Methyl-terminated graphite carbon nitride with regulatable local charge redistribution for ultra-high photocatalytic hydrogen production and antibiotic degradation.

Intramolecular-tailored graphite carbon nitride (g-C3N4) has great potential to greatly optimize the photo-response performance and carrier separation ability, but exquisite molecular structure engineering is still challenging. Firstly, a series of oxygen and terminal methyl moiety co-modified g-C3N4 (CNNx) has been systematically prepared by using N-Hydroxysuccinimide (HOSu) as a novel copolymerized precursor and urea. The density functional theory (DFT) calculations demonstrated that the presence of oxygen can lower the binding energy for the C-C bond to make the terminal modification easier. The terminal methyl and Oxygen not only caused abundant alveolar defects to break the periodic symmetry but also acted as an electron-accepting platform to tune the local charge redistribution within g-C3N4 molecular. The synthesized CNNx (CNN25) achieved ultra-high photocatalytic activity and chemical stability under visible light toward antibiotic degradation (99% tetracycline, 92% doxycycline, 65% ofloxacin and 74% sulfathiazole degradation within 30 min) and hydrogen production (an apparent quantum efficiency of 2.10% at 400 nm). CNN25 also maintains good efficiency in surface water and groundwater. Moreover, the TC solution treated with CNN25 had hardly any harm to the growth of E. coli. We believe our findings will provide a facile and green strategy for the preparation of non-metallic modified g-C3N4.

Depressing relaxation and conduction loss of polar polymer materials by inserting bulky charge traps for superior energy storage performance in high-pulse energy storage capacitor applications.

Polymer-based dielectrics are chiefly used in high-pulse energy storage capacitors for their high breakdown strength, prominent processability, and low cost. Nevertheless, state-of-the-art commercial polymer-based dielectrics such as biaxially oriented polypropylene (BOPP), cannot satisfy the high energy density requirement in many fields because of their low permittivity. Limited success has been achieved in developing polar polymeric dielectrics with high energy density because of the quickly increased energy loss from polarization relaxation and charge conduction under a high electric field and temperature. To achieve high energy density and low loss in polar polymer dielectrics simultaneously, electron-deficient vinyl quinoline (VQQ) units are pre-copolymerized with methyl methacrylate (MMA) followed by blending with a PMMA matrix. The bulky and electron-deficient VQQs have successfully depressed the relaxation of PMMA and significantly decreased charge conduction under an elevated electric field. As a result, a rather high energy discharging efficiency (over 90%) could be finely maintained up to 800 MV m-1, and an energy density of 16.1 J cm-3 could be obtained, which are much better than those of reported polymer dielectrics. The strong space charge trapping effect of the low content of VQQ is well addressed by thermally stimulated depolarization currents (TSDC) and density functional theory analysis (DFT) of increasing breakdown strength, energy density and discharging efficiency. This work offers a promising strategy for achieving high energy density and low loss in polar polymer dielectrics for their commercial application in energy storage capacitors.

N,S co-doped Co3O4 core-shell nanospheres with high peroxidase activity for the fast colorimetric detection of catechol.

It is necessary to develop nanoperoxidases with high activity to construct a fast and cheap sensing platform for real-time detection of some pollutants. In this study, the as-prepared N and S co-doped core-shell cobaltosic oxide nanospheres (N,S-Co3O4) exhibit excellent peroxidase-like activity. The oxidation reaction of the colorless chromogenic substrate TMB by H2O2 is used to evaluate the peroxidase-like behaviors of N,S-Co3O4. As expected, the N,S-Co3O4 nanospheres accelerated the oxidation of TMB accompanied by a blue shift only in 1 min. Thus, the N,S-Co3O4 nanoperoxidase exhibits high affinity towards TMB (Km = 0.072 mM) and H2O2 (Km = 3.78 mM). Moreover, as the catalytic process of N,S-Co3O4 can be inhibited in the presence of catechol, a fast inexpensive colorimetric sensor of catechol with high sensitivity and good selectivity was constructed. The enhanced catalytic activity of N,S-Co3O4 is attributed to some active species, including h+ and ˙O2-, owing to the more active sites on N,S-Co3O4. The colorimetric method has been validated by detecting catechol in real water samples for practical application.

