Preparation of nitrogen and sulfur co-doped ultrathin graphitic carbon via annealing bagasse lignin as potential electrocatalyst towards oxygen reduction reaction in alkaline and acid media

Renewable lignin used for synthesizing materials has been proven to be highly potential in specific electrochemistry.Here,we report a simple method to synthesize nitrogen and sulfur co-doped carbon nanosheets by using bagasse lignin,denoted as lignin-derived carbon(LC).By adjusting the ratio of nitrogen source and annealing temperature,we obtained the ultrathin graphitic lignin carbon(LC-4-1000)with abundant wrinkles with high surface area of 1208 m2g_1 and large pore volume of 1.40 cm3g_1.In alkaline medium,LC-4-1000 has more positive half-wave potential and nearly current density compared to commercial Pt/C for oxygen reduction reaction(ORR).More importantly,LC-4-1000 also exhibits comparable activity and superior stability for ORR in acid medium due to its high graphitic N ratio and a direct four electron pathway for ORR.This study develops a cost-effective and highly efficient method to prepare biocarbon catalyst for ORR in fuel cells.

Nitrogen and Sulfur Co-doped Porous Carbon Derived from ZIF-8 as Oxygen Reduction Reaction Catalyst for Microbial Fuel Cells

Nitrogen and sulfur co-doped porous nanocarbon (ZIF-C-N-S) catalyst was successfully synthesized derived from ZIF-8 and thiourea precursors.The electrochemical measurements indicate that the as-obtained ZIF-C-N-S catalyst exhibits higher electrocatalytic activity for oxygen reduction reaction (ORR) in alkaline electrolyte and superior durability-longer than commercial Pt/C catalyst.The enhancment of electrocatalytic activity mainly be come from the open pore structure,large specific surface area as well as the synergistic effect resulted from the co-doping of N and S atoms.In addition,the ZIF-C-N-S catalyst is also used as the air cathode catalyst in the microbial fuel cell (MFC) device.The maximum power density and stable output voltage of ZIF-C-N-S based MFC are 1315 mW/m2 and 0.48 V,respectively,which is better than that of Pt/C based MFC.

Controllable active sites and facile synthesis of cobalt nanoparticle embedded in nitrogen and sulfur co-doped carbon nanotubes as efficient bifunctional electrocatalysts for oxygen reduction and evolution reactions

Development of efficient and promising bifunctional electrocatalysts for oxygen reduction and evolutionreactions is desirable. Herein, cobalt nanoparticles embedded in nitrogen and sulfur co-doped carbonnanotubes(Co@NSCNT) were prepared by a facile pyrolytic treatment. The cobalt nanoparticles and co-doping of nitrogen and sulfur can improve the electron donor-acceptor characteristics of the carbon nan-otubes and provide more active sites for catalytic oxygen reduction and evolution reactions. The preparedCo@NSCNT, annealed at 900℃, showed excellent electrocatalytic performance and better durability thancommercial platinum catalysts. Additionally, Co@NSCNT-900 catalysts exhibited comparable onset poten-tials and Tafel slopes to ruthenium oxide. Overall, Co@NSCNT showed high activity and improved dura-bility for both oxygen evolution and reduction reactions.

Effective exposure of nitrogen heteroatoms in 3D porous graphene framework for oxygen reduction reaction and lithium–sulfur batteries

The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.

EFFECT OF OXYGEN CONTENT ON NITROGEN ABSORPTIVE MECHANISM IN WELD FOR FLUX-CORED WIRE

By measuring the content of oxygen and nitrogen in welds of six kinds of self-shielded flux-cored wires,the effect of oxygen on nitrogen content in weld is studied and the different absorptive mechanisms of nitrogen at a low oxygen level([O] lower than 0.02%) and a high oxygen level ([O] higher than 0.03%) have been discovered.The results indicate that the content of nitrogen in weld can be made lowest by modifying the composition of flux and controlling the content of oxygen to the range of 0.02%～0.03%.

