A new strategy for improving the energy efficiency of electro-Fenton: Using N-doped activated carbon cathode with strong Fe(III) adsorption capacity to promote Fe(II) regeneration.

Fe(II) regeneration plays a crucial role in the electro-Fenton process, significantly influencing the rate of ·OH formation. In this study, a method is proposed to improve Fe(II) regeneration through N-doping aimed at enhancing the adsorption capacity of the activated carbon cathode for Fe(III). N-doping not only enriched the pore structure on the surface of activated carbon, providing numerous adsorption sites, but also significantly increased the adsorption energy for Fe(III). Among the types of nitrogen introduced, pyridine-N exhibited the most substantial enhancement effect, followed by pyrrole-N, while graphite-N showed a certain degree of inhibition. Furthermore, N-doping facilitated the adsorption of all forms of Fe(III) by activated carbon. The adsorption and electrosorption rates of the NAC-900 electrode for Fe(III) were 30.33% and 42.36%, respectively. Such modification markedly enhanced the Fe3+/Fe2+ cycle within the electro-Fenton system. The NAC-900 system demonstrated an impressive phenol degradation efficiency of 93.67%, alongside the lowest electricity consumption attributed to the effective "adsorption-reduction" synergy for Fe(III) on the NAC-900 electrode. Compared to the AC cathode electro-Fenton system, the degradation efficiency of the NAC-900 cathode electro-Fenton system at pH = levels ranging from 3 to 5 exceeded 90%; thus, extending the pH applicability of the electro-Fenton process. The degradation efficiency of phenol using the NAC-900 cathode electro-Fenton system in various water matrices approached 90%, indicating robust performance in real wastewater treatment scenarios. This research elucidates the impact of cathodic Fe(III) adsorption on Fe(II) regeneration within the electro-Fenton system, and clarifies the influence of different N- doping types on the cathodic adsorption of Fe(III).

Investigation of the Mechanisms of CO2/O2 Adsorption Selectivity on Carbon Materials Enhanced by Oxygen Functional Groups.

Power plant flue gas and industrial waste gas are produced in large quantities. Using these as feedstocks for CO2 electroreduction has important practical significance for the treatment of excessive CO2 emissions. However, O2 in such sources strongly inhibits the electrochemical conversion of CO2. The inhibitory effect of O2 can be mitigated by constructing CO2-enriched regions on the surface of the cathode. In this study, the reaction zone was controlled by the selective adsorption of CO2 on oxygen-functionalized carbon materials. The results of quantum chemical simulations showed that CO2 adsorption was mainly influenced by electrostatic interactions, whereas O2 adsorption was completely regulated by dispersion interactions. This distinction indicated that introducing polar oxygen functional groups at the edge of the carbon plane can significantly enhance the selectivity for CO2/O2 adsorption. The difference in the adsorption energy between CO2 and O2 increased most noticeably after the carboxyl groups were introduced. The results of the adsorption experiments showed that oxygen-functionalization increased the CO2/O2 selectivity of the carbon material under an atmosphere of multicomponent gases by more than 4.9 times. The carboxyl groups played a dominant role. Our findings might act as a reference for the selective adsorption of polar molecules over nonpolar molecules.

Strategies for promoting the degradation of phenol by electro-Fenton: Simultaneously promoting the generation and utilization of H2O2.

The use of the electro-Fenton process to continuously generate H2O2 and efficiently degrade organic pollutants is considered a promising technology. The ratio of generation of H2O2 is usually regarded as the critical step; however, how the H2O2 is utilized is also of particular importance. Herein, activated carbon was activated at different temperatures and used to explore the effect of nitrogen doping on the production and utilization of H2O2 in the electro-Fenton-based degradation of organic pollutants. The experimental results indicate that nitrogen-doped activated carbon simultaneously promotes the generation and utilization of H2O2, which is attributed to the regulation of the competition between phenol and O2 adsorption by the doped nitrogen. Nitrogen doping not only improves 2e-ORR selectivity but also aggregates phenol near the cathode to balance the concentrations of phenol and ·OH. Density functional theory (DFT) calculations further confirmed that pyrrole-N as a dopant promoted the adsorption of phenol, while pyridine-N was more favorable for O2 adsorption. The unique balance of nitrogen types possessed by modified activated carbon NAC-750 permits the efficient synergistic generation and utilization of H2O2 in a balanced manner during the degradation of phenol. This work provides a new direction for the rational nitrogen-doping modification of activated carbon for the electro-Fenton-based degradation of organic pollutants.

Synergistic mechanism of formaldehyde adsorption by intrinsic defects and carboxyl groups on the surface of carbon materials.

