Sperm-Associated Antigen 5 Knockout Reduces Doxorubicin and Docetaxel Resistance in Triple-Negative Breast Cancer MDA-MB-231 and BT549 Cells.

Sperm-associated antigen 5 (SPAG5), also known as Astrin, was previously demonstrated as a biomarker for cellular resistance to major breast cancer therapies, including chemo-, endocrine- and targeted therapy. However, the contribution of SPAG5 to anthracycline- and taxane-based chemotherapy in triple-negative breast cancer (TNBC) remains controversial. In the present study, the SPAG5 knockout cell model was established by using clustered regularly interspaced palindromic repeats (CRISPR)-CRISPR-associated protein 9 (Cas9) system in MDA-MB-231 and BT549 TNBC cell lines. The knockout of SPAG5 was confirmed on both gene and protein levels using genomic PCR, DNA sequencing and western blotting. The functional loss of SPAG5 was determined by colony-formation assay. SPAG5-regulated doxorubicin- and docetaxel-resistance was assessed by MTT and apoptosis assays. The results indicated that all the SPAG5 knockout MDA-MB-231 and BT549 clones were biallelic, where one allele was replaced by the donor template, and the other allele had the same "T" insertion (indel) adjacent to the cutting sites of gRNAs at the exon 1 boundary, irrespective of the gRNAs and cell lines. The locus of indel interrupted the SPAG5 transcription by damaging the GT-AG mRNA processing rule. Deletion of SPAG5 decreased clonogenicity in both MDA-MB-231 and BT549 cells. SPAG5 was able to regulate the resistance and the drug-induced apoptosis of both doxorubicin and docetaxel. In conclusion, recombinant plasmid-based CRISPR-Cas9 technology can be used to delete the SPAG5 gene in the TNBC cell lines. SPAG5 has an important role in regulating cell proliferation and doxorubicin- and docetaxel-resistance in MDA-MB-231 and BT549 cells.

Enhanced Sb(V) removal of sulfate-rich wastewater by anaerobic granular sludge assisted with Fe/C amendment.

Antimony (Sb) and sulfate are two common pollutants in Sb mine drainage and Sb-containing textile wastewater. In this paper, it was found that iron­carbon (Fe/C) enhanced Sb(V) removal from sulfate-rich wastewater by anaerobic granular sludge (AnGS). Sulfate inhibited Sb(V) removal (S + Sb, k = 0.101), while Fe/C alleviated the inhibition and increased Sb(V) removal rate by 2.3 times (Fe/C + S + Sb, k = 0.236). Fe/C could promote the removal of Sb(III), and Sb(III) content decreased significantly after 8 h. Meanwhile, Fe/C enhanced the removal of sulfate. The 3D-EEM spectrum of supernatant in Fe/C + S + Sb group (at 24 h) showed that Fe/C stimulated the production of soluble microbial products (SMP) in wastewater. SMP alleviated the inhibition of sulfate, promoting AnGS to reduce Sb(V). Sb(V) could be reduced to Sb(III) both by AnGS and sulfides produced from sulfate reduction. Further analysis of extracellular polymeric substances (EPS) and AnGS showed that Fe/C increased the adsorbed Sb(V) in EPS and the c-type cytochrome content in AnGS, which may be beneficial for Sb(V) removal. Sb(V) reduction in Fe/C + S + Sb group may be related to the genus Acinetobacter, while in Sb group, several bacteria may be involved in Sb(V) reduction, such as Acinetobacter, Pseudomonas and Corynebacterium. This study provided insights into Fe/C-enhanced Sb(V) removal from sulfate-rich wastewater.

Selective Nitrate Electroreduction to Ammonia on CNT Electrodes with Controllable Interfacial Wettability.

