Great interests have arisen over the last decade in the development of hierarchically porous materials. The hierarchical structure enables materials to have maximum structural functions owing to enhanced accessibility and mass transport properties, leading to improved performances in various applications. Hierarchical porous materials are in high demand for applications in catalysis, adsorption, separation, energy and biochemistry. In the present review, recent advances in synthesis routes to hierarchically porous materials are reviewed together with their catalytic contributions.
Self-standing porous WP2 nanosheet arrays on carbon fiber cloth (WP2 NSs/CC) were synthesized and used as a 3D flexible hydrogen evolution electrode. Because of its 3D porous nanoarray structure, the WP2 NSs/CC exhibits a remarkable catalytic activity and a high stability. By using the experimental measurements and first-principle calculations, the underlying reasons for the excellent catalytic activity were further explored. Our work makes the present WP2 NSs as a promising electrocatalyst for hydrogen evolution and provides a way to design and fabricate efficient hydrogen evolution electrodes through 3D porous nano-arrays architecture.
Copper nanoparticles-decorated polyaniline-derived mesoporous carbon that can serve as noble metal-free electrocatalyst for the hydrazine oxidation reaction (HzOR) is synthesized via a facile synthetic route. The material exhibits excellent electrocatalytic activity toward HzOR with low overpotential and high current density. The material also remains stable during the electrocatalytic reaction for long time. Its good electrocatalytic performance makes this material a promising alternative to conventional noble metal-based catalysts (e.g., Pt) that are commonly used in HzOR-based fuel cells.
The synthesis of new Schiff base-like ligands with asymmetric substituents pattern and their iron complexes with pyridine as axial ligand is described. Two of the ligands and one of the iron(II) complexes were characterized by single crystal X-ray structure analysis. One of the the iron(II) complexes shows spin crossover behavior while the others remain in the high spin state. The influence of the reduced symmetry of the ligand on the properties of the complexes is discussed.
A palladium catalyst supported on 2-aminopyridine functionalized cellulose was synthesized and fully characterized by inductively coupled plasma atomic emission spectroscopy, transmission electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectrometry. This catalyst can be applied in the Suzuki cross-coupling reaction of aryl halides with arylboronic acids in 50% ethanol to afford biaryls in good yields, and easily recycled by simple filtration after reaction without the loss of metal Pd.
Poly(2,6-dimethyl-1,4-phenylene oxide) was tethered with a 1,5-disubstituted tetrazole through a quaternary ammonium linkage. The formation of a tetrazole-ion network in the resulting polymers was found to promote the hydroxide ion transport through the Grotthus-type mechanism.
A mild and efficient synthesis for the biaryl acids via rhodium-catalyzed cross-dehydrogenative coupling reaction has been developed. This novel protocol with sodium chlorite as an oxidant featured many advantages such as mild reaction conditions, high regioselectivity, tolerance of various functional groups, and good to excellent yields.
The synthetic chromosome rearrangement and modification by loxP-mediated evolution (SCRaMbLE) system has been used to improve prodeoxyviolacein (PDV) production in haploid yeast containing chromosome synV. To rapidly and continuously generate genome diversification with the desired phenotype, the multiplex SCRaMbLE iterative cycle strategy has been developed for the screening of high PDV production strains. Wholegenome sequencing analysis reveals large duplications, deletions, and even the whole genome duplications. The deletion of YER151C is proved to be responsible for the increase. This study demonstrates that artificial DNA rearrangement can be used to accelerate microbial evolution and the production of biobased chemicals.
This study described a template-free method for the synthesis of hierarchically macro-mesoporous Mn-TiO2 catalysts. The promoting effect of Mn doping and the hierarchically macro-mesoporous architecture on TiO2 based catalysts was also investigated for the selective reduction of NO with NH3. The results show that the catalytic performance of TiO2 based catalysts was improved greatly after Mn doping. Meanwhile, the Mn-TiO2 catalyst with the hierarchically macro-mesoporous architecture has a better catalytic activity than that without such an architecture.
