Atomic transition‐metal‐nitrogen‐carbon catalysts (M‐N‐Cs) hold great promise as Pt‐group‐metal‐free candidates for electrochemical reactions, yet their rational design and controllable synthesis remain fundamental challenges. Here, the molten‐salts mediated pyrolysis is demonstrated to be an effective and facile strategy for simultaneous morphology and electronic structure modulation of prototypical Fe‐N‐C materials, which functions as efficient oxygen reduction electrocatalysts. Taking advantage of the strong polarity and salt templating effects, the as‐obtained Fe‐N/C‐single atom catalyst (SAC) possesses hierarchical porous nanosheet morphology with an impressive specific surface area of 2237 m2 g−1 and unique FeN4Cl moieties as isolated active centers. The Fe‐N/C‐SAC delivers remarkable alkaline oxygen reduction reaction (ORR) activity with a half‐wave potential of 0.91 V and record kinetic current density up to 55 mA cm−2, outperforming the benchmark Pt/C. By virtue of dechlorination treatment, it is experimentally identified that the enhanced ORR activities are essentially governed by the axially bound Cl. Theoretical calculations rationalize this finding and demonstrate that the well‐defined fivefold‐coordinated configuration accelerates 4e− pathway kinetics through near‐optimal adsorption of the *OH intermediates and tunes the potential determining step from *OH reduction to *OOH formation. This study provides fundamental insights into the coordination‐engineered strategy in single‐atom catalysis.
Identifying reaction intermediates in gas-phase investigations will provide understanding for the related catalysts in fundamental aspects including bonding interactions of the reaction species, oxidation states (OSs) of the anchored atoms, and reaction mechanisms. Herein, carbon monoxide (CO) oxidation by praseodymium monoxide (PrO) molecules has been investigated as a model reaction in solid argon using matrix-isolation IR spectroscopy and quantum-chemical calculations. Two reaction intermediates, OPr(η 1 -CO) and OPr(η 2 -CO), have been trapped and characterized in argon matrixes. The intermediate OPr(η 2 -CO) shows an extremely low C−O stretching band at 1624.5 cm −1 . Quantum-chemistry studies indicate that the bonding in OPr(η 1 -CO) is described as "donor−acceptor" interactions conforming to the Dewar−Chatt−Duncanson motif. However, the bonding in OPr(η 2 -CO) results evidently from a combination of dominant ionic forces and normal Lewis "acid−base" interactions. The electron density of the singly occupied bonding orbital is strongly polarized to the CO fragment in OPr(η 2 -CO). Electronic structure analysis suggests that the two captured species exhibit Pr(III) OSs. Besides, the pathways of CO oxidation have been discussed.
Optical properties of the UO2+x film deposited by a polymer-assisted deposition method have been investigated by spectroscopic ellipsometry (SE). This epitaxial film contains at least two kinds of uranium oxides of U3O8 and UO3, and the O/U ratio is 2.74, which is confirmed by x-ray diffraction (XRD) and scanning Auger microscopy methods. By investigating the optical constants, the bandgaps of U3O8 and UO3 are determined as 2.3 and 1.0 eV, respectively, and 80% of the epitaxial film is U3O8 and 20% is UO3. The speciation signatures from the XRD and band structures show that the UO2+x epitaxial film reduced to U3O8 with the heating treatment at 480 K in a vacuum while oxidized to UO3 at 650 K. This work demonstrates a useful tool for studying the optical properties, band structures, and phase transition of uranium oxide film by SE.
CdSe/ZnS core/shell quantum dots (QDs) were synthesized and adsorbed onto nanocrystalline TiO2 films for application in quantum dot sensitized solar cells(QDSSCs). Femtosecond transient absorption spectra was measured to investigate the effect of the ZnS shell coating on electron injection from CdSe QDs to nanocrystalline TiO2 films. The results showed a decrease in electron injection rate from 7.14 × 10 11 to 2.38 × 10 11 s -1 after ZnS shell coating, which means the electron injection rate only remained 1/3. The fill factor(FF) and stability of QDSSCs were improved by ZnS coating, but the photocurrent decreased, resulting in an overall decrease in efficiency. The slower electron injection rate is found to be the main cause for this decrease in photocurrent and efficiency, which matches well with the photovoltaic property test. These results provide information for optimizing the current and efficiency of QDSSCs employing core/shell QDs.
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