Active-site stabilized Bi metal-organic framework-based catalyst for highly active and selective electroreduction of CO2 to formate over a wide potential window.

Bismuth-based materials have been validated to be a kind of effective electrocatalyst for electrocatalytic CO2 reduction (ECR) to formate (HCOO-). However, the established studies still encounter the problems of low current density, low selectivity, narrow potential window, and poor catalyst stability. Herein, a bismuth-terephthalate framework (Bi-BDC MOF) material was successfully synthesized. The optimized Bi-BDC-120 °C exhibited excellent activity, selectivity, and durability for formate production. At an operating potential of -1.1 V vs. RHE in 0.1 mol L-1 KHCO3 electrolyte, the ECR catalyzed by Bi-BDC-120 °C achieved a Faraday efficiency (FE) of 97.2% towards formate generation, and the total current density reached about 30 mA cm-2. The operating potential window with FEformate values > 95% ranged in -0.9 to -1.5 V vs. RHE. The density-functional theory (DFT) calculation demonstrated that the (001) crystalline planes of Bi-BDC are preferable for the adsorption of CO2 and the conversion of *OCHO intermediates, thus ultimately promoting the electrocatalytic production of formate. Although the MOF structure of Bi-BDC-120 °C was insufficiently stabilized, the FEformate could be maintained at around 90% after 36 h of ECR operation. The long-term durability for formate production was attributed to the fact that the in situ reconstructed Bi2O2CO3 could retain the Bi-O active sites in the structure. These results offer an opportunity to design CO2 reduction electrocatalysts with high activity and selectivity for potential applications.

Super-Pixel Guided Low-Light Images Enhancement with Features Restoration.

Dealing with low-light images is a challenging problem in the image processing field. A mature low-light enhancement technology will not only be conductive to human visual perception but also lay a solid foundation for the subsequent high-level tasks, such as target detection and image classification. In order to balance the visual effect of the image and the contribution of the subsequent task, this paper proposes utilizing shallow Convolutional Neural Networks (CNNs) as the priori image processing to restore the necessary image feature information, which is followed by super-pixel image segmentation to obtain image regions with similar colors and brightness and, finally, the Attentive Neural Processes (ANPs) network to find its local enhancement function on each super-pixel to further restore features and details. Through extensive experiments on the synthesized low-light image and the real low-light image, the experimental results of our algorithm reach 23.402, 0.920, and 2.2490 for Peak Signal to Noise Ratio (PSNR), Structural Similarity (SSIM), and Natural Image Quality Evaluator (NIQE), respectively. As demonstrated by the experiments on image Scale-Invariant Feature Transform (SIFT) feature detection and subsequent target detection, the results of our approach achieve excellent results in visual effect and image features.

Online on-Road Motion Planning Based on Hybrid Potential Field Model for Car-Like Robot.

The application of Middle-sized Car-like Robots (MCRs) in indoor and outdoor road scenarios is becoming broader and broader. To achieve the goal of stable and efficient movement of the MCRs on the road, a motion planning algorithm based on the Hybrid Potential Field Model (HPFM) is proposed in this paper. Firstly, the artificial potential field model improved with the eye model is used to generate a safe and smooth initial path that meets the road constraints. Then, the path constraints such as curvatures and obstacle avoidance are converted into an unconstrained weighted objective function. The efficient least-squares & quasi-Newton fusion algorithm is used to optimize the initial path to obtain a smooth path curve suitable for the MCR. Finally, the speed constraints are converted into a weighted objective function based on the path curve to get the best speed profile. Numerical simulation and practical prototype experiments are carried out on different road scenes to verify the performance of the proposed algorithm. The results show that re-planned trajectories can satisfy the path constraints and speed constraints. The real-time re-planning period is 184 ms, which demonstrates the proposed approach's effectiveness and feasibility.

Adsorption of phenanthrene and its monohydroxy derivatives on polyvinyl chloride microplastics in aqueous solution: Model fitting and mechanism analysis.