Preparation of Supported Perovskite Catalyst to Purify Membrane Concentrate of Coal Chemical Wastewater in UV-Catalytic Wet Hydrogen Peroxide Oxidation System.

The effective treatment of membrane concentrate is a major technical challenge faced by the new coal chemical industry. In this study, a supported perovskite catalyst LaCoO3/X was prepared by a sol-impregnation two-step method. The feasibility of the supported perovskite catalyst LaCoO3/X in the UV-catalytic wet hydrogen peroxide oxidation (UV-CWPO) system for the purification of concentrated liquid of coal chemical wastewater was investigated. The effects of catalyst support, calcination temperature, calcination time, and re-use time on catalytic performance were investigated by batch experiments. The catalysts were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS). Experimental results showed that the supported perovskite catalyst LaCoO3/CeO2 prepared using CeO2 as support, calcination temperature of 800 °C, and calcination time of 8 h had the best catalytic effect. The catalytic performance of the catalyst remained excellent after seven cycles. The best prepared catalyst was used in UV-CWPO of coal chemical wastewater membrane concentrate. The effects of H2O2 dosage, reaction temperature, reaction pressure, and catalyst dosage on UV-CWPO were determined. Under the conditions of H2O2 dosage of 40 mM, reaction temperature of 120 °C, reaction pressure of 0.5 MPa, catalyst dosage of 1 g/L, pH of 3, and reaction time of 60 min, the removal efficiencies of COD, TOC, and UV254 were 89.7%, 84.6%, and 98.1%, respectively. Under the optimal operating conditions, the oxidized effluent changed from high toxicity to non-toxicity, the BOD5/COD increased from 0.02 to 0.412, and the biodegradability of the oxidized effluent was greatly improved. The catalyst has a simple synthesis procedure, excellent catalytic performance, and great potential in the practical application of coal chemical wastewater treatment.

Magnetic Flower-like Fe-Doped CoO Nanocomposites with Dual Enzyme-like Activities for Facile and Sensitive Determination of H2O2 and Dopamine.

Herein, a new series of magnetic Fe-doped CoO nanocomposites (Fe-CoO NCs) with dual enzyme-like activities (peroxidase and oxidase) were successfully synthesized. The molar ratio of Fe3+/Co2+ salts during the solvothermal process determined the morphology and catalytic activity of the NCs. Among them, the flower-like 0.15Fe-CoO NCs showed high peroxidase-mimicking activity over a wider pH range of 4-5 and a temperature range of 30-50 °C. Such nanozymes were applied for constructing a facile and sensitive colorimetric sensor to detect H2O2 and dopamine (DA) in the linear ranges of 6-20 and 2-10 µM with limits of detection (LODs) of 4.40 and 1.99 µM, respectively. The excellent magnetic separation performance and successful DA detection in human urine samples validated the promising application of CoO-based nanozymes in medical diagnosis. The superior catalytic behaviors of 0.15Fe-CoO NCs could be ascribed to the high surface area, open mesoporous structure, increased surface active species, and the facile redox of Fe3+/Fe2+ and Co3+/Co2+. Based on the results of the fluorescent probe and radical trapping tests, the possible mechanism that Fe doping promoted the decomposition of H2O2 to produce hydroxyl radical (•OH) and superoxide radical (•O2-) was proposed.

Hydroquinone colorimetric sensing based on platinum deposited on CdS nanorods as peroxidase mimics.

Pt deposited on CdS nanorods (Pt/CdS) have been prepared via the UV light photoreduction method. The Pt/CdS nanocomposites possess highly significant peroxidase-like activity with the assistance of the colorless substrate 3,3,5,5-tetramethylbenzidine (TMB). In the presence of peroxidase mimic Pt/CdS, TMB is quickly oxidized into a typical blue product (oxTMB, which has an obvious absorption at 652 nm) by H2O2 only in 3 min, which is easily detected visually. The catalytic activity of Pt/CdS originates from the accelerated electron transfer between the reactants. Combining the peroxidase-like activity of Pt/CdS with the blue change of TMB, a fast colorimetric sensing platform for detection of H2O2 has been constructed with a linear range 0.10-1.00 mM and a detection limit of 45.5 µM. The platform developed is further used to detect hydroquinone (HQ) in the range1.0-10 µM with a lower detection limit of 0.165 µM. The colorimetric platform has a potential to detect HQ residue in real water samples with recoveries ranging from 83.56 to 91.76%. Graphical abstract.

