Simultaneous biodegradation of nitrogen-containing aromatic compounds in a sequencing batch bioreactor

Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from contaminated water is one of the main challenges facing wastewater treatment plants. In this study, synthetic wastewater containing NB, 4-NP, 2,4-DNP, and AN at concentrations ranging from 50 to 180 mg/L was fed into a sequencing batch reactor （SBR）. Analyses of the SBR system indicated that it simultaneously removed more than 99% of the NACs at loading rates of 0.36 kg NB/（m^3·d）, 0.3 kg 4-NP/（m^3·d）, 0.25 kg AN/（m^3·d）, and 0.1 kg 2,4-DNP/（m^3·d）. Bacterial groups of Bacteriodetes, Candidate division TM7, α-Proteobacteria, and β-Proteobacteria were dominant in the clone libraries of 16S rRNA genes retrieved from the microbial communities in the SBR system. ＂Cycle tests＂ designed to alter feeding and aeration parameters of the SBR system demonstrated that the resident microbial biome of the SBR system responded rapidly to changing conditions. Consumption of O2 was concomitant with the apparent mineralization of NACs. Aromatic ring-cleaving dioxygenase activities suggested that （1） AN and NB were degraded via catechol 2,3-dioxygenase; （2） 4-NP was degraded via 1,2,4-benzentriol 1,2-dioxygenase; and （3） 2,4-DNP was degraded via an unresolved pathway.

Adsorptive removal of nitrogen-containing compounds from fuel by metal-organic frameworks

The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.

Stress Corrosion Cracking of Nitrogen-containing Stainless Steel 316LN in High Temperature Water Environments

Stress corrosion cracking （SCC） of stainless steels and Ni-based alloys in high temperature water coolant is one of the key problems affecting the safe operation of nuclear power plants （NPPs）. The nitrogen-added stainless steel is a kind of possible candidate materials for mitigating SCC since reducing the carbon content and adding nitrogen to offset the loss in strength caused by the decrease in carbon content can mitigate the problem of sensitization. However, the reports of SCC of nitrogen-added stainless steels in high temperature water are few available. The effects of applied potential and sensitization treatment on the SCC of a newly developed nitrogen-containing stainless steel （SS） 316LN in high temperature water doped with chloride at 250 ℃ were studied by using slow strain rate tests （SSRTs）. The SSRT results are compared with our data previously published for 316 SS without nitrogen and 304NG SS with nitrogen, and the possible mechanism affecting the SCC behaviors of the studied steels is also discussed based on SSRT and microstucture analysis results. The susceptibility to cracking of 316LN SS normally increases with increasing potential. The susceptibility to SCC of 316LN SS was less than that of 316 SS and 304NG SS. Sensitization treatment at 700℃ for 30 h showed little effect on the S CC of 316LN S S and significant effect on the S CC of 316 S S. The predominant cracking mode for the 316LN S S in both annealed state and the state after the sensitization treatment was transgranular. The presented conditions of mitigating stress corrosion cracking are some useful information for the safe use of 316LN SS in NPPs.

Characterization of nitrogen-containing aromatics in Baiyinhua lignite and its soluble portions from thermal dissolution

Soluble portions(SPs) 1-4(SP1-SP4) were afforded from sequentially dissolution and alkanolyses of Baiyinhua lignite(BL) in cyclohexane,CH3OH,CH3CH2OH,and(CH3)2CHOH at 300℃.They were analyzed with a gas chromatograph/mass spectrometer and quadrupole exactive orbitrap mass spectrometer(QEOTMS) with an atmosphere pressure chemical ionization source in positive-ion mode,while BL was characterized with an X-ray photoelectron spectrometer(XRPES).The results show that the yields of SP2 and SP3 are much higher than those of SP1 and SP4,and the total SP yield is ca.39.0%.According to the analysis with XRPES,pyrrolic nitrogen atoms are the most abundant nitrogen existing forms in BL.Thousands of nitrogen-containing aromatics(NCAs) were resolved with QEOTMS and their molecular masses are mainly in the range of 200-450 u.The main NCAs are N1O1 and N1O2 class species with double bond equivalent values of 4-18 and carbon numbers of 7-30.The nitrogen atoms appear in pyridine s,quinolines,benzoquinolines or acridine,and dibenzoquinolines or naphthoquinolines,while the oxygen atoms exist in methoxy and furan rings.

