Research status and prospects of the fractal analysis of metal material surfaces and interfaces

As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal materials at various scales and dimensions.Conventional methods make it difficult to quantitatively describe the relationship between the regular characteristics and properties of metal material surfaces and interfaces.However,fractal analysis can be used to quantitatively describe the shape characteristics of metal materials and to establish the quantitative relationships between the shape characteristics and various properties of metal materials.From the perspective of two-dimensional planes and three-dimensional curved surfaces,this paper reviews the current research status of the fractal analysis of metal precipitate interfaces,metal grain boundary interfaces,metal-deposited film surfaces,metal fracture surfaces,metal machined surfaces,and metal wear surfaces.The relationship between the fractal dimensions and properties of metal material surfaces and interfaces is summarized.Starting from three perspectives of fractal analysis,namely,research scope,image acquisition methods,and calculation methods,this paper identifies the direction of research on fractal analysis of metal material surfaces and interfaces that need to be developed.It is believed that revealing the deep influence mechanism between the fractal dimensions and properties of metal material surfaces and interfaces will be the key research direction of the fractal analysis of metal materials in the future.

Deep eutectic solvents for separation and purification applications in critical metal metallurgy:Recent advances and perspectives

Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.

Molecule‑Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.

Methanol Tolerant Non-noble Metal Co-C-N Catalyst for Oxygen Reduction Reaction Using Urea as Nitrogen Source

A non-noble metal oxygen reduction reaction （ORR） catalyst labeled as Co-C-N（800） was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmosphere. X-ray diffraction pattern indicates that a metallic β-Co is generated after the heat-treating process. The results from cyclic voltammograms show that the obtained Co-C-N（800） catalyst has good ORR catalytic activity in 0.5 mol/L H2SO4 solution. The catalyst is also good at methanol tolerance and stability in the acidic solution.

Nitrogen ligands in two-dimensional covalent organic frameworks for metal catalysis

We introduced bipyridine ligands into a series of two‐dimensional （2D） covalent organic frame‐works （COFs） using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde （2,2’‐BPyDCA） as a component in the mixed building blocks. The framework of the COFs was formed by the linkage of imine groups. The ligand content in the COFs was synthetically tuned by the content of 2,2’‐BPyDCA, and thus the amount of metal, palladium（II） acetate, bonded to the nitrogen ligands could be manipulated. Both the bipyri‐dine ligands and imine groups can coordinate with Pd（II） ions, but the loading position can be var‐ied, with one ligand favoring binding in the space between adjacent COFs’ layers and the other lig‐and favoring binding within the pores of the COFs. The Pd（II）‐loaded COFs exhibited good catalytic activity for the Heck reaction.

Fabrication and sintering behavior of high-nitrogen nickel-free stainless steels by metal injection molding

High-nitrogen nickel-free stainless steels were fabricated by the metal injection molding technique using high nitrogen alloying powders and a mixture of three polymers as binders.Mixtures of metal powders and binders with various proportions were also investigated, and an optimum powder loading capacity was determined as 64vol%.Intact injection molded compacts were successfully obtained by regulating the processing parameters.The debinding process for molded compacts was optimized with a combination of thermo-gravimetric analysis and differential scanning calorimetry analysis.An optimum relative density and nitrogen content of the specimens are obtained at 1360℃,which are 97.8%and 0.79wt%,respectively.

Transition metal-nitrogen sites for electrochemical carbon dioxide reduction reaction

Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.

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.

