Swapping catalytic active sites from cationic Ni to anionic F in Fe–F–Ni3S2 enables more efficient alkaline oxygen evolution reaction and urea oxidation reaction

Electrolysis of water for producing hydrogen instead of traditional fossil fuels is one of the most promising methods to alleviate environmental pollution and energy crisis. In this work, Fe and F ion co-doped Ni₃S₂ nanoarrays grown on Ni foam substrate were prepared by typical hydrothermal and sulfuration processes for the first time. Density functional theory (DFT) calculation demonstrate that the adsorption energy of the material to water is greatly enhanced due to the doping of F and Fe, which is conducive to the formation of intermediate species and the improvement of electrochemical performance of the electrode. The adsorption energy of anions (F and S) and cations (Fe and Ni) to water in each material was also calculated, and the results showed that F ion showed the most optimal adsorption energy of water, which proved that the doping of F and Fe was beneficial to improve the electrochemical performance of the electrode. It is worth noting that the surface of Fe–F–Ni₃S₂ material will undergo reconstruction during the process of water oxidation reaction and urea oxidation reaction, and amorphous oxides or hydroxides in situ would be formed on the surface of electrode, which are the real active species.     

Porous Ni2P nanoflower supported on nickel foam as an efficient three-dimensional electrode for urea electro-oxidation in alkaline medium

Porous Ni₂P nanoflower supported on nickel foam (Ni₂P@Ni foam) electrodes are synthesized via a simple hydrothermal growth strategy accompanied with further phosphating treatment. The prepared electrodes are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). Electro-catalytic performances towards urea electro-oxidation are tested by cyclic voltammetry (CV), chronoamperometry (CA) coupled with electrochemical impedance spectroscopy (EIS). By phosphating Ni(OH)₂ precursor, the final obtained Ni₂P@Ni foam electrode presents a porous Ni₂P nanoflower structure within abundant porosity, and so exposes a large amount of electro-catalytic active sites and electronic transmission channels to accelerate the interfacial reaction. Compared with Ni(OH)₂@Ni foam precursor, the Ni₂P@Ni foam catalyst exhibits more excellent electro-catalytic activity as well as lower onset oxidation potential. Remarkably, the Ni₂P@Ni foam catalyst reaches a peak current density of 750 mA cm^?2 with an onset oxidation potential of 0.24 V (vs. Ag/AgCl) accompanied by an excellent stability in 0.60 M urea with 5.00 M KOH solutions. Benefiting from the unique porous nanosheet structure, the as-synthesized Ni₂P@Ni foam catalyst performs a highly enhanced catalytic behavior for alkaline urea electro-oxidation, indicating that the material can be hopefully applied in direct urea fuel cells.     

Simulation of Methanol and Urea Production from Catalytic Conversion of Steel Mill Gases

The time-dependent operation of methanol, ammonia, and urea production units embedded in a steel mill environment is analyzed with dynamic simulation models. From different process concepts and gas availability scenarios, a set of simulation cases is defined with blast furnace gas as carbon and coke oven gas as hydrogen source. Dynamic simulations indicate that significant CO₂ reductions require large amounts of additional H₂ from sustainable sources. From the results, global data such as carbon footprint or energy demands and details about process unit operation are obtained and processed.     

Electro-synthesis of tungsten carbide containing catalysts in molten salt for efficiently electrolytic hydrogen generation assisted by urea oxidation

Energy-efficient production of hydrogen through urea electrolysis is still challenging due to the lack of satisfactory catalysts for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) in urea containing solution. In this study, Ni–W_xC/C (x = 1,2) composite with high activity for urea electrocatalysis was prepared by direct electro-reduction of affordable feedstock of NiO–CaWO₄–C in molten CaCl₂–NaCl at 873–973 K. The addition of graphite in precursor decreases the particle size of Ni. Introducing W_xC into Ni particles can reduce the overpotential for UOR. As a result, the obtained Ni-W_xC/graphite composite exhibits high current density for urea oxidation, which is about 11-folds and 52-folds higher than that of Ni/graphite and Ni (@1.53 V vs. RHE), respectively. After changing the carbon source from graphite to CNTs, the anodic current density was further increased by 43%, reaching 50.31 mA cm^?2. Moreover, the cathodic catalyst W_xC/CNTs obtained by the same preparation process exhibits high performance towards HER, with a low onset potential of 131.5 mV and a Tafel slope of 69.5 mV dec^?1. Assembling an electrolyzer using Ni-W_xC/CNTs as anode and W_xC/CNTs as cathode can yield a current density of 10 mA cm^?2 at merely 1.65 V in 1 M KOH/0.33 M urea aqueous solution, with excellent long-term electrochemical durability. The environmental-friendly production process uses affordable feedstocks for the synthesis of efficient catalysts toward urea electrolysis, promising an energy-saving hydrogen production as well as waste treatment.     

Maximum Spreading of Urea Water Solution during Drop Impingement

Droplet impingement of urea water solution (UWS) is a common source for liquid film and solid deposits formed in the tailpipe of diesel engines. In order to better understand and predict wetting phenomena on the tailpipe wall, this study focuses on droplet spreading dynamics of urea water solution. Impingement of single droplets is investigated under defined conditions by high‐speed imaging using shadowgraphy technique. The experimental studies are complemented by numerical simulations with a phase‐field method. Computational results are in good agreement with experimental data for the advancing phase of spreading and the maximum and terminal spreading radius, whereas for the receding phase notable differences occur. For the maximum spreading radius, an empirical correlation derived for glycerol‐water‐ethanol mixtures is found to be valid for millimeter‐sized UWS droplets as well. A numerical simulation for a much smaller droplet however indicates that this correlation is not valid for the tiny droplets of UWS sprays in technical applications.     