Synthesis and Thermal Properties of a Novel Nitrogen-containing Epoxy Resin

A new nitrogen-containing epoxy resin (XT resin) was synthesized from chain extension of xylenephenolformaldehyde resin (XPF) and triglycidyl isocyanurate (TGIC) in the presence of base catalyst. FT-IR and H-NMR analysis confirmed the chemical structure of XT resin. It was 1 cured with dicyandiamide (DICY) and diaminodiphenyl sulfone (DDS). Dynamic mechanical analysis (DMA) results showed that the introduction of triazine ring provides epoxy polymer with good thermal stability. Furthermore, high char yields at 800℃ in thermogravimetric (TGA) analysis indicated that XT resin had potential flame retardance.

Molecular Simulation Studies on Basicity of Nitrogen-containing Compounds

The DFT-based （density fimctional theory） ab initio quantum mechanical methods have been applied to study the basicity of the nitrogen-containing compounds in petroleum. The results have indicated that there is a distinct relationship between the protonation energy of nitrogen-containing compounds and their basicity. The more negative the protonation energy, the stronger the basicity is. It has been also found that aliphatic amines are more basic than pyridines or aromatic amines, and all these compounds are more basic than pyrroles. The addition of the aromatic rings can influence the basicity of anilines, while the 5- and 6-membered heterocyclic compounds function differently. The solvent properties may affect the basicity of these nitrogen-containing compounds.

Influence of Fe_(2)O_(3) on Release Mechanism of NH_(3) and Other Nitrogen-Containing Compounds from Pyrolysis of Three Typical Amino Acids in Urban Sludge

To elucidate the effects of Fe_(2)O_(3) on nitrogen transformation during sludge pyrolysis,thermogravimetry coupled with mass spectrometry(TG-MS)was used to investigate the influences of Fe_(2)O_(3) on the pyrolysis characteristics and the release of important gaseous NO_(x) precursors such as HCN and NH_(3) during pyrolysis of three typical amino acids in urban sludge.The results show that after Fe_(2)O_(3) addition,the total weight loss rate of the three amino acids and the initial decomposition temperature of proline are reduced.The release amounts of NH_(3),HCN,CH_(3)CN,and HNCO from these three representative amino acids—glumatic,arginine,and proline,decrease in the order of arginine,glutamic,proline.The generation of Fe-N complexes,reduces the generation of NH_(3),HCN,CH_(3)CN,and HNCO while the catalysis effects of Fe_(2)O_(3) on the formation of H and H2 play a promoting role in the generation of NH_(3),HCN,CH_(3)CN,and HNCO.The results would provide an experimental and theoretical basis for subsequent research on the NOx precursor formation mechanisms during pyrolysis or combustion of Fe-containing sludge or sludge with additives containing Fe.

The Synthesis of Aromatic Hydrazones as Nitrogen-Containing Prostaglandin Congeners

We synthesized a series of hydrazones, a novel type of nitrogen-containing prostaglandins, from different aromatic hydrazines and variant 2-substituted amino-3-hydroxy bicycle [3.2.0]hept-6-ones IV.