Effects of Different Nitrogen Sources and Metal Ions on Biogas Generation by Corn Stalk Fermentation

[Objective] The present study was conducted to explore the effects of dif- ferent nitrogen sources and metal ions on the biogas production process and biogas yield by fermentation of corn stalk powder using self-designed anaerobic fermenta- tion system. [Method] The biogas produced during fermentation was collected by water displacement, and measured by ignition. [Result] Ammonium bicarbonate, urea and yeast extract powder all increased biogas yield. Among them, ammonium bi- carbonate was the best nitrogen source. Ammonium dihydrogen phosphate showed an inhibitory effect on biogas production. Biogas yield was significantly increased by adding NaCl, KCl, MgCl2 or CaCl2, among which, NaCl had the best effect. [Conclu- sion] It is not conducive to the growth and development of methanogenic flora in the production of biogas using corn stalks as the only material in fermentation. The biogas yield can be increased by adding exogenous nitrogen, which reduces the carbon to nitrogen （C：N） ratio of fermentation materials. The biogas yield can be significantly increased by adding appropriate types and amount of electrolytes, with appropriate C：N ratio. The methanogenic flora is more tolerant to NaCl and KCl than to MgCl2 and CaCl2. Moreover, NaCl can not only significantly increase the biogas production, but also shorten startup period of methanogenic flora, thereby shortening the gas producing cycle.

Excessive Cu and Zn affecting on distribution of the metals and activities of glycolytic and nitrogen incorporating key enzymes in mycelia of ectomycorrhizal fungi Suillus bovinus

Concentration of copper and zinc in isolated Suillus bovinus mycelia, used nutrient solution and 0.5 mol/L EDTA mycelia washing solution were measured to investigate the distribution of heavy metals in mycelia growth in excess copper or zinc nutrient solution. Treated with zinc, most of added zinc maintained in used solution, and 9.8%/14.6% was in/on mycelia in treatment, and in treatment 2 was 3.9%/8.0% in/on mycelia. In the copper applications, copper stimulated in more than on mycelia, i.e., 25.9%/4.5% in/on mycelia in treatment, and 7%/18.8% in/on mycelia while most of copper retained in used nutrient solution. Certain amount of copper or zinc uptake by mycelia led to pronounced influence on glycolysis and nitrogen incorporating process of Suillus bovinus, while the tested enzymes kept constant in treatment. In crude extracts of copper treatment 2 mycelia, activities of HK, PFK and GS were inhibited and decrease to 63%, 48% and 38% and GIDH increased by 68% of the control, respectively. The behaviors of these tested enzymes toward zinc corresponded in general with that towards copper. The potential protection of Suillus bovinus for its host plant under excess copper or zinc threaten was discussed.

Simple synthesis of nitrogen‐doped carbon spheres as a highly efficient metal‐free electrocatalyst for the oxygen reduction reaction

In the present work, nitrogen‐doped carbon spheres were synthesized through a simple hydro‐thermal treatment using glucose and melamine as inexpensive carbon and nitrogen sources, re‐spectively. The ratio of melamine to glucose and annealing temperature were optimized. The final optimal sample exhibited a catalytic activity for the oxygen reduction reaction（ORR） that was supe‐rior than that of commercial 20%Pt/C in 0.1 mol/L KOH. It revealed an onset potential of –22.6 mV and a half‐wave potential of –133.6 mV （vs. Ag/AgCl）, which are 7.2 and 5.9 mV more positive than those of the 20%Pt/C catalyst, respectively, as well as a limiting current density of 4.6 mA/cm^2, which is 0.2 mA/cm^2 higher than that of the 20%Pt/C catalyst. The catalyst also exhibited higher stability and superior durability against methanol than 20%Pt/C. Moreover, ORRs on this catalyst proceed through a more effective 4 e^– path. The above mentioned superiority of the as‐prepared catalyst makes it promising for fuel cells.

Pyridinic nitrogen enriched porous carbon derived from bimetal organic frameworks for high capacity zinc ion hybrid capacitors with remarkable rate capability

Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.

Spatial and temporal distributions of nitrogen,phosphorus and heavy metals in the intertidal sediment of the Chang jiang River Estuary in China

Spatial and temporal distributions of nutrients （N and P） and heavy metals （Cu, Zn, Pb and Cd） in the intertidal sediments at Dongtan wetland of the Changjiang River （Yangtze River） Estuary were examined by laying one transect running seaward to landward during January, April, June, August and October of 2005. Total nitrogen （TN） and heavy metal concentrations in the intertidal sediment showed an increasing trend from open bare flat to the high marsh, with the maximum concentrations in the high marsh and the minimum values in open bare flat. In contrast, sediment total phosphorus （TP） concentrations changed little among sampling sites. One-way ANOVA found that there were significantly temporal variations of nutrients and heavy metals concentrations in the intertidal sediment （P 〈0.05）. The concentrations of heavy metals generally showed an increasing trend from January to October. As compared with other large estuaries, heavy metal contamination in the intertidal sediment of the Changjiang River Estuary was relatively low.

Effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite

This work evaluated the effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite at the temperature of 873-1173 K in a fluidized-bed/fixed-bed quartz reactor. The results indicated that the alkali metal Na and alkaline earth metals Ca, Mg in coal have different effects on inherent nitrogen transformation to NH3, HCN and char-N during the lignite steam gasification. Specifically during the steam gasification of Shengli lignite, Na and Ca, Mg not only catalyze the inherent nitrogen conversions to NH3, but also promote the secondary reactions of the nascent char-N as well as the generation of NH3 from the generated HCN, meanwhile they also inhibited the inherent nitrogen conversion to HCN and char-N. The presence of Na, Ca and Mg hindered the formation of oxidized nitrogen (N-X) functional groups, but enhanced pyridinic nitrogen (N-6) and quaternary nitrogen's (N-Q) formation in char.

Orthogonal tests of copper-clad aluminum bimetal continuous casting by nitrogen pressure core-illing

To provide theoretical basis and practical guidance for preparing composite rods by direct continuous casting, copper-clad aluminum composite rods of external copper layer diameter 12 mm and inner aluminum core diameter 8 mm were manufactured. Orthogonal tests consisted of three factors and three levels were carried out to research the effects of melting copper temperature, continuous casting speed and nitrogen pressure on the performance of composite rods. Results showed that nitrogen pressure is the most important factor in influencing the surface quality; continuous casting speed is the most important factor in influencing copper & aluminum inter diffusion amount. Nitrogen pressure can noticeably improve the surface quality and make the rods easily be drawn out, but the surface quality does not show visible improvement when the nitrogen pressure is above 0.05 MPa. Measured by tests, the compound layer can be divided into three types according to its cladding layer degree: deficient cladding, normal cladding and excess cladding. The diameter of normal copper-clad aluminum composite rods can be successfully drawn less than 0.6 mm without annealing.

Insights into electrochemical nitrogen reduction reaction mechanisms:Combined effect of single transition-metal and boron atom

Developing single-atom catalysts(SACs) for electrochemical devices is a frontier in energy conversion.The comparison of stability,activity and selectivity between various single atoms is one of the main research focuses in SACs.However,the in-depth understanding of the role that the coordination atoms of single atom play in the catalytic process is lacking.Herein,we proposed a graphene-like boroncarbon-nitride(BCN) monolayer as the support of single metal atom.The electrocatalytic nitrogen reduction reaction(eNRR) performances of 3 d,4 d transition metal(TM) atoms embedded in defective BCN were systematically investigated by means of density functional theory(DFT) computations.Our study shows that the TM-to-N and B-to-N π-back bonding can contribute to the activation of N_(2).Importantly,a combined effect is revealed between single TM atom and boron atom on eNRR:TM atom enhances the nitrogen reduction process especially in facilitating the N_(2) adsorption and the NH3 desorption,while boron atom modulates the bonding strength of key intermediates by balancing the charged species.Furthermore,Nb@BN3 possesses the highest electrocata lytic activity with limiting potential of-0.49 V,and exhibits a high selectivity for nitrogen reduction reaction(NRR) to ammonia compared with hydrogen evolution reaction(HER).As such,this work can stimulate a research doorway for designing multi-active sites of the anchored single atoms and the innate atoms of substrate based on the mechanistic insights to guide future eNRR research.

