Kinetic Evaluation on Lithium Polysulfide in Weakly Solvating Electrolyte toward Practical Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are highly considered as next-generation energy storage techniques. Weakly solvating electrolyte with low lithium polysulfide (LiPS) solvating power promises Li anode protection and improved cycling stability. However, the cathodic LiPS kinetics is inevitably deteriorated, resulting in severe cathodic polarization and limited energy density. Herein, the LiPS kinetic degradation mechanism in weakly solvating electrolytes is disclosed to construct high-energy-density Li-S batteries. Activation polarization instead of concentration or ohmic polarization is identified as the dominant kinetic limitation, which originates from higher charge-transfer activation energy and a changed rate-determining step. To solve the kinetic issue, a titanium nitride (TiN) electrocatalyst is introduced and corresponding Li-S batteries exhibit reduced polarization, prolonged cycling lifespan, and high actual energy density of 381 Wh kg-1 in 2.5 Ah-level pouch cells. This work clarifies the LiPS reaction mechanism in protective weakly solvating electrolytes and highlights the electrocatalytic regulation strategy toward high-energy-density and long-cycling Li-S batteries.

Inductive Effect on Single-Atom Sites.

Single-atom catalysts exhibit promising electrocatalytic activity, a trait that can be further enhanced through the introduction of heteroatom doping within the carbon skeleton. Nonetheless, the intricate relationship between the doping positions and activity remains incompletely elucidated. This contribution sheds light on an inductive effect of single-atom sites, showcasing that the activity of the oxygen reduction reaction (ORR) can be augmented by reducing the spatial gap between the doped heteroatom and the single-atom sites. Drawing inspiration from this inductive effect, we propose a synthesis strategy involving ligand modification aimed at precisely adjusting the distance between dopants and single-atom sites. This precise synthesis leads to optimized electrocatalytic activity for the ORR. The resultant electrocatalyst, characterized by Fe-N3P1 single-atom sites, demonstrates remarkable ORR activity, thus exhibiting great potential in zinc-air batteries and fuel cells.

Molecular Recognition Regulates Coordination Structure of Single-Atom Sites.

Coordination engineering for single-atom sites has drawn increasing attention, yet its chemical synthesis remains a tough issue, especially for tailorable coordination structures. Herein, a molecular recognition strategy is proposed to fabricate single-atom sites with regulable local coordination structures. Specifically, a heteroatom-containing ligand serves as the guest molecule to induce coordination interaction with the metal-containing host, precisely settling the heteroatoms into the local structure of single-atom sites. As a proof of concept, thiophene is selected as the guest molecule, and sulfur atoms are successfully introduced into the local coordination structure of iron single-atom sites. Ultrahigh oxygen reduction electrocatalytic activity is achieved with a half-wave potential of 0.93 V versus reversible hydrogen electrode. Furthermore, the strategy possesses excellent universality towards diversified types of single-atom sites. This work makes breakthroughs in the fabrication of single-atom sites and affords new opportunities in structural regulation at the atomic level.

Correlating Polysulfide Solvation Structure with Electrode Kinetics towards Long-Cycling Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are promising due to ultrahigh theoretical energy density. However, their cycling lifespan is crucially affected by the electrode kinetics of lithium polysulfides. Herein, the polysulfide solvation structure is correlated with polysulfide electrode kinetics towards long-cycling Li-S batteries. The solvation structure derived from strong solvating power electrolyte induces fast anode kinetics and rapid anode failure, while that derived from weak solvating power electrolyte causes sluggish cathode kinetics and rapid capacity loss. By contrast, the solvation structure derived from medium solvating power electrolyte balances cathode and anode kinetics and improves the cycling performance of Li-S batteries. Li-S coin cells with ultra-thin Li anodes and high-S-loading cathodes deliver 146 cycles and a 338 Wh kg-1 pouch cell undergoes stable 30 cycles. This work clarifies the relationship between polysulfide solvation structure and electrode kinetics and inspires rational electrolyte design for long-cycling Li-S batteries.