Carbon,Nitrogen,and Sulfur Contents in Marine Phytoplankton Cells and Biomass Conversion

In this study,we isolated and cultured phytoplankton along the coast of China and measured the cellular carbon,nitrogen,and sulfur contents under four temperatures.The results showed that the contents of the cellular elements varied widely among different phytoplankton.We found that temperature is one of the important factors affecting the carbon,nitrogen,and sulfur contents in phytoplankton cells;however,the degree of influence of temperature is different for different kinds of phytoplankton.By measuring the nitrogen content in cells,we found that the C:N ratio indirectly measured in the experiment fluctuated in the range of 3.50-8.97,and the average C:N ratio was 5.52.In this experiment,we accurately measured the cell elemental contents at different temperatures and transformed the cell count results into carbon,nitrogen,and sulfur contents to express the biomass.This method ensures that the contribution of species that are small in number but with a large cell volume in biomass is considered.Moreover,this method comprehensively considers the interspecific differences of species and the uneven distribution of elements in phytoplankton cells,which is of significance in the estimation of marine carbon and nitrogen budget.The distribution of nitrogen content in marine phytoplankton can well indicate the marine eutrophication caused by human activities.Climate change can affect the community structure and element composition of marine phytoplankton,meanwhile marine carbon and nitrogen element can regulate the climate to a certain extent.

Atomically Dispersed Fe-N_4 Modified with Precisely Located S for Highly Efficient Oxygen Reduction

Immobilizing metal atoms by multiple nitrogen atoms has triggered exceptional catalytic activity toward many critical electrochemical reactions due to their merits of highly unsaturated coordination and strong metal-substrate interaction.Herein,atomically dispersed Fe-NC material with precise sulfur modification to Fe periphery(termed as Fe-NSC) was synthesized,X-ray absorption near edge structure analysis confirmed the central Fe atom being stabilized in a specific configuration of Fe(N3)(N-C-S).By enabling precisely localized S doping,the electronic structure of Fe-N4 moiety could be mediated,leading to the beneficial adjustment of absorption/desorption properties of reactant/intermediate on Fe center.Density functional theory simulation suggested that more negative charge density would be localized over Fe-N4 moiety after S doping,allowing weakened binding capability to *OH intermediates and faster charge transfer from Fe center to O species.Electrochemical measurements revealed that the Fe-NSC sample exhibited significantly enhanced oxygen reduction reaction performance compared to the S-free Fe-NC material(termed as Fe-NC),showing an excellent onset potential of 1.09 V and half-wave potential of 0.92 V in 0.1 M KOH.Our work may enlighten relevant studies regarding to accessing improvement on the catalytic performance of atomically dispersed M-NC materials by managing precisely tuned local environments of M-Nx moiety.

Hierarchically porous Fe/N/S/C nanospheres with high-content of Fe-Nx for enhanced ORR and Zn-air battery performance

Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.

Rhizosphere Aeration Improves Nitrogen Transformation in Soil, and Nitrogen Absorption and Accumulation in Rice Plants

Two rice cultivars(Xiushui 09 and Chunyou 84)were used to evaluate the effects of various soil oxygen(O2)conditions on soil nitrogen(N)transformation,absorption and accumulation in rice plants.The treatments were continuous flooding(CF),continuous flooding and aeration(CFA),and alternate wetting and drying(AWD).The results showed that the AWD and CFA treatments improved soil N transformation,rice growth,and N absorption and accumulation.Soil NO3–content,nitrification activity and ammonia-oxidising bacteria abundance,leaf area,nitrate reductase activity,and N absorption and accumulation in rice all increased in both cultivars.However,soil microbial biomass carbon and pH did not significantly change during the whole period of rice growth.Correlation analysis revealed a significant positive correlation between the nitrification activity and ammonia-oxidising bacteria abundance,and both of them significantly increased as the total N accumulation in rice increased.Our results indicated that improved soil O2 conditions led to changing soil N cycling and contributed to increases in N absorption and accumulation by rice in paddy fields.

N-doped graphitic carbon encapsulating cobalt nanoparticles derived from novel metal–organic frameworks for electrocatalytic oxygen evolution reaction

Nitrogen-doped carbon catalysts with hierarchical porous structure are promising oxygen evolution reaction(OER)catalysts due to the faster mass transfer and better charge carrying ability.Herein,an exquisite high nitrogen-containing ligand was designed and readily synthesized from the low-cost biomolecule adenine.Accordingly,three new MOFs(TJU-103,TJU-104 and TJU-105)were prepared using the Co(II)or Mn(II)ions as metal nodes.Through rationally controlling pyrolysis condition,in virtue of the high nitrogen content in well-defined periodic structure of the pristine MOFs,TJU-104–900 among the derived MOFs with hierarchical porous structure,i.e.,N-doped graphitic carbon encapsulating homogeneously distributed cobalt nanoparticles,could be conveniently obtained.Thanks to the synergistic effect of the hierarchical structure and well dispersed active components(i.e.,C=O,Co–Nx,graphitic C and N,pyridinic N),it could exhibit an overpotential of 280 mV@10mA/cm^(2)on carbon cloth for OER activity.This work provides the inspiration for fabrication of nitrogen-doped carbon/metal electrocatalysts from cost-effective and abundant biomolecules,which is promising for practical OER application.

