Clusters Induced Electron Redistribution to Tune Oxygen Reduction Activity of Transition Metal Single-Atom for Metal-Air Batteries.

Oxygen reduction reaction (ORR) activity can be effectively tuned by modulating the electron configuration and optimizing the chemical bonds. Herein, a general strategy to optimize the activity of metal single-atoms is achieved by the decoration of metal clusters via a coating-pyrolysis-etching route. In this unique structure, the metal clusters are able to induce electron redistribution and modulate M-N species bond lengths. As a result, M-ACSA@NC exhibits superior ORR activity compared with the nanoparticle-decorated counterparts. The performance enhancement is attributed to the optimized intermediates desorption benefiting from the unique electronic configuration. Theoretical analysis reinforces the significant roles of metal clusters by correlating the ORR activity with cluster-induced charge transfer. As a proof-of-concept, various metal-air batteries assembled with Fe-ACSA@NC deliver remarkable power densities and capacities. This strategy is an effective and universal technique for electron modulation of M-N-C, which shows great potential in application of energy storage devices.

Dual-Active Sites Engineering of N-Doped Hollow Carbon Nanocubes Confining Bimetal Alloys as Bifunctional Oxygen Electrocatalysts for Flexible Metal-Air Batteries.

Since the sluggish kinetic process of oxygen reduction (ORR)/evolution (OER) reactions, the design of highly-efficient, robust, and cost-effective catalysts for flexible metal-air batteries is desired but challenging. Herein, bimetallic nanoparticles encapsulated in the N-doped hollow carbon nanocubes (e.g., FeCo-NPs/NC, FeNi-NPs/NC, and CoNi-NPs/NC) are rationally designed via a general heat-treatment strategy of introducing NH3 pyrolysis of dopamine-coated metal-organic frameworks. Impressively, the resultant FeCo-NPs/NC hybrid exhibits superior bifunctional electrocatalytic performance for ORR/OER, manifesting exceptional discharging performance, outstanding lifespan, and prime flexibility for both Zn/Al-air batteries, superior to those of state-of-the-art Pt/C and RuO2 catalysts. X-ray absorption near edge structure and density functional theory indicate that the strong synergy between FeCo alloy and N-doped carbon frameworks has a distinctive activation effect on bimetallic Fe/Co atoms to synchronously modify the electronic structure and afford abundant dual-active Fe/Co-Nx sites, large surface area, high nitrogen doping level, and conductive carbon frameworks to boost the reversible oxygen electrocatalysis. Such N-doped carbon with bimetallic alloy bonds provides new pathways for the rational creation of high-efficiency energy conversion and storage equipment.

Necklace-like Multishelled Hollow Spinel Oxides with Oxygen Vacancies for Efficient Water Electrolysis.

The durability and reactivity of catalysts can be effectively and precisely controlled through the careful design and engineering of their surface structures and morphologies. Herein, we develop a novel "adsorption-calcination-reduction" strategy to synthesize spinel transitional metal oxides with a unique necklace-like multishelled hollow structure exploiting sacrificial templates of carbonaceous microspheres, including NiCo2O4 (NCO), CoMn2O4, and NiMn2O4. Importantly, benefiting from the unique structures and reduction treatment to offer rich oxygen vacancies, the unique reduced NCO (R-NCO) as a bifunctional electrocatalyst exhibits the dual characteristics of good stability as well as high electrocatalytic activity for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). At 1.61 V cell voltage, a 10 mA cm-2 water splitting current density is obtained from the dual-electrode, alkaline water electrolyzer. Calculations based on density functional theory (DFT) reveal a mechanism for the promotion of the catalytic reactions based on a decrease in the energy barrier for the formation of intermediates resulting from the introduction of oxygen vacancies through the reduction process. This method could prove to be an effective general strategy for the preparation of complex, hollow structures and functionalities.

Nitrogen removal performance of anaerobic ammonia oxidation (ANAMMOX) in presence of organic matter.

