Enhancing Photoelectrochemical Water Oxidation on WO3 via Electrochromic Modulation: Universal Effects and Mechanistic Insights.

Although WO3 exhibits both electrochromic and photoelectrochemical (PEC) properties, there is no research conducted to investigate the correlation between them. The study herein reports the electrochromic enhancement of PEC activity on WO3. The electrochromic WO3 (e-WO3) exhibits a significantly enhanced activity for PEC water oxidation compared to raw WO3 (r-WO3), with a limiting photocurrent density three times that of r-WO3. The electrochromic enhancement of PEC activity is universal and independent of the type of cations inserted during electrochromism. Decoloring reduces the PEC activity but a simple re-coloring restores the activity to its maximum value. Electrochromism induces large amounts of oxygen vacancies and surface states, the former improving the electron density of WO3 and the latter facilitating the hole transfer across e-WO3/electrolyte interface. It is proved that the electrochromic enhancement effect is due to the significantly improved electron-hole separation efficiency and the charge transfer efficiency across the WO3/electrolyte interface.

Role of composition and texture on bifunctional catalytic performance of extruded Au-Cu alloys.

The catalytic activity of Au2Cu and AuCu samples for the electro-oxidation of CH3OH and HCOOH, together with their structure and micro-hardness were investigated using various techniques. The addition of Cu can improve the micro-hardness of samples, which is ascribed to the solid solution strengthening effect. The Schmid factor and low angle grain boundary fraction confirm the difference of plastic deformation ability for samples, being consistent with hardness results. The Au-Cu samples exhibit good bifunctional catalytic performance due to the synergistic effect between Au and Cu. In addition, the Au2Cu sample exhibits a higher catalytic activity than the AuCu sample, suggesting that appropriate preferred orientation plays a key role in the improvement of catalytic activities of Au based catalysts.

Investigations on the Thermodynamics Characteristics, Thermal and Dielectric Properties of Calcium-Activated Zinc-Containing Metallurgical Residues.

An activate pretreatment of zinc-containing metallurgical residues were proposed by adding CaO and introducing microwave heating approach into the CaO activation pretreatment process to realize the conversion of refractory ore phases into pre-treated ore phase. Thermodynamic characteristics analysis indicated that adding CaO can realize the conversion of refractory ore phases, with the same effect as the carbon additives. Thermal conductivity properties analysis denoted that the thermal conductivity properties of ZnS and ZnFe2O4 were relatively poor. Meanwhile, the thermal conductivity properties of the residues sample added with 25% CaO were significantly superior to the residues added with other CaO contents, with the maximum specific heat value of 1.348 J/g·K at 350 °C. Dielectric properties analysis highlighted that adding CaO with the dielectric constant properties significantly higher than that of other substances can enhance the microwave absorption capacity of zinc-containing residues. The decrease in dielectric loss and loss tangent value with the increase of temperature and the residues having large microwave penetration depth guaranteed to obtain better uniformity of microwave heating. Furthermore, adding 25% CaO promoted the microwave penetration depth of the residues sample increased in the range of 300-500 °C. This work can lay a theoretical research foundation for solving the key difficulty for efficient Zn recovery from complex zinc-containing metallurgical residues.

Kinetics characteristics and microwave reduction behavior of walnut shell-pyrolusite blends.

Combining biomass pyrolysis with microwave heating technologies provides a novel and efficient approach for low-grade pyrolusite reduction. The microwave reduction behavior and pyrolysis kinetic characteristics of walnut shell-pyrolusite blends were explored. Results indicated the optimal reduction parameters were: reduction temperature of 650 °C, holding time of 30 min, Mbio/More of 1.8:10, and microwave power of 1200 W. The co-pyrolysis characteristics of the blends included four stages: dehydration, pre-pyrolysis, intense pyrolysis and reduction, and slow pyrolysis and reduction. Fitting analysis based on Coats-Redfern method revealed that chemical reaction was the control step of the process of reducing pyrolusite by biomass, which the finding matched to the isothermal kinetic analysis results determined through unreacted shrinking nuclear model. The activation energies and pre-exponential factors were determined at 5.62 kJ·mol-1-16.69 kJ·mol-1 and 0.0426 min-1-0.515 min-1. The work provides sound references for promoting the industrial application of the combined method on minerals reduction.

