Uncovering the performance and intrinsic mechanism of different hydrolyzed AlTi species in polystyrene nanoplastics coagulation.

Hydrolyzed AlTi species are essential metal-based coagulants in a coagulation process to remove nanoplastics (NPs). Understanding the molecular interactions between hydrolyzed AlTi species and NPs is key to promoting coagulation efficiency. In this study, the coagulation performance and intrinsic mechanism of different AlTi species (including monomeric AlTi and polymeric AlTi species-Al13Ti13) for NPs removal were systematically investigated. We found that the polymeric AlTi species exhibited higher turbidity removal (95.0 %) and lower residual Al content (20.67 µg/L) at a low dosage over monomeric AlTi species. Al13 and Al13Ti13 formed by in situ hydrolysis were the dominant species to destabilize and aggregate NPs at pH 6. Main coagulation mechanisms were dominated by charge neutralization, complexation between the aliphatic CH of NPs and Al/Ti-OH, and cation-π interaction between polycations and the aromatic structure of NPs. The preformed Al13Ti13 showed multiple positive charge binding sites assisting its easy adsorption on NPs by electrostatic attraction, and then formed microscale aggregates through charge neutralization or intermolecular interaction. The preformed Al13Ti13 demonstrated a high stability and coagulation performance with respect to pH changes in raw water, whereas the promotion of µ-OH bridges dissociation by OH- and the presence of electrostatic repulsion significantly decreased the NPs removal by monomeric AlTi at high pH. This study provides valuable theoretical insights into the interaction between NPs and various hydrolyzed AlTi species.

A membrane fouling control strategy based on a combination of pre-treatment mitigation and in-situ membrane surface regulation using a composite coagulant.

Ultrafiltration technology (UF) is efficient in surface water treatment, but its development and widespread application are limited by membrane fouling. Herein, an efficient and stable polymerized ferric titanium coagulant (PFTC) was synthesized and used as a UF pretreatment agent in actual lake water treatment. The control mechanism of PFTC on membrane fouling was investigated from the perspective of organic removal efficiency and in-situ membrane surface regulation. PFTC demonstrated a remarkable affinity for soluble metabolic intermediates and hydrophilic proteins through complexation and hydrogen bonding force, achieving removal efficiencies of 66.4 % for UV254 and 81.3 % for DOC, respectively. The hydrophilic pollutants with high molecular weight and non-saturated structure could be preferentially removed by PFTC due to its diverse hydrolysates including positively charged Fe-based hydrolysates, amorphous Ti-based hydrolysates, and highly polymerized Fe-Ti copolymers. The flocs generated by PFTC exhibited strong hydrophilicity, allowing for the formation of a loose porous cake layer on the ultrafiltration membrane, which acted as a hydrophilic layer to enhance the anti-fouling performance of ultrafiltration membrane. With its dual function of contaminant removal and in-situ membrane surface regulation, PFTC alleviated 98.9 % of membrane fouling. This study provides new insights into membrane fouling control by coagulation pretreatment and efficient treatment of surface water.

Multi-interface interaction mechanism of pulp reject-based flocculants for the removal of antibiotics and its combined pollutants.

The efficient removal of antibiotics and its combined pollutants is essential for aquatic environment and human health. In this study, a lignin-based organic flocculant named PRL-VAc-DMC was synthesized using pulp reject as the raw material, with vinyl acetate (VAc) and methacryloxyethyltrimethyl ammonium chloride (DMC) as the grafting monomers. A series of modern characterization methods were used to confirm the successful preparation of PRL-VAc-DMC and elucidate its polymerization mechanism. It was found that the Ph-OH group and its contiguous carbon atoms of lignin served as the primary active sites to react with grafting monomers. Flocculation experiments revealed that PRL-VAc-DMC could react with tetracycline (TC) through π-π* interaction, hydrophobic interaction, hydrogen bonding, and electrostatic attraction. With the coexistence of humic acid (HA) and Kaolin, the aromatic ring, hydroxyl, and amide group of TC could react with the benzene ring, hydroxyl group, and carboxyl group of HA, forming TC@HA@Kaolin complexes with Kaolin particles acting as the hydrophilic shell. The increase in particle size, electronegativity, and hydrophily of TC@HA@Kaolin complexes facilitated their interaction with PRL-VAc-DMC through strong interfacial interactions. Consequently, the presence of HA and Kaolin promoted the removal of TC. The synergistic removal mechanism of TC, HA, and Kaolin by PRL-VAc-DMC was systematically analyzed from the perspective of muti-interface interactions. This paper is of great significance for the comprehensive utilization of pulp reject and provides new insights into the flocculation mechanism at the molecular scale.

