On-line Preconcentration of Trace Nickel from Electrolytic Manganese Using Minicolumn Packed Activated Carbon for Electrothermal Atomic Absorption Spectrometry

The online flow injection preconcentration and electrothermal atomic absorption spectrometry method were used for the determination of trace nickel in electrolytic manganese samples by sorption on a conical minicolumn packed with activated carbon at pH 9.0. The nickel was eluted from the minicolumn with 10%(v/v) nitric acid. An enrichment factor of 190-fold for a sample volume of 10mL was obtained. The detection limit (DL) of nickel with the use of the preconcentration method was 13ng·g -1in the original solid sample. The precision for 10 replicate determinations at 150ng·g -1 nickel concentration was 5.2% relative standard deviation (RSD). The calibration graph was linear with a correlation coefficient of r=0.9996 up to concentration of 660ng·g -1 nickel.

Treatment of mine water high in Fe and Mn by modified manganese sand

The iron and manganese absorption properties of several filter media were studied. Four plain filter media and six surface-modified media were examined. The surface modification was performed using potassium permanganate as a surface treatment. The surface-modified manganese sand was found to be most efficient at removing iron and manganese from water. The metal concentrations in filtered effluent were between 0.01 and 0.04 mg/L, which is far lower than the standard for recycle water. A concen-tration of 5% KMnO4 was found to be most effective as surface modifier. The surface of the manganese sand modified by 5% KMnO4 was examined and found to be covered with a dense membrane of some compound. The membrane had the advantages of uniform texture, large surface area and physical and chemical stability. It was effective at removing iron and manganese from mine water.

Mn/beta and Mn/ZSM-5 for the low-temperature selective catalytic reduction of NO with ammonia: Effect of manganese precursors

Two series of Mn/beta and Mn/ZSM‐5catalysts were prepared to study the influence of how different Mn precursors,introduced to the respective parent zeolites by wet impregnation,affected the selective catalytic reduction(SCR)of NO by NH3across a low reaction temperature window of50–350°C.In this study,the catalysts were characterized using N2adsorption/desorption,X‐ray diffraction,X‐ray fluorescence,H2temperature‐programmed reduction,NH3temperature‐programmed desorption and X‐ray photoelectron spectroscopy.As the manganese chloride precursor only partially decomposed this primarily resulted in the formation of MnCl2in addition to the presence of low levels of crystalline Mn3O4,which resulted in poor catalytic performance.However,the manganese nitrate precursor formed crystalline MnO2as the major phase in addition to a minor presence of unconverted Mn‐nitrate.Furthermore,manganese acetate resulted principally in a mixture of amorphous Mn2O3and MnO2,and crystalline Mn3O4.From all the catalysts screened,the test performance data showed Mn/beta‐Ac to exhibit the highest NO conversion(97.5%)at240°C,which remained>90%across a temperature window of220–350°C.The excellent catalytic performance was ascribed to the enrichment of highly dispersed MnOx(Mn2O3and MnO2)species that act as the active phase in the NH3‐SCR process.Furthermore,together with a suitable amount of weakly acidic centers,higher concentration of surface manganese and a greater presence of surface labile oxygen groups,SCR performance was collectively enhanced at low temperature.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Flow Injection Semi-online Preconcentration Graphite Furnace Atomic Absorption Spectrometry for Determination of Cadmium,Copper and Manganese

A micro-flow injection sorbent extraction preconcentration system was combined with a graphite furnace atomic absorption spectrometry that formed an integrated system for the determination of trace amounts of elements. The analytical performances of the prospsed method for determining Cd, Cu and Mn were studied. The analytes were preconcentrated with a thiol resin(Type 190, produced by Nankai University, China) whose active group is -SH. The elements to be determined were preconcentrated onto the column for 60 s and then rinsed with deionized water and eluted with 30 μL of 1 mol/L HCl. The graphite furnace atomic absorption spectrometry(GFAAS) determination of the concentrated analyte was carried out in parallel with the next preconcentration cycle. Enrichment factors 41, 22 and 20 and detection limits(3 σ , n =10) 0.36, 3.8 and 7.0 ng/L for Cd, Cu and Mn, respectively, along with a sampling frequency of 20 h -1 , were obtained with a 60 s loading time at a sample flow rate of 3.5 mL/min. The analytical results for a number of water samples show that the flow-injection semi-online column preconcentration can not only eliminate the effect of some concomitant elements, such as Li, Na, K, Ca and Mg, on the determination of the analyte, but also enhance the sensitivity.