Investigations on the microwave absorption properties and thermal behavior of vanadium slag: Improvement in microwave oxidation roasting for recycling vanadium and chromium.

Vanadium slag contains high contents of vanadium and chromium with complex and dense structures, hence microwave heating instead of conventional methods is expected to destroy the dense structure and further to improve the extraction rate of vanadium and chromium, and exploring its dielectric properties is the prerequisite work. Microwave absorption properties and thermal behavior of vanadium slag were investigated. Results indicated that vanadium slag endowed excellent microwave absorption properties, with minimum εr' value of 34.447 (F/M). Dielectric properties of vanadium slag varied with temperature, which changing trend was matched to the three stages of microwave heating characteristics identified by heating rates. Meanwhile, the changing process of dielectric properties also corresponded to the three processes of thermogravimetric characteristics: dehydration stage (30 °C-280 °C), oxidation decomposition of olivine phase and normal spinel phase (280 °C-650 °C), and oxidation decomposition of vanadium chromium spinel (650 °C-950 °C). Moreover, the maximum dielectric constant and highest microwave heating rate of vanadium slag both appeared at the temperature regime of 500 °C-550 °C, which was also the main temperature regime for oxidation decomposition of olivine phase and normal spinel phase in vanadium slag, demonstrating the appropriate process temperature for microwave heating technology to recycle vanadium slag.

Simultaneous removal of Cr(III) and V(V) and enhanced synthesis of high-grade rutile TiO2 based on sodium carbonate decomposition.

Rutile TiO2 is widely applied as the raw material to produce titanium dioxide and titanium sponge, whereas the Cr (III) and V (V) impurities in rutile TiO2 significantly affect the performance of related products. In the present work, the sodium carbonate decomposition treatment on Panzhihua titanium slag was attempted, to improve the preparation process of rutile TiO2 with high crystallinity and simultaneously reduce the chromium (Cr) and vanadium (V) content as hazardous elements. Effects of sodium carbonate decomposition treatment on the crystal composition, microstructure of rutile TiO2 were determined using XRD, SEM and Raman characterization. The recovery of Cr(III) and V(V) was achieved through leaching the roasted titanium slag by dilute sulfuric acid, with the chromium and vanadium content in the residue decreasing up to 0.03 % and 0.04 %, respectively, followed by the final product rutile TiO2 was produced by the leaching residue calcined at 1323.15 K with a duration time of 120 min, with 85.56 % of TiO2 grade. The work highlights the feasibility of synchronously preparing rutile TiO2 and removing hazardous Cr (III) and V (V) impurities from titanium slag using sodium carbonate decomposition.

Dielectric properties and thermal behavior of electrolytic manganese anode mud in microwave field.

Exploring the dielectric properties of a material can provide guidance for applications of microwave technology to the material. In this work, dielectric properties and thermal behavior of manganese anode mud and pure MnO2, CaSO4 and PbSO4 components were systematically investigated. Results indicated that manganese anode mud showed excellent responsiveness to microwaves, with εr' value of 17.971 (F/M) at room temperature and a maximum value of 20.816 (F/M) at 150 °C, rendering it took only 5.5 min for manganese anode mud to be heated from room temperature to 1000 °C. The dielectric properties of manganese anode mud were related to its thermal behavior, mainly affected by MnO2 component. Moreover, the heating process of manganese anode mud was divided into four stages identified by temperatures: less than 200 °C, 200 °C-700 °C, 700 °C-900 °C, greater than 900 °C, corresponding to the five stages of thermal behavior: the removal of absorption water and combined water, the decomposition reaction of Pb2Mn8O16, and the deoxidation reactions of PbO2, MnO2 and Mn3O4. The work highlights the feasibility of processing manganese anode mud by microwave heating.

