Folic Acid Self-Assembly Enabling Manganese Single-Atom Electrocatalyst for Selective Nitrogen Reduction to Ammonia

Efficient and robust single-atom catalysts(SACs)based on cheap and earth-abundant elements are highly desirable for electrochemical reduction of nitrogen to ammonia(NRR)under ambient conditions.Herein,for the first time,a Mn-N-C SAC consisting of isolated manganese atomic sites on ultrathin carbon nanosheets is developed via a template-free folic acid self-assembly strategy.The spontaneous molecular partial dissociation enables a facile fabrication process without being plagued by metal atom aggregation.Thanks to well-exposed atomic Mn active sites anchored on two-dimensional conductive carbon matrix,the catalyst exhibits excellent activity for NRR with high activity and selectivity,achieving a high Faradaic efficiency of 32.02%for ammonia synthesis at−0.45 V versus reversible hydrogen electrode.Density functional theory calculations unveil the crucial role of atomic Mn sites in promoting N_(2) adsorption,activation and selective reduction to NH_(3) by the distal mechanism.This work provides a simple synthesis process for Mn-N-C SAC and a good platform for understanding the structure-activity relationship of atomic Mn sites.

Supported Manganese Oxide on Graphite Oxide: Catalytic Oxidation of Nitrogen Oxide in Waste Gas

The catalytic oxidation of nitrogen oxide( NO) from waste gas was investigated using advanced oxidation process based on sulfate radicals. The manganese oxide immobilized on graphene oxide( GO) can activate peroxymonosulfate( PMS) for the oxidation of NO in waste gas. The Mn3O4 / GO catalyst system was characterized via X-ray diffraction( XRD), Fourier transform infrared spectrocopy( FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy( XPS), energy dispersive X-ray spectroscopy( EDS),and scanning electron microscope( SEM).The results showed that Mn3O4 was distributed on GO. The Mn3O4 /GO catalyst system exhibited efficient activity for NO oxidation when the Mn3O4 /GO catalyst had an optimum Mn3O4 loading. In addition,the best catalytic oxidation could be achieved within 60 min with 0. 25 mmol /L Mn3 O4 /GO catalyst, and2 mmol /L PMS dosage at 25 ℃. The catalysts also exhibited stable performance after several rounds of regeneration. Therefore,the results may have significant technical implication for utilizing Mn3O4 /PMS to oxidize NO for offgas treatment.

Role of Amorphous Manganese Oxide in Nitrogen Loss

Studies have been made, by 15N-tracer technique on nitrogen loss resulting from adding amorphous manganese oxide to NH4+-N medium under anaerobic conditions. The fact that the total nitrogen recovery was decreased and that 15NO2, 15N2O, 15N14NO, 15NO, 15N2and 15N14N were emitted has proved that, like amorphous iron oxide, amorphous manganese oxide can also act as an electron acceptor in the oxidation of NH4+-N under anaerobic conditions and give rise to nitrogen loss. This once again illustrates another mechanism by which the loss of ammonium nitrogen in paddy soils is brought about by amorphous iron and manganese oxides. The quantity of nitrogen loss by amorphous manganese oxide increased with an increase in the amount of amorphous manganese oxide added and lessened with time of its aging. The nitrogen loss resulting from amorphous manganese oxide was less than that from amorphous iron oxide. And the nitrogen loss by cooperation of amorphous manganese oxide and microorganisms (soil suspension ) was larger than that by amorphous manganese oxide alone. In the system, nitrogen loss was associated with the specific surface area and oxidation-reduction of amorphous manganese oxide. However, their quantitative relationship and the exact reaction processes of nitrogen loss induced by amorphous manganese oxide remain to be further studied.

Selective catalytic oxidation of NO over iron and manganese oxides supported on mesoporous silica

The selective catalytic oxidation （SCO） of NO was studied on a catalyst consisting of iron-manganese oxide supported on mesoporous silica （MPS） with different Mn/Fe ratios. Effects of the amount of manganese and iron, oxygen, and calcination temperature on NO conversion were also investigated. It was found that the Mn-Fe/MPS catalyst with a Mn/Fe molar ratio of 1 showed the highest activity at the calcination temperature of 400 °C. The results showed that over this catalyst, NO conversion reached 70% under the condition of 280 °C and a space velocity of 5000 h-1. SO2 and H2O had no adverse impact on the reaction activity when the SCO reaction temperature was above 240 °C. In addition, the SCO activity was suppressed gradually in the presence of SO2 and H2O below 240 °C, and such an effect was reversible after heating treatment.

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.

