Visible light induced photodegradation of organic pollutants on nitrogen and fluorine co-doped TiO_2 photocatalyst

The nitrogen and fluorine co doped TiO 2 polycrystalline powder was synthesized by calcinations of the hydrolysis product of tetra butyl titanate with ammonium fluoride. Nitrogen and fluorine co doping causes the absorption edge of TiO 2 to shift to a lower energy region. The photocatalytic activity of co doped TiO 2 with anatase phases was found to be 2 4 times higher than that of the commercial TiO 2 photocatalyst Degussa P25 for phenol decomposition under visible light irradiation. The co doped TiO 2 powders only contain anatase phases even at 1000℃. Apparently, ammonium fluoride added retarded phase transformation of the TiO 2 powders from anatase to rutile. The substitutional fluorine and interstitial nitrogen atoms in co doped TiO 2 polycrystalline powder were responsible for the vis light response and caused the absorption edge of TiO 2 to shift to a lower energy region.

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.

Nickel nanoparticles supported on nitrogen-doped carbon nanotubes are a highly active,selective and stable CO_(2) methanation catalyst

CO_(2) methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route.Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation,calcination and reduction and characterized by elemental analysis,X-ray powder diffraction,H_(2) temperature-programmed reduction,CO pulse chemisorption and transmission electron microscopy.The Ni/NCNT catalysts were highly active in CO_(2) methanation at atmospheric pressure,reaching over 50% CO_(2) conversion and over 95% CH_(4) selectivity at 340℃ and a GHSV of50,000 mL g^(-1) h^(-1) under kinetically controlled conditions.The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs.The optimum loading of 30 wt%-40 wt% Ni was found to result in the highest Ni surface area,the highest degree of conversion and the highest selectivity to methane.A constant TOF of 0.3 s^(-1) was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt%to 50 wt% Ni loading.Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream.

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.

Photocatalytic Destruction of Nitrogen Monoxide over La^(3+) and N Co-doped SrTiO_3 Powders under Visible Light Irradiation

Lanthanum and nitrogen co-doped SrTiO_3 was prepared by a mechanochemical reaction using SrTiO_3, urea and La_2O_3 as the raw materials. The samples were characterized by X-ray diffraction, X-ray photoelectron spectrometer, transmission electron microscopy, and nitrogen adsorption-desorption isotherm measurements. Lanthanum doping could increase the doping content of nitrogen in the sample. The sample prepared with 0.2 mol% La_2O_3, 22 mol% urea and 77.8 mol% SrTiO_3 by mechanochemical reaction, which has nearly the same nitrogen and lanthanum doping fractions, exhibited high photocatalytic activities. Under the irradiation of light with wavelength larger than 400, and 290 nm, the photocatalytic activity of nitrogen and lanthanum co-doped SrTiO_3 were 2.6 and 2 times greater than that of pure SrTiO_3.

Strain rate and cold rolling dependence of tensile strength and ductility in high nitrogen nickel-free austenitic stainless steel

The tensile strength and ductility of a high nitrogen nickel-free austenitic stainless steel with solution and cold rolling treatment were investigated by performing tensile tests at different strain rates and at room temperature. The tensile tests demonstrated that this steel exhibits a significant strain rate and cold rolling dependence of the tensile strength and ductility.With the increase of the strain rate from 10^-4s^-1to 1 s^-1, the yield strength and ultimate tensile strength increase and the uniform elongation and total elongation decrease. The analysis of the double logarithmic stress–strain curves showed that this steel exhibits a two-stage strain hardening behavior, which can be well examined and analyzed by using the Ludwigson equation. The strain hardening exponents at low and high strain regions（n2and n1） and the transition strain（εL） decrease with increasing strain rate and the increase of cold rolling RA. Based on the analysis results of the stress–strain curves, the transmission electron microscopy characterization of the microstructure and the scanning electron microscopy observation of the deformation surfaces, the significant strain rate and cold rolling dependence of the strength and ductility of this steel were discussed and connected with the variation in the work hardening and dislocation activity with strain rate and cold rolling.

