Amphiphilic Polymer Electrolyte Blocking Lattice Oxygen Evolution from High-Voltage Nickel-rich Cathodes for Ultra-Thermal Stabile Batteries.

Ni-rich cathodes have been intensively adopted in Li-ion batteries to pursuit high energy density, which still suffering irreversible degradation at high voltage. Some unstable lattice O2- species in Ni-rich cathodes would be oxidized to singlet oxygen 1O2 and released at high volt, which lead to irreversible phase transfer from the layered rhombohedral (R) phase to a spinel-like (S) phase. To overcome the issue, the amphiphilic copolymers (UMA-Fx) electrolyte were prepared by linking hydrophobic C-F side chains with hydrophilic subunits, which could self-assemble on Ni-rich cathode surface and convert to stable cathode-electrolyte interphase layer. Thereafter, the oxygen releasing of polymer coated cathode was obviously depressed and substituted by the Co oxidation (Co3+→Co4+) at high volt (>4.2 V), which could suppressed irreversible phase transfer and improve cycling stability. Moreover, the amphiphilic polymer electrolyte was also stable with Li anode and had high ion conductivity. Therefore, the NCM811//UMA-F6//Li pouch cell exhibited outstanding energy density (362.97 Wh/kg) and durability (cycled 200 times at 4.7 V), which could be stalely cycled even at 120°C without short circuits or explosions.

Molecular structure regulation of FCCs enabling N/S co-doped hollow amorphous carbon with enlarged interlayer spacing and rich defects for superior potassium storage.

Constructing high-performance and low-cost carbon anodes for potassium-ion batteries (PIBs) is highly desirable but faces great challenges. In this study, we present a novel approach to fabricating N/S co-doped hollow amorphous carbon (LNSHAC) for superior potassium storage through a template-assisted molecular structure regulation strategy. By tailoring a 3D crosslinked aromatics precursor from fluid catalytic cracking slurry (FCCs), the LNSHAC features a N/S co-doped hollow structure with enlarged interlayer spacing of up to 0.405 nm and rich defects. Such unique microstructure offers fast transport channels for K-ion intercalation/deintercalation and provides more active sites, leading to boosted reaction kinetics and potassium storage capacity. Consequently, the LNSHAC electrode delivers an impressive reversible capacity (466.2 mAh g-1 at 0.1 A/g), excellent rate capability (336.3 mAh g-1 at 2 A/g), and superior cyclic performance (256.9 mAh g-1 after 5000 cycles at 5 A/g with admirable retention of 76.9 %), standing out among the reported carbon-based anodes. When KFeHCF is employed as the cathode, the LNSHAC-based K-ion full cell exhibits a high reversible capacity of 176.6 mAh g-1 at 0.1 A/g and excellent cyclic stability over 200 cycles. This work will inspire the development and application of advanced carbon-based materials for potassium electrochemical energy storage.

Efficient electrocatalytic reduction of CO2 to CO enhanced by the synergistic effect of N,P on carbon aerogel.

A metal-free catalyst, N,P-codoped carbon aerogel, was used to realize the high efficiency reduction of CO2 to CO. Therein, the pyridinic N acts as the active center to activate and reduce CO2 and the atom of P acts as the "transition atom" of the proton to reduce the free energy barrier from *CO2 to *COOH.

Application of metal-organic frameworks and their derivates for thermal-catalytic C1 molecules conversion.

One-carbon (C1) catalysis refers to the conversion of compounds with a single carbon atom, especially carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4), into clean fuels and valuable chemicals via catalytic strategy is crucial for sustainable and green development. Among various catalytic strategies, thermal-driven process seems to be one of the most promising pathways for C1 catalysis due to the high efficiency and practical application prospect. Notably, the rational design of thermal-driven C1 catalysts plays a vital role in boosting the targeted products synthesis of C1 catalysis, which relies heavily on the choice of ideal active site support, catalyst fabrication precursor, and catalytic reaction field. As a novel crystalline porous material, metal-organic frameworks (MOFs) has made significant progress in the design and synthesis of various functional nanomaterials. However, the application of MOFs in C1 catalysis faces numerous challenges, such as thermal stability, mechanical strength, yield of MOFs, and so on. To overcome these limitations and harness the advantages of MOFs in thermal-driven C1 catalysis, researchers have developed various catalyst/carrier preparation strategies. In this review, we provide a concise overview of the recent advancements in the conversion of CO, CO2, and CH4 into clean fuels and valuable chemicals via thermal-catalytic strategy using MOFs-based catalysts. Furthermore, we discuss the main challenges and opportunities associated with MOFs-based catalysts for thermal-driven C1 catalysis in the future.

Defluoroalkylation of gem-Difluoroalkenes with Alcohols via C-F/C-H Coupling.

