Facile Synthesis of Nitrogen‐Doped Graphene Aerogels for Electrode Materials in Supercapacitors

Three‐dimensional porous nitrogen‐doped graphene aerogels (NGAs ) were synthesized by using graphene oxide (GO ) and chitosan (CS ) via a self‐assembly process by one‐pot hydrothermal method. The morphology and structure of the as‐prepared materials were characterized by means of scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, XPS spectroscopy, Raman spectroscopy, nitrogen adsorption/desorption measurement and Fourier transform infrared spectroscopy. The electrochemical performance of NGAs was studied by cyclic voltammetry, galvanostatic charge/discharge and impedance spectroscopy measurements. The microstructure, surface area and capacitance of NGAs could be facilely controlled by adding different amounts of chitosan. The prepared NGA ‐4 showed a specific capacitance of 148.0 F/g at the discharge current density of 0.5 A/g and also retained 95.3% of the initial capacitance after 5000 cycles at the scan rate of 10 mV /s. It provided a possible way to obtain graphene based materials with high surface area and capacitance.     

壳聚糖制备多孔炭及其在电化学超级电容器中的应用(英文)

以壳聚糖为原料在 600、700、800和900℃直接炭化制备多孔炭 C-600,C-700, C-800 和C-900,其BET比表面积分别为278、461、515和625 m2·g-1.用恒流充放电和循环伏安法表征了其电化学性能. 结果表明, 由 C-800 制备电极的循环伏安图形更接近矩形, 在恒电流充放电实验中阴极和阳极过程基本对称, 说明该电极具有较好的电容性能.在 50 mA·g-1 的电流密度下,C-600、C-700、C-800和C-900的电容分别为96、120、154 和 28 F·g-1.由 C-800 制备电极的循环充放电稳定性好, 电流密度为1 A·g-1循环1000次后电容损失小于2%,说明壳聚糖制备多孔碳具有作为超级电容器电极材料的潜在价值. 同时还考察了不同浓度的电解液对C-800电化学性质的影响,发现在KOH浓度为 30%时的电容最大.依据实验结果,对多孔炭制备及其电化学性质间的关系进行了探讨.     

Preparation and thermal analysis of synthetic malachite CuCO3·Cu(OH)2

The synthesis of malachite CuCO₃·Cu(OH)₂ or Cu₂CO₃(OH)₂ was studied through titrations of copper(II) salt solutions with a solution of sodium carbonate at different temperatures. The precipitates were characterized by TG, IR and chemical analysis. The composition varies depending on thepH of the solution and the temperature. Purer malachite was synthesized by simple mixing of a solution of copper(II) nitrate or sulfate with a solution of sodium carbonate at 50°C.The kinetics of the thermal decomposition of synthetic malachite was described by eitherR ₃ orA _m(m=1.2–1.4) law, according to TG analysis, both isothermal and nonisothermal. The Arrhenius parameters determined using three different integral methods showed the kinetic compensation effect, which is correlated to the working temperature interval analyzed.The authors thank Mr. H. Takemoto for analyzing kinetics of the thermal decomposition of synthetic malachite.     

纳米MoS_2催化剂的合成及其在加氢脱硫反应中的应用

通过羰基钼和升华硫反应制备了晶片层数为3～5,比表面积为71m2/g的纳米MoS2催化剂,并考察了其催化十二硫醇或二苯并噻吩的加氢脱硫活性.结果表明,在3.0MPa初始氢气压力下,该催化剂在200C和280C就可使十二硫醇和二苯并噻吩转化接近100%.     

Hierarchical Nanoboxes Composed of Co9S8−MoS2 Nanosheets as Efficient Electrocatalysts for the Hydrogen Evolution Reaction

