Facilitated Unidirectional Electron Transmission by Ru Nano Particulars Distribution on MXene Mo2C@g-C3N4 Heterostructures for Enhanced Photocatalytic H2 Evolution.

Precious metals exhibit promising potential for the hydrogen evolution reaction (HER), but their limited abundance restricts widespread utilization. Loading precious metal nanoparticles (NPs) on 2D/2D heterojunctions has garnered considerable interest since it saves precious metal consumption and facilitates unidirectional electron transmission from semiconductors to active sites. In this study, Ru NPs loaded on MXenes Mo2C by an in-site simple strategy and then formed 2D/2D heterojunctions with 2D g-C3N4 (CN) via electrostatic self-assembly were used to enhance photocatalytic H2 evolution. Evident from energy band structure analyses such as UV-vis and TRPL, trace amounts of Ru NPs as active sites significantly improve the efficiency of the hydrogen evolution reaction. More interestingly, MXene Mo2C, as substrates for supporting Ru NPs, enriches photoexcited electrons from CN, thereby enhancing the unidirectional electron transmission. As a result, the combination of Ru-Mo2C and CN constructs a composite heterojunction (Ru-Mo2C@CN) that shows an improved H2 production rate at 1776.4 µmol∙g-1∙h-1 (AQE 3.58% at 400 nm), which is facilitated by the unidirectional photogenerated electron transmission from the valence band on CN to the active sites on Ru (CN→Mo2C→Ru). The study offers fresh perspectives on accelerated unidirectional photogenerated electron transmission and saved precious metal usage in photocatalytic systems.

Synthesis and utilization of polyol-modified high specific surface area Ca(OH)2: an investigation.

Calcium hydroxide (Ca(OH)2) finds widespread use in the petrochemical industry, particularly in flue gas desulfurization applications. However, its conventional usage is limited by its inherently low specific surface area, hampering its efficiency. To address this limitation, this study aims to develop a simple and industrially scalable preparation process for Ca(OH)2 with a high specific surface area, thereby enhancing its effectiveness in various applications. This study aimed to develop a preparation process for making Ca(OH)2 with a high specific surface area, suitable for industry and easy to make. Ca(OH)2 with a specific surface area of 41.555 m2/g was successfully synthesized by incorporating polyols during lime digestion. The prepared high specific surface area Ca(OH)2 is more than five times the specific surface area of ordinary Ca(OH)2. Incorporation of polyols within the lime digestion process induces a reduction in both Ca(OH)2 grain size and particle dimensions, concurrently amplifying the specific surface area and optimizing mass transfer efficiency. Specifically, the desulfurization breakthrough time for Ca(OH)2 subject to a 15% triethanolamine modification was notably extended to 879 s, surpassing the desulfurization breakthrough time of unaltered Ca(OH)2 by more than tenfold. Moreover, the modified Ca(OH)2 exhibited remarkable efficacy in neutralizing acidic wastewater. A new approach for the preparation of high-performance Ca(OH)2 is proposed in this study, which could facilitate the industrial production of Ca(OH)2 with high specific surface area.

Modulating the pore and electronic structure for targeted recovery of platinum: Accelerated kinetic and reinforced coordination.

Adsorption for recovery of low-concentration platinum (Pt) from the complex composition of acidic digestates was challenging because of slow kinetic and poor affinity. It was expected to be overcome by the improvement of pore size distribution and adsorption site activity. Herein, a series of Prussian blue etchings (PBE) with porosity-rich and activity-high cyano (CN) was synthesized to recover low-concentration Pt. The N2 isotherm results showed that the pore structure evolved from mesoporous to microporous. The Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations results revealed that the modulation of electronic structure converted FeII to FeIII in [FeII(CN)6]4-. The coexistence of micro- and meso-pore structures provided channels to accelerate adsorption and ensured PtII enrichment. The regulation of Fe valence state activated CN, which reinforced the strength of coordination interaction between Pt and Fe-CN- at N-atom. The adsorption rate and maximum capacity of PBE1 were 4.4 and 2.5 times higher than those of PB, respectively, due to the dual efficacy of accelerated kinetic and reinforced coordination. This study systematically analyzes the pivotal role of pore and electronic structure modulation in adsorption kinetic and affinity, which provides a novel strategy for PtII targeted recovery.

