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.

Turning on Zn 4s Electrons in a N2 -Zn-B2 Configuration to Stimulate Remarkable ORR Performance.

A zinc-based single-atom catalyst has been recently explored with distinguished stability, of which the fully occupied Zn2+ 3d10 electronic configuration is Fenton-reaction-inactive, but the catalytic activity is thus inferior. Herein, we report an approach to manipulate the s-band by constructing a B,N co-coordinated Zn-B/N-C catalyst. We confirm both experimentally and theoretically that the unique N2 -Zn-B2 configuration is crucial, in which Zn+ (3d10 4s1 ) can hold enough delocalized electrons to generate suitable binding strength for key reaction intermediates and promote the charge transfer between catalytic surface and ORR reactants. This exclusive effect is not found in the other transition-metal counterparts such as M-B/N-C (M=Mn, Fe, Co, Ni and Cu). Consequently, the as-obtained catalyst demonstrates impressive ORR activity, along with remarkable long-term stability in both alkaline and acid media. This work presents a new concept in the further design of electrocatalyst.

Pollution in the urban soils of Lianyungang, China, evaluated using a pollution index, mobility of heavy metals, and enzymatic activities.

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.

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.

Typhoon-induced stormwater drives nutrient dynamics and triggers phytoplankton blooms in Laizhou Bay, China.

In this study, we investigated the hydrological and ecological impacts of heavy rainfall caused by the storm Rumbia and Typhoon Lekima on Laizhou Bay (LZB) through land‒sea synchronous field surveys, online remote sensors, and simulated enclosure experiments. Within two weeks of Rumbia, approximately 9% and 16% of the annual riverine total nitrogen (TN) and total phosphorus (TP) fluxes, respectively, were transported to the LZB and the proportions were 17% and 35%, respectively, for Lekima. The land use on the watersheds increased the rates of land-derived nutrient loading and altered their biogeochemical forms. Consequently, the average concentrations of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) in the LZB increased by 2.6 and 1.0 times post-Rumbia and by 3.5 and 1.3 times post-Lekima, respectively. Relatively lower salinity and temperature, sudden increases in DIN, and strengthened coastal currents stimulated the growth of highly adaptable and small diatoms, resulting in the first diatom blooms. Subsequently, a bloom of Noctiluca scintillans formed.

Seasonal dynamics of dissolved organic matter bioavailability coupling with water mass circulation in the South Yellow Sea.

As a typical shelf-marginal sea, the South Yellow Sea (SYS) is significantly influenced by various factors such as land-based inputs and water mass movements, leading the complex biogeochemical processes of dissolved organic matter (DOM) to become highly dynamic. However, the bioavailability of dissolved organic matter (DOM) coupled with water mass circulation has not been accurately assessed, despite being crucial for understanding the source-sink pattern of organic carbon in marginal sea. In this study, four cruises were conducted in the SYS to analyze the spatial and temporal distribution characteristics of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and total dissolved amino acids (TDAA). Combined with the bioassay experiments, TDAA carbon normalized yield [TDAA (%DOC)] and TDAA degradation index (DIAA) were used as indicators to explore the bioavailability of DOM across different water masses. Results show that the DOC of the SYS exhibits higher average value in late autumn and early winter, and lower value in spring and summer due to the seasonal alternation of water mass and biological activities. The collective results indicate that DOM bioavailability is higher in the Changjiang River diluted water (CDW) and lower in the Yellow Sea warm current (YSWC) and the Yellow Sea cold water mass (YSCWM). Approximately 20 % of DON can be degraded in the YSCWM during autumn. Notably, although the YSCWM constitutes merely constitutes 10 % of the SYS volume, it stores 18.1 % dissolved inorganic nitrogen (DIN) and 23.9 % PO43- of total nutrients, indicating that the YSCWM is a significant nutrient reservoir within the SYS.

Nutrient budgets for the Bohai Sea: Implication for ratio imbalance of nitrogen to phosphorus input under intense human activities.