The pervasiveness of microplastics, which can absorb pollutants, has a certain impact on pollutant migration in natural waters. Differences in functional groups, such as the hydroxyl group, of pollutants will affect their adsorption on microplastics. In this study, the adsorption of phenanthrene (PHE) or its monohydroxy derivatives, including 1-hydroxyphenanthrene (1-OHP), 2-hydroxyphenanthrene (2-OHP), 4-hydroxyphenanthrene (4-OHP), and 9-hydroxyphenanthrene (9-OHP), on polyvinyl chloride (PVC, measured mean particle size = 134 µm) microplastics was studied. The adsorption efficiency of PHE was shown to be higher than that of either of OHPs. A better fit for pseudo-second-order and Freundlich isotherm models was obtained, indicating different binding sites on the surface of PVC microplastics. The adsorption processes of PHE and OHPs on PVC microplastics were demonstrated to be exothermic and spontaneous. Combined with FT-IR analysis, theoretical calculation, and comparative adsorption experiments, hydrophobic interaction was the dominant mechanism during the adsorption process. In contrast, electrostatic repulsion, CH/π interaction, and halogen bonding played a minor role, to an extent, in the adsorption of PHE/OHPs on PVC microplastics. These findings indicate the influence of the hydroxyl group on adsorption and improve the understanding of interactions between PVC microplastics and PHE/OHPs.

Fe3O4-assisted laser desorption ionization mass spectrometry for typical metabolite analysis and localization: Influencing factors, mechanisms, and environmental applications.

Fe3O4 has been suggested as an efficient matrix for small-molecule analysis by laser desorption ionization mass spectrometry (LDI-MS), but thus far there has been no systematic study exploring the influencing factors of nano-Fe3O4 on the detection of typical metabolites, or the mechanism by which nano-Fe3O4 assists the desorption and ionization of analytes after receiving laser energy. In this study, Fe3O4 nanoparticles with different physicochemical properties were synthesized and characterized. The results revealed that smaller particle size and greater surface hydroxyl amount of nano-spherical Fe3O4 could improve the intensity and relative standard deviation of typical metabolites by LDI-MS. The thermally driven desorption process played a vital role in LDI performance, but the chemical interactions between nano-Fe3O4 and analytes did not. Good intra- or inter-spot repeatability and linearity of analytes were obtained by the optimum Fe3O4-assisted LDI-MS. Finally, the developed method was successfully used for the rapid analysis and localization of endogenous metabolites in biofluids and whole zebrafish tissue section samples. Our results not only elucidate the influencing factors and mechanisms of nano-Fe3O4 for the detection of typical metabolites in LDI-MS but also reveal an innovative tool for the imaging of chemicals in the regions of interest in terms of eco-toxicological research.

CPG-Based Gait Generation of the Curved-Leg Hexapod Robot with Smooth Gait Transition.

This paper presents a novel CPG-based gait generation of the curved-leg hexapod robot that can enable smooth gait transitions between multi-mode gaits. First, the locomotion of the curved leg and instability during the gait transitions are analyzed. Then, a modified Hopf oscillator is applied in the CPG control, which can realize multiple gaits by adjusting a simple parameter. In addition, a smooth gait switching method is also proposed via smooth gait transition functions and gait planning. Tripod gait, quadruped gait, and wave gait are planned for the hexapod robot to achieve quick and stable gait transitions smoothly and continuously. MATLAB and ADAMS simulations and corresponding practical experiments are conducted. The results show that the proposed method can achieve smooth and continuous mutual gait transitions, which proves the effectiveness of the proposed CPG-based hexapod robot control.

Surface Impedance of Metasurfaces/Graphene Hybrid Structures.

Understanding and manipulation of surface impedance in graphene hybrid structure is a significant issue for applications of graphene-based optoelectronics devices. In order to achieve this purpose in the terahertz region, analytical expressions for the impedances of metasurface were derived, which allows us to easily understand the relationship between physical dimensions and impedance. Simulation results show an excellent agreement with the analytical predictions. In addition, we focus on the synthetic impedance when square patch and graphene sheet joined together, discuss the influence of the size of metasurface as well as chemical potentiality as for graphene on the synthetic impedance. Based on these results, a number of absorbers as well as optical devices can be designed that utilize impedance metasurfaces.