Insights into the efficient water treatment over N-doped carbon nanosheets with layered minerals as template: The role of interfacial electron tunneling and transfer.

Peroxymonosulfate (PMS) oxidation reactions have been extensively studied recently. Due to the high material cost and low catalytic capability, PMS oxidation technology cannot be effectively applied in an industrial water treatment process. In this work, we developed a modification strategy based on enhancing the neglected electron tunneling effect to optimize the intrinsic electron transport process of the catalyst. The 2D nitrogen-doped carbon-based nanosheets with small interlayer spacing were prepared by self-polymerization of dopamine hydrochloride inserted into the natural layered bentonite template. Systematic characterizations confirmed that the smaller layer spacing in the 2D nitride-doped carbon-based nanosheets reduces the depletion layer width. The weak electronic shielding effect derived by the small layer spacing on the material subsurface enhanced the bulk electron tunneling effect. More bulk electrons could be migrated to the catalyst surface to activate PMS molecules. The PMS activation system showed ultrafast oxidation capability to degrade organic pollutants and strong ability to resist interference from environmental matrixes due to the optimized electron transfer process. Furthermore, the developed membrane reactor exhibited strong catalytic stability during the continuous degradation of P-Chlorophenol (CP).

Coagulation performance and mechanism of different hydrolyzed aluminum species for the removal of composite pollutants of polyethylene and humic acid.

Microplastics (MPs) and natural organic matter (NOM) composite pollutants have become emerging contaminants with potential threats. Coagulation has been widely used to remove MPs and NOM, but the underlying mechanisms for the removal of MPs-NOM composite pollutants by hydrolyzed Al species remain unclear. Therefore, the coagulation performance and mechanism of AlCl3, polyaluminum chloride with basicity of 2.2 (PAC22), and PAC25 in treating polyethylene (PE), humic acid (HA), and PE-HA composite systems were systematically investigated. The results showed that in the single PE system, PAC25 with hexagonal clusters achieved the maximum removal (68.09 %) (pH: 5, dosage: 0.5 mM) since adsorption bridging and sweeping effect were the main mechanisms for PE removal. The adsorption of HA on the PE surface enhanced its hydrophilicity and electrostatic repulsion, resulting in decreased PE removal. In the AlCl3-PE-HA system, the oligomeric Al first interacted with the -COOH and C-OH of HA through complexation, followed by the meso- and polymers of Al interacted with PE by electrostatic adsorption. The pre-formed medium polymeric Al species (Alb) and colloidal or solid Al species (Alc) in PAC22 and PAC25 formed complexes with the -OH and -COOH groups of HA, respectively, and then removed PE by adsorption bridging and sweeping effect.

Intrinsic mechanism for the removal of antibiotic pollution by a dual coagulation process from the perspective of the interaction between NOM and antibiotic.

