Fujian Liu

Transesterification Catalyzed by Ionic Liquids on Superhydrophobic Mesoporous Polymers: Heterogeneous Catalysts That Are Faster than Homogeneous Catalysts

Homogeneous catalysts usually show higher catalytic activities than heterogeneous catalysts because of their high dispersion of catalytically active sites. We demonstrate here that heterogeneous catalysts of ionic liquids functionalized on superhydrophobic mesoporous polymers exhibit much higher activities in transesterification to form biodiesel than homogeneous catalysts of the ionic liquids themselves. This phenomenon is strongly related to the unique features of high enrichment and good miscibility of the superhydrophobic mesoporous polymers for the reactants. These features should allow the design and development of a wide variety of catalysts for the conversion of organic compounds.

ZSM-5 Zeolite Single Crystals with b-Axis-Aligned Mesoporous Channels as an Efficient Catalyst for Conversion of Bulky Organic Molecules

The relatively small and sole micropores in zeolite catalysts strongly influence the mass transfer and catalytic conversion of bulky molecules. We report here aluminosilicate zeolite ZSM-5 single crystals with b-axis-aligned mesopores, synthesized using a designed cationicamphiphilic copolymer as a mesoscale template. This sample exhibits excellent hydrothermal stability. The orientation of the mesopores was confirmed by scanning and transmission electron microscopy. More importantly, the b-axis-aligned mesoporous ZSM-5 shows much higher catalytic activities for bulky substrate conversion than conventional ZSM-5 and ZSM-5 with randomly oriented mesopores. The combination of good hydrothermal stability with high activities is important for design of novel zeolite catalysts. The b-axis-aligned mesoporous ZSM-5 reported here shows great potential for industrial applications.

Sulfated graphene as an efficient solid catalyst for acid-catalyzed liquid reactions

Graphene with its two-dimensional sheet of sp2-hybridized carbon is a hot topic in the fields of materials and chemistry due to its unique features. Herein, we demonstrate that sulfated graphene is an efficient solid catalyst for acid-catalyzed liquid reactions. The sulfated graphene was synthesized from a facile hydrothermal sulfonation of reduced graphene oxide with fuming sulfuric acid at 180 °C. Combined characterizations of XRD, Raman, and AFM techniques show that G-SO3H has a sheet structure (1–4 layers). IR spectroscopy shows that G-SO3H has a SO bond, and the XPS technique confirms the presence of an S element in G-SO3H. Acid–base titration indicates that the acidic concentration of sulfonic groups in the sulfated graphene is 1.2 mmol g−1. TG curves shows that the decomposition temperature (268 °C) of the sulfonic groups on the sulfated graphene is much higher than that of conventional SO3H-functionalized ordered mesoporous carbon (237 °C). Catalytic tests of the esterification of acetic acid with cyclohexanol, the esterification of acetic acid with 1-butanol, the Peckmann reaction of resorcinol with ethyl acetoacetate, and the hydration of propylene oxide show that sulfated graphene is much more active than the conventional solid acid catalysts of Amberlyst 15, OMC-SO3H, SO3H-functionalized ordered mesoporous silica (SBA-15-SO3H), graphene oxide, and reduced graphene oxide, which is attributed to the fact that the sulfated graphene almost has no limitation of mass transfer due to its unique sheet structure. Very importantly, the sulfated graphene has extraordinary recyclability in these reactions, which is attributed to the stable sulfonic groups on the sulfated graphene. The advantages, including high activities and good recyclability as well as simple preparation, are potentially important for industrial applications of the sulfated graphene as an efficient heterogeneous solid acid catalyst in the future.

Recent development of metal hydroxides as electrode material of electrochemical capacitors

Electrochemical capacitors, also known as supercapacitors, are energy storage devices, characterized by rapid rates of charging and discharging and high power density. In recent years, electrochemical capacitors have attracted significant attention as ‘bridges’ for the power/energy gap between traditional capacitors and batteries/fuel cells. The integrated performance of an electrochemical capacitor is essentially determined by its electrode materials. This is a review of electrode materials for electrochemical capacitors, chiefly concerning transition metal hydroxides. In this work, we focused particularly on recently published reports using cheap metal hydroxides as electrode materials for electrochemical capacitors, based on classification of metal hydroxide by composition and microstructure. Some important experimental data on this issue are indicated and summarized. Furthermore, a brief discussion of future development, challenges, and opportunities in this area is also provided.

Binary Nickel–Cobalt Oxides Electrode Materials for High-Performance Supercapacitors: Influence of its Composition and Porous Nature

Nickel-cobalt oxides were prepared by coprecipitation of their hydroxides precursors and a following thermal treatment under a moderate temperature. The preformed nickel-cobalt bimetallic hydroxide exhibited a flower-like morphology with single crystalline nature and composed of many interconnected nanosheets. The ratio of Ni to Co in the oxides could easily be controlled by adjusting the composition of the original reactants for the preparation of hydroxide precursors. It was found that both the molecular ratio of Ni to Co and the annealing temperature had significant effects on their porous structure and electrochemical properties. The effect of the Ni/Co ratio on the pseudocapacitive properties of the binary oxide was investigated in this work. The binary metal oxide with the exact molar ratio of Ni:Co = 0.8:1 annealed at 300 °C, showing an optimum specific capacitance of 750 F/g. However, too high an annealing temperature would lead to a large crystal size, a low specific surface area, as well as a much lower pore volume. With the use of the binary metal oxide with Ni:Co = 0.8:1 and activated carbon as the positive and negative electrode, respectively, the assembled hybrid capacitor could exhibit a high-energy density of 34.9 Wh/kg at the power density of 875 W/kg and long cycling life (86.4% retention of the initial value after 10000 cycles).

