Enhanced electrolytic production of hypochlorous acid using phosphorus-modified carbon felt electrodes: A study in disinfectant synthesis.

In this study, we fabricated phosphorus-modified carbon felt electrode anodes for chloride oxidation in saline solutions to produce HClO via electrocatalysis, forming a compound fungicide saline applicable for debridement and disinfection. A low-cost phosphorus-modified carbon felt electrode (P@CF) with high chlorine evolution reaction activity was synthesized to address the reduced efficiency of CER and the solution's pH increase. Heteroatoms P and O were introduced into the carbon felt by phosphoric acid activation followed by heat treatment. The maximum active chlorine concentration on the P@CF electrode could reach 616.8 mg/L in 60 min under the optimal synthesis conditions of a phosphoric acid mass fraction of 30%, a phosphoric acid impregnation time of 3 h, and a heat treatment temperature of 300 °C. The active chlorine concentration was 1.8 times higher on the P@CF electrode compared to the original carbon felt electrode. The optimal reaction conditions for the generation of active chlorine were as follows: salt concentration of 9 g/L, voltage of 7 V, and electrode spacing of 2 cm as verified by response surfaces. This electrolysis reaction follows one-stage reaction kinetics. Subsequently, the disinfection efficacy of the produced disinfectants was examined. The prepared disinfectant was also compared to a commercially available hypochlorite disinfectant, showing similar disinfection effects on E. coli for both.

Mott Schottky CoSx-MoOx@NF heterojunctions electrode for H2 production and urea-rich wastewater purification.

The sluggish kinetics of oxygen evolution reaction (OER) is the bottleneck of alkaline water electrolysis. The urea oxidation reaction (UOR) with much faster kinetics was to replace OER. To further promote UOR, a heterojunction structure assembled of CoSx and MoOx was established, and then its superior catalytic activity was predicted by DFT calculation. After that, an ultra-thin CoSx-MoOx@nickel foam (CoSx-MoOx@NF) electrode with a Mott-Schottky structure was prepared via a facile hydrothermal method, followed by a low-temperature vulcanization. Results highlighted CoSx-MoOx@NF electrode presented a superior performance toward UOR, OER, and H2 evolution reaction (HER). Notably, it exhibited excellent electrocatalytic performance for OER (1.32 V vs. RHE, 10 mA cm-2), UOR (1.305 V vs. RHE, 10 mA cm-2), and urea-assisted overall water splitting with a low voltage (1.38 V, 10 mA cm-2) when CoSx-MoOx@NF electrode served as both anode and cathode. It is promising to use CoSx-MoOx@NF in an electrochemical system integrated with H2 generation and urea-rich wastewater purification.

Enhanced visible light photo-Fenton catalysis by lanthanum-doping BiFeO3 for norfloxacin degradation.

Efficient photo-Fenton removal of antibiotic effluent is a widely followed and significant attempt to deal with the growing environmental pollution. In this study, BiFeO3 and lanthanum doped BiFeO3 catalysts were synthesized via one-step hydrothermal method as hydrogen peroxide activator for mineralization of norfloxacin (NOR). Various characterization measurements were used to verify La was successfully doped into the lattice of perovskite and investigated the effect of La doping molar ratio on BiFeO3 through the characterization of the morphology and physicochemical properties. The degradation experiment and reaction rate constants showed that the La-doped BiFeO3 particle exhibited superior photo-Fenton catalytic performance to undoped BiFeO3. Especially, the degradation efficiency of 15% La-doped BiFeO3 could reach up to 84.94%. And the first order kinetic constant of optimized conditions was 0.01638 min-1, which was about 6.9 times than that of undoped BiFeO3.The influence of pH, oxidizer content and catalyst dosage in photo-Fenton reaction were investigated detailedly. Besides, the synthetic catalyst possessed favorable stability and reusability with little metal leaching after many cycles of use. Radical scavenger experiments and electron spin resonance tests were carried out to conclude that the ·OH and holes were regarded as the dominate active species in the catalytic process. The narrow band gap and excellent electron transfer efficiency were the key factors for La-doped BiFeO3 to have high catalytic efficiency in the photo-Fenton system. Current works demonstrated the great promise of La-doped BiFeO3 in the elimination of antibiotic organics.