The development of electrocatalysts that can efficiently reduce nitrate (NO3-) to ammonia (NH3) has garnered increasing attention due to their potential to reduce carbon emissions and promote environmental protection. Intensive efforts have focused on catalyst development, but a thorough understanding of the effect of the microenvironment around the reactive sites of the catalyst is also crucial to maximize the performance of the electrocatalysts. This study explored an electrocatalytic system that utilized quaternary ammonium surfactants with a range of alkyl chain lengths to modify an electrode made of carbon nanotubes (CNT), with the goal of regulating interfacial wettability toward NO3- reduction. Trimethyltetradecylammonium bromide with a moderate alkyl chain length created a very hydrophobic interface, which led to a high selectivity in the production of NH3 (∼87%). Detailed mechanistic investigations that used operando Fourier-transform infrared (FTIR) spectroscopy and online differential electrochemical mass spectrometry (DEMS) revealed that the construction of a hydrophobic modified CNT played a synergistic role in suppressing a side reaction involving the generation of hydrogen, which would compete with the reduction of NO3-. This electrocatalytic system led to a favorable process for the reduction of NO3- to NH3 through a direct electron transfer pathway. Our findings underscore the significance of controlling the hydrophobic surface of electrocatalysts as an effective means to enhance electrochemical performance in aqueous media.

Selective Phosphate Adsorption Using Topologically Regulated Binary-Defect Metal-Organic Frameworks: Essential Role of Interfacial Electron Mobility.

Metal-organic framework (MOF)-modified biochars (BC) have gained recognition as potent adsorbents for phosphate. However, essential insights into the electronic interfacial state of the MOFs remain lacking. In this study, we propose a novel topological transformation strategy to directionally regulate the interfacial electronic states of BC/MOFs composites. The optimized BC/MOFs exhibited an excellent selective phosphate adsorption capacity of 188.68 mg·g-1, coupled with rapid sorption kinetics of 6.81 mg·(g·min0.5)-1 in simulated P-laden wastewater. When challenged with real bioeffluent, such efficacy was still maintained (5 mg·L-1, 25.92 mg·g-1). This superior performance was due to the Fe(III) → Fe(II) transition, promoting electron mobility and leading to the anchoring of Mg(II) to form specific coordination unsaturated sites (Mg-CUS) for phosphate adsorption. Importantly, the simultaneous regulation of binary defects further enhances electron mobility, resulting in the formation of sp3 unequal hybrid orbitals with a stronger internal coupling capability between Mg 3s in Mg-CUS and O 2p in phosphate. Furthermore, the high electron affinity of Mg effectively promotes electron cycling, endowing BC/MOFs with a distinct self-healing capability to facilitate phosphate desorption. The outcomes of this study provide novel perspectives for electronic regulated phosphate adsorption.

The segmentation and intelligent recognition of structural surfaces in borehole images based on the U2-Net network.

Structural planes decrease the strength and stability of rock masses, severely affecting their mechanical properties and deformation and failure characteristics. Therefore, investigation and analysis of structural planes are crucial tasks in mining rock mechanics. The drilling camera obtains image information of deep structural planes of rock masses through high-definition camera methods, providing important data sources for the analysis of deep structural planes of rock masses. This paper addresses the problems of high workload, low efficiency, high subjectivity, and poor accuracy brought about by manual processing based on current borehole image analysis and conducts an intelligent segmentation study of borehole image structural planes based on the U2-Net network. By collecting data from 20 different borehole images in different lithological regions, a dataset consisting of 1,013 borehole images with structural plane type, lithology, and color was established. Data augmentation methods such as image flipping, color jittering, blurring, and mixup were applied to expand the dataset to 12,421 images, meeting the requirements for deep network training data. Based on the PyTorch deep learning framework, the initial U2-Net network weights were set, the learning rate was set to 0.001, the training batch was 4, and the Adam optimizer adaptively adjusted the learning rate during the training process. A dedicated network model for segmenting structural planes was obtained, and the model achieved a maximum F-measure value of 0.749 when the confidence threshold was set to 0.7, with an accuracy rate of up to 0.85 within the range of recall rate greater than 0.5. Overall, the model has high accuracy for segmenting structural planes and very low mean absolute error, indicating good segmentation accuracy and certain generalization of the network. The research method in this paper can serve as a reference for the study of intelligent identification of structural planes in borehole images.

