Ultrasensitive Fluorescence Detection of Peroxymonosulfate Based on a Sulfate Radical-Mediated Aromatic Hydroxylation.

Recently, peroxymonosulfate (PMS)-based advanced oxidation processes have exhibited broad application prospects in the environment field. Accordingly, a simple, rapid, and ultrasensitive method is highly desired for the specific recognition and accurate quantification of PMS in various aqueous solutions. In this work, SO4•--induced aromatic hydroxylation was explored, and based on that, for the first time, a novel fluorescence method was developed for the PMS determination using Co2+ as a PMS activator and benzoic acid (BA) as a chemical probe. Through a suite of spectral, chromatographic, and mass spectrometric analyses, SO4•- was proven to be the dominant radical species, and salicylic acid was identified as the fluorescent molecule. As a result, a whole radical chain reaction mechanism for the generation of salicylic acid in the BA/PMS/Co2+ system was proposed. This fluorescence method possessed a rapid reaction equilibrium (<1 min), an ultrahigh sensitivity (detection limit = 10 nM; quantification limit = 33 nM), an excellent specificity, and a wide detection range (0-100 µM). Moreover, it performed well in the presence of possible interfering substances, including two other peroxides (i.e., peroxydisulfate and hydrogen peroxide), some common ions, and organics. The detection results for real water samples further validated the practical utility of the developed fluorescence method. This work provides a new method for the specific recognition and sensitive determination of PMS in complex aqueous solutions.

Degradation of Bisphenol A by Peroxymonosulfate Catalytically Activated with Mn1.8Fe1.2O4 Nanospheres: Synergism between Mn and Fe.

A high-efficient, low-cost, and eco-friendly catalyst is highly desired to activate peroxides for environmental remediation. Due to the potential synergistic effect between bimetallic oxides' two different metal cations, these oxides exhibit superior performance in the catalytic activation of peroxymonosulfate (PMS). In this work, novel Mn1.8Fe1.2O4 nanospheres were synthesized and used to activate PMS for the degradation of bisphenol A (BPA), a typical refractory pollutant. The catalytic performance of the Mn1.8Fe1.2O4 nanospheres was substantially greater than that of the Mn/Fe monometallic oxides and remained efficient in a wide pH range from 4 to 10. More importantly, a synergistic effect between solid-state Mn and Fe was identified in control experiments with Mn3O4 and Fe3O4. Mn was inferred to be the primary active site in the surface of the Mn1.8Fe1.2O4 nanospheres, while Fe(III) was found to play a key role in the synergism with Mn by acting as the main adsorption site for the reaction substrates. Both sulfate and hydroxyl radicals were generated in the PMS activation process. The intermediates of BPA degradation were identified and the degradation pathways were proposed. This work is expected to help to elucidate the rational design and efficient synthesis of bimetallic materials for PMS activation.

Synthesis of BiOClx Br1-x Nanoplate Solid Solutions as a Robust Photocatalyst with Tunable Band Structure.

The use of bismuth oxyhalides as photocatalysts has received extensive interest because of their high photocatalytic activity and stability. However, available methods for the synthesis of bismuth oxyhalides with tailored morphologies, well-defined facets, and tunable band gaps are still lacking. In this work, two-dimensional BiOClx Br1-x solid solution with exposed {001} facets and tunable band gaps were synthesized by using solvothermal methods. The BiOClx Br1-x solid solution nanoplates crystallized in a homogeneous crystal structure but possessed continuously tuned band gaps from 3.39 to 2.78 eV by decreasing the ratio of Cl/Br. Among the synthesized nanoplates, the BiOCl0.5 Br0.5 sample exhibited the highest photocatalytic activity for degrading Rhodamine B (RhB), a typical organic pollutant, under visible light. The highest photoactivity of the BiOCl0.5 Br0.5 sample was attributed to a synergetic effect of higher surface area, facets exposed, and optimized band structure. The results are of profound significance for the design of novel photocatalyst materials.

Efficiency and mechanism of phosphate adsorption and desorption of a novel Mg-loaded biochar material.

