A Sustainable Solid Electrolyte Interphase for High‐Energy‐Density Lithium Metal Batteries Under Practical Conditions

High‐energy‐density Li metal batteries suffer from a short lifespan under practical conditions, such as limited lithium, high loading cathode, and lean electrolytes, owing to the absence of appropriate solid electrolyte interphase (SEI). Herein, a sustainable SEI was designed rationally by combining fluorinated co‐solvents with sustained‐release additives for practical challenges. The intrinsic uniformity of SEI and the constant supplements of building blocks of SEI jointly afford to sustainable SEI. Specific spatial distributions and abundant heterogeneous grain boundaries of LiF, LiN_xO_y, and Li₂O effectively regulate uniformity of Li deposition. In a Li metal battery with an ultrathin Li anode (33 μm), a high‐loading LiNi_0.5Co_0.2Mn_0.3O₂ cathode (4.4 mAh cm^?2), and lean electrolytes (6.1 g Ah^?1), 83 % of initial capacity retains after 150 cycles. A pouch cell (3.5 Ah) demonstrated a specific energy of 340 Wh kg^?1 for 60 cycles with lean electrolytes (2.3 g Ah^?1).     

Topochemical Synthesis of Two‐Dimensional Transition‐Metal Phosphides Using Phosphorene Templates

Transition‐metal phosphides (TMPs) have emerged as a fascinating class of narrow‐gap semiconductors and electrocatalysts. However, they are intrinsic nonlayered materials that cannot be delaminated into two‐dimensional (2D) sheets. Here, we demonstrate a general bottom‐up topochemical strategy to synthesize a series of 2D TMPs (e.g. Co₂P, Ni₁₂P₅, and Co_xFe_2?xP) by using phosphorene sheets as the phosphorus precursors and 2D templates. Notably, 2D Co₂P is a p‐type semiconductor, with a hole mobility of 20.8 cm² V^?1 s^?1 at 300 K in field‐effect transistors. It also behaves as a promising electrocatalyst for the oxygen evolution reaction (OER), thanks to the charge‐transport modulation and improved surface exposure. In particular, iron‐doped Co₂P (i.e. Co_1.5Fe_0.5P) delivers a low overpotential of only 278 mV at a current density of 10 mA cm^?2 that outperforms the commercial Ir/C benchmark (304 mV).     

Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode

Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal layered‐tunnel heterostructure Na_0.44Co_0.1Mn_0.9O₂ cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.     

Dendrite‐Free Sodium Metal Anodes Enabled by a Sodium Benzenedithiolate‐Rich Protection Layer

Sodium metal is an ideal anode material for metal rechargeable batteries, owing to its high theoretical capacity (1166 mAh g^?1), low cost, and earth‐abundance. However, the dendritic growth upon Na plating, stemming from unstable solid electrolyte interphase (SEI) film, is a major and most notable problem. Here, a sodium benzenedithiolate (PhS₂Na₂)‐rich protection layer is synthesized in situ on sodium by a facile method that effectively prevents dendrite growth in the carbonate electrolyte, leading to stabilized sodium metal electrodeposition for 400 cycles (800 h) of repeated plating/stripping at a current density of 1 mA cm^?2. The organic salt, PhS₂Na₂, is found to be a critical component in the protection layer. This finding opens up a new and promising avenue, based on organic sodium slats, to stabilize sodium metals with a protection layer.     

On‐Surface Synthesis and Characterization of Triply Fused Porphyrin–Graphene Nanoribbon Hybrids

On‐surface synthesis offers a versatile approach to prepare novel carbon‐based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine‐tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non‐benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on‐surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond‐resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV.     

2D sp2 Carbon‐Conjugated Porphyrin Covalent Organic Framework for Cooperative Photocatalysis with TEMPO

2D covalent organic frameworks (COFs) are receiving ongoing attention in semiconductor photocatalysis. Herein, we present a photocatalytic selective chemical transformation by combining sp² carbon‐conjugated porphyrin‐based covalent organic framework (Por‐sp²c‐COF) photocatalysis with TEMPO catalysis illuminated by 623 nm red light‐emitting diodes (LEDs). Highly selective conversion of amines into imines was swiftly afforded in minutes. Specifically, the π‐conjugation of porphyrin linker leads to extensive absorption of red light; the sp² ?C=C? double bonds linkage ensures the stability of Por‐sp²c‐COF under high concentrations of amine. Most importantly, we found that crystalline framework of Por‐sp²c‐COF is pivotal for cooperative photocatalysis with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO). This work foreshadows that the outstanding hallmarks of COFs, particularly crystallinity, could be exploited to address energy and environmental challenges by cooperative photocatalysis.     

Synthesis of Zinc Tetraaminophthalocyanine Functionalized Graphene Nanosheets as an Enhanced Material for Sensitive Electrochemical Determination of Uric Acid

A new electrochemical sensor material has been fabricated via the non‐covalent functionalization of reduced graphene oxide (rGO) and soluble tetramino zincphthalocyanines (ZnPc‐NH₂). Immobilization of uricase onto the synthesized nanohybrids can evidently improve the electrocatalytic activity and selectivity. The obtained composite membrane possesses a great enhancement of electron transfer rate and excellent synergistic electrocatalytic effect toward uric acid (UA) oxidation under the working potential at 0.620 V vs. Ag/AgCl with a scan rate of 0.125 V/s. The effects of the experimental parameters on the electrochemical oxidation responses of UA were investigated and optimized in detail. Under the optimized conditions, the peak currents were proportional to the UA concentration in a range from 0.5 to 100 μmol/L with detection limit of 0.15 μmol/L. Moreover, the developed sensor was applied for UA determination in human urine samples with high accuracy and satisfactory recovery, which is envisioned to have promising applications in monitoring UA in clinical research.     

A Keggin-Type Tungstovanadate-Based Hybrid Compound: Synthesis,Crystal Structure,and Electrocatalytic Oxidation of Ascorbic Acid

Russian Journal of Coordination Chemistry - A new V-centered Keggin polyoxometalate-based inorganic-organic hybrid (HPpz)3[VW12O40] (I) (Ppz = piperazine) has been hydrothermal synthesized and...     

New phosphorus- and nitrogen-containing poly(methyl methacrylate)-based copolymer

Journal of Thermal Analysis and Calorimetry - Pure poly(methyl methacrylate) (PMMA) always exhibits high flammability and low thermal stability. To address that, a novel reactive comonomer...     

Thermal decomposition behaviour and kinetics of a mixed solution: n-propyl nitrate and nitric acid solution

Journal of Thermal Analysis and Calorimetry - To provide a theoretical basis for improving the thermal safety of spent acid, its decomposition behaviour was studied. A mixed solution of n-propyl...