Alterations in patients with major depressive disorder before and after electroconvulsive therapy measured by fractional amplitude of low-frequency fluctuations (fALFF).

BACKGROUND: Electroconvulsive therapy (ECT) is an important treatment option for patients with major depressive disorder (MDD). However, the mechanisms of ECT in MDD are still unclear. METHODS: Twenty-four patients with severe MDD and 14 healthy controls were enrolled in this study. Eight ECT sessions were conducted for MDD patients using brief-pulse square-wave signal at bitemporal locations. To investigate the regional cerebral blood flow in MDD patients before and after ECT treatments by resting-state functional magnetic resonance imaging (rs-fMRI), the patients were scanned twice (before the first ECT and after the eighth ECT) for data acquisition. Afterward, we adopted fractional amplitude of low-frequency fluctuations (fALFF) to assess the alterations of regional brain activity. RESULTS: Compared with healthy controls, the fALFF in the cerebellum lobe, parahippocampal gyrus, fusiform gyrus, anterior cingulate gyrus, and thalamus in MDD patients before ECT (pre-ECT) was significantly increased. In another comparison, the fALFF in the cerebellum anterior lobe, fusiform gyrus, insula, parahippocampal gyrus, middle frontal gyrus, and inferior frontal gyrus in pre-ECT patients was significantly greater than the post-ECT fALFF. LIMITATIONS: Only two rs-fMRI scans were conducted at predefined times: before the first and after the eighth ECT treatment. More scans during the ECT sessions would yield more information. In addition, the sample size in this study was limited. The number of control subjects was relatively small. A larger number of subjects would produce more robust findings. CONCLUSIONS: The fALFF of both healthy controls and post-ECT patients in cerebellum anterior lobe, fusiform gyrus, and parahippocampal gyrus is significantly lower than the fALFF of pre-ECT patients. This finding demonstrates that ECT treatment is effective on these brain areas in MDD patients.

A Vision-Based Counting and Recognition System for Flying Insects in Intelligent Agriculture.

Rapid and accurate counting and recognition of flying insects are of great importance, especially for pest control. Traditional manual identification and counting of flying insects is labor intensive and inefficient. In this study, a vision-based counting and classification system for flying insects is designed and implemented. The system is constructed as follows: firstly, a yellow sticky trap is installed in the surveillance area to trap flying insects and a camera is set up to collect real-time images. Then the detection and coarse counting method based on You Only Look Once (YOLO) object detection, the classification method and fine counting based on Support Vector Machines (SVM) using global features are designed. Finally, the insect counting and recognition system is implemented on Raspberry PI. Six species of flying insects including bee, fly, mosquito, moth, chafer and fruit fly are selected to assess the effectiveness of the system. Compared with the conventional methods, the test results show promising performance. The average counting accuracy is 92.50% and average classifying accuracy is 90.18% on Raspberry PI. The proposed system is easy-to-use and provides efficient and accurate recognition data, therefore, it can be used for intelligent agriculture applications.

Investigation of the interaction between the fate of antibiotics in aquafarms and their level in the environment.

China is the largest freshwater aquaculture producer and antibiotics consumer in the world, and rivers in China are generally polluted by antibiotics. However, there is little information available regarding the linkage of antibiotics in aquaculture and the aquatic environment. Therefore, this study investigated the fate of antibiotics in several open water culture-based freshwater aquafarms, including integrated livestock/fish systems and non-integrated fish ponds, and explored the contamination profiles of antibiotics in the Beijiang River. Then the study tried to clarify the two-way interaction of antibiotics in aquaculture and the environment. The results showed that, when compared with the effluent from livestock farms and wastewater treatment plants, the contribution of antibiotics from non-integrated fish pond water without livestock sewage input was limited, while that of effluent from the integrated livestock/fish system was quite high. The total concentrations of antibiotics detected in the aquafarm source water were similar to those in the upper river water and generally higher than those in the corresponding fish pond water, implying that the occurrence of antibiotics in intensive aquafarms can mainly be attributed to the antibiotic residues in nearby river water. Overall, the results underscore the need to develop a sewage infrastructure for the treatment of effluent from integrated livestock/fish aquafarms, and suggest that open water culture-based fish farms should be located far from seriously contaminated sections of rivers.

