A novel PbO2 electrode modified with rare earth elements (La, Ce, Gd and Er) doping (named as Re-PbO2) was prepared by electrodeposition in the present study. The micro-morphology and crystal structure of Re-PbO2 were characterized by scanning electronic microscopy (SEM), energy dispersive spectroscope (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. Their electrochemical properties were determined by linear sweep voltammetry (LSV), cyclic voltammetry (CV), accelerated life test and hydroxyl radicals (•OH) formation analysis. Electrochemical oxidation of p-nitrophenol (p-NP) by Re-PbO2 compared with un-doped PbO2 has been investigated and the degradation rate followed the order of Er-PbO2 > Gd-PbO2 > La-PbO2 > Ce-PbO2 > PbO2. Especially for Er-PbO2, the pseudo-first order kinetic for p-NP (kp-NP) degradation was 0.41, which was only 0.19 for un-doped PbO2. Rare earths elements doping improved the oxidation ability of Re-PbO2 mainly through reducing grain size, increasing oxygen evolution potential, enlarging electrochemical active surface area and enhancing •OH formation ability. In addition, existing formation of oxygen species on PbO2 electrode surface was investigated by XPS. For Re-PbO2, percentage of lattice oxygen species (Oads) were higher than that on the un-doped one. These results demonstrated that rare earth elements can enhance the oxidation ability of PbO2 electrode significantly.
MnFe Prussian blue analogues (MnFe PBAs) were fabricated for acetamiprid degradation with peroxymonosulfate (PMS) as an oxidant. MnFe PBAs (200) are the most active facets for PMS activation due to the superior chemisorption affinity and electron-transfer ability. Density functional theory calculation verified that Mn(III) served as an electron donor and acceptor to adjust the electron density between Fe and Mn, which played a crucial role in the high activation performance of MnFe PBAs (200). PBA lattice (−C═N) did not exhibit direct PMS activation capability in this system, which differed from previously reported Fenton counterparts. Based on the electronic localization function calculation and probe experiments, the O–O of HSO5– was broken, and the bonds of PBA could be restored during the activation reaction, leading to the continuous generation of reactive oxygen species in the MnFe PBAs/PMS system. Transformation product studies indicated that the oxidized products were primarily the result of aromatic hydroxylation, N–C bond cleavage, azo reaction, and so forth, achieving the mineralization and ecotoxicity mitigation of acetamiprid efficiently. Findings in this study provided new insights into developing advanced facet-dependent catalysts to activate PMS for the efficient degradation of emerging contaminants in the aqueous environment.
Precisely identifying the atomic structures in single-atom sites and establishing authentic structure–activity relationships for single-atom catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted the underlying catalytic activity of Fe–NxC4–x sites with diverse first-shell coordination environments. Substituting N with C to coordinate with the central Fe atom induces an inferior Fenton-like catalytic efficiency. Then, Fe-SACs carrying three configurations (Fe–N2C2, Fe–N3C1, and Fe–N4) fabricate facilely and demonstrate that optimized coordination environments of Fe–NxC4–x significantly promote the Fenton-like catalytic activity. Specifically, the reaction rate constant increases from 0.064 to 0.318 min–1 as the coordination number of Fe–N increases from 2 to 4, slightly influencing the nonradical reaction mechanism dominated by 1O2. In-depth theoretical calculations unveil that the modulated coordination environments of Fe-SACs from Fe–N2C2 to Fe–N4 optimize the d-band electronic structures and regulate the binding strength of peroxymonosulfate on Fe–NxC4–x sites, resulting in a reduced energy barrier and enhanced Fenton-like catalytic activity. The catalytic stability and the actual hospital sewage treatment capacity also showed strong coordination dependency. This strategy of local coordination engineering offers a vivid example of modulating SACs with well-regulated coordination environments, ultimately maximizing their catalytic efficiency.