Composition and recovery method for electrolytic manganese residue

According to the statistic analysis,the reserve of manganese in electrolytic manganese residue deposit is over 780 kt. The average contents of available manganese and ammonium reach 3.90% and 1.68% (mass fraction),respectively. Large amount of manganese compounds and ammonium sulfate are detruded without any treatment or recovery. The compositions of the main elements in electrolytic manganese residue were analyzed comprehensively based on the extensive research data. According to the new development of electrolytic manganese residue comprehensively used in recent years,a water washing residue-twice precipitation process was also proposed. The experimental results indicate that manganese dioxide silicon dioxide and calcium sulfate are presented as amorphous state in the manganese residues. The recovery rates of manganese and nitrogen reach up to 99.5% and 94.5 %,respectively. The recovery process can be easily implemented,environment-friendly and fitting for industrial production.

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.

Roles of Ceria on Copper and Manganese Oxides Catalyst——Adsorption of NO and CO

A microreactor system and TPD techniques were used to study the reaction kinetics of the CO+ NO reaction and the adsorption of CO,NO,CO_2 and N_2O over Cu-Mn-O(Ⅰ)and Cu-Mn-Ce-O(Ⅱ) catalysts.The results show that the catalytic activity of(Ⅱ)is higher than that of(Ⅰ)for the CO+NO reac- tion,and the higher the conversion of NO,the larger was the activity difference between(Ⅰ)and(Ⅱ).For (Ⅰ)the rate of NO elimination is dependent on the partial pressures of NO,CO,CO_2 with the kinetics or- ders of 0.48,0.56,0.08,respectively.The TPD study shows that the presence of Ce in(Ⅱ)may promote the adsorption of NO,CO on the surface,i.e.an increase of the coverage θ_(NO),θ_(CO),which result in a decrease of the hindrance of the reaction products.For CO_2 and N_2O the situation is in the opposite,the presence of Ce makes the θ_(CO)_2)and θ_(NO)on(Ⅱ)decrease,which weakens the inhibition of CO_2 for the reaction.

Control of the Electronic Structure of Manganese Nitrido Complexes by Para Ring Substituents：a Theoretical Study

The relationship between the electronic structures of manganese nitrido complexes and the substituted ligands is investigated by using density functional theory.By designing a series of manganese nitrido complexes [Mn（SalenR）N]＋ with different para ring substituents（R = H,CH_3,NH_2,OCH_3,NMeF,etc） of the ancillary ligand,the properties of manganese-nitrogen bonds were compared for two kinds of electronic structures,of which the radical resides on metal center or the coordinated ring ligand.Our calculation shows that for R = H,CH_3 and NH_2,the [Mn（SalenR）N]＋ complexes have a high-valent Mn（VI） center,and for R = OCH_3 and NMeF,the complexes represent a configuration where the radical delocalizes on the ligand.It is found that the relative energies of these two species depend on electronic properties of the substituent,originating from the intrinsic property of HOMO-LUMO gaps.

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.

Evaluation of metal-doped manganese oxide octahedral molecular sieves in catalytic reduction of NO_x from cigarette mainstream smoke

A series of Ag,Cu and Co-doped manganese oxide octahedral molecular sieves(OMS-2) were synthesized and evaluated to remove nitrogen oxides(NOx) from cigarette mainstream smoke.The three kinds of catalysts were added to cigarettes for studying the capabilities of reducing NOx from cigarette mainstream smoke.The catalysis and reduction of NO in laboratory were studied.A mechanism for NOx catalytic reduction from burning cigarettes with the catalysts adding to cigarettes was described.The catalysts show excellent catalytic activity for NOx removal,especially the Ag-doped OMS-2 catalyst.0.5%(mass fraction) Ag-doped OMS-2 catalyst has the best ability to remove NOx from cigarette mainstream smoke.The use of Ag-doped OMS-2 as catalyst for removing carcinogenic compounds from cigarette smoke will be an effective strategy to protect the environment and public health.

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.

MnO_(2) cathode materials with the improved stability via nitrogen doping for aqueous zinc-ion batteries

The research and exploration of manganese-based aqueous zinc-ion batteries have been controversial of cycle stability and mechanism investigation,thus improving the stability and exploring storage mechanism are still the most main issue.Defect engineering has become an effective method to improve cycle stability.Herein,a nitrogen-doped ε-MnO_(2)(MnO_(2)@N)has been prepared using electrochemical deposition and heat treatment under nitrogen atmosphere.As the cathode for zinc-ion batteries,the capacity retention rate of MnO_(2)@N cathode is close to 100%after 500 cycles at 0.5 A g^(-1),while the capacity retention rate for the initial MnO_(2) cathode is 62%.At 5 A g^(-1),the capacity retention rate of MnO_(2)@N cathode is 83%after 1000 cycles,which is much higher than the 27%capacity retention rate for the original MnO_(2) cathode.And it can be found that the oxygen vacancies increase after nitrogen doping,which can improve the conductivity of the MnO_(2)@N cathode.Also,there is Mn-N bond in MnO_(2)@N,which can enhance the electrochemical stability of MnO_(2)@N cathode.In addition,the electrochemical mechanism of MnO_(2)@N cathode has been explored by the CV,GCD and GITT tests.It is found that nitrogen doping promotes the intercalation of H^(+) and the corresponding capacity contribution.Compared with the original MnO_(2) cathode,the diffusion coefficient of H^(+) and Zn^(2+) in MnO_(2)@N cathode increases.Also,the reactions during the charging and discharging process are explored through the ex-situ XRD test.And this work may provide some new ideas for improving the stability of manganese-based zinc-ion batteries.

