Excellent capacitive performance of a three-dimensional hierarchical porous graphene/carbon composite with a superhigh surface area.

Three-dimensional hierarchical porous graphene/carbon composite was successfully synthesized from a solution of graphene oxide and a phenolic resin by using a facile and efficient method. The morphology, structure, and surface property of the composite were investigated intensively by a variety of means such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption, Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). It is found that graphene serves as a scaffold to form a hierarchical pore texture in the composite, resulting in its superhigh surface area of 2034 m(2) g(-1), thin macropore wall, and high conductivity (152 S m(-1)). As evidenced by electrochemical measurements in both EMImBF4 ionic liquid and KOH electrolyte, the composite exhibits ideal capacitive behavior, high capacitance, and excellent rate performance due to its unique structure. In EMImBF4 , the composite has a high energy density of up to 50.1 Wh kg(-1) and also possesses quite stable cycling stability at 100 °C, suggesting its promising application in high-temperature supercapacitors. In KOH electrolyte, the specific capacitance of this composite can reach up to an unprecedented value of 186.5 F g(-1), even at a very high current density of 50 A g(-1), suggesting its prosperous application in high-power applications.

The transition-metal-catalyst-free oxidative homocoupling of organomanganese reagents prepared by the insertion of magnesium into organic halides in the presence of MnCl2·2LiCl.

Organomanganese reagents were prepared by the insertion of magnesium into aryl halides in the presence of MnCl2·2LiCl. These organomanganese reagents smoothly undergo 1,2-addition, acylation, and Pd-catalyzed cross-coupling with various electrophiles. Especially, the oxidative homocoupling of organomanganese reagents was completed in one pot without an additional transition-metal catalyst.

Design and multilevel regulation of transition metal phosphides for efficient and industrial water electrolysis.

Renewable energy electrolysis of water to produce hydrogen is an effective measure to break the energy dilemma. However, achieving activity and stability at a high current density is still a key problem in water electrolyzers. Transition metal phosphides (TMPs), with high activity and relative inexpensiveness, have become excellent candidates for the production of highly pure green hydrogen for industrial applications. In this mini-review, multilevel regulation strategies including nanoscale control, surface composition and interface structure design of high-performance TMPs for hydrogen evolution are systematically summarized. On this basis, in order to achieve large-scale hydrogen production in industry, the hydrogen evolution performance and stability of TMPs at a high current density are also discussed. Peculiarly, the practical application and requirements in proton exchange membrane (PEM) or anion exchange membrane (AEM) electrolyzers can guide the advanced design of regulatory strategies of TMPs for green hydrogen production from renewable energy. Finally, the challenges and prospects in the future development trend of TMPs for efficient and industrial water electrolysis are given.

Oxygen-deficient WO3-x spheres for electrochemical N2 oxidation to nitrate.

Nitrate synthesis via the electrochemical nitrogen oxidation reaction (e-NOR) is widely recognized as a potential alternative to the energy-intensive Ostwald process. However, electrocatalysts with strong N2 adsorption and activation abilities remain largely undeveloped due to kinetic hindrances caused by the high bond energy of NN. Here we designed a hollow WO3 sphere with an optimal concentration of oxygen vacancies and studied its e-NOR performance. The optimally synthesized oxygen-deficient WO3 (WO3-x) achieved a high nitrate yield of 311.15 µmol h-1gcat.-1 and a Faraday efficiency of 2.00 %, which is probably due to the presence of a moderate amount of oxygen vacancies on the WO3-x surface and the hollow spherical structure, which further improves the accessibility of the inner active surface. Our work could potentially stimulate research into transition metal oxide-based materials for e-NOR applications.

Isobutane dehydrogenation over high-performanced sulfide V-K/γ-Al2O3 catalyst: Modulation of vanadium species and intrinsic effect of potassium.