Selective Catalytic Production of 5-Hydroxymethylfurfural from Glucose by Adjusting Catalyst Wettability

The development of highly-efficient catalysts for conversion of glucose and fructose to 5-hydroxymethylfurfural (HMF) is of great importance. In this work, theoretical simulations form the basis for rational design and synthesis of a superhydrophobic mesoporous acid, that can completely prevent HMF hydration, giving HMF as sole product from full conversion of fructose. Interestingly, the combined superhydrophobic solid acid and superhydrophilic solid base catalysts are very efficient for one-pot conversion of glucose to HMF, giving a yield as high as 95.4 %. The excellent catalytic data in the conversion of glucose to HMF is attributed to the unique wettabilities of the solid acid and base catalysts.

Effect of calcination temperature on the porous structure of cobalt oxide micro-flowers

Mesoporous cobalt oxide micro-flowers have been synthesized by a simple, surfactant-free method without employing any templates. In this method, cobalt hydroxide micro-flowers were initially prepared in a solution medium. Subsequently, they were applied as a precursor of cobalt oxide by heat treatment, to transform into porous micro-flowers. The morphology of cobalt oxide retained that of its precursor. Experimental analysis confirmed that calcination temperature had great influence on the pore structure and crystal size. The average size of cobalt oxide crystals increased with increasing calcination temperature. Nitrogen adsorption/desorption data showed that the pore size increased and the BET surface area decreased with the gradual increase of calcination temperature. The electrochemical properties of the cobalt oxide were investigated by cyclic voltammetry measurements.

High-temperature synthesis of stable and ordered mesoporous polymer monoliths with low dielectric constants

Highly ordered body cubic (Im-3m) mesoporous phenol-formaldehyde resins (OMR) monoliths were successfully synthesized at high temperatures (200–260 °C) by the assembly of copolymer surfactant (F127) with preformed resol. The preformed resol was obtained from heating a mixture of phenol and formaldehyde at 70 °C. These ordered mesoporous resins synthesized at relatively high temperatures (OMR-200 and OMR-260) show extraordinary thermal and mechanical stabilities, compared with mesoporous polymers synthesized at low temperature (OMR-100 and FDU-15). OMR-200 and OMR-260 samples were characterized with NMR spectroscopy and numerous other techniques. Characterization results suggest that OMR-200 and OMR-260 have much higher cross-linking degree than OMR-100, which might be responsible for the high thermal and mechanical stabilities of OMR-200 and OMR-260 samples. Furthermore, the dielectric constant tests of samples show that OMR-200 and OMR-260 are better than conventional resins, which are reasonably attributed to the presence of porosity in the samples. The unique features of OMR-200 and OMR-260 with superior thermal and mechanical stabilities as well as low-k values might be potentially important for their applications such as heat insulator.

Rapid growth of magnetite nanoplates by ultrasonic irradiation at low temperature

Two-dimensional plate-like Fe(3)O(4) nanocrystals were synthesized by a facile method using ultrasonic irradiation in aqueous solution at low temperature without protection from oxygen. The crystals were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier Transform infrared spectroscopy. The products subjected to ultrasound showed a two-dimensional morphology. The results obtained indicate that the morphologies of the magnetite crystals depend more on the ultrasonic irradiation than on the growth temperature. The thickness and width of the crystals increased with increasing temperature of the reaction medium. In addition, the magnetic hysteresis loop of the magnetite nanoplates was obtained at room temperature.

Solvent‐Free Self‐Assembly to the Synthesis of Nitrogen‐Doped Ordered Mesoporous Polymers for Highly Selective Capture and Conversion of CO2

A solvent-free induced self-assembly technology for the synthesis of nitrogen-doped ordered mesoporous polymers (N-OMPs) is developed, which is realized by mixing polymer precursors with block copolymer templates, curing at 140-180 °C, and calcination to remove the templates. This synthetic strategy represents a significant advancement in the preparation of functional porous polymers through a fast and scalable yet environmentally friendly route, since no solvents or catalysts are used. The synthesized N-OMPs and their derived catalysts are found to exhibit competitive CO2 capacities (0.67-0.91 mmol g-1 at 25 °C and 0.15 bar), extraordinary CO2 /N2 selectivities (98-205 at 25 °C), and excellent activities for catalyzing conversion of CO2 into cyclic carbonate (conversion >95% at 100 °C and 1.2 MPa for 1.5 h). The solvent-free technology developed in this work can also be extended to the synthesis of N-OMP/SiO2 nanocomposites, mesoporous SiO2 , crystalline mesoporous TiO2 , and TiPO, demonstrating its wide applicability in porous material synthesis.