Bioelectrocatalytic reduction by integrating pyrite assisted manganese cobalt-doped carbon nanofiber anode and bacteria for sustainable antimony catalytic removal.

A novel manganese cobalt metal-organic framework based carbon nanofiber electrode (MnCo/CNF) was prepared and used as microbial fuel cell (MFC) anode. Pyrite was introduced into the anode chamber (MnCoPy_MFC). Synergistic function between pyrite and MnCo/CNF facilitated the pollutants removal and energy generation in MnCoPy_MFC. MnCoPy_MFC showed the highest chemical oxygen demand removal efficiency (82 ± 1%) and the highest coulombic efficiency (35 ± 1%). MnCoPy_MFC achieved both efficient electricity generation (maximum voltage: 658 mV; maximum power density: 3.2 W/m3) and total antimony (Sb) removal efficiency (99%). The application of MnCo/CNF significantly enhanced the biocatalytic efficiency of MnCoPy_MFC, attributed to its large surface area and abundant porous structure that provided ample attachment sites for electroactive microorganisms. This study revealed the synergistic interaction between pyrite and MnCo/CNF anode, which provided a new strategy for the application of composite anode MFC in heavy metal removal and energy recovery.

Selective electrocatalytic transformation of highly toxic phenols in wastewater to para-benzoquinone at ambient conditions.

The selective transformation of organics from wastewater to value-added chemicals is considered an upcycling process beneficial for carbon neutrality. Herein, we present an innovative electrocatalytic oxidation (ECO) system aimed at achieving the selective conversion of phenols in wastewater to para-benzoquinone (p-BQ), a valuable chemical widely utilized in the manufacturing and chemical industries. Notably, 96.4% of phenol abatement and 78.9% of p-BQ yield are synchronously obtained over a preferred carbon cloth-supported ruthenium nanoparticles (Ru/C) anode. Such unprecedented results stem from the weak Ru-O bond between the Ru active sites and generated p-BQ, which facilitates the desorption of p-BQ from the anode surface. This property not only prevents the excessive oxidation of the generated p-BQ but also reinstates the Ru active sites essential for the rapid ECO of phenol. Furthermore, this ECO system operates at ambient conditions and obviates the need for potent chemical oxidants, establishing a sustainable avenue for p-BQ production. Importantly, the system efficacy can be adaptable in actual phenol-containing coking wastewater, highlighting its potential practical application prospect. As a proof of concept, we construct an electrified Ru/C membrane for ECO of phenol, attaining phenol removal of 95.8% coupled with p-BQ selectivity of 73.1%, which demonstrates the feasibility of the ECO system in a scalable flow-through operation mode. This work provides a promising ECO strategy for realizing both phenols removal and valuable organics recovery from phenolic wastewater.

Bioinspired Tandem Electrode for Selective Electrocatalytic Synthesis of Ammonia from Aqueous Nitrate.