Electrocatalytic water splitting at nitrogen-doped carbon layers-encapsulated nickel cobalt selenide

Generally,the catalytic overpotentials of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)are unavoidable because of the low charge transfer.In this work,two strategies of alloying of Co with Ni and enclosing of electrocatalysts with carbonaceous materials were both used to accelerate the catalytic efficiency of cobalt selenide for water splitting.The nitrogen-doped carbon(NC)layer improves the reaction kinetics by efficient charge transfer.The alloying of metal into composited electrocatalysts can modify the electronic properties of host materials,thereby tuning the adsorption behavior of intermediate and improving the electrocatalytic activity.As expected,Nyquist plots reveal that the charge-transfer resistance(Rct)of nickel cobalt selenide encapsulated into nitrogen-doped carbon layer(CoNiSe/NC-3,Co:Ni=1:1)are just 5 and 9 for HER and OER,respectively,which are much lower than those of CoSe/NC-1(Co:Ni=1:0)(81 and 138)and CoNiSe/NC-3 without NC(CoNiSe-3)(54 and 25).With the high charge transfer and porous structure,CoNiSe/NC-3 shows good performance for both HER and OER.When current density reaches 10 m A cm-2,only 100 and 270 mV overpotentials are required for HER and OER,respectively.With the potential of 1.65 V,full water splitting also can be catalyzed by Co Ni Se/NC-3 with current density of 20 m A cm-2,suggesting that CoNiSe/NC-3 could be used as replacement for noble metal electrocatalysts.

Dimerization of Propylene by Nickel (Ⅱ) and Cobalt (Ⅱ) Catalysts Based on Bidentate Nitrogen-phosphino Chelating Ligands

The catalytic property of propylene dimerization by several nickel (Ⅱ), cobalt (Ⅱ) complexes containing N-P bidentate ligands was studied in combination with organoaluminum co-catalysts. The effects of the type of aluminum co-catalysts and its relative amount, the nature of precursors in terms of ligand backbone and metal center were investigated. The results indicated that precursor I (N,N-dimethyl-2-(diphenylphosphino)aniline nickel (Ⅱ) dichloride) exhibited high activity in propylene dimerization in the presence of the strong Lewis acid Et3Al2Cl3, whereas low productivity by its cobalt analogues was observed under identical reaction conditions.

A universal multifunctional dual cation doping strategy towards stabilized ultra-high nickel cobalt-free lithium layered oxide cathode

Ultra-high nickel cobalt-free lithium layered oxides are promising cathode material for lithium-ion batteries(LIBs)because of their relatively high capacity and low cost.Nevertheless,the high nickel content would induce bulk structure degradation and interfacial environment deterioration,and the absence of Co element reduces the lithium diffusion kinetics,severely limiting the performance liberation of this kind of cathodes.Herein,a multifunctional Ti/Zr dual cation co-doping strategy has been employed to improve the lithium storage performance of LiNi_(0.9)Mn_(0.1)O_(2)(NM91)cathode.On the one hand,the Ti/Zr co-doping weakens the Li^(+)/Ni^(2+)mixing through magnetic interactions due to the inexistence of unpaired electrons for Ti^(4+)and Zr^(4+),increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases.On the other hand,they enhance the lattice oxygen stability because of the strong Ti-O and Zr-O bonds,inhibiting the undesired H3 phase transition and lattice oxygen loss,improving the bulk structure and cathode-electrolyte interface stability.As a result,the Ti/Zr co-doped NM91(NMTZ)exhibits a 91.2%capacity retention rate after 100 cycles,while that of NM91 is only82.9%.Also,the NMTZ displays better rate performance than NM91 with output capacities of 115 and93 mA h g^(-1)at a high current density of 5 C,respectively.Moreover,the designed NMTZ could enable the full battery to deliver an energy density up to 263 W h kg^(-1),making the ultra-high nickel cobaltfree lithium layered oxide cathode closer to practical applications.

