More Like this

1. Enhanced oxygen evolution over dual corner-shared cobalt tetrahedra

   https://doi.org/10.1038/s41467-022-33000-w  

   Chen, Yubo; Seo, Joon Kyo; Sun, Yuanmiao; Wynn, Thomas A.; Olguin, Marco; Zhang, Minghao; Wang, Jingxian; Xi, Shibo; Du, Yonghua; Yuan, Kaidi; et al (December 2022, Nature Communications)

   Abstract Developing efficient catalysts is of paramount importance to oxygen evolution, a sluggish anodic reaction that provides essential electrons and protons for various electrochemical processes, such as hydrogen generation. Here, we report that the oxygen evolution reaction (OER) can be efficiently catalyzed by cobalt tetrahedra, which are stabilized over the surface of a Swedenborgite-type YBCo 4 O 7 material. We reveal that the surface of YBaCo 4 O 7 possesses strong resilience towards structural amorphization during OER, which originates from its distinctive structural evolution toward electrochemical oxidation. The bulk of YBaCo 4 O 7 composes of corner-sharing only CoO 4 tetrahedra, which can flexibly alter their positions to accommodate the insertion of interstitial oxygen ions and mediate the stress during the electrochemical oxidation. The density functional theory calculations demonstrate that the OER is efficiently catalyzed by a binuclear active site of dual corner-shared cobalt tetrahedra, which have a coordination number switching between 3 and 4 during the reaction. We expect that the reported active structural motif of dual corner-shared cobalt tetrahedra in this study could enable further development of compounds for catalyzing the OER. 

   more » « less
2. Synthesis, chiral crystal structure, and magnetic properties of Ba ₃ Ga ₂ O ₅ Cl ₂

   https://doi.org/10.1107/S2052520622004723  

   Rine, Jeremy; Yang, Yongqi; Shu, Zhixue; Zhao, Jianda; Xie, Weiwei; Kong, Tai (August 2022, Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials)

   A new compound, Ba 3 Ga 2 O 5 Cl 2 , isostructural with Ba 3 Fe 2 O 5 Cl 2 , was synthesized by solid-state reaction in air. Through single-crystal and powder X-ray diffraction analysis, the crystal structure was determined to be cubic with chiral space group I 2 1 3 and unit-cell parameter a  = 9.928 (1) Å. The Ga 3+ ions in Ba 3 Ga 2 O 5 Cl 2 are coordinated by O atoms and form GaO 4 tetrahedra. Ten neighboring GaO 4 tetrahedra are further bridged through corner sharing and rotation along the body diagonal, producing the chiral structure. Magnetization measurements indicate temperature-independent diamagnetic behavior, which is qualitatively consistent with core diamagnetism from all the constituent elements. 

   more » « less
3. Local structure of Sr ₂ CuO _3.3 , a 95 K cuprate superconductor without CuO ₂ planes

   https://doi.org/10.1073/pnas.1918890117  

   Conradson, Steven D.; Geballe, Theodore H.; Jin, Changqing; Cao, Lipeng; Baldinozzi, Gianguido; Jiang, Jack M.; Latimer, Matthew J.; Mueller, Oliver (February 2020, Proceedings of the National Academy of Sciences)

   The local structure of the highly “overdoped” 95 K superconductor Sr₂CuO_3.3determined by Cu K X-ray absorption fine structure (XAFS) at 62 K in magnetically oriented samples shows that 1) the magnetization is perpendicular to thecaxis; 2) at these levels of precision the Cu sublattice is tetragonal in agreement with the crystal structure; the O sublattice has 3) continuous -Cu-O- chains that orient perpendicular to an applied magnetic field; 4) approximately half-filled -Cu-O- chains that orient parallel to this field; 5) a substantial number of apical O vacancies; 6) O ions at some apical positions with expanded Cu-O distances; and 7) interstitial positions that imply highly displaced Sr ions. These results contradict the universally accepted features of cuprates that require intact CuO₂planes, magnetization along thecaxis, and a termination of the superconductivity when the excess charge on the CuO₂Cu ions exceeds 0.27. These radical differences in charge and structure demonstrate that this compound constitutes a separate class of Cu-O–based superconductors in which the superconductivity originates in a different, more complicated structural unit than CuO₂planes while retaining exceptionally high transition temperatures. 

