Highly dispersed Mn–Ce mixed oxides supported on carbon nanotubes for low-temperature NO reduction with NH3

A series of Mn–Ce mixed-oxide catalysts supported on carbon nanotubes (CNTs) were prepared for the first time and used for the selective catalytic reduction of NO with NH₃. Mn(0.4)-Ce/CNTs catalysts with loading from 0.6% to 1.8% (molar ratio) in our tests showed more than 90% NO conversion at 120–180 °C at a high space velocity of 42,000 h^− 1. Transmission electron microscopy confirmed that the particle size of Mn–Ce mixed oxides supported on CNTs was 2 to 4 nm. BET result indicated Mn–Ce mixed-oxide catalysts obtained enlarged surface area and pore volume which was beneficial to the catalytic activity.     

High-surface area carbons from renewable sources with a bimodal micro-mesoporosity for high-performance ionic liquid-based supercapacitors

Highly porous materials with a bimodal pore size distribution in the micro-mesopore range have been produced from biomass by adding melamine to the hydrochar/KOH mixture used in the activation process. These carbons are characterized by BET surface areas in excess of ∼3300 m² g⁻¹ and a porosity equally distributed between micropores and mesopores. The use of melamine in the synthesis process not only extends the pore size distribution into the mesopore region, but leads to the incorporation of a certain amount of nitrogen atoms into the carbon framework. These materials combine high ion adsorption capacities (micropores) and enhanced ion-transport kinetics (mesopores) leading to an outstanding capacitive performance in ionic liquid-based supercapacitors. Thus, they have specific capacitances >160 F g⁻¹ at 1 A g⁻¹ and >140 F g⁻¹ at 60 A g⁻¹ in both pure ionic liquid and in acetonitrile-diluted ionic liquid, enabling these materials to store up to a maximum of ca. 60 W h kg⁻¹ in both kinds of electrolytes and deliver ca. 20 W h kg⁻¹ at ∼42 kW kg⁻¹ (discharge time ca. 2 s) in pure ionic liquid and ∼25–30 W h kg⁻¹ at ∼97–100 kW kg⁻¹ (discharge time ∼1 s) in acetonitrile-diluted ionic liquid.     

Efficient carbon-based solid acid catalysts for the esterification of oleic acid

A series of carbon-based solid acid catalysts was prepared by the sulfonation of mesoporous carbon substrates with thin pore walls, and catalytic activity for the esterification of oleic acid with methanol was tested. The highest turnover frequency (TOF) observed was 78 h^− 1, five times that of Amberlyst-15. The high catalytic activity may be attributed to the good dispersion of the catalysts in methanol. Catalysts with improved dispersion were obtained by a modified preparation, after which the highest TOF observed was 109 h^− 1, seven times that of Amberlyst-15.     

The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.     

Preparation processes and characterizations of alumina-coated alumina support layers and alumina-coated natural material-based support layers for microfiltration

Recently, porous ceramic membranes have become a subject of significant interest due to their outstanding thermal and chemical stability. To reduce the high manufacturing costs of these porous ceramic membranes, recent research has focused on the utilization of inexpensive natural materials. However, there have not been any well-established direct comparisons of the membrane properties between typical alumina-based membranes and novel natural material-based membranes. Therefore, we compared alumina-coated alumina support layers (with average pore sizes ranging from 0.10 µm ~0.18 µm), alumina-coated diatomite-kaolin composite support layers (with an average pore size of 0.12 µm), and alumina-coated pyrophyllite-diatomite composite support layers (with an average pore size of 0.11 µm) via the dip-coating method and subsequent heat treatment ranging from 1200 °C–1400 °C for 1 h. The pure water permeability of the alumina-coated diatomite-kaolin composite support layer and the alumina-coated pyrophyllite-diatomite composite support layer was found to be approximately 2.0×10² L m⁻² h⁻¹ bar⁻¹, which is similar to that of an alumina-coated alumina support layer. Therefore, we suggest that the average pore size of an alumina-coated natural material-based support layer can be effectively controlled while exhibiting acceptable water permeability.     