Defect engineering for advanced electrocatalytic conversion of nitrogen-containing molecules

Electrocatalytic conversion of nitrogen-containing molecules into valuable chemicals is a promising strategy to alleviate anthropogenic imbalances in the global nitrogen cycle,but developing efficient electrocatalysts remains a formidable challenge.In recent years,the exploration of high-performance electrocatalysts has achieved significant progress by resorting to defect engineering strategy,which encouraged the researchers to understand the relationship between defects in catalysts and electrocatalytic performance.In this review,recent advances in defect engineering for advanced electrocatalytic conversion of nitrogen-containing molecules are systematically summarized,with special focus on electrocatalytic nitrogen oxidation and reduction,electrocatalytic nitric oxide oxidation and reduction,electrocatalytic nitrate reduction,and the construction of C–N bonds.Defects can effectively tune the electronic structure of catalysts,facilitate species diffusion,and provide more adsorption/active sites for reaction intermediates,thereby enhancing the electrocatalytic performance.Moreover,objective issues and future trends for optimizing electrocatalyst by defect engineering are proposed,which will contribute to the further development of advanced electrocatalytic conversion of nitrogen-containing molecules.

Visible light-induced synthesis of biomass-derived quinoxaline by using Co phthalocyanine immobilized on pyridine-doped g-C_(3)N_(4)

Visible light-driven valorization of biomass has recently been a pioneering field for nitrogen-containing heterocyclics syntheses due to its sustainable features.Herein,various aromatic ring-doped g-C_(3)N_(4) nanosheets(Ar-g-C_(3)N_(4);Ar=Py,Pm,Ph)were precisely designed to modulate their intrinsic electronic and band structure,which involves pyridine(Py),pyrimidine(Pm),and benzene(Ph)-doped g-C_(3)N_(4).Photocatalysts(CoPc/Ar-g-C_(3)N_(4)) of cobalt(II)phthalocyanine(CoPc)-fabricated Ar-g-C_(3)N_(4) were then developed for oxidative cyclization of furoin with 1,2-phenylenediamines for syntheses of various biomass-derived quinoxalines under visible-light irradiation.The catalytic activity(in terms of TOFs)of serial CoPc/Ar-g-C_(3)N_(4) samples increased with their transient photocurrents with CoPc/Py-g-C_(3)N_(4) as the most active one.For CoPc/Py-g-C_(3)N_(4),CoPc species functioned as both sensitizer and catalytic sites;while,doped Py led to a narrowed bandgap energy.Mechanism research further demonstrated that O_(2) was activated to superoxide radical(·O_(2)^(-)) by photoexcited high-level-energy electron(HLEE)transfer from Py-g-C_(3)N_(4) to CoPc for the subsequent aerobic oxidation.

铝硅聚苯酯封严涂层全尺寸刮磨实验

目的研究航空发动机气路密封配副中铝硅聚苯酯封严涂层的摩擦磨损性能。方法利用等离子喷涂技术制备铝硅聚苯酯封严涂层试样,采用特定台架刮磨实验装置,对低温封严涂层的可磨耗性能的失效机理进行研究,利用3D激光共聚焦显微镜和扫描电镜,分别观察了低硬度、中间硬度、高硬度的封严涂层在低、高刮磨转速条件下的刮痕表面形貌及表面粗糙度。结果低刮磨速度下,3种硬度涂层的刮痕截面轮廓深度分别为150、350、360μm,表面粗糙度依次为16.236、22.155、47.300μm;高速刮磨下,涂层的刮磨深度均明显增加,依次为280、570、570μm。结论不同硬度涂层展现出不同的刮磨机理,低硬度涂层(HR15Y 45)的刮磨机理主要是粘着磨损,中间硬度涂层(HR15Y 60)以微观切削为主,高硬度涂层(HR15Y75)展现出腐蚀磨损和磨粒磨损机理。相较硬度对涂层性能的影响,叶尖线速度对刮痕深度起主导作用,高刮磨速度时,刮痕深度明显增加。刮痕表面粗糙度和轮廓深度是衡量涂层性能好坏的重要指标。

