Achieving Non-Interfacial Blocking Zinc Ion Transport Based on MOF Derived Manganese Oxides and Amorphous Carbon Hybrid Materials.

How to coordinate electron and ion transport behavior across scales and interfaces within ion battery electrodes? The exponential increase in surface area observed in nanoscale electrode materials results in an incomprehensibly vast spatial interval. Herein, to address the problems of volume expansion, dissolution of cathode material, and the charge accumulation problem existing in manganiferous materials for zinc ion batteries, metal organic framework is utilized to form the architecture of non-interfacial blocking ~10 nm Mn2O3 nanoparticles and amorphous carbon hybrid electrode materials, demonstrating a high specific capacity of 361 mAh g-1 (0.1 A g-1), and excellent cycle stability of 105 mAh g-1 after 2000 cycles under 1 A g-1. The uniform and non-separated disposition of Mn and C atoms constitutes an interconnected network with high electronic and ionic conductivity, minimizing issues like structural collapse and volume expansion of the electrode material during cycling. The cooperative insert mechanism of H+ and Zn2+ are analyzed via ex-situ XRD and in-situ Raman tests. The model battery is assembled to present practical possibilities. The results indicate that MOF-derived carbonization provides an effective strategy for exploring Mn-based electrode materials with high ion and electron transport capacity.

Multifunctional Luminescent 3D Ln-MOFs with High Sensitivity for Trace Detection of Micronutrients.

The synthesis of two versatile fluorescent metal-organic frameworks (MOFs), [Eu(4-NCP)(1,4-bdc)]n·0.5H2O (1) and [Eu(4-NCP)(4,4'-bpdc)]n·0.75H2O (2) (HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline, 1,4-H2bdc = benzene-1,4-dicarboxylic acid, 4,4'-H2bpdc = 4,4'-biphenyldicarboxylic acid), was carried out using a hydrothermal method. These MOFs were characterized through various advanced technologies to determine their structural information. The results indicate that both MOFs exhibited 3D network structures with specific topologies. Furthermore, these MOFs demonstrated exceptional thermal stabilities and adsorption capabilities. Additionally, complex 2 was utilized for studying the fluorescence sensing properties of various micronutrients including metal ions, nitro aromatic compounds, and biological small molecules. Notably, complex 2 showed promising potential as a multifunctional sensor for selectively detecting Fe3+, nitrobenzene, and ascorbic acid in aqueous solutions through fluorescence quenching with low limits of detection (LODs ∼ 10-7 M) and high quenching constants (Ksv ∼ 103 M-1). Moreover, the detection mechanism of complex 2 was further investigated by using experimental methods and DFT calculations.

Tunable multiple light emissions of core-shell structures based on rare earth ions doped on the surfaces of organic cocrystals.

The charge transfer (CT) interactions play a vital role in tuning the luminescence of organic crystals. The enhanced energy transfer (ET) effect in rare earth (RE) ions is a significant method to achieve long-lifetime fluorescence. These studies are of great significance in the fields of photoelectric functional materials. However, the effect of CT interactions on the process of ET from the cocrystal ligand group to RE ions is unknown. In this work, we have doped Eu3+ ions, Tb3+ ions and Eu3+/Tb3+ mixed ions on the surfaces of Phen-TCNB (Phen = 1,10-phenanthroline, and TCNB = 1,2,4,5-tetracyanobenzene) to construct organic cocrystal-type core-shell structures by the epitaxial growth method. The core-shell structures exhibited multiple photoluminescence depending on the types and proportions of RE3+ ions that are doped on the surfaces of the cocrystals. Experimental and theoretical investigations prove that the ET enhancements from ligand groups to Eu3+ ions originate from appropriate energy differences between the lowest triplet states of Phen-TCNB and the lowest excited state of RE3+ ions. In contrast, the reduced Tb3+ 5D4 lifetime is caused by the energy back transfer process since the energy difference becomes small. These results reveal that the multiple luminescences of the cocrystal-type core-shell structures can be adjusted by the CT and ET, and this study provides a new strategy for developing novel optoelectronic materials.

Significant influences of TiO2 crystal structures on NO2 and HONO emissions from the nitrates photolysis.