Degradation mechanism of BPA under VUV irradiation: efficiency contribution and DFT calculations.

Bisphenol A (BPA) is regarded as a hazardous pollutant that exists widely in aquatic environments, posing a severe threat to human health. In this study, a vacuum ultraviolet (VUV) lamp emitting a hybrid of 254 nm and 185 nm light was used to degrade BPA. Results indicated that photolysis via 254 nm wavelength accounted for 24.93% for BPA decay, while indirect oxidation was responsible for 52.27% of decay. Results confirmed that the degradation of BPA under VUV illumination mainly occurred via photo-excited degradation and ·OH electrophilic addition reactions based on average local ionization energy (ALIE) calculation and density functional theory (DFT) calculations. Therefore, only light with a wavelength of 254 nm was able to induce the first three excited states of BPA, forming the electron transition type of n → π* from O atom to a single benzene ring and π → π* in the single benzene ring. Indirect oxidation by ·OH occurred as it preferentially attacked the C6 atom in BPA ring A. Moreover, the energy required for photo-excited degradation was about twofold than that of ·OH electrophilic addition reactions.

A mechanism in boosting H2 generation: nanotip-enhanced local temperature and electric field with the boundary layer.

The sluggish kinetics of oxygen evolution reaction (OER) is the bottleneck of water splitting. Hence, we designed a nanowire Co3O4@nickel foam (Co3O4-NW@NF) electrode to boost OER utilizing the locally enhanced interfacial Joule heating and electric field within the diffusion layer. Results show that the morphology of Co3O4@NF could be regulated in nanowires, nanosheets, and nanoclusters by controlling the doping amount of fluoride ions (F-). F- served as a complexing agent to regulate the rate of crystal nucleus, and then morphologies could be tuned. compared to others, nanowire structures have a much lower potential (298 mV vs. RHE, 10 mA cm-2) and Tafel slope (48.11 mV dec-1). This better electrochemical performance was confirmed by the Density Functional Theory (DFT) that the (311) facet with oxygen vacancies of Co3O4 has a low onset potential (0.36 V) for the kinetic rate of OER. A much better mass transfer by the nanowire-enhanced interfacial Joule heating and electric field within the diffusion layer also accounted for superior OER activity, confirmed by COMSOL simulation. In a word, the design of the nanotip structure offers a novel way to boost the OER rate by enhancing electron transfer and mass transport simultaneously.

Occurrence of Iodophenols in Aquatic Environments and the Deiodination of Organic Iodine with Ferrate(VI).

Toxic and odorous iodophenols are commonly identified as disinfection by-products (DBPs) in drinking water. Herein, ng/L levels of iodophenols were identified in river water, wastewater treatment plant effluent, and medical wastewater, with the simultaneous identification of µg/L to mg/L levels of iodide (I-) and total organic iodine (TOI). Oxidation experiment suggested that the I-, TOI, and iodophenols could be oxidized by ferrate [Fe(VI)], and more than 97% of TOI had been transformed into stable and nontoxic IO3-. Fe(VI) initially cleaved the C-I bond of iodophenols and led to the deiodination of iodophenols. The resulted I- was swiftly oxidized into HOI and IO3-, with the intermediate phenolic products be further oxidized into lower molecular weight products. The Gibbs free energy change (ΔG) of the overall reaction was negative, indicating that the deiodination of iodophenols by Fe(VI) was spontaneous. In the disinfection of iodine-containing river water, ng/L levels of iodophenols and chloro-iodophenols formed in the reaction with NaClO/NH2Cl, while Fe(VI) preoxidation was effective for inhibiting the formation of iodinated DBPs. Fe(VI) exhibited multiple functions for oxidizing organic iodine, abating their acute toxicity/cytotoxicity and controlling the formation of iodinated DBPs for the treatment of iodide/organic iodine-containing waters.

Synthesis of polydopamine modified MgAl-LDH for high efficient Cr(VI) removal from wastewater.

