A crystalline carbon nitride-based separator for high-performance lithium metal batteries.

Lithium metal anodes with ultrahigh theoretical capacities are very attractive for assembling high-performance batteries. However, uncontrolled Li dendrite growth strongly retards their practical applications. Different from conventional separator modification strategies that are always focused on functional group tuning or mechanical barrier construction, herein, we propose a crystallinity engineering-related tactic by using the highly crystalline carbon nitride as the separator interlayer to suppress dendrite growth. Interestingly, the presence of Cl- intercalation and high-content pyrrolic-N from molten salt treatment along with highly crystalline structure enhanced the interactions of carbon nitride with Li+ and homogenized lithium flux for uniform deposition, as supported by both experimental and theoretical evidences. The Li-Li cell with the modified separator therefore delivered ultrahigh stability even after 3,000 h with dendrite-free cycled electrodes. Meanwhile, the assembled Li-LiFePO4 full-cell also presented high-capacity retention. This work opens up opportunities for design of functional separators through crystallinity engineering and broadens the use of C3N4 for advanced batteries.

Superstructure-Assisted Single-Atom Catalysis on Tungsten Carbides for Bifunctional Oxygen Reactions.

Single-atom catalysis (SAC) attracts wide interest for zinc-air batteries that require high-performance bifunctional electrocatalysts for oxygen reactions. However, catalyst design is still highly challenging because of the insufficient driving force for promoting multiple-electron transfer kinetics. Herein, we report a superstructure-assisted SAC on tungsten carbides for oxygen evolution and reduction reactions. In addition to the usual single atomic sites, strikingly, we reveal the presence of highly ordered Co superstructures in the interfacial region with tungsten carbides that induce internal strain and promote bifunctional catalysis. Theoretical calculations show that the combined effects from superstructures and single atoms strongly reduce the adsorption energy of intermediates and overpotential of both oxygen reactions. The catalyst therefore presented impressive bifunctional activity with an ultralow potential gap of 0.623 V and delivered a high power density of 188.5 mW cm-2 for assembled zinc-air batteries. This work opens up new opportunities for atomic catalysis.

A Short-Range Ordered α-MoO3 with Modulated Interlayer Structure via Hydrogen Bond Chemistry for NH4 + Storage.

The layered orthorhombic molybdenum trioxide (α-MoO3) is a promising host material for NH4 + storage. But its electrochemical performances are still unsatisfactory due to the absence of fundamental understanding on the relationship between structure and property. Herein, NH4 + storage properties of α-MoO3 are elaborately studied. Electrochemistry together with ex situ physical characterizations uncover that irreversible H+/NH4 + co-intercalation in the initial cycle confines the electrochemically reactive domain to the near surface of α-MoO3 thus resulting in a low reversible NH4 + storage capacity. This issue can be resolved by decreasing ion diffusion pathway to construct short-range ordered α-MoO3 (SMO), which improves the specific capacity to 185 mAh g-1. SMO suffers from dissolution issue. In view of this the interlayer structure of SMO is reconstructed via hydrogen bond chemistry to reinforce the structural stability and it is discovered that the hydrogen bond network only with moderate intensity endows SMO with both high capacity and ability against dissolution. This work presents a new avenue to improve the NH4 + storage properties of α-MoO3 and highlights the important role of hydrogen bond intensity in optimizing electrochemical properties.

Realization of Long-Life Proton Battery by Layer Intercalatable Electrolyte.

Proton batteries have attracted increasing interests because of their potential for grid-scale energy storage with high safety and great low-temperature performances. However, their development is significantly retarded by electrolyte design due to free water corrosion. Herein, we report a layer intercalatable electrolyte (LIE) by introducing trimethyl phosphate (TMP) into traditional acidic electrolyte. Different from conventional role in batteries, the presence of TMP intriguingly achieves co-intercalation of solvent molecules into the interlayer of anode materials, enabling a new working mechanism for proton reactions. The electrode corrosion was also strongly retarded with expanded electrochemical stability window. The half-cell therefore showed an outstanding long-term cycling stability with 91.0% capacity retention at 5 A g-1 after 5000 cycles. Furthermore, the assembled full batteries can even deliver an ultra-long lifetime with a capacity retention of 74.9% for 2 months running at -20 °C. This work provides new opportunities for electrolyte design of aqueous batteries.