Promotion of activation ability of N vacancies to N2 molecules on sulfur-doped graphitic carbon nitride with outstanding photocatalytic nitrogen fixation ability

Nitrogen vacancies and sulfur co-doped g-C3N4 with outstanding N2 photofixation ability was synthesized via dielectric barrier discharge plasma treatment. X-ray diffraction, ultraviolet–visible spectroscopy, N2 adsorption, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and temperature-programmed desorption were used to characterize the as-prepared catalyst. The results showed that plasma treatment cannot change the morphology of the as-prepared catalyst but introduces nitrogen vacancies and sulfur into g-C3N4 lattice simultaneously. The as-prepared co-doped g-C3N4 displays an ammonium ion production rate as high as 6.2 mg·L^-1·h^-1·gcat^-1, which is 2.3 and 25.8 times higher than that of individual N-vacancy-doped g-C3N4 and neat g-C3N4, respectively, as well as showing good catalytic stability. Experimental and density functional theory calculation results indicate that, compared with individual N vacancy doping, the introduction of sulfur can promote the activation ability of N vacancies to N2 molecules, leading to promoted N2 photofixation performance.

Nitrogen vacancies enriched Ce-doped Ni_(3)N hierarchical nanosheets triggering highly-efficient urea oxidation reaction in urea-assisted energy-saving electrolysis

Urea oxidation reaction (UOR),which has favorable thermodynamic energy barriers compared with oxygen evolution reaction (OER),can provide more cost-effective electrons for the renewable energy systems,but is trapped by its sluggish UOR kinetics and intricate reaction intermediates formation/desorption process.Herein,we report a novel and effective electrocatalyst consisting of carbon cloth supported nitrogen vacancies-enriched Ce-doped Ni_(3)N hierarchical nanosheets (Ce-Ni_(3)N @CC) to optimize the flat-footed UOR kinetics,especially the stiff rate-determine CO_(2)desorption step of UOR.Upon the introduction of valance state variable Ce,the resultant nitrogen vacancies enriched Ce-Ni_(3)N @CC exhibits an enhanced UOR performance where the operation voltage requires only 1.31 V to deliver the current density of 10 mA cm^(-2),which is superior to that of Ni_(3)N @CC catalyst (1.36 V) and other counterparts.Density functional theory (DFT) results demonstrate that the incorporation of Ce in Ni_(3)N lowers the formation energy of nitrogen vacancies,resulting in rich nitrogen vacancies in Ce-Ni_(3)N @CC.Moreover,the nitrogen vacancies together with Ce doping optimize the local charge distribution around Ni sites,and balance the adsorption energy of CO_(2)in the rate-determining step (RDS),as well as affect the initial adsorption structure of urea,leading to the superior UOR catalytic performance of Ce-Ni_(3)N @CC.When integrating the Ce-Ni_(3)N catalyst in UOR//HER and UOR//CO_(2)R flow electrolyzer,both of them perform well with low operation voltage and robust long-term stability,proofing that the thermodynamically favorable UOR can act as a suitable substitute anodic reaction compared with that of OER.Our findings here not only provide a novel UOR catalyst but also offer a promising design strategy for the future development of energy-related devices.

Nickel-free Stainless Steel for Medical Applications

BIOSS4 steel is essentially a nickel-free austenitic stainless steel developed by the Institute of Metal Research, Chinese Academy of Sciences, in response to nickel allergy problems associated with nickel-containing stainless steels that are widely used in medical applications. The high nitrogen content of this steel effectively maintains the austenitic stability and also contributes to the high levels of corrosion resistance and strength. BIOSS4 steel possesses a good combination of high strength and toughness, better corrosion resistance, and better blood compatibility, in comparison with the medical 316L stainless steel. Potential applications of BIOSS4 steel can include medical implantation material and orthodontic or orthopedic devices, as well as jewelries and other decorations.