A highly efficient absorbent was developed in this study by modifying polydopamine film on Mg-Al layered double hydroxide (PDA/MgAl-LDH) to remove Cr(VI) from wastewater. The characterization results showed that the polydopamine film was successfully coated on the MgAl-LDH surface. The preparation ratio, pH, and adsorbent dosage influencing absorption by PDA/MgAl-LDH were systematically investigated. The absorption capacity of Cr(VI) by PDA/MgAl-LDH was 87 mg/g. The equilibrium adsorption isotherm of PDA/MgAl-LDH was in good agreement with that of the Langmuir model. Therefore, the pseudo-second-order kinetic model is suitable for describing adsorption kinetics. The interaction between PDA and Cr(VI) and Cr(III) was investigated using density generalized function theory (DFT), which demonstrated that the PDA amino group could provide electrons for Cr(VI) reduction. Hydrogen and covalent bonding were dominant during the chemisorption process of PDA absorbing Cr(VI), the nitrogen of 5,6-dihydroxyindole was the primary active site for absorbing Cr(III), and electrostatic attraction was mainly responsible for Cr(III) absorption. Therefore, PDA/MgAl-LDH has the potential to adsorb and remove Cr(VI) from wastewater.

Synergistic optimization of syngas quality and heavy metal immobilization during continuous microwave pyrolysis of sludge: Competitive relationships, reaction mechanisms, and energy efficiency assessment.

To realize the efficient resource utilization of sewage sludge, this work explored the competitive relationship and reaction mechanisms between syngas quality optimization and heavy metals (HMs) immobilization. The results showed that continuous microwave pyrolysis (CMP) technology with an instantaneous temperature increase could shorten the pyrolysis time, and the biogas yield and syngas concentration reached 51.68 wt% and 83.6 vol%, respectively. Although a higher pyrolysis (750 °C) temperature could optimize the syngas quality, the HMs immobilization efficiency was reduced due to the deep pyrolysis of the biochar. The moderate pyrolysis temperature (650 °C) facilitated the rapid formation of biochar with abundant surface functional groups and pore structure, thus enhancing HMs immobilization. Furthermore, the HMs could also form more stable crystalline compounds with inorganic components (SiO2, Al2O3, inorganic sulfur). By optimizing the process parameters, the risk factor of HMs in the sludge decreased from 117.36 to 62.5 while obtaining high-quality syngas. The energy utilization efficiency of microwave pyrolysis also increased significantly from 11.20% to 82.01%. This work provided new insight into the efficient resource utilization and environmentally friendly treatment of sludge, and demonstrated that CMP technology has significant potential for future industrial applications as an alternative to traditional pyrolysis.

Water-based Fe3O4 magnetic fluid-coated Aspergillus niger spores for treating liquid contaminated with Cr(VI).

The use of magnetic biosorbents for the remediation of heavy metals has attracted increasing attention due to their ease of separation and reusability. We developed a method for preparing superparamagnetic biosorbent materials using water-based magnetic fluids. Water-based magnetic fluid-spores (WMFSs) were obtained by combining water-based magnetic fluid (WMF) with Aspergillus niger spores at ratios of 0.6:1 (WMFS1), 0.8:1 (WMFS2), 1:1 (WMFS3), 1.2:1 (WMFS4), and 1.4:1 (WMFS5). A magnetic composite material was prepared from magnetic nanoparticles and spores in a ratio of 1:1 as a control. The adsorption efficiency and separation effect of WMFS3 were significantly better than those of the magnetic composite material. The morphology and structure of WMFS3 were characterized by performing transmission electron microscopy. The results showed that Fe3O4 magnetic particles were uniformly coated on the spore surface. The superparamagnetism of WMFS3 was tested using a vibrating sample magnetometer. At pH 2.0, the maximum adsorption capacity of WMFS3 for Cr(VI) was 105 mg/g; in the pH range of 2.0-3.0, the adsorption equilibrium time of WMFS3 was 60 min. Thus, the adsorption process conformed to the pseudo-second-order kinetic model and Freundlich isotherm. Thermodynamic studies showed that the process was spontaneous and endothermic. The adsorption mechanisms of WMF3 for Cr(VI) included electrostatic, reduction, and complexation adsorption. This biosorbent material showed excellent adsorption performance for Cr(VI) and is promising for wastewater resource applications.

Mechanistic insights into soil heavy metals desorption by biodegradable polyelectrolyte under electric field.