No tillage increases soil organic carbon storage and decreases carbon dioxide emission in the crop residue-returned farming system.

Soil organic carbon (SOC) storage and carbon dioxide (CO2) emission under different tillage methods in a crop residue-returned farming system may not be consistent with result from studies of the usual tillage researches because crop residues are important carbon sources with significant effects on soil carbon input and output. Herein, we address a knowledge gap over the "hot spot" research on tillage practices on SOC storage and CO2 emission in crop residue-returned farming systems. In this study, a long-term (2007-2019) field experiment was conducted, and the crop residues were returned to the soil after harvest; then, three tillage methods were conducted: no tillage (NT), subsoiling tillage (ST), and a moldboard plow tillage (CT). Our results showed that in the crop residue-returned farming system, NT and ST still showed advantages of lower CO2 flux compared with CT, as well as a reduced average CO2 flux of 14.5% and 8.5%, respectively, over a two-year average. The results of our long-term study suggest that the NT had advantages of SOC accumulation. In addition, as of June 2018, NT increased SOC stocks with 5.85 Mg hm-2 at a 0-60-cm soil depth compared with CT, whereas no significant difference was found between ST and CT. Overall, adopting NT in a crop residue-returned farming system improved SOC storage to 5.85 Mg hm-2 after 11 years as well as decreased CO2 flux by 14.5% in comparison with CT, which is meaningful in improving soil carbon pool and decreasing soil CO2 emission during agriculture production.

Engineering High-Performance MoO2 -Based Nanomaterials with Supercapacity and Superhydrophobicity by Tuning the Raw Materials Source.

Herein, a simple self-assembly method is proposed for the fabrication of MoO2 -based superhydrophobic material with record high contact angles (contact angle up to about 173°) for conductive metal oxides on hard/soft substrates. The spin-coated surface demonstrates excellent oil-water separation efficiency (>98%) after 50 cycles and robust corrosion resistance after immersion into different pH solutions for 20 d. These water-resistant coatings retain excellent superhydrophobicity after oil immersion, knife-scratch, and long-cycle sandpaper abrasion, which is not observed on most artificial surfaces. Meanwhile, the functionality switching from superhydrophobicity to supercapacity, which have an inverse relationship in aqueous solutions because of poor electrode wettability, is achieved simply by editing the raw materials source. Tuning of the raw materials leads to the same product MoO2 /graphitic carbon with different morphologies and functionalities. Different from superhydrophobic MoO2 /carbon ball flowers, MoO2 nanotubes with carbon exhibit excellent supercapacity with a large gravimetric capacitance and great cycling stability.

Extreme ultraviolet resist materials for sub-7 nm patterning.

Continuous ongoing development of dense integrated circuits requires significant advancements in nanoscale patterning technology. As a key process in semiconductor high volume manufacturing (HVM), high resolution lithography is crucial in keeping with Moore's law. Currently, lithography technology for the sub-7 nm node and beyond has been actively investigated approaching atomic level patterning. EUV technology is now considered to be a potential alternative to HVM for replacing in some cases ArF immersion technology combined with multi-patterning. Development of innovative resist materials will be required to improve advanced fabrication strategies. In this article, advancements in novel resist materials are reviewed to identify design criteria for establishment of a next generation resist platform. Development strategies and the challenges in next generation resist materials are summarized and discussed.

Deriving High-Resolution Emission Inventory of Open Biomass Burning in China based on Satellite Observations.