A sequencing batch reactor (SBR) was used to test the nitrogen removal performance of anaerobic ammonium oxidation (ANAMMOX) in presence of organic matter. Mesophilic operation (30 ± 0.5 °C) was performed with influent pH 7.5. The results showed, independent of organic matter species, ANAMMOX reaction was promoted when COD was lower than 80 mg/L. However, specific ANAMMOX activity decreased with increasing organic matter content. Ammonium removal efficiency decreased to 80% when COD of sodium succinate, sodium potassium tartrate, peptone and lactose were 192.5, 210, 225 and 325 mg/L, respectively. The stoichiometry ratio resulting from different OM differed largely and R1 could be as an indicator for OM inhibition. When COD concentration was 240 mg/L, the loss of SAA resulting from lactose, peptone, sodium potassium tartrate and sodium succinate were 28, 36, 50 and 55%, respectively. Sodium succinate had the highest inhibitory effect on SAA. When ANAMMOX process was used to treat wastewater containing OM, the modified Logistic model could be employed to predict the NREmax.

Performance and granulation in an upflow anaerobic sludge blanket (UASB) reactor treating saline sulfate wastewater.

An upflow anaerobic sludge blanket reactor was employed to treat saline sulfate wastewater. Mesophilic operation (35 ± 0.5 °C) was performed with hydraulic retention time fixed at 16 h. When the salinity was 28 g L(-1), the chemical oxygen demand and sulfate removal efficiencies were 52 and 67 %, respectively. The salinity effect on sulfate removal was less than that on organics removal. The methane productions were 887 and 329 cm(3) L(-1) corresponding to the NaCl concentrations of 12 and 28 g L(-1), respectively. High salinity could stimulate microbes to produce more extracellular polymeric substances (EPSs) and granulation could be performed better. Besides, with the high saline surroundings, a great deal of Na(+) compressed the colloidal electrical double-layer, neutralized the negative charge of the sludge particles and decreased their electrostatic repulsion. The repulsion barrier disappeared and coagulation took place. The maximum size of granules was 5 mm, which resulted from the coupled triggering forces of high EPSs and Na(+) contents. Sulfate-reducing bacteria (SRB) were dominant in the high saline surroundings while the methane-producing archaea dominated in the low saline surroundings. The SRB were affected least by the salinity.

Increasing carbon to nitrogen ratio promoted anaerobic ammonia-oxidizing bacterial enrichment and advanced nitrogen removal in mainstream anammox system.

The effects of fluctuating organic carbon to nitrogen (C/N) ratios on mainstream simultaneous partial nitrification, anammox, and denitrification (SNAD) process were studied over 376-day period. The nitrogen removal efficiency decreased from 85.0 ± 6.6 % to 75.8 ± 2.8 % as C/N ratio decreased (3.4 â†’ 1.7), but increased to 82.0 ± 1.9 % when C/N ratio raised to 2.9 and to 78.4 ± 3.0 % when C/N ratio decreased again (2.9 â†’ 2.1), indicating that high C/N ratios promoted nitrogen removal. As C/N ratio raised (1.7 â†’ 2.9), anaerobic ammonia-oxidizing bacteria (AnAOB) abundance increased from 1.3 × 109 to 2.0 × 109 copies/L, which explained the improved nitrogen removal. With an elevated C/N ratio, partial nitrification and endogenous partial denitrification reactions were enhanced, providing more nitrite for AnAOB. Additionally, the aerobic_chemoheterotrophy function and particle sizes increased, forming more stable anoxic microenvironment for AnAOB. Overall, increasing C/N ratio promoted the stability of mainstream SNAD.

Inadvertently enriched cyanobacteria prompted bacterial phosphorus uptake without aeration in a conventional anaerobic/oxic reactor.