The electrocatalytic nitrate reduction reaction (NO3RR) has recently emerged as a promising technique for readily converting aqueous nitrate (NO3-) pollutants into valuable ammonia (NH3). It is vital to thoroughly understand the mechanism of the reaction to rationally design and construct advanced electrocatalytic systems that can effectively and selectively drive the NO3RR. There are several natural enzymes that incorporate molybdenum (Mo) and that can activate NO3-. Based on this, a cadmium (Cd) single-atom anchored Mo2TiC2Tx electrocatalyst (referred to as CdSA-Mo2TiC2Tx) through the NO3RR to generate NH3 was rationally designed and demonstrated. In an H-type electrolysis cell and at a current density of 42.5 mA cm-2, the electrocatalyst had a Faradaic efficiency of >95% and an impressive NH3 yield rate of 48.5 mg h-1 cm-2. Moreover, the conversion of NO3- to NH3 on the CdSA-Mo2TiC2Tx surface was further revealed by operando attenuated total reflection Fourier-transform infrared spectroscopy and an electrochemical differential mass spectrometer. The electrocatalyst significantly outperformed Mo2TiC2Tx as well as reported state-of-the-art catalysts. Density functional theory calculations revealed that CdSA-Mo2TiC2Tx decreased the ability of the d-p orbital to hybridize with NH3* intermediates, thereby decreasing the activation energy of the potential-determining step. This work not only highlights the application prospects of heavy metal single-atom catalysts in the NO3RR but also provides examples of bio-inspired electrocatalysts for the synthesis of NH3.

Water Flow-Driven Coupling Process of Anodic Oxygen Evolution and Cathodic Oxygen Activation for Water Decontamination and Prevention of Chlorinated Byproducts.

Electrochemical advanced oxidation process (EAOP) is a promising technology for decentralized water decontamination but is subject to parasitic anodic oxygen evolution and formation of toxic chlorinated byproducts in the presence of Cl-. To address this issue, we developed a novel electrolytic process by water flow-driven coupling of anodic oxygen evolution reaction (OER) and cathodic molecular oxygen activation (MOA). When water flows from anode to cathode, O2 produced from OER is carried by water through convection, followed by being activated by atomic hydrogen (H*) on Pd cathode to produce •OH. The water flow-driven OER/MOA process enables the anode to be polarized at low potential (1.7 V vs SHE) that is lower than that of conventional EAOP whose •OH is produced from direct water oxidation (>2.3 V vs SHE). At a flow rate of 30 mL min-1, the process could achieve 94.8% removal of 2,4-dichlorophenol (2,4-DCP) and 71.5% removal of chemical oxygen demand (COD) within 45 min at an anode potential of 1.7 V vs SHE and cathode potential of -0.5 V vs SHE. To achieve the comparable 2,4-DCP removal performance, 4.3-fold higher energy consumption was needed for the conventional EAOP with titanium suboxide anode (anode potential of 2.9 V vs SHE), but current efficiency declined by 3.5 folds. Unlike conventional EAOP, chlorate and perchlorate were not detected in the OER/MOA process, because low anode potential <2.0 V vs SHE was thermodynamically unfavorable for the formation of chlorinated byproducts by anodic oxidation, indicated by theoretical calculations and experimental data. This study provides a proof-in-concept demonstration of water flow-driven OER/MOA process, representing a paradigm shift of electrochemical technology for water decontamination and prevention of chlorinated byproducts, making electrochemical water decontamination more efficient, more economic, and more sustainable.

Co-treatment of copper electrolytic sludges and copper scraps for the recycled utilization of copper and arsenic.

The Cu electrolytic sludge is a hazardous waste because of its high Cu and As contents. In contrast, As content in Cu scraps is low but causes massive floating slime to be formed during its electrolytic refining, thus decreasing quality of the obtained cathode Cu. In this study, an innovative process was developed to transfer As from the electrolytic Cu sludge into Cu scraps, realizing the recycled utilization of As and Cu from them. The Cu electrolytic sludge was firstly subjected to oxidization roasting in the presence of Ca(OH)2, where the As2O3, Cu3As, and elemental As from the sludge were oxidized and immobilized into Cu3(AsO4)2 and Ca3(AsO4)2. The Cu3(AsO4)2 and Ca3(AsO4)2 retained in the roasted residue. The As volatilization efficiency was only 3.7% under the optimized roasting condition. In the next co-fire-refining of the roasted residue and Cu scraps, the As in Cu3(AsO4)2 and Ca3(AsO4)2 was reduced and transferred into the refined Cu at a content of 0.17 wt%. Although a volatile As2O3 could be generated in this co-fire-refining, the molten Cu scraps restricted As volatilization by forming a Cu-As alloy. With the obtained As-containing refined Cu used in electrolytic refining, the formation of floating slime could be decreased and consequently the quality of the cathode Cu would be increased. This research provided an alternative technology for Cu and As recycling by co-treating Cu electrolytic sludges and Cu scraps.