The consequences of changes planned in the European Union legislation relevant to the disposal of sewage sludges are discussed. A specific municipal waste water treatment plant is analyzed in terms of drying and subsequent combustion or pyrolysis of the produced stabilized sludge, and the respective net energy balances are carried out. A simplified economic analysis of the two disposal options is presented, which suggest that combustion of the sludge would be economically infeasible while pyrolysis of the sludge in a modular, self-sufficient container unit can bring a small financial benefit due to the selling of the produced phosphorus-rich biochar.
Establishment of the regeneratable whole-cell catalyst platform for the production of biobased polymeric materials is a typical topic of synthetic biology. In this commentary, discovery story of a “lactate-polymerizing enzyme” (LPE) and LPE-based achievements for creating a new variety of polyesters with incorporated unnatural monomers are presented. Besides the importance of microbial platform itself is discussed referring to the “ballooning”-Escherichia coli.
The polypyrrole(PPy)@NiCo hybrid nanotube arrays have been successfully fabricated as a high performance electrocatalyst for hydrogen evolution reaction (HER) in alkaline solution. The strong electronic interactions between PPy and NiCo alloy are confirmed by X-ray photoelectron spectroscopy and Raman spectra. Because these interations can remarkably reduce the apparent activation energy (Ea) for HER and enhance the turnover frequency of catalysts, the electrocatalytic performance of PPy@NiCo hybrid nanotube arrays are significantly improved. The electrochemical tests show that the PPy@NiCo hybrid catalysts exhibit a low overpotential of ~186 mV at 10.0 mA·cm–2 and a small tafel slope of 88.6 mV·deg–1 for HER in the alkaline solution. The PPy@NiCo hybrid nanotubes also exhibit high catalytic activity and high stability for HER.
Biodegradable poly(ether-imide-ester) elastomers were synthesized from succinic acid, 1,4-butanediol, polyethylene glycol 1000 and N′,N-bis(2-carboxyethyl)- pyromellitimide which was derived from pyromellitic dianhydride and glycine. The chemical structures, crystallinities, thermal stabilities, mechanical properties, hydrophilicities and biodegradabilities of these elastomers were investigated. The hard segments of the linear aliphatic poly (ether-ester) exhibited monoclinic chain packing. Increasing the amount of aromatic bisimide moieties in the poly (ether-ester) reduced the crystallinity of the material and improved the thermal stability and tensile strength of the elastomers. In addition, introducing a suitable amount of aromatic bisimide moieties into the poly(ether-ester) backbones endowed the elastomers with improved biodegradability but too many aromatic bisimide groups reduced the biodegradability of the elastomers.
Biomass is of growing interest as a secondary energy source and can be converted to fuels with higher energy density especially by pyrolysis or gasification. Understanding the mechanism and the kinetics of biomass pyrolysis (thermal decomposition) and gasification (conversion of organic material to gases) could be the key to the design of industrial devices capable of processing vast amounts of biomass feedstock. In our work real product components obtained in pyrolysis were took into consideration as well as char and oil as lumped components, and the kinetic constants for a biomass model compound (cellulose) pyrolysis and gasification were identified based on a proposed simplified reaction mechanism within a compartment model structure. A laboratory scale reactor was used for the physical experiments containing consecutive fast pyrolysis and gasification stages using alkali metal (K) containing feedstock, which has a significant effect on the cellulose pyrolysis and gasification. The detailed model was implemented in MATLAB/Simulink environment, and the unknown kinetic parameters were identified based on experimental data. The model was validated based on measurement data, and a good agreement was found. Based on the validated first principle model the optimal parameters were determined as 0.15 mL/min steam flow rate, and 4% K content.
Nanostructured metal surfaces have been known to exhibit properties that deviate from that of the bulk material. By simply modifying the texture of a metal surface, various unique optical properties can be observed. In this paper, we present a simple two step electrochemical process combining electrodeposition and anodization to generate black gold surfaces. This process is simple, versatile and up-scalable for the production of large surfaces. The black gold films have remarkable optical behavior as they absorb more than 93% of incident light over the entire visible spectrum and also exhibit no specular reflectance. A careful analysis by scanning electron microscopy reveals that these unique optical properties are due to their randomly rough surface, as they consist in a forest of dendritic microstructures with a nanoscale roughness. This new type of black films can be fabricated to a large variety of substrates, turning them to super absorbers with potential applications in photovoltaic solar cells or highly sensitive detectors and so on.
