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Designing efficient catalyst for the oxygen evolution reaction (OER) is of importance for energy conversion devices. The anionic redox allows formation of O-O bonds and offers higher OER activity than the conventional metal sites. Here, we successfully prepare LiNiO2 with a dominant 3d8L configuration (L is a hole at O 2p) under high oxygen pressure, and achieve a double ligand holes 3d8L2 under OER since one electron removal occurs at O 2p orbitals for NiIII oxides. LiNiO2 exhibits super-efficient OER activity among LiMO2, RMO3 (M = transition metal, R = rare earth) and other unary 3d catalysts. Multiple in situ/operando spectroscopies reveal NiIII→NiIV transition together with Li-removal during OER. Our theory indicates that NiIV (3d8L2) leads to direct O-O coupling between lattice oxygen and *O intermediates accelerating the OER activity. These findings highlight a new way to design the lattice oxygen redox with enough ligand holes created in OER process. Lattice-oxygen redox is pivotal for high oxygen evolution reaction (OER) activity. Here, LiNiO2, a unary 3d-transition metal oxide catalyst, exhibits superefficient activity during the OER due to the creation of double O 2p holes states, according to operando XAS, XRD, and Raman spectroscopy observations. [ABSTRACT FROM AUTHOR]

The production of ecologically compatible fuels by electrochemical water splitting is highly desirable for modern industry. The Zhang-Rice singlet is well known for the superconductivity of high-temperature superconductors cuprate, but is rarely known for an electrochemical catalyst. Herein, we observe two steps of surface reconstruction from initial catalytic inactive Cu1+ in hydrogen treated Cu2O to Cu2+ state and further to catalytic active Zhang-Rice singlet state during the oxygen evolution reaction for water splitting. The hydrogen treated Cu2O catalyst exhibits a superior catalytic activity and stability for water splitting and is an efficient rival of other 3d-transition-metal catalysts. Multiple operando spectroscopies indicate that Zhang-Rice singlet is real active species, since it appears only under oxygen evolution reaction condition. This work provides an insight in developing an electrochemical catalyst from catalytically inactive materials and improves understanding of the mechanism of a Cu-based catalyst for water oxidation. The Zhang-Rice singlet is known for the superconductivity of high-temperature superconductors cuprate but is rarely studied for an electrochemical catalyst. Here, the authors use operando spectroscopic tools and observe Cu active site evolves into high-valent CuO4 geometry with Cu3+ active species, so-called Zhang-Rice singlet state, during oxygen evolution reaction. [ABSTRACT FROM AUTHOR]

Structural degradation in manganese oxides leads to unstable electrocatalytic activity during long-term cycles. Herein, we overcome this obstacle by using proton exchange on well-defined layered Li2MnO3 with an O3-type structure to construct protonated Li2-xHxMnO3-n with a P3-type structure. The protonated catalyst exhibits high oxygen reduction reaction activity and excellent stability compared to previously reported cost-effective Mn-based oxides. Configuration interaction and density functional theory calculations indicate that Li2-xHxMnO3-n has fewer unstable O 2p holes with a Mn3.7+ valence state and a reduced interlayer distance, originating from the replacement of Li by H. The former is responsible for the structural stability, while the latter is responsible for the high transport property favorable for boosting activity. The optimization of both charge states to reduce unstable O 2p holes and crystalline structure to reduce the reaction pathway is an effective strategy for the rational design of electrocatalysts, with a likely extension to a broad variety of layered alkali-containing metal oxides. Structural degradation in manganese oxides leads to unstable activity during long-term cycles. Herein, authors demonstrated that reduced unstable O 2p holes and the short interlayer distance of layered lithium manganese oxide are favorable for excellent electrocatalytic stability and activity. [ABSTRACT FROM AUTHOR]

PbMO3 (M = 3d transition metals) family shows systematic variations in charge distribution and intriguing physical properties due to its delicate energy balance between Pb 6s and transition metal 3d orbitals. However, the detailed structure and physical properties of PbFeO3 remain unclear. Herein, we reveal that PbFeO3 crystallizes into an unusual 2ap × 6ap × 2ap orthorhombic perovskite super unit cell with space group Cmcm. The distinctive crystal construction and valence distribution of Pb2+0.5Pb4+0.5FeO3 lead to a long range charge ordering of the -A-B-B- type of the layers with two different oxidation states of Pb (Pb2+ and Pb4+) in them. A weak ferromagnetic transition with canted antiferromagnetic spins along the a-axis is found to occur at 600 K. In addition, decreasing the temperature causes a spin reorientation transition towards a collinear antiferromagnetic structure with spin moments along the b-axis near 418 K. Our theoretical investigations reveal that the peculiar charge ordering of Pb generates two Fe3+ magnetic sublattices with competing anisotropic energies, giving rise to the spin reorientation at such a high critical temperature. PbFeO3 is part of a family of lead based perovskites with many intriguing properties; however, difficulties in synthesis have hampered investigation. Here, the authors present a detailed study of the structure of PbFeO3 observing unique charge ordering and spin orientation among the constituent ions. [ABSTRACT FROM AUTHOR]

