Enhancement of Mass and Charge Transfer during Carbon Dioxide Photoreduction by Enhanced Surface Hydrophobicity without a Barrier Layer

The CO₂ reduction reaction (CRR) represents a promising route for the clean utilization of renewable resources. But mass-transfer limitations seriously hinder the forward step. Enhancing the surface hydrophobicity by using polymers has been proved to be one of the most efficient strategies. However, as macromolecular organics, polymers on the surface hinder the transfer of charge carriers from catalysts to reactants. Herein, we describe an in-situ surface fluorination strategy to enhance the surface hydrophobicity of TiO₂ without a barrier layer of organics, thus facilitating the mass transfer of CO₂ to catalysts and charge transfer. With less obstruction to charge transfer, a higher CO_2, and lower H⁺ surface concentration, the photocatalytic CRR generation rate of methanol (CH₃OH) is greatly enhanced to up to 247.15 μmol g⁻¹ h⁻¹. Furthermore, we investigated the overall defects; enhancing the surface hydrophobicity of catalysts provides a general and reliable method to improve the competitiveness of CRR.     

Remarkable durability of the antibacterial function achieved via a coordination effect of Cu(II) ion and chitosan grafted on cotton fibers

Cellulose - We report here a simple and effective method applying a combination of chitosan (Cs) and Cu(II) ion to fabricate antibacterial cotton fabric with a remarkable durability against...     

Aggregation of Electrochemically Active Conjugated Organic Molecules and Its Impact on Aqueous Organic Redox Flow Batteries

Molecule aggregation in solution is acknowledged to be universal and can regulate the molecule's physiochemical properties, which however has been rarely investigated in electrochemistry. Herein, an electrochemical method is developed to quantitatively study the aggregation behavior of the target molecule methyl viologen dichloride. It is found that the oxidation state dicationic ions stay discrete, while the singly-reduced state monoradicals yield a concentration-dependent aggregation behavior. As a result, the molecule's energy level and its redox potential can be effectively regulated. This work does not only provide a method to investigate the molecular aggregation, but also demonstrates the feasibility to tune redox flow battery's performance by regulating the aggregation behavior.     

CoMn@NC催化5-羟甲基糠醛常压氧化为2, 5-呋喃二甲酸二甲酯

Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co₃Mn₂@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―N_x (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN⁻ ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.     

Synthesis of FeS2/CoS heterostructure microspheres as anodes for high-performance Li-ion batteries

Journal of Solid State Electrochemistry - FeS2/CoS and FeS2/CoS/C composites were synthesized by solvothermal method and following vapor phase vulcanization at mild temperature with binary oxide...     

Grain Boundary Electronic Insulation for High-Performance All-Solid-State Lithium Batteries

Sulfide electrolytes with high ionic conductivities are one of the most highly sought for all-solid-state lithium batteries (ASSLBs). However, the non-negligible electronic conductivities of sulfide electrolytes (≈10⁻⁸ S cm⁻¹) lead to electron smooth transport through the sulfide electrolyte pellets, resulting in Li dendrite directly depositing at the grain boundaries (GBs) and serious self-discharge. Here, a grain-boundary electronic insulation (GBEI) strategy is proposed to block electron transport across the GBs, enabling Li−Li symmetric cells with 30 times longer cycling life and Li−LiCoO₂ full cells with three times lower self-discharging rate than pristine sulfide electrolytes. The Li−LiCoO₂ ASSLBs deliver high capacity retention of 80 % at 650 cycles and stable cycling performance for over 2600 cycles at 0.5 mA cm⁻². The innovation of the GBEI strategy provides a new direction to pursue high-performance ASSLBs via tailoring the electronic conductivity.     

Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

High-throughput Synthesis of Solution-Processable van der Waals Heterostructures through Electrochemistry

Two-dimensional van der Waals heterostructures (2D vdWHs) have recently gained widespread attention because of their abundant and exotic properties, which open up many new possibilities for next-generation nanoelectronics. However, practical applications remain challenging due to the lack of high-throughput techniques for fabricating high-quality vdWHs. Here, we demonstrate a general electrochemical strategy to prepare solution-processable high-quality vdWHs, in which electrostatic forces drive the stacking of electrochemically exfoliated individual assemblies with intact structures and clean interfaces into vdWHs with strong interlayer interactions. Thanks to the excellent combination of strong light absorption, interfacial charge transfer, and decent charge transport properties in individual layers, thin-film photodetectors based on graphene/In₂Se₃ vdWHs exhibit great promise for near-infrared (NIR) photodetection, owing to a high responsivity (267 mA W⁻¹), fast rise (72 ms) and decay (426 ms) times under NIR illumination. This approach enables various hybrid systems, including graphene/In₂Se₃, graphene/MoS₂ and graphene/MoSe₂ vdWHs, providing a broad avenue for exploring emerging electronic, photonic, and exotic quantum phenomena.     

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR ( pGNR ) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor ( P1 ) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds ( 1 a , 1 b ) containing the same pore size as the shortcuts of pGNR , are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π–π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.     

Ferric Single-Site Catalyst Confined in a Zeolite Framework for Propane Dehydrogenation

Non-oxidative dehydrogenation of propane is a highly efficient approach for industrial preparation of propene that is commonly catalyzed by noble Pt or toxic Cr catalysts and suffers from coking. In this work, ferric catalyst confined in a zeolite framework was synthesized by a hydrothermal procedure. The isolated Fe in the framework formed distorted tetrahedra, which were beneficial for the selective dehydrogenation of propane and reached over 95 % propene selectivity and over 99 % total olefins selectivity. This catalyst had a silanol-free structure and was oxygen tolerant, hydrothermally stable, and coke free, with a deactivation constant of 0.01 h⁻¹. This study provided guidance for the synthesis of structural heteroatomic zeolite and efficient propane non-oxidative dehydrogenation over early transition metals.