Oxalate modification enabled advanced phosphate removal of nZVI: In Situ formed surface ternary complex and altered multi-stage adsorption process.

Nano zero-valent iron (nZVI) is a promising phosphate adsorbent for advanced phosphate removal. However, the rapid passivation of nZVI and the low activity of adsorption sites seriously limit its phosphate removal performance, accounting for its inapplicability to meet the emission criteria of 0.1 mg P/L phosphate. In this study, we report that the oxalate modification can inhibit the passivation of nZVI and alter the multi-stage phosphate adsorption mechanism by changing the adsorption sites. As expected, the stronger anti-passivation ability of oxalate modified nZVI (OX-nZVI) strongly favored its phosphate adsorption. Interestingly, the oxalate modification endowed the surface Fe(III) sites with the lowest chemisorption energy and the fastest phosphate adsorption ability than the other adsorption sites, by in situ forming a Fe(III)-phosphate-oxalate ternary complex, therefore enabling an advanced phosphate removal process. At an initial phosphate concentration of 1.00 mg P/L, pH of 6.0 and a dosage of 0.3 g/L of adsorbents, OX-nZVI exhibited faster phosphate removal rate (0.11 g/mg/min) and lower residual phosphate level (0.02 mg P/L) than nZVI (0.055 g/mg/min and 0.19 mg P/L). This study sheds light on the importance of site manipulation in the development of high-performance adsorbents, and offers a facile surface modification strategy to prepare superior iron-based materials for advanced phosphate removal.

Picometer-Level In Situ Manipulation of Ferroelectric Polarization in Van der Waals layered InSe.

Ferroelectric 2D van der Waals (vdW) layered materials are attracting increasing attention due to their potential applications in next-generation nanoelectronics and in-memory computing with polarization-dependent functionalities. Despite the critical role of polarization in governing ferroelectricity behaviors, its origin and relation with local structures in 2D vdW layered materials have not been fully elucidated so far. Here, intralayer sliding of approximately six degrees within each quadruple-layer of the prototype 2D vdW ferroelectrics InSe is directly observed and manipulated using sub-angstrom resolution imaging and in situ biasing in an aberration-corrected scanning transmission electron microscope. The in situ electric manipulation further indicates that the reversal of intralayer sliding can be achieved by altering the electric field direction. Density functional theory calculations reveal that the reversible picometer-level intralayer sliding is responsible for switchable out-of-plane polarization. The observation and manipulation of intralayer sliding demonstrate the structural origin of ferroelectricity in InSe and establish a dynamic structural variation model for future investigations on more 2D ferroelectric materials.

Formic Acid-Intensified Photoreduction of NOx on Iron Minerals Triggers Daytime HONO Formation through Active Hydrogen.

Nitrous acid (HONO) is crucial in atmospheric chemistry as a precursor to morning peak hydroxyl radicals and significantly affects urban air quality by forming secondary pollutants, yet the mechanisms of its daytime formation is not fully understood. This study investigates the role of formic acid (HCOOH), a prevalent electron and proton donor, in the transformation of nitrogen oxides (NOx) and the formation of HONO on photoactive mineral dust. Exploiting hematite (Fe2O3) as an environmental indicator, we demonstrate that HCOOH significantly promotes the photoreduction of NO2 to HONO, while suppressing nitrate accumulation. This occurs through the formation of a surface ≡Fe-OOCH complex, where sunlight activates the C-H bond to generate and transfer active hydrogen, directly converting NO2 to HONO. Additionally, HCOOH can trigger the photolysis of nitrates as predeposited on Fe2O3, further increasing HONO production. These findings show that HCOOH-mediated photochemical reactions on iron minerals may contribute to elevated atmospheric HONO levels, highlighting a crucial pathway with broad effects on atmospheric chemistry and public health.

Mechanochemical Thioglycolate Modification of Microscale Zero-Valent Iron for Superior Heavy Metal Removal.