Cathode Kinetics Evaluation in Lean-Electrolyte Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries afford great promise on achieving practical high energy density beyond lithium-ion batteries. Lean-electrolyte conditions constitute the prerequisite for achieving high-energy-density Li-S batteries but inevitably deteriorates battery performances, especially the sulfur cathode kinetics. Herein, the polarizations of the sulfur cathode are systematically decoupled to identify the key kinetic limiting factor in lean-electrolyte Li-S batteries. Concretely, an electrochemical impedance spectroscopy combined galvanostatic intermittent titration technique method is developed to decouple the cathodic polarizations into activation, concentration, and ohmic parts. Therein, activation polarization during lithium sulfide nucleation emerges as the dominant polarization as the electrolyte-to-sulfur ratio (E/S ratio) decreases, and the sluggish interfacial charge transfer kinetics is identified as the main reason for degraded cell performances under lean-electrolyte conditions. Accordingly, a lithium bis(fluorosulfonyl)imide electrolyte is proposed to decrease activation polarization, and Li-S batteries adopting this electrolyte provide a discharge capacity of 985 mAh g-1 under a low E/S ratio of 4 µL mg-1 at 0.2 C. This work identifies the key kinetic limiting factor of lean-electrolyte Li-S batteries and provides guidance on designing rational promotion strategies to achieve advanced Li-S batteries.

The Crucial Role of Electrode Potential of a Working Anode in Dictating the Structural Evolution of Solid Electrolyte Interphase.

The performance of rechargeable lithium (Li) batteries is highly correlated with the structure of solid electrolyte interphase (SEI). The properties of a working anode are vital factors in determining the structure of SEI; however, the correspondingly poor understanding hinders the rational regulation of SEI. Herein, the electrode potential and anode material, two critical properties of an anode, in dictating the structural evolution of SEI were investigated theoretically and experimentally. The anode potential is identified as a crucial role in dictating the SEI structure. The anode potential determines the reduction products in the electrolyte, ultimately giving rise to the mosaic and bilayer SEI structure at high and low potential, respectively. In contrast, the anode material does not cause a significant change in the SEI structure. This work discloses the crucial role of electrode potential in dictating SEI structure and provides rational guidance to regulate SEI structure.

Regulating Lithium Salt to Inhibit Surface Gelation on an Electrocatalyst for High-Energy-Density Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have great potential as high-energy-density energy storage devices. Electrocatalysts are widely adopted to accelerate the cathodic sulfur redox kinetics. The interactions among the electrocatalysts, solvents, and lithium salts significantly determine the actual performance of working Li-S batteries. Herein, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), a commonly used lithium salt, is identified to aggravate surface gelation on the MoS2 electrocatalyst. In detail, the trifluoromethanesulfonyl group in LiTFSI interacts with the Lewis acidic sites on the MoS2 electrocatalyst to generate an electron-deficient center. The electron-deficient center with high Lewis acidity triggers cationic polymerization of the 1,3-dioxolane solvent and generates a surface gel layer that reduces the electrocatalytic activity. To address the above issue, Lewis basic salt lithium iodide (LiI) is introduced to block the interaction between LiTFSI and MoS2 and inhibit the surface gelation. Consequently, the Li-S batteries with the MoS2 electrocatalyst and the LiI additive realize an ultrahigh actual energy density of 416 W h kg-1 at the pouch cell level. This work affords an effective lithium salt to boost the electrocatalytic activity in practical working Li-S batteries and deepens the fundamental understanding of the interactions among electrocatalysts, solvents, and salts in energy storage systems.

Working Zinc-Air Batteries at 80 °C.

