Synergistic effect triggered by Fe2O3 and oxygen-induced hydroxyl radical enhances formation of amino-phenolic humic-like substance.

Metal oxides play a promising role in the transformation of polyphenols and amino acids involved in naturally occurring humification. The objective of this study was to explore the synergistic interactions between Fe2O3 and O2 in the formation of humic substances under a controlled O2 atmosphere (0%, 21% and 40% O2 levels). The results indicate that an O2 level of 21% with Fe2O3 was optimal for humic acid (HA) production. Hydroxyl radicals (∙OH) formed and promoted the formation of HA in the presence of O2, and O2 improved the enhancing capacity of Fe2O3 by oxidizing Fe(II) to Fe(III). Moreover, the combination of these processes resulted in a synergistic improvement in humification. The evolution of functional groups in HA suggested that O2 promoted the formation of oxygen-containing groups such as lipids, and Fe2O3 was conducive to the formation of dark-coloured polymers during the darkening process of humification. Furthermore, the O2 level of 40% inhibited the formation of HA by reducing the transformation from Fe(III) to Fe(II). The XRD results showed few changes in the composition of Fe2O3 before and after humification, which indicated that Fe2O3 was a catalyst and an oxidant. The heterospectral UV-Vis/FTIR results suggested that ∙OH attacked phenolic rings to form the aromatic ring skeleton of HA and benefit the ring-opening copolymerization of humic precursors. In addition, structural equation modelling demonstrated that dissolved Fe was the key parameter affecting the HA yield. These findings provide new insights into the synergism of O2-mediated ∙OH production associated with metal oxide-facilitated humification.

Robust Secure Resource Allocation for RIS-Aided SWIPT Communication Systems.

Aiming at the influence of channel uncertainty, user information leakage and harvested energy improvement, this paper proposes a robust resource allocation algorithm for reconfigurable intelligent reflector (RIS) multiple-input single-output systems based on imperfect channel state information. First, considering the legal user minimum secret rate constraint, the base station maximum transmit power constraint and the RIS phase shift constraint with the bounded channel uncertainty, a joint optimization of the base station active beam, energy beam and RIS phase shift is established. A multivariate coupled nonlinear resource allocation problem for matrices is addressed. Then, using S-procedure and alternating optimization methods, the original non-convex problem is transformed into a deterministic convex optimization problem and an alternating optimization algorithm based on continuous convex approximation is proposed. The simulation results show that the proposed algorithm has better fairness harvested energy compared with the traditional robust algorithm.

Simultaneous Measurements of Refractive Index and Methane Concentration through Electromagnetic Fano Resonance Coupling in All-Dielectric Metasurface.

Dual-parameter measurements of refractive index and methane concentration based on electromagnetic Fano resonance are proposed. Two independent Fano resonances can be produced through electric dipole and toroidal dipole resonance in an all-dielectric metasurface separately. The linear relationship between the spectral peak-shifts and the parameters to be measured will be obtained directly. The refractive index (RI) sensitivity and gas sensitivity are 1305.6 nm/refractive index unit (RIU), -0.295 nm/% for one resonance peak (dip1), and 456.6 nm/RIU, -0.61 nm/% for another resonance peak (dip2). Such a metasurface has simpler structure and higher sensitivity, which is beneficial for environmental gas monitoring or multi-parameter measurements.

Persulfate oxidation for alternative sludge treatment and nutrient recovery: An assessment of technical and economic feasibility.

The introduce of tighter waste disposal regulations and increasing resource scarcity make the re-utilization of waste activated sludge a hot and crucial research topic. Compared with traditional sludge disposal technologies (e.g. landfill and incineration), advanced oxidation processes have been proven to be an environmentally friendly method for sludge stabilization and disintegration. However, the effectiveness of persulfate oxidation for sludge degradation, and the re-utilization of its embedded nutrients have been rarely reported. Therefore, this work is to investigate the technical and economic feasibility of using persulfate oxidation and struvite precipitation for sludge degradation and nutrient recovery. The results show that with the assistance of ultraviolet radiation, released phosphate and ammonia nitrogen from sludge could reach 233.4 and 265.6 mg/L. Besides, 92.8% phosphate and 32.6% ammonia-nitrogen could be recovered by struvite precipitation at a pH of 9.5, with an Mg: P molar ratio of 1.1:1. The economic analysis shows that the operational cost of the proposed process was 25% higher than traditional sludge disposal (267.5 $/ton), but its capital investment is much lower. Investigations on chemical dosage minimization, energy reclamation and process optimization are suggested to reduce the process's operating cost in the future.