A feasible and effective method to synthesize α-fluoroalkenyl alcohols was reported. With the cooperation of photoredox and hydrogen atom transfer (HAT) processes, defluoroalkylations of gem-difluoroalkenes occurred smoothly with alcohols under visible-light irradiation. Notably, the protocols feature broad scopes, mild conditions, and validity for the late-stage functionalization of bioactive molecule derivatives. Mechanistic studies suggested that the reaction occurred through the radical coupling of the alkyl radical and the fluoroalkenyl radical.

Electrochemically Exfoliated Graphene Additive-Free Inks for 3D Printing Customizable Monolithic Integrated Micro-Supercapacitors on a Large Scale.

Three-dimensional (3D) printing technology with enhanced fidelity can achieve multiple functionalities and boost electrochemical performance of customizable planar micro-supercapacitors (MSCs), however, precise structural control of additive-free graphene-based macro-assembly electrode for monolithic integrated MSCs (MIMSCs) remains challenging. Here, the large-scale 3D printing fabrication of customizable planar MIMSCs is reported utilizing additive-free, high-quality electrochemically exfoliated graphene inks, which is not required the conventional cryogenic assistance during the printing process and any post-processing reduction. The resulting MSCs reveal an extremely small engineering footprint of 0.025 cm2, exceptionally high areal capacitance of 4900 mF cm-2, volumetric capacitance of 195.6 F cm-3, areal energy density of 2.1 mWh cm-2, and unprecedented volumetric energy density of 23 mWh cm-3 for a single cell, surpassing most previously reported 3D printed MSCs. The 3D printed MIMSC pack is further demonstrated, with the maximum areal cell count density of 16 cell cm-2, the highest output voltage of 192.5 V and the largest output voltage per unit area of 56 V cm-2 up to date are achieved. This work presents an innovative solution for processing high-performance additive-free graphene ink and realizing the large-scale production of 3D printed MIMSCs for planar energy storage.

Diastereoselective dearomatization of indoles via photocatalytic hydroboration on hydramine-functionalized carbon nitride.

A protocol for trans-hydroboration of indole derivatives using heterogeneous photocatalysis with NHC-borane has been developed, addressing a persistent challenge in organic synthesis. The protocol, leveraging high crystalline vacancy-engineered polymeric carbon nitride as a catalyst, enables diastereoselective synthesis, expanding substrate scope and complementing existing methods. The approach emphasizes eco-friendliness, cost-effectiveness, and scalability, making it suitable for industrial applications, particularly in renewable energy contexts. The catalyst's superior performance, attributed to its rich carbon-vacancies and well-ordered structure, surpasses more expensive homogeneous alternatives, enhancing viability for large-scale use. This innovation holds promise for synthesizing bioactive compounds and materials relevant to medicinal chemistry and beyond.

Advances in the Stability of Catalysts for Electroreduction of CO2 to Formic Acid.

The electroreduction of CO2 to high-value products is a promising approach for achieving carbon neutrality. Among these products, formic acid stands out as having the most potential for industrialization due to its optimal economic value in terms of consumption and output. In recent years, the Faraday efficiency of formic acid from CO2 electroreduction has reached 90~100 %. However, this high selectivity cannot be maintained for extended periods under high currents to meet industrial requirements. This paper reviews excellent work from the perspective of catalyst stability, summarizing and discussing the performance of typical catalysts. Strategies for preparing stable and highly active catalysts are also briefly described. This review may offer a useful data reference and valuable guidance for the future design of long-stability catalysts.

Salt Effect Engineering Single Fe-N2P2-Cl Sites on Interlinked Porous Carbon Nanosheets for Superior Oxygen Reduction Reaction and Zn-Air Batteries.

Developing efficient metal-nitrogen-carbon (M-N-C) single-atom catalysts for oxygen reduction reaction (ORR) is significant for the widespread implementation of Zn-air batteries, while the synergic design of the matrix microstructure and coordination environment of metal centers remains challenges. Herein, a novel salt effect-induced strategy is proposed to engineer N and P coordinated atomically dispersed Fe atoms with extra-axial Cl on interlinked porous carbon nanosheets, achieving a superior single-atom Fe catalyst (denoted as Fe-NP-Cl-C) for ORR and Zn-air batteries. The hierarchical porous nanosheet architecture can provide rapid mass/electron transfer channels and facilitate the exposure of active sites. Experiments and density functional theory (DFT) calculations reveal the distinctive Fe-N2P2-Cl active sites afford significantly reduced energy barriers and promoted reaction kinetics for ORR. Consequently, the Fe-NP-Cl-C catalyst exhibits distinguished ORR performance with a half-wave potential (E1/2) of 0.92 V and excellent stability. Remarkably, the assembled Zn-air battery based on Fe-NP-Cl-C delivers an extremely high peak power density of 260 mW cm-2 and a large specific capacity of 812 mA h g-1, outperforming the commercial Pt/C and most reported congeneric catalysts. This study offers a new perspective on structural optimization and coordination engineering of single-atom catalysts for efficient oxygen electrocatalysis and energy conversion devices.