Phosphate removal is complicated by the need for resource recovery. Biochar shows promise for efficient phosphate adsorption, but it must be modified to enhance its adsorption capacity. In this work, magnesium (Mg)-loaded biochar was synthesized through a two-step dipping and calcination process, and the MgBC600 product was used to adsorb phosphate from simulated water and biogas slurry wastewater. The phosphate adsorption capacity of Mg-loaded biochar was 109.35 mg/g, which was 12 times higher than that of unmodified biochar. The R2 of the Langmuir and pseudo-second-order kinetic models were 0.988 and 0.990, respectively, which fitted the phosphate adsorption process of MgBC600. Phosphate adsorption by MgBC600 was a spontaneous and endothermic process. The adsorption mechanism study showed that phosphate adsorption was controlled by the formation and electrostatic attraction of MgHPO4. In addition, 98% of chemically adsorbed phosphate was released after regeneration. Using phosphate-adsorbed MgBC600 as a soil amendment, Arabidopsis thaliana was 1.47 times higher than that in the biochar-only group, demonstrating that this is a promising strategy for enhancing phosphate adsorption efficiency and adsorbent recycling.

Adsorption of phosphate over a novel magnesium-loaded sludge-based biochar.

The production of sludge-based biochar to recover phosphorus (P) from wastewater and reuse the recovered phosphorus as agricultural fertilizer is a preferred process. This article mainly studied the removal of phosphate (PO4-P) from aqueous solution by synthesizing sludge-based biochar (MgSBC-0.1) from anaerobic fermentation sludge treated with magnesium (Mg)-loading-modification, and compared it with unmodified sludge-based biochar (SBC). The physicochemical properties, adsorption efficiency, and adsorption mechanism of MgSBC-0.1 were studied. The results showed that the surface area of MgSBC-0.1 synthesized increased by 5.57 times. The material surface contained MgO, Mg(OH)2, and CaO nanoparticles. MgSBC-0.1 can effectively remove phosphate in the initial solution pH range of 3.00-7.00, with a fitted maximum phosphorus adsorption capacity of 379.52 mg·g-1. The adsorption conforms to the pseudo second-order kinetics model and Langmuir isotherm adsorption curve. The characterization of the adsorbed composite material revealed the contribution of phosphorus crystal deposition and electrostatic attraction to phosphorus absorption.

Efficiency, mechanism and application prospect of ammonium adsorption and desorption over a sodium-acetate-modified synthetic zeolite.

Adsorption is an effective approach for remediating ammonium pollution, and zeolite has exceptional efficacy for the adsorption of ammonium. The investigation of ammonium adsorption using coal-fly-ash-based zeolite has gained remarkable attention in contemporary research. In this work, a sodium-acetate-modified synthetic zeolite (MSZ) was used to absorb ammonium in simulated wastewater. The MSZ had an adsorption capacity for ammonium of 27.46 mg g-1, and the adsorption process followed the Langmuir isotherm model and pseudo-second-order kinetics model. The adsorption and desorption of ammonium were controlled by ion exchange, pore diffusion, and electrostatic attraction processes. Ion exchange was responsible for 77.90% of the adsorption process and 80.16% of the desorption process. The MSZ was capable of continuously removing large amounts of ammonium from wastewater through fixed bed adsorption. After 5 regeneration cycles, MSZ still maintained 75% adsorption characteristics for ammonium. Using MSZ adsorbed with ammonium as a soil amendment increased the germination rate of mung beans by 10%. Furthermore, it also increased the stem length, root length, and fresh weight by 20-30%. These findings suggest that MSZ provides a promising application prospect to mitigate ammonium pollution and recycle ammonium resources.

Enhanced photocatalytic degradation of tetracycline hydrochloride over Au-doped BiOBr nanosheets under visible light irradiation.