Protein-derived nitrogen and sulfur co-doped carbon for efficient adsorptive removal of heavy metals

A nitrogen and sulfur co-doped carbon has been synthesized employing egg white as a sustainable protein-rich precursor.According to CHNS elemental analysis,N,S and O heteroatoms accounted for mass fractions of 3.66%,2.28%and 19.29%respectively,and the types of surface functionalities were further characterized by FT-IR and XPS measurements.Although the carbon possessed a smaller surface area(815 m2·g-1)compared to a commercial activated carbon(1100 m2·g-1),its adsorption capacity towards Co2+reached 320.3 mg·g-1,which was over 8 times higher compared to the limited 34.0 mg·g-1 over the activate carbon.Furthermore,the carbon was found to be an efficient adsorbent towards a series of metal ions including VO2+,Cr3+,Ni2+,Cu2+and Cd2+.Combined with its environmental merits,the protein derived carbon may be a promising candidate for heavy metal pollution control.

Nitrogen-doped cobalt nanoparticles/nitrogen-doped plate-like ordered mesoporous carbons composites as noble-metal free electrocatalysts for oxygen reduction reaction

In this work, nitrogen-doped cobalt nanoparticlesinitrogen-doped plate-like ordered mesoporous carbons (N/Co/OMCs) were used as noble-metal free electrocatalysts with high catalytic efficiency. Compared with OMCs with long channel length, due to more entrances for catalytic target accessibility and a short pathway for rapid diffusion, the utilization efficiency of cobalt nanoparticles inside the plate-like OMCs with short pore length is well improved, which can take full advantage of porous structure in electrocatalysis and increase the utilization of catalysts. The active sites in N/Co/OMCs for oxygen reduction reaction (ORR) are highly exposed to oxygen molecule, which results in a high activity for ORR. By combination of the catalytic properties of nitrogen dopant, incorporation of Co nanoparticles, and structural properties of OMCs, the N/Co/plate-like OMCs are highly active noble-metal free catalysts for ORR in alkaline solution. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Effect of Combined Heavy Metal Pollution on Nitrogen Mineralization Potential,Urease and Phosphatase Activities in a Typic Udic Ferrisol

Individual and combined effects of Cu, Pb, Zn and Cd on N mineralization, urease and phosphatase were examined in a Typic Udic Ferrisol in laboratory by employing an uniform design and a single factor design.Soil pollution caused by heavy metals inhibited N mineralization (No value) and urease and phosphatase activities. The combined pollution of metals alleviated their toxicity to N mineralization to some extent,whereas aggravated the toxicity to urease and phosphatase. Phosphorous application could mitigate the toxic effect of heavy metals on phosphatase activities, while alleviating effect of N application on the toxicity of heavy metals to urease was inconsistent. However, the mitigating effect of the fertilizers was limited in heavily polluted soils.

Atmospheric Deposition and Critical Loads for Nitrogen and Metals in Arctic Alaska: Review and Current Status

To protect important resources under their bureau’s purview, the United States National Park Service’s (NPS) Arctic Network (ARCN) has developed a series of “vital signs” that are to be periodically monitored. One of these vital signs focuses on wet and dry deposition of atmospheric chemicals and further, the establishment of critical load (CL) values (thresholds for ecological effects based on cumulative depositional loadings) for nitrogen (N), sulfur, and metals. As part of the ARCN terrestrial monitoring programs, samples of the feather moss Hylocomium splendens are being collected and analyzed as a cost-effective means to monitor atmospheric pollutant deposition in this region. Ultimately, moss data combined with refined CL values might be used to help guide future regulation of atmospheric contaminant sources potentially impacting Arctic Alaska. But first, additional long-term studies are needed to determine patterns of contaminant deposition as measured by moss biomonitors and to quantify ecosystem responses at particular loadings/ ranges of contaminants within Arctic Alaska. Herein we briefly summarize 1) current regulatory guidance related to CL values 2) derivation of CL models for N and metals, 3) use of mosses as biomonitors of atmospheric deposition and loadings, 4) preliminary analysis of vulnerabilities and risks associated with CL estimates for N, 5) preliminary analysis of existing data for characterization of CL values for N for interior Alaska and 6) implications for managers and future research needs.