Microscale zero-valent iron (mZVI) is widely used for water pollutant control and environmental remediation, yet its reactivity is still constrained by the inert oxide shell. Herein, we demonstrate that mechanochemical thioglycolate (TG) modification can dramatically enhance heavy metal (NiII, CrVI, CdII, PbII, HgII, and SbIII) removal rates of mZVI by times of 16.7 to 88.0. Compared with conventional impregnation (wet chemical process), this dry mechanochemical process could construct more robust covalent bonding between TG and the inert oxide shell of mZVI through its electron-withdrawing carboxylate group to accelerate the electron release from the iron core, and more effectively strengthen the surface heavy metal adsorption through metal(d)-sulfur(p) orbital hybridization between its thiol group and heavy metal ions. Impressively, this mechanochemically TG-modified mZVI exhibited an unprecedented NiII removal capacity of 580.4 mg Ni g-1 Fe, 17.1 and 9.5 times those of mZVI and wet chemically TG-modified mZVI, respectively. Its application potential was further validated by more than 10 days of stable groundwater NiII removal in a column flow reactor. This study offers a promising strategy to enhance the reactivity of mZVI, and also emphasizes the importance of the modification strategy in optimizing its performance for environmental applications.

Reversed I1Cu4 single-atom sites for superior neutral ammonia electrosynthesis with nitrate.

Electrochemical ammonia (NH3) synthesis from nitrate reduction (NITRR) offers an appealing solution for addressing environmental concerns and the energy crisis. However, most of the developed electrocatalysts reduce NO3- to NH3 via a hydrogen (H*)-mediated reduction mechanism, which suffers from undesired H*-H* dimerization to H2, resulting in unsatisfactory NH3 yields. Herein, we demonstrate that reversed I1Cu4 single-atom sites, prepared by anchoring iodine single atoms on the Cu surface, realized superior NITRR with a superior ammonia yield rate of 4.36 mg h-1 cm-2 and a Faradaic efficiency of 98.5% under neutral conditions via a proton-coupled electron transfer (PCET) mechanism, far beyond those of traditional Cu sites (NH3 yield rate of 0.082 mg h-1 cm-2 and Faradaic efficiency of 36.5%) and most of H*-mediated NITRR electrocatalysts. Theoretical calculations revealed that I single atoms can regulate the local electronic structures of adjacent Cu sites in favor of stronger O-end-bidentate NO3- adsorption with dual electron transfer channels and suppress the H* formation from the H2O dissociation, thus switching the NITRR mechanism from H*-mediated reduction to PCET. By integrating the monolithic I1Cu4 single-atom electrode into a flow-through device for continuous NITRR and in situ ammonia recovery, an industrial-level current density of 1 A cm-2 was achieved along with a NH3 yield rate of 69.4 mg h-1 cm-2. This study offers reversed single-atom sites for electrochemical ammonia synthesis with nitrate wastewater and sheds light on the importance of switching catalytic mechanisms in improving the performance of electrochemical reactions.

Experimental study on the degradation of sandstone-petroglyph carriers in Helankou: Effects of freeze-thaw and wet-dry cycles.

The Helankou petroglyphs offer precious data for understanding the lifeways of ancient pastoralists. However, in Helankou, the combination of unique climate conditions and complex hydrochemical environments has accelerated the weathering of the sandstone-petroglyph carriers, leading to numerous petroglyphs at risk of vanishing. In response, this study employed freeze-thaw and wet-dry cycle experiments to simulate the actual environmental conditions for sandstone. Subsequently, the sandstone that underwent the experiments was subjected to further testing and analysis. The goal was to comprehensively understand the performance change patterns and micro-mechanisms in sandstone under environmental stress, thus providing scientific theoretical support for Helankou petroglyph conservation. The results indicate that under the effects of freeze-thaw and wet-dry, the degradation processes can be attributed to a diverse combination of mechanisms such as swelling-shrinkage, hydrolysis, frost heave, dissolution, and salt crystallization, which alter the physical parameters, particle size distribution, mineral composition, and structural integrity of the sandstone.