Effective and simultaneous removal of organic/inorganic arsenic using polymer-based hydrated iron oxide adsorbent: Capacity evaluation and mechanism.

In this study, resin-based hydrated iron oxide (HFOR) composites were prepared and used as a functional adsorbent for the simultaneous removal of p-Arsanilic acid (p-ASA) and arsenate (As (V)). The effects of solution pH and coexisting substances on the adsorption of different arsenic species were also investigated. Results showed that the coexisting substances slightly affected the adsorption process of two arsenic species. Analysis of the adsorption behavior, isotherm equilibrium, and adsorption kinetics, as well as that results of the X-ray photoelectron spectroscopy, zeta potential, and other analytical methods revealed that the satisfactory adsorption performance of HFOR can be attributed to the electrostatic interactions induced by the positively charged groups and the coordination of the hydrated iron oxide nanoparticles, which exhibited excellent specific adsorption for both arsenic species. Moreover, HFOR showed high acid and alkali resistance and reusability, as well as a constant co-removal performance for different arsenic species in five consecutive operating cycles (55 mg As/g of As(V) and 18 mg/g of p-ASA). Results of continuous running fixed-bed column experiments confirmed that HFOR enabled excellent simultaneous adsorption for p-ASA and As(V).

Mechanical activation to enhance the natural floatability of waste printed circuit boards.

The metal in the waste printed circuit boards (WPCBs) is an excellent secondary metal resource. WPCBs were ground to dissociate, and impurities in the dissociated product were removed by gradient flotation to recover valuable metals in this study. The effects of crushing methods on size composition and dissociation state of the crushed products were studied. Then the gradient flotation experiment was designed to verify the natural floatability of ground materials. Grinding test shows that impact crushing has greater grinding fineness (-0.074 mm) than shear crushing, which is 42.14% and 26.18% respectively with 5 min grinding. The flotation test results illustrate that the natural floatability of impurities increases with the grinding fineness, that is, the yield of floats increases without flotation reagents. For impact crushing and shear crushing, the floats yields are 38.48% and 31.75% respectively, accompanied by 70.53% and 65.46% impurity removal for ground materials with 5 min grinding. Subsequently, 21.61% and 26.35% of impurities can be further removed with the aid of collector. Finally, the recovery of Cu in concentrate reaches 67.84% and 65.75%, respectively. FT-IR proves that the excellent floatability of particles is caused by the significant hydrophobic group. Mechanical grinding has been proved to have double effects of improving dissociation and natural floatability.

Enhanced removal of tris(2-chloroethyl) phosphate using a resin-based nanocomposite hydrated iron oxide through a Fenton-like process: Capacity evaluation and pathways.

The effective removal of organophosphorus compounds (OPs) effectively from water environment remains an important but challenging task. In this study, a resin-based nanocomposite of hydrated iron oxide (HD1) was used as Fenton-like catalyst for effectively catalyzing the decomposition of hydrogen peroxide to degrade tris(2-chloroethyl) phosphate (TCEP). The results showed that HD1 was successfully prepared, which had great versatility, catalytic performance and adsorption capacity. Besides, HD1/H2O2 was capable of degrading TCEP completely with less than 0.2 mg/L of inorganic phosphorus (IP) in the effluent at the initial TCEP of 38 mg/L, pH = 4, H2O2 dosage of 20 mM, and the Kobs could result in about 1.0530 min-1 under identical conditions. More attractively, inorganic ions (i.e., Cl-, CO32-, SO42-, NO3-, HCO3-, Ca2+, and Mg2+) exhibited moderate effect on TCEP degradation. The negative effect of natural organic matters (NOM) (i.e., HA) on the degradation of TCEP was responsible for competition for the active oxygen species. Combined with electron paramagnetic resonance (EPR) spectra, X-ray photoelectron spectroscopy (XPS) and other analytical methods and radical quenching experiments, the possible removal process of TCEP was discussed, including two processes of oxidative degradation and immobilization of IP. Besides, hydroxyl radicals (•OH) was the key active species that contributed to TCEP degradation through hydroxylation-oxidation and C-O bond cracking, and specificity adsorption of HFO on IP was revealed. Furthermore, the results showed that HD1 had desirable acid and alkali resistance. In the continuous running fixed bed column experiment, HD1 showed a satisfactory performance in cycle operations. This work proposed a new enhanced process for removing TCEP in water environment by HD1/H2O2, and the multi-functional material, HD1 was promising in treatment of water containing organic phosphorus pollutants. This will be believed that this study will provide new ideas and new materials for the treatment of organic phosphorus-based organic pollutants, and lay the foundation for further deepening and expanding the application of adsorption resins in the field of water pollution control.