Porous membrane based on chitosan–SiO2 for coin cell proton battery

Porous chitosan–SiO₂ membranes were prepared by ultrasonic mixing solution-cast and porogen removal method at different SiO₂ weight ratios. To remove SiO₂ from chitosan membranes, NaOH solution was used to dissolve SiO₂. Porous chitosan:SiO₂ membrane with the weight ratio 1:2 produced optimum average pore size (8.5 μm) with an amorphous structure and the highest water uptake (257.1%). Further soaking of this membrane in NH₄CH₃COO electrolyte solution for two days produced the highest conductivity (3.6×10⁻³ S cm⁻¹) and optimum breakdown voltage (1.8 V). Fabrication of coin cell proton battery displayed an open circuit potential of 1.5 V for 7 days, maximum power density (6.7 mW cm⁻²) and small current resistance (0.03 Ω). The specific discharge capacities obtained from discharge profile of 39.7 mA h g⁻¹ (0.5 mA) and 43.8 mA h g⁻¹ (1.0 mA) increased as the discharge currents were increased. These results showed that a porous chitosan–SiO₂ membrane is suitable membrane for the proton batteries.     

Preparation and characterization of porous MgAl2O4 spinel ceramic supports from bauxite and magnesite

Porous magnesium aluminate spinel (MgAl₂O₄) ceramic supports were fabricated by reactive sintering from low-cost bauxite and magnesite at different temperatures ranging from 1100 to 1400 °C and their sintering behavior and phase evolution were evaluated. The effects of sintering temperature on the pore structure, size and distribution as well as on the main properties of spinel ceramic supports such as flexural strength, nitrogen permeation flux and chemical resistance were investigated. The supports prepared at 1300 °C showed a homogeneous pore structure with the average pore size of 4.42 μm, and exhibited high flexural strength (35.6 MPa), high gas permeability (with nitrogen gas flux of 3057 m³ m⁻² h⁻¹ under a trans-membrane pressure of 0.1 MPa) and excellent chemical resistance.     

Supercapacitors based on carbons with tuned porosity derived from paper pulp mill sludge biowaste

Hydrothermal carbonization followed by chemical activation is utilized to convert paper pulp mill sludge biowaste into high surface area (up to 2980 m² g⁻¹) carbons. This synthesis process employs an otherwise unusable byproduct of paper manufacturing that is generated in thousands of tons per year. The textural properties of the carbons are tunable by the activation process, yielding controlled levels of micro and mesoporosity. The electrochemical results for the optimized carbon are very promising. An organic electrolyte yields a maximum capacitance of 166 F g⁻¹, and a Ragone curve with 30 W h kg⁻¹ at 57 W kg⁻¹ and 20 W h kg⁻¹ at 5450 W kg⁻¹. Two ionic liquid electrolytes result in maximum capacitances of 180–190 F g⁻¹ with up to 62% retention between 2 and 200 mV s⁻¹. The ionic liquids yielded energy density–power density combinations of 51 W h kg⁻¹ at 375 W kg⁻¹ and 26–31 W h kg⁻¹ at 6760–7000 W kg⁻¹. After 5000 plus charge–discharge cycles the capacitance retention is as high at 91%. The scan rate dependence of the surface area normalized capacitance highlights the rich interplay of the electrolyte ions with pores of various sizes.     

Sulfonated-polysulfone membrane surface modification by employing methacrylic acid through UV-grafting: Optimization through response surface methodology approach

Membrane surface modification through UV-grafting method was studied and optimized using response surface methodology (RSM) approach. Sulfonated-polysulfone (SPS) membrane was modified through grafting process by employing methacrylic acid (MAA) monomer solution under the exposure of UV light. The parameters used were the concentration of MAA in the range of 0–6 wt% and UV activation time of 0–50 min. The optimized parameters from RSM were 2.61 wt% of MAA and 21.10 min of UV activation time. The optimized water permeability obtained was 8.75 L m⁻² h⁻¹ bar⁻¹, while the rejection percentages for humic acid, NaCl and MgSO₄ solution were 95.0%, 65.7% and 48.3%, respectively.     