In this study, we firstly used alginate to enhance an electrokinetic technology to remediate soil contaminated with divalent heavy metals (Pb2+, Cu2+, Zn2+). The mechanisms of alginate-associated migration of metal ions in electric field were confirmed. Alginate resulted in a high electrical current during electrokinetic process, and soil conductivity also increased after remediation. Obvious changes in both electroosmotic flow and soil pH were observed. Moreover, these factors were affected by increasing alginate dosage. The highest Cu (95.82%) and Zn (97.33%) removal efficiencies were obtained by introducing 1 wt% alginate. Alginate can desorb Cu2+ and Zn2+ ions from soil by forming unstable gels, which could be dissociated through electrolysis. However, Pb2+ ions did not easily migrate out of the contaminated soil. The density functional theory (DFT) calculations show Pb2+ ions could form a more stable coordination sphere in metal complexes than Cu2+ and Zn2+ ions. The metal removal efficiency was decreased by increasing alginate dosage at a high level. More alginate could provide more carboxyl ligands for divalent metal ions to stabilize gels, which were difficult to dissociate by electrolysis. In summary, the results indicate it is potential for introducing alginate into an electrokinetic system to remediate Cu- and Zn- contaminated soil.

Effects of oxygen vacancy defect on microwave pyrolysis of biomass to produce high-quality syngas and bio-oil: Microwave absorption and in-situ catalytic.

This paper proposed to use ferric oxide (Fe2O3) and ferroferric oxide (Fe3O4) as catalysts with both microwave absorption and catalytic properties. Carbon dioxide (CO2) was introduced as the reaction atmosphere to further improve the quality of biofuel produced by microwave pyrolysis of food waste (FW). The results showed the bio-gas yield and the syngas concentration (H2 + CO) increased to 70.34 wt% and 61.50 mol%, respectively, using Fe3O4 as the catalyst. The content of aliphatic hydrocarbons in bio-oil produced with the catalyst Fe2O3 increased to 67.48% and the heating value reached 30.45 MJ/kg. Compared with Fe2O3 catalyst, Fe3O4 exhibited better microwave absorption properties and catalytic properties. Transmission electron microscopy (TEM) and Electron paramagnetic resonance (EPR) characterizations confirmed that the crystal surface of Fe3O4 formed more oxygen vacancy defects and unpaired electrons. Additionally, according to the X-ray photoelectron spectroscopy (XPS) analysis, the content of lattice oxygen in Fe3O4 was 14.11%, a value that was much lower than Fe2O3 (38.54%). The oxygen vacancy defects not only improved the efficient utilization of microwave energy but also provided the reactive sites for the reaction between the volatile organic compounds (VOCs) and CO2 to generate CO. This paper provides a new perspective for selecting catalysts that have both microwave absorption and catalytic properties during the microwave pyrolysis of biomass.

Enhanced electrokinetic remediation of heavy metals contaminated soil by biodegradable complexing agents.

In this study, an electrokinetic technique for remediation of Pb2+, Zn2+ and Cu2+ contaminated soil was explored using sodium alginate (SA) and chitosan (CTS) as promising biodegradable complexing agents. The highest Cu2+ (95.69%) and Zn2+ (95.05%) removal rates were obtained at a 2 wt% SA dosage, which demonstrated that SA significantly improved the Cu2+ and Zn2+ removal efficiency during electrokinetic process. The abundant functional groups of SA allowed metal ions desorption from soil via ion-exchange, complexation, and electrolysis. Pb2+ ions were difficult to remove from soil by SA due to the higher gelation affinity with Pb2+ than Cu2+ and Zn2+, despite the Pb2+ exchangeable fraction partially transforming to the reducible and oxidizable fractions. CTS could complex metal ions and migrate into the catholyte under the electric field to form crosslinked CTS gelations. Consequently, this study proved the suitability of biodegradable complexing agents for treating soil contaminated with heavy metals using electrokinetic remediation.

Freezing/thawing pretreatment of dormant Aspergillus niger spores to increase the Cr(vi) adsorption capacity: process and mechanism.