Rapid separation of the low concentration Pd from Pd-Pt coexisting systems: Cyano-group's monomer-specific affinity.

Rapid separation of low concentration palladium (Pd) from Pd-Platinum (Pt) coexisting systems remains a formidable challenge, primarily due to the undifferentiated substitution of ligands in Pd/Pt complexes by adsorption sites. The development of an adsorbent featuring monomer-specific affinity adsorption sites for Pd/Pt could mitigate this drawback. Herein, Manganese hexacyanoferrate (MnHCF) possessing the sensitivity and specificity to Pd ions (Pd(II)) was synthesized via the facile co-precipitation method. MnHCF could rapidly and selectively capture 90.30 % of Pd(II) from a 10 ppm Pd-Pt coexisting system within just 5 min. Spectroscopic analyses and density functional theory (DFT) calculations indicated that cyano-group (CN) in MnHCF exhibited the monomer-specific affinity for targeted capturing Pd via the direct and strong coordination interaction (Fe-CN-PdCl2), which was co-determined by the electron-losing of C (0.06 e) and N (0.07 e) atom. At the same time, CN could neither react directly with the fully coordinated [PtCl6]2- species nor substitute the Cl- ligand, both of which contributed to the non-adsorption of Pt, thus triggering the Pd-Pt separation. This study provides a promising candidate adsorbent for practical applications in platinum group metals recovery by the design of adsorption sites with monomer-specific affinity.

Surface reconstructed Fe@C1000 for enhanced Fenton-like catalysis: Sustainable ciprofloxacin degradation and toxicity reduction.

The Fe-based catalysts typically undergo severe problems such as deactivation and Fe sludge emission during the peroxymonosulfate (PMS) activation, which commonly leads to poor operation and secondary pollution. Herein, an S-doped Fe-based catalyst with a core-shell structure (Fe@CT, T = 1000°C) was synthesized, which can solve the above issues via the dynamic surface evolution during the reaction process. Specifically, the Fe0 on the surface of Fe@C1000 could be consumed rapidly, leaving numerous pores; the Fe3C from the core would subsequently migrate to the surface of Fe@C1000, replenishing the consumed active Fe species. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses demonstrated that the reaction surface reconstructed during the PMS activation, which involved the FeIII in-situ reduction by S species as well as the depletion/replenishment of effective Fe species. The reconstructed Fe@C1000 achieved near-zero Fe sludge emission (from 0.59 to 0.08-0.23 mg L-1) during 5 cycles and enabled the dynamic evolution of dominant reactive oxygen species (ROS) from SO4·- to FeIVO, sustainably improving the oxidation capacity (80.0-92.5% in following four cycles) to ciprofloxacin (CIP) and reducing the toxicity of its intermediates. Additionally, the reconstructed Fe@C1000/PMS system exhibited robust resistance to complex water matrix. This study provides a theoretical guideline for exploring surface reconstruction on catalytic activity and broadens the application of Fe-based catalysts in the contaminants elimination.

Spontaneous FeIII/FeII redox cycling in single-atom catalysts: Conjugation effect and electron delocalization.

The mechanism of spontaneous FeIII/FeII redox cycling in iron-centered single-atom catalysts (I-SACs) is often overlooked. Consequently, pathways for continuous SO4 ·-/HO⋅ generation during peroxymonosulfate (PMS) activation by I-SACs remain unclear. Herein, the evolution of the iron center and ligand in I-SACs was comprehensively investigated. I-SACs could be considered as a coordination complex created by iron and a heteroatom N-doped carbonaceous ligand. The ligand-field theory could well explain the electronic behavior of the complex, whereby electrons delocalized by the conjugation effect of the ligand were confirmed to be responsible for the FeIII/FeII redox cycle. The possible pyridinic ligand in I-SACs was demonstrably weaker than the pyrrolic ligand in FeIII reduction due to its shielding effect on delocalized π orbitals by local lone-pair electrons. The results of this study significantly advance our understanding of the mechanism of spontaneous FeIII/FeII redox cycling and radical generation pathways in the I-SACs/PMS process.

The enhanced removal of arsenite from water by double-shell CuOx@MnOy hollow spheres (DCMHS): behavior and mechanisms.

