In Situ Topochemical Transformation of ZnIn2S4 for Efficient Photocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran

Photocatalytic selective oxidation of 5-hydroxymethylfurfural (HMF) coupled H₂ production offers a promising approach to producing valuable chemicals. Herein, an efficient in situ topological transformation tactic is developed for producing porous O-doped ZnIn₂S₄ nanosheets for HMF oxidation cooperative with H₂ evolution. Aberration-corrected high-angle annular dark-field scanning TEM images show that the hierarchical porous O-ZIS-120 possesses abundant atomic scale edge steps and lattice defects, which is beneficial for electron accumulation and molecule adsorption. The optimal catalyst (O-ZIS-120) exhibits remarkable performance with 2,5-diformylfuran (DFF) yields of 1624 µmol h⁻¹ g⁻¹ and the selectivity of >97%, simultaneously with the H₂ evolution rate of 1522 µmol h⁻¹ g⁻¹. Mechanistic investigations through theoretical calculations show that O in the O-ZIS-120 lattice can reduce the oxidation energy barrier of hydroxyl groups of HMF. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) results reveal that DFF^* (C₄H₂(CHO)₂O^*) intermediate has a weak interaction with O-ZIS-120 and desorb as the final product. This study elucidates the topotactic structural transitions of 2D materials simultaneously with electronic structure modulation for efficient photocatalytic DFF production.     

2D Bi2O2Te Semiconductor with Single-Crystal Native Oxide Layer

Following logic in the silicon semiconductor industry, the existence of native oxide and suitable fabrication technology is essential for 2D semiconductors in planar integronics, which are surface-sensitive to typical coating technologies. To date, very few types of integronics are found to possess this feature. Herein, the 2D Bi₂O₂Te developed recently is reported to possess large-area synthesis and controllable thermal oxidation behavior toward single-crystal native oxides. This shows that surface-adsorbed oxygen atoms are inclined to penetrate across [Bi₂O₂]_n²ⁿ⁺ layers and bond with the underlying [Te]_n²ⁿ⁻ at elevated temperatures, transforming directly into [TeO₄]_n²ⁿ⁻ with the basic architecture remaining stable. The oxide can be adjusted to form in an accurate layer-by-layer manner with a low-stress sharp interface. The native oxide Bi₂TeO₆ layer (bandgap of ≈2.9 eV) exhibits visible-light transparency and is compatible with wet-chemical selective etching technology. These advances demonstrate the potential of Bi₂O₂Te in planar-integrated functional nanoelectronics such as tunnel junction devices, field-effect transistors, and memristors.     

Optimizing the Oxygen-Catalytic Performance of Zn–Mn–Co Spinel by Regulating the Bond Competition at Octahedral Sites

By using the more electro-negative Mn³⁺ ion to partially replace Co³⁺ at the octahedral site of spinel ZnCo₂O₄, i.e., forming ternary Zn–Mn–Co spinel oxide, the electrocatalytic oxygen reduction/evolution activity is found to be significantly increased. Considering the physical characterization and theoretical calculations, it demonstrated that the bond competition played a key role in regulating the cobalt valence state and the electrocatalytic activity. The partial replacement of octahedral-site-occupied Co³⁺ by Mn³⁺ can effectively modulate the adjacent Co–O bond and induce the Jahn–Teller effect, thus changing the originally stable crystal structure and optimizing the binding strength between the active center and reaction intermediates. Certainly, the Mn-substituted ZnMn_1.4Co_0.6O₄/NCNTs exhibit higher electrocatalytic oxygen reduction reaction (ORR) activity than that of ZnCo₂O₄/NCNTs and ZnMn₂O₄/NCNTs, supporting that the Co–O bond covalency determines the ORR activity of spinel ZnCo₂O₄. This study offers the competition between adjacent Co–O and Mn–O bonds via the B_Oh–O–B_Oh edge-sharing geometry. The ion substitution at octahedral sites by less electronegative cations can be a new and effective way to improve the electrocatalytic performance of cobalt-based spinel oxides.     

Ultra-Stable and Sensitive Ultraviolet Photodetectors Based on Monocrystalline Perovskite Thin Films

The detection of ultraviolet (UV) radiation with effective performance and robust stability is essential to practical applications. Metal halide single-crystal perovskites (ABX₃) are promising next-generation materials for UV detection. The device performance of all-inorganic CsPbCl₃ photodetectors (PDs) is still limited by inner imperfection of crystals grown in solution. Here wafer-scale single-crystal CsPbCl₃ thin films are successfully grown by vapor-phase epitaxy method, and the as-constructed PDs under UV light illumination exhibit an ultralow dark current of 7.18 pA, ultrahigh ON/OFF ratio of ≈5.22 × 10⁵, competitive responsivity of 32.8 A W⁻¹, external quantum efficiency of 10867% and specific detectivity of 4.22 × 10¹² Jones. More importantly, they feature superb long-term stability toward moisture and oxygen within twenty-one months, good temperature tolerances at low and high temperatures. The ability of the photodetector arrays for excellent UV light imaging is further demonstrated.     

A Stable Polymer-based Solid-State Lithium Metal Battery and its Interfacial Characteristics Revealed by Cryogenic Transmission Electron Microscopy

Solid-state lithium metal batteries (SSLMBs) are a promising candidate for next-generation energy storage systems due to their intrinsic safety and high energy density. However, they still suffer from poor interfacial stability, which can incur high interfacial resistance and insufficient cycle lifespan. Herein, a novel poly(vinylidene fluoride‑hexafuoropropylene)-based polymer electrolyte (PPE) with LiBF₄ and propylene carbonate plasticizer is developed, which has a high room-temperature ionic conductivity up to 1.15 × 10⁻³ S cm⁻¹ and excellent interfacial stability. Benefitting from the stable interphase, the PPE-based symmetric cell can operate for over 1000 h. By virtue of cryogenic transmission electron microscopy (Cryo-TEM) characterization, the high interfacial compatibility between Li metal anode and PPE is revealed. The solid electrolyte interphase is made up of an amorphous outer layer that can keep intimate contact with PPE and an inner Li₂O-dominated layer that can protect Li from continuous side reactions during battery cycling. A LiF-rich transition layer is also discovered in the region of PPE close to Li metal anode. The feasibility of investigating interphases in polymer-based solid-state batteries via Cryo-TEM techniques is demonstrated, which can be widely employed in future to rationalize the correlation between solid-state electrolytes and battery performance from ultrafine interfacial structures.     

Flow injection analysis methods for determination of diffusion coefficients

Two flow injection analyses (FIA) methods for the determination of diffusion coefficients in a straight single tube FIA system were developed. Based on the analytical solution of the convection-diffusion equation, linear relationships of the logarithmic values of the dispersion coefficient (D) and the half-peak width (W_1/2) with the diffusion coefficient (D_m) were obtained. Experiments were designed to verify these methods. For example, for potassium hexacyanoferrate (III) a D_m value of 0.72 × 10⁵ cm² s⁻¹ was found versus a literature value of 0.76 × 10⁵ cm² s⁻¹ (error, 5%). For potassium hexacyanoferrate (II) a D_m value of 0.67 × 10⁵ cm² s⁻¹ was obtained versus a literature value of 0.63 × 10⁵ cm² s⁻¹ (error, 6%). The diffusion coefficients of some important biomedical compounds, such as dopamine, epinephrine, norepinephrine and ascorbic acid, were then determined. The values of 10⁵ D_m/cm² s⁻¹ are 0.60 ± 0.03, 0.44 ± 0.02, 0.60 ± 0.01 and 0.68 ± 0.06, respectively.