Controllable synthesis of mesoporous alumina with large surface area for high and fast fluoride removal

Gamma phase of mesoporous alumina (MA) with large surface area was successfully synthesized by a facile hydrothermal method followed by thermal treatment for fluoride removal. The as-synthesized MA nanoparticles with average size of 20 nm–150 nm have ordered wormhole-like mesoporous structure. The pore size is 5 nm with a narrow distribution, and the specific surface area reaches 357 m² g⁻¹ while the bulk density is 0.45 cm³ g⁻¹. Glucose as a small-molecule template plays an important role on the morphology, surface area and pore diameter of the MA. As an ionic adsorbent for fluoride removal, the maximum adsorption capacity of MA is 8.25 mg g⁻¹, and the remove efficiency reaches 90% in several minutes at pH of 3. The Langmuir equilibrium model is found to be suitable for describing the fluoride sorption on MA and the adsorption behavior follows the pseudo-second-order equation well with a correlation coefficient larger than 0.99. The larger surface area and relatively narrow pore size of MA are believed to be responsible for improving the adsorption efficiency for fluoride in aqueous solution.     

Effects of TiO2 starting materials on the synthesis of Li2ZnTi3O8 for lithium ion battery anode

Lithium zinc titanate (Li₂ZnTi₃O₈) anode materials have been successfully synthesized using rutile-TiO₂ with different particle sizes as titanium sources via a molten-salt method. Various physical and electrochemical methods are applied to characterize the effects of TiO₂ particle sizes on the structures and physicochemical properties of the Li₂ZnTi₃O₈ materials. When the particle size of TiO₂ is too small (10 nm), it is difficult to homogeneously mix TiO₂ with the other raw materials. Thus, the final product Li₂ZnTi₃O₈ has poor crystallinity, large particle size, small specific surface area, pore volume and average pore diameter, which are disadvantageous to its electrochemical performance. Using TiO₂ with the proper particle size of 100 nm as the titanium source, the Li₂ZnTi₃O₈ (R-100-LZTO) with excellent electrochemical performance can be obtained. At 1 A g⁻¹, 175.8 and 163.6 mA h g⁻¹ are delivered at the 1st and the 200th cycles, respectively. The largest capacities of 163, 133.3 and 122.5 mA h g⁻¹ are delivered at 2.5, 5 and 6 A g⁻¹, respectively. The good high-rate performance of the R-100-LZTO originates from the good crystallinity, small particle size, large specific surface area and average pore diameter, low charge-transfer resistance and high Li⁺ diffusion coefficient.     

Bioconversion of barley straw and corn stover to butanol (a biofuel) in integrated fermentation and simultaneous product recovery bioreactors

In these studies concentrated sugar solutions of barley straw and corn stover hydrolysates were fermented using Clostridium beijerinckii P260 with simultaneous product recovery and compared with the performance of a control glucose batch fermentation process. The control glucose batch fermentation resulted in the production of 23.25 g L⁻¹ ABE from 55.7 g L⁻¹ glucose solution resulting in an ABE productivity and yield of 0.33 g L⁻¹ h⁻¹ and 0.42, respectively. The control reactor (I) was started with 62.5 g L⁻¹ initial glucose and the culture left 6.8 g L⁻¹ unused sugar due to butanol toxicity resulting in incomplete sugar utilization. Barley straw (BS) hydrolysate sugars (90.3 g L⁻¹) resulted in the production of 47.20 g L⁻¹ ABE with a productivity of 0.60 g L⁻¹ h⁻¹ and a yield of 0.42. Fermentation of corn stover (CS) hydrolysate sugars (93.1 g L⁻¹) produced 50.14 g L⁻¹ ABE with a yield of 0.43 and a productivity of 0.70 g L⁻¹ h⁻¹. These productivities are 182–212% higher than the control run. The culture was able to use 99.4–100% sugars (CS & BS respectively) present in these hydrolysates and improve productivities which were possible due to simultaneous product removal. Use of >100 g L⁻¹ hydrolysate sugars was not considered as it would have been toxic to the culture in the integrated (simultaneous fermentation and recovery) process.     

