For the 2D metal-free carbon catalysts, the atomic coplanar architecture enables a large number of pz orbitals to overlap laterally, thus forming π-electron delocalization, and the delocalization degree of the central atom dominates the catalytic activity. Herein, designing sulfur-doped defect-rich graphitic carbon nitride (S-Nv-C3N4) materials as a model, we propose a strategy to promote localized electron polarization by enhancing the ferromagnetism of ultra-thin 2D carbon nitride nanosheets. The introduction of sulfur (S) further promotes localized ferromagnetic coupling, thereby inducing long-range ferromagnetic ordering and accelerating the electron interface transport. Meanwhile, the hybridization of sulfur atoms breaks the symmetry and integrity of the unit structure, promotes electron enrichment and stimulating electron delocalization at the active site. This optimization enhances the *OOH desorption, providing a favorable kinetic pathway for the production of hydrogen peroxide (H2O2). Consequently, S-Nv-C3N4 exhibits high selectivity (>95%) and achieves a superb H2O2 production rate, approaching 4374.8 ppm during continuous electrolysis over 300-hour. According to theoretical calculation and in-situ spectroscopy, the ortho-S configuration can provide ferromagnetic perturbation in carbon active centers, leading to the electron delocalization, which optimizes the OOH* adsorption during the catalytic process.
Efficient oxygen evolution reaction electrocatalysts are essential for sustainable clean energy conversion. However, catalytic materials followed the conventional adsorbate evolution mechanism (AEM) with the inherent scaling relationship between key oxygen intermediates *OOH and *OH, or the lattice-oxygen-mediated mechanism (LOM) with the possible lattice oxygen migration and structural reconstruction, which are not favorable to the balance between high activity and stability. Herein, we propose an unconventional Co-Fe dual-site segmentally synergistic mechanism (DSSM) for single-domain ferromagnetic catalyst CoFeSx nanoclusters on carbon nanotubes (CNT) (CFS-ACs/CNT), which can effectively break the scaling relationship without sacrificing stability. Co3+ (L.S, t2g6eg0) supplies the strongest OH* adsorption energy, while Fe3+ (M.S, t2g4eg1) exposes strong O* adsorption. These dual-sites synergistically produce of Co-O-O-Fe intermediates, thereby accelerating the release of triplet-state oxygen ( ↑ O = O ↑ ). As predicted, the prepared CFS-ACs/CNT catalyst exhibits less overpotential than that of commercial IrO2, as well as approximately 633 h of stability without significant potential loss.
To date, precisely tailoring local active sites of well-defined earth-abundant metal-free carbon-based electrocatalysts for attractive electrocatalytic oxygen reduction reaction (ORR), remains challenging. Herein, the authors successfully introduce a strain effect on active C-C bonds adjacent to edged graphitic nitrogen (N), which raises appropriate spin-polarization and charge density of carbon active sites and kinetically favor the facilitation of O2 adsorption and the activation of O-containing intermediates. Thus, the constructed metal-free carbon nanoribbons (CNRs-C) with high-curved edges exhibit outstanding ORR activity with half-wave potentials of 0.78 and 0.9 V in 0.5 m H2 SO4 and 0.1 m KOH, respectively, overwhelming the planar one (0.52 and 0.81 V) and the N-doped carbon sheet (0.41 and 0.71 V). Especially in acidic media, the kinetic current density (Jk ) is 18 times higher than that of the planar one and the N-doped carbon sheet. Notably, these findings show the spin polarization of the asymmetric structure by introducing a strain effect on the C-C bonds for boosting ORR.
With the increasing impact of human activities on the environment, evapotranspiration (ET) has changed in arid areas, which further affects the water resources availability in the region. Therefore, understanding the impact of human activities on ET and its components is helpful to the management of water resources in arid areas. This study verified the accuracy of Fisher's model (PT-JPL model) for ET estimation in southern Xinjiang, China by using the evaporation complementarity theory dataset (AET dataset). The ET and the evapotranspiration components (T:E) of six land-use types were estimated in southern Xinjiang from 1982 to 2015, and the impact of human activities on ET was analyzed. In addition, the impact of four environmental factors (temperature (Temp), net radiation (Rn), relative humidity (RH), and NDVI) on ET were evaluated. The results showed that the calculated ET values of the PT-JPL model were close to the ET values of the AET dataset. The correlation coefficient (R2) was more than 0.8, and the NSE was close to 1. In grassland, water area, urban industrial and mining land, forest land, and cultivated land, the ET values were high, and in unused land types, the ET values were the lowest. The T:E values varied greatly in urban industrial and mining land, forest land, and cultivated land, which was due to the intensification of human activities, and the values were close to 1 in summer in recent years. Among the four environmental factors, temperature largely influenced the monthly ET. These findings suggest that human activities have significantly reduced soil evaporation and improved water use efficiency. The impact of human activities on environmental factors has caused changes in ET and its components, and appropriate oasis expansion is more conducive to regional sustainable development.
