Covalent Grafting of BPin functions on Carbon Nanotubes and Chan–Lam–Evans Post-Functionalization

The chemical functionalization of carbon nanotubes is often a prerequisite prior to their use in various applications. The covalent grafting of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BPin) functional groups directly on the surface of multi- and single-walled carbon nanotubes, activated by nucleophilic addition of nBuLi, was carried out. Thermogravimetric analysis (TGA) coupled with mass spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) confirmed the efficiency of this methodology and proved the integrity and covalent grafting of the BPin functional groups. These groups were further reacted with various nucleophiles in the presence of a copper(II) source in the conditions of the aerobic Chan–Lam–Evans coupling. The resulting materials were characterized by TGA, XPS and ToF-SIMS. This route is efficient, reliable and among the scarce reactions that enable the direct grafting of heteroatoms at carbonaceous material surfaces.     

Impregnated copper ferrite on mesoporous graphitic carbon nitride: An efficient and reusable catalyst for promoting ligand‐free click synthesis of diverse 1,2,3‐triazoles and tetrazoles

Magnetic CuFe₂O₄/g‐C₃N₄ hybrids were synthesized through a facile method and their catalytic performances were evaluated in click chemistry for the first time. The structural and morphological characterization of prepared materials was carried out by different techniques such as X‐ray diffraction, high‐resolution transmission electron microscopy, field emission scanning electron microscopy, Fourier infrared spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, and N₂ adsorption–desorption analysis (Brunauer–Emmett–Teller surface area). The utilization of magnetic CuFe₂O₄/g‐C₃N₄ enabled superior performance in the one‐pot azide–alkyne cycloaddition reaction in water using alkyl halides and epoxides as azide precursors without the need of any additional agents. The present system is broad in scope and especially practical for the synthesis of macrocyclic triazoles and also tetrazoles. In addition, the catalytic system highly fulfills the demands of “green click chemistry” with its convenient conditions, especially easy access to a variety of significant products in low catalyst loading and simple work‐up and isolation procedure.     

Porous Molybdenum Carbide Nanostructures Synthesized on Carbon Cloth by CVD for Efficient Hydrogen Production

Molybdenum carbide (Mo₂C) is a promising noble-metal-free electrocatalyst for the hydrogen evolution reaction (HER), due to its structural and electronic merits, such as high conductivity, metallic band states and wide pH applicability. Here, a simple CVD process was developed for synthesis of a Mo₂C on carbon cloth (Mo₂C@CC) electrode with carbon cloth as carbon source and MoO₃ as the Mo precursor. XRD, Raman, XPS and SEM results of Mo₂C@CC with different amounts of MoO₃ and growth temperatures suggested a two-step synthetic mechanism, and porous Mo₂C nanostructures were obtained on carbon cloth with 50 mg MoO₃ at 850 °C (Mo₂C-850(50)). With the merits of unique porous nanostructures, a low overpotential of 72 mV at current density of 10 mA cm⁻² and a small Tafel slope of 52.8 mV dec⁻¹ was achieved for Mo₂C-850(50) in 1.0 m KOH. The dual role of carbon cloth as electrode and carbon source resulted into intimate adhesion of Mo₂C on carbon cloth, offering fast electron transfer at the interface. Cyclic voltammetry measurements for 5000 cycles revealed that Mo₂C@CC had excellent electrochemical stability. This work provides a novel strategy for synthesizing Mo₂C and other efficient carbide electrocatalysts for HER and other applications, such as supercapacitors and lithium-ion batteries.     

BiVO4/TiO2 heterojunction with rich oxygen vacancies for enhanced electrocatalytic nitrogen reduction reaction

The large-scale production of ammonia mainly depends on the Haber–Bosch process, which will lead to the problems of high energy consumption and carbon dioxide emission. Electrochemical nitrogen fixation is considered to be an environmental friendly and sustainable process, but its efficiency largely depends on the activity and stability of the catalyst. Therefore, it is imperative to develop highefficient electrocatalysts in the field of nitrogen reduction reaction (NRR). In this paper, we developed a BiVO₄/TiO₂ nanotube (BiVO₄/TNT) heterojunction composite with rich oxygen vacancies as an electrocatalytic NRR catalyst. The heterojunction interface and oxygen vacancy of BiVO₄/TNT can be the active site of N₂ dynamic activation and proton transition. The synergistic effect of TiO₂ and BiVO₄ shortens the proton transport path and reduces the over potential of chemical reaction. BiVO₄/TNT has high ammonia yield of 8.54 μg·h⁻¹·cm⁻² and high Faraday efficiency of 7.70% in −0.8 V vs. RHE in 0.1 M Na₂SO₄ solution.     

Metal–Organic Framework (MOF)-Derived Carbon-Mediated Interfacial Reaction for the Synthesis of CeO2−MnO2 Catalysts

CeO₂-based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO₂ and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal–organic framework (MOF)-derived carbon and KMnO₄ to synthesize CeO₂−MnO₂, in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO₂ crystallites under a high calcination temperature and, more importantly, intimate contact within CeO₂/C is conveyed to CeO₂/MnO₂ after the interfacial reaction; this is responsible for the high catalytic activity of CeO₂−MnO₂ towards CO oxidation.     