Photocatalytic reduction of CO2 to energy products using Cu–TiO2/ZSM-5 and Co–TiO2/ZSM-5 under low energy irradiation

Copper or cobalt incorporated TiO₂ supported ZSM-5 catalysts were prepared by a sol–gel method, and then were characterized by XRD, BET, XPS and UV–vis diffuse reflectance spectroscopy. Ti^3 + was the main titanium specie in TiO₂/ZSM-5 and Cu–TiO₂/ZSM-5, which will be oxide to Ti^4 + after Co was doped. With the deposition of Cu or Co, the efficiency of the CO₂ conversion to CH₃OH was increased under low energy irradiation. The peak production rate of CH₃OH reached 50.05 and 35.12 μmol g^− 1 h^− 1, respectively. High photo energy efficiency (PEE) and quantum yield (φ) were also reached. The mechanism was discussed in our study.     

Influence of process variables on biooxidation of ferrous sulfate by an indigenous Acidithiobacillus ferrooxidans. Part II: Bioreactor experiments

The oxidation of ferrous iron in solution using Acidithiobacillus ferrooxidans has industrial applications in the regeneration of ferric iron as an oxidant agent for the removal of hydrogen sulfide from waste gases, desulphurization of coal, leaching of non-ferrous metallic sulfides and treatment of acid mine drainage. The aim of this attempt was to increase the biooxidation rate of ferrous sulfate by using immobilized cells. Rate of ferrous iron oxidation was determined in a packed-bed reactor configuration with low density polyethylene (LDPE) particles as support material in order to find the most practical system for scale-up. The present work studies the influence of basic parameters on the ferrous iron biooxidation process using an indigenous iron-oxidizing microorganism, namely A. ferrooxidans, in a 2 L packed-bed bioreactor. Effects of several process variables such as initial pH, temperature, dilution rate, initial concentrations of ferrous and ferric ions on oxidation of ferrous sulfate were investigated. Experimental results indicate that in the temperature range of 31–34 °C the biooxidation of ferrous ions to ferric ions could be resulted efficiently. A pH range of 2–2.2 was optimum for the growth of the culture and effective bacterial activity for oxidation of ferrous ions to ferric ions. The highest oxidation rate of 2.9 g Fe²⁺ L⁻¹ h⁻¹ was obtained using a culture initially containing 25 g L⁻¹ Fe⁺² at the dilution rate of 0.4 h⁻¹. This rate is very high compared to that achieved in other bioreactors found in the literature. In addition the biooxidation of Fe²⁺ to Fe³⁺ conversion could be achieved effectively in the presence of the Fe³⁺ in the concentration range of 0.1–0.7 g/L.     

A green approach for efficient p-nitrophenol hydrogenation catalyzed by a Pd-based nanocatalyst

A magnetically recyclable nanocatalyst, Pd–Fe₃O₄, has been synthesized through a simple one-pot, cost effective method. The electrostatic interaction between the catalyst and the support in the synthesis led to the formation of highly dispersed ultra-fine Pd clusters supported on magnetite. The Pd-based catalyst shows a turnover frequency of 476 h^− 1, which is eight times higher in the efficiency for p-nitrophenol (PNP) hydrogenation than that of the commercial Pd/C (62 h^− 1) under ambient conditions in water. This efficient and green chemical transformation system for the PNP hydrogenation shows promising perspective.     

Promoting effect of Pd on H2 production from cellulose pyrolysis over mesocellular-foam-supported Ni catalysts

Noble-metal promoters have been added to catalysts for reactions such as steam-methane reforming, but have rarely been applied to systems that produce H₂ from larger, biomass-derived molecules, such as polyols or cellulose. We have previously found that nickel catalysts supported on mesocellular-foam-(MCF)-type silica catalyze H₂ formation during cellulose pyrolysis, and sought to increase their activity. Thus, palladium-promoted nickel catalysts supported on MCF were prepared, and their activities were tested in cellulose pyrolysis (RT → 800 °C, 40 °C/min) under dry argon. A thermogravimetric analyzer–mass spectrometer (TG–MS) was used to semi-quantitatively monitor the gases, especially H₂, that were released during pyrolysis over catalysts with and without Pd promoters. Although the Pd promoters had little impact on the fraction of H₂ in the product gas, adding ≥ 0.4 wt.% Pd enhanced the H₂ yield from cellulose pyrolysis by increasing the total gas yield from the reaction. Thus the promoter improved H₂ yield by enhancing the tar-cracking activity of the catalyst. A 5%Ni/MCF catalyst that was doped with 0.7 wt.% Pd yielded 85 cm³ H₂/g cellulose, which was 15% more H₂ than was obtained when the catalyst was 5%Ni/MCF.     