Nanostructures have drawn great attentions for functional device applications. Among the various techniques developed for fabricating arrayed nanostructures of functional materials, nanostructuring technique with porous anodic aluminum oxide (AAO) membrane as templates becomes more attractive owing to the superior geometrical characteristics and low-cost preparation process. In this mini review, we summarize our recent progress about functional nanostructuring based on perfectly-ordered AAO membrane to prepare perfectly-ordered nanostructure arrays of functional materials toward constructing high-performance energy conversion and storage devices. By employing the perfectly-ordered AAO membrane as templates, arrayed nanostructures in the form of nanodot, nanorod, nanotube and nanopore have been synthesized over a large area. These as-obtained nanostructure arrays have large specific surface area, high regularity, large-scale implementation, and tunable nanoscale features. All these advanced features enable them to be of great advantage for the performance improvement of energy conversion and storage devices, including photoelectrochemical water splitting cells, supercapacitors, and batteries, etc.
An innovative and efficient design of solar receivers/reactors can enhance the production of clean fuels via concentrated solar energy. This study presents a new jet-type burner nozzle for gaseous feedstock injection into a cavity solar receiver inspired from the combustion technology. The nozzle design was adapted from a combustion burner and successfully implemented into a solar receiver and studied the influence of the nozzle design on the fluid mixing and temperature distribution inside the solar receiver using a 7 kW solar simulator and nitrogen as working fluid. Finally, a thorough computational fluid dynamics (CFD) analysis was performed and validated against the experimental results. The CFD results showed a variation of the gas flow pattern and gas mixing after the burner nozzle adaptation, which resulted an intense effect on the heat transfer inside the solar receiver.
This paper overviews the development of the anthraquinone auto-oxidation (AO) process for the production of hydrogen peroxide in China and abroad. The characteristics and differences between the fixed-bed and fluidized-bed reactors for the AO process are presented. The detailed comparison indicates that the production of hydrogen peroxide with the fluidized-bed reactor has many advantages, such as lower operation cost and catalyst consumption, less anthraquinone degradation, higher catalyst utilization efficiency, and higher hydrogenation efficiency. The key characters of the production technology of hydrogen peroxide based on the fluidized-bed reactor developed by the Research Institute of Petroleum Processing, Sinopec are also disclosed. It is apparent that substituting the fluidized-bed reactor for the fixed-bed reactor is a major direction of breakthrough for the production technology of hydrogen peroxide in China.
High energy density fuels are critical for hypersonic aerospace propulsion but suffer from difficulties of ignition delay and incomplete combustion. This research reports aluminum nanoparticles (Al NPs) assisted ignition and combustion of high energy density JP-10 fuel. Al NPs with a size of 16 nm were fabricated through a mild and simple method by decomposing AlH3·Et2O with the addition of a surfactant ligand. The uniform size distribution, nanoscaled size and surface ligand make Al NPs stably suspend in JP-10, with 80% NPs being dispersed in the liquid fuel after six months. A shock tube test shows that the presence of 1 wt-% Al NPs can significantly shorten ignition delay time at temperature of 1500 to 1750 K, promote the combustion, and enhance energy release of JP-10. This work demonstrates the potential of Al NPs as ignition and combustion additive for high energy density fuel in hypersonic applications.
A review of recent research related to microporous polymeric membranes formed via thermally induced phase separation (TIPS) and the morphologies of these membranes is presented. A summary of polymers and suitable diluents that can be used to prepare these microporous membranes via TIPS are summarized. The effects of different kinds of polymer materials, diluent types, cooling conditions, extractants and additive agents on the morphology and performance of TIPS membranes are also discussed. Finally new developments in TIPS technology are summarized.