   more » « less
4. ND70 Series Basaltic Glass Reference Materials for Volatile Element ( H₂O , CO₂ , S, Cl, F) Measurement and the C Ionisation Efficiency Suppression Effect of Water in Silicate Glasses in SIMS

   https://doi.org/10.1111/ggr.12572  

   Moussallam, Yves; Towbin, William Henry; Plank, Terry; Bureau, Hélène; Khodja, Hicham; Guan, Yunbin; Ma, Chi; Baker, Michael B; Stolper, Edward M; Naab, Fabian U; et al (July 2024, Geostandards and Geoanalytical Research)

   We present a new set of reference materials, the ND70‐series, forin situmeasurement of volatile elements (H₂O, CO₂, S, Cl, F) in silicate glass of basaltic composition. The materials were synthesised in piston cylinders at pressures of 1 to 1.5 GPa under volatile‐undersaturated conditions. They span mass fractions from 0 to 6%m/mH₂O, from 0 to 1.6%m/mCO₂and from 0 to 1%m/mS, Cl and F. The materials were characterised by elastic recoil detection analysis for H₂O, by nuclear reaction analysis for CO₂, by elemental analyser for CO₂, by Fourier transform infrared spectroscopy for H₂O and CO₂, by secondary ion mass spectrometry for H₂O, CO₂, S, Cl and F, and by electron probe microanalysis for CO₂, S, Cl and major elements. Comparison between expected and measured volatile amounts across techniques and institutions is excellent. It was found however that SIMS measurements of CO₂mass fractions using either Cs⁺or O⁻primary beams are strongly affected by the glass H₂O content. Reference materials have been made available to users at ion probe facilities in the US, Europe and Japan. Remaining reference materials are preserved at the Smithsonian National Museum of Natural History where they are freely available on loan to any researcher. 

   more » « less
5. Semiquinone radical-bridged M ₂ (M = Fe, Co, Ni) complexes with strong magnetic exchange giving rise to slow magnetic relaxation

   https://doi.org/10.1039/d0sc03078c  

   Chakarawet, Khetpakorn; Harris, T. David; Long, Jeffrey R. (August 2020, Chemical Science)

   null (Ed.)

   The use of radical bridging ligands to facilitate strong magnetic exchange between paramagnetic metal centers represents a key step toward the realization of single-molecule magnets with high operating temperatures. Moreover, bridging ligands that allow the incorporation of high-anisotropy metal ions are particularly advantageous. Toward these ends, we report the synthesis and detailed characterization of the dinuclear hydroquinone-bridged complexes [(Me 6 tren) 2 MII2(C 6 H 4 O 2 2− )] 2+ (Me 6 tren = tris(2-dimethylaminoethyl)amine; M = Fe, Co, Ni) and their one-electron-oxidized, semiquinone-bridged analogues [(Me 6 tren) 2 MII2(C 6 H 4 O 2 − ˙)] 3+ . Single-crystal X-ray diffraction shows that the Me 6 tren ligand restrains the metal centers in a trigonal bipyramidal geometry, and coordination of the bridging hydro- or semiquinone ligand results in a parallel alignment of the three-fold axes. We quantify the p -benzosemiquinone–transition metal magnetic exchange coupling for the first time and find that the nickel( ii ) complex exhibits a substantial J < −600 cm −1 , resulting in a well-isolated S = 3/2 ground state even as high as 300 K. The iron and cobalt complexes feature metal–semiquinone exchange constants of J = −144(1) and −252(2) cm −1 , respectively, which are substantially larger in magnitude than those reported for related bis(bidentate) semiquinoid complexes. Finally, the semiquinone-bridged cobalt and nickel complexes exhibit field-induced slow magnetic relaxation, with relaxation barriers of U eff = 22 and 46 cm −1 , respectively. Remarkably, the Orbach relaxation observed for the Ni complex is in stark contrast to the fast processes that dominate relaxation in related mononuclear Ni II complexes, thus demonstrating that strong magnetic coupling can engender slow magnetic relaxation. 

   more » « less