Open biomass burning plays an important role in atmospheric pollution and in climate change. However, the current emission inventory of open biomass burning is generally of highly uncertainty because of missing small fire data and limited resolution because of the lack of localized vegetation data. In this study, the MODIS (MODerate Resolution Imaging Spectroradiometer) burned area product MCD64Al combined with the active fire product MCD14 ML, as well as a high-resolution land cover data set, were applied to develop a high-resolution emission inventory of open biomass burning in China in 2013. Total CO, CH4, NOx, NMVOC (nonmethane volatile organic compounds), SO2, NH3, PM2.5, PM10, OC (organic carbon), BC (black carbon), and CO2 emissions were estimated to be 1.03 × 104, 666, 536, 1.91 × 103, 87, 138, 1.45 × 103, 2.09 × 103, 741, 137, and 2.45 × 105 Gg, respectively. The provinces that contributed the most emissions included Heilongjiang, Henan, Shandong, and Jilin. The major source for all pollutants was cropland burning, whereas Xizang, Xinjiang, and Heilongjiang had greater emissions from natural vegetation. The temporal distribution of average provincial emissions showed that the peaks were in June and October. This study updated the emission information that may support future research and policy-making on air pollution control and GHG emission abatement.

Chemical composition and source apportionment of PM10 and PM2.5 in different functional areas of Lanzhou, China.

To elucidate the air pollution characteristics of northern China, airborne PM10 (atmospheric dynamic equivalent diameter ≤ 10 µm) and PM2.5 (atmospheric dynamic equivalent diameter ≤ 2.5 µm) were sampled in three different functional areas (Yuzhong County, Xigu District and Chengguan District) of Lanzhou, and their chemical composition (elements, ions, carbonaceous species) was analyzed. The results demonstrated that the highest seasonal mean concentrations of PM10 (369.48 µg/m(3)) and PM2.5 (295.42 µg/m(3)) were detected in Xigu District in the winter, the lowest concentration of PM2.5 (53.15 µg/m(3)) was observed in Yuzhong District in the fall and PM10 (89.60 µg/m(3)) in Xigu District in the fall. The overall average OC/EC (organic carbon/elemental carbon) value was close to the representative OC/EC ratio for coal consumption, implying that the pollution of Lanzhou could be attributed to the burning of coal. The content of SNA (the sum of sulfate, nitrate, ammonium, SNA) in PM2.5 in Yuzhong County was generally lower than that at other sites in all seasons. The content of SNA in PM2.5 and PM10 in Yuzhong County was generally lower than that at other sites in all seasons (0.24-0.38), indicating that the conversion ratios from precursors to secondary aerosols in the low concentration area was slower than in the area with high and intense pollutants. Six primary particulate matter sources were chosen based on positive matrix factorization (PMF) analysis, and emissions from dust, secondary aerosols, and coal burning were identified to be the primary sources responsible for the particle pollution in Lanzhou.

Impact of emission control on regional air quality: an observational study of air pollutants before, during and after the Beijing Olympic Games.

An observational study on trace gases and PM2.5 was conducted at three sites in and around Beijing, during the Olympic season from 2007 to 2009. Air quality improved significantly during the Olympic Games due to the special emission control measures. However, concentrations of the primary pollutants and PM were found to have risen significantly after the Games. Although the major O3 precursors (NO(x) and VOCs) were well controlled during the Olympic season, O3 was still found to be the highest in 2008, based on the data of ground-based observation. All this information suggests that while control of regional emissions for the Beijing Olympic Games did improved the air quality in Beijing, more efforts will be needed for the continuous improvement of regional air quality, especially for significant reductions of O3 and fine particulate pollution, and not only in Beijing, but also in the Beijing-Tianjin-Hebei region.

Photochemical properties and source of pollutants during continuous pollution episodes in Beijing, October, 2011.

Beijing suffered from serious air pollution in October, 2011 with the occurrence of three continuous episodes. Here we analyze the pollution status of particulate matter, the relationship between the gaseous pollutants, physical and chemical properties of single particles, and the profile of water-soluble ions in PM2.5 during the three episodes. Regional and photochemically aged air masses, which were characterized as having high values of O3 and SO2, were hypothesized to have played a dominant role in the first episode. After mixing local air masses with freshly-emitted primary pollutants, the concentration of NO(x) continued to increase and the size of SO4(2-), NO3(-) and NH4(+) in the particle population continued to become smaller. The amount of elemental carbon-rich and organic carbon-rich particles in the scaled single particles (0.2-2 microm) and water-soluble K(+) in PM2.5 also increased in the episodes. All the available information suggests that the biomass or fuel burning sources in or around Beijing may have had a huge impact on the last two episodes.

Spatial and temporal variation of particulate matter and gaseous pollutants in 26 cities in China.

