How sediment dredging alters phosphorus dynamics in a lowland rural river?

China's lowland rural rivers are facing severe eutrophication problems due to excessive phosphorus (P) from anthropogenic activities. However, quantifying P dynamics in a lowland rural river is challenging due to its complex interaction with surrounding areas. A P dynamic model (River-P) was specifically designed for lowland rural rivers to address this challenge. This model was coupled with the Environmental Fluid Dynamics Code (EFDC) and the Phosphorus Dynamic Model for lowland Polder systems (PDP) to characterize P dynamics under the impact of dredging in a lowland rural river. Based on a two-year (2020-2021) dataset from a representative lowland rural river in the Lake Taihu Basin, China, the coupled model was calibrated and achieved a model performance (R2>0.59, RMSE<0.04 mg/L) for total P (TP) concentrations. Our research in the study river revealed that (1) the time scale for the effectiveness of sediment dredging for P control was ∼300 days, with an increase in P retention capacity by 74.8 kg/year and a decrease in TP concentrations of 23% after dredging. (2) Dredging significantly reduced P release from sediment by 98%, while increased P resuspension and settling capacities by 16% and 46%, respectively. (3) The sediment-water interface (SWI) plays a critical role in P transfer within the river, as resuspension accounts for 16% of TP imports, and settling accounts for 47% of TP exports. Given the large P retention capacity of lowland rural rivers, drainage ditches and ponds with macrophytes are promising approaches to enhance P retention capacity. Our study provides valuable insights for local environmental departments, allowing a comprehensive understanding of P dynamics in lowland rural rivers. This enable the evaluation of the efficacy of sediment dredging in P control and the implementation of corresponding P control measures.

Global prevalence of liver disease in human and domestic animals caused by Fasciola: A systematic review and meta-analysis.

Background: Liver disease caused by Fasciola is a significant zoonotic and parasitic disease with substantial economic impacts on humans and animals. Many studies have looked at the prevalence of fasciolis worldwide, yet the overall prevalence and risk factors in cattle, ruminants, and humans remains unknown. Methods: We conducted a systematic review and meta-analysis to estimate the global prevalence and risk factors of fascioliasis in humans and domestic ruminants. With this aim, we searched PubMed, ScienceDirect, Web of Science, and Scopus from inception to 8 December 2022 for studies reporting the prevalence of fascioliasis in humans or domestic ruminants post-2000. We then used random effects models to describe the prevalence of fascioliasis; trim-and-fill analysis and Egger's test to assess publication bias; and meta-regression and sensitivity analyses to examine the risk factors for prevalence and heterogeneity. Results: We retrieved 4422 articles, with 371 being included in the analysis, as they concerned fascioliasis in humans and ruminants globally. The pooled prevalence of bovine fasciolosis was 17%, while ovine fasciolosis and human fascioliasis had pooled prevalences of 13% and 5%, respectively. We also conducted subgroup analyses by continents, countries, Fasciola species, sampling years, altitude, rainfall, temperature, humidity, age, sex, feeding mode, and residence. Here, altitude and age emerged as risk factors associated with an increased prevalence of fascioliasis. Both the trim-and-fill analysis and Egger's test confirmed the presence of publication bias, while the sensitivity analysis showed that the omission of any single study did not significantly influence the combined pooled prevalence. Conclusions: Fascioliasis is a widely prevalent zoonosis among humans and livestock worldwide. Strategies targeting risk factors such as altitude and age are urgently needed for prevention and control of this disease, which will consequently reduce Fasciola infection. Additionally, given the inadequacy or absence of data in some countries, greater attention should be paid to Fasciola infection, with further epidemiological studies focussing on improving data quality.

Declined nutrients stability shaped by water residence times in lakes and reservoirs under climate change.

