Overlooked in-situ sulfur disproportionation fuels dissimilatory nitrate reduction to ammonium in sulfur-based system: Novel insight of nitrogen recovery.

Sulfur-based denitrification is a promising technology in treatments of nitrate-contaminated wastewaters. However, due to weak bioavailability and electron-donating capability of elemental sulfur, its sulfur-to-nitrate ratio has long been low, limiting the support for dissimilatory nitrate reduction to ammonium (DNRA) process. Using a long-term sulfur-packed reactor, we demonstrate here for the first time that DNRA in sulfur-based system is not negligible, but rather contributes a remarkable 40.5 %-61.1 % of the total nitrate biotransformation for ammonium production. Through combination of kinetic experiments, electron flow analysis, 16S rRNA amplicon, and microbial network succession, we unveil a cryptic in-situ sulfur disproportionation (SDP) process which significantly facilitates DNRA via enhancing mass transfer and multiplying 86.7-210.9 % of bioavailable electrons. Metagenome assembly and single-copy gene phylogenetic analysis elucidate the abundant genomes, including uc_VadinHA17, PHOS-HE36, JALNZU01, Thiobacillus, and Rubrivivax, harboring complete genes for ammonification. Notably, a unique group of self-SDP-coupled DNRA microorganism was identified. This study unravels a previously concealed fate of DNRA, which highlights the tremendous potential for ammonium recovery and greenhouse gas mitigation. Discovery of a new coupling between nitrogen and sulfur cycles underscores great revision needs of sulfur-driven denitrification technology.

Eutectic-Based Polymer Electrolyte with the Enhanced Lithium Salt Dissociation for High-Performance Lithium Metal Batteries.

The deployment of lithium metal anode in solid-state batteries with polymer electrolytes has been recognized as a promising approach to achieving high-energy-density technologies. However, the practical application of the polymer electrolytes is currently constrained by various challenges, including low ionic conductivity, inadequate electrochemical window, and poor interface stability. To address these issues, a novel eutectic-based polymer electrolyte consisting of succinonitrile (SN) and poly (ethylene glycol) methyl ether acrylate (PEGMEA) is developed. The research results demonstrate that the interactions between SN and PEGMEA promote the dissociation of the lithium difluoro(oxalato) borate (LiDFOB) salt and increase the concentration of free Li+ . The well-designed eutectic-based PAN1.2 -SPE (PEGMEA: SN=1: 1.2 mass ratio) exhibits high ionic conductivity of 1.30 mS cm-1 at 30 °C and superior interface stability with Li anode. The Li/Li symmetric cell based on PAN1.2 -SPE enables long-term plating/stripping at 0.3 and 0.5 mA cm-2 , and the Li/LiFePO4 cell achieves superior long-term cycling stability (capacity retention of 80.3 % after 1500 cycles). Moreover, Li/LiFePO4 and Li/LiNi0.6 Co0.2 Mn0.2 O2 pouch cells employing PAN1.2 -SPE demonstrate excellent cycling and safety characteristics. This study presents a new pathway for designing high-performance polymer electrolytes and promotes the practical application of high-stable lithium metal batteries.

Prospect of denitrifying anaerobic methane oxidation (DAMO) application on wastewater treatment and biogas recycling utilization.

Old-fashioned wastewater treatments for nitrogen depend on heterotrophic denitrification process. It would utilize extra organic carbon source as electron donors when the C/N of domestic wastewater was too low to ensure heterotrophic denitrification process. It would lead to non-compliance with carbon reduction targets and impose an economic burden on wastewater treatment. Denitrifying anaerobic methane oxidation (DAMO), which could utilize methane serving as electron donors to replace traditional organic carbon (methanol or sodium acetate), supplies a novel approach for wastewater treatment. As the primary component of biogas, methane is an inexpensive carbon source. With anaerobic digestion becoming increasingly popular for sludge reduction in wastewater treatment plants (WWTPs), efficient biogas utilization through DAMO can offer an environmentally friendly option for in-situ biogas recycling. Here, we reviewed the metabolic principle and relevant research for DAMO and biogas recycling utilization, outlining the prospect of employing DAMO for wastewater treatment and biogas recycling utilization in WWTPs. The application of DAMO provides a new focal point for enhancing efficiency and sustainability in WWTPs.