Phosphate modified nanoarchitectonics for promoted photocatalytic singlet oxygen generation and carbamazepine degradation of (010) facet-exposed BiOCl.

1O2 generation over (001) or (010) facet exposed BiOCl (B001 or B010) with/without phosphate modification were studied from the aspects of excitons involved energy transfer route, the O2- oxidation based charge transfer route and the H2O2 oxidation by HClO. Phosphate modification not only enhance charge separation thus result in H2O2 oxidation by HClO to release 1O2 but also weaken excitonic effect in the confined layer of BiOCl accordingly affect 1O2 generation via energy transfer. Considering [001] orientation favors the formation of excitons than that of [010] direction over BiOCl, excitons loss was hardly compensated by the H2O2 oxidation by HClO for 1O2 generation over phosphate modified B001. Nevertheless, limited excitonic effect makes the O2- oxidation by h+ via charge transfer as dominant route for 1O2 yielding over B010, the extra H2O2 oxidation with HClO after phosphate modification significantly enhance 1O2 generation over B010 followed with 2.2 times higher carbamazepine photodegradation activity. The initial attack of CC bond via 1O2 to form epoxide played important roles on carbamazepine degradation. This study demonstrated that the facet-specific phosphate modification of photocatalysts can finely tune reactive 1O2 species for superior pharmaceuticals degradations.

Superior Singlet Oxygen Electrosynthesis via Neighboring Dual Molecular Oxygen Coactivation for Selective Tetracycline Detoxification.

Oxygen (O2) electroreduction offers a green approach for singlet oxygen (1O2) synthesis in wastewater contaminants detoxification. However, traditional single O2 activation on single-metal catalytic sites seriously suffers from the kinetically-unfavorable desorption of adsorbed superoxide species (•O2 -*/•OOH*). Here, we demonstrate a novel dual O2 coactivation pathway on shortened Fe1-OV-Ti sites for superior 1O2 electrosynthesis through a rapid disproportionate process between surface-confined •O2 -*/•OOH*. Theoretical calculations combined with in situ electrochemical spectroscopies demonstrated that the shortened distance between Fe single atom and adjacent unsaturated Ti atom facilitates the direct recombination of surface-confined Fe-•OOH and Ti-•OO- to yield 1O2, bypassing the formidable •O2 -*/•OOH* desorption process. Impressively, Fe1-OV-Ti could realize an excellent 1O2 electrosynthesis rate of 54.5 µmol L-1 min-1 with an outstanding 1O2 selectivity of 97.6 % under neutral condition, surpassing that of Fe1-O-Ti (27.1 µmol L-1 min-1, 91.7 %). Using tetracycline (TC) as a model pollutant, the resulting Fe1-OV-Ti electrode achieved nearly 100 % degradation in 120 min at -0.6 V, meanwhile preventing the generation of toxic intermediates. This study provides a new 1O2 electrosynthesis strategy by controlling the distance of adjacent catalytic sites for the coactivation of dual molecular oxygen.

Efficient reduction of antibiotic resistance genes and mobile genetic elements in organic waste composting via fenton-like treatment.

Livestock manure harbors antibiotic resistance genes (ARGs), and aerobic composting (AC) is widely adopted for waste management. However, mitigating ARG resurgence in later stages remains challenging. This work aims to curb ARGs rebounding through a Fenton-like reaction during food waste and swine manure co-composting. Results revealed that 0.025 % zerovalent iron (ZVI) + 0.5 % hydrogen peroxide (H2O2) facilitated maximum ARG, mobile genetic elements (MGEs), and 16 s rRNA removal with reductions of 2.68, 2.69, and 1.4 logs. Spectroscopic analysis confirmed Fenton-like reaction and cell apoptosis analysis indicated that 0.025 % ZVI and 0.5 % H2O2 treatment had the maximum early apoptosis, least observed, and normal cells on day 30. Redundancy analysis highlighted the influence of bacterial communities and physicochemical properties on ARGs, with MGEs playing a crucial role in Fenton treatments. Our findings suggest incorporating ZVI and H2O2 in composting can significantly reduce ARGs and enhance waste management practices.