Organic-Inorganic Composite Nanorods as an Excellent Mimicking Peroxidases for Colorimetric Detection and Evaluation of Antioxidant.

N,N'-Dicarboxy methyl perylene diimide-coated CeO2 nanorods (PDI/CeO2 NR) were synthesized via an ultrasonic-assisted method. PDI/CeO2 exhibits the superb mimic peroxidase functions confirmed by the catalyzed oxidation of TMB by hydrogen peroxide in less than 60 s along with color transformation from colorless to blue. The catalytic mechanism was confirmed to be an electronic transfer mechanism by fluorescence experiment. Thus, a visual colorimetric sensor was constructed for hydrogen peroxide detection with a low detection limit (LOD = 2.23 µM). Comparing the inhibition effects of l-cysteine (Cys), ascorbic acid (AA) and glutathione (GSH) on the catalytic oxidation of TMB, it can be found that they possessed different types of inhibition on the oxidation of TMB by H2O2 using PDI/CeO2, and AA has better antioxidant effect, followed by Cys and GSH. On the basis of the excellent antioxidant effect of AA, a low-cost colorimetric sensor was also used to detect AA, and a lower LOD value (0.68 µM) was obtained in the linear range of 5.0-30 µM.

Rapid colorimetric determination of dopamine based on the inhibition of the peroxidase mimicking activity of platinum loaded CoSn(OH)6 nanocubes.

Platinum nanoparticles were loaded on CoSn(OH)6 nanocubes via a co-precipitation method. The material (NCs) is shown to be a viable peroxidase mimic that catalyzes the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by hydrogen peroxide (H2O2) to generate oxidized TMB (oxTMB) with absorption at 652 nm. The formation of the blue color can be observed in <30 s. Thus, a visual and colorimetric assay was worked out for H2O2. It has a detection limit as low as 4.4 µM and works in the 5 to 200 µM concentration range. The method was also used to detect dopamine (DA) which is found to inhibit the enzyme mimicking activity of the NCs. Hence, less blue color is formed in its presence. The respective DA assay has a linear response in the 5.0 to 60 µM concentration range and a 0.76 µM detection limit. Graphical abstractSchematic diagram of a visual colorimetric method for determination of H2O2 and dopamine (DA) with the aid of color change of 3,3',5,5'-tetramethylbenzidine (oxTMB), based on the peroxidase-like activity of Pt/CoSn(OH)6 nanocubes.

Porphyrin functionalized Co(OH)2/GO nanocomposites as an excellent peroxidase mimic for colorimetric biosensing.

5,10,15,20-Tetrakis(4-carboxyl phenyl)porphyrin (Por) modified Co(OH)2 deposited on the surface of GO nanocomposites (Por/Co(OH)2/GO) were prepared and characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and XRD. For the first time, H2TCPP/Co(OH)2/GO is found to have enhanced peroxidase-like activity and catalyze the oxidation of the substrate 3,3,5,5-tetramethylbenzidine (TMB) by hydrogen peroxide (H2O2). Notably, the colorless TMB rapidly transformed into blue oxTMB in just 60 s, which was easily observed visually. The catalytic kinetics of H2TCPP/Co(OH)2/GO is in accord with the Michaelis-Menten equation. The catalytic mechanism of H2TCPP/Co(OH)2/GO nanocomposites is attributed to hydroxyl radicals (˙OH), due to decomposition of H2O2, which is verified by using terephthalic acid as a fluorescent probe. What's more, H2O2 can be detected in a wide linear detection range from 5 to 35 mM with a detection limit of 0.385 mM. Furthermore, based on the excellent peroxidase-like activity of H2TCPP/Co(OH)2/GO, a colorimetric sensor is established to sensitively detect glutathione (GSH) in a linear range from 10 to 300 µM with a low detection limit of 9.5 µM.