Hexavalent chromium is a widespread pollutant that threatens ecological and human health. However, its removal from the environment is limited by the high cost and energy consumption rate of current technologies. In this study, the Cr(vi) biosorption mechanism of Aspergillus niger spores pretreated by freezing/thawing was studied by batch experiments and surface chemistry analyses. The results indicated that pretreatment enhanced the spores' Cr(vi) removal efficiency. The cell surface, internal functional groups, and morphology of the freezing/thawing-pretreated spores (FTPS) before and after Cr(vi) loading were characterized by advanced spectroscopy techniques such as SEM-EDAX, XPS, FTIR, and FETEM analyses. The SEM and BET data showed that the surface of FTPS was rougher than that of untreated spores. The XPS data showed that FTPS bio-transformed Cr(vi) into Cr(iii). The intracellular localization of chromium was visualized by FETEM, and both surface and intracellular structures removed Cr(vi) following pseudo-second-order biosorption kinetics. The biosorption dynamics of Cr(vi) fit the Langmuir isotherm model describing a monolayer. These results suggest that freezing/thawing pretreatment of A. niger spores could lead to the development of a novel, efficient biomaterial for the removal of Cr(vi).

Remediation of heavy metal-contaminated soils by electrokinetic technology: Mechanisms and applicability.

Electrokinetic remediation is a widely admitted technology forrectifying heavy metal-contaminated soil. Various technologies have been effectively developed to improve the metal removal efficiency of contaminated soil by electrochemical treatment alone or in combination with other remediation technologies. The working components for electrokinetic system, such as supplying power for electric fields, installing electrodes to generate electric fields, introducing electrolytes and other potential materials as a reactive medium are crucial. This review focuses on the specific functions of the working components in electrokinetic systems and their effects on the efficiency of heavy metal removal using electrochemical process. The advancements in working components were systematically summarized, such as power for electric fields, electrodes, electrolytes and ion exchange membrane, which have various impacts on the effectiveness of electrokinetic remediation. Additionally, this study introduces the application of dominating technologies at present coupled with electrokinetics. Overall, a judicious design and reasonable operation in the application of electrokinetic-coupled remediation should be implemented to enhance the removal process of heavy metals from contaminated soil.

Effects of Process Parameters on Sulfur Migration and H2S Generation during Supercritical Water Gasification of Sludge.

The generation of sulfur-containing pollution products affects the quality of biofuels obtained from the supercritical water gasification (SCWG) of sludge. This study investigates the effects of the gasification temperature, moisture content, and reaction atmosphere on the evolution of sulfur-containing compounds. The results showed that temperature was the key parameter causing the migration of sulfur from sludge to biogas and liquid products. The sludge decomposition reaction was dominated by ionic reactions at 360 °C, while the decomposition of organic matter was converted to free radical reactions as the temperature increased from 380 °C to 440 °C. The mercaptan and thioether contents of the bio-oil decreased to 0.3% at 440 °C. Correspondingly, the concentration of H2S increased from 6.7 ppm to 38.0 ppm. The decomposition of organic sulfur with an unstable structure (S-H bond and S-C bond) was the main cause of the increase in the content of H2S. Additionally, the solubility and oxidation properties of supercritical water were extremely strong. Some sulfur-containing organic compounds were converted into SO42- via hydrolysis and oxidation reactions, forming sulfate crystals with heavy metals in the bio-char, which aided in achieving the synergistic immobilization of sulfur and heavy metals.

High adsorption of fulvic acid by amino modified styrene-type macroporous resin and evaluation of its mechanism.

Amino-modified HPD 100 styrene-type macroporous resin (M-HPD 100) was successfully synthesized by the atom transfer radical polymerization process. The modified resin showed excellent performance in the degradation of fulvic acid (FA). FA removal was pH, temperature and flow velocity dependent. The adsorption data could be well interpreted by the Freundlich model. The maximum adsorption efficiency for M-HPD 100 obtained from the Freundlich model was 92.5% at 298 K, which was 37% higher than that of unmodified styrene-type macroporous resin (HPD 100). The adsorption process could be described by the pseudo-second-order kinetic model. The intra-particle diffusion and film diffusion were believed to be the rate-limiting process for both adsorbents. Thermodynamic parameters suggested it was a multi-layer physicochemical process. More importantly, although limited improvements were seen, the results of this study suggested that the surface of resin can be modified with functional groups to enhance the adsorption of FA from aqueous solution and may give other advantages; for example, despite the interference of the pore diffusion coefficient and other substances, M-HPD 100 has excellent regeneration capacity, and the adsorption and desorption efficiency was 74% and 64.28% respectively after six regenerations, which proved it has engineering application value.