Flow-through electrochemical organophosphorus degradation and phosphorus recovery: The essential role of chlorine radical.

Phosphorus scarcity and the deleterious ecological impact of the release of organophosphorus pesticides have emerged as critical global issues. Previous research has shown the ability of electrochemistry to induce the precipitation of calcium phosphate from phosphorus-laden wastewater to recover the phosphorus. The current study presents a flow-through electrochemical system consisting of a column-shaped electrochemical reactor, a tubular stainless-steel (SS) cathode, and a titanium suboxides (TiSO) anode. This system simultaneously oxidizes tetrakis (hydroxymethyl) phosphonium sulfate (THPS) and recycles phosphates. The influence of current density, flow rate, and initial calcium ions concentration were examined under continuous flow operation. To enhance the electrochemical reactor's performance, we elevated the current density from 5 to 30 mA cm-2, which caused the phosphorus recovery efficiency to increase from 37% to 72% within 120 min, accompanied by an enhancement of the THPS mineralization efficiency from 57% to 90%. These improvements were likely due to the higher yield of reactive species chloride species (Cl•) formed at the TiSO anode and the higher local pH at the cathode. By investigating the formation of Cl• at the TiSO anode, we found that THPS mineralization exceeded 75% in the presence of NaCl at a current density of 20 mA cm-2. The demonstrated performance of the flow-through electrochemical system should enable the utilization of anodic oxidation-cathodic precipitation for the recovery of phosphorus from organophosphorus-contaminated wastewater.

Rational design of electrocatalytic system to selective transform nitrate to nitrogen.

Nitrate (NO3-) is one of the most common pollutants in natural bodies of water and as such threatens both human health and the safety of aquatic environment. There are efficient electrochemical techniques to directly remove NO3-, but inexpensive, selective and electrocatalytic strategies to eliminate NO3- by converting it into benign nitrogen (N2) remain challenging. This work studied Cu particles that were formed directly on a Ni foam (Cu-NF) and evaluated their electrocatalytic NO3- reduction performance. The use of carbon nanotubes (CNT) functionalized with titanium suboxides (TiSO) as the anode facilitated the generation of active chlorine species that had a key role in the removal of NH4+. An electrochemical system that integrated a Cu-NF cathode with a TiSO-CNT anode could remove 88.5% of NO3- with a >99% N2 selectivity when operated over 6 h (4.1 × 10-4 h-1) at a potential of -1.2 V vs Ag/AgCl. Because the chloride ions are very common in natural sources of water, this technique offers a sustainable and environmentally friendly approach for the removal of NO3- from contaminated water sources.

A photocatalytic-microbial coupling system for simultaneous removal of harmful algae and enhanced denitrification: Construction, performance and mechanism of action.

Recently, harmful algal blooms (HABs) have become occurred with increasingly frequency worldwide. High nitrate content is one of the primary causes of eutrophication. Research has shown that photocatalytic materials enhance the effectiveness of microbial denitrification while removing other contaminants, despite some shortcomings. Based on this, we loaded TiO2/C3N4 heterojunctions onto weaveable, flexible carbon fibers and established a novel photocatalytically enhanced microbial denitrification system for the simultaneous removal of harmful algae and Microcystin-LR. We found that 99.35% of Microcystis aeruginosa and 95.34% of MC-LR were simultaneously and effectively removed. Compared to existing denitrification systems, the nitrate removal capacity improved by 72.33%. The denitrifying enzyme activity and electron transport system activity of microorganisms were enhanced by 3.54-3.86 times. Furthermore, the microbial community structure was optimized by the regulation of photogenerated electrons, and the relative abundance of main denitrifying bacteria increased from 50.72% to 66.45%, including Proteobacteria and Bacteroidetes. More importantly, we found that the increased secretion of extracellular polymeric substances by microorganisms may be responsible for the persistence of the reinforcing effect caused by photogenerated electrons in darkness. The higher removal of Microcystis aeruginosa and Microcystin-LR (MC-LR) achieved by the proposed system would reduce the frequency of HAB outbreaks and prevent the associated secondary pollution.

