Regulating the Electron Localization of Metallic Bismuth for Boosting CO2 Electroreduction

Electrochemical reduction of CO2 to formate is economically attractive but improving the reaction selectivity and activity remains challenging. Herein, we introduce boron (B) atoms to modify the local electronic structure of bismuth with positive valence sites for boosting conversion of CO2 into formate with high activity and selectivity in a wide potential window. By combining experimental and computational investigations, our study indicates that B dopant differentiates the proton participations of rate-determining steps in CO2 reduction and in the competing hydrogen evolution. By comparing the experimental observations with the density functional theory, the dominant mechanistic pathway of B promoted formate generation and the B concentration modulated effects on the catalytic property of Bi are unravelled. This comprehensive study offers deep mechanistic insights into the reaction pathway at an atomic and molecular level and provides an effective strategy for the rational design of highly active and selective electrocatalysts for efficient CO2 conversion.

Magnetotransport Properties of Semi-Metallic Bismuth Thin Films for Flexible Sensor Applications

In this paper we describe characterization of semi-metallic bismuth thin films. We prepared bismuth thin films by a deposition of bismuth through thermal evaporation onto flexible Kapton substrates and annealing at temperatures close to the melting point of Bi. We studied the morphology and transport properties of these films. Immediately after the deposition we observed competition between vanishing of the grain boundaries and elastic strain energy, which stabilized at larger thicknesses leading to the grain size of 140 nm. This effect was accompanied by a continuous decrease of resistivity which, however, was larger than for the bulk bismuth. The film annealing at temperatures close to the melting point of Bi led to a 300% increase of magnetoresistance at room temperature and in the magnetic field of 7 T. The in situ resistance measurements allowed us to determine the permissible temperature at which the annealing does not cause the loss of film continuity.

Bismuth Oxyhalides for NOx Degradation under Visible Light: The Role of the Chloride Precursor

Photocatalysis is a green technology for tackling water and air contamination. A valid alternative to the most exploited photocatalytic material, TiO2, is bismuth oxyhalides, which feature a wider bandgap energy range and use visible radiation to attain photoexcitation. Moreover, their layered structure favors the separation of photogenerated electron–hole pairs, with an enhancement in photocatalytic activity. Controlled doping of bismuth oxyhalides with metallic bismuth nanoparticles allows for further boosting of the performance of the material. In the present work, we synthesized Y%Bi-doped BiO(Cl0.875Br0.125) (Y = 0.85, 1, 2, 10) photocatalysts, using cetyltrimethylammonium bromide as the bromide source and varying the chloride source to assess the impact that both length and branching of the hydrocarbon chain might have on the framing and layering of the material. A change in the amount of the reducing agent NaBH4 allowed tuning of the percentage of metallic bismuth. After a thorough characterization (XRPD, SEM, TEM, UV-DRS, XPS), the photocatalytic activity of the catalysts was tested in the degradation of NOx under visible light, reaching a remarkable 53% conversion after 3 h of illumination for the material prepared using cetylpyridinium chloride.