The development of hydrogen evolution catalysts based on nonprecious metals is essential for the practical application of water‐splitting devices. Herein, the synthesis of Co₉S₈?MoS₂ hierarchical nanoboxes (HNBs) as efficient catalysts for the hydrogen evolution reaction (HER) is reported. The surface of the hollow cubic structure was organized by CoMoS₄ nanosheets formed through the reaction of MoS₄^2? and Co²⁺ released from the cobalt zeolite imidazole framework (ZIF‐67) templates under reflux in a mixture of water/ethanol. The formation process for the CoMoS₄ HNB structures was characterized by TEM images recorded at various reaction temperatures. The amorphous CoMoS₄ HNBs were converted through sequential heat treatments into CoS_x?MoS₂ and Co₉S₈?MoS₂ HNBs. Owing to their unique chemical compositions and structural features, Co₉S₈?MoS₂ HNBs have a high specific surface area (124.6 m² g^?1) and superior electrocatalytic performances for the HER. The Co₉S₈?MoS₂ HNBs exhibit a low overpotential (η₁₀) of 106 mV, a low Tafel slope of 51.8 mV dec^?1, and long‐term stability in an acidic medium. The electrocatalytic activity of Co₉S₈?MoS₂ HNBs is superior to that of recently reported values, and these HNBs prove to be promising candidates for the HER.     

花生壳制备微孔炭及其在电化学超级电容器中的应用

以未使用和使用氢氧化钠溶液处理的花生壳为碳源分别制备出微孔炭PSC-1和PSC-2.PSC-1和PSC-2的比表面积分别为552和726m2·g-1,其主要孔径都约为0.8nm.用PSC-1和PSC-2制备的电极和对称型超级电容器的循环伏安曲线均接近矩形,表明其具有良好的电容特性.在以微孔炭电极为工作电极、铂电极为对电极和银/氯化银电极为参比电极组成的三电极体系测量表明,在0.1A·g-1的电流密度下,PSC-1和PSC-2的比电容达到233和378F·g-1.经过1000次恒电流充放电循环后,在三电极体系和超级电容器中电极均表现出良好的稳定性和电容保持率.基于实验结果探讨了微孔炭的形成机理及其结构与电化学性质之间的联系.     

Electrochemical Aziridination by Alkene Activation Using a Sulfamate as the Nitrogen Source

The first direct aziridination of triaryl‐substituted alkenes was achieved by means of an electrochemical process that could extend to multisubstituted styrenes. Specifically, hexafluoroisopropanol sulfamate was used as a nucleophilic nitrogen source. Mechanistic experiments suggest that this electrochemical process proceeds by stepwise formation of two C?N bonds through reactions between cationic carbon species and the sulfamate.     

Hexa‐ and Dodecanuclear Polyoxomolybdate Cyclic Compounds: Application toward the Facile Synthesis of Nanoparticles and Film Electrodeposition

Two new compounds based on O₃PCH₂PO₃^4? ligands and {Mo^V₂O₄} dimeric units have been synthesized and structurally characterized. The dodecanuclear Mo^V polyoxomolybdate species in (NH₄)₁₈[(Mo^V₂O₄)₆(OH)₆(O₃PCH₂PO₃)₆]?33 H₂O ( 1 ) is a cyclohexane‐like ring in a chair conformation with pseudo S₆ symmetry. In the solid state, the wheels align side by side, thus delimiting large rectangular voids. The hexanuclear anion in Na₈[(Mo^V₂O₄)₃(O₃PCH₂PO₃)₃(CH₃AsO₃)]? 19 H₂O ( 2 ) has a triangular framework and encapsulates a methylarsenato ligand. ³¹P NMR spectroscopic analysis revealed the stability of 2 in various aqueous media, whereas the stability of 1 depends on the nature of the cations present in solution. It has been evidenced that the transformation of 1 into 2 occurs in the presence of CH₃AsO₃^2? ions. This behavior shows that 1 can be used as a new precursor for the synthesis of Mo^V/diphosphonate systems. The two complexes were very efficient both as reductants of Pt and Pd metallic salts and as capping agents for the resulting Pt⁰ and Pd⁰ nanoparticles. The size of the obtained nanoparticles depends both on the nature of the polyoxometalate (POM; i.e., 1 or 2 ) and on the [metallic salt]/[POM] ratio. In all cases, X‐ray photoelectron spectroscopy (XPS) measurements have revealed the presence of Mo^VI species that stabilize the nanoparticles and the absence of Mo^V moieties. Diffuse‐reflectance FTIR spectra of the Pt nanoparticles show that the capping Mo^VI POMs are identical for both systems and contain the diphosphonato ligand. The colloidal solutions do not show any precipitate and the nanoparticles remain well‐dispersed for several months. The electrochemical reduction of Mo^V species was studied for 2 . Cyclic voltammetry alone and electrochemical quartz crystal microbalance coupled with cyclic voltammetry show the deposition of a film on the electrode surface during this reduction.     