Restricted Growth of Vinylene-Linked Covalent Organic Frameworks along Two-Dimensional Plane Using Heterogeneous Catalysis.

The vinylene-linked covalent organic frameworks (viCOFs) have been generally synthesized in the presence of homogeneous catalysts such as KOH or trifluoroacetic acid. However, highly ordered viCOFs cannot always be obtained due to the uncommitted growth of viCOF layers in the homogeneous system with ubiquitous catalysts. Here, we propose a scalable protocol to restrict the growth of viCOFs along the two-dimensional (2D) plane by introducing a heterogeneous catalyst, polyoxometalates (POMs). With the unique Brønsted alkalinity and catalytic surface, POMs induce the growth of 2D viCOF layers along the surface of the catalytic substrate and restrain the generation of out-of-plane branches. Based on this protocol, six typical 2D viCOFs with high crystallinity and porosity were synthesized within a shorter reaction time as compared with the reported works using the common homogeneous catalysts for viCOF synthesis. On the basis of the density functional theory calculations and experimental results, a bottom intercalation growth pattern of viCOFs was revealed during the heterogeneous reaction. The unique growth pattern greatly promotes the orderly assembly of monomers, thus shortening the reaction time and improving the crystallinity of viCOFs. Furthermore, this heterogeneous catalysis strategy is suitable for the gram-scale preparation of 2D viCOFs. These results provide a novel avenue for the synthesis of high-quality viCOFs and may bring new insights into the synthetic methodology of COFs.

Juvenile bright light exposure ameliorates adult behavioral abnormalities by enhancing neurogenesis in a N-methyl-D-aspartate receptor dysfunction mouse model relevant for cognitive impairment in schizophrenia.

Exposure to light has been demonstrated to stimulate brain regions associated with cognition; however, investigations into its cognitive-enhancing effects have primarily focused on wild-type rodents. This study seeks to elucidate how bright light exposure mitigates cognitive deficits associated with schizophrenia by examining its impact on hippocampal neurogenesis and its potential to alleviate sub-chronic MK-801-induced cognitive impairments in mice. Following three weeks of juvenile bright light exposure (5-8 weeks old), significant increases in proliferating neurons (BrdU+) and immature neurons (DCX+ cells) were observed in the dentate gyrus (DG) and lateral ventricle of MK-801-treated mice. Long-term bright light treatment further promoted the differentiation of BrdU+ cells into immature neurons (BrdU+ DCX+ cells), mature neurons (BrdU+ NeuN+ cells), or astrocytes (BrdU+ GFAP+ cells) in the hippocampal DG. This augmented neurogenesis correlated with the attenuation of sub-chronic MK- 801-induced cognitive deficits, as evidenced by enhancements in Y-maze, novel object recognition (NOR), novel location recognition (NLR), and Morris water maze (MWM) test performances. These findings suggest a promising noninvasive clinical approach for alleviating cognitive impairments associated with neuropsychiatric disorders.

Adjunctive clozapine with bright light mitigates cognitive deficits by synaptic plasticity and neurogenesis in sub-chronic MK-801 treated mice.