Forests , Soil , Humans , Water/analysis , Seasons , Human Activities , China , Ecosystem
Electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reduction (OER) are regarded as the key reactions via the sustainable system (fuel cell and water splitting), respectively. In OER, the transition from singlet oxygen species to triplet oxygen molecules is involved, meanwhile the ORR involves the transition from triplet oxygen molecules to singlet oxygen species. However, in these processes, the number of unpaired electrons is not conserved, which is not thermodynamically favorable and creates an additional energy barrier. Fortunately, regulating the electrocatalysis by spin-state modulation enables a unique effect on the catalytic performance, but the current understanding on spin-state engineering for electro-catalyzing ORR and OER is still insufficient. Herein, this review summarized the in-spin engineering for the state-of-the-art ORR and OER electrocatalysts. It began by introducing engineering of spin-state to egfilling for ORR and OER process, and then moved to spin polarization and spin-pinning effect for OER process. Various designed strategies focusing on how to regulate the spin-state of the active center have been summarized up. The connectivity of the structures of typical ORR (e.g. metal-nitrogen-carbon) and OER (e.g. design strategies oxides, metal organic frameworks) catalysts depending on the spin level is also discussed. Finally, we present the outlook from the aspects of template catalysts, characterization methods, regulation strategies, theoretical calculations, which will further expand the possibility of better electrocatalytic performance through spin-state modulation. This review concluded some open suggestions and prospects, which are worthy of the community's future work.
Hydrogen has emerged as a green and sustainable fuel to meet the demand for future global energy. Distinct from steam reforming, electrochemical water splitting, especially powered by renewables, has been considered as a promising technique for scalable production of high-purity hydrogen with no carbon emission. Its commercialization depends on accelerating reaction kinetics and thus reduction of hydrogen cost, requiring electrocatalysts that are efficient, economical, and capable of stable and sustained hydrogen production. Atomically dispersed metal carbon-based catalysts (ADMCs) have attracted extensive attention due to their high atom utilization, abundant accessible active sites, fast mass transfer, and well-defined and tunable structures as ideal models for commercialized hydrogen production catalysts. However, boosting the performances of ADMCs for HER still requires new-captions of rational structural design. In this review, starting from the recently developed strategies of ADMCs synthesis, the microenvironment regulation of active sites of ADMCs are systematically summarized and discussed, such as atomically metal doping, synergetic atomically doping and ADMCs supported nanocrystals. With attention on the catalytic mechanisms and structure-activity relationships ranging from chemical coordination effects and electronic metal-support interaction, the active origin of ADMCs in the electrocatalytic hydrogen evolution reaction is discussed. Finally, the review outlooks the remaining challenges and emerging research topics in the future, including long service life, amplification preparation techniques, high-output alkaline water electrolysis, seawater electrolysis for hydrogen production and large current density hydrogen evolution. The new insights and knowledge into these aspects will be helpful for filling the existing gaps between scientific communities and industries and open up opportunities for bringing this promising technology into reality.
Landscape fragmentation is considered a serious threat to eco-environmental integrity and socioeconomic development. Although many studies have focused on landscape fragmentation resulting from agricultural production and urbanization, landscape fragmentation from the aspects of patterns, driving forces, and the policy perspective of ecosystems has rarely been investigated. Oases, as a unique landscape, face severe fragmentation in arid and semiarid regions. This study applied a combination of approaches, including remote sensing image interpretations, landscape fragmentation metrics, and community surveys, to analyze patterns and their driving forces, as well as the policy implications for future land consolidation, in the Hotan oasis of Northwest China from the space and time perspectives. Results show that the frequent occurrence of summer flood events changes the patch number, density, size, and splitting degree of oasis-desert ecotone vegetation. The socioeconomic factors including total population and irrigation area are more important driving forces on oasis landscape fragmentation, compared with natural factors such as temperature and precipitation. Rural expansion, road and canal system developments caused by population growth, and the rising number of households increase oasis landscape fragmentation. Rapid economic development, such as agricultural expansion and urbanization, has imposed the intensification of landscape fragmentation. Fragmentation reaches peak when agricultural development makes up 40-50% of study area. Rural residential reconstruction and farmland transfer policies facilitate the intensive utilization of land toward oasis fragmentation solutions, but many factors, such as landholders' household characteristics and living conditions, are partly responsible for the challenges in land consolidation. This study also demonstrates that intense human activities pose a great threat for land consolidation and sustainable development of oasis landscape.