Application of vacuum-ultraviolet (VUV) for phenolic homologues removal in humic acid solution: Efficiency, pathway and DFT calculation.

Vacuum-ultraviolet (VUV) photo-initiated oxidation of phenolic homologues in simulative natural water were investigated, including phenol, o-dihydroxybenzene (ODB), m-dihydroxybenzene (MDB), p-dihydroxybenzene (PDB), paranitrophenol (PNP) and o-chlorophenol (OCP). Results showed the phenolic homologues removal rate reached at least 90% in pure water, which was dependent on temperature, pH, concentration of HA, and functional group of HA. Experimental results indicated that 0.2 mg/L HA might be a critical point. Additionally, the rate constant of the six phenolic homologues reduced by 76.85%, 77.81%, 71.91%, 79.15%, and 55.69%, respectively in the MDB solution, and 79.73%, 82.80%, 95.36%, 80.38%, and 92.64%, respectively in the benzoic acid (BA) solution, compared to the rate constant in pure water. Moreover, quantum chemistry calculation indicated that the variances between phenolic compounds in removal rate were attributed to the substituent on the benzene ring. And, to some extent, the carboxy group of HA was supposed to arose the suppression for phenolic homologues removal rate. Mechanism involved phenolic homologues degradation using vacuum-ultraviolet (VUV) was summarized, where it underwent the formation of quinone structures, ring opening, short-chain organic acid, even eventually the transformation into NO3- and Cl- of PNP and OCP.

AHL-mediated quorum sensing regulates the variations of microbial community and sludge properties of aerobic granular sludge under low organic loading.

Aerobic granular sludge (AGS) is promising in wastewater treatment. However, the formation and existence of AGS under low organic loading rate (OLR) is still not fully understood due to a knowledge gap in the variations and correlations of N-acyl-homoserine lactones (AHLs), the microbial community, extracellular polymeric substances (EPS) and other physiochemical granule properties. This study comprehensively investigated the AHL-mediated quorum sensing (QS) and microbial community characters in the AGS fed with ammonium-rich wastewater under a low OLR of 0.15 kg COD (m3 d)-1. The results showed that the AGS appeared within 90 days, and the size of mature granules was over 700 µm with strong settleability and ammonium removal performance. More tightly-bound extracellular polysaccharide and tightly-bound extracelluar protein were produced in the larger AGS. C10-HSL and C12-HSL gradually became dominant in sludge, and short-chain AHLs dominated in water. EPS producers and autotrophic nitrifiers were successfully retained in the AGS under low OLR. AHL-mediated QS utilized C10-HSL, C12-HSL and 3OC6-HSL as the critical AHLs to regulate the TB-EPS in aerobic granulation, and autotrophic nitrifiers may perform interspecific communication with C10-HSL. The correlations of bacterial genera with AGS properties and AHLs were complex due to the dynamic fluctuations of microbial composition and other variable factors in the mixed-culture system. These findings confirmed the participation of AHL-mediated QS in the regulation of microbial community characters and AGS properties under low OLR, which may provide guidance for the operation of AGS systems under low OLR from a microbiological viewpoint.

Exploiting community structure, interactions and functional characteristics of fungi involved in the biodrying of storage sludge and beer lees.

In this study, the dynamic changes in fungal biodiversity, community structure, fungal associations and functional characteristics were investigated in the biodrying of storage sludge and beer lees by using high throughput sequencing, network and correlation matrix analyses, and FUNGuild database. Additionally, a hypothetical model was provided to better understand the biodrying system. The results showed that fungal diversity decreased after biodrying, while community richness increased in the mesophilic stage and decreased as biodrying progressed. Fungal communities differed in different stages of the biodrying process. Ascomycota and Basidiomycota were the dominant phyla throughout the biodrying process, while Pichia was the dominant genus in the thermophilic stage. Network and correlation matrix analyses provided useful tools for insight into the fungal interactions, allowing us to propose a conceptual model of how succession in fungal associations regulates the dynamics of biodrying systems. Biodrying treatment had a significant effect on fungal trophic modes, with most pathogenic fungi fading away over the process, illustrating that biodrying is an effective bio-treatment method to eliminate pathogenic fungi. These findings provide information that elucidates the fungal interactions and functional characteristics during the biodrying process.