Antibiotics bring potential risks to human health and ecosystem, and their coexistence with natural organic matters (NOMs) could have harmful impacts on the environment. Herein, a polyaluminium chloride (PAC)-polydimethyl diallyl ammonium chloride (PDMDAAC) dual coagulation process was designed to remove the co-pollutants of chlortetracycline (CTC) and humic acid (HA), representing antibiotics and NOMs, respectively. The main research strength was given to understand molecular interactions and their mechanisms associated with the coagulation and flocculation. We found that the co-existing HA and CTC increased the hydrophily and stability of contaminants, and generated HA@CTC complexes with large particles size. The interaction mechanism between CTC and HA was mainly hydrogen bonding, hydrophobic association action, n-π* electron donor-acceptor interaction, and π-π* conjugation. Lewis acid-base interaction was the main force between HA and CTC. The bonding energies of OH…N, OH…O, and hydrophobic association were -12.2 kcal/mol, -13.1 kcal/mol, and -11.4 kcal/mol, respectively, indicating that hydrogen bonding was stronger than hydrophobic association. The interactions between HA and CTC could improve their removal efficiency in the coagulation process. This is due to that the functional groups (COOH and OH) in the HA@CTC could be adsorbed by Al based hydrolysates. Polar interaction dominated the CTC and HA removal, and PAC was more efficient than PDMDAAC to remove HA@CTC complexes due to its higher complexing capacity. Thanks to the low concentration of residual contaminants and the formation of large and loose flocs, the interaction of HA and CTC could alleviate membrane fouling during ultrafiltration process. This study will provide new insight into the efficient removal of combined pollution and membrane fouling control.

Microcosmic mechanism analysis of the combined pollution of aged polystyrene with humic acid and its efficient removal by a composite coagulant.

The composite pollutants formed by aged polystyrene (APS) and natural organic matter are complex and harmful, which lead to the deterioration of water quality. In this work, the interaction mechanism between humic acid (HA) and APS was discussed by investigating the changes in their functional groups. Besides, a novel polyaluminum-titanium chloride composite coagulant (PATC) was prepared, and its binding behaviors with HA@APS under different pH conditions were analyzed from a microscopic perspective. It was found that at pH 4, π-π conjugation was the dominant interaction between HA and APS. And the main removal mechanism of HA@APS by PATC was surface complexation. With the increase of pH, π-π conjugation, n-π electron donor-acceptor interaction (EDA), and hydrogen bonding gradually dominated the interaction between APS and HA. At pH 7, PATC hydrolyzed to form various polynuclear Al-Ti species, which could meet the demand for different binding sites of HA@APS. Under alkaline conditions, HB and n-π EDA in HA@APS were weakened, while π-π conjugation held a dominant position again. At this time, the main coagulation mechanism of PATC changed from charge neutralization to sweeping action, accompanied by hydrogen bonding. ENVIRONMENTAL IMPLICATION: Microplastics (MPs) have attracted the public's attention due to their potential toxicity to humans. The combined pollution of aged microplastics and humic acid (HA) will bring great harm to aquatic environment. The development of novel composite coagulants is hopeful to efficiently remove MPs and their combined pollutants. Elucidating the interactions between HA and aged MPs is helpful to understand the transformation and fate of MPs in actual environments, and to reveal the removal mechanism of composite pollutants by coagulation. The findings presented here will provide theoretical guidance for addressing the challenges of coagulation technology in treating new pollutants in practice.

Sono-enhanced heterogeneous Fenton catalysis: magnetic halloysite nanotube synthesis and accelerated free radical generation.

Although heterogeneous Fenton catalysis has captured increasing attention compared to its homogeneous counterpart, it still confronts some inherent drawbacks in use, such as the dilemma in solid-liquid separation and greater mass transfer resistance. Driven by the acoustic cavitation effect, herein, a sono-enhanced heterogeneous Fenton catalysis process was built to overcome the above two shortcomings, by rapidly synthesizing magnetic Fenton-like catalysts and accelerating electron transfer during the catalytic reaction. The results show that, compared to the traditional chemical coprecipitation method, Fe3O4 with smaller particle size and better crystallinity grew on the surface of halloysite nanotubes (HNTs) by using the sonochemical strategy, leading to displaying the higher catalytic activity toward the degradation of methylene blue (MB, improved by ~2.5 times). In parallel, more •OH and •O2- were produced after the ultrasound was further introduced to the routine Fenton-like catalysis system, thus highly accelerating the removal of MB (improved by ~50%). Besides, benefiting from the robust chemical integration of Fe3O4 and HNTs, Fe3O4@HNTs-S had a lower iron ion leaching in use, showing superior catalytic stability. The speed, simplicity, and generality, together with the enhanced mass transfer rate, make the use of ultrasound an enabling methodology to improve the heterogeneous Fenton catalysis.

