Nanocrystals perovskites photocatalyzed singlet oxygen generation for light-driven organic reactions.

Lead halide perovskite nanocrystals were prepared and used as photocatalysts for the in situ 1O2 generation to perform hetero Diels-Alder, ene and oxidation reactions with suitable dienes and alkenes. The methodology has been reasonably standardized and made applicable to a variety of olefinic substrates. The scope of the method is finely illustrated by the results in all the tested reactions, which allowed to obtain desymmetrized hydroxy-ketone derivatives, unsaturated ketones and epoxides. Some limitations were also observed especially in the case of the alkene oxidations as well as poor chemoselectivity was somewhere observed. 1O2 generated by lead halide perovskite nanocrystals as photocatalyst in organic reactions.

Optical and Structural Property Tuning in Physical Vapor Deposited Bismuth Halides Cs3Bi2(I1-xBrx)9 (0 ≤ x ≤ 1).

Crystalline films of lead-free all-inorganic Cs3Bi2X9 (X = Br, I) perovskites have been deposited by radio frequency (RF)-magnetron sputtering providing high-quality, single-phase films as confirmed by structural, morphological, and optical property characterization. Progressive tuning of crystal structure characteristics and optical absorbance has been achieved in mixed Br/I phases Cs3Bi2(I1-xBrx)9 (0 ≤ x ≤ 1), highlighting a shift of the band gap from about 2.0 eV for Cs3Bi2I9 to 2.64 eV for Cs3Bi2Br9. X-ray diffraction and Raman scattering allowed defining the range of alloyed compositions where single-phase compositions are found. Finally, preliminary photocatalytic activity tests on the degradation of methylene blue provided solid data indicating the future possible exploitation of Bi-based perovskite derivative materials as active photocatalysts.

Water-Stable DMASnBr3 Lead-Free Perovskite for Effective Solar-Driven Photocatalysis.

Water-stable metal halide perovskites could foster tremendous progresses in several research fields where their superior optical properties can make differences. In this work we report clear evidence of water stability in a lead-free metal halide perovskite, namely DMASnBr3 , obtained by means of diffraction, optical and X-ray photoelectron spectroscopy. Such unprecedented water-stability has been applied to promote photocatalysis in aqueous medium, in particular by devising a novel composite material by coupling DMASnBr3 to g-C3 N4 , taking advantage from the combination of their optimal photophysical properties. The prepared composites provide an impressive hydrogen evolution rate >1700 µmol g-1 h-1 generated by the synergistic activity of the two composite costituents. DFT calculations provide insight into this enhancement deriving it from the favorable alignment of interfacial energy levels of DMASnBr3 and g-C3 N4 . The demonstration of an efficient photocatalytic activity for a composite based on lead-free metal halide perovskite in water paves the way to a new class of light-driven catalysts working in aqueous environments.

Air- and water-stable and photocatalytically active germanium-based 2D perovskites by organic spacer engineering.

There is increasing interest in the role of metal halide perovskites for heterogeneous catalysis. Here, we report a Ge-based 2D perovskite material that shows intrinsic water stability realized through organic cation engineering. Incorporating 4-phenylbenzilammonium (PhBz) we demonstrate, by means of extended experimental and computational results, that PhBz2GeBr4 and PhBz2GeI4 can achieve relevant air and water stability. The creation of composites embedding graphitic carbon nitride (g-C3N4) allows a proof of concept for light-induced hydrogen evolution in an aqueous environment by 2D Ge-based perovskites thanks to the effective charge transfer at the heterojunction between the two semiconductors.

Solar-Driven Hydrogen Generation by Metal Halide Perovskites: Materials, Approaches, and Mechanistic View.

Solar-driven photocatalysis by metal halide perovskites (MHPs) is emerging as an exciting and promising field to promote several relevant catalytic reactions taking advantage of the superior optical properties of MHPs. Their electronic structure is suitable to run reduction reactions (H2 generation, CO2 reduction) and even oxidation reactions, in particualr for perovskites with higher band gap values, and further extends their possible use in the field of photochemical organic syntheses. This Mini-Review focuses on the application of MHPs in the solar-driven hydrogen generation with particular emphasis on the materials' design and mechanistic features involved in the catalytic reactions.