To facilitate removing As(III) from water through an "oxidation-adsorption" process, the double-shell CuOx@MnOy hollow spheres (DCMHS) have been fabricated via a two-step co-precipitation route combined with the soft-template method. The surface characterization results showed that Mn oxides were formed without segregation and uniformly distributed on the surface of CuOx hollow spheres. DCMHS could achieve outstanding performance to remove As(III) with an As maximum adsorption capacity of 32.15 mg/g. Meanwhile, the kinetics results illustrated that the oxidative activity of DCMHS was strengthened due to its specific structure, and part of As(III) was converted to As(V) during the adsorption process. Also, air aeration could further enhance As(III) oxidation and thus improving As removal. The As(III) removal performance could be maintained under neutral and weak alkaline conditions. Phosphate, silicate, and carbonate anions could depress the removal performance, while chloride ions and sulfate anions barely influenced As removal. Moreover, DCMHS could be regenerated using NaOH and KMnO4 solutions without breaking the hollow sphere structure. Based on the spectroscopic analysis results, As(III) molecules were converted to As(V) via two pathways, including the oxidation by Mn oxides or superoxide radicals. The Cu-Mn synergistic effect could not only enhance the oxidative activity of Mn oxides but also produce superoxide radicals via the activation of surface-adsorbed oxygen molecules. Afterwards, the newly formed As(V) could be attached to the hydroxyl groups through surface complexation. Therefore, this work has provided insights into the morphology design of Mn-oxide-containing adsorbents and supplemented the interface reaction mechanisms for enhancing As(III) removal.

Monodispersed CuO nanoparticles supported on mineral substrates for groundwater remediation via a nonradical pathway.

Nonradical oxidation based on singlet oxygen (1O2) has attracted great interest in groundwater remediation due to the selective oxidation property and good resistance to background constituents. Herein, recoverable CuO nanoparticles (NPs) supported on mineral substrates (SiO2) were prepared by calcination of surface-coated metal-plant phenolic networks and explored for peroxymonosulfate (PMS) activation to generate 1O2 for degrading organic pollutants in groundwater. CuO NPs with a close particle size (40 nm) were spatially monodispersed on SiO2 substrates, allowing highly exposure of active sites and consequently leading to outstanding catalytic performance. Efficient removal of various organic pollutants was obtained by the supported CuO NPs/PMS system under wide operation conditions, e.g., working pH, background anions and natural organic matters. Chemical scavenging experiments, electron paramagnetic resonance tests, furfuryl alcohol decay and solvent dependency experiments confirmed the formation of 1O2 and its dominant role in pollutants removal. In situ characterization with ATR-FTIR and Raman spectroscopy and computational calculation revealed that a redox cycle of surface Cu(II)-Cu(III)-Cu(II) was responsible for the generation of 1O2. The feasibility of the supported CuO NPs/PMS for actual groundwater remediation was evaluated via a flow-through test in a fixed-bed column, which manifested long-term durability, high mineralization ratio and low metal ion leaching.

Evaluation of potassium ferrate activated biochar for the simultaneous adsorption of copper and sulfadiazine: Competitive versus synergistic.

Combined pollution caused by organic pollutants and heavy metals pose a significant challenge to the adsorption process. In this study, iron-modified biochar (Fe-BC) was prepared by using ferrate (K2FeO4) and wheat stalk as the precursors for the adsorption of copper (Cu2+) and sulfadiazine (SDZ), especially under combined pollution scenarios. Iron modification not only enlarged the surface area but also loaded iron oxide nanoparticles on biochar surface. Accordingly, Fe-BC exhibited better adsorption capability of Cu2+ and SDZ than the pristine biochar (BC). The corresponding maximum adsorption capacities of Fe-BC700 were 46.85 mg g-1 and 45.43 mg g-1 towards Cu2+ and SDZ, respectively. Interestingly, the adsorption was elevated in binary-pollutants system, suggesting a synergistic effect, which was probably attributed to the mutual bridging effects and complexation between Cu2+ and SDZ. The loaded iron oxide particles could serve as a physical barrier to separate the adsorptions of Cu2+ and SDZ and thus inhibited the competitive adsorption. Meanwhile, theoretical calculation demonstrated that sulfonamide group was the most probable binding site. Columns packed with Fe-BC700 showed better performances for Cu2+ and SDZ removal in binary system (635.73 BV for Cu2+ and 4846.26 BV for SDZ) than in single systems (571.60 BV for Cu2+ and 3572.06 BV for SDZ), which was consistent with batch adsorption experiments. These results demonstrated the potential application of Fe-BC700 for simultaneous adsorption of Cu2+ and SDZ and provided a cost-effective way for the remediation of organic and inorganic pollutants.