The suitability and mechanism of polyaluminum-titanium chloride composite coagulant (PATC) for polystyrene microplastic removal: Structural characterization and theoretical calculation.

Microplastics (MPs) particles bring potential threats to the aqueous environment, and the coexistence of natural organic matter (NOM) enhances their toxicity. Coagulation is an efficient method for particle removal and exploring the binding sites and modes of the coagulant hydrolysates with MPs in the presence of NOM is essential to understand the coagulation mechanism. In this study, a novel polymerized polyaluminum-titanium chloride composite coagulant (PATC) was prepared and used to remove polystyrene (PS). It was found that PATC could compress or even destroy the surface layer of the negatively charged PS. In comparison to PAC and PTC, PATC was more efficient in decreasing the energy barrier of the PS particles and increasing their aggregation rate over a wider pH range. The results of the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) calculation revealed that the interaction between the hydrolysates of PATC and PS was mainly polar interaction (VAB), such as hydrogen bonding. The peak intensity and peak shift in Fourier-transformed infrared (FTIR) and X-ray photoelectron spectra (XPS) were analyzed to further explore the interaction between the hydrolysates of PATC and PS. It was found that hydrogen bonding existed between the -OH group of PATC and the aliphatic C-H and C=O groups of PS. And the main interaction between HA and PS was the π-π* conjugation and hydrogen bonding between the -COOH, -OH, and C=O groups of HA and the C=O and aliphatic C-H groups of PS. Therefore, in the HA@PS system, the active sites of HA (e.g. -COOH and -OH) and PS (e.g., C=O and aliphatic C-H) binding with the coagulants were occupied, which accordingly led to the dramatic decline in the removal efficiency of both HA and PS. In actual lake water treatment, although the removal efficiency of PS was significantly poor, PATC performed better for PS removal than PAC and PTC. Besides, the effluent pH was maintained at 6.81±0.08, which met the requirements of the subsequent water treatment process. This study provides systematic knowledge for understanding the interaction between PS, NOM, and coagulant hydrolysates, and further confirms the application potential of PATC for MPs removal.

Revealing the Generation of High-Valent Cobalt Species and Chlorine Dioxide in the Co3O4-Activated Chlorite Process: Insight into the Proton Enhancement Effect.

A Co3O4-activated chlorite (Co3O4/chlorite) process was developed to enable the simultaneous generation of high-valent cobalt species [Co(IV)] and ClO2 for efficient oxidation of organic contaminants. The formation of Co(IV) in the Co3O4/chlorite process was demonstrated through phenylmethyl sulfoxide (PMSO) probe and 18O-isotope-labeling tests. Both experiments and theoretical calculations revealed that chlorite activation involved oxygen atom transfer (OAT) during Co(IV) formation and proton-coupled electron transfer (PCET) in the Co(IV)-mediated ClO2 generation. Protons not only promoted the generation of Co(IV) and ClO2 by lowering the energy barrier but also strengthened the resistance of the Co3O4/chlorite process to coexisting anions, which we termed a proton enhancement effect. Although both Co(IV) and ClO2 exhibited direct oxidation of contaminants, their contributions varied with pH changes. When pH increased from 3 to 5, the deprotonation of contaminants facilitated the electrophilic attack of ClO2, while as pH increased from 5 to 8, Co(IV) gradually became the main contributor to contaminant degradation owing to its higher stability than ClO2. Moreover, ClO2- was transformed into nontoxic Cl- rather than ClO3- after the reaction, thus greatly reducing possible environmental risks. This work described a Co(IV)-involved chlorite activation process for efficient removal of organic contaminants, and a proton enhancement mechanism was revealed.