Construction of the Fast Potassiation Path in Sbx Bi1-x @NC Anode with Ultrahigh Cycling Stability for Potassium-Ion Batteries.

Due to the scarce of lithium resources, potassium-ion batteries (PIBs) have attracted extensive attention due to their similar electrochemical properties to lithium-ion batteries (LIBs) and more abundant potassium resources. Even though there is considerable progress in SbBi alloy anode for LIBs and PIBs, most studies are focused on the morphology/structure tuning, while the inherent physical features of alloy composition's effect on the electrochemical performance are rarely investigated. Herein, combined the nanonization, carbon compounding, and alloying with composition regulation, the anode of nitrogen-doped carbon-coated Sbx Bi1-x (Sbx Bi1-x @NC) with a series of tuned chemical compositions is designed as an ideal model. The density functional theory (DFT) calculation and experimental investigation results show that the K+ diffusion barrier is lower and the path is easier to carry out when element Bi dominates the potassiation reaction, which is also the reason for better circulation. The optimized Sb0.25 Bi0.75 @NC shows an excellent cycling performance with a reversible specific capacity of 301.9 mA h g-1 after 500 cycles at 0.1 A g-1 . Meanwhile, the charge-discharge mechanism is intuitively invetigated and analyzed by in situ X-ray diffraction (XRD) and transmission electron microscopy (TEM) in detail. Such an alloy-type anode synthesis approach and in situ observation method provide an adjustable strategy for the designing and investigating of PIB anodes.

Recent Advances in Biotechnologies for the Treatment of Environmental Pollutants Based on Reactive Sulfur Species.

The definition of reactive sulfur species (RSS) is inspired by the reactivity and variable chemical valence of sulfur. Sulfur is an essential element for life and is a part of global geochemical cycles. Wastewater treatment bioreactors can be divided into two major categories: sulfur reduction and sulfur oxidation. We review the origins of the definition of RSS and related biotechnological processes in environmental management. Sulfate reduction, sulfide oxidation, and sulfur-based redox reactions are key to driving the coupled global carbon, nitrogen, and sulfur co-cycles. This shows the coupling of the sulfur cycle with the carbon and nitrogen cycles and provides insights into the global material-chemical cycle. We also review the biological classification and RSS metabolic mechanisms of functional microorganisms involved in the biological processes, such as sulfate-reducing and sulfur-oxidizing bacteria. Developments in molecular biology and genomic technologies have allowed us to obtain detailed information on these bacteria. The importance of RSS in environmental technologies requires further consideration.

Defects-Abundant Ga2 O3 Nanobricks Enabled Multifunctional Solid Polymer Electrolyte for Superior Lithium-Metal Batteries.

Polyethylene oxide (PEO)-based polymer electrolytes with good flexibility and viscoelasticity, low interfacial resistance, and fabricating cost have caught worldwide attention, but their practical application is still hampered by the instability at high voltages and the low ionic conductivity (10-8 to 10-6  S cm-1 ). Herein, we rationally designed defects-abundant Ga2 O3 nanobricks as multifunctional fillers and constructed a PEO-based organic-inorganic electrolyte for lithium metal batteries. Due to the abundant O-defects feature of Ga2 O3 filler, this PEO-based composite electrolyte not only broadens electrochemical stability window (over 5.3 V versus Li/Li+ ) but also in situ forms a Li-Ga alloy and solid electrolyte interphase (SEI) film during the cycling process causing a rapid diffusion of Li+ ions. The as-prepared electrolyte has good interface compatibility with Li metal (without short-circuiting over 500 h at 0.2 mA cm-2 ) and possesses superior high ionic conductivity. The assembled all-solid-state LiFePO4 //Li cells attained an excellent cycling performance of 146 mAh g-1 over 100 cycles at 0.5 C. The XPS analysis reveals that Ga2 O3 nanobricks can form in situ a Li-Ga alloy layer at the polymer/anode interface. This work shed a light on designing high ionic conductivity lithium alloys in the composite electrolyte, which can improve the electrochemical properties of PEO-based polymer electrolytes.