The emissions of NO2 and HONO from the KNO3 photolysis in the presence of TiO2 were measured using a round-shape reactor coupled to a NOx analyzer. TiO2 played important roles in the emission flux density of NO2 (RNO2) and HONO (RHONO), depending on crystal structures and mass ratios of TiO2. RNO2 and RHONO significantly decreased with increasing the rutile and anatase mass ratios from 0 to 8 and 0.5 wt.%, respectively. Nevertheless, with further increasing the anatase mass ratio to 8 wt.%, there was an increase in RNO2 and RHONO. RNO2 on KNO3/TiO2/SiO2 had positive correlation with the KNO3 mass (1-20 wt.%), irradiation intensity (80-400 W/m2) and temperature (278-308 K), while it had the maximum value at the relative humidity (RH) of 55%. RHONO on KNO3/TiO2/SiO2 slightly varied with the KNO3 mass and temperature, whereas it increased with the irradiation intensity and RH. In addition, the mechanism for NO2 and HONO emissions from the nitrates photolysis and atmospheric implications were discussed.

An efficient utilization of chromium-containing vanadium tailings: Extraction of chromium by soda roasting-water leaching and preparation of chromium oxide.

Chromium-containing vanadium tailings (CCVT), an industrial waste, were utilized to extract chromium efficiently by soda roasting-water leaching process and for the preparation of highly pure chromium oxide. The effect of extraction of chromium under different roasting and leaching conditions were analyzed using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The maximum chromium extraction rate of 91.51% was obtained when soda (Na2CO3) and CCVT were mixed in a molar ratio (n (Na2CO3)/n (Cr2O3)) of 8, roasted at 900 °C and maintained for 120 min. Then, the roasted product was leached in water at 60 °C for 60 min with a liquid-solid mass ratio (L/S) of 10. During soda roasting, the chromium-containing phase (Fe0.6Cr0.4)2O3 combines with Na2CO3 to form Na2CrO4, which was then transferred into the leaching liquid, post water leaching. The by-products such as NaFeTiO4, Na2CaSiO4, and Na0.68Fe0.68Si0.32O2 were left in the leaching residue which was called chromium tailings (CT). 87.40% chromium oxide was recovered from the unpurified leaching liquid after reduction and precipitation by adding Na2S, followed by roasting the deposit. This process not only relieved the potential threat of the industrial waste CCVT to the environment but also realized the recovery of the valuable element chromium.

Synthesis of vertically aligned CaTiO3 nanotubes with simple hydrothermal method and its photoelectrochemical property.

Perovskite-type oxides have become the hotspots of functional materials due to their various excellent performances. As a typical material with a perovskite structure, CaTiO3 (CTO) possesses a similar band gap to TiO2 with less defects and recombination centers, which makes it a promising alternative material to TiO2. In particular, the CTO nanotube structure has a large specific surface area and unique photochemical and electron-transport properties, and these advantages further expand its application range. In this paper, a highly ordered and vertically aligned CTO nanotube array was successfully synthesized by a simple hydrothermal method with TiO2 nanotube (TNT) arrays as the precursor. It was found that the CTO nanotube had a higher optical absorption ability (3.4 eV), photovoltage (500 mV) and photocurrent density (0.004 A cm-1) under ultraviolet irradiation, compared to the TNT (350 mV and 0.0036 A cm-1). At the same time, the electrochemical impedance spectroscopy, Mott-Schottky and stability tests indicate that the CTO nanotube might be a promising alternative choice as the photoelectric material for a TNT.

Preparation and Characterization of Zn1-xNixO Nanoparticles: Application as a SERS Substrate.

In this paper, the study of the Zn1-xNixO (x = 0, 0.01, 0.03, 0.05) nanoparticles as SERS active substrate has been reported. The structural, morphological and optical studies are carried out by XRD, XPS, SEM, UV-vis and Raman spectroscopy. The XRD spectra indicate that the four Zn1-xNixO nanoparticles (x = 0, 0.01, 0.03, 0.05) are all single wurtzite structure. XPS study further demonstrates that Ni atoms are successfully doped into ZnO lattice. We have observed strong SERS signals when the 4-mercaptobenzoic acid used as the probe molecules. An interesting phenomenon is that an appropriate amount of the Ni atoms doping can enhance the SERS spectrum, and the maximum SERS intensity appeared when the Zn1-xNixO (x = 0.03) as the SERS active substrate, and we ascribe the SERS mechanism to the charge-transfer mechanism. The energy levels caused by the surface defects of ZnO NPs by Ni doping have influence on the charge-transfer process and have benefit for the SERS performance.

