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The lack of availability of efficient, selective and stable electrocatalysts is a major hindrance for scalable CO2 reduction processes. Herein, we report the generation of Cu-In alloy surfaces for electrochemical reduction of CO2 from mixed metal oxides of CuInO2 as the starting material. The material successfully generates the selective active sites to form CO from CO2 electroreduction at mild overpotentials. Density functional theory (DFT) indicates that the site occupation of the inert In occurs more on the specific sites of Cu. In addition, while In atoms do not preferentially adsorb H or CO, Cu atoms, which neighbor the In atoms, alters the preference of their adsorption. This preference on site occupation and altered adsorption may account for the improved selectivity over that observed for Cu metal. This study demonstrates an example of a scalable synthesis method of bimetallic surfaces utilized with the mixed oxide precursor having the diversity of metal choice, which may drastically alter the electrocatalytic performance, as presented herein.

Density functional theory (DFT) and density functional perturbation theory (DFPT) were applied to study the structural, electronic, and optical properties of a (Na2–x Cu x )Ta4O11 solid solution to accurately calculate the band gap and to predict the optical transitions in these materials using the screened coulomb hybrid (HSE06) exchange-correlation formalism. The calculated density of states showed excellent agreement with UV–vis diffuse reflectance spectra predicting a significant red-shift of the band gap from 4.58 eV (calculated 4.94 eV) to 2.76 eV (calculated 2.60 eV) as copper content increased from 0 to 83.3%. The band gap narrowing in these materials, compared to Na2Ta4O11, results from the incorporation of new occupied electronic states, which are strongly localized on the Cu 3d orbitals, and is located within 2.16–2.34 eV just above the valence band of Na2Ta4O11. These new occupied states, however, possess an electronic character localized on Cu, which makes hole mobility limited in the semiconductor.

The selectivity and sensitivity of sensors are of great interest to the materials chemistry community, and a lot of effort is now devoted to improving these characteristics. More specifically, the selective sensing of anions is one of the largest challenges impeding the sensing-research area due to their similar physical and chemical behaviors. In this work, platinum-metalated porphyrin (Pt(II)TMPyP) was successfully encapsulated in a rho-type zeolite-like metal-organic framework (rho-ZMOF) and applied for anion-selective sensing. The sensing activity and selectivity of the MOF-encaged Pt(II)TMPyP for various anions in aqueous and methanolic media were compared to that of the free (nonencapsulated) Pt(II)TMPyP. While the photoinduced triplet-state electron transfer of Pt(II)TMPyP showed a very low detection limit for anions with no selectivity, the Pt(II)TMPyP encapsulated in the rho-ZMOF framework possessed a unique chemical structure to overcome such limitations. This new approach has the potential for use in other complex sensing applications, including biosensors, which require ion selectivity.

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