O3 and PM2.5 were introduced into the newly revised air quality standard system in February 2012, representing a milestone in the history of air pollution control, and China's urban air quality will be evaluated using six factors (SO2, NO2, O3, CO, PM2.5 and PM10) from the beginning of 2013. To achieve the new air quality standard, it is extremely important to have a primary understanding of the current pollution status in various cities. The spatial and temporal variations of the air pollutants were investigated in 26 pilot cities in China from August 2011 to February 2012, just before the new standard was executed. Hourly averaged SO2, NO2 and PM10 were observed in 26 cities, and the pollutants O3, CO and PM2.5 were measured in 15 of the 26 cities. The concentrations of SO2 and CO were much higher in the cities in north China than those in the south. As for O3 and NO2, however, there was no significant difference between northern and southern cities. Fine particles were found to account for a large proportion of airborne particles, with the ratio of PM2.5 to PM10 ranging from 55% to 77%. The concentrations of PM2.5 (57.5 microg/m3) and PM10 (91.2 microg/m3) were much higher than the values (PM2.5: 11.2 microg/m3; PM10: 35.6 microg/m3) recommended by the World Health Organization. The attainment of the new urban air quality standard in the investigated cities is decreased by 20% in comparison with the older standard without considering O3, CO and PM2.5, suggesting a great challenge in urban air quality improvement, and more efforts will to be taken to control air pollution in China.

Highly Crystalline Poly(heptazine imide)-Based Carbonaceous Anodes for Ultralong Lifespan and Low-Temperature Sodium-Ion Batteries.

Carbon nitrides with layered structures and scalable syntheses have emerged as potential anode choices for the commercialization of sodium-ion batteries. However, the low crystallinity of materials synthesized through traditional thermal condensation leads to insufficient conductivity and poor cycling stability, which significantly hamper their practical applications. Herein, a facile salt-covering method was proposed for the synthesis of highly ordered crystalline C3N4-based all-carbon nanocomposites. The sealing environment created by this strategy leads to the formation of poly(heptazine imide) (PHI), the crystalline phase of C3N4, with extended π-conjugation and a fully condensed nanosheet structure. Meanwhile, theoretical calculations reveal the high crystallinity of C3N4 significantly reduces the energy barrier for electron transition and enables the generation of efficient charge transfer channels at the heterogeneous interface between carbon and C3N4. Accordingly, such nanocomposites present ultrastable cycling performances over 5000 cycles, with a high reversible capacity of 245.1 mAh g-1 at 2 A g-1 delivered. More importantly, they also exhibit an outstanding low-temperature capacity of 196.6 mAh g-1 at -20 °C. This work offers opportunities for the energy storage use of C3N4 and provides some clues for developing long-life and high-capacity anodes operated under extreme conditions.

[Formation Potential of Secondary Organic Aerosols and Sources of Volatile Organic Compounds During an Air Pollution Episode in Autumn, Langfang].

A typical particulate matter pollution process occurred from October 9 to 17,2018,in Langfang,and 99 types of volatile organic compounds (VOCs) were monitored by using ZF-KU-1007. The characteristics of VOCs,formation potential of secondary organic aerosol (SOA),and source of VOCs were systematically analyzed. The results showed that the maximum concentration of PM2.5 was 198 µg·m-3 during the pollution process and was 2.64 times the National Ambient Air Quality Standard (GB 3095-2012). The average concentration of VOCs was 56.8×10-9,127.8×10-9,and 72.5×10-9 in the early,middle,and late stages of the pollution process,respectively,and the concentration of VOCs increased significantly in the middle stage. The formation potential of SOA was significantly positively correlated with PM2.5,and the contribution of aromatic hydrocarbon for SOA was larger and significantly correlated with the concentration of PM2.5. In the middle pollution stage,SOA increased,and the contribution ratio of aromatic hydrocarbon increased significantly. Conversely,the contribution of alkanes and olefin decreased significantly,which showed that aromatic hydrocarbons,namely benzene series,were the dominant species of SOA generation and had a great influence on the pollution process. Benzene,toluene,m-/p-xylene,o-xylene,and ethylbenzene and nonane,n-undecane,and methylcyclohexane were the priority control species in this pollution process. Solvent use source and motor vehicle emission source (gasoline and diesel vehicles) were the main sources affecting the concentration of VOCs during the autumn pollution process of Langfang,among which the contribution of gasoline vehicle emissions increased significantly in the middle pollution contribution and was the key control source.