Aqueous zinc-air batteries possess inherent safety and are especially commendable facing high-temperature working conditions. However, their working feasibility at high temperatures has seldom been investigated. Herein, the working feasibility of high-temperature zinc-air batteries is systemically investigated. The effects of temperature on air cathode, zinc anode, and aqueous electrolyte are decoupled to identify the favorable and unfavorable factors. Specifically, parasitic hydrogen evolution reaction strengthens at high temperatures and leads to declined anode Faraday efficiency, which is identified as the main bottleneck. Moreover, zinc-air batteries demonstrate cycling feasibility at 80 °C. This work reveals the potential of zinc-air batteries to satisfy energy storage at high temperatures and guides further development of advanced batteries towards harsh working conditions.

A clicking confinement strategy to fabricate transition metal single-atom sites for bifunctional oxygen electrocatalysis.

Rechargeable zinc-air batteries call for high-performance bifunctional oxygen electrocatalysts. Transition metal single-atom catalysts constitute a promising candidate considering their maximum atom efficiency and high intrinsic activity. However, the fabrication of atomically dispersed transition metal sites is highly challenging, creating a need for for new design strategies and synthesis methods. Here, a clicking confinement strategy is proposed to efficiently predisperse transitional metal atoms in a precursor directed by click chemistry and ensure successful construction of abundant single-atom sites. Concretely, cobalt-coordinated porphyrin units are covalently clicked on the substrate for the confinement of the cobalt atoms and affording a Co-N-C electrocatalyst. The Co-N-C electrocatalyst exhibits impressive bifunctional oxygen electrocatalytic performances with an activity indicator ΔE of 0.79 V. This work extends the approach to prepare transition metal single-atom sites for efficient bifunctional oxygen electrocatalysis and inspires the methodology on precise synthesis of catalytic materials.

Surface Gelation on Disulfide Electrocatalysts in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are deemed as future energy storage devices due to ultrahigh theoretical energy density. Cathodic polysulfide electrocatalysts have been widely investigated to promote sluggish sulfur redox kinetics. Probing the surface structure of electrocatalysts is vital to understanding the mechanism of polysulfide electrocatalysis. In this work, we for the first time identify surface gelation on disulfide electrocatalysts. Concretely, the Lewis acid sites on disulfides trigger the ring-opening polymerization of the dioxolane solvent to generate a surface gel layer, covering disulfides and reducing the electrocatalytic activity. Accordingly, a Lewis base triethylamine (TEA) is introduced as a competitive inhibitor. Consequently, Li-S batteries with disulfide electrocatalysts and TEA afford high specific capacity and improved rate responses. This work affords new insights on the actual surface structure of electrocatalysts in Li-S batteries.

Semi-Immobilized Molecular Electrocatalysts for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries constitute promising next-generation energy storage devices due to the ultrahigh theoretical energy density of 2600 Wh kg-1. However, the multiphase sulfur redox reactions with sophisticated homogeneous and heterogeneous electrochemical processes are sluggish in kinetics, thus requiring targeted and high-efficient electrocatalysts. Herein, a semi-immobilized molecular electrocatalyst is designed to tailor the characters of the sulfur redox reactions in working Li-S batteries. Specifically, porphyrin active sites are covalently grafted onto conductive and flexible polypyrrole linkers on graphene current collectors. The electrocatalyst with the semi-immobilized active sites exhibits homogeneous and heterogeneous functions simultaneously, performing enhanced redox kinetics and a regulated phase transition mode. The efficiency of the semi-immobilizing strategy is further verified in practical Li-S batteries that realize superior rate performances and long lifespan as well as a 343 Wh kg-1 high-energy-density Li-S pouch cell. This contribution not only proposes an efficient semi-immobilizing electrocatalyst design strategy to promote the Li-S battery performances but also inspires electrocatalyst development facing analogous multiphase electrochemical energy processes.

