Intricate Reaction Pathways on CH3NH3PbI3 Photocatalysts in Aqueous Solution Unraveled by Single-Particle Spectroscopy.

Organic-inorganic hybrid perovskites such as MAPbI3 (MA+ = CH3NH3+) have emerged as promising materials for solar cells and light-emitting devices. Despite their poor stability against moisture, perovskites work as hydrogen-producing photocatalysts or photosensitizers in perovskite-saturated aqueous solutions. However, the fundamental understanding of how chemical species or support materials in the solution affect the dynamics of the photogenerated charges in perovskites is still insufficient. In this study, we investigated the photoluminescence (PL) properties of MAPbI3 nanoparticles in aqueous media at the single-particle level. A remarkable PL blinking phenomenon, along with significant decreases in the PL intensity and lifetime compared to those in ambient air, suggested temporal fluctuations in the trapping rates of photogenerated holes by chemical species (I- and H3PO2) in the solution. Moreover, electron transfer from the excited MAPbI3 to Pt-modified TiO2 proceeds in a concerted fashion for photocatalytic hydrogen evolution under the dynamic solid-solution equilibrium condition.

Size-Controlled Synthesis of Luminescent Few-Atom Silver Clusters via Electron Transfer in Isostructural Redox-Active Porous Ionic Crystals.

Ag clusters with a controlled number of atoms have received significant interest because they show size-dependent catalytic, optical, electronic, or magnetic properties. However, the synthesis of size-controlled, ligand-free, and air-stable Ag clusters with high yields has not been well-established. Herein, it is shown that isostructural porous ionic crystals (PICs) with redox-active polyoxometalates (POMs) can be used to synthesize Ag clusters via electron transfer from POMs to Ag+ . Ag clusters with average numbers of three, four, or six atoms emitting blue, green, or red colors, respectively, are formed and stabilized in the PICs under ambient conditions without any protecting ligands. The cluster size solely correlates with the degree of electron transfer, which is controlled by the reduction time and types of ions or elements of the PICs. Thus, advantages have been taken of POMs as electron sources and PICs as scaffolds to demonstrate a convenient method to obtain few-atom Ag clusters.

Binary dopant segregation enables hematite-based heterostructures for highly efficient solar H2O2 synthesis.

Dopant segregation, frequently observed in ionic oxides, is useful for engineering materials and devices. However, due to the poor driving force for ion migration and/or the presence of substantial grain boundaries, dopants are mostly confined within a nanoscale region. Herein, we demonstrate that core-shell heterostructures are formed by oriented self-segregation using one-step thermal annealing of metal-doped hematite mesocrystals at relatively low temperatures in air. The sintering of highly ordered interfaces between the nanocrystal subunits inside the mesocrystal eliminates grain boundaries, leaving numerous oxygen vacancies in the bulk. This results in the efficient segregation of dopants (~90%) on the external surface, which forms their oxide overlayers. The optimized photoanode based on hematite mesocrystals with oxide overlayers containing Sn and Ti dopants realises high activity (~0.8 µmol min-1 cm-2) and selectivity (~90%) for photoelectrochemical H2O2 production, which provides a wide range of application for the proposed concept.

Ce3+-enriched spherical porous ceria with an enhanced oxygen storage capacity.

Porous ceria was obtained using a unique solvothermal reaction in acetonitrile, applying high temperature and pressure. The resulting material comprised homogeneous and monodisperse spheres and exhibited an extremely large surface area of 152 m2 g-1. From catalytic performance evaluation by vapor- and liquid-phase reactions, the synthesized porous ceria showed superior and different reaction activity compared with commercial CeO2. To examine the origin of the reaction activity of the present porous ceria, synchrotron hard X-ray photoelectron spectroscopy (HAXPES) measurements were carried out. The systematic study of HAXPES measurements revealed that the obtained porous ceria with the present solvothermal method contained a very high concentration of Ce3+. Moreover, O2-pulse adsorption analyses demonstrated a significant oxygen adsorption capacity exceeding 268 µmol-O g-1 at 400 °C owing to its high contents of Ce3+ species.

Porous niobia spheres with large surface area: alcothermal synthesis and controlling of their composition and phase transition behaviour.

Submicron-sized niobia (Nb2O5) porous spheres with a high specific surface area (300 m2 g-1) and nano concave-convex surfaces were synthesized via a rapid one-pot single-step alcothermal reaction. Prolonged reaction time or high reaction temperatures resulted in a morphology change of Nb2O5 from amorphous sphere to rod crystals with hexagonal crystal phase. A similar alcothermal reaction yielded TiO2-Nb2O5 composite porous spheres, whose Ti : Nb molar ratio was controlled by changing the precursor solution component ratios. A simple thermal treatment of amorphous TiO2-Nb2O5 porous spheres consisting of 1 : 2 (molar ratio) Ti : Nb at 600 °C for 2 h induced crystal phase transfer from amorphous to a monoclinic crystal phase of submicron-sized TiNb2O7 porous spheres with a specific surface area of 50 m2 g-1.