Pilot-scale advanced treatment of actual high-salt textile wastewater by a UV/O3 pressurization process: Evaluation of removal kinetics and reverse osmosis desalination process.

Advanced oxidation processes (AOPs) such as ozonation and Fenton processes are widely used in the treatment of high-salt wastewater. The UV/O3 pressurization process was designed and applied at the pilot-scale for treatment of actual high-salt textile wastewater. The UV/O3 pressurization process achieved the highest decolorization (85 %) and chemical oxygen demand (CODCr, 43.2 %) removal efficiency at an O3 dosage of 200 g·t-1 and a pressure of 0.2 MPa. Compared to ordinary ozonation, the UV/O3 pressurization process improved the solubility and gas-liquid mass transfer efficiency of O3 in wastewater and generated a large number of O3 microbubbles. Hydroxyl radical (·OH), superoxide radicals (O2·-) and single oxygen (1O2) all played a significant role on the removal of pollutants in wastewater during the UV/O3 pressurization process. The reverse osmosis (RO) process was used to evaluate the effect of UV/O3 pressurization and Fenton pre-oxidation processes on the desalination process as the last process in treating high-salt organic wastewater. The pre-oxidation processes improved the initial RO water flux. Compared with the Fenton process, the UV/O3 pressurization process had less membrane fouling (thin fouling layer vs thick fouling layer), and final water flux (59.4 LMH) was higher than that of Fenton process (34.9 LHM). The total dissolved solids (TDS), Cl- and SO42- of the effluent from UV/O3 pressurization process (37.2, 7.6 and 3.0 mg·L-1) were better than that of Fenton process (65.7, 13.9 and 7.1 mg·L-1). Therefore, the UV/O3 pressurization process without secondary pollution is more suitable for the advanced treatment of high-salt organic wastewater than the Fenton process.

Versatile crosslinking synthesis of an EDTA-modified UiO-66-NH2/cotton fabric composite for simultaneous capture of heavy metals and dyes and efficient degradation of organophosphate.

The metal-organic frameworks/cotton fabric composites (MOFs/CFCs) have emerged as a new type of prospective materials for environmental cleanup, due to their convenient recyclability and high removal efficiency towards hazardous pollutants. However, their practical applications are limited by complicated synthetic conditions, insufficient interface bonding and poor adsorption capacity. Herein, for the first time, a robust ethylenediaminetetraacetic acid (EDTA)-functionalized MOFs/CFC is prepared based on UiO-66-NH2 crystals by using EDTA dianhydride as the cross-linking agent, and applied for simultaneous removal of heavy metals and dyes, as well as degradation of chemical warfare agents. The as-prepared EDTA-UiO-66-NH2/CFC shows extraordinary monocomponent adsorption performance with maximum adsorption capacity of 158.7, 126.2, 131.5, 117.4 and 104.5 mg/g for Cd(II), Cu(II), methylene blue, crystal violet and safranin O, respectively. Interestingly, in metal-dyes binary system, the uptake of Cu(II) by EDTA-UiO-66-NH2/CFC increases significantly when co-existing high concentration of dyes. The results indicate that the synergistic and simultaneous removal of both dyes and metal from complex systems can be realized by EDTA-UiO-66-NH2/CFC via multiple mechanisms. The EDTA-UiO-66-NH2/CFC also exhibits an outstanding catalytic performance for degrading dimethyl 4-nitrophenylphosphate. Besides, it can be reused for several times without obvious decrease of its adsorption and catalysis efficiencies. More impressively, the cross-linking reaction approach can not only anchor UiO-66-NH2 crystals firmly onto cotton fabric, but also facilitate in-situ formation of abundant adsorption sties on the adsorbent surface. Therefore, this work offers a simple and versatile synthetic strategy to develop high-performance environmental material for multiple pollutants remediation.