Synthesis and Crystal Structure of Bis(S-methyl-β-N- (4-dimethylaminophenyl)methlenedithiocarbazate) Nickel (Ⅱ)

Reaction of nickel (Ⅱ) acetate with S-methyl-β-N-(4 dimethy-laminophenyl) methlenedithiocarbazate gave a mononuclear complex [Ni (C11H14N3S2)2]. Crystal of the title compound belongs to monoclinic systern,space group C2/cwith cell parameters a= 18. 785 (1), b= 17. 274 (1 ), c= 8. 344 (1 ) A, β= 108. 64(2)°, V= 2565(1 ) A3, Z=4, Mr= 563. 36, Dc= 1. 459 g/cm3; μ=10. 05 cm-1 andF(000) = 1176. The final refinement with 2179 observed reflections is converged withR= 0. 044 and R.= 0. 069. X-ray crystal structure analysis revealed that the coordina-tion geometry of Ni (Ⅱ) is a square-planar with two equivalent Ni -N and Ni - Sbonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is coor-dinated to the nickel atom via the mercapto sulphur and the β-nitiogen.

Effects of oxygen/nitrogen co-incorporation on regulation of growth and properties of boron-doped diamond films

Regulation with nitrogen and oxygen co-doping on growth and properties of boron doped diamond films is studied by using laughing gas as dopant. As the concentration of laughing gas(N2O/C) increases from 0 to 10%, the growth rate of diamond film decreases gradually, and the nitrogen-vacancy(NV) center luminescence intensity increases first and then weakens. The results show that oxygen in laughing gas has a strong inhibitory effect on formation of NV centers, and the inhibitory effect would be stronger as the concentration of laughing gas increases. As a result, the film growth rate and nitrogen-related compensation donor decrease, beneficial to increase the acceptor concentration(~3.2×10^(19)cm^(-3)) in the film. Moreover, it is found that the optimal regulation with the quality and electrical properties of boron doped diamond films could be realized by adding appropriate laughing gas, especially the hole mobility(~700cm^(2)/V·s), which is beneficial to the realization of high-quality boron doped diamond films and high-level optoelectronic device applications in the future.

次氯酸钠氧化法处理含镍电镀废水的应用研究

[目的]次氯酸钠具有强氧化性,被广泛应用于电镀、印染、石油化工等领域的废水处理。[方法]采用次氯酸钠氧化法处理电镀废水,通过静态试验探究次氯酸钠的投加量、反应时间、初始pH等因素对电镀废水中总镍、氨氮、总磷等污染物处理效果的影响。对比了在较优条件下分别采用机械搅拌和曝气搅拌时废水的处理效果。[结果]较佳的工艺条件为:10%(质量分数)次氯酸钠溶液投加量100 mL/L,初始pH为6.0,反应时间90 min。在该条件下,废水中总镍、总磷和氨氮的去除率分别达到99.97%、99.94%和99.41%,其出水浓度均满足《电镀污染物排放标准》(GB 21900–2008)中“表3”的要求。电镀废水处理过程采用机械搅拌和曝气搅拌均可,但采用机械搅拌的处理效果更佳。[结论]采用次氯酸钠氧化法可有效去除含镍电镀废水中镍、磷和氨氮,使废水达标排放。

Convenient room-temperature synthesis of sulfur and nitrogen co-doped NiCo-LDH coupled with CNTs on NiCo foam as battery-type electrode for high performance hybrid supercapacitor

The convenient synthesis of the composite electrode with high supercapacitance performance plays an important role in practical application but is challenging.Herein,the carbon nanotubes(CNTs)coupled with lowcrystalline sulfur and nitrogen co-doped Ni Co-LDH(denoted as SN-Ni Co-LDH)nanosheets array are grown on Ni Co foam(NCF)substrate by two convenient steps of metal induced self-assembly and corrosion engineering,which present the advantages of operating at roomtemperature and low preparation costs.Benefiting from the S–N co-doping and low-crystallinity of Ni Co-LDH,the prepared SN-Ni Co-LDH@CNTs@NCF electrode presents a topping charge capacity of 2470 C·g^(-1)(4.94 C·cm^(-2))at 5 m A·cm^(-2).Furthermore,the fabricated asymmetry supercapacitor(ASC)achieves an extraordinary energy density of 77 Wh·kg^(-1)(0.617 m Wh·cm^(-2))at a power density of 438 W·kg^(-1)(3.5 m W·cm^(-2))and outstanding stability(91%capacity retention after 5000 cycles at20 m A·cm^(-2)).Impressively,the structure evolution of Ni Co-LDH during the charge/discharge processes has been thoroughly elucidated by in-situ Raman spectra.Therefore,this work verifies a powerful strategy and practical value for preparing composite electrodes with high supercapacitance performance,and also provides guidance for the rational design of the smart electrodes.