Mutual-activation between Zero-Valent iron and graphitic carbon for Cr(VI) Removal: Mechanism and inhibition of inherent Side-reaction.

The low reactivity of zero-valent iron (ZVI) usually limits its application for pollutant remediation. Therefore, a microscopic galvanic cell (mGC) with short-circuited cathode and anode was synthesized to intensify its galvanic corrosion. The prepared mGC exhibited 7.14 times higher Fe(II) release performance than ordinary nanoscale-ZVI (nZVI), rendering efficient Cr(VI) removal performance. Density functional theory (DFT) revealed mutual-activation of the cathode and anode due to close proximity, dramatically enhancing the galvanic corrosion of Fe(0) in mGC. The corrosion potential of mGC was measured as -0.77 V, which was 100 mV more negative than nZVI. The released electrons and surface-bond Fe(II) from anode in mGC was proved to be the dominant reductive species. More importantly, Cr(VI) reduction was slightly inhibited by hydroxyl radicals generated by a series of inherent side-reactions in the system, which could be well eliminated by low concentrations of 4-acetamido phenol. This study provides a promising strategy for ZVI activation, and sheds light on its environmental applications.

Oxygen vacancies-enriched CoFe2O4 for peroxymonosulfate activation: The reactivity between radical-nonradical coupling way and bisphenol A.

Oxygen vacancies (OV) play a vital role in catalytic activity. Herein, a series of MOF-derived CoFe2O4 nanomaterials with OV tuned by a simple thermal aging strategy are prepared for peroxymonosulfate (PMS) activation. Remarkably, the stability, structural and catalytic properties show dependence on the annealing temperature. The abundant surface OV and functional groups on CoFe2O4 were verified as active sites to boost catalytic activity. Based on the density functional theory (DFT) calculations, (1 1 1), (2 2 2) and (4 2 2) planes exposed at higher temperatures facilitate catalytic performance, ascribed to the intense surface adsorption energy. The quenching and electron paramagnetic resonance (EPR) experiments indicate catalysis degradation is a radical-nonradical coupling process. The reactivity between reactive oxygen species (ROS) and bisphenol A and the radical-nonradical dual degradation pathways are systematically explored by combined DFT and HPLC-MS.

Behaviour of ozone in the hybrid ozonation-coagulation (HOC) process for ibuprofen removal: Reaction selectivity and effects on coagulant hydrolysis.

Simultaneous ozonation and coagulation can be realized in one unit in the developed hybrid ozonation-coagulation (HOC) process. To reveal the reaction sequence within the HOC process, the ibuprofen (IBP) removal efficiency of the ozonation only, HOC and HOC-PO43- (inhibition of the reactions between ozone and metal coagulant) processes at pH 5 and different ozone dosages were investigated. The removal efficiency is almost the same for the three processes at a low ozone dosage (4.8 mg/L), and higher removal performance can be achieved by the HOC process with increasing ozone dosage. It can be implied that ozone preferentially reacts with OH- to generate OH which react with IBP in the HOC process, and subsequently reacts with the surface hydroxyl groups of hydrolysed Al species to enhance OH generation. Moreover, based on the kinetics, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) analyses, the synergistic reactions between ozone and the metal coagulants (SOC) started to take effect from ozone dosage of 9.6 mg/L, which further verified that ozone will be involved in the IBP ozonation prior to the SOC reactions. The subsequent SOC reactions also resulted in the increased generation of polymeric Al species and more abundant intermediates in the HOC process.

Insight into the effect of pH-adjusted acid on thermodynamic properties and crystallization sequence during evaporative-crystallization process of hydrolyzed urine.