Contracting pore channels of a magnesium-based metal-organic framework by decorating methyl groups for effective Xe/Kr separation.

A new magnesium-based metal-organic framework with unprecedented short-chain secondary building units and ultra-micropore channels approaching the kinetic diameters of Xe is fabricated by decorating methyl groups on ligands. Due to the contracted pores, this MOF exhibits very high selectivity values for Xe/Kr, which ranks it among the top porous absorbents.

Resolution of the reciprocity between radical species from precursor and closed pore formation in hard carbon for sodium storage.

Hard carbon (HC) has emerged as a highly promising anode material for sodium ion batteries, drawing tremendous interest in producing this material with low-cost and easily accessible precursors. The determination of the crucial parameters of precursors influencing the formation of key structures, such as closed pores, in the HC is of paramount importance. Considering the potential role of free radicals in the structural evolution of the precursors, we, for the first time, delve into the impact of radical species on the development of closed pores by electron paramagnetic resonance spectroscopy, with petroleum asphalt as the model system. Our findings reveal that carbon centred radicals, with the g value close to that of the free electron (2.0023), exhibit a propensity to form long-range, well-ordered graphitic structures with lower sodium storage capacity. Conversely, the deliberately incorporated oxygen radicals with the g value over 2.005 require a higher energy for ordering the graphitic structures, leading to the creation of closed pores. As a result, the optimal sample showcases a four-fold increase in plateau capacity for sodium ion storage due to the pore filling process. Our research underscores the pivotal role of employing electron paramagnetic resonance spectroscopy studying the critical structural evolution of functional carbon materials.

Unveiling the Mechanism of Plasma-Catalyzed Oxidation of Methane to C2+ Oxygenates over Cu/UiO-66-NH2.

Nonthermal plasma (NTP) offers the potential for converting CH4 with CO2 into liquid products under mild conditions, but controlling liquid selectivity and manipulating intermediate species remain significant challenges. Here, we demonstrate the effectiveness of the Cu/UiO-66-NH2 catalyst in promising the conversion of CH4 and CO2 into oxygenates within a dielectric barrier discharge NTP reactor under ambient conditions. The 10% Cu/UiO-66-NH2 catalyst achieved an impressive 53.4% overall liquid selectivity, with C2+ oxygenates accounting for ∼60.8% of the total liquid products. In situ plasma-coupled Fourier-transform infrared spectroscopy (FTIR) suggests that Cu facilitates the cleavage of surface adsorbed COOH species (*COOH), generating *CO and enabling its migration to the surface of Cu particles. This surface-bound *CO then undergoes C-C coupling and hydrogenation, leading to ethanol production. Further analysis using CO diffuse reflection FTIR and 1H nuclear magnetic resonance spectroscopy indicates that in situ generated surface *CO is more effective than gas-phase CO (g) in promoting C-C coupling and C2+ liquid formation. This work provides valuable mechanistic insights into C-C coupling and C2+ liquid production during plasma-catalytic CO2 oxidation of CH4 under ambient conditions. These findings hold broader implications for the rational design of more efficient catalysts for this reaction, paving the way for advancements in sustainable fuel and chemical production.

Insight into Controllable Metal-Support Interactions in Metal/Metal Electrocatalysts for Efficient Energy-Saving Hydrogen Production.

Controllable metal-support interaction (MSI) modulations have long been studied for improving the performance of catalysts supported on metal oxides. However, the corresponding in-depth study for metal1-metal2 (M1-M2) composited configurations is rarely achieved due to the lack of reliable models and manipulation mechanisms of MSI modifications. We modeled ruthenium on copper support (Ru-Cu) metal catalysts with negligible interfacial contact potential (e0.06 V) and investigated MSI-dependent hydrogen evolution reaction (HER) catalysis kinetics induced by an electronic hydroxyl (HO-) modifier. Comprehensive simulations and characterizations confirmed that adjusting the HO- coverage can readily realize the tailorable improvement of MSI, facilitating charge migration at the Ru-Cu interface and optimizing the overall HER pathway on active Ru. As a result, a 5/10 monolayer (ML) HO-modified catalyst (5/10 ML) exhibits superior HER activity and durability owing to the relatively stronger MSI. This catalyst also ensured sustainable and efficient hydrogen generation in a urea electrolyzer with significant energy savings. Our work provides a valuable reference for optimizing the MSI-activity relationship in M1-M2 catalysts that target more than just HER.