Perfluorinated Amines: Accelerating Lithium Electrodeposition by Tailoring Interfacial Structure and Modulated Solvation for High-Performance Batteries.

Modulating interfacial electrochemistry represents a prevalent approach for mitigating lithium dendrite growth and enhancing battery performance. Nevertheless, while most additives exhibit inhibitory characteristics, the accelerating effects on interfacial electrochemistry have garnered limited attention. In this work, perfluoromorpholine (PFM) with facilitated kinetics is utilized to preferentially adsorb on the lithium metal interface. The PFM molecules disrupt the solvation structure of Li+ and enhance the migration of Li+. Combined with the benzotrifluoride, a synergistic acceleration-inhibition system is formed. The ab initio molecular dynamics (AIMD) and density functional theory (DFT) calculation of the loose outer solvation clusters and the key adsorption-deposition step supports the fast diffusion and stable interface electrochemistry with an accelerated filling mode with C─F and C─H groups. The approach induces the uniform lithium deposition. Excellent cycling performance is achieved in Li||Li symmetric cells, and even after 200 cycles in Li||NCM811 full cells, 80% of the capacity is retained. This work elucidates the accelerated electrochemical processes at the interface and expands the design strategies of acceleration fluorinated additives for lithium metal batteries.

Synergistic Effects of Doping and Strain in Bismuth Catalysts for CO2 Electroreduction.

Doping is a recognized method for enhancing catalytic performance. The introduction of strains is a common consequence of doping, although it is often overlooked. Differentiating the impact of doping and strain on catalytic performance poses a significant challenge. In this study, Cu-doped Bi catalysts with substantial tensile strain are synthesized. The synergistic effects of doping and strain in bismuth result in a remarkable CO2RR performance. Under optimized conditions, Cu1/6-Bi demonstrates exceptional formate Faradaic efficiency (>95%) and maintains over 90% across a wide potential window of 900 mV. Furthermore, it delivers an industrial-relevant partial current density of -317 mA cm-2 at -1.2 VRHE in a flow cell, while maintaining its selectivity. Additionally, it exhibits exceptional long-term stability, surpassing 120 h at -200 mA cm-2. Through experimental and theoretical mechanistic investigations, it has been determined that the introduction of tensile strain facilitates the adsorption of *CO2, thereby enhancing the reaction kinetics. Moreover, the presence of Cu dopants and tensile strain further diminishes the energy barrier for the formation of *OCHO intermediate. This study not only offers valuable insights for the development of effective catalysts for CO2RR through doping, but also establishes correlations between doping, lattice strains, and catalytic properties of bismuth catalysts.

Porphyrin-Thiophene Based Conjugated Polymer Cathode with High Capacity for Lithium-Organic Batteries.

Organic electrode materials are promising for next-generation energy storage materials due to their environmental friendliness and sustainable renewability. However, problems such as their high solubility in electrolytes and low intrinsic conductivity have always plagued their further application. Polymerization to form conjugated organic polymers can not only inhibit the dissolution of organic electrodes in the electrolyte, but also enhance the intrinsic conductivity of organic molecules. Herein, we synthesized a new conjugated organic polymer (COPs) COP500-CuT2TP (poly [5,10,15,20-tetra(2,2'-bithiophen-5-yl) porphyrinato] copper (II)) by electrochemical polymerization method. Due to the self-exfoliation behavior, the porphyrin cathode exhibited a reversible discharge capacity of 420 mAh g-1, and a high specific energy of 900 Wh Kg-1 with a first coulombic efficiency of 96 % at 100 mA g-1. Excellent cycling stability up to 8000 cycles without capacity loss was achieved even at a high current density of 5 A g-1. This highly conjugated structure promotes COP500-CuT2TP combined high energy density, high power density, and good cycling stability, which would open new opportunity for the designable and versatile organic electrodes for electrochemical energy storage.

Spontaneous Desaturation of the Solvation Sheath for High-Performance Anti-Freezing Zinc-Ion Gel-Electrolyte.

In recent years, gel-electrolyte becomes pivotal in preventing hydrogen evolution, reducing dendrite growth, and protecting the zinc metal anode for zinc-ion batteries. Herein, a polyvinyl alcohol-based water-organic hybrid gel electrolyte with Agar and dimethyl sulfoxide is designed to construct the spontaneous desaturation of the solvation sheath for reducing hydrogen evolution and dendrite growth at room temperature and even low temperature. According to experimental characterization and theoretical calculations, the well binding between multihydroxy polymer and H2 O is achieved in the hybrid desaturated gel-electrolyte to regulate the inner and outer sheath. The ionic conductivity of hybrid gel-electrolyte reaches 7.4 mS cm-1 even at -20 °C with only 0.5 m zinc trifluoromethanesulfonate (Zn(OTf)2 ). The Zn symmetric cells cycle over 1200 h under 26 and -20 °C with improved mechanical properties and electrochemical performance. The asymmetric Zn || Cu cell with hybrid gel electrolyte reaches ≈99.02% efficiency after 250 cycles. The capacity of full cell is maintained at around 74 mAh g-1 with almost unchanged retention rate from 50 to 300 cycles at -20 °C. This work provides an effective strategy for desaturated solvation to reach anti-freezing and high-density Zn energy storage devices.

Multiple Heteroatom-Hydrogen Bonds Bridging Electron Transport in Covalent Organic Framework-Based Supramolecular System for Photoreduction of CO2.