Heterogeneous Photochemical Conversion of NO2 to HONO on the Humic Acid Surface under Simulated Sunlight.

The poor understanding of HONO sources in the daytime highlights the importance of the heterogeneous photochemical reaction of NO2 with aerosol or soil surfaces. The conversion of NO2 to HONO on humic acid (HA) under simulated sunlight was investigated using a flow tube reactor at ambient pressure. The uptake coefficient (γ) of NO2 linearly increased with irradiation intensity and HA mass in the range of 0-2.0 µg/cm(2), while it decreased with the NO2 concentration. The HONO yield was found to be independent of irradiation intensity, HA mass, and NO2 concentration. The temperature (278-308 K) had little influence on both γ and HONO yield. Additionally, γ increased continuously with relative humidity (RH, 7-70%), and a maximum HONO yield was observed at 40% RH. The heterogeneous photochemical reaction of NO2 with HA was explained by the Langmuir-Hinshelwood mechanism.

Evaluation of the role of inherent Ca(2+) in phosphorus removal from wastewater system.

The role of inherent Ca(2+) in phosphorus removal from wastewater was evaluated by batch tests. Precipitates were characterized by an X-ray diffractometer (XRD), Fourier transform infrared spectrophotometer (FT-IR) and scanning electron microscope with an energy dispersive spectrometer (EDS) system. Effects of inherent Ca(2+) on phosphorus removal through basic oxygen furnace slag (BOFS) were also analyzed. The results show that upon adjusting the pH to higher than 7.0, inherent Ca(2+) can remove phosphorus from wastewater and form Ca-P precipitates. Residual phosphorus exhibited a linear decreasing trend with increasing the pH from 7.0 to 10.0 and then remained unchanged at higher pH than 10.0. EDS determined that the precipitates contained the elements Ca, P and O. FT-IR spectra demonstrated that the functional groups of precipitates involved PO4(3-), OH(-) and CO3(2-). XRD indicated that the precipitates may consist of CaCO3 and some Ca-P phosphates such as CaHPO4, Ca4H(PO4)3, Ca3(PO4)2, and Ca5(PO4)3(OH). During the removal process of phosphorus by BOFS, due to the presence of inherent Ca(2+) in wastewater, the removal efficiency and rate of phosphorus increased by 15.5% and by a factor of about 3.0, respectively.

Fungal diversity in major oil-shale mines in China.

As an insufficiently utilized energy resource, oil shale is conducive to the formation of characteristic microbial communities due to its special geological origins. However, little is known about fungal diversity in oil shale. Polymerase chain reaction cloning was used to construct the fungal ribosomal deoxyribonucleic acid internal transcribed spacer (rDNA ITS) clone libraries of Huadian Mine in Jilin Province, Maoming Mine in Guangdong Province, and Fushun Mine in Liaoning Province. Pure culture and molecular identification were applied for the isolation of cultivable fungi in fresh oil shale of each mine. Results of clone libraries indicated that each mine had over 50% Ascomycota (58.4%-98.9%) and 1.1%-13.5% unidentified fungi. Fushun Mine and Huadian Mine had 5.9% and 28.1% Basidiomycota, respectively. Huadian Mine showed the highest fungal diversity, followed by Fushun Mine and Maoming Mine. Jaccard indexes showed that the similarities between any two of three fungal communities at the genus level were very low, indicating that fungi in each mine developed independently during the long geological adaptation and formed a community composition fitting the environment. In the fresh oil-shale samples of the three mines, cultivable fungal phyla were consistent with the results of clone libraries. Fifteen genera and several unidentified fungi were identified as Ascomycota and Basidiomycota using pure culture. Penicillium was the only genus found in all three mines. These findings contributed to gaining a clear understanding of current fungal resources in major oil-shale mines in China and provided useful information for relevant studies on isolation of indigenous fungi carrying functional genes from oil shale.