Determination of EGFR mutations in single cells microdissected from enriched lung tumor cells in peripheral blood.

A minimally invasive and repeatable approach for real-time epidermal growth factor receptor (EGFR) mutation surveillance would be highly beneficial for individualized therapy of late stage lung cancer patients whose surgical specimens are often not available. We aim to develop a viable method to detect EGFR mutations in single circulating tumor cells (CTCs). Using a model CTC system of spiked tumor cells in whole blood, we evaluated EGFR mutation determination in single tumor cells enriched from blood. We used magnetic beads labeled with antibody against leukocyte surface antigens to deplete leukocytes and enrich native CTCs independent of epithelial marker expression level. We then used laser cell microdissection (LCM) to isolate individual CTCs, followed by whole-genome amplification of the DNA for exon 19 microdeletion, L858R and T790M mutation detection by PCR sequencing. EGFR mutations were successfully measured in individual spiked tumor cells enriched from 7.5 ml whole blood. Whole-genome amplification provided sufficient DNA for mutation determination at multiple sites. Ninety-five percent of the single CTCs microdissected by LCM (19/20) yielded PCR amplicons for at least one of the three mutation sites. The amplification success rates were 55 % (11/20) for exon 19 deletion, 45 % (9/20) for T790M, and 85 % (17/20) for L858R. Sequencing of the amplicons showed allele dropout in the amplification reactions, but mutations were correctly identified in 80 % of the amplicons. EGFR mutation determination from single captured tumor cells from blood is feasible with the approach described here. However, to overcome allele dropout and to obtain reliable information about the tumor's EGFR status, multiple individual tumor cells should be assayed.

SOX1 acts as a tumor hypnotist rendering nasopharyngeal carcinoma cells refractory to chemotherapy.

SOX1, a well-known tumor suppressor, delays malignant progression in most cancer types. However, high expression of SOX1 in late-stage head and neck squamous cell carcinoma leads to poor prognosis. In this study, we show that SOX1 induces nasopharyngeal carcinoma (NPC) cells to enter a quiescent state. Using a model that mimics therapeutic resistance and tumor recurrence, a subpopulation of SOX1-induced NPC cells is refractory to paclitaxel, a cell cycle-specific chemotherapy drug. These cells maintain a quiescent state with decreased translational activity and down-regulated cell growth potential. However, once SOX1 expression is decreased, the NPC cells recover and enter a proliferative state. The chemotherapy resistance induced by SOX1 can not pass to next generation, as the cells that undergo re-proliferation become sensitive to paclitaxel again. Moreover, SOX1 directly binds to the promoter region of the MYC gene, leading to transcriptional suppression. When switching to a paclitaxel-free culture environment, the cells with decreased levels of SOX1 re-express MYC, resulting in increased abundance of proliferative cancer cells. Our study presents an evolutionary trade-off between tumor growth and chemoresistance orchestrated by SOX1-MYC in NPC. Basing on the dynamic role of SOX1 in different stages of cancer development, SOX1 would be regarded as a "tumor hypnotist".

Characterization, Expression, and Functional Analysis of the Northern Snakehead (Channa argus) Hepcidin.

Hepcidin, an antimicrobial peptide (AMP), is a well-conserved molecule present in various species such as fish, amphibians, birds, reptiles, and mammals. It exhibits broad-spectrum antimicrobial activity and holds a significant role in the innate immune system of host organisms. The northern snakehead (Channa argus) has become a valuable freshwater fish in China and Asia. In this investigation, the cDNA encoding the hepcidin gene of northern snakehead was cloned and named caHep. The amino acid sequences and protein structure of caHep are similar to those of hepcidins from other fish. The eukaryotic expression product of the caHep gene showed broad-spectrum antibacterial activity. Scanning electron microscope analysis indicated that the caHep peptide inhibited bacterial growth by damaging their cell membranes. Lipopolysaccharide (LPS) injection induced significant expression of caHep, implying the involvement of caHep in the innate immune response of northern snakeheads. This investigation showed that the caHep peptide is potentially a robust antibacterial drug against bacterial diseases in aquaculture animals.

