by Keyword: Thermally stimulated polarization

Sans J, Arnau M, Estrany F, Turon P, Alemán C, (2021). Regulating the Superficial Vacancies and OH− Orientations on Polarized Hydroxyapatite Electrocatalysts Advanced Materials Interfaces 8,

Smart designs of hydroxyapatite (HAp) materials with customized electrical properties are drawing increasing attention for their wide range of potential applications. Such enhanced electrical properties directly arise from the number and orientation of OH groups in the HAp lattice. Although different polarization treatments have been proposed to enhance the final conductivity by generating vacancies at high temperatures and imposing specific OH orientations through electric voltages, no direct measurement showing the evolution that OH groups undergo has been described yet. In this article, the first direct empirical observation that allows the characterization of both the generation of vacancies and the polarization of OH groups is reported. The mechanisms behind the electrical enhancement are elucidated allowing to distinguish between charge accumulation at the crystal grains, which is due to the formed vacancies, and charge accumulation in the boundaries of particles. In addition, a linear dependence between the number of vacancies and the superficial charge is observed. Therefore, it is demonstrated that the charge accumulation at the micrometric grain boundaries has a great impact on the catalytic properties of the thermally stimulated polarized HAp. These results will be used for further optimization of the catalyst properties. − − − −

JTD Keywords: electrocatalysts, hydroxyl orientation, thermally stimulated polarization, vacancies, Charge delocalization, Electrocatalysts, Hydroxyl orientation, Thermally stimulated polarization, Vacancies

Sans, J, Sanz, V, del Valle, LJ, Puiggali, J, Turon, P, Aleman, C, (2021). Optimization of permanently polarized hydroxyapatite catalyst. Implications for the electrophotosynthesis of amino acids by nitrogen and carbon fixation Journal Of Catalysis 397, 98-107

The enhanced catalytic activity of permanently polarized hydroxyapatite, which is achieved using a thermally stimulated polarization process, largely depends on both the experimental conditions used to prepare crystalline hydroxyapatite from its calcium and phosphate precursors and the polarization process parameters. A mineral similar to brushite, which is an apatitic phase that can evolve to hydroxyapatite, is found at the surface of highly crystalline hydroxyapatite. It appears after chemical precipitation and hydrothermal treatment performed at 150 degrees C for 24 h followed by a sinterization at 1000 degrees C and a polarization treatment by applying a voltage of 500 Vat high temperature. Both the high crystallinity and the presence of brushite-like phase on the electrophotocatalyst affect the nitrogen and carbon fixation under mild reaction conditions (95 degrees C and 6 bar) and the synthesis of glycine and alanine from a simple gas mixture containing N-2, CO2, CH4 and H2O. Thus, the Gly/Ala ratio can be customized by controlling the presence of brushite on the surface of the catalyst, enabling to develop new strategies to regulate the production of amino acids by nitrogen and carbon fixation. (C) 2021 Elsevier Inc. All rights reserved.

JTD Keywords: Amino acids, Brushite, Carbon, Carbon dioxide fixation, Catalyst activity, Catalytic apatites, Chemical precipitation, Crystalline hydroxyapatite, Crystallinity, Decomposition, Enhanced catalytic activity, Experimental conditions, Heterogeneous catalysis, High crystallinity, Hydrothermal synthesis, Hydrothermal treatments, Hydroxyapatite, Lactic-acid, Mild reaction conditions, Molecular nitrogen fixation, Nitrogen, Nitrogen fixation, Phosphate, Polarization, Precipitation (chemical), Process parameters, Thermally stimulated polarization