Water quality stability in lakes and reservoirs is essential for drinking water safety and ecosystem health, especially given the frequent occurrence of extreme climate events. However, the relationship between water quality stability and water residence time (WRT) has not been well elucidated. In this study, we explored the relationship based on nitrogen (N) and phosphorus (P) concentrations data in 11 lakes and 49 reservoirs in the Yangtze-Huaihe River basin from 2010 to 2022. Additionally, we examined the effects of hydrometeorological characteristics, the geomorphology of water bodies and catchments, and land use on the WRT, establishing a link between climate change and the stability of N and P in these water bodies. The results showed that a significant correlation between the stability of N and P in lakes and reservoirs and their WRT. The longer WRT tends to coincide with decreased stability and higher nutrient concentrations. Hydrometeorological factors are the primary factors on the WRT, with precipitation exerting the greatest effect, particularly under extreme drought. In recent years, extreme climatic events have intensified the fluctuations of WRT, resulting in a renewed increase in N and P concentrations and deterioration in stability. These findings highlight the importance of incorporating meteorological and hydrological factors alongside reinforcing ecological restoration into lake and reservoir management strategies, and providing a scientific basis for future efforts aimed at enhancing lake and reservoir water quality stability and safeguarding aquatic ecosystems.

Study on the Storage Stability and Rheological Property of Bio-Oil/Lignin Composite-Modified Asphalt.

The objective of this study is to investigate the storage stability and rheological property of bio-oil/lignin composite-modified asphalt. The composite-modified asphalt with different proportions of bio-oil was prepared and cured at 105 °C, 135 °C, and 165 °C for 24 h and 48 h. The storage stability of the composite-modified asphalt was evaluated based on the softening point difference, the storage stability index derived from rotational viscosity, the segregation rate based on temperature sweep, and the non-recoverable creep compliance measured through the Multiple Stress Creep Recovery test. The storage stability of bio-oil/lignin composite-modified asphalt was evaluated through testing and analysis of its infrared spectroscopy and scanning electron microscopy before and after thermal storage. The research results indicate that the maximum difference in softening point is 0.9 °C, and the calculated storage stability index is generally below 0.1. The maximum value of the segregation rate is 0.43, indicating excellent storage stability of the bio-oil/lignin composite-modified asphalt. According to the results from infrared spectroscopy, no chemical reactions occurred during the storage process of the composite-modified asphalt. The scanning electron microscope confirmed that the samples became more stable after 48 h of storage.

Bending Forming Characteristics of CoCrFeMnNi High-Entropy Alloy Sheets Induced by Nanosecond Pulse Laser Irradiation.

Laser bending forming, as a flexible and die-less forming approach, facilitates the three-dimensional shaping of sheets through the generation of thermal stress via laser-material interaction. In this study, the bending forming characteristics of CoCrFeMnNi high-entropy alloy sheets induced by nanosecond pulse laser irradiation were systematically investigated. The effects of parameters including laser power, scanning speed, number of scans, scanning interval, and sheet size on the bending angle, cross-sectional morphology, and hardness were studied in detail under both the laser single-line and multi-line scanning modes. The experimental results confirmed the effectiveness of nanosecond pulse laser irradiation for achieving accurate formation of CoCrFeMnNi sheets, with the successful fabrication of J, L, and U-shaped metal components. Apart from the forming ability, the cross-sectional hardness was significantly increased due to the grain refinement effect of nanosecond pulse laser irradiation. Furthermore, employing the laser single-line scanning mode enabled the effective rectification of overbending parts, showcasing complete recovery for small-angle overbending, and a remarkable 91% recovery for larger-angle overbending. This study provides an important basis for the bendability of CoCrFeMnNi sheets by laser forming and elucidates the evolution of the microstructure and mechanical properties in the bending region.

Identification of Methamphetamine Abusers Can Be Supported by EEG-Based Wavelet Transform and BiLSTM Networks.

Methamphetamine (MA) is a neurological drug, which is harmful to the overall brain cognitive function when abused. Based on this property of MA, people can be divided into those with MA abuse and healthy people. However, few studies to date have investigated automatic detection of MA abusers based on the neural activity. For this reason, the purpose of this research was to investigate the difference in the neural activity between MA abusers and healthy persons and accordingly discriminate MA abusers. First, we performed event-related potential (ERP) analysis to determine the time range of P300. Then, the wavelet coefficients of the P300 component were extracted as the main features, along with the time and frequency domain features within the selected P300 range to classify. To optimize the feature set, F_score was used to remove features below the average score. Finally, a Bidirectional Long Short-term Memory (BiLSTM) network was performed for classification. The experimental result showed that the detection accuracy of BiLSTM could reach 83.85%. In conclusion, the P300 component of EEG signals of MA abusers is different from that in normal persons. Based on this difference, this study proposes a novel way for the prevention and diagnosis of MA abuse.