Microwave-Assisted Synthesis of Fe3O4 Nanocrystals with Predominantly Exposed Facets and Their Heterogeneous UVA/Fenton Catalytic Activity.

Fe3O4 nanocrystals with five different morphologies (i.e., nanospheres, nanorods, nanocubes, nano-octahedrons, and nanoplates) were acquired using a simple, efficient, and economic microwave-assisted oxidation technique. The microstructure, morphology, predominant exposed facets, and iron atom local environment of Fe3O4 were revealed by powder X-ray diffraction (PXRD), scanning transmission electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrometer (XPS), and Mössbauer spectrum. We demonstrated that the heterogeneous UVA/Fenton catalytic activities of Fe3O4 nanocrystals are morphology/facets dependent. Under UVA irradiation, the catalytic activity of the as-prepared Fe3O4 was in the sequence of nanospheres > nanoplates > nano-octahedrons ≈ nanocubes > nanorods > nano-octahedrons (by coprecipitation). The dominating factor for the catalytic performance was the particle size and BET specific surface area; moreover, the exposed {111} facets, which contained more Fe2+ species, on the nanocrystal surface led to a stronger UVA/Fenton catalytic activity. Both •OH and O2•- radicals participated in the UVA/Fenton degradation process, and •OH played the dominant role. These morphology-controlled nanomagnetites showed great potential in applications as heterogeneous UVA/Fenton catalysts for effectively treating nonbiodegradable organic pollutants.

Analysis of azole fungicides in fish muscle tissues: Multi-factor optimization and application to environmental samples.

Azole fungicides have been reported to be accumulated in fish tissue. In this study, a sensitive and robust method using high-performance liquid chromatography-tandem mass spectrometry combined with ultrasonic extraction, solid-liquid clean-up, liquid-liquid extraction and solid-phase extraction (SPE) for enrichment and purification have been proposed for determination of azole fungicides in fish muscle samples. According to the results of non-statistical analysis and statistical analysis, ethyl acetate, primary secondary amine (PSA) and mixed-mode cation exchange cartridge (MCX) were confirmed as the best extraction solvent, clean-up sorbent and SPE cartridge, respectively. The satisfied recoveries (81.7-104%) and matrix effects (-6.34-7.16%), both corrected by internal standards, were performed in various species of fish muscle matrices. Method quantification limits of all azoles were in the range of 0.07-2.83ng/g. This optimized method was successfully applied for determination of the target analytes in muscle samples of field fish from Beijiang River and its tributaries. Three azole fungicides including climbazole, clotrimazole and carbendazim were detected at ppb levels in fish muscle tissues. Therefore, this analytical method is practical and suitable for further clarifying the contamination profiles of azole fungicides in wild fish species.

Natural Magnetite: an efficient catalyst for the degradation of organic contaminant.

Iron (hydr)oxides are ubiquitous earth materials that have high adsorption capacities for toxic elements and degradation ability towards organic contaminants. Many studies have investigated the reactivity of synthetic magnetite, while little is known about natural magnetite. Here, we first report the reactivity of natural magnetites with a variety of elemental impurities for catalyzing the decomposition of H2O2 to produce hydroxyl free radicals (•OH) and the consequent degradation of p-nitrophenol (p-NP). We observed that these natural magnetites show higher catalytic performance than that of the synthetic pure magnetite. The catalytic ability of natural magnetite with high phase purity depends on the surface site density while that for the magnetites with exsolutions relies on the mineralogical nature of the exsolved phases. The pleonaste exsolution can promote the generation of •OH and the consequent degradation of p-NP; the ilmenite exsolution has little effect on the decomposition of H2O2, but can increase the adsorption of p-NP on magnetite. Our results imply that natural magnetite is an efficient catalyst for the degradation of organic contaminants in nature.

