Recently, defect engineering has been used to intruduce half‐metallicity into selected semiconductors, thereby significantly enhancing their electrical conductivity and catalytic/electrocatalytic performance. Taking inspiration from this, we developed a novel bifunctional electrode consisting of two monolayer thick manganese dioxide (δ‐MnO2) nanosheet arrays on a nickel foam, using a novel in‐situ method. The bifunctional electrode exposes numerous active sites for electrocatalytic rections and displays excellent electrical conductivity, resulting in strong performance for both HER and OER. Based on detailed structure analysis and density functional theory (DFT) calculations, the remarkably OER and HER activity of the bifunctional electrode can be attributed to the ultrathin δ‐MnO2 nanosheets containing abundant oxygen vacancies lead to the formation od Mn3+ active sites, which give rise to half‐metallicity properties and strong H2O adsorption. This synthetic strategy introduced here represents a new method for the development of non‐precious metal Mn‐based electrocatalysts for eddicient energy conversion.
Lithium‐rich manganese‐based layered oxides show great potential as high‐capacity cathode materials for lithium ion batteries, but usually exhibit a poor cycle life, gradual voltage drop during cycling, and low thermal stability in the highly delithiated state. Herein, a strategy to promote the electrochemical performance of this material by manipulating the electronic structure through incorporation of boracic polyanions is developed. As‐prepared Li[Li0.2Ni0.13Co0.13Mn0.54](BO4)0.015(BO3)0.005O1.925 shows a decreased M‐O covalency and a lowered O 2p band top compared with pristine Li[Li0.2Ni0.13Co0.13Mn0.54]O2. As a result, the modified cathode exhibits a superior reversible capacity of 300 mA h g−1 after 80 cycles, excellent cycling stability with a capacity retention of 89% within 300 cycles, higher thermal stability, and enhanced redox couple potentials. The improvements are correlated to the enhanced oxygen stability that originates from the tuned electronic structure. This facile strategy may further be extended to other high capacity electrode systems.
Enhancement of the semiconductor-molecule interaction, in particular, promoting the interfacial charge transfer process (ICTP), is key to improving the sensitivity of semiconductor-based surface enhanced Raman scattering (SERS). Herein, by developing amorphous ZnO nanocages (a-ZnO NCs), we successfully obtained an ultrahigh enhancement factor of up to 6.62×10 . This remarkable SERS sensitivity can be attributed to high-efficiency ICTP within a-ZnO NC molecule system, which is caused by metastable electronic states of a-ZnO NCs. First-principles density functional theory (DFT) simulations further confirmed a stronger ICTP in a-ZnO NCs than in their crystalline counterparts. The efficient ICTP can even generate π bonding in Zn-S bonds peculiar to the mercapto molecule adsorbed a-ZnO NCs, which has been verified through the X-ray absorption near-edge structure (XANES) characterization. To the best of our knowledge, this is the first time such remarkable SERS activity has been observed within amorphous semiconductor nanomaterials, which could open a new frontier for developing highly sensitive and stable SERS technology.
The mechanism for regulating the critical temperature (TC) of metal-insulator transition (MIT) in ions-doped VO2 systems is still a matter of debate, in particular, the unclear roles of lattice distortion and charge doping effects. To rule out the charge doping effect on the regulation of TC, we investigated Ti4+-doped VO2 (TixV1-xO2) system. It was observed that the TC of TixV1-xO2 samples first slightly decreased and then increased with increasing Ti concentration. X-ray absorption fine structure (XAFS) spectroscopy was used to explore the electronic states and local lattice structures around both Ti and V atoms in TixV1-xO2 samples. Our results revealed the local structure evolution from the initial anatase to the rutile-like structure around the Ti dopants. Furthermore, the host monoclinic VO2 lattice, specifically, the VO6 octahedra would be subtly distorted by Ti doping. The distortion of VO6 octahedra and the variation of TC showed almost the similar trend, confirming the direct effect of local structural perturbations on the phase transition behavior. By comparing other ion-doping systems, we point out that the charge doping is more effective than the lattice distortion in modulating the MIT behavior of VO2 materials.
Na-ion batteries are gaining an increased recognition as the next generation low cost energy storage devices. Here, we present a characterization of Na3FePO4CO3 nanoplates as a novel cathode material for sodium ion batteries. First-principles calculations reveal that there are two paths for Na ion migration along b and c axis. In-situ and ex-situ Fe K-edge X-ray absorption near edge structure (XANES) point out that in Na3FePO4CO3 both Fe2+/Fe3+ and Fe3+/Fe4+ redox couples are electrochemically active, suggesting also the existence of a two-electron intercalation reaction. Ex-situ X-ray powder diffraction data demonstrates that the crystalline structure of Na3FePO4CO3 remains stable during the charging/discharging process within the range 2.0–4.55 V.
Anionic redox processes are vital to realize high capacity in lithium-rich electrodes of lithium-ion batteries. However, the activation mechanism of these processes remains ambiguous, hampering further implementation in new electrode design. This study demonstrates that the electrochemical activity of inert cubic-Li 2 TiO 3 is triggered by Fe 3+ substitution, to afford considerable oxygen redox activity. Coupled with first principles calculations, it is found that electron holes tend to be selectively generated on oxygen ions bonded to Fe rather than Ti. Subsequently, a thermodynamic threshold is unravelled dictated by the relative values of the Coulomb and exchange interactions (U) and charge-transfer energy (Δ) for the anionic redox electron-transfer process, which is further verified by extension to inactive layered Li 2 TiS 3 , in which the sulfur redox process is activated by Co substitution to form Li 1.2 Ti 0.6 Co 0.2 S 2 . This work establishes general guidance for the design of high-capacity electrodes utilizing anionic redox processes.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.