Super-amphiphilic graphene promotes peroxymonosulfate-based emulsion catalysis for efficient oil purification.

Oil fractions containing highly toxic and hazardous organic contaminants can not only cause severe environmental disasters, but also an undesired waste of resources. Given the exceptional performance of persulfates in the removal of persistent and refractory organic pollutants from aqueous media, herein, a peroxymonosulfate-based Pickering emulsion catalytic (PPEC) system was constructed for the hazardous oil purification, using super-amphiphilic graphene as a solid emulsifier and a heterogeneous catalyst simultaneously. Combined detailed instrumental analysis with theoretical calculations, we find that the incorporation of pyridinic N and its oxide significantly facilitated the formation of super-amphiphilic graphene and successfully induced the formation of Pickering emulsion. In addition to stabilizing the PPEC system, super-amphiphilic graphene can also achieve efficient removal of Sudan III (simulated lipophilic organic pollutant) by activating peroxymonosulfate (PMS) to generate •O2- and 1O2. Results showed that 80 mg/L Sudan III (20 mL) could be fully degraded within 30 min using 10 mL 5 mmol PMS. More significantly, our proposed PPEC system also exhibited excellent property in the purification of practical waste engine oil. This study provides new insights into the purification and recovery of waste oil.

One-step synthesis of Enteromorpha graphene aerogel modified by hydrophilic polyethylene glycol achieving high evaporation efficiency and pollutant tolerance.

Photothermal evaporation using solar energy is a sustainable way to produce fresh water from seawater. Aiming to explore functional materials as a solar-energized evaporator with enhanced evaporation rate and pollutant tolerance, this study was to synthesize a self-floating composite graphene aerogel (GA) doped with Enteromorpha and modified polyethylene glycol (PEG), named as PEGA using solar energy for desalination. Physio-chemical properties and evaporative mechanism of PEGA were experimentally investigated and analyzed with respect to molecular weight, PEG dosage, and ratio of Enteromorpha and graphene oxide. Experimental data revealed that the modification of PEG improved hydrophilic functional ability of PEGA, resulting in increasing the evaporation rate and photothermal conversion efficiency up to 2.55 kg/(m2·h) and 105.71 %, respectively. The ion removal rate of seawater exceeds 99.99 % via the PEGA conducted solar evaporation. Furthermore, PEGA possessed an excellent property of salinity emulsion pollution tolerance. Particularly, the evaporation rate of the PEG-modified biomass-based aerogel was 2.84 kg/(m2·h) in a 15 wt% NaCl solution (1 sun, 6 h) and 2.50 kg/(m2·h) at 1 h. The formation of hydrogen bonds between -OH of PEG and water molecules assist to conduct water along the graphene matrix to improve water evaporation. The cost of the graphene aerogel modified by Enteromorpha was reduced by 38.88 % less than the original graphene aerogel. The results from this study will greatly promote the application of graphene aerogel for desalination via solar evaporation.

Visible-Light Photocatalytic Chlorite Activation Mediated by Oxygen Vacancy Abundant Nd-Doped BiVO4 for Efficient Chlorine Dioxide Generation and Pollutant Degradation.

Visible-light photocatalytic chlorite activation has emerged as an efficient oxidation process for micropollutant elimination. However, the in-depth mechanism of chlorite activation is not understood. In this study, using neodymium-doped bismuth vanadate (NdxBi1-xVO4-δ) as a model catalyst, we describe the oxygen vacancy (OV)-mediated chlorite activation process for efficient ClO2 generation and cephalexin (CPX) degradation. DFT calculations and in situ DRIFTS suggest that the OV-introduced surface -OH serves as the Brønsted acidic center for chlorite adsorption. The OV-mediated chlorite activation involves multistep reactions that surface hydroxylation and proton transfer from the surface -OH to chlorite, forming metastable chlorous acid (HClO2) and further disproportionating to ClO2. As compared with vis-photocatalysis, the vis-photocatalysis coupled with chlorite activation (vis/chlorite) technique exhibits superior performance in antibiotic degradation and achieves efficient microorganism inactivation. This work uncovers the role of OVs on chlorite activation and provides a rational strategy for designing visible-light-driven oxidation techniques in water and wastewater treatment.