SPA-H钢低氧出钢的生产技术实践

针对生产SPA-H钢冶炼中低氧控制出钢技术开展研究,分析了相关热力学理论及低氧出钢必要性,确定了SPA-H钢合理低氧范围应为(198~333)×10^(-6)。为实现低氧控制开展了技术改进,合理控制转炉终渣成分,合理排产,实行灵活的溅渣护炉措施;改进冶炼制度,采用“一批料”模式或留少量料模式,改进氧枪工作参数,降低平均枪位,优化枪位控制,保证低枪位拉碳时间,终点温度按照1680℃控制,碳按照0.06%~0.11%控制;采用碳—氧修正模型、转炉质谱仪等辅助手段。改进后,平均终点氧含量降低,氧含量80%控制在选定合理范围,磷、硫、碳及锰含量控制水平均有提升。

芡实对沿淮富营养化水体的净化效果研究

为了解乡土水生植物芡实对沿淮农村富营养化河流净化效果,在模拟沿淮农村地区富营养化河流的水池中种植芡实,定期监测水体中的总氮(TN)、氨氮(NH_(4)^(+)-N)、总磷(TP)、化学需氧量(COD_(Cr))、酸碱度(pH)、可溶性盐含量(EC)、溶解氧(DO)的数值变化,综合分析芡实对富营养化河流的净化效果。结果表明,芡实作为沿淮地区乡土水生植物,对富营养化的河流有着净化作用。芡实在生长过程中能吸收水体95.53%~98.45%的NH_(4)^(+)-N和99.50%~99.65%的TP,净化效果好。芡实对富营养河流中TN和COD_(Cr)的净化效果不明显,而且水体中的pH上升11.05%~11.61%,EC值增加21.12%~22%,DO增加3.82~21.77倍。芡实作为一种乡土水生植物,对沿淮地区富营养化河流具有显著的净化潜力。

Sulfur-encapsulated in heteroatom-doped hierarchical porous carbon derived from goat hair for high performance lithium–sulfur batteries

Biomass-derived carbon materials have aroused widespread concern as host material of sulfur to enhance electrochemical performances for lithium–sulfur batteries. Herein, goat hair, as a low-cost and eco-friendly precursor, is employed to fabricate cauliflower-like in-situ nitrogen, oxygen and phosphorus tri-doped porous biomass carbon(NOPC) by a facile activation with H_3PO_4 and carbonization process.The morphology and microstructure of NOPC can be readily tuned by altering pyrolysis temperature. The as-prepared NOPC matrix material carbonized at 600 °C possesses 3D hierarchical porous structure, high specific surface area(535.352 m^2 g^(-1)), and appropriate pore size and pore size distribution. Encapsulating sulfur into the NOPC depends on a stem-melting technology as cathode materials of Li–S batteries. Due to the synergistic effect of special physical structure and inherent tri-doping of N, O and P, electrons and ions transfer and utilization of active sulfur in the materials are improved, and the shuttle behaviors of soluble lithium polysulfides are also mitigated. Consequently, the S/NOPC-600 composite exhibits excellent electrochemical performance, giving a high initial discharge capacity of 1185 mA h g^(-1) at 0.05 C and maintaining a relatively considerable capacity of 489 m A h g^(-1) at 0.2 C after 300 cycles. Our work shows that a promising candidate for cathode material of Li–S batteries can be synthesized using low-cost and renewable biomass materials by a facile process.

Bimetallic metal-organic framework derived doped carbon nanostructures as high-performance electrocatalyst towards oxygen reactions

Rational design and development of cost-effective, highly active and durable bifunctional electrocatalysts towards oxygen redox reactions is of critical importance but great challenge for the broad implementation of next-generation metal-air batteries for electric transportation. Herein, a high-performance electrocatalyst of cobalt and zinc sulfides nanocrystals embedded within nitrogen and sulfur co-doped porous carbon is successfully designed and derived from bimetallic metal-organic frameworks of cobalt and zinc containing zeolitic imidazolate frameworks. The unique nanostructure contains abundant electrocatalytic active sites of sulfides nanocrystals and nitrogen and sulfur dopants which can be fast accessed through highly porous structure originate from both zinc vaporization and sulfurization processes. Such bifunctional electrocatalyst delivers a superior half-wave potential of 0.86 V towards oxygen reduction reaction and overpotential of 350 mV towards oxygen evolution reaction, as well as excellent durability owing to the highly stable carbon framework with a great graphitized portion. The performance boosting is mainly attributed to the unique nanostructure where bimetallic cobalt and zinc provide synergistic effect during both synthesis and catalysis processes. The design and realization pave a new way of development and understanding of bifunctional electrocatalyst towards clean electrochemical energy technologies.