Simultaneous remediation of arsenic and organic chemicals contaminated soil and groundwater using chemical oxidation and precipitation/stabilization: a case study.

After the departure of industrial facilities, reuse of the land in developed cities in China is problematic, due to the land contamination issues. The rapid remediation of sites with complex contamination is crucial and urgently needed. Herein, the case of on-site remediation of arsenic (As) in soil, as well as benzo(a)pyrene, total petroleum hydrocarbons, and As in groundwater was reported. For contaminated soil, the oxidant and deactivator (consisting of 20% sodium persulfate, 40% ferrous sulfate (FeSO4), and 40% portland cement) were applied to oxidize and immobilize As. As a result, the total amount and lixivium concentration of As were constrained under 20 mg/kg and 0.01 mg/L, respectively. Meanwhile, for contaminated groundwater, As and organic contaminants were treated by FeSO4/ozone and FeSO4/hydrogen peroxide with mass ratios of 1:5 and 1:8, respectively. The continuous monitoring of contaminants in 22 monitoring wells shown that all contaminants in groundwater were treated to meet the standards. In addition, the risk of secondary pollution and operation cost was effectively reduced by proper disposal and resourceful utilization. The findings indicated that the method of oxidation and precipitation/stabilization is technically, environmentally, and economically feasible for the remediation of contaminated sites with similar complex pollutants.

A signature of cuproptosis-related lncRNAs predicts prognosis and provides basis for future anti-tumor drug development in breast cancer.

Background: Breast cancer is the most prevalent malignancy worldwide and the leading culprit for women's death. Cuproptosis is a novel and promising modality of tumor cell death and the relationship with long non-coding RNAs (lncRNAs) remains shrouded in a veil. Studies in cuproptosis-related lncRNAs can aid in the clinical management of breast cancer and provide a basis for anti-tumor drug development. Methods: RNA-Seq data, somatic mutation data, and clinical information were downloaded from The Cancer Genome Atlas (TCGA). Patients were divided into high- and low-risk groups according to the risk score. Cox regression and least absolute shrinkage and selection operator (LASSO) regression analyses were used to select prognostic lncRNAs to construct a risk score system. Its' prognostic value was confirmed in the training and validation cohorts subsequently. Functional analysis regarding cuproptosis-related lncRNAs was performed. Results: Eighteen cuproptosis-related lncRNAs were identified and 11 of them including AL023882.1, AC091588.1, AC138028.2, AC027514.1, AL592301.1, LRRC8C-DT, MFF-DT, NIFK-AS1, MECOM-AS1, OTUD6B-AS1 and RNF32-AS1 were selected for risk score system construction. The risk score was confirmed as an independent prognostic factor and patients in the high-risk group had a worse prognosis. A nomogram based on the independent prognostic factors was constructed for clinical decision aids. Further analyses revealed that patients in the high-risk group faced a heavier tumor mutational burden (TMB) and suppressed anti-tumor immunity. Besides, cuproptosis-related lncRNAs were associated with the expression of immune checkpoint inhibitors, N6-adenylate methylation (m6a), and drug sensitivity in breast cancer. Conclusions: A prognostic risk score system with satisfactory predictive accuracy was constructed. Besides, cuproptosis-related lncRNAs can influence the immune microenvironment, TMB, m6a, and drug sensitivity in breast cancer, which may provide a basis for future anti-tumor drug development.