High-temperature dielectric properties and pyrolysis reduction characteristics of different biomass-pyrolusite mixtures in microwave field.

Exploring the dielectric properties of mineral-biomass mixtures is fundamental to the coupled application with biomass pyrolysis and microwave technology to mineral reduction. In this work, the microwave dielectric properties of five pyrolusite-biomass mixtures were measured by resonant cavity perturbation technique and the pyrolysis reduction characteristics were systematically investigated, including poplar, pine, ageratina adenophora, rapeseed shell and walnut shell. Results indicated that the dielectric properties commonalities of five mixtures with temperature represented by increasing firstly, dropping intensely and finally rising slightly, with excellent responsiveness to microwaves; which the change trend was mainly attributed to the crystal transformation of amorphous MnO2 and pyrolusite reduction reactions by biomass pyrolysis. Meanwhile, the heating characteristics successfully matched the dielectric properties of the mixtures, and the pyrolusite reduction process by biomass can be divided into two stages: biomass pyrolysis and pyrolusite reduction. The work highlights the universal feasibility of the novel coupled method for mineral reduction.

Microwave pyrolysis of walnut shell for reduction process of low-grade pyrolusite.

Replacing fossil energy by utilizing biomass as carbon source to convert metal oxides has meaning for reduction of minerals. Microwave pyrolysis of walnut shell for reduction process of low-grade pyrolusite was proposed. Thermogravimetric analysis indicated biomass pyrolysis process for reduction of pyrolusite was divided into four phases identified by temperatures: dehydration stage (<150 °C), pre-pyrolysis stage (150 °C-290 °C), curing decomposition stage (290 °C-480 °C) and carbonization stage (>480 °C), and manganese recovery reached 92.01% at 650 °C for 30 min with 18% walnut shell. The strongest preferential orientation of MnO was appeared, with good crystalline structure and no MnO2 and FeO peaks detected. The product surface became loose and porous with numerous cracks, pits and holes, and molten granules were interconnected and stacked with regular shape. The methods propose new idea of selective reduction of pyrolusite based on biomass pyrolysis by microwave heating.

Microwave dielectric properties and thermochemical characteristics of the mixtures of walnut shell and manganese ore.

In this work, dielectric properties and thermochemical characteristics of mixtures of walnut shell and manganese ore were systematically investigated. Results indicated that reducing manganese ore by walnut shell was divided into four stages identified by temperatures: <150 °C, 150 °C-300 °C, 300 °C-480 °C, greater than 480 °C. Higher than 200 °C, the dielectric constants (εr'), dielectric loss factors (εr″) and loss tangent coefficients (tan δ) of mixture at a ore/biomass mixing ratio of 10:1.2 were observed to suddenly drop to low levels, with 5.107 (F/M), 8.5 × 10-4 (F/M), 1.66 × 10-4 (F/M), respectively; which were attributed to the MnO2 reduced by the reductive volatiles produced by biomass pyrolysis. Meanwhile, the volatiles rendered a decrease in density and dielectric properties of the mixture. The work highlights the possibility of reducing manganese ore by walnut shell with microwave heating.

[Study on metabolites from a sponge-derived fungus].

We have carried out the investigation on a sponge-derived fungus,which was identified as Emericella variecolor from the south sea of China. Two new chemical constituents,(+)-2-acetyl-dihydroterrein (1) and (+)-3-acetyl-dihydroterrein (2),with four known compounds,anditomin (3),andilesin A (4),andilesin C (5) and andilesin B (6),were isolated from this fungus by column chromatography over silica gel, Sephadex LH-20, and ODS. The structures of 1 and 2 were elucidated by spectroscopic methods including NMR,HR-ESI-MS,and CD.