Interface Engineering of All-Solid-State Batteries Based on Inorganic Solid Electrolytes.

All-solid-state batteries (ASSBs) based on inorganic solid electrolytes (SEs) are one of the most promising strategies for next-generation energy storage systems and electronic devices due to the higher energy density and intrinsic safety. However, the poor solid-solid contact and restricted chemical/electrochemical stability of inorganic SEs both in cathode and anode SE interfaces cause contact failure and the degeneration of SEs during prolonged charge-discharge processes. As a result, the increasing interface resistance significantly affects the coulombic efficiency and cycling performance of ASSBs. Herein, we present a fundamental understanding of physical contact and chemical/electrochemical features of ASSB interfaces based on mainstream inorganic SEs and summarize the recent work on interface modification. SE doping, optimizing morphology, introducing interlayer/coating layer, and utilizing compatible electrode materials are the key methods to prevent side reactions, which are discussed separately in cathode/anode-SE interface. We also highlight the constant extra stack pressure applied during ASSB cycling, which is important to the electrochemical performance. Finally, our perspectives on interface modification for practical high-performance ASSBs are put forward.

The mixed/mixotrophic nitrogen removal for the effective and sustainable treatment of wastewater: From treatment process to microbial mechanism.

Biological nitrogen removal (BNR) is one of the most important environmental concerns in the field of wastewater treatment. The conventional BNR process based on heterotrophic nitrogen removal (HeNR) is suffering from several limitations, including external carbon source dependence, excessive sludge production, and greenhouse gas emissions. Through the mediation of autotrophic nitrogen removal (AuNR), mixed/mixotrophic nitrogen removal (MixNR) offers a viable solution to the optimization of the BNR process. Here, the recent advance and characteristics of MixNR process guided by sulfur-driven autotrophic denitrification (SDAD) and anammox are summarized in this review. Additionally, we discuss the functional microorganisms in different MixNR systems, shedding light on metabolic mechanisms and microbial interactions. The significance of MixNR for carbon reduction in the BNR process has also been noted. The knowledge gaps and the future research directions that may facilitate the practical application of the MixNR process are highlighted. Overall, the prospect of the MixNR process is attractive, and this review will provide guidance for the future implementation of MixNR process as well as deciphering the microbially metabolic mechanisms.

Perspective on inorganic electron donor-mediated biological denitrification process for low C/N wastewaters.

Nitrate is the most common water environmental pollutant in the world. Inorganic electron donor-mediated denitrification is a typical process with significant advantages in treating low carbon-nitrogen ratio water and wastewater and has attracted extensive research attention. This review summarizes the denitrification processes using inorganic substances, including hydrogen, reductive sulfur compounds, zero-valent iron, and iron oxides, ammonium nitrogen, and other reductive heavy metal ions as electron donors. Aspects on the functional microorganisms, critical metabolic pathways, limiting factors and mathematical modeling are outlined. Also, the typical inorganic electron donor-mediated denitrification processes and their mechanism, the available microorganisms, process enhancing approaches and the engineering potentials, are compared and discussed. Finally, the prospects of developing the next generation inorganic electron donor-mediated denitrification process is put forward.

Enhanced methane production in anaerobic digestion: A critical review on regulation based on electron transfer.

Anaerobic digestion (AD) is a potential bioprocess for waste biomass utilization and energy conservation. Various iron/carbon-based CMs (e.g., magnetite, biochar, granular activated carbon (GAC), graphite and zero valent iron (ZVI)) have been supplemented in anaerobic digestors to improve AD performance. Generally, the supplementation of CMs has shown to improve methane production, shorten lag phase and alleviate environmental stress because they could serve as electron conduits and promote direct interspecies electron transfer (DIET). However, the CMs dosage varied greatly in previous studies and CMs wash out remains a challenge for its application in full-scale plants. Future work is recommended to standardize the CMs dosage and recover/reuse the CMs. Moreover, additional evidence is required to verify the electrotrophs involved in DIET.

Uniform In Situ Grown ZIF-L Layer for Suppressing Hydrogen Evolution and Homogenizing Zn Deposition in Aqueous Zn-Ion Batteries.