An Organodiselenide Comediator to Facilitate Sulfur Redox Kinetics in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are considered as promising next-generation energy storage devices due to their ultrahigh theoretical energy density, where soluble lithium polysulfides are crucial in the Li-S electrochemistry as intrinsic redox mediators. However, the poor mediation capability of the intrinsic polysulfide mediators leads to sluggish redox kinetics, further rendering limited rate performances, low discharge capacity, and rapid capacity decay. Here, an organodiselenide, diphenyl diselenide (DPDSe), is proposed to accelerate the sulfur redox kinetics as a redox comediator. DPDSe spontaneously reacts with lithium polysulfides to generate lithium phenylseleno polysulfides (LiPhSePSs) with improved redox mediation capability. The as-generated LiPhSePSs afford faster sulfur redox kinetics and increase the deposition dimension of lithium sulfide. Consequently, the DPDSe comediator endows Li-S batteries with superb rate performance of 817 mAh g-1 at 2 C and remarkable cycling stability with limited anode excess. Moreover, Li-S pouch cells with the DPDSe comediator achieve an actual initial energy density of 301 Wh kg-1 and 30 stable cycles. This work demonstrates a novel redox comediation strategy with an effective organodiselenide comediator to facilitate the sulfur redox kinetics under pouch cell conditions and inspires further exploration in mediating Li-S kinetics for practical high-energy-density batteries.

[Effect of Alkaline Sludge Fermentation Products on the Nitrification Process and Performance].

The aim of the present study was to investigate the effect of alkaline sludge fermentation products as a carbon source on the nitrification process and performance. During the operation of a biological nitrogen removal (BNR) system with sludge fermentation mixture as the carbon source, the activities of ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) were inhibited at the beginning. After 16 days, the activity of AOB began to recover rapidly, but the activity of NOB was still inhibited. The specific nitrate production rate (SNaPR, N/VSS) decreased from 0.1791 g·(g·d)-1 to 0.0078 g·(g·d)-1. At the same time, the nitrite accumulation rate increased from 8.12% to 91.42% and remained stable. The sludge fermentation mixture was separated into sludge fermentation liquid and sludge fermentation sediment. The changes in nitrification activity by adding different types of fermentation products were investigated. The results showed that the activity of NOB decreased in the experimental group fed with the sludge fermentation mixture and the fermentation liquid. The SNaPR decreased from an initial 0.1793 g·(g·d)-1 to 0.1510 g·(g·d)-1 and 0.1617 g·(g·d)-1, respectively. In the experimental group fed with fermentation sediment, the activity of NOB increased. SNaPR rose from 0.1793 g·(g·d)-1 to 0.1864 g·(g·d)-1. Therefore, the activity of the NOB can be inhibited when the sludge fermentation mixture and the fermentation liquid are used as a carbon source in the nitrification process. In addition, the short-range nitrification process can be realized, which is beneficial to accelerating the reaction speed and saving investment in this type of carbon source.

[Advanced Denitrification of Municipal Wastewater Achieved via Partial ANAMMOX in Anoxic MBBR].

Anoxic MBBR is a process to achieve advanced denitrification from municipal wastewater. Here, anoxic MBBR was applied as a post-denitrification SBR to achieve advanced denitrification by partial anammox (anaerobic ammonium oxidation). During a 250-day operation, denitrification performance gradually improved and the total nitrogen concentration of the effluent was approximately 5 mg·L-1. The average nitrate, ammonia, and total inorganic nitrogen removal efficiencies were (97.7±2.9)%, (93.3±2.9)%, and (94.3±2.7)%, respectively, between day 211 and 250. The simultaneous removal of ammonia and nitrate was observed in the anoxic reactor. Analysis of the ammonia removal pathway revealed that assimilation and nitrification were poor in the anoxic MBBR. The anammox activity test and the denitrification performance showed that anammox occurred and played a not insignificant role in the anoxic MBBR. The results of real-time quantitative PCR showed that anammox bacteria enriched in anoxic MBBR, especially in the anoxic carrier biofilms, where the abundance of anammox bacteria increased from 4.37×107 copies·g-1 to 2.28×1010 copies·g-1. This study demonstrates that anoxic carrier biofilms may have potential applications in anammox bacterial enrichment to enhance denitrification from municipal wastewater.