Ferromagnetic semiconductors with luminescent effects provide a unique platform for studying magneto-electric-optical multifunctional devices. However, little is known about such materials with spin ordering well above room temperature. By using a unique high-pressure annealing method, a Cr and Fe disordered perovskite oxide SrCr0.5Fe0.5O2.875 (SCFO) with a simple cubic structure was prepared. Magnetic measurements demonstrated the ferromagnetic behavior with a spin ordering temperature as high as 600 K. In contrast to metallic SrCrO3 and SrFeO3, SCFO, with a moderate oxygen deficiency, is a direct bandgap semiconductor with an energy gap of 2.28 eV, which is within the visible light region. As a consequence, SCFO displays a green fluorescent effect arising from the d–p bonding and anti-bonding states. Moreover, the photoluminescence intensity can be tuned by a magnetic field. This work opens up a new avenue for research on room-temperature multifunctional materials with coupled magnetic, electrical, and optical performance. Semiconductors: Maintaining magnetism at high temperature A magnetic semiconductor that retains its magnetic properties at high temperatures has been developed by researchers in China and Germany. Semiconductor materials do much of the processing in computers and cell phones whereas magnetic materials store and retrieve information. A magnetic semiconductor merges these two functions in a single material and offers unique functionality not seen in the other materials. However, the magnetic properties of most of the known magnetic semiconductors disappear at high temperatures, limiting their application. Youwen Long from the Beijing National Laboratory for Condensed Matter Physics and colleagues used high pressures and high temperatures to create a SrCrFeO compound. This perovskite (a compound with a similar crystal structure to CaTiO3) demonstrated ferromagnetic behavior up to 600 K. Ferromagnetic semiconductors are promising candidates for high-performance multifunctional spintronic devices due to the peculiar magneto-electric and magneto-optical properties. However, the low spin ordering temperature limits their applications. By using high pressure to stabilize the crystal structure and oxygen content, an oxygen-deficient perovskite SrCr0.5Fe0.5O2.875 was synthesized. This compound displays ferromagnetic behavior with a spin ordering temperature as high as 600 K. Benefiting from the semiconducting direct bandgap (~2.28 eV), a field-tunable green fluorescent effect is observed. This work opens up a new avenue for research on room-temperature multifunctional materials with coupled magnetic, electrical, and optical performance. [ABSTRACT FROM AUTHOR]

A series of Eu3+-activated strontium silicate phosphors, Sr2SiO4:xEu3+ (SSO:xEu3+, x = 1.0, 2.0 and 5.0%), were synthesized by a sol–gel method, and their crystalline structures, photoluminescence (PL) behaviors, electronic/atomic structures and bandgap properties were studied. The correlation among these characteristics was further established. X-ray powder diffraction analysis revealed the formation of mixed orthorhombic α'-SSO and monoclinic β-SSO phases of the SSO:xEu3+ phosphors. When SSO:xEu3+ phosphors are excited under ultraviolet (UV) light (λ = 250 nm, ~ 4.96 eV), they emit yellow (~ 590 nm), orange (~ 613 nm) and red (~ 652 and 703 nm) PL bands. These PL emissions typically correspond to 4f–4f electronic transitions that involve the multiple excited 5D0 → 7FJ levels (J = 1, 2, 3 and 4) of Eu3+ activators in the host matrix. This mechanism of PL in the SSO:xEu3+ phosphors is strongly related to the local electronic/atomic structures of the Eu3+–O2− associations and the bandgap of the host lattice, as verified by Sr K-edge and Eu L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure, O K-edge XANES and Kα X-ray emission spectroscopy. In the synthesis of SSO:xEu3+ phosphors, interstitial Eu2O3-like structures are observed in the host matrix that act as donors, providing electrons that are nonradiatively transferred from the Eu 5d and/or O 2p–Eu 4f/5d states (mostly the O 2p–Eu 5d states) to the 5D0 levels, facilitating the recombination of electrons that have transitioned from the 5D0 level to the 7FJ level in the bandgap. This mechanism is primarily responsible for the enhancement of PL emissions in the SSO:xEu3+ phosphors. This PL-related behavior indicates that SSO:xEu3+ phosphors are good light-conversion phosphor candidates for use in near-UV chips and can be very effective in UV-based light-emitting diodes. [ABSTRACT FROM AUTHOR]

