatile materials with applications across fields such as catalysis, diagnostic imaging, and therapeutic drugs. However, oxidative stabilization of Sn(II) has remained an unresolved challenge as its reactivity with water and dioxygen results in loss of functionality, limiting technological advancement. Approaches to slow Sn(II) oxidation with chelating ligands or sacrificial electron donors have yielded only moderate improvements. We demonstrate here that the addition of nitrate to pyrophosphate-chelated Sn(II)(aq) suppresses Sn(II) oxidation in water across a broad pH range. Evidence of hydroxyl radical concentration reduction and detection of a radical nitrogen species that only forms in the presence of chelated Sn(II) point to a radical-based reaction mechanism. While this chemistry can be broadly applied, we present that this approach maintains Sn(II)'s antibacterial and anti-inflammatory efficacies as an example of sustained oral chemotherapeutic functionality.
RESUMO
We report an unassisted solar water splitting system powered by a diketopyrrolopyrrole (DPP)-containing semitransparent organic solar cell. Two major merits of this fullerene-free solar cell enable its integration with a BiVO4 photoanode. First is the high open circuit voltage and high fill factor displayed by this single junction solar cell, which yields sufficient power to effect water splitting when serially connected to an appropriate electrode/catalyst. Second, the wavelength-resolved photoaction spectrum of the DPP-based solar cell has minimal overlap with that of the BiVO4 photoanode, thus ensuring that light collection across these two components can be optimized. The latter feature enables a new water splitting device configuration wherein the solar cell is placed first in the path of incident light, before the BiVO4 photoanode, although BiVO4 has a wider bandgap. This configuration is accessed by replacing the reflective top electrode of the standard DPP-based solar cell with a thin metal film and an antireflection layer, thus rendering the solar cell semitransparent. In this configuration, incident light does not travel through the aqueous electrolyte to reach the solar cell or photoanode, and therefore, photon losses due to the scattering of water are reduced. Moreover, this new configuration allows the BiVO4 photoanode to be back-illuminated, i.e., through the BiVO4/back contact interface, which leads to higher photocurrents compared to front illumination. The combination of a semitransparent single-junction solar cell and a BiVO4 photoanode coated with oxygen evolution catalysts in a new device configuration yielded an unassisted solar water splitting system with a solar-to-hydrogen conversion efficiency of 2.2% in water.