The evaporative-crystallization process (ECP) is a frequently used approach for complete nutrient recovery from human urine, and crystallization sequence is related to the selection of seed and the optimization of crystallization process. In this study, three hydrolyzed urine (HU) samples, which were acidified to an initial pH of 4 with HCl, H2SO4, and H3PO4, were used to recover crystallized products by ECP, their crystallization process and thermodynamic properties during ECP were compared, and the detailed crystallization sequence was analyzed using the PHREEQC-2 simulation. The results showed that the pH-adjusted acid has a significant effect on crystal precipitation, and the new crystal in HCl-4-HU, H2SO4-4-HU, and H3PO4-4-HU first appeared at volume concentration factors (CFV) of 19.61, 9.90, and 9.96, respectively. Furthermore, the simulated crystallization process characteristics of HU by PHREEQC-2 have a good fit with the actual experimental data, and crystallization sequence of HCl-4-HU, H2SO4-4-HU, H3PO4-4-HU during ECP were NH4Cl (CFV from 10.25 to 100) / NaCl (CFV from 71.43 to 100), NH4NaSO4 (CFV from 10.25 to 55.56) / NH4Cl (CFV from 20 to 100) / (NH4)2SO4 (CFV from 40.45 to 100), NH4H2PO4 (CFV from 10.25 to 100) / NaH2PO4 (CFV from38.46 to 55.5) / NaCl (CFV from 45.46 to 100), respectively. The present study clearly reveals the crystallization sequence and thermodynamic properties of nutrient elements in acidified HU, which provides an important theoretical basis for the optimization of crystallized products obtained from HU for future study.

Performance and mechanisms of sulfadiazine removal using persulfate activated by Fe3O4@CuOx hollow spheres.

A Fe-Cu bimetal catalyst (FCHS) was synthesized by depositing Fe3O4 on the shell of CuOx hollow spheres, which were prepared via a soft template method. Several characterization methods, including XRD, SEM-EDS&mapping, TEM, FTIR, and XPS, were used to reveal the morphology and surface properties of FCHS. The characterization results demonstrated that the double-shell hollow structure is formed with a dense coating of Fe3O4 nanoparticles on the surface of CuOx hollow spheres. FCHS can exhibit excellent catalytic activity to degrade sulfadiazine (SDZ) with the oxidant of persulfate (PS). The optimal SDZ removal performance was explored by adjusting reaction parameters, including catalyst dosage, oxidant dosage, and solution pH. The SDZ removal efficiency in the FCHS + PS system could reach 95% at the optimal reaction condition ([catalyst]0 = 0.2 g/L, [PS]0 = 2 mM, pH = 7.0) with 5 mg/L of SDZ. Meanwhile, the degradation efficiency decreased with the coexistence of phosphate or carbonate anions. According to the results of radicals scavenging experiments and the electron paramagnetic resonance analysis, the radicals of SO4·-, O2·- and ·OH generated in the FCHS + PS system contribute to the degradation of SDZ. Moreover, the results of XPS revealed that the solid-state charge-transfer redox couple of Fe(III)/Fe(II) and Cu(I)/Cu(II) can promote the activation of PS. It means that the cooperation effect between Cu oxides and Fe oxides in the double-shell structure is beneficial to the catalytic degradation of SDZ. Furthermore, four possible pathways for SDZ degradation were proposed according to the analysis of intermediate products detected by the LCMS-IT-TOF.

Interactions between flocs and bubbles in the separation zone of dissolved air flotation system.

The interaction between flocs and bubbles is crucial to achieve separation efficiency in the separation zone of the dissolved air flotation process. In this study, a micro-scale observation system was established to investigate the interaction between flocs and bubbles in the separation zone of the system. Four periodic interactions were observed-collision, adhesion, coalescence, and desorption (CACD). Small flocs achieved higher unit buoyancy (buoyancy per surface area) than that of large flocs. High collision probability can be obtained between bubbles and small flocs according to Stokes' law and Reynolds experiments. Simulation using Fluent indicated that low-pressure drag acting on small flocs resulted in a high probability of collision. Therefore, small flocs can capture bubbles and accumulate high enough buoyancy in a short time due to the high collision probability and low buoyancy required for small flocs to float. Moreover, the small flocs have a limited number of bubbles on the surface within such a short time, leading to a low probability of desorption and coalescence. The practical verification also show that small flocs are favorable for the high separation efficiency of the flotation process.

