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The temperature dependence of the crystal structure and electronic properties of brownmillerite-like Ca(2.5)Sr(0.5)GaMn(2)O(8) has been studied by neutron powder diffraction and muSR spectroscopy. The results show that short-range 2D magnetic order begins to develop within the perovskite-like bilayers of MnO(6) octahedra approximately 50 K above the 3D Néel temperature of approximately 150 K. The bilayers show a structural response to the onset of magnetism throughout this temperature range whereas the GaO(4) layers that separate the bilayers only respond below the 3D ordering temperature. XANES spectroscopy shows that the sample contains Mn(3+) and Mn(4+) cations in a 1:1 ratio, and the behavior in the region of the Néel transition is interpreted as a local charge ordering. Electron diffraction and high-resolution electron microscopy have been used to show that the local microstructure is more complex than the average structure revealed by neutron diffraction, and that microdomains exist in which the GaO(4) tetrahedra show different orientations. It is argued that the bonding requirements of diamagnetic gallium control the electronic behavior within the perovskite-like bilayers.
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http://dx.doi.org/10.1021/ja0465000 | DOI Listing |
Nanoscale Horiz
September 2025
Department of Physical Chemistry, São Carlos Institute of Chemistry, University of São Paulo, Brazil.
This study developed heterogeneous catalysts composed of ZnO and CeO supported on H-ZSM-5 for the direct conversion of methane (CH) and carbon dioxide (CO) into acetic acid. The acid-base and electronic properties were modulated through oxide impregnation and reduction, aiming to create active sites capable of simultaneously activating both reactants. The samples were characterized by XRD, N physisorption, HRTEM/EDS, NH-TPD, CO-TPD, TPR, FTIR, XPS, CO-DRIFTS, and TGA, and tested in a batch reactor at 300 °C and 10 bar.
View Article and Find Full Text PDFPhys Chem Chem Phys
September 2025
Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025, China.
Transition metal dichalcogenides (TMDs) have been extensively studied as efficient photocatalysts for water splitting. However, the utilization efficiency of photogenerated carriers remains a major limitation for their practical applications. An effective approach to address this issue is the construction of Z-scheme heterostructures.
View Article and Find Full Text PDFMater Horiz
September 2025
MOE Key Laboratory of Macromolecule Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, PR China.
Globular proteins, traditionally regarded as non-structural biomolecules due to the limited load-bearing capacity in their monomeric states, are increasingly recognized as valuable building blocks for functional-mechanical materials. Their inherent bioactivity, chemical versatility, and structural tunability enable the design of materials that combine biological functionality with tailored mechanical performance. This review highlights recent advances in engineering globular proteins-spanning natural systems (serum albumins, enzymes, milk globulins, silk sericin, and soy protein isolates) to recombinant architectures including tandem-repeat proteins-into functional-mechanical platforms.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Universidad de Córdoba, Grupo de Química Computacional, Facultad de Ciencias Básicas, Carrera 6, No. 77-305, Montería-Córdoba, Colombia.
This study explores the photochemical conversion of BN-Dewar benzene into BN-benzvalene derivatives, offering a strategic route to heteroatom-containing valence isomers with distinctive electronic properties. Using time-dependent density functional theory (TD-DFT) and electron localization function (ELF) analyses, the excited-state mechanism and associated structural rearrangements were elucidated. Vertical excitation to the S state was found to weaken the CC and B-N bonds while strengthening the N-Si bond in silyl-substituted derivatives, a key factor enabling efficient BN-benzvalene formation.
View Article and Find Full Text PDFJ Comput Chem
September 2025
Department of Electrical and Electronic Engineering, Begum Rokeya University, Rangpur, Bangladesh.
This study presents a comprehensive first-principles and device-performance investigation of alkali metal-based anti-perovskites ZBrO (Z = K, Rb, Cs, and Fr) for advanced optoelectronic and photovoltaic applications. Using density functional theory (DFT) with GGA-PBE and mGGA-rSCAN functionals, we analyzed the structural, electronic, optical, mechanical, phonon, population, and thermoelectric properties of these compounds. All ZBrO materials exhibit direct band gaps and strong optical absorption in the visible-UV spectrum.
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