Facile Synthesis of A 3D Flower‐Like Mesoporous Ni@C Composite Material for High‐Energy Aqueous Asymmetric Supercapacitors

A 3D flower‐like mesoporous Ni@C composite material has been synthesized by using a facile and economical one‐pot hydrothermal method. This unique 3D flower‐like Ni@C composite, which exhibited a high surface area (522.4 m² g^?1), consisted of highly dispersed Ni nanoparticles on mesoporous carbon flakes. The effect of calcination temperature on the electrochemical performance of the Ni@C composite was systematically investigated. The optimized material (Ni@C 700) displayed high specific capacity (1306 F g^?1 at 2 A g^?1) and excellent cycling performance (96.7 % retention after 5000 cycles). Furthermore, an asymmetric supercapacitor (ASC) that contained Ni@C 700 as cathode and mesoporous carbon (MC) as anode demonstrated high energy density (60.4 W h kg^?1 at a power density of 750 W kg^?1).     

An Ultrastable Porous Polyhedral Oligomeric Silsesquioxane/Tetraphenylthiophene Hybrid as a High-Performance Electrode for Supercapacitors

In this study, we synthesized three hybrid microporous polymers through Heck couplings of octavinylsilsesquioxane (OVS) with 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (OXD-Br₂), tetrabromothiophene (Th-Br₄), and 2,5-bis(4-bromophenyl)-3,4-diphenylthiophene (TPTh-Br₂), obtaining the porous organic–inorganic polymers (POIPs) POSS-OXD, POSS-Th, and POSS-TPTh, respectively. Fourier transform infrared spectroscopy and solid state ¹³C and ²⁹Si NMR spectroscopy confirmed their chemical structures. Thermogravimetric analysis revealed that, among these three systems, the POSS-Th POIP possessed the highest thermal stability (T₅: 586 °C; T₁₀: 785 °C; char yield: 90 wt%), presumably because of a strongly crosslinked network formed between its OVS and Th moieties. Furthermore, the specific capacity of the POSS-TPTh POIP (354 F g⁻¹) at 0.5 A g⁻¹ was higher than those of the POSS-Th (213 F g⁻¹) and POSS-OXD (119 F g⁻¹) POIPs. We attribute the superior electrochemical properties of the POSS-TPTh POIP to its high surface area and the presence of electron-rich phenyl groups within its structure.     

CF3SO2Na as a Bifunctional Reagent: Electrochemical Trifluoromethylation of Alkenes Accompanied by SO2 Insertion to Access Trifluoromethylated Cyclic N‐Sulfonylimines

An unprecedented electrochemical trifluoromethylation/SO₂ insertion/cyclization process has been achieved in an undivided cell in an atom‐economic fashion. The protocol relies on tandem cyclization of N‐cyanamide alkenes by using Langlois’ reagent as a source of both CF₃ and SO₂ under direct anodically oxidative conditions, in which two C?C bonds, two C?X bonds (N?S and S?C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N‐sulfonylimines from readily accessible materials.     

Hollow 3D Frame Structure Modified with NiCo2S4 Nanosheets and Spinous Fe2O3 Nanowires as Electrode Materials for High-Performance All-Solid-State Asymmetric Supercapacitors

Supercapacitors have attracted tremendous research interest, since they are expected to achieve battery-level energy density, while having a long calendar life and short charging time. Herein, a novel asymmetric supercapacitor has been successfully assembled from NiCo₂S₄ nanosheets and spinous Fe₂O₃ nanowire modified hollow melamine foam decorated with polypyrrole as positive and negative electrodes, respectively. Owing to the well-designed nanostructure and suitable matching of electrode materials, the assembled asymmetric supercapacitor (ASC) exhibits an extended operation voltage window of 1.6 V with an energy density of 20.1 Wh kg⁻¹ at a power density of 159.4 kW kg⁻¹. Moreover, the ASC shows stable cycling stability, with 81.3 % retention after 4000 cycles and a low internal resistance of 1.03 Ω. Additionally, a 2.5 V light-emitting diode indicator can be lit up by three ASCs connected in series; this provides evidence of the practical application potential of the assembled energy-storage system. The excellent electrochemical performances should be credited to the significant enhancement of the specific surface area, charge transport, and mechanical stability resulting from the unique 3D morphology.     