Ecosystem , Environmental Monitoring , Agriculture , Environmental Monitoring/methods , Humans , Policy , Urbanization
An oasis is an important habitat for humans, plants, and wildlife in arid desert areas. The sustainability of an oasis is crucial for a smooth regional ecological functioning and healthy economic development. However, the overexploitation of groundwater will result in unsustainable oasis development. Due to the lack of long-term groundwater monitoring data, the impact of groundwater level changes on the sustainability of an oasis has not been studied extensively. In the present study, we used the ground water storage anomaly (GWSA) in combination with the Gravity Recovery and Climate Experiment (GRACE) and the Global Land Data Assimilation System (GLDAS) for the rapid identification of oasis sustainability, which has been tested and evaluated in Hotan and Qira oasis located in arid areas. The results showed that (1) the GWSA is a suitable and reliable indicator for trend change analysis in small-scale oasis and, (2) additionally, M-K test results for long-term trend change of GWSA showed a positive correlation with water resource carrying capacity (WRCC). These results suggest that GWSA can be used as a reliable index for the rapid assessment of oasis sustainability status in arid areas. Moreover, the potential applicability of GRACE satellite data in evaluating the groundwater sustainability in arid areas lacking proper data has also been proved in this study. These findings have provided a foundation to evaluate the sustainability status of an oasis and set a reference point to formulate future policies for the oasis.
Environmental Monitoring , Groundwater , Climate , Conservation of Natural Resources , Ecosystem , Environmental Monitoring/methods , Humans
Electrocatalytic carbon dioxide (CO2) reduction (ECR) has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy, but there are still some problems such as poor stability, low activity, and selectivity. While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost, high activity, and long-term stability. Recently, defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials. Here, the present review mainly summarizes the latest research progress of the construction of the diverse types of defects (intrinsic carbon defects, heteroatom doping defects, metal atomic sites, and edges detects) for carbon materials in ECR, and unveil the structure-activity relationship and its catalytic mechanism. The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed, as well as possible future solutions. It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.
The three-dimensional (3D) hierarchical WO3-SnO2 nanoflowers (NFs) composites were successfully synthesized via a simple impregnation method by using WO3 and SnO2 prepared by hydrothermal method as precursors. The structure and morphology of the as-prepared samples were investigated by the techniques of X-ray diffraction (XRD), field-emission electron scanning microscopy (FESEM), transmission electron microscopy (TEM) and N2 sorption. These results indicated that SnO2 and WO3-SnO2 nanostructures with a diameter of about 500â¯nm self-assembled by numerous nanorods of about 200â¯nm in length. Gas sensing test results show that the nanostructure WO3-SnO2 nanocomposites possess better methane sensing properties than that of pure SnO2. The modification of WO3 nanoplates reduces the optimum working temperature of SnO2 based sensor from 120⯰C to 110⯰C, the response of WO3-SnO2 based sensor to 500â¯ppm methane at 110⯰C is 2.3 times of that of pure SnO2 based sensor. In addition, the WO3-SnO2 based sensor possesses lower detection limit, good repeatability and stability. The improved gas-sensing mechanism of the nanocomposite based sensors for methane detection is also discussed in detail.
Methane detection is extremely difficult, especially at low temperatures, due to its high chemical stability. Here, WO3 nanosheets loaded with SnO2 nanoparticles with a particle size of about 2 nm were prepared by simple impregnation and subsequent calcination using SnO2 and WO3·H2O as precursors. The response of SnO2-loaded WO3 nanosheet composites to methane is about 1.4 times higher than that of pure WO3 at the low optimum operating temperature (90 °C). Satisfying repeatability and long-term stability are ensured. The dominant exposed (200) crystal plane of WO3 nanosheets has a good balance between easy oxygen chemisorption and high reactivity at the dangling bonds of W atoms, beneficial for gas-sensing properties. Moreover, the formation of a nâ»n type heterojunction at the SnO2-WO3 interface and additionally the increase of specific surface area and defect density via SnO2 loading enhance the response further. Therefore, the SnO2-WO3 composite is promising for the development of sensor devices to methane.
Developing the triethylamine sensor with excellent sensitivity and selectivity is important for detecting the triethylamine concentration change in the environment. In this work, flower-like CeO2-SnO2 composites with different contents of CeO2 were successfully synthesized by the one-step hydrothermal reaction. Some characterization methods were used to research the morphology and structure of the samples. Gas-sensing performance of the CeO2-SnO2 gas sensor was also studied and the results show that the flower-like CeO2-SnO2 composite showed an enhanced gas-sensing property to triethylamine compared to that of pure SnO2. The response value of the 5 wt.% CeO2 content composite based sensor to 200 ppm triethylamine under the optimum working temperature (310 °C) is approximately 3.8 times higher than pure SnO2. In addition, CeO2-SnO2 composite is also significantly more selective for triethylamine than pure SnO2 and has better linearity over a wide range of triethylamine concentrations. The improved gas-sensing mechanism of the composites toward triethylamine was also carefully discussed.