The hydrogen evolution and dendrite of Zn anode are the major troubles hindering the commercialization of aqueous Zn-ion batteries (AZIBs). ZIF-Ls, a typical metal-organic framework (MOF) with a highly ordered structure and abundant functional groups, seem to be the answer for the above bottlenecks. In this paper, a uniform ZIF-L layer was obtained on the Zn surface (Zn@ZIF-L) via an in situ synthesis method to moderate the solvation structure of solid-liquid interface electrolyte reducing the contact between water and Zn, thereby relieving the hydrogen evolution and corrosion. Furthermore, density functional theory (DFT) analysis reveals the binding energy of H (-4.01 eV) and Zn (-0.82 eV) for ZIF-L is superior to that of pure Zn (H (-1.49 eV) and Zn (-0.68 eV)). Due to the multifunctional ZIF-L layer, the Zn@ZIF-L can regulate Zn deposition to overcome the dendrite for obtaining a long-life Zn anode. Consequently, the modified Zn@ZIF-L anode can cycle for 800 h at 0.25 mA cm-2 for 0.25 mAh cm-2, while the bare Zn anode is only maintained for 422 h. Finally, a designed V2O5 grown on carbon cloth (V2O5@CC) was used as the cathode and coupled with the Zn@ZIF-L anode to assemble the full-cell. The Zn@ZIF-L//V2O5@CC full-cell possesses a capacity retention rate of 84.9% after 250 cycles at 0.5 C, prominently higher than Zn//V2O5@CC (40.7%).

Reduced Graphene Oxide-Coated Separator to Activate Dead Potassium for Efficient Potassium Batteries.

Potassium (K) metal batteries (KMBs) have the advantages of relatively low electric potential (-2.93 V), high specific capacity (687 mAh g-1), and low cost, which are highly appealing to manufacturers of portable electric products and vehicles. However, the large amounts of "dead K" caused by K dendrite growth and volumetric expansion can cause severe K metal anode deactivation. Here, a thin layer of conductive reduced graphene oxide (rGO) was coated on a GF separator (rGO@GF) to activate the generated dead K. Compared with the batteries adopting an original separator, those adopting a modified separator have significantly improved specific capacity and cycling stability. The life of full-cell of KMBs combining an rGO@GF separator with synthesized K0.51V2O5 is expected to exceed 400 cycles, with an initial capacity of 92 mAh g-1 at 0.5 A g-1 and an attenuation rate per cycle as low as 0.03%. Our work demonstrates that a composite separator of high conductivity is beneficial for high performance KMBs.

A novel sulfide-driven denitrification methane oxidation (SDMO) system: Operational performance and metabolic mechanisms.

Microbial denitrification is a crucial biological process for the treatment of nitrogen-polluted water. Traditional denitrification process consumes external organic carbon leading to an increase in treatment costs. We developed a novel sulfide-driven denitrification methane oxidation (SDMO) system that integrates autotrophic denitrification (AD) and denitrification anaerobic methane oxidation (DAMO) for cost-effective denitrification and biogas utilization in situ. Two SDMO systems were operated for 735 days, with nitrate and nitrite serving as electron acceptors, to explore the performance of sewage denitrification and characterize metabolic mechanisms. Results showed SDMO system could reach as high as 100% efficiency of nitrogen removal and biogas desulfurization without an external carbon source when HRT was 10 days and inflow nitrogen concentrations were 50-100 mgN·L-1. Besides, nitrate was a preferable electron acceptor for SDMO system. Biogas not only enhanced nitrogen removal but also intensified the DAMO, nitrogen removed through DAMO contribution doubled as original period from 2.9 mgN·(L·d)-1 to 6.2 mgN·(L·d)-1, and the ratio of nitrate removal through AD to DAMO was 1.2:1 with nitrate as electron acceptor. While nitrogen removed almost all through AD contribution and DAMO was weaken as before, the ratio of nitrate removal through AD to DAMO was 21.2:1 with nitrite as electron acceptor. Biogas introduced into SDMO system with nitrate inspired the growth of DAMO bacteria Candidatus Methylomirabilis from 0.3% to 19.6% and motivated its potentiality to remove nitrate without ANME archaea participation accompanying with gene mfnE upregulating ∼100 times. According to the reconstructed genome from binning analysis, the dramatically upregulated gene mfnE was derived from Candidatus Methylomirabilis, which may represent a novel metabolism pathway for DAMO bacteria to replace the role of archaea for nitrate reduction.