Analysis of alpha-1-antitrypsin (AAT)-regulated, glucocorticoid receptor-dependent genes in macrophages reveals a novel host defense function of AAT.

Alpha-1-antitrypsin (AAT) plays a homeostatic role in attenuating excessive inflammation and augmenting host defense against microbes. We demonstrated previously that AAT binds to the glucocorticoid receptor (GR) resulting in significant anti-inflammatory and antimycobacterial consequences in macrophages. Our current investigation aims to uncover AAT-regulated genes that rely on GR in macrophages. We incubated control THP-1 cells (THP-1control) and THP-1 cells knocked down for GR (THP-1GR-KD) with AAT, performed bulk RNA sequencing, and analyzed the findings. In THP-1control cells, AAT significantly upregulated 408 genes and downregulated 376 genes. Comparing THP-1control and THP-1GR-KD cells, 125 (30.6%) of the AAT-upregulated genes and 154 (41.0%) of the AAT-downregulated genes were significantly dependent on GR. Among the AAT-upregulated, GR-dependent genes, CSF-2 that encodes for granulocyte-monocyte colony-stimulating factor (GM-CSF), known to be host-protective against nontuberculous mycobacteria, was strongly upregulated by AAT and dependent on GR. We further quantified the mRNA and protein of several AAT-upregulated, GR-dependent genes in macrophages and the mRNA of several AAT-downregulated, GR-dependent genes. We also discussed the function(s) of selected AAT-regulated, GR-dependent gene products largely in the context of mycobacterial infections. In conclusion, AAT regulated several genes that are dependent on GR and play roles in host immunity against mycobacteria.

Molecular Engineering of Hydrogen-Bonded Organic Framework for Enhanced Nitrate Electroreduction to Ammonia.

Electrocatalytic nitrate reduction is an efficient way to produce ammonia sustainably. Herein, we rationally designed a copper metalloporphyrin-based hydrogen-bonded organic framework (HOF-Cu) through molecular engineering strategies for electrochemical nitrate reduction. As a result, the state-of-the-art HOF-Cu catalyst exhibits high NH3 Faradaic efficiency of 93.8%, and the NH3 production rate achieves a superior activity of 0.65 mmol h-1 cm-2. The in situ electrochemical spectroscopic combined with density functional theory calculations reveals that the dispersed Cu promotes the adsorption of NO3- and the mechanism is followed by deoxidation of NO3- to *NO and accompanied by deep hydrogenation. The generated *H participates in the deep hydrogenation of intermediate with fast kinetics as revealed by operando electrochemical impedance spectroscopy, and the competing hydrogen evolution reaction is suppressed. This research provides a promising approach to the conversion of nitrate to ammonia, maintaining the nitrogen balance in the atmosphere.

Copper as an Electron Hunter for Enhancing Bi2O2CO3 Electrocatalytic CO2 Conversion to Formate.

Cu-doped Bi2O2CO3 catalyst with copper (Cu) acting an electron hunter for conversion of carbon dioxide into formate is developed. The Cu-Bi2O2CO3 catalyst with hollow microsphere structure extends the duration of CO2 retention on the catalyst, providing a greater number of active sites. It exhibits remarkable performance with conversion efficacy of 98.5% and current density of 800 mA cm-2 across a wide potential window (-0.8 to -1.3 V vs RHE). Density functional theory investigations reveal that the presence of copper (Cu) significantly enhances the charge density at the active sites and influences the local electronic structure of bismuth (Bi), thereby reducing the energy barrier associated with the transformation of *OCHO species into formate.

Hydrometeorological conditions drive long-term changes in the spatial distribution of Potamogeton crispus in a subtropical lake.

