Organic semiconductors have been proven to be suitable for efficient photovoltaic generation during the last decade but have been scarcely assessed as photoelectrochemical devices. In this work we present the fabrication and characterization of a new efficient hybrid organic/inorganic photocathode for hydrogen evolution showing both a positive onset potential (+0.702 V vs. RHE) and a maximum power point (+0.303 V vs. RHE). We demonstrate that a conventional P3HT:PCBM bulk heterojunction architecture enclosed between a solution-processed cuprous iodide hole selective layer and a Pt-decorated nanostructured TiO₂ layer can efficiently photogenerate hydrogen under acidic conditions under simulated 1 Sun illumination. This architecture showed initial photocurrents as high as 8 mA cm⁻² at 0 V vs. RHE, IPCE above 50%, 100% faradaic efficiency and an ideal ratiometric power-saved figure of merit equal to 1.21%. Finally, with the addition of a solution-processed polyethyleneimine protective coating, we improved the device stability. This work paves the way to the use of hybrid organic/inorganic photocathodes for efficient solar hydrogen generation.

Charge order in underdoped and optimally doped high-$T_{\mathrm{c}}$ superconductors ${\mathrm{Bi}}_2{\mathrm{Sr}}_{2-x}{\mathrm{La}}_x{\mathrm{CuO}}_{6+\delta }$ (Bi2201) is investigated by Cu $L_3$ edge resonant inelastic x-ray scattering. We have directly observed charge density modulation in the optimally doped Bi2201 at momentum transfer $Q_{\parallel }\simeq 0.23$ reciprocal lattice units, with smaller intensity and correlation length with respect to the underdoped sample. This demonstrates the short-range charge order in Bi2201 persists up to optimal doping, as in other hole-doped cuprates. We explored the nodal (diagonal) direction and found no charge order peak, confirming that charge density modulates only along the Cu-O bond directions. We measured the out-of-plane dependence of charge order, finding a flat response and no maxima at half integer L values. This suggests there is no out-of-plane phase correlation in single layer Bi2201, at variance from ${\mathrm{YBa}}_2{\mathrm{Cu}}_3{\mathrm{O}}_{6+x}$ and ${\mathrm{La}}_{2-x}{(\text{Ba},\text{Sr})}_x{\mathrm{CuO}}_4$. Combining our results with data from the literature we assess that charge order in Bi2201 exists in a large doping range across the phase diagram, i.e., $0.07\lesssim p\lesssim 0.16$, demonstrating thereby that it is intimately entangled with the antiferromagnetic background, the pseudogap, and superconductivity.

Micro- and nanoplastic (pMP and pNP, respectively) release is an emerging issue since these particles constitute a ubiquitous and growing pollutant, which not only threatens the environment but may have potential consequences for human health. In particular, there is concern about the release of secondary pMP and pNP from the degradation of plastic consumer products. The phenomenon is well-documented in relation to plastic waste in the environment but, more recently, reports of pMP generated even during the normal use of plastic food contact materials, such as water bottles, tea bags, and containers, have been published. So far, a validated and harmonized strategy to tackle the issue is not available. In this study, we demonstrate that plastic breakdown to pMP and pNP can occur during the normal use of polyethylene (PE) rice cooking bags and ice-cube bags as well as of nylon teabags. A multi-instrumental approach based on Raman microscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and particular attention on the importance of sample preparation were applied to evaluate the chemical nature of the released material and their morphology. In addition, a simple method based on Fourier transform infrared (FT-IR) spectroscopy is proposed for pNP mass quantification, resulting in the release of 1.13 ± 0.07 mg of nylon 6 from each teabag. However, temperature was shown to have a strong impact on the morphology and aggregation status of the released materials, posing to scientists and legislators a challenging question: are they micro- or nanoplastics or something else altogether?

The photocathode exhibits 100% Faradaic efficiency and a photocurrent density of 3 mA cm²at 0.0 V RHE.

Silver nanoparticles (AgNPs) may be synthesized by many different methods, with those based on the thermal reduction of silver salts by citric acid or citric acid/tannic acid being amongst the most commonly used. These methods, although widely used and technically simple, can produce particles in which the size, polydispersivity and morphology can vary greatly. In this work nearly mono-dispersed spherical AgNPs have been synthesized via a one-step reduction method by using sodium citrate and varying quantities of Tannic Acid (TA), which was thermally conditioned prior to use in the growth process. It was found that the final size can be further tailored by controlling the amount of TA and the thermal conditioning of the TA at 60 °C at different time points, which changes the size and polydispersivity of AgNPs. To better understand the origin of this effect, optical spectroscopic analysis and ¹H NMR of the TA following mild thermal conditioning of the solution have been done. Comparison of thermally conditioned TA and TA exposed to basic pH shows that similar chemical modifications occur and consequently produce similar effects on growth when used in the synthesis of AgNPs. It is proposed that thermal preconditioning of the TA introduces either chemical or structural changes, which decrease the final particle size under a given total silver content.