Preparation and characterization of micro/nanocellulose reinforced PVDF/wood composites.

Polyvinylidene fluoride (PVDF) is commonly used in the chemical, electronic, and petrochemical industries because of its chemical and physical attributes. This study aimed to make novel PVDF-based composite with a high loading of silanized wood powder and micro/nanocellulose fibers, where glycerol acts as both a dispersant and a plasticizer all-in-one composite application for the first time. The purpose was also extended to systematically investigate their mechanical properties and melt flow. Results have demonstrated the efficiency of utilizing the cellulose fibers in bio-composites. With the addition of 30 wt% of filling materials, When the content of silanized cellulose fibers in glycerol dispersion is 25 wt%, the flexural strength and tensile strength reach the maximum value 72.30 MPa and 52.28 MPa. The experimental results indicate that silanized micro/nanocellulose fiber-reinforced PVDF/wood composites are a promising composite formula to help improve performance and reduce costs. It is an excellent example of utilizing biomass resources as a renewable/recyclable, sustainable and low-cost material to reduce the use of petroleum-based polymer, and improve the mechanical properties of composites.

Construction of Fe7Se8@Carbon nanotubes with enhanced sodium/potassium storage.

The Fe7Se8@Carbon (C) nanotubes are successfully synthesized using Fe3O4@C nanotubes as sacrificial templates. Fe7Se8@C nanotubes exhibit excellent rate behaviour and maintainable capacity (319 mAh g-1 at 2 A g-1 upon 720 cycles), when utilized as SIBs anode. Moreover, for PIBs anode, Fe7Se8@C nanotubes also exhibit outstanding rate behaviour and maintainable capacity 222 mAh g-1 at 2 A g-1 upon 500 cycles). The superior electrochemical performance of Fe7Se8@C nanotubes is ascribed to the unique structure, where the hierarchical hollow tubular characteristic of Fe7Se8@C composites can mitigate the volume expansion of Fe7Se8 and supply effective transmission paths for both Na+(K+) and electrons within repeated cycle processes, and additionally, N-doped carbon layer can further protect the integrality of Fe7Se8@C nanotubes from destruction within the cycle processes, and enhance electronic conductivity.

A novel intra- and extracellular distribution pattern of elemental sulfur in Pseudomonas sp. C27-driven denitrifying sulfide removal process.

Pseudomonas sp. C27 can achieve the conversion of toxic sulfide to economical elemental sulfur (S0) with various electron acceptors. In this study the distribution pattern of S0 produced by C27 in denitrifying sulfide removal (DSR) process was explored. The SEM observation identified that the particle size of the biogenic S0 was at micron level. Strikingly, a novel distribution pattern of S0 was revealed that the produced S0 was not directly secreted extracellularly, but be stored temporarily in the cell interior. Pyrolysis at 65 °C for 20 min were recommended prior to S0 recovery, which could maximize the separation of extracellular polymeric substances (EPS) from C27. Furthermore, the effects of N/S molar ratio, initial sulfide concentration, and micro-oxygen condition were investigated to improve the production of S0 by C27. The highest S0 production was obtained at S/N of 3 and anaerobic condition seemed to favor the S0 production by C27. This study would provide a theoretical support for highly efficient sulfide removal as well as S0 recovery in sulfide-laden wastewater treatment.

Cryptic Sulfur and Oxygen Cycling Potentially Reduces N2O-Driven Greenhouse Warming: Underlying Revision Need of the Nitrogen Cycle.