Modulating the Active Hydrogen Adsorption on Fe─N Interface for Boosted Electrocatalytic Nitrate Reduction with Ultra-Long Stability.

The electrocatalytic reduction of nitrate (NO3 - ) to nitrogen (N2 ) is an environmentally friendly approach for efficient N-cycle management (toward a nitrogen-neutral cycle). However, poor catalyst durability and the competitive hydrogen evolution reaction significantly impede its practical application. Interface-chemistry engineering, utilizing the close relationship between the catalyst surface/interface microenvironment and electron/proton transfer process, has facilitated the development of catalysts with high intrinsic activity and physicochemical durability. This study reports the synthesis of a nitrogen-doped carbon-coated rice-like iron nitride (RL-Fe2 N@NC) electrocatalyst with excellent electrocatalytic nitrate-reduction reaction activity (high N2 selectivity (≈96%) and NO3 - conversion (≈86%)). According to detailed mechanistic investigations by in situ tests and theoretical calculations, the strong hydrogenation ability of iron nitride and enhanced nitrate enrichment of the system synergistically contribute to the rapid hydrogenation of nitrogen-containing species, increasing the intrinsic activity of the catalyst and reducing the occurrence of the competing hydrogen-evolution side reaction. Moreover, RL-Fe2 N@NC shows excellent stability, retaining good NO3 - -to-N2 electrocatalysis activity for more than 40 cycles (one cycle per day). This paper could guide the interfacial design of Fe-based composite nanostructures for electrocatalytic nitrate reduction, facilitating a shift toward nitrogen neutrality.

Copper Nanowire Networks: An Effective Electrochemical Peroxymonosulfate Activator toward Nitrogenous Pollutant Abatement.

Herein, we developed an electrochemical filtration system for effective and selective abatement of nitrogenous organic pollutants via peroxymonosulfate (PMS) activation. Highly conductive and porous copper nanowire (CuNW) networks were constructed to serve simultaneously as catalyst, electrode, and filtration media. In one demonstration of the CuNW network's capability, a single pass through a CuNW filter (τ < 2 s) degraded 94.8% of sulfamethoxazole (SMX) at an applied potential of -0.4 V vs SHE. The exposed {111} crystal plane of CuNW triggered atomic hydrogen (H*) generation on sites, which contributed to effective PMS reduction. Meanwhile, with the involvement of SMX, a Cu-N bond was formed by the interactions between the -NH2 group of SMX and the Cu sites of CuNW, accompanied by the redox cycling of Cu2+/Cu+, which was facilitated by the applied potential. The different charges of the active Cu sites made it easier to withdraw electrons and promote PMS oxidation. Theoretical calculations and experimental results were combined to suggest a mechanism for pollution abatement with CuNW networks. The results showed that system efficacy for the degradation of a wide array of nitrogenous pollutants was robust across a broad range of solution pH and complex aqueous matrices. The flow-through operation of the CuNW filter outperformed conventional batch electrochemistry due to convection-enhanced mass transport. This study provides a new strategy for environmental remediation by integrating state-of-the-art material science, advanced oxidation processes, and microfiltration technology.

Fluidic MXene Electrode Functionalized with Iron Single Atoms for Selective Electrocatalytic Nitrate Transformation to Ammonia.