Kinetics and mechanism of hexavalent chromium removal by basic oxygen furnace slag.

Basic oxygen furnace slag (BOFS) has the potential to remove hexavalent chromium (Cr(VI)) from wastewater by a redox process due to the presence of minerals containing Fe(2+). The effects of the solution pH, initial Cr(VI) concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr(VI) was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS) system and X-ray diffractometer (XRD). The results show that Cr(VI) in wastewater can be efficiently removed by Fe(2+) released from BOFS under appropriate acidic conditions. The removal of Cr(VI) by BOFS significantly depended on the parameters mentioned above. The reaction of Cr(VI) with BOFS followed the pseudo-second-order kinetic model. Fe(2+) responsible for Cr(VI) removal was primarily derived from the dissolution of FeO and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum (CaSO4·2H2O) could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe(2+) and the removal of Cr(VI). Finally, the main mechanism of Cr(VI) removal by BOFS was described using several consecutive reaction steps.

Removal kinetics of phosphorus from synthetic wastewater using basic oxygen furnace slag.

Removal kinetics of phosphorus through use of basic oxygen furnace slag (BOF-slag) was investigated through batch experiments. Effects of several parameters such as initial phosphorus concentration, temperature, BOF-slag size, initial pH, and BOF-slag dosage on phosphorus removal kinetics were measured in detail. It was demonstrated that the removal process of phosphorus through BOF-slag followed pseudo-first-order reaction kinetics. The apparent rate constant (kobs) significantly decreased with increasing initial phosphorus concentration, BOF-slag size, and initial pH, whereas it exhibited an opposite trend with increasing reaction temperature and BOF-slag dosage. A linear dependence of kobs on total removed phosphorus (TRP) was established with kobs=(3.51±0.11)×10(-4)×TRP. Finally, it was suggested that the Langmuir-Rideal (L-R) or Langmuir-Hinshelwood (L-H) mechanism may be used to describe the removal process of phosphorus using BOF-slag.

Photocatalytic activity of Fe-doped CaTiO3 under UV-visible light.

The photocatalytic degradation of methylene blue (MB) over Fe-doped CaTiO3 under UV-visible light was investigated. The as-prepared samples were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS) system, Fourier transform infrared spectra (FT-IR), and UV-visible diffuse reflectance spectroscopy (DRS). The results show that the doping with Fe significantly promoted the light absorption ability of CaTiO3 in the visible light region. The Fe-doped CaTiO3 exhibited higher photocatalytic activity than CaTiO3 for the degradation of MB. However, the photocatalytic activity of the Fe-doped CaTiO3 was greatly influenced by the calcination temperature during the preparation process. The Fe-doped CaTiO3 prepared at 500°C exhibited the best photocatalytic activity, with degradation of almost 100% MB (10ppm) under UV-visible light for 180 min.

[Research on the progress in the light-emitting mechanism of ZnO in the visible region].

In the past few years we have witnessed a revival of, and subsequent rapid expansion in, the research on zinc oxide (ZnO). We present a review of current research on the optical properties of ZnO. The wide range of useful properties displayed by ZnO has been recognized for a long time. The high electron mobility, high thermal conductivity, wide and direct band gap and large exciton binding energy make ZnO suitable for a wide range of devices, including two light-emitting tubes, transparent thin-film transistors, laser diodes that operate in the blue and ultraviolet region of the spectrum, and ultraviolet detector. Optically pumped lasing has been reported in ZnO platelets, ZnO thin films, and clusters consisting of ZnO nanocrystals and ZnO nanowires. Up to now, a number of synthetic methods including electrospinning, hydrothermal, sol-hydrothermal, chemical vapor deposition, spin coating and electrochemical deposition have been used to prepare ZnO nanomaterials such as nanofibers, nanowires, nanorods and so on. The growth and properties of ZnO nanostructures have been extensively studied, but the photoluminescence mechanism in the visible range has seldom been summarized. The photoluminescence spectra can reflect some important information such as surface defects and oxygen vacancies, surface states, photo-induced charge carrier separation and recombination processes in nano-sized semiconductor materials. The optical emission of ZnO is equally complex, with a variety of defect emission states whose structural origins remain controversial. A detailed discussion of photoluminescence, in the visible spectral range, is provided. In this review, we provided a detailed overview on the luminescence mechanism of ZnO nanostructures in the visible range. The review detail exhibits the following four mechanisms of the optical properties of ZnO in the visible range: the influence of the quantum confinement effect, the band edge modulation that has effect of photoluminescence, the influence of surface modification, and the control of defects' concentration.