Improved degradation of anthraquinone dye by electrochemical activation of PDS.

Electrochemical oxidation (EO) coupled with peroxydisulfate (PDS) activation as a synergistic wastewater treatment process (PDS/EO) was performed to degrade anthraquinone dye-Reactive Brilliant Blue (RBB) in aqueous solution. Introducing PDS into the EO improved the RBB removal than the sole PDS and conventional EO systems. The RBB could activate PDS to a certain degree by itself. By the comparison of various inorganic ions addition, it showed that adding NO3- as the background electrolyte was more effective than the systems using the Cl- and SO42-, respectively. In this PDS/EO-NO3- system, increasing PDS concentration (1-5 mmol L-1) and current density (5-10 mA cm-2) considerably promoted the degradation of RBB. The adjustment of the solution pH displayed that the acidic and neutral condition was beneficial to the RBB removal, and the synergistic effect was inverse ratio to the RBB initial concentration. Furthermore, the scavenger experiments verified that both SO4·- and HO· were the major active substances in the RBB decomposition, and other reactive oxygen species also had considerable contributions. Thereinto NO3- only act a catalytic agent to improve the generation of active matters in the PDS/EO-NO3-. Overall, the proposed synergistic process could serve as an efficient method for the degradation of anthraquinone dye.

A High-Sensitivity Methane Sensor with Localized Surface Plasmon Resonance Behavior in an Improved Hexagonal Gold Nanoring Array.

This paper proposes a methane sensor based on localized surface plasmon resonance (LSPR) of a hexagonal periodic gold nanoring array. The effects of structural parameters on the extinction spectrum and refractive index (RI) sensitivity are analyzed to obtain optimal parameters. In particular, the RI sensitivity can reach 550.08 nm/RIU through improvement of the sensor structure, which is an increase of 17.4% over the original value. After coating a methane-sensitive membrane on the inner and outer surfaces of the gold rings, the methane concentration can be accurately measured with a gas sensitivity of -1.02 nm/%. The proposed method is also applicable to quantitative analyses of components concentration and qualitative analyses of gas composition.

Hierarchical self-assembly flower-like ammonium nickel phosphate as high-rate performance electrode material for asymmetric supercapacitors with enhanced energy density.

Ammonium nickel phosphate has a large specific capacitance as an electrode material at low current density, but its capacitance decays fast at high current density, which directly affects the rate performance of supercapacitors. Herein, we demonstrate a facile route for the controllable synthesis of hierarchical self-assembly flower-like ammonium nickel phosphate as a high-rate electrode material for asymmetric supercapacitors, which is an important strategy to enhance the energy density at high power density. The flower-like structures are hierarchically assembled by a mass of rectangular sheets, which can provide fast electron transport and short ion diffusion path, thereby exhibiting excellent electrochemical performance with ultrahigh specific capacitance of 1016 F g-1 at 1.0 A g-1. More importantly, the NH4NiPO4 · H2O materials exhibit outstanding rate performance (800 F g-1 even at large current density of 30 A g-1) and superior long-term cycle life (83% of capacity retention up to 3000 cycles at 5 A g-1). Furthermore, the NH4NiPO4 · H2O//AC asymmetric supercapacitors are assembled in aqueous KOH electrolyte, and exhibit high energy density (46.2 Wh kg-1 at 160 W kg-1 and 26.7 Wh kg-1 at a large power density of 4000 W kg-1, respectively). Due to the outstanding electrochemical performance, the all-solid-state asymmetric supercapacitors are successfully constructed using these materials.

Evaluation of antibiotic oxytetracycline removal in water using a gas phase dielectric barrier discharge plasma.