Ion leaching from pure-phase oxygen-evolving electrocatalysts generally exists, leading to the collapse and loss of catalyst crystalline matrix. Here, different from previous design methodologies of pure-phase perovskites, we introduce soluble BaCl2 and SrCl2 into perovskites through a self-assembly process aimed at simultaneously tuning dual cation/anion leaching effects and optimizing ion match in perovskites to protect the crystalline matrix. As a proof-of-concept, self-assembled hybrid Ba0.35Sr0.65Co0.8Fe0.2O3-δ (BSCF) nanocomposite (with BaCl2 and SrCl2) exhibits the low overpotential of 260 mV at 10 mA cm-2 in 0.1 M KOH. Multiple operando spectroscopic techniques reveal that the pre-leaching of soluble compounds lowers the difference of interfacial ion concentrations and thus endows the host phase in hybrid BSCF with abundant time and space to form stable edge/face-sharing surface structures. These self-optimized crystalline structures show stable lattice oxygen active sites and short reaction pathways between Co–Co/Fe metal active sites to trigger favorable adsorption of OH− species. Water oxidation catalysis may provide the electrons needed for sustainable fuel production, but catalysts often degrade under working conditions. Here, authors introduce soluble species into perovskites to exert positive ion leaching effects for enhancing perovskite stability and activity. [ABSTRACT FROM AUTHOR]

The ability to determine the electronic structure of catalysts during electrochemical reactions is highly important for identification of the active sites and the reaction mechanism. Here we successfully applied soft X-ray spectroscopy to follow in operando the valence and spin state of the Co ions in Li2Co2O4 under oxygen evolution reaction (OER) conditions. We have observed that a substantial fraction of the Co ions undergo a voltage-dependent and time-dependent valence state transition from Co3+ to Co4+ accompanied by spontaneous delithiation, whereas the edge-shared Co–O network and spin state of the Co ions remain unchanged. Density functional theory calculations indicate that the highly oxidized Co4+ site, rather than the Co3+ site or the oxygen vacancy site, is mainly responsible for the high OER activity. Determining catalyst electronic structures during electrochemical reactions is crucial to understand mechanisms. Here authors perform in operando soft X-ray spectroscopy on a cobalt oxide catalyst during O2 evolution and observe voltage and time-dependent valence state transitions. [ABSTRACT FROM AUTHOR]

The state-of-the-art active HER catalysts in acid media (e.g., Pt) generally lose considerable catalytic performance in alkaline media mainly due to the additional water dissociation step. To address this issue, synergistic hybrid catalysts are always designed by coupling them with metal (hydro)oxides. However, such hybrid systems usually suffer from long reaction path, high cost and complex preparation methods. Here, we discover a single-phase HER catalyst, SrTi0.7Ru0.3O3-δ (STRO) perovskite oxide highlighted with an unusual super-exchange effect, which exhibits excellent HER performance in alkaline media via atomic-scale synergistic active centers. With insights from first-principles calculations, the intrinsically synergistic interplays between multiple active centers in STRO are uncovered to accurately catalyze different elementary steps of alkaline HER; namely, the Ti sites facilitates nearly-barrierless water dissociation, Ru sites function favorably for OH* desorption, and non-metal oxygen sites (i.e., oxygen vacancies/lattice oxygen) promotes optimal H* adsorption and H2 desorption. Efficient electrocatalysts are crucial for the sustainable hydrogen production as an alternative clean fuel. Here, the authors explore a single-phase perovskite oxide as a high-performance hydrogen evolution electrocatalyst via super-exchange induced atomic scale synergistic active sites. [ABSTRACT FROM AUTHOR]

In the past decades, mesocrystal, a kind of nanocrystals with specific crystallographic orientation, has drawn a lot of attention due to its intriguing functionalities. While the research community keeps searching for new mesocrystal systems, it is equally crucial to develop new approaches to tune the properties of mesocrystals. In this work, a self-organized two-dimensional mesocrystal composed of highly oriented CoFe2O4 (CFO) nano-crystals with assistance of different perovskite matrices is studied as a model system. We have demonstrated that the strain state and corresponding magnetic properties of the CFO mesocrystal can be modulated by changing the surrounding perovskite matrix through their intimate structural coupling. Interestingly, this controllability is more strongly correlated to the competition of bonding strength between the matrices and the CFO mesocrystals rather than the lattice mismatch. When embedded in a matrix with a higher melting point or stiffness, the CFO mesocrystal experiences higher out-of-plane compressive strain and shows a stronger magnetic anisotropy as well as cation site-exchange. Our study suggests a new pathway to tailor the functionalities of mesocrystals. [ABSTRACT FROM AUTHOR]