A Low-cost and Green Zinc-Iron Battery Achieved by Ethaline Deep Eutectic Solvent.

Deep eutectic solvents (DESs) were considered as a potential electrolyte because of their low price, harmless to environment and wider electrochemical window potential compared to water. In this work, Fe(Ⅲ)/Fe(Ⅱ) and Zn(Ⅱ)/Zn redox couples were used as the positive and negative active materials, respectively, in a DES system using choline chloride and ethylene glycol in a molar ratio of 1:2 (ethaline). The possible working mechanism of the battery was studied by cyclic voltammetry, spectroscopic and simulation methods. The effects of different temperatures, concentrations of zinc ions in the anolyte and current densities on battery performance were evaluated. The results showed that the designed zinc-iron battery should preferably be operated at a current density of 0.5 mA cm-2 and the temperature of 313~323 K, which will improve the energy efficiency and maintain a high coulombic efficiency. The variation of cycle performance test presents a different pattern from the usual batteries, which is due to the effect of RO- group. At 313 K and 0.5 mA cm-2, the coulombic efficiency increases from 14.1% to 100.2% after 46 cycles, and then remains at about 100% during the rest 54 cycles, which demonstrates a good cycle stability of DES-based zinc-iron battery.

A novel three-dimensional porous Ag/TiO2 hybrid aerogels with high dense hot spot as effective SERS substrate for ultrasensitive detection.

This research focuses on preparing a series of new TiO2/Ag hybrid aerogels with varying TiO2 contents, and demonstrates their application as ultrasensitive SERS substrates. The synthesized TiO2/Ag hybrid aerogels exhibited excellent SERS behavior when detecting 4-Mercaptobenzoic acid (4-MBA), and the calculated SERS enhancement factor (EF) was 6.34 × 106. 3D structured aerogels can create more hot spots and adsorption sites, and multiple interband chemical transfer (CT) pathways emerged and enhanced CT efficiency because of the large number of surface oxygen vacancies of meso-TiO2 NPs. Therefore, the synergy of electromagnetic field enhancement and chemical enhancement leads to SERS enhancement. In addition, the composite SERS substrate has high sensitivity, and the detection limit of adsorbed 4-MBA probe molecules reaches 10-11 M. Furthermore, the TiO2/Ag hybrid aerogels demonstrate good reproducibility with minimal standard deviation in terms of SERS signals. In addition, even after standing for 6 months, there is almost no attenuation in the SERS signal intensity, which highlights the excellent stability of this substrate. Therefore, these highly sensitive TiO2/Ag hybrid aerogels SERS substrates have important practical value in environmental monitoring, medical inspection and food supervision.

Electrodeposition of Bi from Choline Chloride-Malonic Acid Deep Eutectic Solvent.

Deep eutectic solvent (DES) has been widely used in the field of metal electrodeposition as an economical and environmentally friendly green solvent. Metallic bismuth films were prepared by electrodeposition from choline chloride-malonic acid (ChCl-MA) deep eutectic solvent (DES) containing BiCl3. Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy were used to study the structure of ChCl-MA-BiCl3, and the results showed that Bi(III) was in the form of [BiCl6]3- ions. The viscosity of ChCl-MA-BiCl3 ranges from 200 to 1200 mPa·s at temperatures from 363 K to 323 K. The conductivity of 0.01 M Bi(III) in ChCl-MA is 3.24 ms·cm-1 at 363 K. The electrochemical behavior and electrodeposition of Bi(III) in DES were investigated by cyclic voltammetry (CV) and chronoamperometry. The results showed that the electrodeposition reaction was a quasi-reversible reaction controlled by the diffusion and the nucleation of bismuth was a three-dimensional instantaneous nucleation. The diffusion coefficient of Bi(III) in ChCl-MA was 1.84 × 10-9 cm2·s-1. The electrodeposition product was observed by scanning electron microscopy (SEM), and the results showed that the deposition potential has a significant influence on the morphology of the bismuth film. X-ray photoelectron spectroscopy (XPS) shows that bismuth and bismuth oxides are present in the deposited film obtained by electrodeposition.