Synergistic Adsorption and Oxidation of Ciprofloxacin by Biochar Derived from Metal-Enriched Phytoremediation Plants: Experimental and Computational Insights.

Biochar is a promising candidate for the adsorptive removal of organic/inorganic pollutants, yet its role in metal-free catalyzed advanced oxidation processes still remains ambiguous. In this work, five biochar samples (PPBKx, where x represents the pyrolysis temperature) were prepared by using metal-enriched phytoremediation plant residue as the feedstock. Notably, PPBK exhibited a high specific surface area (as high as 1090.7 m2 g-1) and outstanding adsorption capacity toward ciprofloxacin (CIP, as much as 1.51 ± 0.19 mmol g-1). By introducing peroxymonosulfate (PMS, 5 mM) as the chemical oxidant, over 2 mmol g-1 CIP was synergistically adsorbed and oxidized within 30 min although PMS itself could not oxidize CIP efficiently, suggesting the formation of reactive oxidative species. Theoretical calculations revealed that PMS anions preferentially adsorbed on the activated C atoms adjacent to the graphitic N dopant, where the carbon matrix served as the electron donor, instead of as an electron mediator. The adsorbed PMS possessed a smaller molecular orbital energy gap, indicating that it was much easier to be activated than free PMS anions. Surface-bound reactive species were elucidated to be the dominant contributor through chemical quenching experiments and electrochemical characterizations. The catalytic activity of PPBK700 could be greatly retained in repeated oxidations because of the stable N species, which serve as the active catalytic sites, while the CIP adsorption was greatly deteriorated because of the diminishing active adsorption sites (carbon matrix edge) caused by the partial oxidation of PMS. This work not only provides a facile and low-cost approach for the synthesis of functional biochar toward environmental remediation but also deepens the understanding of biochar-catalyzed PMS activation and nonradical oxidation.

Sol-Gel Synthesis of Spherical Mesoporous High-Entropy Oxides.

High-entropy oxides (HEOs) have attracted increasing interest owing to their unique structures and fascinating physicochemical properties. Spherical mesoporous HEOs further inherit the advantages of spherical mesoporous materials including high surface area and tunable pore size. However, it is still a huge challenge to construct HEOs with uniform spheres and a mesoporous framework. Herein, a wet-chemistry sol-gel strategy is demonstrated for the synthesis of spherical mesoporous HEOs (e.g., Ni-Co-Cr-Fe-Mn oxide) with high specific surface area (42-143 m2/g), large pore size (5.5-8.3 nm), unique spherical morphology (∼55 nm), and spinel structure without any impure crystal phase using polyphenol as a polymerizable ligand. The metal/polyphenol-formaldehyde resin colloidal spheres are first synthesized via a sol-gel process. Because of their abundant catechol groups and strong chelating ability with different metal species, polyphenols can not only accommodate five different metal ions in their networks but also be well polymerized by formaldehyde to form colloidal spheres. After calcination, the metal species aggregate together to form HEOs, while the organic resin is fully decomposed to produce mesopores. Because of the open framework with accessible mesopores, they could be used as a peroxymonosulfate catalyst for degradation of organic pollutants and a nanoplatform for efficient detection of DNA. This work demonstrates a straightforward sol-gel strategy for design and synthesis of spherical mesoporous high-entropy materials, which would promote the exploration of new properties of high-entropy materials and extend their application.

The removal of tetracycline, oxytetracycline, and chlortetracycline by manganese oxide-doped copper oxide: the behaviors and insights of Cu-Mn combination for enhancing antibiotics removal.