Color-Tuning and Near-Sunlight White Emission in Highly Stable Rod-Spacer MOFs with Defective Dicubane Based Lead(II)-Carboxyl Chains.

The active lone pair electron effect and highly flexible coordination geometry of Pb2+ prevented the rational construction of metal-organic frameworks (MOFs) but promoted excellent fluorescence tuning. The regulation on organic and alkali templates facilitated the assemblies of three new Pb-MOFs: [Pb2(pia)2(DMA)]·DMA (1), [Pb2(pia)2(DMF)]·1.5DMF (2), and [Pb2(pia)2(DMF)]·NEt3 (3). They were rigid rod-spacer and double-walls frameworks, which possess defective dicubane [Pb4O6] based metal-carboxyl chains constructed from both semidirected and holodirected Pb2+ ions. These MOFs exhibited thermal stability up to 370 °C and unprecedented chemical stability in H2O and acidic (pH 2) and alkaline (pH 12) aqueous solutions, found for the first time in Pb-MOFs. A single-phase and rare-earth-free white-emitting phosphor, 1, was screen out, which showed a near-sunlight and human-vision-friendly broadband spectrum covering the full visible region, possessing the close-to-pure-white chromaticity coordinates of (0.332, 0.347), a near-daylight color temperature of 5696 K, and a high color rendering index of 95. The replacement of DMF as apical ligand and guest in 2 resulted in an intrinsic single and narrow emission at 562 nm with yellow color. The convenient yellow-and-blue color-tuning until white for 2 was realized by either solution or solid blending with blue-emissive H2pia, benefited from their highly matched excitation spectra. Using large NEt3 as template guest induced great framework distortion for 3 and led to white emission with chromaticity coordinates of (0.302, 0.294), stemming from nonequivalent dual emission at 450 and 545 nm. In-depth structure analysis revealed intra-/interchain Pb···Pb interactions in the lead(II)-carboxyl chains greatly affected the photochemical output.

Near sunlight continuous broadband white-light emission by single-phase Zn(ii)-1,3,5-benzenetricarboxylate MOFs.

A new white light MOF was constructed from low-cost 1,3,5-benzenetricarboxylate and nontoxic Zinc(ii) ions. The compound possessed the most sophisticated crystallographic asymmetric unit containing sixteen metal ions and twelve ligands. Near sunlight and human eye friendly white-light emission under a wide ultraviolet radiation range of 300 to 390 nm was observed for this photoemitter, without the use of expensive rare earth and complicated organic ligands.

[Identification and Nitrogen Removal Characteristics of the Heterotrophic Nitrification and Aerobic Denitrification Bacterial Strain DK1].

Nitrogen removal by a newly discovered Pseudomons sp. strain, DK1, isolated from activated sludge was investigated. Using glucose as a carbon source and a n(C)/n(N) ratio of five, batch experiments showed that the aerobic denitrification removal rate was 4.09 mg·(L·h)-1 and 4.43 mg·(L·h)-1 with NaNO3 or NaNO2, respectively. Completely nitrogen removal was achieved when using these two nitrogen sources. DK1 was also found to heterotrophically remove NH4+ -N at a rate of 2.32 mg·(L·h)-1 and to carry out anoxic denitrification of a range of concentrations of NO2- -N (from about 100 to 300 mg·L-1) within a maximum of 36 hours of inoculation. In the presence of both NO3- -N and NO2- -N, DK1 was found to preferentially denitrify NO3- -N. Simultaneous nitrification and denitrification (SND) capacity of the DK1 strain was observed when using ammonium and nitrate or ammonium and nitrite and the corresponding nitrogen removal rates reached as high as 95.06% and 94.69% within 30 hours of inoculation, respectively. Ammonium with both nitrate and nitrite resulted in a 100% nitrogen removal within the same time frame. The ability to achieve SND and to denitrify both NO3- -N and NO2- -N makes the DK1 strain potentially useful for future application in nitrogenous wastewater treatment.

