Facile Synthesis of Heterogeneous Indium Nanoparticles for Formate Production via CO2 Electroreduction.

In this study, a simple and scalable method to obtain heterogeneous indium nanoparticles and carbon-supported indium nanoparticles under mild conditions is described. Physicochemical characterization by X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed heterogeneous morphologies for the In nanoparticles in all cases. Apart from In0, XPS revealed the presence of oxidized In species on the carbon-supported samples, whereas these species were not observed for the unsupported samples. The best-in-class catalyst (In50/C50) exhibited a high formate Faradaic efficiency (FE) near the unit (above 97%) at -1.6 V vs. Ag/AgCl, achieving a stable current density around -10 mA·cmgeo-2, in a common H-cell. While In0 sites are the main active sites for the reaction, the presence of oxidized In species could play a role in the improved performance of the supported samples.

LED-driven controlled deposition of Ni onto TiO2 for visible-light expanded conversion of carbon dioxide into C1-C2 alkanes.

Photocatalytic gas-phase hydrogenation of CO2 into alkanes was achieved over TiO2-supported Ni nanoparticles under LED irradiation at 365 nm, 460 nm and white light. The photocatalysts were prepared using photo-assisted deposition of Ni salts under LED irradiation at 365 nm onto TiO2 P25 nanoparticles in methanol as a hole scavenger. This procedure yielded 2 nm Ni particles decorating the surface of TiO2 with a nickel mass content of about 2%. Before the photocatalytic runs, Ni/TiO2 was submitted to thermal reduction at 400 °C in a 10% H2 atmosphere which induced O-defective TiO2-x substrates. The formation of oxygen vacancies, Ti3+ centers and metallic Ni sites upon photocatalytic CO2 hydrogenation was confirmed by operando EPR analysis. In situ XPS under reaction conditions suggested a strong metal-support interaction and the co-existence of zero and divalent Ni states. These photoactive species enhanced the photo-assisted reduction of CO2 below 300 °C to yield CO, CH4 and C2H6 as final products.

Towards Extending Solar Cell Lifetimes: Addition of a Fluorous Cation to Triple Cation-Based Perovskite Films.

Organohalide perovskites have emerged as highly promising replacements for thin-film solar cells. However, their poor stability under ambient conditions remains problematic, hindering commercial exploitation. The addition of a fluorous-functionalized imidazolium cation during the preparation of a highly stable cesium-based mixed perovskite material Cs0.05 (MA0.15 FA0.85 )0.95 Pb(I0.85 Br0.15 )3 (MA=methylammonium; FA=formamidinium) has been shown to influence its stability. The resulting materials, which vary according to the amount of the fluorous-functionalized imidazolium cation present during fabrication, display a prolonged tolerance to atmospheric humidity (>100 days) along with power conversion efficiencies exceeding 16 %. This work provides a general route that can be implemented in a variety of perovskites and highlights a promising way to increase perovskite solar cell stability.

Sonogashira cross-coupling and homocoupling on a silver surface: chlorobenzene and phenylacetylene on Ag(100).

Scanning tunneling microscopy, temperature-programmed reaction, near-edge X-ray absorption fine structure spectroscopy, and density functional theory calculations were used to study the adsorption and reactions of phenylacetylene and chlorobenzene on Ag(100). In the absence of solvent molecules and additives, these molecules underwent homocoupling and Sonogashira cross-coupling in an unambiguously heterogeneous mode. Of particular interest is the use of silver, previously unexplored, and chlorobenzene-normally regarded as relatively inert in such reactions. Both molecules adopt an essentially flat-lying conformation for which the observed and calculated adsorption energies are in reasonable agreement. Their magnitudes indicate that in both cases adsorption is predominantly due to dispersion forces for which interaction nevertheless leads to chemical activation and reaction. Both adsorbates exhibited pronounced island formation, thought to limit chemical activity under the conditions used and posited to occur at island boundaries, as was indeed observed in the case of phenylacetylene. The implications of these findings for the development of practical catalytic systems are considered.

In situ spectroscopic detection of SMSI effect in a Ni/CeO2 system: hydrogen-induced burial and dig out of metallic nickel.

In situ APPES technique demonstrates that the strong metal support interaction effect (SMSI) in the Ni-ceria system is associated with the decoration and burial of metallic particles by the partially reduced support, a phenomenon reversible by evacuation at high temperature of the previously absorbed hydrogen.