Schizophrenia impacts about 1 % of the global population, with clozapine (CLZ) being a critical treatment for refractory cases despite its limitations in effectiveness and adverse effects. Therefore, the search for more effective treatments remains urgent. Light treatment (LT) recognized for enhancing cognition and mood, presents a promising complementary approach. This study investigated the effects of CLZ and LT on cognitive impairments in a sub-chronic MK-801 induced schizophrenia mouse model. Results showed that both CLZ and CLZ + LT treatment elevate cognitive performance of sub-chronic MK-801 treated mice in serial behavioral tests over two months. Histological analysis revealed increased dendritic spine density and branching, and synaptic repair in the hippocampus with CLZ and CLZ + LT interventions. Furthermore, both treatments increased brain-derived neurotrophic factor (BDNF) expression in the hippocampus, likely contributing to cognitive amelioration in MK-801 treated mice. Additionally, BrdU labeling revealed that CLZ + LT further enhances neurogenesis in the dentate gyrus (DG) and lateral ventricle (LV) of sub-chronic MK-801 treated mice. These findings may have implications for the development of noninvasive and adjunctive treatment strategies aimed at alleviating cognitive impairments and improving functional outcomes in individuals with schizophrenia.

Ultrastable and efficient slight-interlayer-displacement 2D Dion-Jacobson perovskite solar cells.

Stability has been a long-standing concern for solution-processed perovskite photovoltaics and their practical applications. However, stable perovskite materials for photovoltaic remain insufficient to date. Here we demonstrate a series of ultrastable Dion-Jacobson (DJ) perovskites (1,4-cyclohexanedimethanammonium)(methylammonium)n-1PbnI3n+1 (n ≥ 1) for photovoltaic applications. The scalable technology by blade-coated solar cells for the designed DJ perovskites (nominal n = 5) achieves a maximum stabilized power conversion efficiency (PCE) of 19.11% under an environmental atmosphere. Un-encapsulated cells by blade-coated technology retain 92% of their initial efficiencies for over 4000 hours under ~90% relative humidity (RH) aging conditions. More importantly, these cells also exhibit remarkable thermal (85 °C) and operational stability, which shows negligible efficiency loss after exceeding 5000-hour heat treatment or after operation at maximum power point (MPP) exceeding 6000 hours at 45 °C under a 100 mW cm-2 continuous light illumination.

Highly selective urea electrooxidation coupled with efficient hydrogen evolution.

Electrochemical urea oxidation offers a sustainable avenue for H2 production and wastewater denitrification within the water-energy nexus; however, its wide application is limited by detrimental cyanate or nitrite production instead of innocuous N2. Herein we demonstrate that atomically isolated asymmetric Ni-O-Ti sites on Ti foam anode achieve a N2 selectivity of 99%, surpassing the connected symmetric Ni-O-Ni counterparts in documented Ni-based electrocatalysts with N2 selectivity below 55%, and also deliver a H2 evolution rate of 22.0 mL h-1 when coupled to a Pt counter cathode under 213 mA cm-2 at 1.40 VRHE. These asymmetric sites, featuring oxygenophilic Ti adjacent to Ni, favor interaction with the carbonyl over amino groups in urea, thus preventing premature resonant C⎓N bond breakage before intramolecular N-N coupling towards N2 evolution. A prototype device powered by a commercial Si photovoltaic cell is further developed for solar-powered on-site urine processing and decentralized H2 production.

KRAS Promotes GLI2-Dependent Transcription during Pancreatic Carcinogenesis.

Aberrant activation of GLI transcription factors has been implicated in the pathogenesis of different tumor types including pancreatic ductal adenocarcinoma. However, the mechanistic link with established drivers of this disease remains in part elusive. In this study, using a new genetically engineered mouse model overexpressing constitutively active mouse form of GLI2 and a combination of genome-wide assays, we provide evidence of a novel mechanism underlying the interplay between KRAS, a major driver of pancreatic ductal adenocarcinoma development, and GLI2 to control oncogenic gene expression. These mice, also expressing KrasG12D, show significantly reduced median survival rate and accelerated tumorigenesis compared with the KrasG12D only expressing mice. Analysis of the mechanism using RNA sequencing demonstrate higher levels of GLI2 targets, particularly tumor growth-promoting genes, including Ccnd1, N-Myc, and Bcl2, in KrasG12D mutant cells. Furthermore, chromatin immunoprecipitation sequencing studies showed that in these cells KrasG12D increases the levels of trimethylation of lysine 4 of the histone 3 (H3K4me3) at the promoter of GLI2 targets without affecting significantly the levels of other major active chromatin marks. Importantly, Gli2 knockdown reduces H3K4me3 enrichment and gene expression induced by mutant Kras. In summary, we demonstrate that Gli2 plays a significant role in pancreatic carcinogenesis by acting as a downstream effector of KrasG12D to control gene expression.