The enhanced biological phosphorus removal (EBPR) process requires alternate anaerobic and aerobic conditions, which are regulated respectively by aeration off and on. Recently, in an ordinary EBPR reactor, an abnormal orthophosphate concentration (PO43--P) decline in the anaerobic stage (namely non-aerated phosphorus uptake) aroused attention. It was not occasionally but occurred in each cycle and lasted for 101 d and shared about 16.63 % in the total P uptake amount. After excluding bio-mineralization and surface re-aeration, indoor light conditions (180 to 260 lx) inducing non-aerated P uptake were confirmed. High-throughput sequencing analysis revealed that cyanobacteria could produce oxygen via photosynthesis and were inhabited inside wall biofilm. The cyanobacteria (Pantalinema and Leptolyngbya ANT.L52.2) were incubated in a feeding transparent silicone hose, entered the reactor along with influent, and outcompeted Chlorophyta, which existed in the inoculum. Eventually, this work deciphered the reason for non-aerated phosphorus uptake and indicated its potential application in reducing CO2 emissions and energy consumption via the cooperation of microalgal-bacterial and biofilm-sludge.

Granulation characteristics of anammox sludge in response to different signal-molecule-stimulants; mediated through programmed cell death.

During the anammox process, mitigation of biomass washout to increase sludge retention is an important parameter of process efficiency. Signal molecular stimulants (SMS) initiate the sludge granulations controlled by programmed cell death (PCD) of microorganisms. In this study, the aerobic granular sludge (AGS), cell fragments, extracellular polymeric substances (EPS), and AGS process effluent were tested as SMS to identify their effect on anammox granulation. The results showed that the addition of SMS increased the nitrogen removal efficiency to varying degrees, whereas the addition of AGS process supernatant, as SMS, increased the ammonia removal efficiency up to 96%. The addition of SMS was also found to increase EPS production and contributed to sludge granulation. In this process, the proportion of PCD increased and both Gaiella and Denitratisoma abundance increased from 3.54% to 5.59%, and from 1.8% to 3.42%, respectively. In conclusion, PCD was found important to increase anaerobic ammonia oxidation performance through the granulation mechanism.

Migration of microorganisms between nitrification-denitrification flocs, anammox biofilms and blank carriers during mainstream anammox start-up.

To solve the shortage of inoculum, the feasibility of establishing simultaneous partial nitrification, anammox, and denitrification (SNAD) reactor through inoculating nitrification-denitrification sludge, anammox biofilm and blank carriers was investigated. Advanced nitrogen removal efficiency of 91.2 ± 3.6 % was achieved. Bacteria related to nitrogen removal and fermentation were enriched in anammox biofilm, blank carriers and flocs, and the abundance of dominant anaerobic ammonia oxidizing bacteria (AnAOB), Candidatus Brocadia, reached 3.4 %, 0.5 % and 0.3 %, respectively. Candidatus Competibacter and Calorithrix became the dominant denitrifying bacteria (DNB) and fermentative bacteria (FB), respectively. The SNAD system was successfully established, and new mature biofilms formed in blank carriers, which could provide inoculum for other anammox processes. Partial nitrification, partial denitrification and aerobic_chemoheterotrophy were existed and facilitated AnAOB enrichment. Microbial correlation networks revealed the cooperation between DNB, FB and AnAOB that promoted nitrogen removal. Overall, the SNAD process was started up through inoculating more accessible inoculum.

Partial nitrification in a sequencing batch reactor treating acrylic fiber wastewater.

A sequencing batch reactor was employed to treat the acrylic fiber wastewater. The dissolved oxygen and mixed liquor suspended solids were 2-3 and 3,500-4,000 mg/L, respectively. The results showed ammonium oxidizing bacteria (AOB) had superior growth rate at high temperature than nitrite oxidizing bacteria (NOB). Partial nitrification could be obtained with the temperature of 28 °C. When the pH value was 8.5, the nitrite-N accumulation efficiency was 82 %. The combined inhibitions of high pH and free ammonium to NOB devoted to the nitrite-N buildup. Hydraulic retention time (HRT) was a key factor in partial nitrification control, and the optimal HRT was 20 h for nitrite-N buildup in acrylic fiber wastewater treatment. The ammonium oxidation was almost complete and the transformation from nitrite to nitrate could be avoided. AOB and NOB accounted for 2.9 and 4.7 %, respectively, corresponding to the pH of 7.0. When the pH was 8.5, they were 6.7 and 0.9 %, respectively. AOB dominated nitrifying bacteria, and NOB was actually washed out from the system.