The adsorption of formaldehyde on the original carbon material is limited. Determining the synergistic adsorption of formaldehyde by different defects on the carbon material is necessary for comprehensively understanding the mechanism of formaldehyde adsorption on the surface of the carbon material. The synergistic effect of intrinsic defects and oxygen-containing functional groups on formaldehyde adsorption on the surface of carbon materials was simulated and verified by experiments. Based on the density functional theory, the adsorption of formaldehyde on different carbon materials was simulated by quantum chemistry. The synergistic adsorption mechanism was studied by energy decomposition analysis, IGMH, QTAIM, and charge transfer, and the binding energy of hydrogen bonds was estimated. The results showed that the energy for the adsorption of formaldehyde adsorbed by the carboxyl group on the vacancy defect was the highest, at -11.86 kcal/mol, the hydrogen bond binding energy was -9.05 kcal/mol, and a larger charge transfer was recorded. The mechanism of synergy was studied comprehensively, and the simulation results were verified at multiple scales. This study provides valuable insights into the effect of carboxyl groups on the adsorption of formaldehyde by activated carbon.

Quantitative analysis on the oil content of oilfield wastewater based on a convolutional neural network model and ultraviolet transmission spectroscopy.

Oil content (OC) is one of the important evaluation indicators in oilfield wastewater (OW) treatment. The purpose of this study is to realize online real-time detection of OC in OW by combining ultraviolet spectrophotometry with the convolutional neural network (CNN). In this paper, 80 groups of OW transmission data were measured for model establishment. Three CNN models with different structures are established to generalize the super parametric optimization process of the model. Furthermore, as a common method used in spectroscopy, the synergy interval partial least squares (siPLS) model is built in order to compare its accuracy with the CNN model. The results indicated the CNN model has a better performance than siPLS, in which the CNN model numbered Model 3 has the lowest root mean square error (MSE) of prediction (RMSEP) of 1.606 mg/L. As a consequence, the CNN model can be used in the monitoring of OW. This article will guide a rapid analysis of the OC of OW.

Effect of oxygen functional groups on competitive adsorption of benzene and water on carbon materials: Density functional theory study.

It is important to study the effect of oxygen-containing functional groups on the competitive adsorption mechanism of benzene and water on the surface of carbon materials, and to directional modification of activated carbon to improve its selective adsorption of benzene in air. In this study, the adsorption characteristics of benzene and water on original and linked ester, carboxyl, hydroxyl, carbon materials linked by ether groups were calculated by quantum chemical simulation based on density functional theory. The types and proportions of weak interactions in the adsorption process were calculated by energy decomposition analysis, and the adsorption mechanism of carbon materials for water and benzene was described. The influence and contribution of oxygen-containing functional groups on the adsorption of benzene and water were further analyzed by van der Waals potential and electrostatic potential, respectively, so as to determine the difference in the adsorption effect of different types of oxygen-containing functional groups on the two molecules. It was found that the carboxyl group has a great influence on the hydrophilicity of carbon materials, and the electrostatic potential distribution before and after linking the carboxyl group changed significantly. Therefore, they can attract each other with water through hydrogen bonds and occupy the surface adsorption sites of carbon materials, thereby inhibiting the adsorption of benzene on carbon materials. On the contrary, due to its hydrophobic properties, the ether group will free up adsorption space for the adsorption of benzene on the surface of the carbon material, which is beneficial to the adsorption of benzene. The adsorption experiments were carried out, and the results were consistent with the simulation. This study provides an idea for preparing efficient carbonaceous adsorbent of benzene and reducing benzene pollution in industry.

Promotion of formaldehyde degradation by electro-Fenton: Controlling the distribution of ·OH and formaldehyde near cathode to increase the reaction probability.

The mismatch of pollutant concentration and ·OH concentration is the key reason for the inefficient degradation of formaldehyde in the electro-Fenton system. Therefore, formaldehyde and ·OH are adsorbed near the cathode, and the high concentration reaction region is constructed to increase the reaction probability, which is called control of the reaction region. Through nitrogen doping modification of the activated carbon cathode, the adsorption capacity of the modified cathode for formaldehyde and active species, and the selectivity of the two-electron oxygen reduction reaction were deeply analyzed. The results show that the suitable nitrogen doping form of the modified cathode significantly promotes the adsorption capacity of formaldehyde and H2O2, which is beneficial to realizing the promotion of formaldehyde degradation by nitrogen doped cathodes in the electro-Fenton system through control of the reaction region. Graphite nitrogen and pyrrolic nitrogen improve formaldehyde adsorption by enhancing the van der Waals force (8.897 mg g-1), and pyridinic nitrogen improve H2O2 adsorption (1.841 mg g-1) by enhancing the effect of hydrogen bonding interaction. Nitrogen doping enhances Fe2+ regeneration, which contributes to the generation of ·OH at the cathode, and promotes formaldehyde degradation. The control of the reaction region through modification of the electro-Fenton cathode achieved formaldehyde degradation of 35.1 mg L-1 (48.51% higher than that of the unmodified cathode), which provides a promising process for formaldehyde treatment.