Globally, anthropogenic disturbance and climate change caused a rapid decline of submerged macrophytes in lake ecosystems. Potamogeton crispus (P. crispus), a species that germinates in winter, explosively expanded throughout many Chinese lakes, yet the underlying mechanism remained unclear. Here, this study examined the long-term changes in the distribution patterns of P. crispus in Lake Gaoyou by combining remote sensing images and hydrometeorological data from 1984 to 2022 and water quality data from 2009 to 2022. It aims to unravel the relationships between the distribution patterns of P. crispus and hydrometeorological and water quality factors. The results showed that the area of P. crispus in Lake Gaoyou showed a slight increase from 1984 to 2009, a marked increase from 2010 to 2019, followed by a decline after 2020. Spatially, P. crispus was primarily distributed in the western and northern parts of Lake Gaoyou, with less distribution in the central and southeastern parts of the lake. Wind speed (WS), temperature (Temp), water level (WL), ammonia nitrogen (NH3-N), and Secchi depth (SD) were identified as the key factors regulating the variation in the P. crispus area in Lake Gaoyou. We found that the P. crispus area showed an increasing trend with increasing Temp, WL, and SD and decreasing WS and NH3-N. The influence of environmental factors on the area of P. crispus in Lake Gaoyou varied among seasons. The results indicated that hydrometeorology (WS, Temp, and WL) may override water quality (NH3-N and SD) in driving the succession of P. crispus distribution. The findings of this study offer valuable insights into the recent widespread expansion of P. crispus in shallow lakes across Eastern China.

Microfluidic Continuous Synthesis of Size- and Facet-Controlled Porous Bi2O3 Nanospheres for Efficient CO2 to Formate Catalysis.

Bismuth-based catalysts are effective in converting carbon dioxide into formate via electrocatalysis. Precise control of the morphology, size, and facets of bismuth-based catalysts is crucial for achieving high selectivity and activity. In this work, an efficient, large-scale continuous production strategy is developed for achieving a porous nanospheres Bi2O3-FDCA material. First-principles simulations conducted in advance indicate that the Bi2O3 (111)/(200) facets help reduce the overpotential for formate production in electrocatalytic carbon dioxide reduction reaction (ECO2RR). Subsequently, using microfluidic technology and molecular control to precisely adjust the amount of 2, 5-furandicarboxylic acid, nanomaterials rich in (111)/(200) facets are successfully synthesized. Additionally, the morphology of the porous nanospheres significantly increases the adsorption capacity and active sites for carbon dioxide. These synergistic effects allow the porous Bi2O3-FDCA nanospheres to stably operate for 90 h in a flow cell at a current density of ≈250 mA cm- 2, with an average Faradaic efficiency for formate exceeding 90%. The approach of theoretically guided microfluidic technology for the large-scale synthesis of finely structured, efficient bismuth-based materials for ECO2RR may provide valuable references for the chemical engineering of intelligent nanocatalysts.

Prevalence and Molecular Characterization of Cryptosporidium spp., Giardia duodenalis, and Enterocytozoon bieneusi in Cattle in Heilongjiang Province, Northeast China.

Crytosporidium spp., Giardia duodenalis, and Enterocytozoon bieneusi are important diarrheal pathogens with a global distribution that threatens the health of humans and animals. Despite cattle being potential transmission hosts of these protozoans, the associated risks to public health have been neglected. In the present study, a total of 1155 cattle fecal samples were collected from 13 administrative regions of Heilongjiang Province. The prevalence of Cryptosporidium spp., G. duodenalis, and E. bieneusi were 5.5% (64/1155; 95% CI: 4.2-6.9), 3.8% (44/1155; 95% CI: 2.7-4.9), and 6.5% (75/1155; 95% CI: 5.1-7.9), respectively. Among these positive fecal samples, five Cryptosporidium species (C. andersoni, C. bovis, C. ryanae, C. parvum, and C. occultus), two G. duodenalis assemblages (E and A), and eight E. bieneusi genotypes (BEB4, BEB6, BEB8, J, I, CHS7, CHS8, and COS-I) were identified. Phylogenetic analysis showed that all eight genotypes of E. bieneusi identified in the present study belonged to group 2. It is worth noting that some species/genotypes of these intestinal protozoans are zoonotic, suggesting a risk of zoonotic disease transmission in endemic areas. The findings expanded our understanding of the genetic composition and zoonotic potential of Cryptosporidium spp., G. duodenalis, and E. bieneusi in cattle in Heilongjiang Province.