Highly efficient Al-Ti gel as a coagulant for surface water treatment: Insights into the hydrolysate transformation and coagulation mechanism.

In view of the insufficient coagulation efficiency of traditional inorganic coagulants, a series of Al-Ti gels with different Ti/triethanolamine (TEA), Ti/H2O, and Ti/Al molar ratios were prepared by sol-gel process in this study. Fourier transform infrared (FTIR) spectra of the Al-Ti gels preliminarily confirmed the interaction between Al and Ti by detecting the appearance of the Al-O-Ti bond. The peak shift of the chemical bonds in X-ray photoelectron spectra (XPS) and the transformation of the hydrolysate species in the Al-Ti gels were analyzed to further explore the interaction mechanism between Al and Ti. It was found that moderate TEA could inhibit the hydrolysis of Ti precursors by taking up the coordination sites of H2O to form a CO-Ti bond. Density functional theory (DFT) calculation results showed that Ti could be incorporated into the framework of aluminum hydrolysates to form an Al-O-Ti bond, and [Al2Ti2(OH)x(TEA)y(H2O)8-x-y]14-x was the most possible copolymerization hydrolysate. Based on the above research results, the most efficient Al-Ti gel was selected and applied to the actual lake water treatment. The highest UV254 removal efficiency with the addition of Al-Ti gel was > 60%, nearly 25% higher than that of Ti gel. The hydrolysates of Al-Ti gel, such as TiO(OH)2(am), Al(OH)3(am), and [Al2Ti2(OH)x(TEA)y(H2O)8-x-y]14-x, could remove organic matters through the incorporation of charge neutralization, adsorption, complexation, and sweeping effects. These results provide a new idea for studying the interaction mechanism between Al and Ti in composite coagulants, and have theoretical guiding significance to actual water treatment.

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co-N4-C Intensified Radical and Nonradical Pathways.

Single-atom catalysts (SACs)-based peroxymonosulfate (PMS) systems are highly selective to the type of organic pollutants while the mechanisms remain ambiguous. In this work, we carried out experimental and theoretical investigations to reveal the origins of selectivity of radical and nonradical pathways in a designated Co-N4-C/PMS system. Two typical pollutants [bisphenol A (BPA) and metronidazole (MNZ)] with different molecular structures were employed for comparison. We found that radical oxidation (SO4•- and HO•) and nonradical electron-transfer pathway (ETP) co-existed in the Co-N4-C/PMS system. Pollutants (e.g., MNZ) with a high redox potential were degraded primarily by free radicals rather than ETP, while the oxidization of low-redox pollutants (e.g., BPA) was dominated by ETP at the surface region of Co-N4-C which overwhelmed the contributions of radicals in the homogeneous phase. Intriguingly, the contributions of radical and nonradical pathways could be manipulated by the PMS loading, which simultaneously increased the radical population and elevated the oxidation potential of Co-N4-C-PMS* complexes in ETP. Findings from this work will unravel the mysterious selective behavior of the SACs/PMS systems in the oxidation of different micropollutants.

Selective capture of Pd(II) from aqueous media by ion-imprinted dendritic mesoporous silica nanoparticles and re-utilization of the spent adsorbent for Suzuki reaction in water.