Novel nitrogen removal process in marine aquaculture wastewater treatment using Enteromorpha ferment liquid as carbon.

The process performance of partial denitrification of a novel anaerobic fermentation integrated fixed-film activated sludge (IFAS-AFPD) of Enteromorpha was studied. The response surface method was used to determine the optimal reaction conditions, and the operation experiment was carried out under the optimal conditions. The results showed that the nitrogen removal effect was the best when the salinity was 12.2 g•L-1, the Carbon-Nitrogen ratio (C/N) was 4, the pH was 8.5, and the Nitrite Accumulation Rate, Nitrate Removal Rate, Chemical Oxygen Demand Utilization Rate could reach 77%, 89% and 51%. Experimental results have shown that the NAR of the Enteromorpha ferment liquid system could be maintained at about 74%, which was noteworthy higher than that of the sodium acetate (CH3COONa) system at 42%; Microbial community analysis showed that Enteromorpha ferment liquid was more beneficial to the growth of Bacteroidetes than CH3COONa.

Nitrite soaking pretreatment induced initial denitrifying nitrite accumulation.

Partial denitrification (PD) could be another method for obtaining nitrite. However, PD startup takes a long time limiting its investigation and application. This study proposed nitrite soaking as a pretreatment method for starting PD. Results showed that denitrifying nitrite accumulation (4.20 mg/L) emerged after previously soaking by 10 mg/L nitrite for 9 h. When the duration was 6 h, comparing different soaked nitrite concentrations, the highest denitrifying nitrite accumulation amount (4.92 mg/L) was obtained in the 20 mg/L group. Nevertheless, high pH of 9 and frequent feeding could further advantage denitrifying nitrite accumulation. Pretreatment as a disturbance would impel the microbial community to change from complete denitrification towards PD.

Ultrafast Combustion Synthesis of Robust and Efficient Electrocatalysts for High-Current-Density Water Oxidation.

The scalable production of inexpensive, efficient, and robust catalysts for oxygen evolution reaction (OER) that can deliver high current densities at low potentials is critical for the industrial implementation of water splitting technology. Herein, a series of metal oxides coupled with Fe2O3 are in situ grown on iron foam massively via an ultrafast combustion approach for a few seconds. Benefiting from the three-dimensional nanosheet array framework and the heterojunction structure, the self-supporting electrodes with abundant active centers can regulate mass transport and electronic structure for prompting OER activity at high current density. The optimized Ni(OH)2/Fe2O3 with robust structure can deliver a high current density of 1000 mA cm-2 at the overpotential as low as 271 mV in 1.0 M KOH for up to 1500 h. Theoretical calculation demonstrates that the strong electronic modulation plays a crucial part in the hybrid by optimizing the adsorption energy of the intermediate, thereby enhancing the efficiency of oxygen evolution. This work proposes a method to construct cheap and robust catalysts for practical application in energy conversion and storage.

A novel simultaneous partial nitrification, anammox, denitrification and fermentation process: Enhancing nitrogen removal and sludge reduction in a single reactor.

This study verified the feasibility of simultaneous partial nitrification, anammox, denitrification and fermentation process under intermittent aeration in a single reactor, and explored the impact of dissolved oxygen (DO) on the synergy between fermentation and nitrogen removal. An advanced nitrogen removal efficiency of 92.8 % and a low observed sludge yield of 0.0268-0.1474 kgMLSS/kgCOD were achieved. In-situ test showed that nitrate and ammonium decreased synchronously in the absence of organic matter, indicating the possibility of simultaneous partial denitrification, anammox and fermentation. Additionally, the abundance of functional genes for acetate production was 66,894 hits, while the key genes relevant to methanogenesis were only 348 hits, which suggested that fermentation might stop at the acid-producing stage and promote partial denitrification-anammox reaction, achieving simultaneous sludge reduction and advanced nitrogen removal performance. When DO increased from 0.1-0.3 to 0.4-0.6 mg/L, the nitrogen removal efficiency was increased (63.9 %→92.8 %) while sludge reduction was negatively affected.