DPD simulations on mixed polymeric DOX-loaded micelles assembled from PCL-SS-PPEGMA/PDEA-PPEGMA and their dual pH/reduction-responsive release.

The design of mixed polymeric micelles by a combination of two or more dissimilar polymers is a potential strategy to achieve multiple stimuli-response for anti-cancer drug delivery. However, their drug loading co-micellization behavior and multiple stimuli-responsive drug release mechanism have been poorly understood at the mesoscopic level, especially in the system that involves reduction-response due to the difficulty of simulation on the cleavage of chemical bonds. In this work, the co-micellization behavior, drug distribution regularities and dual pH/reduction-responsive drug release process of mixed micelles formed by disulfide-linked polycaprolactone-b-polyethylene glycol methyl ether methacrylate (PCL-SS-PPEGMA) and poly(ethylene glycol) methyl ether-b-poly(N,N-diethylamino ethyl methacrylate) (PDEA-PPEGMA) were studied by dissipative particle dynamics (DPD) mesoscopic simulations. A dedicated bond-breaking script was employed to accomplish the disulfide bond-breaking simulations. The results showed that PCL55-SS-PPEGMA10 and PDEA34-PPEGMA11 could be well mixed to form superior DOX-loaded micelles with good drug-loading capacity and drug-controlled release performance. To prepare the DOX-loaded micelles with optimized properties, the simulation results suggested the feed ratio of DOX:PCL55-SS-PPEGMA10:PDEA34-PPEGMA11 set to 3:4:4. Compared with the two single stimuli-response, the dual pH/reduction-response process perfectly combined both pH-response and reduction-response together, providing a higher release rate of DOX. Therefore, this study provides theoretical guidance aimed at the property optimization and micellar structure design of the dual pH/reduction-responsive mixed micelles.

Cost-effective method of benzene-containing wastewater treatment using floating electro-Fenton system.

Traditional electro-Fenton systems must continuously supply oxygen to the cathode, which leads to extensive volatilisation of benzene in solutions. In this study, we adopted a floating cathode electro-Fenton system without bubbling oxygen into the solution to treat benzene-containing wastewater. The effects of the floating cathode position and main reaction parameters on benzene degradation were analysed, and the degradation cost was estimated. The results indicated that the electro-Fenton system with floating cathode could effectively degrade benzene in solutions. For the cathode, the complete utilisation of air and oxygen released from the anode was crucial. The benzene degradation rate increased with an increase in benzene concentrations. Additionally, pH mainly affected the existing ionic state of iron and production ratio of active substances. The current intensity significantly influenced the reaction activity. Using the floating cathode electro-Fenton method, the benzene removal ratio in the solution could reach 74.80% after 60 min under the optimum reaction conditions. For the floating cathode electro-Fenton system, the cost of treating benzene-containing sewage per cubic metre was $1.2187, which is significantly lower than that for traditional electro-Fenton technology ($1.4000). Hence, the floating cathode electro-Fenton system is an economical and efficient method for benzene degradation in solutions.

Numerical study for removing wax deposition by thermal washing for the waxy crude oil gathering pipeline.

Exploring the wax removal process by numerical simulation is beneficial for guiding field operations. In this paper, enthalpy-porosity and volume of fluid (VOF) methods were adopted to simulate the melting process of wax in the crude oil gathering pipeline. The melting patterns and liquid fraction of the wax were used to validate the mathematical model. The results show that the wax melts quickly before the liquid fraction reaches 80%, while the remaining 20% melts very slowly. Since the water with higher density sinks to the lower part of the pipeline, the wax in the lower part of the pipeline melts first, while the wax in the upper part of the pipeline melts slowly. The water temperature and flow rate disproportionately affect the melting process. Increasing the water temperature and flow rate can accelerate the melting process, but the effects on shortening the melting time of wax gradually decrease. Increasing the flow rate, the heat transfer rate and the melting rate are increasing progressively, the change of flow rate also affects the outlet temperature of the pipeline.

Roles of free radicals in NO oxidation by Fenton system and the enhancement on NO oxidation and H2O2 utilization efficiency.

Low H2O2 utilization efficiency is the main problem when Fenton system was used to oxidize NO in flue gas. To understand the behaviour of the free radicals during NO oxidation process in Fenton system is crucial to solving this problem. The oxidation capacity of [Formula: see text] and [Formula: see text] on NO in Fenton system was compared and the useless consumption path of [Formula: see text] and [Formula: see text] that caused the low utilization efficiency of H2O2 were studied. A method to enhance the oxidation ability and H2O2 utilization efficiency by adding reducing additives in Fenton system was proposed. The results showed that both of [Formula: see text] and [Formula: see text] were active substances that oxidize NO. However, the oxidation ability of [Formula: see text] radicals was stronger. The vast majority of [Formula: see text] and [Formula: see text] was consumed by rapid reaction [Formula: see text] , which was the primary reason for the low utilization efficiency of H2O2 in Fenton system. Hydroxylamine hydrochloride and ascorbic acid could accelerate the conversion of Fe3+ to Fe2+, thereby increase the generation rate of ·OH and decrease the generation rate of [Formula: see text]. As a result, the oxidation ability and H2O2 utilization efficiency were enhanced.