Supramolecular systems consisting of covalent organic frameworks (COFs) and Ni complex are designed for robust photocatalytic reduction of CO2 . Multiple heteroatom-hydrogen bonding between the COF and Ni complex is identified to play a decisive role in the photoexcited electron transfer across the liquid-solid interface. The diminution of steric groups on COF or metal complex can optimize catalytic performance, which is more attributable to the enhanced hydrogen-bond interaction rather than their intrinsic activity. The photosystem with relatively strong strength of hydrogen bonds exhibits remarkable photocatalytic CO2 -to-CO conversion, far superior to photosystems with supported atomic Ni or metal complex alone in the absence of hydrogen-bond effect. Such heteroatom-hydrogen bonds bridging electron transport pathway confers supramolecular system with high photocatalytic performance, providing an avenue to rationally design efficient and steadily available photosystems.

In situself-assembly fabrication of ultrathin sheet-like CuS modified g-C3N4heterojunction and its enhanced visible-light photocatalytic performance.

Photocatalysts with heterojunction structure have been widely used for organic degradation. In this study, CuS/g-C3N4heterojunction was formed byin situself-assembly via a simply hydrothermal method. A series of characterizations were applied to analyzing the morphology, structure, optical properties and photo-induced electron transfer of the samples. The effect of CuS mass ratio in the CuS/g-C3N4composite on methyl blue (10 mg l-1) degradation under visible-light illumination was discussed. When CuS mass ratio was 60%, CuS/g-C3N4behaved the highest photocatalytic efficiency which is 17 times higher than that of pure g-C3N4, and the optimal heterojunction exhibited promising photocatalytic stability as well. The synthesized CuS/g-C3N4with intimate contact and promising photocatalytic performance provides important implications on analogous researches on g-C3N4-based heterojunctions for photocatalytic applications.

Donor-Acceptor Pairs in Covalent Organic Frameworks Promoting Electron Transfer for Metal-Free Photocatalytic Organic Synthesis.

The donor-acceptor-type covalent organic frameworks (COFs) have recently gained increasing interest in photocatalysis, but the photoinduced electron-transfer regimes in the COFs are underexplored. Herein, we demonstrate a designed porphyrinic COF possessing a donor-acceptor structure together with its photocatalytic performance in aerobic coupling of primary amines. The COF could be photoexcited by the full range of visible light to generate electron-hole pairs that could be separated by donor-acceptor pairs. Electron transfer as the mechanism of the reaction from anthracene unit to porphyrin unit was revealed by natural transition orbitals analyses. The electrons migrate to the adsorbed O2 to generate reactive oxidative species. The COF displays remarkable photocatalytic activities in the coupling of amines to imines, which can be explained mainly by the sufficient charge separation and mobility, benefiting from the donor-acceptor pairs in the COF and their interactions to the reactants and intermediates.

Zinc Manganate: Synthesis, Characterization, and Electrochemical Application toward Flufenamic Acid Detection.

The construction of novel electrocatalysts for efficient and economic electrochemical sensors is continuously a significant conceptual barrier for the point-of-care technology. Binary metal oxides with heterostructures have gained plenty of attention due to their promising physicochemical properties. Herein, we develop a rapid and sensitive electrochemical probe for the detection of flufenamic acid (FFA) by using a zinc manganate (ZnMnO)-modified electrode. The formation of ZnMnO was confirmed by various analytical techniques, such as X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, and field-emission scanning electron microscopy with energy dispersive X-ray spectroscopy and elemental mapping. The ZnMnO-based electrocatalyst, which was used for the electrochemical detection of FFA, shows better performance than the previously reported electrode materials. The ZnMnO assay shows a linear quantitative range from 0.05 to 116 µM with a limit of detection of 0.003 µM and sensitivity of 0.385 µA µM-1 cm-2. Its good electrochemical performance can be ascribed to the large surface area, rapid charge mass transfer, copious active sites, and high carrier mobility. The electrochemical study displays that the fabricated ZnMnO-based sensor has the potential to be applied in the clinical analysis. This work constructs an advanced functional electrode material with a microscale architecture for the point-of-care technology.

Mechanistic studies of Cp*Ir(III)/Cp*Rh(III)-catalyzed branch-selective allylic C-H amidation: why is Cp*Ir(III) superior to Cp*Rh(III)?

Density functional theory calculations have revealed the mechanism and origins of the reactivity and regioselectivity of the Cp*Ir(iii)/Cp*Rh(iii)-catalyzed allylic C-H amidation of alkenes and dioxazolones. Generally, the catalytic cycle consists of alkene coordination, C(sp3)-H activation, dioxazolone oxidative addition, reductive elimination and proto-demetallation to give the final amidation product. The C-H activation is found to be the rate-determining step, and it controls the reactivity of the reaction. For the Cp*Ir(iii)-catalyzed system, the C-H activation undergoes an Ir(iii)-assisted proton transfer process with a low energy barrier, elucidating its high reactivity. In contrast, the C-H activation step is more like a direct deprotonation in the Cp*Rh(iii)-catalyzed system, which is responsible for its higher barrier and lower reactivity. The branched-selectivity arises from the electronic effect of the alkyl group on the charge distribution over the allylic moiety. Herein, iridium(v) polarizes the allylic group greater than that of the rhodium(v) system, which accounts for its good regioselectivity. The mechanistic insights will be useful for the further development of transition metal-catalyzed selective C-H amination reactions.

Mechanism of Pd-catalysed C(sp3)-H arylation of thioethers with Ag(I) additives.

Mechanistic studies reveal that Pd-catalyzed C(sp3)-H arylation of thioethers with silver(i) additives takes place via C(sp3)-H activation, oxidative addition and reductive elimination, wherein all steps proceed via the heterodimeric Pd-Ag pathway. Besides, the active heterodimeric Pd-Ag species are detected by mass spectrometry via control experiments.