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Antimony chalcogenides represent a family of materials of low toxicity and relative abundance, with a high potential for future sustainable solar energy conversion technology. However, solar cells based on antimony chalcogenides present open-circuit voltage losses that limit their efficiencies. These losses are attributed to several recombination mechanisms, with interfacial recombination being considered as one of the dominant processes. In this work, we exploit atomic layer deposition (ALD) to grow a series of ultrathin ZnS interfacial layers at the TiO2/Sb2S3interface to mitigate interfacial recombination and to increase the carrier lifetime. ALD allows for very accurate control over the ZnS interlayer thickness on the ångström scale (0–1.5 nm) and to deposit highly pure Sb2S3. Our systematic study of the photovoltaic and optoelectronic properties of these devices by impedance spectroscopy and transient absorption concludes that the optimum ZnS interlayer thickness of 1.0 nm achieves the best balance between the beneficial effect of an increased recombination resistance at the interface and the deleterious barrier behavior of the wide-bandgap semiconductor ZnS. This optimization allows us to reach an overall power conversion efficiency of 5.09% in planar configuration.

Pollution of water with heavy metals is a global environmental problem whose impact is especially severe in developing countries. Among water-purification methods, adsorption of heavy metals has proven to be simple, versatile, and cost-effective. However, there is still a need to develop adsorbents with a capacity to remove multiple metal pollutants from the same water sample. Herein, we report the complementary adsorption capacities of metal–organic frameworks (here, UiO-66 and UiO-66-(SH)2) and inorganic nanoparticles (iNPs; here, cerium-oxide NPs) into composite materials. These adsorbents, which are spherical microbeads generated in one step by continuous-flow spray-drying, efficiently and simultaneously remove multiple heavy metals from water, including As(III and V), Cd(II), Cr(III and VI), Cu(II), Pb(II), and Hg(II). We further show that these microbeads can be used as a packing material in a prototype of a continuous-flow water treatment system, in which they retain their metal-removal capacities upon regeneration with a gentle acidic treatment. As proof-of-concept, we evaluated these adsorbents for purification of laboratory water samples prepared to independently recapitulate each of two strongly polluted rivers: the Bone (Indonesia) and Buringanga (Bangladesh) rivers. In both cases, our microbeads reduced the levels of all the metal contaminants to below the corresponding permissible limits established by the World Health Organization (WHO). Moreover, we demonstrated the capacity of these microbeads to lower levels of Cr(VI) in a water sample collected from the Sarno River (Italy). Finally, to create adsorbents that could be magnetically recovered following their use in water purification, we extended our spray-drying technique to simultaneously incorporate two types of iNPs (CeO2and Fe3O4) into UiO-66-(SH)2, obtaining CeO2/Fe3O4@UiO-66-(SH)2microbeads that adsorb heavy metals and are magnetically responsive.

A critical bottleneck for the use of metal–organic frameworks (MOFs) as drug delivery systems has been allowing them to reach their intracellular targets without being degraded in the acidic environment of the lysosomes. Cells take up particles by endocytosis through multiple biochemical pathways, and the fate of these particles depends on these routes of entry. Here, we show the effect of functional group incorporation into a series of Zr-based MOFs on their endocytosis mechanisms, allowing us to design an efficient drug delivery system. In particular, naphthalene-2,6-dicarboxylic acid and 4,4′-biphenyldicarboxylic acid ligands promote entry through the caveolin-pathway, allowing the particles to avoid lysosomal degradation and be delivered into the cytosol and enhancing their therapeutic activity when loaded with drugs.

In this manuscript we reveal the formation of bilayered hybrid perovskites of a new lower dimensional perovskite family, (CHMA)2(MA)n−1PbnI3with n= 1–5, with high ambient stability via its crystallization driven self-assembly process. The spun-coated perovskite solution tends to crystallize and undergo phase separation during annealing, resulting in the formation of 2D/3D bilayered hybrid perovskites. Remarkably, this 2D/3D hybrid perovskites possess striking moisture resistance and displays high ambient stability up to 65 days. The bilayered approach in combining 3D and 2D perovskites could lead to a new era of perovskite research for high-efficiency photovoltaics with outstanding stability, with the 3D perovskite providing excellent electronic properties while the 2D perovskite endows it moisture stability.