he simultaneous precipitation of (Fe, Cr)(OH)3 nanoparticles in solution (homogeneous) and on soil surfaces (heterogeneous), which controls Cr transport in soil and aquatic systems, was quantified for the first time in the presence of model surfaces, i.e., bare and natural organic matter (NOM)-coated SiO2 and Al2O3. Various characterization techniques were combined to explore the surface-ion-precipitate interactions and the controlling mechanisms. (Fe, Cr)(OH)3 accumulation on negatively charged SiO2 was mainly governed by electrostatic interactions between hydrolyzed ion species or homogeneous (Fe, Cr)(OH)3 and surfaces. The elevated pH through protonation of Al2O3 surface hydroxyls resulted in higher Cr/Fe ratios in both homogeneous and heterogeneous coprecipitates. Due to ignorable NOM adsorption onto SiO2, the amounts of (Fe, Cr)(OH)3 precipitates on bare/NOM-SiO2 were similar; contrarily, attributed to favored NOM adsorption onto Al2O3 and consequently carboxyl association with metal ions or (Fe, Cr)(OH)3 nanoparticles, remarkably more heterogeneous precipitates harvested on NOM-Al2O3 than bare-Al2O3. With the same solution supersaturation, the total amounts of homogeneous and heterogeneous precipitates were similar irrespective of the substrate type. With lower pH, decreased electrostatic forces between substrates and precipitates shifted (Fe, Cr)(OH)3 distribution from heterogeneous to homogeneous phases. The quantitative knowledge of (Fe, Cr)(OH)3 distribution and the controlling mechanisms can assist in better Cr sequestration in natural and engineered settings.
Intermittent demand forecasting is a ubiquitous and challenging problem in production systems and supply chain management. In recent years, there has been a growing focus on developing forecasting approaches for intermittent demand from academic and practical perspectives. However, limited attention has been given to forecast combination methods, which have achieved competitive performance in forecasting fast-moving time series. The current study aims to examine the empirical outcomes of some existing forecast combination methods and propose a generalized feature-based framework for intermittent demand forecasting. The proposed framework has been shown to improve the accuracy of point and quantile forecasts based on two real data sets. Further, some analysis of features, forecasting pools and computational efficiency is also provided. The findings indicate the intelligibility and flexibility of the proposed approach in intermittent demand forecasting and offer insights regarding inventory decisions.
This study investigates the effect of firm performance on corporate social responsibility (CSR) in a specific spatial context. The results for a sample of 1,557 listed companies in China suggest that a firm’s CSR performance level is influenced by that of nearby firms. This study also confirms the indirect link between financial and CSR performance through the mediating role of institutional and executive shareholding rates. In addition, the empirical evidence in this study not only supports the spatial context-sensitive thesis but, more importantly, proposes a spatiotemporal context-sensitive thesis. It provides strong empirical support for the true relative value of the spatiotemporal context affecting CSR performance, which yields important theoretical, methodological, and policy implications.
The wake-up and fatigue effects exhibited by ferroelectric hafnium oxide (HfO2) during electrical cycling are two of the most significant obstacles limiting its development and application. Despite a mainstream theory relating these phenomena to the migration of oxygen vacancies and the evolution of the built-in field, no supportive experimental observations from a nanoscale perspective have been reported so far. By combining differential phase contrast scanning transmission electron microscopy (DPC-STEM) and energy dispersive spectroscopy (EDS) analysis, we directly observe the migration of oxygen vacancies and the evolution of the built-in field in ferroelectric HfO2 for the first time. These solid results indicate that the wake-up effect is caused by the homogenization of oxygen vacancy distribution and weakening of the vertical built-in field whereas the fatigue effect is related to charge injection and transverse local electric field enhancement. In addition, using a low-amplitude electrical cycling scheme, we exclude field-induced phase transition from the root cause of the wake-up and fatigue in Hf0.5Zr0.5O2. With direct experimental evidence, this work clarifies the core mechanism of the wake-up and fatigue effects, which is important for the optimization of ferroelectric memory devices.