Degradation of oxytetracycline (OTC), a primary member of antibiotics in water, was performed by a gas phase dielectric barrier discharge (GPDBD) plasma reactor. The influences of operation conditions including applied voltages, air bubbling rates, initial OTC concentrations and initial pH values on OTC abatement were investigated respectively. The results showed that the decontamination process can be fitted by first order kinetics, and the removal ratio and rate were affected obviously by those parameters. After 20 min of discharge treatment, approximately 93.4% of OTC was removed under the experimental conditions: applied voltage of 7.5 kV, air flow rate of 1.0 L/min, initial OTC concentration of 100 mg/L, and initial pH of 5.0. In addition, TOC and COD removal efficiency reached 43.0% and 73.7% at the original pH 9.3, respectively. Furthermore, the amounts of hydrogen peroxide and ozone in aqueous were quantitatively measured to evaluate their roles during antibiotic removal, and the main function of hydroxyl radicals was demonstrated by the radicals scavenger test. At last, the analyses of UV-Vis spectra and HPLC-MS were employed to study the OTC elimination mechanism, and the possible decomposition pathway was proposed based on the speculated intermediates.

Controllable synthesis of nickel bicarbonate nanocrystals with high homogeneity for a high-performance supercapacitor.

The electrochemical performance of supercapacitors might be associated with the homogeneous structure of the electrode materials. However, the relationship between the degree of uniformity for the electrode materials and the electrochemical performance of the supercapacitor is not clear. Herein, we synthesize two types of nickel bicarbonate nanocrystals with different degrees of uniformity to investigate this relationship. As the electroactive material, the nickel bicarbonate nanocrystals with a homogeneous structure could provide a larger space and offer more exposed atoms for the electrochemical reaction than the nanocrystals with a heterogeneous structure. The homogeneous nickel bicarbonate nanocrystals exhibit better electrochemical performance and show excellent specific capacitance (1596 F g-1 at 2 A g-1 and 1260 F g-1 at 30 A g-1), which is approximately twice that of the heterogeneous nickel bicarbonate nanocrystals. The cycling stability for the homogeneity (∼80%) is higher than the inhomogeneity (∼61%) at a high current density of 5 A g-1.

Organic cocatalysts improved Fenton and Fenton-like processes for water pollution control: A review.

In recent times, organic compounds have been extensively utilized to mitigate the limitations associated with Fe(Ⅲ) reduction and the narrow pH range in Fenton and Fenton-like processes, which have garnered considerable attention in relevant studies. This review presents the latest advancements in the comprehensive analysis and applications of organic agents as assistant/cocatalysts during Fenton/Fenton-like reactions for water pollution control. The primary focus includes the following: Firstly, the mechanism of organic co-catalytic reactions is introduced, encompassing both complexation and reduction aspects. Secondly, these organic compounds are classified into distinct categories based on their functional group structures and applications, namely polycarboxylates, aminopolycarboxylic acids, quinones, phenolic acids, humic substances, and sulfhydryl compounds, and their co-catalytic functions and mechanisms of each category are discussed in meticulous detail. Thirdly, a comprehensive comparison is conducted among various types of organic cocatalysts, considering their relative merits, cost implications, toxicity, and other pertinent factors. Finally, the review concludes by addressing the universal challenges and development prospects associated with organic co-catalytic systems. The overarching objective of this review is to provide insights into potential avenues for the future advancement of organic co-catalytic Fenton/Fenton-like reactions in the context of water purification.

Promoted elimination of metronidazole in ferrous ions activated peroxydisulfate process by gallic acid complexation.

We applied gallic acid (GA) as the complexing agent to stabilizing the regeneration of Fe2+ during the Fe2+/peroxydisulfate (PDS) Fenton-like reaction for promoting the removal of metronidazole (MTZ). This research evaluated the elimination of MTZ by optimizing the dose of GA and Fe2+ and pH condition. MTZ removal reached 83% at the GA: Fe2+ molar ratio of 1:1 (30 µM) and initial pH 5 and 6.2 after 120 min, and the kinetics showed two degradation phases (kobs1 = 0.09636 for the rapid stage and kobs2 = 0.01056 for the slow stage). The Fe2+ and GA complexes could expand the range of pH applicability and effectively stabilize the regeneration of Fe2+, which ultimately promoted the decontamination of MTZ. Sulfate radical (SO4.-), hydroxyl radicals, and singlet oxygen were proved to exist in this ternary system and contribute to MTZ removal, and SO4.- played the dominant role. Furthermore, the possible pathways and mechanisms for MTZ degradation were proposed, and the simulation result indicated that the toxicity of degradation intermediates of MTZ were declined. The GA assisted Fe2+/PDS system provided an improved promising advanced oxidation process for organic wastewater disposal.