Increasing global deoxygenation has widely formed oxygen-limited biotopes, altering the metabolic pathways of numerous microbes and causing a large greenhouse effect of nitrous oxide (N2O). Although there are many sources of N2O, denitrification is the sole sink that removes N2O from the biosphere, and the low-level oxygen in waters has been classically thought to be the key factor regulating N2O emissions from incomplete denitrification. However, through microcosm incubations with sandy sediment, we demonstrate here for the first time that the stress from oxygenated environments does not suppress, but rather boosts the complete denitrification process when the sulfur cycle is actively ongoing. This study highlights the potential of reducing N2O-driven greenhouse warming and fills a gap in pre-cognitions on the nitrogen cycle, which may impact our current understanding of greenhouse gas sinks. Combining molecular techniques and kinetic verification, we reveal that dominant inhibitions in oxygen-limited environments can interestingly undergo triple detoxification by cryptic sulfur and oxygen cycling, which may extensively occur in nature but have been long neglected by researchers. Furthermore, reviewing the present data and observations from natural and artificial ecosystems leads to the necessary revision needs of the global nitrogen cycle.

Advances in the Development of Single-Atom Catalysts for High-Energy-Density Lithium-Sulfur Batteries.

Although lithium-sulfur (Li-S) batteries are promising next-generation energy-storage systems, their practical applications are limited by the growth of Li dendrites and lithium polysulfide shuttling. These problems can be mitigated through the use of single-atom catalysts (SACs), which exhibit the advantages of maximal atom utilization efficiency (≈100%) and unique catalytic properties, thus effectively enhancing the performance of electrode materials in energy-storage devices. This review systematically summarizes the recent progress in SACs intended for use in Li-metal anodes, S cathodes, and separators, briefly introducing the operating principles of Li-S batteries, the action mechanisms of the corresponding SACs, and the fundamentals of SACs activity, and then comprehensively describes the main strategies for SACs synthesis. Subsequently, the applications of SACs and the principles of SACs operation in reinforced Li-S batteries as well as other metal-S batteries are individually illustrated, and the major challenges of SACs usage in Li-S batteries as well as future development directions are presented.

Self-Sacrifice Template Construction of Uniform Yolk-Shell ZnS@C for Superior Alkali-Ion Storage.

Secondary batteries have been widespread in the daily life causing an ever-growing demand for long-cycle lifespan and high-energy alkali-ion batteries. As an essential constituent part, electrode materials with superior electrochemical properties play a vital role in the battery systems. Here, an outstanding electrode of yolk-shell ZnS@C nanorods is developed, introducing considerable void space via a self-sacrificial template method. Such carbon encapsulated nanorods moderate integral electronic conductivity, thus ensuring rapid alkali-ions/electrons transporting. Furthermore, the porous structure of these nanorods endows enough void space to mitigate volume stress caused by the insertion/extraction of alkali-ions. Due to the unique structure, these yolk-shell ZnS@C nanorods achieve superior rate performance and cycling performance (740 mAh g-1 at 1.0 A g-1 after 540 cycles) for lithium-ion batteries. As a potassium-ion batteries anode, they achieve an ultra-long lifespan delivering 211.1 mAh g-1 at 1.0 A g-1 after 5700 cycles. The kinetic analysis reveals that these ZnS@C nanorods with considerable pseudocapacitive contribution benefit the fast lithiation/delithiation. Detailed transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses indicate that such yolk-shell ZnS@C anode is a typical reversible conversion reaction mechanism accomplished by alloying processes. This rational design strategy opens a window for the development of superior energy storage materials.

In-Situ Synthesis of Carbon-Encapsulated Atomic Cobalt as Highly Efficient Polysulfide Electrocatalysts for Highly Stable Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have been considered as one of the most promising electrochemical energy storage systems because of their high energy density. However, a series of issues severely limit the practical performances of Li-S batteries such as low conductivity, significant volume change, and shuttle effect. The hollow carbon spheres with huge voids and high electrical conductivity are promising as sulfur hosts. Unfortunately, the nonpolar nature of carbon materials cannot prevent the shuttle effect effectively. In this case, the atomic cobalt is introduced to a nitrogen-doped hollow carbon sphere (ACo@HCS) through polymerization and controlled pyrolysis. The atomic cobalt dopants not only act as active sites to restrict the shuttle effect, but also can promote the kinetics of the sulfur redox reactions. ACo@HCS acting as sulfur host exhibits a high discharge capacity (1003 mAh g-1 ) at a 1.0 C rate after 500 cycles, and the corresponding decay rate is as low as 0.002% per cycle. This exciting work paves a new way to design high-performance Li-S batteries.