锌基复合镀层中含氮聚合物的定量分析

采用微量基耶达法将有机氮以无机氮的形式从锌基复合镀层中分离出来，然后用滴定法对氨进行定量分析，进而计算出样品中含氮聚合物的含量，实验操作简便，测量精度高，相对标准偏差小于６％ 。

Performance and microbial community analysis of bioaugmented activated sludge for nitrogen-containing organic pollutants removal

Nitrogen-containing organic pollutants(quinoline,pyridine and indole)are widely distributed in coking wastewater,and bioaugmentation with specific microorganisms may enhance the removal of these recalcitrant pollutants.The bioaugmented system(group B)was constructed through inoculation of two aromatics-degrading bacteria,Comamonas sp.Z1(quinoline degrader)and Acinetobacter sp.JW(indole degrader),into the activated sludge for treatment of quinoline,indole and pyridine,and the non-bioaugmented activated sludge was used as the control(group C).Both groups maintained high efficiencies(>94%)for removal of nitrogen-containing organic pollutants and chemical oxygen demand(COD)during the long-term operation,and group B was highly effective at the starting period and the operation stage fed with raw wastewater.High-throughput sequencing analysis indicated that nitrogen-containing organic pollutants could shape the microbial community structure,and communities of bioaugmented group B were clearly separated from those of non-bioaugmented group C as observed in non-metric multidimensional scaling(NMDS)plot.Although the inoculants did not remain their dominance in group B,bioaugmentation could induce the formation of effective microbial community,and the indigenous microbes might play the key role in removal of nitrogen-containing organic pollutants,including Dokdonella,Comamonas and Pseudoxanthomonas.Phylogenetic Investigation of Communities by Reconstruction of Unobserved States(PICRUSt)analysis suggested that bioaugmentation could facilitate the enrichment of functional genes related to xenobiotics biodegradation and metabolism,probably leading to the improved performance in group B.This study indicated that bioaugmentation could promote the removal of nitrogen-containing organic pollutants,which should be an effective strategy for wastewater treatment.

The influence of the type of N dopping on the performance of bifunctional N-doped ordered mesoporous carbon electrocatalysts in oxygen reduction and evolution reaction

To develop more ideal bifunctional heteroatom-doped carbon electrocatalysts toward the oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) for regenerative fuel cells and rechargeable metal–air batteries, herein, tobacco-derived N-containing ordered mesoporous carbon(N-OMC) electrocatalysts with different N species distributions are designed. Results indicate that the as-prepared N-OMC with more pyrrolic and pyridinic Ns exhibits much higher activities for the ORR and OER than N-OMC with more graphitic N in both acidic and alkaline media, suggesting that the increase of pyrrolic and pyridinic Ns favors the improvement of ORR and OER activities of the N-containing carbon catalysts, and showing a great potential for the designing of more effective, lower-cost ORR and OER bifunctional electrocatalysts for future regenerative fuel cells and rechargeable metal–air batteries.

Purified oxygenand nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Oxygen and nitrogen-functionalized carbon nanotubes （OCNTs and NCNTs） were applied as metal-free catalysts in selective olefin hydro- genation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 ℃ led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.

Impregnated Sulfur in Carbonized Nitrogen-containing Porous Organic Frameworks as Cathode with High Rate Performance and Long Cycle Life for Lithium-sulfur Batteries

The undesirable cycling performance caused by soluble poly sulfides shuttling between anode and cathode has been considered as the main challenge that has hindered its practical applications for lithium-sulfiir(Li-S) batteries. To solve tliis issue effectively, a nitrogen-containing porous carbon, namely JUC-Z2-900,developed from a porous organic framework, namely JUC-Z2, bearing a high surface area(805 m^2/g),small pore size(0.5 mil) and nitrogen doping(2.15%, mass fraction), has been used as a host material for Li-S batteries. The micropores of JUC-Z2-900 can confine the smaller sulfur molecules S2-4, which can essentially alleviate the critical problem of poly sulfide dissolution.Furthermore, nitrogen-containing JUC-Z2-900 can promote chemical adsorption of sulfur. The above two factors can improve the electrochemical performance of Li-S batteries effectively. To compare the eftects of sulfur contents and melt-difiusion strategy in JUC-Z2-900/S composites, a series of JUC-Z2-900/S composites was synthesized and tlieir electrochemical perfbnnances were explored, indicating good rate performance and excellent cycling stability of the composites contributed by both appropriate mass percentage of sulfiir and its confinement in the micropores.