Bismuth(III) oxybromide (BiOBr) is a typical photocatalyst with a unique layered structure. However, the response of BiOBr to visible light is not strong enough for practical application. Moreover, the charge separation efficiency of BiOBr still needs to be improved. In this study, series of Au-doped BiOBr photocatalysts was prepared through a facile one-step hydrothermal method. The as-prepared Au0.3-BiOBr nanosheets exhibited an excellent electrochemical performance. The charge separation efficiency of Au0.3-BiOBr nanosheets was enhanced by 18.5 times compared with that of BiOBr. The intrinsic photocatalytic activity of Au0.3-BiOBr nanosheets in the degradation of tetracycline hydrochloride was approximately twice higher than that of BiOBr under visible light irradiation. In addition, three pathways were identified for the photocatalytic degradation and mineralization of tetracycline hydrochloride, which involve four reactions: hydroxylation, demethylation, ring opening and mineralization. Accordingly, this study proposes a feasible and effective Au-doped BiOBr photocatalyst, and describes a promising strategy for the design and synthesis of high-performance photocatalysts.

Visible-Light-Driven Ag-Doped BiOBr Nanoplates with an Enhanced Photocatalytic Performance for the Degradation of Bisphenol A.

Based on the low utilization rate of visible light and the high-charge carriers-recombination efficiency of bismuth oxybromide (BiOBr), in this work, noble metal Ag was used to modify BiOBr, and Ag-doped BiOBr nanoplates (Ag-BiOBr) were obtained through a one-step hydrothermal method. Compared with BiOBr, the absorption edge of Ag-BiOBr showed a redshift from 453 nm to 510 nm, and the absorption efficiency of visible light was, obviously, improved. Bisphenol A (BPA) was chosen as the target pollutant, to evaluate the photocatalytic performance of the samples. Ag0.1-BiOBr showed the highest degradation efficiency. The intrinsic photocatalytic activity of Ag0.1-BiOBr, under visible light, was approximately twice as high as that of BiOBr. In this way, a new visible-light-driven photocatalyst was proposed, to fight against organic pollution, which provides a promising strategy for water and wastewater treatment.

Electron-Level Mechanistic Insights into Ce Doping for Enhanced Efficiency Degradation of Bisphenol A under Visible Light Irradiation.

Bismuth oxybromide (BiOBr), with its special layered structure, is known to have potential as a visible-light-driven photocatalyst. However, the rapid recombination and short lifetime of the photogenerated carriers of BiOBr restrict its photocatalytic efficiency for the degradation of organic pollutants. Given the similar ionic size of Ce and Bi, Ce atoms might be easily introduced into the crystal of BiOBr to tailor its band structure. In this study, Ce doped BiOBr (Ce-BiOBr) samples with different percentages of Ce contents were prepared via a hydrothermal method. The intrinsic photocatalytic efficiency of Ce0.2-BiOBr for the degradation of bisphenol A (BPA) was 3.66 times higher than that of pristine BiOBr under visible light irradiation. The mechanism of Ce-doping modification for the enhanced photocatalytic performance was demonstrated based on a series of experiments and DFT calculation. The narrowed bandgap, the enhanced charge separation efficiency and Ce-doping energy level contributed to the remarkable photocatalytic performance of Ce-BiOBr.

Novel S-doped BiOBr nanosheets for the enhanced photocatalytic degradation of bisphenol A under visible light irradiation.

Bisphenol A (BPA), a typical endocrine disrupting chemical, is widespread in aqueous environment and cannot be efficiently treated by traditional water treatment technologies. Bismuth oxybromide (BiOBr) is a promising photocatalyst with a special layered structure. However, its band gap (2.8 eV) is not narrow enough for the efficient harvesting of visible light, severely restricting its practical use. Given that the band gap of Bi2S3 is only 1.3 eV, S-doping modification could be used to tailor the band structure of BiOBr. Here, series of S-doped BiOBr nanosheets was prepared through a facile hydrothermal procedure. The as-prepared S0.2-BiOBr nanosheets showed a narrower band gap of 2.33 eV. The intrinsic photocatalytic activity of S0.2-BiOBr sample for the degradation of BPA was 2.78 times higher than that of BiOBr under visible light degradation. Moreover, the mechanism of BPA degradation over the S-doped BiOBr under visible light irradiation was elucidated based on the experimental results and density functional theoretical calculations. Overall, a feasible and effective doping method was proposed to improve the utilization efficiency of visible light.