Abstract The detection of surface electromyography (sEMG) signals on the skin has attracted increasing attention because of its ability to monitor muscle conditions in a noninvasive manner and thus possesses great application potential to assess athletic status and training efficiency in real time or to evaluate postoperative muscle rehabilitation conveniently. Here, a flexible wireless sEMG monitoring system that consists of a stretchable sEMG epidermal patch and a flexible printed circuit board to provide real-time evaluation of muscle strength and fatigue is reported. The epidermal patch is designed to have good stretchability and permeability and optimized to ensure a low contact impedance with the skin and minimized background noise for sEMG signal acquisition with high fidelity. Six commonly used time-domain and two frequency-domain features extracted from sEMG signals are systematically analyzed, and a strategy for feature selection and pattern identification is proposed that eventually enables the real-time assessment of muscle strength and fatigue by using an integrated system in a wearable form.
Tight and shale reservoirs are forming important components of the global hydrocarbon landscape, which impede the free thermal movement of fluid molecules, with numerous nanoscale pores. The confined hydrocarbons in the nanopores cannot be industrially produced from conventional exploration and development methods, with deviated fluid phase behavior under nano-confinement effects. Most commonly important fluid phase behavior in nanopores has been simulated and compared with the bulk cases previously, including phase coexistence, critical properties, and density distribution of confined fluids. This paper focuses on the deviated fluid phase behavior under nano-confinement effects by Monte Carlo modeling. The Monte Carlo simulation is still limited to modeling the macroscopic pore-related behavior like capillarity and complex fluid and solid materials. Moreover, the Monte Carlo simulation is usually scale-restricted and the pore-size range where the nano-confinement effect fails to work needs to be quantitatively determined. Overall, for the tight and shale fluid phase behavior, a functional Monte Carlo model, coupled with the long-range correction and configuration bias techniques, is suggested to include both the multi-component fluids and skeleton.
The sensitivity of fluvial sediment load to climate change and predictions of future sediment load in cold basins remain poorly investigated, although changes in river sediment transport have important geomorphological, ecological, and societal implications. Here, we adapt a sediment elasticity approach to examine the sensitivity of fluvial suspended sediment load to changes in air temperature and precipitation in the headwater of the Yangtze River (HYR) on the inner Tibetan Plateau. Results show that every 1 °C increase in air temperature can increase the suspended sediment load by 14–27 % by intensifying thermally-driven glacial and permafrost erosional processes, and every 10 % increase in precipitation can increase the suspended sediment load by 16–24 % through enhancing pluvial-driven erosional processes. We predict an increase of 60–85 % in the suspended sediment loads in HYR by 2050 relative to the present-day period under the Representative Concentration Pathway 4.5, as both air temperature and precipitation are projected to increase. Our analysis highlights that smaller upland rivers appear to respond to modern climate change more rapidly and intensively than larger downstream rivers due to the larger glacier and permafrost coverages, poorer vegetation, as well as steeper fluvial relief, and higher sediment connectivity. This study provides a framework and a data-driven sediment elasticity approach to predict climate change and cryosphere degradation-driven changes in future fluvial suspended sediment load in cold basins, highlights the importance of the spatial scale effects in modulating fluvial responses, and has implications for assessing the impacts of climate change on channel morphology and aquatic ecosystems.
Forecast combinations have flourished remarkably in the forecasting community and, in recent years, have become part of mainstream forecasting research and activities. Combining multiple forecasts produced for a target time series is now widely used to improve accuracy through the integration of information gleaned from different sources, thereby avoiding the need to identify a single “best” forecast. Combination schemes have evolved from simple combination methods without estimation to sophisticated techniques involving time-varying weights, nonlinear combinations, correlations among components, and cross-learning. They include combining point forecasts and combining probabilistic forecasts. This paper provides an up-to-date review of the extensive literature on forecast combinations and a reference to available open-source software implementations. We discuss the potential and limitations of various methods and highlight how these ideas have developed over time. Some crucial issues concerning the utility of forecast combinations are also surveyed. Finally, we conclude with current research gaps and potential insights for future research.