Ultrathin TiO2is deposited on conventional hydrothermal grown hematite nanorod arrays by atomic layer deposition (ALD). Significant photoelectrochemical water oxidation performance improvement is observed when the ALD TiO2-treated samples are annealed at 650 °C or higher temperatures. The electrochemical impedance spectroscopy (EIS) study shows a surface trap-mediated charge transfer process exists at the hematite–electrolyte interface. Thus, one possible reason for the improvement could be the increased surface states at the hematite surface, which leads to better charge separation, less electron–hole recombination, and hence, greater improvement of photocurrent. Our Raman study shows the increase in surface defects on the ALD TiO2-coated hematite sample after being annealed at 650 °C or higher temperatures. A photocurrent of 1.9 mA cm–2at 1.23 V (vs RHE) with a maximum of 2.5 mA cm–2at 1.8 V (vs RHE) in 1 M NaOH under AM 1.5 simulated solar illumination is achieved in optimized deposition and annealing conditions.

We report a simple method to produce a stable and repeatable photoanode for water splitting with a core–shell hematite (α-Fe2O3) nanorods system by combining spray pyrolysis and hydrothermal synthesis. Impedance spectroscopy revealed passivation of the surface states by the shell layer, which results in an increase of the charge injection through the hematite conduction band. In pristine hematite more holes are accumulated on the surface and the charge transfer to the electrolyte occurs through surface states, whereas in the core–shell hematite photoanode the majority of hole transfer process occurs through the valence band. As a result the photoactivity of the core–shell nanorods, 1.2 mA cm–2, at 1.23 V vs RHE, is twice that of pristine hematite nanorods. The alteration of the interface energetics is supported by TEM, showing that the crystallinity of the surface has been improved by the deposition of the shell.

A novel approach to produce earth-abundant Cu2FeSnS4(CFTS) thin film using spray pyrolysis of nontoxic aqueous precursors followed by sulfurization is reported. The CFTS phase formation was confirmed by both Raman spectroscopy and X-ray diffraction techniques. Hall measurements of these films reveal p-type conductivity with good charge carrier density and mobilities appropriate for solar harvesting devices. To the best of our knowledge, this is the first report on the electrical properties of solution-processed Cu2FeSnS4thin films estimated using Hall measurements. Dye-sensitized solar cells (DSSC) fabricated with CFTS thin film as a photocathode in iodine/iodide electrolyte exhibit good power conversion efficiency, 8.03%, indicating that CFTS would be a promising cheaper alternative to replace Pt as a counter electrode in DSSCs.

A setup capable of conducting gas pulse–X-ray probe ambient pressure photoelectron spectroscopy with high time resolution is presented. The setup makes use of a fast valve that creates gas pulses with an internal pressure in the mbar range and a rising edge of few hundreds of microseconds. A gated detector based on a fast camera is synchronized with the valve operation to measure X-ray photoemission spectra with up to 20 μs time resolution. The setup is characterized in several experiments in which the N2gas is pulsed either into vacuum or a constant flow of another gas. The observed width of the pulse rising edge is 80 μs, and the maximum internal pulse pressure is ∼1 mbar. The CO oxidation reaction over Pt (111) was used to demonstrate the capability of the setup to correlate the gas phase composition with that of the surface during transient supply of CO gas into an O2stream. Thus, formation of both chemisorbed and oxide oxygen species was observed prior to CO gas perturbation. Also, the data indicated that both the Langmuir–Hinshelwood and Mars-van-Krevelen mechanisms play an important role in the oxidation of carbon monoxide under ambient conditions.

Heavy-metal contamination of water is a global problem with an especially severe impact in countries with old or poorly maintained infrastructure for potable water. An increasingly popular solution for ensuring clean and safe drinking water in homes is the use of adsorption-based water filters, given their affordability, efficacy, and simplicity. Herein, we report the preparation and functional validation of a new adsorbent for home water filters, based on our metal–organic framework (MOF) composite containing UiO-66 and cerium(IV) oxide (CeO2) nanoparticles. We began by preparing CeO2@UiO-66 microbeads and then encapsulating them in porous polyethersulfone (PES) granules to obtain millimeter-scale CeO2@UiO-66@PES granules. Next, we validated these granules as an adsorbent for the removal of metals from water by substituting them for the standard adsorbent (ion-exchange resin spheres) inside a commercially available water pitcher from Brita. We assessed their performance according to the American National Standards Institute (ANSI) guideline 53-2019, “Drinking Water Treatment Units—Health Effects Standard”. Remarkably, a pitcher loaded with a combination of our CeO2@UiO-66@PES granules and activated carbon at standard ratios met the target reduction thresholds set by NSF/ANSI 53-2019 for all the metals tested: As(III), As(V), Cd(II), Cr(III), Cr(VI), Cu(II), Hg(II), and Pb(II). Throughout the test, the modified pitcher proved to be robust and stable. We are confident that our findings will bring MOF-based adsorbents one step closer to real-world use.