Adsorption process is suitable to the advanced treatment of tetracycline antibiotics (TCs; including tetracycline (TTC), oxytetracycline (OTC), and chlortetracycline (CTC)) in poultry wastewater. In this research, Mn oxide-doped Cu oxide (MODCO) was synthesized and used for the removal of TTC, OTC, and CTC. According to the XRD and SEM analysis results, MODCO has an amorphous crystal structure and is formed by the aggregation of nano-sized particles with a uniform distribution of Cu and Mn elements. In addition, MODCO has a BET surface area of 67.7 m2/g and a pHIEP value of 7.8. The results of batch experiments illustrated that the reaction rates for the removal of three TCs were in the order of OTC > CTC > TTC. In addition, the theoretical maximum amounts of TTC, OTC, and CTC adsorbed on MODCO were determined to be 2.90 mmol/g, 4.15 mmol/g, and 2.20 mmol/g via the Langmuir model, respectively. The optimal removal performances of TCs were achieved in the pH range of 6~9, and the coexistence of anions posed an unnoticeable effect on the removal efficiencies. The spectroscopic analysis results demonstrated that the removal mechanism of TCs was mainly attributed to surface complexation. Furthermore, a part of TCs may be decomposed by Mn oxides during the removal process according to the UV spectrogram results. Overall, MODCO has exhibited a great potential for the removal of TCs from aqueous solution.

Evaluation of the adsorption of ammonium-nitrogen and phosphate on a granular composite adsorbent derived from zeolite.

To remove the extra ammonium-nitrogen (NH3-N) and phosphorus (P) from contaminated water, a novel granular adsorbent (GAZCA) was fabricated with zeolite powders and Al-Mn binary oxide (AMBO) via the compression method. The SEM-EDS and mapping and XRD results illustrated the microstructure of GAZCA: the homogeneous aggregation of zeolite and AMBO nanoparticles with their crystal integrity and the uniform distribution of Al/Mn/Si/O elements on the adsorbent surface. FTIR and XPS results demonstrated the existence of impregnated sodium cations and hydroxyl groups, which were responsible for the removal of NH3-N and P, respectively. The results of BET analysis and compression tests exhibited a high surface area (14.4 m2/g) and a satisfactory mechanical strength of GAZCA. Kinetic adsorption results showed a fast adsorption rate for NH3-N and P, and mutual inference was not observed between the adsorption kinetics of NH3-N and P in the bi-component system. The adsorption isotherm results demonstrated that the maximum adsorption capacities of NH3-N and P were calculated as 12.9 mg/g and 9.3 mg/g via the Langmuir model, respectively. In the bi-component system, the adsorption capacities of NH3-N and P were maintained at low and moderate concentrations and decreased at high concentrations due to the blockage effects of NH4MnPO4·H2O precipitates. The removal efficiency of NH3-N could be maintained in a wide pH range of 4~10, while P adsorption was inhibited at alkali conditions. The solution of sodium bicarbonate (0.4 M) was used for the regeneration of saturated adsorbents, which permitted GAZCA to keep 98% and 78% of its adsorption capacity for NH3-N and P even after three regeneration and reuse cycles. Dynamic experiments illustrated that a satisfactory performance was obtained for the in situ treatment of simulated N- and P-contaminated water by using a column reactor packed with GAZCA, thus further confirming its great potential for the control of eutrophication.

Degradation of antibiotics in multi-component systems with novel ternary AgBr/Ag3PO4@natural hematite heterojunction photocatalyst under simulated solar light.

Abatement of antibiotics from aquatic systems is of great importance but remains a challenge. Herein, we prepared ternary AgBr/Ag3PO4@natural hematite (AgBr/Ag3PO4@NH) heterojunction composite via a simple route for the photocatalytic degradation of antibiotic pollutants. By adjusting the dose of Ag species, four products with different Ag content (denoted as Ag0.5BrPFe, Ag1BrPFe, Ag1.5BrPFe, and Ag2BrPFe) were developed. Among them, Ag1.5BrPFe exhibited the best photocatalytic activity. Four antibiotics (i.e. ciprofloxacin (CIP), norfloxacin (NOR), sulfadiazine (SDZ), and tetracycline (TTC)) could be degraded with synthesized Ag1.5BrPFe in multi-component systems. Water matrix indexes including solution pH, coexisting anions, humic acids exhibited distinct effects on the degradation process. The results revealed that the degradation process was accelerated at acidic conditions while depressed at basic conditions. Superoxide radical and hole were detected by in situ electron spin resonance technique and played the dominant roles. The degradation pathway TTC was tentatively established followed with the identification of the degradation intermediates and computational analysis. This work would shed light on the photocatalytic degradation mechanism of organic pollutants by the AgBr/Ag3PO4@NH composite.