High-performance peroxidase mimics for rapid colorimetric detection of H2O2 and glucose derived from perylene diimides functionalized Co3O4 nanoparticles.

N,N'-di-caboxy methyl perylene diimides (PDI), as one of the most promising functional materials in optional chemosensing, was first used to combine with Co3O4 nanoparticles through a facile two-step hydrothermal method and obtain the PDI functionalized Co3O4 nanocomposites (PDI-Co3O4 NCs). PDI-Co3O4 NCs were characterized by a series of technical analysis including transmission electron microscope (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR), respectively. The experimental results indicated that the as-prepared PDI-Co3O4 NCs possessed the higher peroxidase-like activity than that of Co3O4 nanoparticles without PDI, and could rapidly catalyze oxidation reaction of the chromogenic substrate TMB in the presence of H2O2 to a blue product (oxTMB) observed by the naked eye. The improved catalytic activity of PDI-Co3O4 NCs for colorimetric reactions could be attributed to the synergistic effects of PDI and Co3O4 nanoparticles. On the basis of these experimental results, a convenient colorimetric system based on PDI-Co3O4 as enzyme mimic that is highly sensitive and selective was developed for glucose detection. Meanwhile, the electron transfer between H2O2 and TMB was responsible for the oxidation of TMB. The present work demonstrates a general strategy for the design of organic molecules functionalized oxide for different applications, such as nanocatalysts, biosensors and nanomedicine.

[Feasibility investigation of hydrogen instead of helium as carrier gas in the determination of five organophosphorus pesticides by gas chromatography-mass spectrometry].

Helium is almost the only choosable carrier gas used in gas chromatography-mass spectrometry (GC-MS). A mixed standard solution of five organophosphorus pesticides was analyzed by using GC-MS, and hydrogen or helium as carrier gas, so as to study the feasibility of hydrogen instead of helium as carrier gas for the determination of organophosphorus pesticides. Combining a mass spectrum database built by ourselves, the results were deconvolved and identified by Automated Mass Spectral Deconvolution & Identification System (AMDIS32), a software belonging to the workstation of the instrument. Then, the statistical software, IBM SPSS Statistics 19.0 was used for the clustering analysis of the data. The results indicated that when hydrogen was used as carrier gas, the peaks of the pesticides detected were slightly earlier than those when helium used as carrier gas, but the resolutions of the chromatographic peaks were lower, and the fraction good indices (Frac. Good) were lower, too. When hydrogen was used as carrier gas, the signals of the pesticides were unstable, the measuring accuracies of the pesticides were reduced too, and even more, some compounds were undetectable. Therefore, considering the measuring accuracy, the signal stability, and the safety, etc., hydrogen should be cautiously used as carrier gas in the determination of organophosphorus pesticides by GC-MS.

[Effects of forest gap on herbaceous plant diversity in mixed birch-fir forest of Taibai Mountain].

To better understand the effects of forest gap on the herbaceous species community in a mixed birch-fir forest of Taibai Mountain in Qinling, CCA ordination and random permutation test were employed to analyze the distribution pattern of the species composition across a gradient of gap size, and the relationships between the distribution of 55 herbaceous species with > or = 5 individuals and the habitat variables (convexity, slope, and soil total N, total P, available N, available P, pH, and organic matter). In this forest, gap area occupied 19.8% of the total land area, gap density was 20.7 per hm2, and gap size varied from 25.6 to 279.1 m2, with a mean of 93.7 m2. The species richness in herbaceous layer in gaps was significantly positively correlated with gap size, but of the 69 herbaceous species identified in the gaps, most species were found across all gap sizes, and only eight species were found in larger gaps (>120 m2). No successional change was observed in the herbaceous species distribution with gap size. The CCA ordination and random permutation test also showed that 27.3% of the 55 species with abundance > or = 5 had significant association with the eight habitat variables. It was concluded that gap size contributed to the species richness, but determined the diversity constitution in random.