Novel Insight into Rechargeable Aluminum Batteries with Promising Selenium Sulfide@Carbon Nanofibers Cathode.

Due to the unique electronic structure of aluminum ions (Al3+ ) with strong Coulombic interaction and complex bonding situation (simultaneously covalent/ionic bonds), traditional electrodes, mismatching with the bonding orbital of Al3+ , usually exhibit slow kinetic process with inferior rechargeable aluminum batteries (RABs) performance. Herein, to break the confinement of the interaction mismatch between Al3+ and the electrode, a previously unexplored Se2.9 S5.1 -based cathode with sufficient valence electronic energy overlap with Al3+ and easily accessible structure is potentially developed. Through this new strategy, Se2.9 S5.1 encapsulated in multichannel carbon nanofibers with free-standing structure exhibits a high capacity of 606 mAh g-1 at 50 mA g-1 , high rate-capacity (211 mAh g-1 at 2.0 A g-1 ), robust stability (187 mAh g-1 at 0.5 A g-1 after 3,000 cycles), and enhanced flexibility. Simultaneously, in/ex-situ characterizations also reveal the unexplored mechanism of Sex Sy in RABs.

Towards low carbon demand and highly efficient nutrient removal: Establishing denitrifying phosphorus removal in a biofilm-based system.

The combined denitrifying phosphorus removal (DPR) and Anammox process is expected to achieve advanced nutrient removal with low carbon consumption. However, exchanging ammonia/nitrate between them is one limitation. This study investigated the feasibility of conducting DPR in a biofilm reactor to solve that problem. After 46-day anaerobic/aerobic operation, high phosphorus removal efficiency (PRE, 83.15 %) was obtained in the activated sludge (AS) and biofilm co-existed system, in which the AS performed better. Phosphate-accumulating organisms might quickly adapt to the anoxic introduced nitrate, but the following aerobic stage ensured a low effluent orthophosphate (<1.03 mg/L). Because of waste sludge discharging and AS transforming to biofilm, the suspended solids dropped below 60 mg/L on Day 100, resulting in PRE decline (17.17 %) and effluent orthophosphate rise (4.23 mg/L). Metagenomes analysis revealed that Pseudomonas and Thiothrix had genes for denitrification and encoding Pit phosphate transporter, and Candidatus_Competibacter was necessary for biofilm formation.

Enhancing nitrite production rate made anammox bacteria have a competitive advantage over nitrite oxidizing bacteria in mainstream anammox system.

Nitrite oxidizing bacteria (NOB) is easy to accumulate in the mainstream anammox process, leading to the decrease of anammox bacterial abundance and deterioration of nitrogen removal. In this study, anammox bacteria was gradually enriched by increasing nitrite production rate under intermittent aeration despite high NOB abundance. With the DO increased from 0.4 to 0.6 mg/L, Nitrosomonas increased from 0.14% to 0.22%, providing more nitrite for anammox bacteria and promoting its enrichment (grew by 77.4%). Adding extra nitrite of 7.14 mg N/(L·h) during the aeration phase to reactor could further increase anammox bacterial abundance by 117.6%, which was higher than the control reactor (40.2%). In contrast, NOB abundance decreased from 1.4 × 1010 to 1.2 × 1010 copies/L. The results suggested that anammox bacteria had a competitive advantage for nitrite over NOB with increasing nitrite production rate. In addition, Thauera and Dechloromonas, which were responsible for reducing nitrate to nitrite, provided additional substrates for anammox bacteria. Overall, this research provides a new idea for mainstream anammox applications. PRACTITIONER POINTS: Inhibiting NOB might be no longer necessary and difficult for mainstream anammox. Anammox bacteria competed for more nitrite with NOB when nitrite production rate increased. Increasing DO from 0.4 to 0.6 mg/L facilitated anammox bacterial growth and nitrogen removal.