Risk assessment of coal mine water inrush based on PCA-DBN.

To provide an effective risk assessment of water inrush for coal mine safety production, a BP neural network prediction method for water inrush based on principal component analysis and deep confidence network optimization was proposed. Because deep belief network (DBN) is disadvantaged by a long training time when establishing a high-dimensional data classification model, the principal component analysis (PCA) method is used to reduce the dimensionality of many factors affecting the water inrush of the coal seam floor, thus reducing the number of variables of the research object, redundancy and the difficulty of feature extraction and shortening the training time of the model. Then, a DBN network was used to extract secondary features from the processed nonlinear data, and a more abstract high-level representation was formed by combining low-level features to find the expression of the nonlinear relationship between the characteristics of water in bursts. Finally, a prediction model was established to predict the water inrush in coal mines. The superiority of this method was verified by comparing the prediction of the actual working face with the actual situation in typical mining areas of North China. The prediction accuracy of coal mine water inrush obtained by this algorithm is 94%, while the prediction accuracy of traditional BP algorithm is 70%, and the prediction accuracy of SVM algorithm is 88%.

Fe3O4 nanoparticles three-dimensional electro-peroxydisulfate for improving tetracycline degradation.

In this work, Fe3O4 nanoparticle employed as the three-dimensional electrode, were introduced into the electro-oxidation system with peroxydisulfate to improve the tetracycline (TC) degradation. The coprecipitation method prepared Fe3O4 was proved to be the irregular sphere-like form through the characterizations of XRD, SEM, N2 adsorption isotherms, and XPS. By the contrast experiments, the EO-Fe3O4-PDS exhibited the outstanding TC degradation capability, which achieved 86.53% after 60 min treatment with current intensity of 20 mA cm-2, Fe3O4 dose of 0.2 g L-1, PDS amount of 2 mmol L-1, initial pH 4.5, and TC concentration of 25 mg L-1. Besides, the influence of current intensity, Fe3O4 dosage, PDS concentration, and beginning pH on the TC degradation was investigated systemically. The consecutive five recycles of Fe3O4 demonstrated that a favorable stability for the coupling process. The EO-Fe3O4-PDS could improve the PDS decomposition and H2O2 production. The sulfate and hydroxyl radicals both took charge of the antibiotic degradation as certified by scavenger test. The TC degradation evolution was presented based on the HPLC-MS analyses of degradation byproducts.

Elimination of humic acid in water: comparison of UV/PDS and UV/PMS.

Humic substances are polyelectrolytic macromolecules; their presence in water leads to many environmental problems without effective treatment. In this work, the elimination of humic acid (HA), a typical humic substance, has been examined through ultraviolet (UV) activation systems in the presence of peroxydisulfate (PDS) and peroxymonosulfate (PMS), respectively. The results indicated that 92.9% and 97.1% of HA were eliminated with rate constants of 0.0328 ± 0.0006 and 0.0436 ± 0.0011 min-1 with 180 and 60 min treatment times at pH 6 and 3 when adding 3 and 1 mmol L-1 oxidant during UV/PDS and UV/PMS, respectively; the corresponding electric energies per order were 0.0287 and 0.0131 kW h m-3. The HA removal was systematically investigated by varying different reaction parameters, including radical scavengers, persulphate dose, solution pH, and initial HA concentration, and by addition of various common ions. Moreover, the decomposition details were identified through the changes in the dissolved organic carbon, unique UV absorbances, and UV spectroscopic ratios. Furthermore, the destruction mechanism was verified by fluorescence spectroscopy, demonstrating that the HA structure was decomposed to small molecular fractions in the two UV/persulphate systems. In addition, the purification of HA by the two UV/persulphate processes was assessed in actual water matrices.