Preparation and characterization of new inorganic–organic hybrid catalyst H3PMo12O40/Hyd‐SBA‐15 and its application in the domino multi‐component reaction

We present novel inorganic–organic hybrid catalyst to accomplish domino multi‐component reaction (MCR) for synthesis of 3‐amino‐2′‐oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐carbonitrile/carboxylate derivatives. This methodology offers remarkable development by easy production of H₃PMo₁₂O₄₀/Hyd‐SBA‐15 in regard to solving the problem of using harsh catalysts, also it demonstrates to be impressive and environmentally friendly in term of low reaction times and high yields.     

Synthesis of nano‐sized magnetite mesoporous carbon for removal of Reactive Yellow dye from aqueous solutions

In this study, core‐shell structures of magnetite nanoparticles coated with CMK‐8 ordered mesoporous carbon (Fe₃O₄@SiO₂‐CMK‐8 NPs) have been successfully synthesized for the first time by carbonizing sucrose inside the pores of the Kit‐6 mesoporous silica. The nano‐sized mesoporous particles were characterized by X‐ray diffraction, Fourier transform‐infrared spectroscopy, scanning electron microscope, dynamic light scattering, vibrating‐sample magnetometer, Brunauer–Emmett–Teller (BET) and transmission electron microscopy instruments. The obtained nanocomposite was used for removal of Reactive Yellow 160 (RY 160) dye from aqueous samples. The N₂ adsorption–desorption method (at 77 K) confirmed the mesoporous structure of synthesized Fe₃O₄@SiO₂‐CMK‐8 NPs. Also, the surface area was calculated by the BET method and Langmuir plot as 276.84 m²/g and 352.32 m²/g, respectively. The surface area, volume and pore diameter of synthesized nanoparticles (NPs) were calculated from the pore size distribution curves using the Barrett–Joyner–Halenda formula (BJH). To obtain the optimum experimental variables, the effect of various experimental parameters on the dye removal efficiency was studied using Taguchi orthogonal array experimental design method. According to the experimental results, about 90.0% of RY 160 was removed from aqueous solutions at the adsorbent amount of 0.06 g, pH 3 and ionic strength = 0.05 m during 10 min. The pseudo‐second order kinetic model provided a very good fit for the RY 160 dye removal (R² = 0.999). The Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models were applied to describe the equilibrium isotherms, and the Langmuir isotherm showed the best fit to data with the maximum adsorption capacity of 62.893 mg/g. Furthermore, the Fe₃O₄@SiO₂‐CMK‐8 NPs could be simply recovered by external magnet, and exhibited recyclability and reusability for a subsequent six runs.     

Vertically Grown Few-Layer MoS2 Nanosheets on Hierarchical Carbon Nanocages for Pseudocapacitive Lithium Storage with Ultrahigh-Rate Capability and Long-Term Recyclability

Molybdenum disulfide (MoS₂) is an intensively studied anode material for lithium-ion batteries (LIBs) owing to its high theoretical capacity, but it is still confronted by severe challenges of unsatisfactory rate capability and cycle life. Herein, few-layer MoS₂ nanosheets, vertically grown on hierarchical carbon nanocages (hCNC) by a facile hydrothermal method, introduce pseudocapacitive lithium storage owing to the highly exposed MoS₂ basal planes, enhanced conductivity, and facilitated electrolyte access arising from good hybridization with hCNC. Thus, the optimized MoS₂/hCNC exhibits reversible capacities of 1670 mAh g⁻¹ at 0.1 A g⁻¹ after 50 cycles, 621 mAh g⁻¹ at 5.0 A g⁻¹ after 500 cycles, and 196 mAh g⁻¹ at 50 A g⁻¹ after 2500 cycles, which are among the best for MoS₂-based anode materials. The specific power and specific energy, which can reach 16.1 kW and 252.8 Wh after 3000 cycles, respectively, indicate great potential in high-power and long-life LIBs. These findings suggest a promising strategy for exploring advanced anode materials with high reversible capacity, high-rate capability, and long-term recyclability.     

FeOOH Nanocubes Anchored on Carbon Ribbons for Use in Li/O2 Batteries

A composite of FeOOH nanocubes anchored on carbon ribbons has been synthesized and used as a cathode material for Li/O₂ batteries. Fe²⁺ ion-exchanged resin serves as a precursor for both FeOOH nanocubes and carbon ribbons, which are formed simultaneously. The as-prepared FeOOH cubes are proposed to have a core–shell structure, with FeOOH as the shell and Prussian blue as the core, based on information from XPS, TEM, and EDS mapping. As a cathode material for Li/O₂ batteries, FeOOH delivers a specific capacity of 14816 mA h g⁻¹_cathode with a cycling stability of 67 cycles over 400 h. The high performance is related to the low overpotential of the oxygen reduction/evolution reaction on FeOOH. The cube structure, the supporting carbon ribbons, and the -OOH moieties all contribute to the low overpotential. The discharge product Li₂O₂ can be efficiently decomposed in the FeOOH cathode after a charging process, leading to higher cycling stability. Its high activity and stability make FeOOH a good candidate for use in non-aqueous Li/O₂ batteries.