Shifts of the pond area ratio for lowland polders: Implication for nutrient control.

Shifts for natural ecosystems were increasingly concerned due to its profound impacts on ecosystem services. Ponds within lowland artificial watersheds (polders) play a critical role in nitrogen (N) and phosphorus (P) cycling. From the perspective of N & P control in management practices, it is needed to determine an optimal pond area ratio for polders. For this purpose, our study proposed a process-based modelling framework to investigate the response of polder N & P loss to pond area, and thus to determine the threshold value of pond area ratio to achieve maximum N & P reduction for polders. The proposed framework included two process-based models (NDP and PDP) specially developed to describe N & P dynamics in lowland polders. To evaluate the proposed performance of the framework, it was applied to 171 polders in Zhong River Watershed in Lake Taihu Basin, eastern China. Our investigation results revealed that the correlation between polder N & P reduction rate and pond area ratio had an abrupt shift of 13.6 %, 14.7 % for N & P, respectively. Therefore, polders with a pond area ratio of 13.6-14.7 % had the largest N & P reduction (5.27 and 0.19 kg/ha). Polder size affected P reduction rate, with smaller polders (<200 ha) showing a higher P reduction rate, while it did not affect N reduction rate. Compared with annual precipitation, rainy-season precipitation more significantly (P<0.01) determined polder N & P reduction. This study demonstrated the use of our process-based framework in characterizing the shifts for the pond area ratio for polders, and thus provided technical support for N & P control of lowland areas in water management practices.

Lycopene Promotes Osteogenesis and Reduces Adipogenesis through Regulating FoxO1/PPARγ Signaling in Ovariectomized Rats and Bone Marrow Mesenchymal Stem Cells.

Recent interest in preventing the development of osteoporosis has focused on the regulation of redox homeostasis. However, the action of lycopene (LYC), a strong natural antioxidant compound, on osteoporotic bone loss remains largely unknown. Here, we show that oral administration of LYC to OVX rats for 12 weeks reduced body weight gain, improved lipid metabolism, and preserved bone quality. In addition, LYC treatment inhibited ROS overgeneration in serum and bone marrow in OVX rats, and in BMSCs upon H2O2 stimulation, leading to inhibiting adipogenesis and promoting osteogenesis during bone remodeling. At the molecular level, LYC improved bone quality via an increase in the expressions of FoxO1 and Runx2 and a decrease in the expressions of PPARγ and C/EBPα in OVX rats and BMSCs. Collectively, these findings suggest that LYC attenuates osteoporotic bone loss through promoting osteogenesis and inhibiting adipogenesis via regulation of the FoxO1/PPARγ pathway driven by oxidative stress, presenting a novel strategy for osteoporosis management.

Restore polder and aquaculture enclosure to the lake: Balancing environmental protection and economic growth for sustainable development.

The restoration of lakes and their buffer zones is crucial for understanding the intricate interplay between human activities and natural ecosystems resulting from the implementation of environmental policies. In this study, we investigated the ecological restoration of shallow lakes and buffer zones in the Yangtze-Huaihe River Basin, specifically focusing on the removal of polder and aquaculture enclosure areas within the lakes. By examining data from eight shallow lakes and their corresponding buffer zones, encompassing lake morphology, water quality parameters, and land use/land cover (LULC) data spanning from 2008 to 2022, which shed light on the complex relationships involved. During the process of restoring polder and aquaculture enclosure areas, we observed a general decrease in the extent of polders and aquaculture enclosures within the lakes. Notably, the removal of aquaculture enclosures had a more pronounced effect (reduction rate of 83.37 %) compared to the withdrawal of polders (reduction rate of 48.76 %). Linear regression analysis revealed a significant decrease in the concentrations of seven water quality parameters, including COD, CODMn, TN, TP, NH3-N, Chl-a, and F, while pH and DO factors exhibit a distinct increasing trend. The results of redundancy analysis and Pearson correlation analysis demonstrated significant correlations between the area of polders and aquaculture enclosures and the changes in lake water quality. Encouragingly, the withdrawal of polders and the removal of aquaculture enclosures had a positive impact on the lake water quality improvement. In contrast, the LULC in the buffer zones of the lakes experienced a gradual decline owing to land degradation, resulting in a reduction in ecosystem service value (ESV). These results offer valuable support for policymakers in their endeavors to restore lake water quality, mitigate the degradation of buffer zones land, and promote the sustainable development of land and water resources.