Compared with industrial used Pt- and Cr-based catalyst in dehydrogenation (DH) of light alkanes, the sulfide V-K/γ-Al2O3 catalyst reported in this study shows lower cost and toxicity, and significant DH performance. The yield to isobutene reached as high as 52.9%, which is among the highest reported to date. We attribute such high isobutene yield to the precise modulation of polymerization degree for vanadium species via doping of potassium and indicating that the synergy between vanadium species and acid sites is critical to enhance the DH performance. Our previous work showed sulfidation promoted the increase of DH performance for vanadium-based catalyst, and we go further in this study to explore the correlation between increased range of DH performance and the added potassium. The different loaded potassium leads to variation in sulfidation degree, affecting the properties of vanadium species and acid properties consequently. The potassium was distributed uniformly on surface of the sulfide vanadium-based catalyst and was predominantly bonded with the vanadium species rather than with the γ-Al2O3 support. With increasing the potassium amount from 0 to 3 wt%, the acid amount kept decreasing, and some specific strong acid sites appeared once adequate sulfur was introduced in the V-K/γ-Al2O3 catalyst. The characterization and DFT results both revealed that the doped potassium contributes to regulating the vanadium species in the oligomeric state. The synergy between vanadium species and acid properties was regulated by the added potassium simultaneously, and thus the DH performance was enhanced. This study provides promising strategy for preparation of environment-friendly model industrial DH catalyst.

Diffusion and catalyst efficiency in hierarchical zeolite catalysts.

The preparation of hierarchical zeolites with reduced diffusion limitation and enhanced catalyst efficiency has become a vital focus in the field of zeolites and porous materials chemistry within the past decades. This review will focus on the diffusion and catalyst efficiency of hierarchical zeolites and industrial catalysts. The benefits of diffusion and catalyst efficiency at two levels of hierarchies (zeolitic component level and industrial catalyst level) from a chemical reaction engineering point of view will be analysed. At zeolitic component level, three types of mesopores based on the strategies applied toward enhancing the catalyst effectiveness factor are presented: (i) 'functional mesopores' (raising effective diffusivity); (ii) 'auxiliary mesopores' (decreasing diffusion length); and (iii) 'integrated mesopores' (a combination thereof). At industrial catalyst level, location and interconnectivity among the constitutive components are revealed. The hierarchical pore interconnectivity in multi-component zeolite based industrial catalysts is exemplified by fluid catalytic cracking and bi-functional hydroisomerization catalysts. The rational design of industrial zeolite catalysts at both hierarchical zeolitic component and catalyst body levels can be fully comprehended using the advanced in situ and/or operando spectroscopic, microscopic and diffraction techniques.

Adsorption of bulky molecules of nonylphenol ethoxylate on ordered mesoporous carbons.

Ordered mesoporous carbons (OMCs) with varying pore sizes were prepared using ordered mesoporous silica SBA-15 as hard templates. The OMCs possess abundant mesopores with narrow pore size distribution, on which the adsorption behavior of bulky molecules of nonylphenol ethoxylate (NPE) were investigated. The isotherms of NPE on OMCs can be fitted by Langmuir adsorption model, evidenced by the adsorption data. The surface area of the pores larger than 1.5 nm is a crucial factor to the adsorption capacity of NPE, whereas the most probable pore diameter of OMCs is crucial to the adsorption rate of NPE. The adsorption temperature has more significant effects on adsorption rate than the adsorption capacity. Theoretical studies show that the adsorption kinetics of NPE on OMCs can be depicted with the pseudo-second-order kinetic model. In addition, thermodynamic parameters of adsorption were evaluated based on the equilibrium constants related to the equilibrium of adsorption at different temperatures.

Combined alkali dissolution and re-assembly approach toward ZSM-5 mesostructures with extended lifetime in cumene cracking.

The basis and contribution of mesopores created in ZSM-5 structures at different treatment conditions are systematically investigated. The results reveal that the mesopores originated from the alkali dissolution of pristine ZSM-5 are mainly intracrystalline and they contribute to excessive Brønsted acid sites, while the mesopores originated from the re-assembly of alkali dissolved aluminosilicate species possess Lewis acid sites. These ZSM-5 mesostructures showed an extended lifespan during the cracking of cumene (88.0%) in comparison to the pristine ZSM-5 (27.0%) after 460 min. The zeolite mesostructures obtained in this study could be used as a base for further design of new porous materials with desired acidic properties.

Aqueous dye adsorption on ordered mesoporous carbons.