Sulfur–nitrogen co-doped graphene supported cobalt–nickel sulfide rGO@SN-CoNi_(2)S_(4) as highly efficient bifunctional catalysts for hydrogen/oxygen evolution reactions

Designing highly active and stable electrocata-lysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is a challenge for energy con-version and storage technology.In this work,a S and N co-doped graphene supported cobalt–nickel sulfide composite catalyst(rGO@SN-CoNi_(2)S_(4))was synthesized simply via a one-step hydrothermal method.The as-synthesized CoNi_(2)S_(4)particles grew in a mosaic manner inside GO lamellae and were encapsulated with graphene.As a bifunctional catalyst,the r GO@SN-CoNi_(2)S_(4)exhibits excellent electrocatalytic performance under alkaline con-ditions,which only required the overpotential of 142.6 mV(vs.RHE)and 310 m V(vs.RHE)to deliver a current density of 10 mA·cm^(-2) for HER and OER,respectively.The good hydrophilicity of the r GO@SN,the pure phase of bimetallic structure,and the chemical coupling/interaction between the CoNi_(2)S_(4)and the rGO@SN are attributable to be the possible reasons responsible for the higher HER and OER catalytic activities.Additionally,the rGO@SN-CoNi_(2)S_(4)also shows a great potential for serving as an excellent cathode and anode electrolyzer during the water splitting process.

Enhanced photocatalytic hydrogen production from Co-MOF/CN by nitrogen and sulfur co-doped coal-based carbon quantum dots

A novel composite photocatalyst for photocatalytic decomposition of water for hydrogen evolution was successfully synthesized by in-situ growth of nitrogen and sulfur co-doped coal-based carbon quantum dots(NSCQDs)nanoparticles on the surface of sheet cobalt-based metal-organic framework(Co-MOF)and graphitic carbon nitride(g-C_(3)N_(4),CN).The structure and properties of the obtained catalysts were systematically analyzed.NSCQDs effectively broaden the absorption of Co-MOF and CN in the visible region.The new composite photocatalyst has high hydrogen production activity and the hydrogen production rate reaches 6254μmol/(g·h)at pH=9.At the same time,NSCQDs synergy Co-MOF/CN composites have good stability.After four cycles of hydrogen production,the performance remains relatively stable.The tran sient photocurrent response and Nyquist plot experimental results further demonstrate the improvement of carrier separation efficiency in composite catalysts.The semiconductor type(n-type semico nductor)of the single-phase catalyst was determined by the Mott-Schottky test,and the band structure was analyzed.The conductive and valence bands of CN are-0.99 and 1.72 eV,respectively,and the conduction and valence bands of Co-MOF are-1.85 and 1.33 eV,respectively.Th e mechanism of the photocatalytic reaction can be inferred,that is,Z-type heterojunction is formed between CN an d Co-MOF,and NSCQDs was used as cocatalyst.

焦炉尾气镍基催化剂脱硝性能研究

制备活性炭负载金属Ni催化剂催化还原焦炉尾气中NO,探究制备条件对催化剂活性的影响。结果表明,金属Ni催化剂具有较强还原NO的能力,3Ni/CAC-600催化剂在325℃时,NO转化率可达100%。随着金属负载量的增加,催化剂分散性逐渐降低,催化还原NO活性增强;随着煅烧温度的升高,催化剂分散性及还原NO活性逐渐降低。反应过程中,金属Ni被氧化,导致催化剂失活。