木质素纳米炭的制备及作为锂离子电池负极的性能研究

采用生物炼制工业中残渣提取的酶解木质素与乙酸锌在碱性条件下水热复合, 制备出低分子量木质素/氧化锌复合物(LWL/ZnO), 再通过碳化和酸洗后得木质素纳米炭材料(NLC). 通过对其形貌结构进行表征后发现, NLC呈粒径小于50 nm的纳米颗粒结构, 比表面积为833.25 m²/g, 介孔率高达58.07%, 其中孔径约10 nm的介孔发达. 电化学性能测试结果表明, NLC作为锂离子电池负极材料具有良好的循环性能和倍率性能, 在200 mA/g的电流密度下循环200次后仍能保持705 mA·h/g的可逆比容量.     

Facile Green Synthesis of BCN Nanosheets as High‐Performance Electrode Material for Electrochemical Energy Storage

Two‐dimensional hexagonal boron carbon nitride (BCN) nanosheets (NSs) were synthesized by new approach in which a mixture of glucose and an adduct of boric acid (H₃BO₃) and urea (NH₂CONH₂) is heated at 900 °C. The method is green, scalable and gives a high yield of BCN NSs with average size of about 1 μm and thickness of about 13 nm. Structural characterization of the as‐synthesized material was carried out by several techniques, and its energy‐storage properties were evaluated electrochemically. The material showed excellent capacitive behaviour with a specific capacitance as high as 244 F g^?1 at a current density of 1 A g^?1. The material retains up to 96 % of its initial capacity after 3000 cycles at a current density of 5 A g^?1.     

MnO2 Nanosheets Grown on Nitrogen‐Doped Hollow Carbon Shells as a High‐Performance Electrode for Asymmetric Supercapacitors

A hierarchical hollow hybrid composite, namely, MnO₂ nanosheets grown on nitrogen‐doped hollow carbon shells (NHCSs@MnO₂), was synthesized by a facile in situ growth process followed by calcination. The composite has a high surface area (251 m²g^?1) and mesopores (4.5 nm in diameter), which can efficiently facilitate transport during electrochemical cycling. Owing to the synergistic effect of NHCSs and MnO₂, the composite shows a high specific capacitance of 306 F g^?1, good rate capability, and an excellent cycling stability of 95.2 % after 5000 cycles at a high current density of 8 A g^?1. More importantly, an asymmetric supercapacitor (ASC) assembled by using NHCSs@MnO₂ and activated carbon as the positive and negative electrodes exhibits high specific capacitance (105.5 F g^?1 at 0.5 A g^?1 and 78.5 F g^?1 at 10 A g^?1) with excellent rate capability, achieves a maximum energy density of 43.9 Wh kg^?1 at a power density of 408 W kg^?1, and has high stability, whereby the ASC retains 81.4 % of its initial capacitance at a current density of 5 A g^?1 after 4000 cycles. Therefore, the NHCSs@MnO₂ electrode material is a promising candidate for future energy‐storage systems.     

Preparation and Thermal Decomposition of Synthetic Bayerite

The formation process of bayerite, from an aqueous solution of sodium aluminate through enforced decomposition of aluminate ions by introducing CO₂ gas and aging with mechanical stirring, was investigated by pH measurements of the mother solution during preparation reaction and characterization of precipitates obtained at various stages of preparation. An amorphous precipitate, produced initially by the reaction of introduced CO₂, transformed to bayerite via pseudoboehmite during aging. It was found that the crystalline particle size and morphology of the crystallized bayerite change depending systematically on the preparation conditions. The reaction pathway of the thermal decomposition of the synthesized bayerite was investigated by using thermoanalytical techniques. This revised version was published online in July 2006 with corrections to the Cover Date.     

MoS2 Nanosheets Supported on 3D Graphene Aerogel as a Highly Efficient Catalyst for Hydrogen Evolution

The development of efficient catalysts for electrochemical hydrogen evolution is essential for energy conversion technologies. Molybdenum disulfide (MoS₂) has emerged as a promising electrocatalyst for hydrogen evolution reaction, and its performance greatly depends on its exposed edge sites and conductivity. Layered MoS₂ nanosheets supported on a 3D graphene aerogel network (GA‐MoS₂) exhibit significant catalytic activity in hydrogen evolution. The GA‐MoS₂ composite displays a unique 3D architecture with large active surface areas, leading to high catalytic performance with low overpotential, high current density, and good stability.