Photocatalytic hydrogen production by Au–MxOy (MAg,Cu, Ni) catalysts supported on TiO2

Au–M_xO_y (MAg, Cu, Ni) nanoparticles supported on TiO₂–P25 were prepared by the deposition–precipitation method and were evaluated for the photocatalytic water splitting reaction for hydrogen production, using a mixture of water–methanol (1:1). The combinations of Au–Cu₂O/TiO₂ and Au–NiO/TiO₂ effectively increased the hydrogen production (2064 and 1636 μmol·h^− 1·g^− 1) obtained by Au/TiO₂ (1204 μmol·h^− 1·g^− 1). The higher photoactivities achieved by Au–Cu₂O and Au–NiO nanoparticles deposited on TiO₂ were attributed to an enhancement of the electron charge transfer from TiO₂ to the Au–M_xO_y systems and the effect of surface plasmon resonance of gold nanoparticles.     

Sulfur-doped mesoporous carbon from surfactant-intercalated layered double hydroxide precursor as high-performance anode nanomaterials for both Li-ion and Na-ion batteries

We describe a preparation of sulfur-doped mesoporous amorphous carbon (SMAC) from a commercially available alkyl surfactant sulfonate anion-intercalated NiAl-layered double hydroxide precursor via thermal decomposition and subsequent acid leaching. The resultant amorphous carbon is endowed with the integrated advantage of featuring high reversible capacity and long cycling stability: intrinsic doping of sulfur, large specific area, and broad mesopore size distribution. Electrochemical evaluation shows that the SMAC electrode exhibits highly enhanced electrochemical performances, compared with the electrode of non-doped mesoporous and amorphous carbon prepared by using a different surfactant (sodium laurate). A high reversible capacity of 958 mA h g⁻¹ is achieved for the SMAC electrode after 110 cycles at 200 mA g⁻¹, and especially a superlong cycle life with a reversible capacity of 579 mA h g⁻¹ after 970 cycles at 500 mA g⁻¹. Moreover, the SMAC electrode can facilitate the reversible insertion/extraction of Na ion, owing to the proper specific area and mesopore size distribution, as well as the improved electronic conductivity resulted from doping of sulfur.     

Structure and electrochemical performance of highly nanoporous carbons from benzoate–metal complexes by a template carbonization method for supercapacitor application

A series of highly nanoporous carbons have been prepared by converting benzoate–metal complexes, including zinc benzoate, magnesium benzoate and aluminium benzoate through a template carbonization process. The carbonization temperature plays a pivotal role in determining the carbon structures as well as the resultant electrochemical behaviors in supercapacitors. The carbon–Zn-900 sample derived from zinc benzoate complex has a high specific surface area (1466.4 m² g^–1), large pore volume (2.54 cm³ g^–1) and hierarchical pore size distribution. It can also deliver a large specific capacitance of 314.1 F g⁻¹ at a current density of 0.5 A g⁻¹, together with a large energy density of 67.2 Wh kg⁻¹ when measured in a three-electrode system using 6 mol L⁻¹ KOH as electrolyte. Besides, the carbon–Zn-900 sample has been tested in a two-electrode system using [EMIm]BF₄/AN as electrolyte at different operation temperatures of 25/50/80 °C.     

Synthesis and electrochemical properties of artificial graphite as an anode for high-performance lithium-ion batteries

Artificial graphite containing abundant in situ grown onion-like carbon hollow nanostructures (OCHNs) was prepared from nickel nanoparticles doped pitch and natural graphite flakes by hot-pressing sintering method. Galvanostatic discharge–charge tests indicate that the synthetic graphite with abundant OCHNs exhibits a high specific capacity of 460 mA h g⁻¹ at 20 mA g⁻¹ as well as an excellent rate capability, with a reversible capacity of 220 mA h g⁻¹ at 1 A g⁻¹. Besides the advantages of common graphite anode materials, these superiorities make synthetic graphite a very promising anode for high-performance lithium-ion batteries.