Metabolome-microbiome insights into therapeutic impact of 8-O-acetylharpagide against breast cancer in a murine model.

Iridoid glycosides extract, which is the main active extract of Ajuga decumbens Thunb, has been proved to have anti-breast cancer activity in previous studies. However, it is still unknown whether 8-O-acetylharpagide, a main active compound in the extract, has anti-breast cancer activity. In this study, 4 T1 breast cancer mice model was first successfully established. Then the anti-breast cancer effect of 8-O-acetylharpagide was systematically investigated. Feces were collected for metabolomics and 16S rRNA analysis to assess the potential mechanism. The results showed that 8-O-acetylharpagide was effective in reducing 4 T1 mouse tumor volume and weight compared with the model group. Metabolome analysis revealed 12 potential metabolite biomarkers in feces, mainly involved in primary bile acid biosynthesis and arachidonic acid metabolism. The 16S rRNA sequencing results demonstrated that 8-O-acetylharpagide modulated the abundance of the intestinal flora in 4 T1 mice. Spearman correlation analysis showed that calcitriol and prostaglandin G2 strongly correlated with Akkermansia, Firmicutes and Muribaculum. Overall, the active compound 8-O-acetylharpagide could inhibit significantly breast cancer growth in 4 T1 breast cancer model mice. The mechanism of the anti-breast cancer effect of 8-O-acetylharpagide may be related to the regulation of primary bile acid biosynthesis and arachidonic acid metabolism and modulation of the abundance of Akkermansia and Firmicutes.

Hydro-meteorological factors and inflowing nutrients drive water quality in an impounded lake of China's South-to-North Water Diversion Project.

Freshwater lakes play a vital role in global hydrological and biogeochemical cycles, serving various functions and maintaining ecological balance. However, freshwater resources are more vulnerable to deterioration due to multiple stressors. Gaoyou Lake is one of the impounded lakes of the Eastern route of South-to-North Water Diversion Project in China, and as an important source of drinking water, the lake has been routinely monitored. Long-term monitoring of water quality in Gaoyou Lake showed that concentrations of nutrients and chlorophyll a as well as trophic state in the water column increased while water transparency decreased, indicating that the water quality has declined during the last 12 years. Specifically, there was a notable and statistically significant increase in chlorophyll a concentrations, averaging an annual rate of 9.9%. Despite a slight decline in trophic level index until 2014, subsequent years saw an upward trend, ranging from 50.7 to 56.4 and indicating a light eutrophic state. Spatially, the western area displayed higher nutrient and chlorophyll a concentrations. Changes in hydro-meteorological variables and nutrients from inflowing rivers were the main factors correlated with water quality in Gaoyou Lake. Thus, pollution source apportionment and management within Huaihe River basin should be considered to reduce the external loadings of nutrients in order to improve and sustain long-term water quality.

Temporal and spatial variability of dynamic microstate brain network in disorders of consciousness.