Ordered mesoporous carbons (OMCs) with varying pore size, and microporous carbon, CFY, were synthesized using ordered mesoporous silica SBA-15 and NaY zeolite as hard templates, respectively. N(2) adsorption tests show that the synthesized OMCs possess abundant mesopores and centralized mesopore distribution. Methylene blue (MB) and neutral red (NR) were used as probe molecules to investigate their adsorption behaviors on OMCs and CFY. As evidenced by adsorption tests, the volume of mesopores of which the pore size is larger than 3.5 nm is a crucial factor for the adsorption capacity and adsorption rate of MB on OMCs. However, the most probable pore diameter of OMCs was found to be vital to the adsorption capacity and adsorption rate of NR. Theoretical studies show that the adsorption kinetics of MB and NR on OMCs can be well depicted by using pseudo-second-order kinetic model.

A colorimetric assay for measuring iodide using Au@Ag core-shell nanoparticles coupled with Cu(2+).

Au@Ag core-shell nanoparticles (NPs) were synthesized and coupled with copper ion (Cu(2+)) for the colorimetric sensing of iodide ion (I(-)). This assay relies on the fact that the absorption spectra and the color of metallic core-shell NPs are sensitive to their chemical ingredient and dimensional core-to-shell ratio. When I(-) was added to the Au@Ag core-shell NPs-Cu(2+) system/solution, Cu(2+) can oxidize I(-) into iodine (I2), which can further oxidize silver shells to form silver iodide (AgI). The generated Au@AgI core-shell NPs led to color changes from yellow to purple, which was utilized for the colorimetric sensing of I(-). The assay only took 10 min with a lowest detectable concentration of 0.5 µM, and it exhibited excellent selectivity for I(-) over other common anions tested. Furthermore, Au@Ag core-shell NPs-Cu(2+) was embedded into agarose gels as inexpensive and portable "test strips", which were successfully used for the semi-quantitation of I(-) in dried kelps.

Au@Ag core/shell nanoparticles as colorimetric probes for cyanide sensing.

We synthesize Au@Ag core/shell nanoparticles (NPs) using a Au NP assisted Tollens reaction. The as-synthesized NPs are used for the colorimetric cyanide sensing with a detection limit of 0.4 µM. The bimetallic NPs are immobilized into agarose gels as portable "test strips".

A colorimetric agarose gel for formaldehyde measurement based on nanotechnology involving Tollens reaction.

Gold nanoparticles (Au NPs) coupled with Tollens reagent were used for measuring formaldehyde. Au@Ag core-shell NPs were formed along with distinct color changes from pink to deep yellow. This colorimetric system was further immobilized into an agarose gel, which was used for monitoring of gaseous formaldehyde.

Fabrication and biosensing with CNT/aligned mesostructured silica core-shell nanowires.

We report the synthesis of carbon nanotubes (CNTs)/mesostructured silica core-shell nanowires via an interfacial surfactant templating approach. The nanowires possess perpendicularly aligned and uniform accessible mesopores, high surface area and large pore volume. When dimethyl sulfoxide reductase (DMSOR) enzyme is immobilized on the core-shell nanowires, the complex can enhance the electrical communication between the active sites of the enzyme and the electrode surface in the presence of a mediator. The unique properties of the CNTs and the uniform accessible mesopores of the nanowires have made this material promising in the applications as carbon nanotubes field-effect transistors, electrochemical detection, and biosensors.

Copolymer-controlled homogeneous precipitation for the synthesis of porous microfibers of alumina.

Mesoporous aluminas with a uniform fibrous morphology were synthesized using a copolymer-controlled homogeneous precipitation method under hydrothermal conditions. Scanning electron microscopy, X-ray diffraction, solid-state magic-angle spinning nuclear magnetic resonance, transmission electron microscopy, thermogravimetric analysis, nitrogen adsorption, Fourier transform infrared spectrometry, and elemental analysis techniques were used to characterize the samples. The effect of various synthesis conditions on the morphology and mesoporous structure of the alumina fibers was investigated. Such porous alumina microfibers may find applications in nanotechnology and catalysis. They can also be used as advanced high-temperature composite materials and templates for fabrication of fibrous materials of various compositions, such as carbon, transition-metal oxides, and polymers.