Redox Reactions of Organic Molecules Using Rotating Magnetic Field and Metal Rods.

In recent years, redox reactions have harnessed light or mechanical energy to enable the formation of chemical bonds. We postulated a complementary approach that electromagnetic induction could promote the redox reaction of organic molecules using a rotating magnetic field and metal rods. Here, we report that electromotive force activates the redox-active trifluoromethylating reagents. This magnetoredox system can be applied to the trifluoromethylation of heteroarenes with high regioselectivity and hydrotrifluoromethylation of alkenes without the need for catalysts and organic additives.

Endometrial microbial dysbiosis and metabolic alteration promote the development of endometrial cancer.

OBJECTIVE: Emerging evidence suggests that the endometrial microbiome plays important roles in the development of endometrial cancer (EC). Here, we evaluate stage-specific roles of microbial dysbiosis and metabolic disorders in patients with EC, patients with endometrial hyperplasia (EH), and patients afflicted with benign uterine conditions (CK). METHODS: This prospective cohort study included 33 women with EC, 15 women with endometrial EH, and 15 women with benign uterine conditions (CK) from November 2022 to September 2023. Different typical endometrial samples were imaged with a scanning electron microscope and a transmission electron microscope. The endometrial microbiome was assessed by sequencing the V3-V4 region of the 16S rRNA gene and the ITS1 to fill the gap in relation to the study of the uterine fungal microbiome. Moreover, liquid chromatography-mass spectrometry-based metabolomics was used to identify and quantify metabolic changes among these groups. RESULTS: The endometrial microbiome revealed that there is a structural microbiome shift and an increase in the α-diversity in the EC and EH cases, distinguishable from the benign cases, especially the fungal community structure. The fungal microbiome from patients with EC and EH was altered relative to controls and dominated by Penicillium sp. By contrast, Sarocladium was more abundant in controls. Significant differences were observed in the composition and content of compounds between benign cases and EC, especially estradiol-like metabolism-related substances. Altered microbiota was correlated with the concentrations of interleukin-6 (IL-6), IL-11, transforming growth factor-beta, and ß-glucuronidase activity especially the relative abundance increase of Penicillium sp. CONCLUSIONS: This study suggested that the endometrial microbiome is complicit in modulating the development of EC such as estrogen activity and a pro-inflammatory response. Our work provides a new insight into the endometrial microbiome from a perspective of stages, which opens up new avenues for EC prognosis and therapy.

[Effects of water-nitrogen interactions on NH3 and N2O emissions and yield in winter wheat cropland]. / 水氮互作对冬小麦农田NH3和N2O排放及产量的影响.