Ammonia sensing by closely packed WO3 microspheres with oxygen vacancies.

Ammonia (NH3), is a precursor for the formation of atmospheric fine particulate matter (PM2.5), and thus establishing efficient and cost-effective methods to detect ammonia emission is highly desired. Transition metal oxide semiconductors-based sensors for electrochemical gas sensing have been extensively explored. Among various types of semiconductors, tungsten oxide (WO3) possesses an anisotropic layered crystalline structure and is recognized as a promising material for gas sensing. However, the performance of commercial WO3 is unsatisfactory because of its high impedance and low charge transportation efficiency. Thus, the modification of commercial WO3 is needed to make it an efficient ammonia sensor material. In this work, closely packed WO3 microspheres with oxygen vacancies were synthesized successfully through a novel two-step hydrothermal route. Our WO3 showed a good selectivity to ammonia sensing, and its response intensity was 2.6 times higher than that of commercial WO3 because of its optimized conductivity. Moreover, the mechanism behind its robust ammonia sensing performance was elucidated. The effectiveness of the as-prepared WO3 microspheres for ammonia sensing also suggests a new strategy for modifying transition metal oxide materials.

Fabrication of BiOBrxI(1-x) photocatalysts with tunable visible light catalytic activity by modulating band structures.

A series of BiOBrxI(1-x) solid solutions were explored as novel visible light-sensitive photocatalysts. These BiOBrxI(1-x) solid-solution photocatalysts grew into two-dimensional nanoplates with exposed (001) facets and possessed continuously modulated band gaps from 2.87 to 1.89 eV by decreasing the Br/I ratio. The photocatalytic activities of these samples were measured, and the samples exhibited visible light-driven activities for the degradation of Rhodamine B (RhB). In particular, BiOBr0.8I0.2 exhibited the highest activity for the degradation of RhB. This result could be attributed to the balance between the effective light absorption and adequate redox potential. Additionally, investigations into the photocatalytic mechanism showed that the photodegradation of RhB over BiOBr0.8I0.2 solid-solution photocatalysts involved direct holes oxidation, in which the reaction that dominated during photocatalysis was determined by the potential of the valence band. Furthermore, a high stability in the photocatalytic activity of BiOBr0.8I0.2 was demonstrated by the cycling photocatalytic experiment and long-term irradiation, which might offer opportunities for its practical application as a catalyst.

Novel Bi12O15Cl6 Photocatalyst for the Degradation of Bisphenol A under Visible-Light Irradiation.

Bisphenol A (BPA), a typical endocrine-disrupting chemical, is widely present in water environments, and its efficient and cost-effective removal is greatly needed. Among various physicochemical methods for BPA degradation, visible-light-driven catalytic degradation of BPA is a promising approach because of its utilization of solar energy. Bismuth oxychloride (BiOCl) is recognized as an efficient photocatalyst, but its band gap, >3.0 eV, makes it inefficient for solar energy utilization, especially for degrading nondye pollutants like BPA. Thus, preparation and application of bismuth oxychloride photocatalysts with an increased visible-light activity are essential. In this work, inspired by density functional theory calculations, a novel bismuth oxychloride photocatalyst, Bi12O15Cl6, was designed. The nanosheets were successfully synthesized using a facile solvothermal method followed by a thermal treatment route. The prepared Bi12O15Cl6 nanosheets had a favorable energy band structure and thus exhibited a superior visible-light photocatalytic activity for degrading BPA. The BPA degradation rate by the Bi12O15Cl6 was determined to be 13.6 and 8.7 times faster than those for BiOCl and TiO2 (P25), respectively. The photogenerated reactive species and degradation intermediates were identified, and the photocatalytic mechanism was elucidated. Furthermore, the as-synthesized Bi12O15Cl6 nanosheets remained stable in the photocatalytic process and could be used repeatedly, demonstrating their promising application in the degradation of diverse pollutants in water and wastewater.