Elucidating performance failure in the use of an Anaerobic-Oxic-Anoxic (AOA) plug-flow system for biological nutrient removal.

The Anaerobic-oxic-anoxic (AOA) process is a carbon-saving and high-efficiency way to treat municipal wastewater and gets more attention. Recent reports suggest that in the AOA process, well-performed endogenous denitrification (ED), conducted by glycogen accumulating organisms (GAOs), is crucial to advanced nutrient removal. However, the consensuses about starting up and optimizing AOA, and in-situ enriching GAOs, are still lacking. Hence, this study tried to verify whether AOA could be established in an ongoing anaerobic-oxic (AO) system. For this aim, a lab-scale plug-flow reactor (working volume of 40 L) previously operated under AO mode for 150 days, during that 97.87 % of ammonium was oxidized to nitrate and 44.4 % of orthophosphate was absorbed. Contrary to expectations, under AOA mode, little nitrate reduction (only 6.3 mg/L within 5.33 h) indicated the failure of ED. According to high-throughput sequencing analysis, GAOs (Candidatus_Competibacter and Defluviicoccus) were enriched within the AO period (14.27 % and 3 %) and then still dominated during the AOA period (13.9 % and 10.07 %) but contributed little to ED. Although apparent alternate orthophosphate variations existed in this reactor, no typical phosphorus accumulating organisms were abundant (< 2 %). More than that, within the long-term AOA operation (109 days), the nitrification weakened (merely 40.11 % of ammonium been oxidized) since the dual effects of low dissolved oxygen and long unaerated duration. This work reveals the necessity of developing practical strategies for starting and optimizing AOA, and then three aspects in future studying are pointed out.

Start-up of mainstream anammox process through inoculating nitrification sludge and anammox biofilm: Shift in nitrogen transformation and microorganisms.

The feasibility of starting up mainstream single-stage partial nitrification-anammox (SPNA) system by inoculating nitrification sludge and anammox biofilm was investigated. The SPNA system treating low-strength synthetic wastewater was rapidly started up with TN removal efficiency of 88.5 ± 1.8% and effluent nitrate concentration of 7.2 ± 1.2 mg/L. Both the abundance and maximum activity of nitrite oxidizing bacteria (NOB) in flocs decreased obviously. Interestingly, the abundance of anaerobic ammonium oxidizing bacteria (AnAOB) in flocs increased from 0.213% to 0.346% despite the sludge retention time (SRT) of flocs decreased to 60 days, the AnAOB in biofilm was 0.434%. That meant AnAOB gradually enriched in flocs and accounted for a fairly high proportion. The inhibition of NOB, partial denitrification and increased aerobic_chemoheterotrophy function in flocs might be the main reasons for AnAOB enrichment. The possibility of simultaneous fermentation, partial denitrification and anammox reaction was predicted in biofilm, further improving the stability of the system.

A novel process of salt tolerance partial denitrification and anammox (ST-PDA) for treating saline wastewater.

In the study, the salt-tolerant partial denitrification and Anammox (ST-PDA) process was established, meanwhile, the feasibility of salinity inhibition model as the boundary control method and the subsequent operation performance were studied. Study indicated that the performance of salt-tolerant PD sludge was the optimum under the 10 g·L-1 salinity, and AnAOB also maintained high activity at the salinity. Haldane and Aiba models verified that NO3--N (substrate) and FNA (product) would have negative consequences for performance of ST-PDA system. However, the effect of FNA would be eliminated by self-alkalization in the denitrification process. A 90% nitrogen removal rate was achieved and the average effluent total nitrogen of 17.8 mg·L-1 was maintained in the system. The high throughput sequencing revealed that the species richness decreased with the salinity increased, while Thauera played a major role in nitrogen removal in saline environment. The study provides a novel insights for salt-containing industrial wastewater.