To investigate the effects of different irrigation and nitrogen application modes on nitrogen gaseous loss in winter wheat farmland, we conducted a field experiment at Changqing Irrigation Experiment Station in Shandong Province, with two irrigation levels (80%-90% θf(I1) and 70%-80% θf(I2)) and three nitrogen application levels (conventional nitrogen application of 240 kg·hm-2(N1), nitrogen reduction of 12.5% (N2), and nitrogen reduction of 25% (N3)). The results showed that ammonia volatilization and nitrous oxide emission rate peak appeared within 2-4 days after fertilization or irrigation. The ammonia volatilization rate during the chasing fertilizer period was significantly higher than that during the basal fertilizer period. Compared with other treatments, the ave-rage ammonia volatilization rate of I2N2 treatment during the chasing fertilizer period was reduced by 10.1%-51.6%, and the average nitrous oxide emission rate over the whole growth period was reduced by 15.4%-52.2%. The ammonia volatilization rate was significantly positively associated with surface soil pH value and ammonium nitrogen content, while the nitrous oxide emission rate was significantly positively associated with nitrate content in topsoil. The accumulation amount of soil ammonia volatilization and nitrous oxide emission ranged from 0.83-1.42 and 0.11-0.33 kg·hm-2, respectively. Moderate reduction of irrigation water and nitrogen input could effectively reduce cumulative amounts of ammonia volatilization and nitrous oxide emission from winter wheat farmland. The cumulative amounts of ammonia volatilization and nitrous oxide emission under I1N3 and I2N2 treatments were signi-ficantly lower than those under other treatments. The highest winter wheat yield (5615.6 kg·hm-2) appeared in I2N2 treatment. The irrigation water utilization efficiency of I2 was significantly higher than that of I1, with the maximum increase rate of 45.2%. Compared with N1 and N3 treatments, the maximum increase rate of nitrogen fertilizer productivity and agricultural utilization efficiency in N2 reached 15.2% and 31.8%, respectively. In conclusion, the treatment with 70%-80% θf irrigation level and 210 kg·hm-2 nitrogen input could effectively improve the utilization efficiency of irrigation water and nitrogen fertilization and reduce gaseous loss from winter wheat farmland.

Cu1-Fe Dual Sites for Superior Neutral Ammonia Electrosynthesis from Nitrate.

The electrochemical nitrate reduction reaction (NO3RR) is able to convert nitrate (NO3 -) into reusable ammonia (NH3), offering a green treatment and resource utilization strategy of nitrate wastewater and ammonia synthesis. The conversion of NO3 - to NH3 undergoes water dissociation to generate active hydrogen atoms and nitrogen-containing intermediates hydrogenation tandemly. The two relay processes compete for the same active sites, especially under pH-neutral condition, resulting in the suboptimal efficiency and selectivity in the electrosynthesis of NH3 from NO3 -. Herein, we constructed a Cu1-Fe dual-site catalyst by anchoring Cu single atoms on amorphous iron oxide shell of nanoscale zero-valent iron (nZVI) for the electrochemical NO3RR, achieving an impressive NO3 - removal efficiency of 94.8 % and NH3 selectivity of 99.2 % under neutral pH and nitrate concentration of 50 mg L-1 NO3 --N conditions, greatly surpassing the performance of nZVI counterpart. This superior performance can be attributed to the synergistic effect of enhanced NO3 - adsorption on Fe sites and strengthened water activation on single-atom Cu sites, decreasing the energy barrier for the rate-determining step of *NO-to-*NOH. This work develops a novel strategy of fabricating dual-site catalysts to enhance the electrosynthesis of NH3 from NO3 -, and presents an environmentally sustainable approach for neutral nitrate wastewater treatment.

Spin Hall effect modulated by an electric field in asymmetric two-dimensional MoSiAs2Se.

Spin current generation from charge current in nonmagnetic materials promises an energy-efficient scheme for manipulating magnetization in spintronic devices. In some asymmetric two-dimensional (2D) materials, the Rashba and valley effects coexist owing to strong spin-orbit coupling (SOC), which induces the spin Hall effect due to spin-momentum locking of both effects. Herein, we propose a new Janus structure MoSiAs2Se with both valley physics and the Rashba effect and reveal an effective way to modulate the properties of this structure. The results demonstrated that applying an external electric field is an effective means to modulating the electronic properties of MoSiAs2Se, leading to both type I-II phase transitions and semiconductor-metal phase transitions. Furthermore, the coexistence of the Rashba and valley effects in monolayer MoSiAs2Se contributes to the spin Hall effect (SHE). The magnitude and direction of spin Hall conductivity can also be manipulated with an out-of-plane electric field. Our results enrich the physics and materials of the Rashba and valley systems, opening new opportunities for the applications of 2D Janus materials in spintronic devices.