Fe3+-sulfite complexation enhanced persulfate Fenton-like process for antibiotic degradation based on response surface optimization.

To improve the cycle between Fe3+ and Fe2+ in persulfate (PS) Fenton-like system, sulfite (Na2SO3) was used as the iron complexing agent to enhance the degradation of sulfamethoxazole (SMX) antibiotic in water. Response surface methodology (RSM) was applied to regulate the operation parameters for the Fe3+/Na2SO3/PS synergistic system. Based on the RSM, the SMX could be completely degraded when the concentration of Fe3+, Na2SO3, and PS were 0.4, 0.5, and 2.5 mM, respectively. The result showed that the synergistic process represented a high Fe3+ utilization rate and SMX degradation efficiency. After 1 h reaction, 100.00% of SMX and 27.80% of total organic carbon were removed under the ambient conditions containing the initial SMX concentration of 10 µM and initial pH of 5.96. Free radical masking and electron spin-resonance tests proved that hydroxyl radical (HO) and oxysulfur radicals (SOx-, x = 3, 4, 5) were all played the significant role in the antibiotic removal, and the primary active radical was HO. The SMX decomposition pathways based on the formed intermediates was proposed through the high-performance liquid chromatography and mass spectrum analyses. The toxicity assessment prediction indicated that the toxicities of decomposed SMX byproducts were reduced after the coupling treatment.

Comparison of different K-struvite crystallization processes for simultaneous potassium and phosphate recovery from source-separated urine.

Controlled K-struvite crystallization is an attractive technology to simultaneously recover phosphate and potassium from urine. This study investigated the recovery of phosphate and potassium from source-separated urine by K-struvite crystallization using different use models of low-grade MgO (LG-MgO): LG-MgO alone (model 1, M1), LG-MgO plus phosphorus acid (model 2, M2), and a pre-formed stabilizing agent by adding LG-MgO plus phosphorus acid (model 3, M3). Results showed that 100% phosphate and 25% K could be recovered from urine by M1. M2 at an MgO:K:P molar ratio of 4:1:1.6 provided a maximum P and K recovery efficiency at 100% and 70%. M3 achieved a same K-removal efficiency as M2, but the phosphate recovery efficiency was lower than that of M2 due to the dissolution of phosphate in the stabilizing agent. K-struvite crystallization was closely accompanied by severe co-precipitation of Na-struvite. Increasing the Na concentration markedly improved the ability of Na co-precipitation, but the variation of pH did not affect the competition precipitation of K and Na. When the Na:K molar ratio was >10, the precipitation of Na was more than that of K. A process performance evaluation indicated that M3 is more suitable for simultaneous K and P recovery from source-separated urine.

Percarbonate promoted antibiotic decomposition in dielectric barrier discharge plasma.

A coupling technique introducing sodium percarbonate (SPC) into a dielectric barrier discharge (DBD) plasma was investigated to enhance the degradation of antibiotic tetracycline (TC) in aqueous. The dominant effects of SPC addition amount and discharge voltage were evaluated firstly. The experiments indicated that the moderate SPC dosages in the DBD presented an obvious synergistic effect, improving the TC decomposition efficiency and kinetics. Elevating the voltage was conducive for the promotion of antibiotic abatement. After 5 min treatment, the removal reached 94.3% at the SPC of 52.0 µmol/L and voltage of 4.8 kV for 20 mg/L TC. Especially the defined synergy factors were greater than one since the SPC being added, and the energy yield was increased by 155%. Besides, the function mechanism was explained by the hydrogen peroxide and ozone quantitative determinations and radical scavenger test, and the results confirmed that the collaborative method could increase the generation of reactive species, and the produced hydroxyl and superoxide radicals both played the significant roles for the TC elimination. Furthermore, the decomposition and mineralization of the synergism were verified by UV-vis spectroscopy, TOC and COD analyses, and the degradation byproducts and transformation pathways were identified based on the analysis of HPLC-MS finally.

Comparative study of persulfate oxidants promoted photocatalytic fuel cell performance: Simultaneous dye removal and electricity generation.

