不同盐沼湿地类型脱氮除磷效能及影响因素分析

采用沉水植物表面流湿地(沉水组)、挺水植物表面流湿地(挺水组)和浮床湿地(浮床组)3种盐沼湿地对长江口近岸低污染水体进行脱氮除磷效能的研究。结果表明,HRT为3 d时,水组、挺水组、浮床组对NO3^--N的去除率在高温时段分别为79.9%±13.2%、71.8%±15.2%、77.2%±13.2%,中温时段分别为39.4%±13.7%、31.5%±8.5%、18.4%±16.6%,低温时段分别为15.6%±14.6%、19.7%±8.6%、2.%5±8.6%。沉水组和挺水组对TP的去除率受温度影响较小,分别为66.4%±32.4%、55.5%±29.4%;而浮床组除磷效果受温度影响较大。当HRT缩短为1.5 d时,3组湿地系统在高温时段仍可达到相近的脱氮除磷效果,在中低温时段脱氮除磷效果都有不同程度的下降。     

变压吸附制氮(PSA)设备在炼油生产中的应用

针对某炼油装置氮气供需矛盾突出的问题,提出采用变压吸附(PSA)制氮设备,利用空压站净化风生产氮气方案,(1)降低空压站多余风量放空,减少浪费;(2)正常生产情况下,利用PSA设备生产氮气,对供氮管网压力调节。针对上述方案,结合空压站供风现状进行分析,得出结论:利用PSA制氮设备满足炼油装置高峰用氮是可行的,并提出了具体措施和运行过程中应注意的问题。     

Iron-based sulfur and nitrogen dual doped porous carbon as durable electrocatalysts for oxygen reduction reaction

The widespread use of fuel cell technology is hampered by the use of expensive and scarce platinum metal in electrodes which is required to facilitate the sluggish oxygen reduction reaction (ORR). In this work, a viable synthetic approach was developed to prepare iron-based sulfur and nitrogen dual doped porous carbon (Fe@SNDC) for use in ORR. Benzimidazole, a commercially available monomer, was used as a precursor for N doped carbon and calcined with potassium thiocyanate at different temperatures to tune the pore size, nitrogen content and different types of nitrogen functionality such as pyridinic, pyrrolic and graphitic. The Fe@SNDC–950 with high surface area, optimum N content of about 5 at% and high amount of pyridinic and graphitic N displayed an onset potential and half-wave potential of 0.98 and 0.83 V vs RHE, respectively, in 0.1 M KOH solution. The catalyst also exhibits similar oxygen reduction reaction performance compared to Pt/C (20 wt%) in acidic media. Furthermore, when compared to commercially available Pt/C (20 wt%), Fe@SNDC–950 showed enhanced durability over 6 h and poison tolerance in case of methanol crossover with the concentration up to 3.0 M in oxygen saturated alkaline electrolyte. Our study demonstrates that the presence of N and S along with Fe-N moieties synergistically served as ORR active sites while the high surface area with accessible pores allowed for efficient mass transfer and interaction of oxygen molecules to the active sites contributing to the ORR activity of the catalyst.     

Preparation of faceted TaN grains by heating Ta-containing oxides in BN crucible with Na

Single-crystal grains of TaN were synthesized by heating Ta₂O₅, FeTa₂O₆, or FeTaO₄ in a BN crucible together with Na metal in an Ar atmosphere at 1100 °C. The BN crucible acted a solid source of nitrogen. Aggregates of columnar ε-TaN single crystals 10–150 μm in size were formed on the inner wall of the BN crucible when either Ta₂O₅ or FeTa₂O₆ was used. On the other hand, platelet-like single crystals of θ-TaN 1–50 μm in size were obtained from FeTaO₄. The results of wavelength-dispersive X-ray spectrometry indicated that the compositions of the ε-TaN and θ-TaN crystals were close to the stoichiometric ideal.     

Fe(III) grafted MoO3 nanorods for effective electrocatalytic fixation of atmospheric N2 to NH3

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO₃ nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H⁺ during the NRR process in neutral electrolyte. In 0.1 M Na₂SO₄ solution, the electrocatalyst exhibited a remarkable NRR activity with an NH₃ yield of 9.66 μg h^?1 mg^?1_cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO₃. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.     

Oxidation State Modulation of Bismuth for Efficient Electrocatalytic Nitrogen Reduction to Ammonia

Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH₃) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi⁰/Bi³⁺ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900  ° C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH₃ yield rate and remarkable Faradaic efficiency of 15.10  ± 0.43% at − 0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p-filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential-determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis.     

Zinc doped Fe2O3 for boosting Electrocatalytic Nitrogen Fixation to ammonia under mild conditions

Artificial nitrogen fixation is emerging as a promising approach for synthesis of ammonia at mild conditions. Inspired by biological nitrogen fixation based on bacteria containing iron, zinc doped Fe₂O₃ nanoparticles are proposed as an efficient and earth abundant electrocatalyst for converting N₂ to NH₃. In neutral media, it achieves a maximum Faradaic efficiency (FE) of 10.4% and a large NH₃ yield rate of 15.1 μg h^?1 mg^?1_cat. at ?0.5 V vs. reversible hydrogen electrode. This catalyst also exhibits excellent selectivity and stability. Theoretical calculations suggest the reaction follows the associative enzymatic mechanism and it has a barrier of as low as 0.68 eV.     

Hydrogen carriers: Production,transmission, decomposition,and storage

Recognizing the potential role of liquid hydrogen carriers in overcoming the inherent limitations in transporting and storing gaseous and liquid hydrogen, a complete production and use scenario is postulated and analyzed for perspective one-way and two-way carriers. The carriers, methanol, ammonia and toluene/MCH (methylcyclohexane), are produced at commercially viable scales in a central location, transmitted by rail or pipelines for 2000 miles, and decomposed near city gates to generate fuel-cell quality hydrogen for distribution to refueling stations. In terms of the levelized cost of H₂ distributed to the stations, methanol is less expensive to produce ($1.22/kg-H₂) than MCH ($1.35/kg-H₂) or ammonia ($2.20/kg-H₂). Levelized train transmission cost is smaller for methanol ($0.63/kg-H₂) than ammonia ($1.29/kg-H₂) or toluene/MCH system ($2.07/kg-H₂). Levelized decomposition cost is smaller for ammonia ($0.30–1.06/kg-H₂) than MCH ($0.54–1.22/kg-H₂) or methanol ($0.43–1.12/kg-H₂). Over the complete range of demand investigated, 10–350 tpd-H₂, the levelized cost of H₂ distributed to stations is aligned as methanol « ammonia ~ MCH. With pipelines at much larger scale, 6000 tpd-H₂, the levelized cost decreases by ~1 $/kg-H₂ for ammonia and MCH and much less for methanol. Methanol is a particularly attractive low-risk carrier in the transition phase with lower than 50-tpd H₂ demand.     

Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.