Free radical behaviours during methylene blue degradation in the Fe2+/H2O2 system.

Behaviours of the free radicals during the methylene blue (MB) oxidation process in the Fe2+/H2O2 system were studied to reveal the reason for the low utilization efficiency of H2O2. The roles of O2-∙ , ∙OH and HO2∙ radicals were proven to be different in the MB oxidation process. The results showed that O2-∙ radicals had a strong ability to oxidize MB; however, they were not the main active substances for MB degradation due to the low concentration in the traditional Fe2+/H2O2 system. HO2∙ radicals could not oxidize MB. ∙OH radicals were the main active substances for MB oxidation. In the short initial stage, the utilization efficiency of H2O2 was high, because the generation rate of ∙OH was much higher than that of HO2∙ . More ∙OH radicals were involved in the MB oxidation reaction. In the long deceleration stage (after the short initial stage), a large amount of H2O2 was consumed, but the amount of oxidized MB was very small. Most of the ∙OH radicals were consumed via the rapid useless reaction between ∙OH and HO2∙ in this stage, resulting in the serious useless consumption of H2O2. It is a feasible method to improve the utilization efficiency of H2O2 by adding suitable additives into the Fe2+/H2O2 system to weaken the useless reaction between ∙OH and HO2∙ .

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

Drastic Enhancement of H2O2 Electro-generation by Pulsed Current for Ibuprofen Degradation: Strategy Based on Decoupling Study on H2O2 Decomposition Pathways.

Efficient H2O2 electrogeneration from 2-electron oxygen reduction reaction (ORR) represents an important challenge for environmental remediation application. H2O2 production is determined by 2-electron ORR as well as H2O2 decomposition. In this work, a novel strategy based on the systematical investigation on H2O2 decomposition pathways was reported, presenting a drastically improved bulk H2O2 concentration. Results showed that bulk phase disproportion, cathodic reduction, and anodic oxidation all contributed to H2O2 depletion. To decrease the extent of H2O2 cathodic reduction, the pulsed current was applied and proved to be highly effective to lower the extent of H2O2 electroreduction. A systematic study of various pulsed current parameters showed that H2O2 concentration was significantly enhanced by 61.6% under pulsed current of "2s ON + 2s OFF" than constant current. A mechanism was proposed that under pulsed current, less H2O2 molecules were electroreduced when they diffused from the porous cathode to the bulk electrolyte. Further results demonstrated that a proper pulse frequency was necessary to achieve a higher H2O2 production. Finally, this strategy was applied to Electro-Fenton (EF) process with ibuprofen as model pollutant. 75.0% and 34.1% ibuprofen were removed under pulsed and constant current at 10 min, respectively. The result was in consistent with the higher H2O2 and ·OH production in EF under pulsed current. This work poses a potential approach to drastically enhance H2O2 production for improved EF performance on organic pollutants degradation without making any changes to the system except for power mode.

The role of quinone cycle in Fe2+-H2O2 system in the regeneration of Fe2.

The reaction between Fe2+ and H2O2 generates highly reactive ·OH. However, the weak conversion from Fe3+ to Fe2+ limits its continuous reaction. Here, the difference between the Fenton system and modified Fenton system for the regeneration of Fe2+ was analyzed. A UV-vis spectrometer and redox potential measurements were used to detect Fe2+ concentration. Results indicated that Fe2+ could be better regenerated in the modified Fenton system. The regeneration of Fe2+ was facilitated by the consumption of NH2OH, while in hydroquinone (HQ)- and 1,4-bezoquinone (1,4-BQ)-modified Fenton systems, the quinone cycle could be built up and Fe3+ could be converted to Fe2+ continuously. However, results showed that HQ and 1,4-BQ reacted with ·OH, which caused a gradual decline in the enhancement effect. In order to keep Fe2+ concentration stable for a longer time, the influence of [HQ/1,4-BQ]0/[Fe2+]0 on Fe2+ concentration was carefully studied. When the mole ratio was 5:1, Fe2+ concentration remained nearly 90% of total iron at 40 min. But when the mole ratios were 0.5:1 and 0.1:1, Fe2+ concentration decreased to a very low level at 20 min. Oxidation-reduction potential (ORP) results further confirmed the role of quinone cycle.