Introducing peroxymonosulfate (PMS) and peroxydisulfate (PDS) into the photocatalytic fuel cell (PFC) system were investigated by comparing the Reactive Brilliant Blue (KN-R) degradation and synchronous electricity production. The two persulfates (PS) themselves are strong oxidant, and could be activated and as electron sacrificial agent in the PFCs, facilitating the photoelectrocatalysis and expanding redox to the entire cell space. Hence, the two established PFC/PS systems manifested prominent cell performances, enhancing the KN-R decomposition and electric power production relative to the virgin PFC. Thereinto, the KN-R removal rate of PFC/PMS was faster than that of PFC/PDS, but an opposite trend appeared in the electricity generation. Besides, the cell performances of the two cooperative systems were evaluated at different operation conditions, including PS dosage, solution pH, and irradiation strength. Moreover, the dye elimination principle was explored by radicals scavenging experiment, and the consequence revealed that hydroxyl radical (HO•), sulfate radical (SO4•-) and singlet oxygen were chief active species in the PFC/PMS, and HO•, SO4•- and superoxide anion played the key roles in the PFC/PDS. Furthermore, the calculated economic indicator demonstrated that the economy of the two synergistic processes were greater than that of UV/PS and solo PFC, and the PFC/PDS was more cost-effective than PFC/PMS.

Enhancing CaO2 fenton-like process by Fe(II)-oxalic acid complexation for organic wastewater treatment.

Hydrogen peroxide (H2O2) is used widely as Fenton's reagent for organic wastewater treatment. However, the application range of the optimum Fenton reaction is narrow, needing to adjust pH before and after treatment. Besides, the disproportionation of H2O2 and generated iron precipitation also confine the normal operation of Fenton method. To overcome the drawbacks of the traditional Fenton process, a Fe(II) catalyzed calcium peroxide (CaO2) Fenton-like process assisted by oxalic acid (OA) for aqueous organic pollutants degradation was proposed (Fe2+/OA/CaO2). The methyl orange (MO) as a typical organic pollutant, its removal performances by this Fe2+/OA/CaO2 system were evaluated. In the optimized conditions, 99% of MO was degraded within 15 min, and 38% mineralized after 180 min when the molar ratio of Fe2+: OA: CaO2 was 1: 2: 2 (Fe2+ = 1.5 mM). Radicals detection indicated that hydroxyl radical (HO•) was the main reactive species for the MO elimination. Furthermore, density functional theory calculation was in good agreement with the experimental results, which proved that the Fe2+/OA/CaO2 could improve the circulation between Fe2+ and Fe3+, promoting the oxygen reactive species generation and pollutant removal. The main intermediates were identified and the degradation pathways were proposed based on the results of the mass spectrum analysis, and the attack of HO• was suggested as the main function for the MO decomposition. The matrix effects of water constituents on the performance of Fe2+/OA/CaO2 were investigated, and the results showed that a certain amount of Cl-, NO3-, HCO3-, and HA affected the elimination than SO42-. Finally, the attempt of actual wastewater disposal indicated the synergistic system possessed good potential for future practical application.

Simultaneous structure and luminescence property control of barium carbonate nanocrystals through small amount of lanthanide doping.

Rare earth doping has been widely applied in many functional nanomaterials with desirable properties and functions, which would have a significant effect on the growth process of the materials. However, the controlling strategy is limited into high concentration of lanthanide doping, which produces concentration quenching of the lanthanide ion luminescence with an increase in the Ln3+ concentration, resulting in lowering the fluorescence quantum yield of lanthanide ion. Herein, for the first time, we demonstrate simultaneous control of the structures and luminescence properties of BaCO3 nanocrystals via a small amount of Tb3+ doping strategy. In fact, Tb3+ would partially occupy Ba2+ sites, resulting in the changes to the structures of the BaCO3 nanocrystals, which is primarily determined by charge modulation, including the contributions from the surfaces of crystal nuclei and building blocks. These structurally modified nanocrystals exhibit tunable luminescence properties, thus emerging as potential candidates for photonic devices such as light-emitting diodes and color displays.