The distinct effects of Mn substitution on the reactivity of magnetite in heterogeneous Fenton reaction and Pb(II) adsorption.

In this study, a series of Mn substituted magnetites were synthesized and used in catalyzing the heterogeneous Fenton degradation of acid orange II and Pb(II) adsorption, in order to investigate the effect of Mn substitution on the reactivity of magnetite. The valence and local environment of both Fe and Mn in the spinel structure of magnetite were investigated by X-ray absorption fine structure (XAFS) spectroscopy. The incorporation of Mn did not change the valence and local structure of Fe in the synthetic magnetite, while Mn was in the valences of +2 and +3. The Mn distribution on the octahedral sites of magnetite surface increased with the increase in Mn content. The Mn introduction led to an improvement of catalytic activity of magnetite. The sample with the minimum Mn content displayed the best efficiency in OH production and the degradation of acid orange II, while the other substituted samples did not show obvious difference in their catalytic performance. The adsorption capacity of magnetite samples toward Pb(II) gradually increased with the increase in Mn content. The above influences of Mn substitution on the reactivity of magnetite were discussed in views of the variations in microstructural environment and physicochemical properties.

The UV/Fenton degradation of tetrabromobisphenol A catalyzed by nanocrystalline chromium substituted magnetite.

The heterogeneous UV/Fenton degradation of tetrabromobisphenol A (TBBPA) catalyzed by nanocrystalline Fe3O4 and Fe2.04Cr0.96O4 was investigated, with focus on the influence of UV light and initial pH, degradation pathways and effect of Cr substation. The catalysts were prepared by a precipitation-oxidation method and characterized by chemical analysis, XRD, XAFS, TG-DSC, BET surface area and magnetometer. At pH 6.7 and under UV irradiation, almost complete degradation of TBBPA by Fe2.04Cr0.96O4 was accomplished within 240 min, and the leaching Fe ions were negligible. The substitution of chromium greatly increased the BET specific surface area and surface hydroxyl amount, which improved the heterogeneous UV/Fenton catalytic activity of magnetite. Moreover, Cr3+ on the octahedral sites enhanced the electron transfer process in the magnetite structure to accelerate the *OH generation. The produced *OH radicals preferentially attacked the C-Br bonds of TBBPA and then ß-cleavaged the C-C bonds between benzene rings and isopropyl groups. The above results are of great significance for well understanding the effect of transition metal substitution on the UV/Fenton catalytic activity of magnetite and prospecting the application of magnetite minerals in environmental purification.

Heterogeneous UV/Fenton degradation of TBBPA catalyzed by titanomagnetite: catalyst characterization, performance and degradation products.

Tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant, could negatively affect various aspects of mammalian and human physiology, which triggers effective techniques for its removal. In this work, the degradation characteristics of TBBPA in heterogeneous UV/Fenton reaction catalyzed by titanomagnetite (Fe(3-x)Ti(x)O4) were studied. Batch tests were conducted to evaluate the effects of titanomagnetite dosage, H2O2 concentration and titanium content in magnetite on TBBPA degradation. In the system with 0.125 g L⁻¹ of Fe2.02Ti0.98O4 and 10 mmol L⁻¹) of H2O2, almost complete degradation of TBBPA (20 mg L⁻¹) was accomplished within 240 min UV irradiation at pH 6.5. The titanium incorporation obviously enhanced the catalytic activity of magnetite. As shown by the XRD and XANES results, titanomagnetite had a spinel structure with Ti4⁺ occupying the octahedral sites. On the basis of the degradation products identified by GC-MS, the degradation pathways of TBBPA were proposed. TBBPA possibly underwent the sequential debromination to form TriBBPA, DiBBPA, MonoBBPA and BPA, and ß-scission to generate seven brominated compounds. All of these products were finally completely removed from reaction solution. In addition, the reused catalyst Fe2.02Ti0.98O4 still retained the catalytic activity after three cycles, indicating that titanomagnetite had good stability and reusability. These results demonstrated that heterogeneous UV/Fenton reaction catalyzed by titanomagnetite is a promising advanced oxidation technology for the treatment of wastewater containing TBBPA.