Protocatechuic acid inhibits osteoclast differentiation and stimulates apoptosis in mature osteoclasts.

BACKGROUND: Imbalance in bone remodeling causes osteoporosis. PURPOSE: In the present study, we identified that protocatechuic acid inhibits osteoclast differentiation and induces apoptosis in RAW264.7 murine macrophage cells. METHODS: Tartrate-resistance acid phosphatase (TRAP) activity was used to determine osteoclast formation. Oxidative stress was analyzed through ROS, lipid peroxide and antioxidant enzyme activities. Osteoclast and inflammatory marker expressions were determined through western blot. Apoptosis induction was determined through membrane potential analysis, Cyt c release and caspase activation. RESULTS: Protocatechuic acid dose dependently reduced RANKL-induced tartrate-resistance acid phosphatase (TRAP) activity and multinucleated osteoclasts formation. Protocatechuic acid inhibited oxidative stress by reducing ROS and lipid peroxide levels with concomitant increase in antioxidant status. Osteoclast specific marker expression (MMP, c-Src, TRAP, TRAF-6, Cathepsin) and transcription factor AP-1 and NFATc1 expression were significantly down regulated by protocatechuic acid. Further, MAPK activation and inflammatory proteins such as NF-kB and COX-2 expressions were significantly down regulated by protocatechuic acid treatment. Further, protocatechuic acid enhanced Nrf-2 translocation into the nucleus. In mature osteoclasts, protocatechuic acid induced apoptosis by inducing mitochondrial membrane potential, cytochrome c release and caspase activation. INTERPRETATION: The present findings shows evidence that, protocatechuic acid prevents osteoclast differentiation through regulating oxidative stress, inflammation and inducing apoptosis in RAW264.7 murine macrophage cells.

[Capacity of denitrification by polyphosphate accumulating organism at different electron donors].

SBR reactor was performed to incubate polyphosphate accumulating organism (PAO), and it was checked out of the system by fluorescence in situ hybridization. As PAO is a kind of ordinary heterotrophic bacteria, it was excluded the ability of phosphate release and uptake and it was considered only the capacity of denitrification of the target biomass. The results indicated that acetate and PHB can be the electron donors of PAO to denitrify. When fed with acetate, the denitrifying rate and PHB producing rate were independent of initial nitrate concentration. However, served as more nitrate in the reactor, it would be less PHB produced and fewer nitrate reducing when using same amount of acetate. In view of PHB stored as an internal carbon and energy source, it presented as a reaction of zero-order to the substrate by PAO to denitrify, such as nitrate, besides, the specific denitrifying rate was 0.9733 mg/(g x h) and the specific PHB consuming rate was 2.4626 mg/(g x h).

[Cultivation and characteristic of aerobic granular sludge enriched by phosphorus accumulating organisms].

This research focused on the enrichment of phosphorus accumulating organisms (PAO) and the formation of granular sludge simultaneously. After fed with flocculent sludge the SBR was run for two months for the cultivation of PAO. Then the granular sludge enriched by PAO was found. After that acetate was used instead of propionate to inhibit the glycogen accumulating organisms(GAO). The experiment testified that acetate was beneficial to the growth of the PAO granules. The system could release and take up more phosphorus when it was fed by acetate. Moreover, when the size of the granules became bigger, the performance indexes of the granules, for example the settling velocity, OUR, density, aquiferous rate and integral rate were also improved. On the other hand, the amount of PAO was found to become more and more in this process by the system performance evaluation and FISH analysis. As a result, the ratio of PAO could reach 70% of the total bacteria. The aerobic granular sludge enriched by PAO showed very good capability of COD and phosphorus removal. The COD removal efficiency could reach about 95% and phosphorus removal efficiency could reach almost 100%.