Eutrophication is a global problem for coastal ecosystems, one that the Bohai Sea (BHS), China, is severely afflicted by due to rapid economic and social development over the last forty years. For sustainable nutrients management in the BHS, comprehensive budgets for Nitrogen (N) and Phosphorus (P) was characterized in 2017, and the relative contributions of river input, submarine fresh groundwater discharge, atmospheric deposition, sediment diffusion, and exchange with the Yellow Sea were quantified. The annual N and P fluxes into the BHS were 362 × 103 t and 10.4 × 103 t, respectively. The terrigenous N inputs occupied the highest proportion, while the largest P input was from sediment diffusion. The ratio of N:P was 77 for total external inputs, while that of the Yellow River was 680; both exceeded the Redfield ratio, indicating an imbalance in the nutrient structure and a P limitation in the BHS.

An Amorphous Anode for Proton Battery.

Developing advanced electrode materials is crucial for improving the electrochemical performances of proton batteries. Currently, the anodes are primarily crystalline materials which suffer from inferior cyclic stability and high electrode potential. Herein, we propose amorphous electrode materials for proton batteries by using a general ion-exchange protocol to introduce multivalent metal cations for activating the host material. Taking Al3+ as an example, theoretical and experimental analysis demonstrates electrostatic interaction between metal cations and lattice oxygen, which is the primary barrier for direct introduction of the multivalent cations, is effectively weakened through ion exchange between Al3+ and pre-intercalated K+. The as-prepared Al-MoOx anode therefore delivered a remarkable capacity and outstanding cycling stability that outperforms most of the state-of-the-art counterparts. The assembled full cell also achieved a high voltage of 1.37 V. This work opens up new opportunities for developing high-performance electrodes of proton batteries by introducing amorphous materials.

An ultralong-life SnS-based anode through phosphate-induced structural regulation for high-performance sodium ion batteries.

As a star representative of transition metal sulfides, SnS is viewed as a promising anode-material candidate for sodium ion batteries due to its high theoretical capacity and unique layered structure. However, the extremely poor electrical conductivity and severe volume expansion strongly hinder its practical application while achieving a high reversible capacity with long-cyclic stability still remains a grand challenge. Herein, different from the conventional enhancement method of elemental doping, we report a rational strategy to introduce PO43- into the SnS layers using phytic acid as the special phosphorus source. Intriguingly, the presence of PO43- in the form of Sn-O-P covalent bonds can act as a conductive pillar to buffer the volume expansion of SnS while expanding its interlay spacing to allow more Na+ storage, supported by both experimental and theoretical evidences. Profiting from this effect combined with microstructural metrics by loading on high pyridine N-doped reduced graphene oxide, the as-prepared material presented an unprecedented ultra-long cyclic stability even after 10,000 cycles along with high reversible capacity and excellent full-cell performances. The findings herein open up new opportunities for elevating electrochemical performances of metal sulfides and provide inspirations for the fabrication of advanced electrode materials for broad energy use.

Historical records of trace metals in core sediments from the Lianyungang coastal sea, Jiangsu, China.

We analyzed element concentrations in cores from the Lianyungang coastal sea to determine depositional trends and geochemical sources of metals. Enrichment factors (EFs) and pollution load index (PLI) were used to assess the enrichment and pollution of metals. Profiles of vertical distributions of the elements reflected different depositional environments in 3 cores. Cores A and C deposited sediments with rich terrestrial elements by rivers, corresponding to mixed-up patterns in the sediment. Meanwhile, core B was mainly deposited in a less undisturbed depositional environment. Correlations and principal component analysis indicated that sediments were influenced by natural and anthropogenic impacts. According to the EFs, most metals showed no significant enrichment and pollution in the core sediments. Lastly, PLI values (<1) of sediments indicated that the Lianyungang coastal sea was a lowly polluted area despite PLI value of metals in average sediment was lower than that in surface sediment.