BACKGROUND: Accurately diagnosing patients with the vegetative state (VS) and the minimally conscious state (MCS) reached a misdiagnosis of approximately 40%. METHODS: A method combined microstate and dynamic functional connectivity (dFC) to study the spatiotemporal variability of the brain in disorders of consciousness (DOC) patients was proposed. Resting-state EEG data were obtained from 16 patients with MCS and 16 patients with VS. Mutual information (MI) was used to assess the EEG connectivity in each microstate. MI-based features with statistical differences were selected as the total feature subset (TFS), then the TFS was utilized to feature selection and fed into the classifier, obtaining the optimal feature subsets (OFS) in each microstate. Subsequently, an OFS-based MI functional connectivity network (MIFCN) was constructed in the cortex. RESULTS: The group-average MI connectivity matrix focused on all channels revealed that all five microstates exhibited stronger information interaction in the MCS when comparing with the VS. While OFS-based MIFCN, which only focused on a few channels, revealed greater MI flow in VS patients than in MCS patients under microstates A, B, C, and E, except for microstate D. Additionally, the average classification accuracy of OFS in the five microstates was 96.2%. CONCLUSION: Constructing features based on microstates to distinguish between two categories of DOC patients had effectiveness.

Transition metal small clusters anchored on biphenylene for effective electrocatalytic nitrogen reduction.

The synthesis of ammonia via an electrochemical nitrogen reduction reaction (NRR, N2 + 6H+ + 6e- → 2NH3), which can weaken but not directly break an inert NN bond under mild conditions via multiple progressive protonation steps, has been proposed as one of the most attractive alternatives for the production of NH3. However, the development of appropriate catalyst materials is a major challenge in the application of NRRs. Recently, single- or multi-metal atoms anchored on two-dimensional (2D) substrates have been demonstrated as ideal candidates for facilitating NRRs. In this work, by applying spin-polarized density functional theory and ab initio molecular dynamic simulations, we systematically explored the performances of nine types of transition metal multi-atoms anchored on a recently developed 2D biphenylene (BPN) sheet in nitrogen reduction. Structural stability and NRR performance catalyzed by TMn (TM = V, Fe, Ni, Mo, Ru, Rh, W, Re, Ir; n = 1-4) clusters anchored on BPN sheets were systematically explored. After a strict six-step screening strategy, it was found that W2, Ru2 and Mo4 clusters loaded on BPN demonstrate superior potential for nitrogen reduction with extremely low onset potentials of -0.26, -0.36 and -0.17 V, respectively. Electronic structure analysis revealed that the enhanced ability of these multi-atom catalysts to effectively capture and reduce the N2 molecule can be attributed to bidirectional charge transfer between the d orbitals of transition metal atoms and molecular orbitals of the adsorbed N2 through a "donation-back donation" mechanism. Our findings highlight the value of BPN sheets as a substrate for designing multi-atom nitrogen reduction reaction catalysts.

Atomic insight into the effects of precursor clusters on monolayer WSe2.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been attracting much attention due to their rich physical and chemical properties. At the end of the chemical vapor deposition growth of 2D TMDCs, the adsorption of excess precursor clusters onto the sample is unavoidable, which will have significant effects on the properties of TMDCs. This is a concern to the academic community. However, the structures of the supported precursor clusters and their effects on the properties of the prepared 2D TMDCs are still poorly understood. Herein, taking monolayer WSe2 as the prototype, we investigated the structure and electronic properties of SeN, WN (N = 1-8), and W8-NSeN (N = 1-7) clusters adsorbed on monolayer WSe2 to gain atomic insight into the precursor cluster adsorption. In contrast to W clusters that tightly bind to the WSe2 surface, Se clusters except for Se1 and Se2 are weakly adsorbed onto WSe2. The interaction between W8-NSeN (N = 1-7) clusters and the WSe2 monolayer decreases with the increase in the Se/W ratio and eventually becomes van der Waals interaction for W1Se7. According to the phase diagram, increasing the Se/W ratio by changing the experimental conditions will increase the ratio of SeN and W1Se7 clusters in the precursor, which can be removed by proper annealing after growth. W clusters induce lots of defect energy levels in the band gap region, while the adsorption of W1Se7 and SeN clusters (N = 3-6, 8) promotes the spatial separation of photo generated carriers at the interface, which is important for optoelectronic applications. Our results indicate that by controlling the Se/W ratio, the interaction between the precursor clusters and WSe2 as well as the electronic properties of the prepared WSe2 monolayer can be effectively tuned, which is significant for the high-quality growth and applications of WSe2.