Extractive desulfurization of model fuels with a nitrogen-containing heterocyclic ionic liquid

A nitrogen-containing ionic liquid was synthesized using an aromatic nitrogen-containing heterocyclic and an amino acid,and applied to the extractive desulfurization process to remove benzothiophene,dibenzothiophene,and 4,6-dimethyldibenzothiphene from a model fuel oil.Chemical characterizations and simulation using Gaussian 09 software confirmed the rationality of an ionic liquid structure.Classification of non-covalent interactions between the ionic liquid and the three sulfur-containing contaminants was studied by reduced density gradient analysis.The viscosity of the ionic liquid was adjusted by addition of polyethylene glycol.Under extraction conditions of the volume of ionic liquid to oil as 1:1 and temperature as room temperature,the desulfurization selectivity of ionic liquid followed the order of 4,6-dimethyldibenzothiphene(15 min)<benzothiophene(15 min)≈dibenzothiophene(10 min).Addition of p-xylene and cyclohexene to the fuel oil had little effect.The extractant remained stable and effective after multiple regeneration cycles.

Catalytic conversion of biomass-derived compounds to various amino acids: status and perspectives

Amino acids are important nitrogen-containing chemicals that have a variety of applications.Currently,fermentation is the widely employed method to produce amino acids;however,the products are mostly limited to natural amino acids in the L-configuration.Catalytic synthesis is an alternative approach for the synthesis of amino acids with different types and configurations,where the use of renewable biomass-based feedstocks is highly attractive.To date,several lignocellulose and triacylglycerol-derived intermediates,typicallyα-keto acids andα-hydroxyl acids,have been transformed into amino acids via the amination reaction in the presence of additional nitrogen sources(i.e.,NH3·H2O).Making full use of inherent nitrogen in biomass(i.e.,chitin and protein)to produce amino acids avoids the use of extra nitrogen sources and meets the requirements of green chemistry,which is attracting increasing attention.In this review,we summarize different chemical-catalytic systems for the transformation of biomass to amino acids.An outlook on the challenges and opportunities for more effective production of amino acids from biomass by catalytic methods is provided.

Recent advances in visible-light photoredox-catalyzed nitrogen radical cyclization

Visible-light photoredox catalysis is a powerful and attractive strategy for organic molecule activation and new reaction design owing to its environmental-friendly characteristics and unique catalytic mechanisms,and has found wide applications in organic synthesis.This catalytic strategy enables controllable generation of diverse nitrogen-centered radicals(NCRs)under mild conditions,providing access to construction of diverse nitrogencontaining compounds.In this review,we critically illustrate the recent advances in the field of visible-light photoredox-catalyzed cyclization of nitrogen-centered radicals,based on the different radical precursors and activation modes.Wherever possible,particular emphasis is also put on working models and synthetic applications.

Chiral Recognition of Carboxylic Acids by Chiral Nitrogen Containing Calix[4]arene

Chiral nitrogen-containing calix[4]arene was easily synthesized by the reaction of 25,27-di（2-bromoethoxy）- 26,28-dihydroxy-5,11,17,23-tetrakis（t-butyl）calix[4]arene with S-（-）-1-phenylethylamine in excellent yield, and showed good ability to recognize the enantiomers of mandelic acid and 2,3-dibenzoyltartaric acid. This finding has potential application to assay and separation of enantiomers of the carboxylic acids.