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.

Effect of nitrogen concentration in culture mediums on growth and enzyme production of Phanerochaete chrysosporium

Effect of different nitrogen concentration in the mediums on growth and enzyme production of Phanerochaete chrysosporium was studied when glucose concentration was 10 g/L. The results showed that the medium contained 0.8 g/L ammonium tartrate is the best. It not only supply abundant nutrients for the growth of Phanerochaete chrysosporium, which make mycelia the best grow compared with the other medium, but also produce higher manganese-dependent peroxidase(Mnp) and laccase(Lac) activity. In addition, it is observed that the variation of mycelia surface is related to ligninolytic enzyme secreted by Phanerochaete chrysosporium. When the surface of mycelium pellets appeared burs, it predicts secondary metabolism begin. This experimentation demonstrated that when the ratio of carbon and nitrogen in nitrogen limited medium is equal to 100∶8, growth and enzyme production of Phanerochaete chrysosporium is the best, it could achieve the maximum Mnp and Lac activity.

Influence of welding parameters on nitrogen content in welding metal of 32Mn-7Cr-1Mo-0.3N austenitic steel

The transfer behavior of nitrogen into the welding metal during gas tungsten arc welding process of 32Mn-7Cr-1Mo-0.3N steel was investigated. The effects of gas tungsten arc welding process variables, such as the volume fraction of nitrogen in shielding gas, arc holding time and arc current on the nitrogen content in the welding metal were also evaluated. The results show that the volume fraction of nitrogen in gas mixture plays a major role in controlling the nitrogen content in the welding metal. It seems that there exhibits a maximum nitrogen content (depending) on the arc current and arc holding time. The optimum volume fraction of nitrogen in shielding gas is 4% or so. The role of gas tungsten arc welding processing parameters in controlling the transfer of nitrogen is further (confirmed) by the experimental results of gas tungsten arc welding process with feeding metal.

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.

红层包气带铁、锰对氮素生物转化的影响

研究红层土介导下Fe(Ⅲ)、Mn(Ⅱ)对硝化与反硝化优势菌种功能酶及氮转化的影响,结果表明Acinetobacter及Pseudomonas分别是红层包气带中硝化和反硝化效率最高的优势菌种.当Fe(Ⅲ)、Mn(Ⅱ)浓度分别为20、10mg/L时,优势菌硝化和反硝化效率最佳;当达到30mg/L左右后,受到抑制;达到60mg/L时,抑制明显.加入灭菌红层土的SFe0组硝化酶AMO、HAO比酶活比未加红层土的Fe0组提高了4.69%~107.5%,红层土添加明显促进了后期NH_4^(+)向NH_(2)OH的转化;反硝化酶NAR、NIR、NOS比酶活提高了9.16%~73.36%,明显促进了初期NO向N_(2)O的转化.SMn0组AMO、HAO提高了22.23%~120.29%,明显促进了后期NH_(2)OH向NO_(2)^(-)和NO_(3)^(-)的转化;反硝化酶NAR、NOR、NOS总体均有提高,明显促进了初期NO_(2)^(-)向NO的转化;在最适浓度下,SFe20组硝化和反硝化速率在0~12h分别提高了58.91%、121.17%,SMn10组分别提高了42.17%、55.68%;在抑制浓度下,SFe60组分别提高了61.79%、65.91%,SMn60组分别提高了30.26%、80.03%.红层土能够有效促进硝化和反硝化过程,缓解高浓度Fe(Ⅲ)、Mn(Ⅱ)的抑制作用.

铁路辙叉用新型高氮高锰钢的耐腐蚀性能研究

本文以铁路辙叉用新型高氮高锰钢Mn18Cr7C0.6N0.2钢和传统高锰钢Mn13C1.1钢为研究对象,在模拟海洋工业大气环境中对其进行了电化学测试和盐雾腐蚀试验,并使用金相显微镜、扫描电子显微镜和X射线衍射分析仪对比研究了其耐腐蚀性能和腐蚀产物。电化学测试结果表明,在模拟海洋工业大气环境中,Mn18Cr7C0.6N0.2钢较Mn13C1.1钢具有更高的腐蚀电位和更小的腐蚀电流密度,腐蚀倾向更小,这归功于对高锰钢进行了低C和高Cr、N的合金化处理;盐雾腐蚀试验表明,经相同的腐蚀时间后,Mn18Cr7C0.6N0.2钢的腐蚀增重小于Mn13C1.1钢,具有更加优异的耐腐蚀性能,这主要归功于其锈层较为致密且生成了防护性较好的α-FeOOH。