A solar and wind driven energy system for hydrogen and urea production with CO2 capturing

A novel solar PV and wind energy based system is proposed in this study for capturing carbon dioxide as well as producing hydrogen, urea and power. Both Aspen Plus and EES software packages are employed for analyses and simulations. The present system is designed in a way that PEM electrolyzer is powered by the wind turbines for hydrogen production, which is further converted into ammonia and then synthesizes urea by capturing CO₂ and additional power is supplied to the community. The solar PV is employed to power the cryogenic air separation unit and the additional power is used for the industrial purpose. In the proposed system, ammonia does not only capture CO₂ but also synthesizes urea for fertilizer industry. The amount of electrical power produced by the system is 2.14 MW. The designed system produces 518.4 kmol/d of hydrogen and synthesizes 86.4 kmol/d of urea. Furthermore, several parametric studies are employed to investigate the system performance.     

Facile synthesis of Ni doped CoWO4 nanoarrays grown on nickel foam substrates for efficient urea oxidation

Urea electrolysis is a promising technology for hydrogen production, which can alleviate environmental pollution of urea-rich wastewater. It's worth noting that electrochemistry activity can be significantly improved by reasonably regulating the electron configuration around the active site for the doped materials. In this work, a series of well-tuned Ni doped CoWO₄ nanoarrays on Ni foam supports have been prepared through a typical hydrothermal approach for the first time. Moreover, the resulting Ni–CoWO₄-2 material significantly promotes urea oxidation performance with an applied potential of 1.35 V at 50 mA cm^?2, which is lower than that of water oxidation reaction (1.60 V). Density functional theory results suggest that the Ni doped CoWO₄ has larger urea adsorption energy compared with CoWO₄ and the CO(NH₂)₂ molecule is strongly adsorbed on surface of Ni doped CoWO₄, which is beneficial to accelerate the kinetics of the reaction and improve the electrocatalytic activity of the urea electrolysis.     

Design and analysis of a new solar hydrogen plant for power,methane, ammonia and urea generation

In this paper, a solar power-based combined plant for power, hydrogen, methane, ammonia and urea production is proposed. A parabolic trough collector is utilized for the system prime mover. Moreover, steam Rankine cycle, organic Rankine cycle, hydrogen production and compression subsystem, ammonia, methane and urea production units, single-effect absorption cooling unit, and freshwater production plant are integrated together to develop the present system for better system performance and cost-effectiveness and reduced environmental impact. In order to analyze and evaluate the proposed multigeneration plant, thermodynamic, parametric and economic studies are performed. According to the assessment results, it is found that energetic and exergetic efficiencies of the present multigeneration plant are 66.12% and 61.56%, respectively. The comparisons of the subsystem and overall plant efficiencies show that the highest energetic and energetic efficiencies belong to freshwater production plant by 79.24% and 75.62%, respectively. In addition, the present parametric analysis indicates that an increase in the reference temperature, solar radiation intensity and working pressure of the solar process has a positive effect on the plant's performance. The cost analysis reveals that as the solar radiation intensity and the working pressure of the solar process increase, the hydrogen generation cost decreases. Furthermore, the hydrogen generation cost is achieved to be 1.94 $/kgH₂ at 650 W/m² of the solar radiation intensity, with other parameters remaining constant.     

Ru-doped 3D porous Ni3N sphere as efficient Bi-functional electrocatalysts toward urea assisted water-splitting

Developing efficient, stable and ideal urea oxide (UOR) electrocatalyst is key to produce green hydrogen in an economical way. Herein, Ru doped three dimensional (3D) porous Ni₃N spheres, with tannic acid (TA) and urea as the carbon and nitrogen resources, is synthesized via hydrothermal and low-temperature treated process (Ru–Ni₃N@NC). The porous nanostructure of Ni₃N and the nickel foam provide abundant active sites and channel during catalytic process. Moreover, Ru doping and rich defects favor to boost the reaction kinetics by optimizing the adsorption/desorption or dissociation of intermediates and reactants. The above advantages enable Ru–Ni₃N@NC to have good bifunctional catalytic performance in alkaline media. Only 43 and 270 mV overpotentials are required for hydrogen evolution (HER) and oxygen evolution (OER) reactions to drive a current of 10 mA cm^?2. Moreover, it also showed good electrocatalytic performance in neutral and alkaline seawater electrolytes for HER with 134 mV to drive 10 mA cm^?2 and 83 mV to drive 100 mA cm^?2, respectively. Remarkably, the as-designed Ru–Ni₃N@NC also owns extraordinary catalytic activity and stability toward UOR. Moreover, using the synthesized Ru–Ni₃N@NC nanomaterial as the anode and cathode of urea assisted water decomposition, a small potential of 1.41 V was required to reach 10 mA cm^?2. It can also be powered by sustainable energy sources such as wind, solar and thermal energies. In order to make better use of the earth's abundant resources, this work provides a new way to develop multi-functional green electrocatalysts.     

二氧化碳脱氢系统管道腐蚀原因分析与对策

介绍尿素装置二氧化碳脱氢系统碳钢管道的腐蚀情况,分析腐蚀产生的原因,针对腐蚀原因合理设计管道、优化工艺指标、选用耐腐蚀材料等防护对策,取得了良好的效果.