Reversible protonic ceramic cells (rPCCs) combine two different operation regimes, fuel cell and electrolysis cell modes, which allow reversible chemical-to-electrical energy conversion at reduced temperatures with high efficiency and performance. Here we present novel technological and materials science approaches, enabling a rPCC with symmetrical functional electrodes to be prepared using a single sintering step. The response of the cell fabricated on the basis of P⁻N⁻BCZD|BCZD|PBN⁻BCZD (where BCZD = BaCeZrDyO, PBN = PrBaNiO, P = Pr₂O₃, N = Ni) is studied at different temperatures and water vapor partial pressures (pH₂O) by means of volt-ampere measurements, electrochemical impedance spectroscopy and distribution of relaxation times analyses. The obtained results demonstrate that symmetrical electrodes exhibit classical mixed-ionic/electronic conducting behavior with no hydration capability at 750 °C; therefore, increasing the pH₂O values in both reducing and oxidizing atmospheres leads to some deterioration of their electrochemical activity. At the same time, the electrolytic properties of the BCZD membrane are improved, positively affecting the rPCC's efficiency. The electrolysis cell mode of the rPCC is found to be more appropriate than the fuel cell mode under highly humidified atmospheres, since its improved performance is determined by the ohmic resistance, which decreases with pH₂O increasing.
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http://dx.doi.org/10.3390/ma12010118 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697, United States.
The development of molecular species with switchable magnetic properties has been a long-standing challenge in chemistry. One approach involves binding an analyte, such as protons, to a compound to trigger a change in magnetism. Transition metal complexes have been targeted for this type of magnetic modulation because they can undergo changes in their spin states.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Dipartimento di Scienze Fisiche e Chimiche, Universita degli Studi dellAquila, Coppito, 67100 L'Aquila, Italy.
We present a comprehensive theoretical study, using state-of-the-art density functional theory simulations, of the structural and electrochemical properties of amorphous pristine and iron-doped nickel-(oxy)hydroxide catalyst films for water oxidation in alkaline solutions, referred to as NiCat and Fe:NiCat. Our simulations accurately capture the structural changes in locally ordered units, as reported by X-ray absorption spectroscopy, when the catalyst films are activated by exposure to a positive potential. We emphasize the critical role of proton-coupled electron transfer in the reversible oxidation of Ni(II) to Ni(III/IV) during this activation.
View Article and Find Full Text PDFInorg Chem
January 2025
Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577, Japan.
Sodium borohydride dihydrate (NaBH·2HO) forms through dihydrogen bonding between the hydridic hydrogen of the BH ion and the protonic hydrogen of the water molecule. High-pressure structural changes in NaBH·2HO, observed up to 11 GPa through X-ray diffraction and Raman scattering spectroscopy, were analyzed to assess the influence of dihydrogen bonds on its crystal structure. At approximately 4.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Harbin Institute of Technology (Shenzhen), Department of Materials Science and Engineering, College Park, Building C, 404, Shenzhen, CHINA.
Conventional SEI in aqueous Zn-ion batteries mainly acts as a physical barrier to prevent HER, which is prone to structural deterioration stemming from uneven Zn deposition at high current densities. Herein, we propose an in-situ structural design of polymer-inorganic bilayer SEI with a proton holder feature by aniline-modulated electrolytes. The inner ZnF2 with high stiffness and strength effectively suppresses Zn dendrites.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Nanjing University of Aeronautics and Astronautics, College of Materials Science and Technology, No. 169 Sheng Tai West Road, Jiangning District, Nanjing, Jiangsu, China, 211106, Nanjing, CHINA.
The neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis.
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