Evaluation of the potential of recovering various valuable elements from a vanadiferous titanomagnetite tailing based on chemical and process mineralogical characterization.

In order to evaluate the potential of recovering various valuable elements from vanadiferous titanomagnetite tailing (VTMT), the chemical and process mineralogical characterization of VTMT were investigated in this study by various analytical techniques such as XRF, XRD, optical microscopy, SEM, EDS, and AMICS. It was found that VTMT is a coarser powder in general; about 50% of the particle size is greater than 54.30 µm. The total iron content of the VTMT was 22.40 wt.%, and its TiO2 grade is 14.45 wt.%, even higher than those found in natural ilmenite ores. The majority of iron and titanium were located in ilmenite and hematite; 62.84% of hematite and 90.27% of ilmenite were present in monomeric form. However, there is still a portion of ilmenite and hematite embedded in gangue such as anorthite, diopside, and serpentite. For the recovery of valuable fractions such as Fe and TiO2 from VTMT, a treatment process including ball milling-high-intensity magnetic separation-one roughing and three refining flotation was proposed. Finally, a concentrate with TiO2 grade of 47.31% and total Fe (TFe) grade of 35.44% was produced; TiO2 and TFe had recovery rates of 57.71% and 28.23%, respectively. The recovered product is adequate as a raw material for the production of rutile. This study provides a reference and a new research direction for the recycling and comprehensive utilization of VTMT.

Atomic-scale imaging of ytterbium ions in lead halide perovskites.

Lanthanide-doped lead halide perovskites have demonstrated great potential for photoelectric applications. However, there is a long-standing controversy about the existence of lanthanide ions, e.g., whether the doping of Ln3+ is successful or not; the substituting sites of Ln3+ in lead halide perovskites are unclear. We directly identify the doped Yb3+ in CsPbCl3 perovskites by using the state-of-the-art transmission electron microscopy and three-dimensional atom probe tomography at atomic scale. Different from the previous assumptions and/or results, we evidence that Yb3+ simultaneously replace Pb2+ and occupy the lattice interstitial sites. Furthermore, we directly observe the cluster phenomenon of CsPbCl3 single crystal at near atomic scale. Density functional theory modeling further confirms and explains the mechanisms of our findings. Our findings thus provide an atomic-level understanding of the doping mechanism in perovskites and will stimulate a further thinking of the doping effect on the performance of perovskites.

Controllable preparation of Ti3C2Tx/Ag composite as SERS substrate for ultrasensitive detection of 4-nitrobenzenethiol.

Currently, metal carbonitride (MXene) has been identified as a hot research topic in the research area of surface-enhanced Raman scattering (SERS). In this study, Ti3C2Tx/Ag composite was fabricated as SERS substrate with different Ag contents. The fabricated Ti3C2Tx/Ag composites show good SERS behavior by detecting 4-Nitrobenzenethiol (4-NBT) probe molecules. Through calculation, the SERS enhancement factor (EF) of the Ti3C2Tx/Ag substrate was as high as 4.15 × 106. It is worth noting that the detection limit of 4-NBT probe molecules can be achieved ultralow concentration of 10-11 M. In this system, electromagnetic enhancement mechanism and chemical enhancement mechanism have synergistic effects on SERS phenomenon. Meanwhile, the Ti3C2Tx/Ag composite substrate exhibited good SERS reproducibility. In addition, the SERS detection signal hardly changed after 6 months of natural standing, and the substrate showed good stability. This work suggests that the Ti3C2Tx/Ag substrate could be used as a sensitivity SERS sensor for practical application, and could be applied in the field of environmental monitoring.