The growth of renewable energy industries and the ongoing need for fertilizer in agriculture have created a need for sustainable production of ammonia (NH3) using low-cost, environment-friendly techniques. The electrocatalytic nitrate (NO3-) reduction reaction (NO3RR) has the potential to improve both the management of environmental nitrogen and the recycling of synthetic nutrients. However, NO3RR is frequently hindered by the incomplete NO3- conversion, sluggish reaction kinetics, and suppression of the hydrogen evolution reaction (HER). Inspired by specific local electronic structures that are adjustable for single-atom catalysts, this work presents a nanohybrid electrocatalytic filter with iron single atoms (FeSA) immobilized on MXene. The fabricated FeSA/MXene filter exhibited maximum NH3 Faradaic efficiency and selectivity (82.9 and 99.2%, respectively) that were higher than those for filters made of Fe nanoparticles anchored on MXene (FeNP/MXene) (69.2 and 81.3%, respectively) and MXene alone (32.8 and 52.4%, respectively), measured at an initial pH of 7 and an applied potential of -1.4 V vs Ag/AgCl. Density functional theory calculations revealed that, compared to the FeNP/MXene filter, the FeSA/MXene filter prevented the competition from the HER and reduced the activation energy of the potential-limiting step (*NO to *NHO) that made the NH3 synthesis thermodynamically favorable . This work highlights an alternative strategy for achieving a synergistic NO3- removal and nutrient recovery with durable catalytic activity and stability.

A General Strategy to Synthesize Fluidic Single Atom Electrodes for Selective Reactive Oxygen Species Production.

Fine-tuning the geometric and electronic structure of catalytic metal centers via N-coordination engineering offers an effective design for the electrocatalytic transformation of O2 to singlet oxygen (1O2). Herein, we develop a general coordination modulation strategy to synthesize fluidic single-atom electrodes for selective electrocatalytic activation of O2 to 1O2. Using a single Cr atom system as an example, >98% 1O2 selectivity can be achieved from electrocatalytic O2 activation due to the subtle engineering of Cr-N4 sites. Both theoretical simulations and experimental results determined that "end-on" adsorption of O2 onto the Cr-N4 sites lowers the overall activation energy barrier of O2 and promotes the breakage of Cr-OOH bonds to form •OOH intermediates. In addition, the flow-through configuration (k = 0.097 min-1) endowed convection-enhanced mass transport and improved charge transfer imparted by spatial confinement within the lamellar electrode structure compared to that of batch reactor (k = 0.019 min-1). In a practical demonstration, the Cr-N4/MXene electrocatalytic system exhibits a high selectivity toward electron-rich micropollutants (e.g., sulfamethoxazole, bisphenol A, and sulfadimidine). The flow-through design of the fluidic electrode achieves a synergy with the molecular microenvironment that enables selective electrocatalytic 1O2 generation, which could be used in numerous ways, including the treatment of environmental pollution.

Electrochemical CNT filter functionalized with metal-organic framework for one-step antimonite decontamination.

Currently, there is a lack of advanced nanotechnology designed to efficiently remove antimony (Sb) from contaminated water systems. Sb most commonly appears as antimonite (Sb(III)) or as the anion antimonate (Sb(V)). Sb(III) is approximately ten times more toxic than Sb(V), and Sb(III) is also harder to eliminate because of its motility and charge neutrality. The work presented here developed an electrochemical filtration technology for the direct elimination of Sb(III) from contaminated water. The primary components of the filtration system were an electroactive carbon nanotube (CNT) membrane that were functionalized with the Sb-specific UiO-66(Zr), an metal-organic framework. In an electric field, the UiO-66(Zr)/CNT nanohybrid filter enabled in situ transformation of Sb(III) to less harmful Sb(V). The Sb(V) was then effectively adsorbed by the UiO-66(Zr). The removal efficiency (90.5%) and rate constant (k1 = 0.0272 min-1) toward Sb(III) removal was 1.3 and 1.4 times greater than that of CNT filter. The abundance of available adsorption sites of the nanohybrid filter, flow-through construction, and electrochemical activity combined to rapidly remove Sb(III) from water. The underlying functioning of the nanohybrid filter was determined with a series of process experiments and structural characterizations. The filter was effective over a broad range of pH values and in a variety of complex aqueous environments. Once loaded with Sb, the UiO-66(Zr)/CNT filter could be washed with a dilute NaOH solution to efficiently refresh its activity. The results of this work offer a direct, efficient strategy that integrates nanotechnology, electrochemistry, and membrane separation to remove antimony and potentially other heavy metals from contaminated water.