The development of highly efficient adsorptive material for the selective capture of Pd(II), and re-utilization of spent Pd(II)-loaded adsorbent as an efficient catalyst for organic synthesis are of great significance, but challenging. Particularly, the heterogeneous palladium-catalyzed Suzuki reaction in aqueous media is much more challenging than that of homogeneous. Herein, several novel Pd(II) ion-imprinted polymers (PIIPs) based on dendritic fibrous silica particles are constructed by surface ion imprinting technology (SIIT), using Schiff base and pyridine groups functionalized organosilicon as functional monomer. The PIIP-3 prepared by 3 g of functional monomer exhibits the best adsorption performance, and shows ultrafast (10 min) and selective capture of Pd(II) with high uptake capacity (382.5 mg/g). Moreover, the waste Pd(II) loaded PIIP-3 (PIIP-3-Pd) can serve as a catalyst towards the Suzuki reaction in water, affording 94.2 % yield of the desired product. Interestingly, the PIIP-3-Pd can be reused 12 times without an appreciable decrease in catalytic activity, which is probably due to the imprinted cavity and specific recognition site of PIIP-3 can match and recapture Pd active species in a complex catalytic environment. Thus, this work demonstrates huge potentials of SIIT to enhance the selectivity of adsorption process and increase the lifetime of catalysts.

Coagulation behavior of polyaluminum-titanium chloride composite coagulant with humic acid: A mechanism analysis.

The hydrolysate species of metal-based coagulants and the binding sites of humic acid (HA) are highly dependent on the pH conditions. Exploring the binding sites and modes between coagulant hydrolysates and HA molecules is critical to understanding the coagulation mechanism. In this paper, the binding behavior between HA molecules and the hydrolysates of a polyaluminum-titanium chloride composite coagulant (PATC) was investigated under different pH conditions by semi-quantitative FTIR and XPS. It was found that oligomeric and mesopolymeric hydrolysates were the dominant species under acid conditions, which could complex with the hydroxyl and carboxyl groups of HA by forming COAl/Ti coordinate bonds. However, large amounts of H+ could compete with Al3+ and weaken the removal efficiency of HA. With the increase of pH, the hydrolysis process of the PATC and the deprotonation of HA were simultaneously underway. Under weakly acid conditions, the complexation of the aluminum hydrolysates with carboxyl groups was improved due to the gradually diminishing competition of H+ and the enhanced charge neutralization of the further polymerized hydrolysates. Consequently, the maximum UV254 removal by adding PATC was observed at pH 6. Under alkaline conditions, the sweeping effect of amorphous hydroxide dominated the HA removals, which was accompanied by the surface complexation of Al/Ti nuclear with carboxyl groups as well as the hydrogen bonds between hydroxyl and hydroxide. This study provides a new clue for the interaction mechanisms between the hydrolysates of composite coagulants and the dominant functional groups of HA at various pH conditions.

Fabrication of superhydrophobic Enteromorpha-derived carbon aerogels via NH4H2PO4 modification for multi-behavioral oil/water separation.

Hydrophobic and oleophilic biomass-based block materials are considered to be highly promising candidates used for oil/water separation. However, the crucial hydrophobic modification process often involves various toxic and hazardous organic substances or requires high energy inputs. Inspired by the flame retardant principle of phosphorus-containing flame retardants, herein, an Enteromorpha-derived carbon (ADP-EP) aerogel with a water contact angle of 144.2° was prepared by successive freeze-shaping, freeze-drying and low-temperature carbonization treatment (300 °C), using NH4H2PO4 (ADP) as a modifier. The results demonstrated that the introduction of NH4H2PO4 could largely facilitate the removal of oxygenated groups from the pristine EP aerogels and enhance their surface roughness, thereby achieving surface hydrophobic modification. Featuring intrinsic low density, rich porosity and strong lipophilicity, the as-fabricated ADP-EP aerogels exhibited exceptional performance in both oil spill adsorption (~140 g/g) and water-in-oil emulsion separation. Moreover, the good reusability for oil uptake was also realized thanks to its robust mechanical compressibility and thermal stability. This work provides a facile, economical and eco-friendly route to obtain a desirable hydrophobic/oleophilic surface.