高硅钢不同脱氧工艺下精炼渣系控制

针对“转炉→RH精炼→连铸”工艺流程生产的高硅钢精炼渣精准控制的难题,借助FactSage7.2商业热力学计算软件,计算了两种不同脱氧工艺下合理的精炼渣系控制范围。采用A脱氧工艺(铝脱氧硅合金化工艺)时,合理精炼渣系控制范围为氧化钙含量为53%~55%,二氧化硅含量在15%~18%,三氧化二铝含量为25%~30%,氧化镁含量为3%~5%,碱度为3~5;采用B脱氧工艺(硅脱氧铝合金化工艺)时,合理的精炼渣系的主要成分范围为:氧化钙含量为53%~56%,二氧化硅含量为12%~17%,三氧化二铝含量为25%~30%,氧化镁含量为3%~5%,碱度为3~4.5。采用工业两种对不同脱氧工艺精炼渣系吸附夹杂能力进行分析,结果表明B脱氧工艺下夹杂物数量、尺寸分布方面均优于A脱氧工艺。

河南省冬季PM_(2.5)水溶性离子及污染特征研究

为了解河南省多个城市间PM_(2.5)中水溶性离子组成及污染特征,研究选取2020年12月至2021年1月四个城市空气自动监测点位的PM_(2.5)水溶性离子进行监测和分析,并结合了水溶性离子浓度占比、NO_(3)^(-)与SO_(4)^(2-)比值、SOR和NOR转化率、主成分分析及后向轨迹分析等方法进行探究。结果表明,离子浓度整体上呈现NO_(3)^(-)>NH_(4)^(+)>SO_(4)^(2-)>Cl^(-)>F^(-)>K^(+)>Ca^(2+)>Na^(+)>Mg^(2+)的特征,二次离子(NO_(3)^(-)、NH_(4)^(+)和SO_(4)^(2-))是主要离子成分,累计占比为81.36%~88.10%;NO_(3)^(-)与SO_(4)^(2-)比值大于1,以移动源(机动车尾气)污染为主;SOR平均值为0.28~0.36,NOR平均值为0.22~0.63,硫氧率和氮氧率二次转化程度高,相对湿度与SOR和NOR值相关性较好;冬季河南省各点位主要受西北季风的控制。

氧氮燃烧测硫氯的影响因素分析

文章通过对危险废物中的高含硫精馏残渣进行热值测定,采用不同浓度、不同体积的吸收液对产生的酸性气体进行吸收,而后采用国标方法对其中的硫、氯含量进行检测,最终确定高含硫危险废物测定热值及硫、氯含量时的准确参数,从而指导高含硫危险废物的检测。这为危险废物后续的规范化处置提供准确的数据支持,降低危险废物在处置过程中原辅料的消耗量,同时减少酸性气体对回转窑的腐蚀,增加设备使用寿命,以达到提质增效的目的。

退火炉氮气用量大的原因与对策

退火炉开启旁冷系统后,炉内氧含量会上升至1.0%~1.5%,而退火工艺要求炉仓内氧含量稳定在0.2%以下,因此需要消耗大量氮气来降低氧含量。经过分析,对旁冷系统加装氮气进气管路,排气管路及相应阀门和传感器等。在旁冷系统开启前充入氮气,排出原有的空气,同时排除氮气流经途径上可能的泄漏。采取这些措施后,每台退火炉每年约降低氮气使用量9763.2 m^(3),同时提高了产品质量。

基于改进气相色谱法的大气中S、N含量监测

为了提高气相色谱法对大气中硫、氮含量的监测效果,此次研究通过优化色谱条件参数、进样技术以及检测器响应对气相色谱法进行改进。在对改进气相色谱法的对比实验中发现,研究提出的改进方法的检测准确度和精确度分别为99.3%和1.5%,均优于对比的气相色谱法。上述结果说明,此次研究提出的改进气相色谱法实现了大气中的硫、氮含量的高效准确检测,为大气环境污染控制提供了有力手段。

氯化氢中氧气含量分析方法浅析

介绍了2种氯化氢中氧气含量的分析方法:①通过预处理柱消耗氯化氢,然后由色谱柱分离出氧气后进行定量;②通过氮氧气和值来确定氧气含量是否超标。这2种方法均能解决氯化氢分析仪腐蚀的问题。