Particle number size distribution and new particle formation: new characteristics during the special pollution control period in Beijing.

New particle formation is a key process in shaping the size distribution of aerosols in the atmosphere. We present here the measurement results of number and size distribution of aerosol particles (10-10000 nm in diameter) obtained in the summer of 2008, at a suburban site in Beijing, China. We firstly reported the pollution level, particle number size distribution, diurnal variation of the particle number size distribution and then introduced the characteristics of the particle formation processes. The results showed that the number concentration of ultrafine particles was much lower than the values measured in other urban or suburban areas in previous studies. Sharp increases of ultrafine particle count were frequently observed at noon. An examination of the diurnal pattern suggested that the burst of ultrafine particles was mainly due to new particle formation promoted by photochemical processes. In addition, high relative humidity was a key factor driving the growth of the particles in the afternoon. During the 2-month observations, new particle formation from homogeneous nucleation was observed for 42.7% of the study period. The average growth rate of newly formed particles was 3.2 nm/hr, and varied from 1.2 to 8.0 nm/hr. The required concentration of condensable vapor was 4.4 x 10(7) cm(-3), and its source rate was 1.2 x 106 cm(-3) sec(-1). Further calculation on the source rate of sulphuric acid vapor indicated that the average participation of sulphuric acid to particle growth rates was 28.7%.

Size distributions and sources of elements in particulate matter at curbside, urban and rural sites in Beijing.

Size distributions of 29 elements in aerosols collected at urban, rural and curbside sites in Beijing were studied. High levels of Mn, Ni, As, Cd and Pb indicate the pollution of toxic heavy metals cannot be neglected in Beijing. Principal component analysis (PCA) indicates 4 sources of combustion emission, crust related sources, traffic related sources and volatile species from coal combustion. The elements can be roughly divided into 3 groups by size distribution and enrichment factors method (EFs). Group 1 elements are crust related and mainly found within coarse mode including Al, Mg, Ca, Sc, Ti, Fe, Sr, Zr and Ba; Group 2 elements are fossil fuel related and mostly concentrated in accumulation mode including S, As, Se, Ag, Cd, Tl and Pb; Group 3 elements are multi-source related and show multi-mode distribution including Be, Na, K, Cr, Mn, Co, Ni, Cu, Zn, Ga, Mo, Sn and Sb. The EFs of Be, S, Cr, Co, Ni, Cu, Ga, Se, Mo, Ag, Cd, Sb, Tl and Pb show higher values in winter than in summer indicating sources of coal combustion for heating in winter. The abundance of Cu and Sb in coarse mode is about 2-6 times higher at curbside site than at urban site indicating their traffic sources. Coal burning may be the major source of Pb in Beijing since the phase out of leaded gasoline, as the EFs of Pb are comparable at both urban and curbside sites, and about two times higher in winter than that in summer.

Constructing porous carbon nitride nanosheets for efficient visible-light-responsive photocatalytic hydrogen evolution.

The photocatalytic performance of polymeric carbon nitride (CN) is mainly restricted by the poor mass charge separation efficiency and poor light absorption due to its polymeric nature. The conventional strategies to address these problems involved constructing a nanosheets structure would result in a blue shifted light absorption and increased exciton binding energy. Here, with combination of ammonia etching and selectively hydrogen-bond breaking, holey carbon nitride nanosheets (hCNNS) were constructed, thus widening the light absorption range, and spontaneously shortening the migration distance of electrons and holes in the lateral and vertical directions, respectively. Further analysis also found out the reserved atomic structure order endowed hCNNS with the relatively high redox potential. When irradiated with visible light (λ > 420 nm) and loaded with 3 wt% Pt as the cocatalyst, the hydrogen evolution rate of hCNNS was about 40 times higher than the bulk CN, and the apparent quantum yield (AQY) of hCNNS is 1.47% at 435 ± 15 nm. We expect this research can provide a new sight for achieving highly efficient solar utilization of CN-based photocatalysts.