The contribution of vanadium and titanium on improving methylene blue decolorization through heterogeneous UV-Fenton reaction catalyzed by their co-doped magnetite.

This study investigated the methylene blue (MB) decolorization through heterogeneous UV-Fenton reaction catalyzed by V-Ti co-doped magnetites, with emphasis on comparing the contribution of V and Ti cations on improving the adsorption and catalytic activity of magnetite. In the well crystallized spinel structure, both Ti(4+) and V(3+) occupied the octahedral sites. Ti(4+) showed a more obvious effect on increasing specific surface area and superficial hydroxyl amount than V(3+) did, resulting in a significant improvement of the adsorption ability of magnetite to MB. The UV introduction greatly accelerated MB degradation. And magnetite with more Ti and less V displayed better catalytic activity in MB degradation through heterogeneous UV-Fenton reaction. The transformation of degradation products and individual contribution from vanadium and titanium on improving adsorption and catalytic activity of magnetite were also investigated. These new insights are of high importance for well understanding the interface interaction between contaminants and metal doped magnetites, and the environmental application of natural and synthetic magnetites.

[Adsorption of methylene blue onto vanadium-doped magnetite].

A series of vanadium-doped magnetite (Fe3-x VxO4, x < 0.4) synthesized by an oxidation-precipitation method, were characterized using chemical analysis, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), as well as thermogravimetric and differential scanning calorimetry (TG-DSC) analyses. The obtained results show that the synthetic Fe3-x VxO4 has spinel structure while vanadium mostly replaces Fe3+ in the octahedral sites. The synthetic Fe3-x VxO4 is magnetic material, with crystal size ranging from 28 to 35 nm. The substitution of vanadium in the magnetite structure increases the amount of surface hydroxyls. The experimental adsorption results indicate that, in neutral pH condition, the maximum adsorption capacities of Fe3-x VxO4 increase obviously with the increase of vanadium concentration in magnetite while the adsorption isotherm complies well with the Langmuir model. The adsorption of methylene blue (MB) on Fe3-x VxO4 can get equilibrium in the first 25 min, supporting a pseudo-second order equation. Moreover, the rise of the solution pH value results in an increase of the adsorption capability of MB on Fe3-x VxO4.

The decolorization of Acid Orange II in non-homogeneous Fenton reaction catalyzed by natural vanadium-titanium magnetite.

The catalytic activity of natural vanadium-titanium magnetite was investigated in the decolorization of Acid Orange II by non-homogeneous Fenton process. The natural catalysts purified by magnetic separation were characterized using X-ray diffraction (XRD), polarizing microscope, X-ray absorption fine structure (XAFS) analysis and Mössbauer spectroscopy. The obtained results show that the natural samples after magnetic separation mainly contain titanomagnetite, with a small amount of ilmenite and chlorite. Titanomagnetite is doped with vanadium, whose the valency is mainly +3 and occupies the octahedral site. Batch decolorization studies were performed to evaluate the influences of various experimental parameters like initial pH, the amount of catalyst and initial concentration of hydrogen peroxide on the decolorization efficiency of Acid Orange II. The decolorization of the dye mainly relied on degradation. The degradation efficiency was strongly dependent on pH of the medium where it increased as the pH decreased in acid range. The increase of catalyst and hydrogen peroxide could accelerate the degradation. The catalytic property of natural vanadium-titanium magnetite in the degradation of Acid Orange II was stronger than that of synthetic magnetite (Fe(3)O(4)). The catalytic activity of the natural samples was greatly related to the titanomagnetite content. The degradation process was dominated by heterogeneous Fenton reaction, complying with pseudo-first-order rate law. The natural catalyst has a good catalytic stability.