Synthesis of amorphous manganese borohydride in the(NaBH_4–MnCl_2) system, its hydrogen generation properties and crystalline transformation during solvent extraction

The mixture of(2NaBH4+ MnCl2) was ball milled in a magneto-mill. No gas release was detected. The XRD patterns of the ball milled mixture exhibit only the Bragg diffraction peaks of the Na Cl-type salt which on the basis of the present X-ray diffraction results and the literature is likely to be a solid solution Na(Cl)x(BH4)(1-x), possessing a cubic Na Cl-type crystalline structure. No presence of any crystalline hydride was detected by powder X-ray diffraction which clearly shows that NaBH4in the initial mixture must have reacted with MnCl2forming a Na Cl-type by-product and another hydride that does not exhibit X-ray Bragg diffraction peaks. Mass spectrometry(MS) of gas released from the ball milled mixture during combined MS/thermogravimetric analysis(TGA)/differential scanning calorimetry(DSC) experiments, confirms mainly hydrogen(H2) with a small quantity of diborane gas, B2H6. The Fourier transform infra-red(FT-IR) spectrum of the ball milled(2NaBH4+ MnCl2) is quite similar to the FT-IR spectrum of crystalline manganese borohydride, c-Mn(BH4)2, synthesized by ball milling, which strongly suggests that the amorphous hydride mechano-chemically synthesized during ball milling could be an amorphous manganese borohydride. Remarkably, the process of solvent filtration and extraction at 42 °C, resulted in the transformation of mechano-chemically synthesized amorphous manganese borohydride to a nanostructured,crystalline, c-Mn(BH4)2hydride.

Determination of Trace Selenium in Electrolytic Manganese by Graphite Furnace Atomic Absorption Spectrometry

The effects of four types of graphite tube and five matrix modifiers on the determination of selenium by graphite furnace atomic absorption spectrometry were compared.The results show that platform thermolysis coat graphite tube and magnesium nitrate and cobaltco as matrix modifer can get a high sensitivity and a good recovery.The optimized working conditions and interference in the determination were invesigated.This result is consistent with that of XRF.The recovery is from 100.8 % to102.2 %,the relative standard deviation is from 3.47% to 5.56 % (n=9),and the detection limit of selenium is 378 pg (C=44.5μg/g to 97.3μg/g.).The proposed method can be applied to the rapid determination of selenium in electrolytic manganese.

High-Performance Aqueous Zinc–Manganese Battery with Reversible Mn^(2+)/Mn^(4+) Double Redox Achieved by Carbon Coated MnO_x Nanoparticles

There is an urgent need for low-cost,high-energy-density,environmentally friendly energy storage devices to fulfill the rapidly increasing need for electrical energy storage.Multi-electron redox is considerably crucial for the development of high-energy-density cathodes.Here we present highperformance aqueous zinc-manganese batteries with reversible Mn2+/Mn4+ double redox.The active Mn4+is generated in situ from the Mn2+-containing MnOx nanoparticles and electrolyte.Benefitting from the low crystallinity of the birnessite-type MnO2 as well as the electrolyte with Mn2+additive,the MnOX cathode achieves an ultrahigh energy density with a peak of845.1 Wh kg-1 and an ultralong lifespan of 1500 cycles.The combination of electrochemical measurements and material characterization reveals the reversible Mn2+/Mn4+double redox(birnessite-type MnO2? monoclinic MnOOH and spinel ZnMn2O4 H?Mn2+ions).The reversible Mn2+/Mn4+double redox electrode reaction mechanism offers new opportunities for the design of low-cost,high-energy-density cathodes for advanced rechargeable aqueous batteries.

Determination of Manganese in Tri Calcium Phosphate (TCP) by Atomic Absorption Spectrometry

Tricalcium phosphate Anhydrous Powder typically contains less than 10 ppm (mg/Kg) (w/w) manganese. This level can be determined utilizing Flame Atomic Absorption Spectrometer (AAS) and standard based on known standards. A number of analytical methods are presently used for the analysis of metals in the biochemical. The instrumental techniques available are Inductively Coupled Plasma (ICP/MS), X-Ray Fluorescence, UV-VIS Spectrophotometry, and Atomic Absorption Spectrometry. Flame AA has gained widespread acceptance as an analytical technique and is used for many applications. In this study, we have determined the amount of manganese metal present in Tricalcium Phosphate (TCP) using Flame Atomic Absorption Spectrophotometer. The method has high precision and accuracy. The percent recovery was found to be 99.8% for spiked sample. The results meet the requirement.

Oxygen Atom Transfer Reaction of Manganese-oxo Corrole toward Dimethyl Sulfide: a Density Functional Study

The effects of axial ligand on the oxygen atom transfer(OAT)reaction from 5,10,15-tris(pentafluorophenyl)corrole((tpfc)MnVO)to dimethyl sulfide(DMS)have been investigated by density functional theory(DFT)calculations.Imidazole(Im),4-methylimidazole(4-MI)and pyridine(Py)were selected as the axial ligands.The results revealed that the axial ligand can form coordinate bond with(tpfc)MnVO in the transition state(TS)of the OAT reaction.The axial coordination favored charge transferring from(tpfc)MnVO to DMS,and weakened the Mn≡O bond in both singlet and triplet states.Furthermore,axial coordination can reduce the energy barrier of neutral(tpfc)MnVO from 23.62 kJ·mol^-1 to less than 3 kJ·mol^-1 in the triplet state,which is significantly lower than in the singlet state.This makes(tpfc)MnVO tend to direct the OAT reaction via triplet state pathway.On the other hand,the energy barriers of[(tpfc)MnVIO]+species from disproportionation pathway increased from 1.26 to 33.95 kJ·mol^-1 in a doublet state.This suggests axial ligands were conducive for direct(tpfc)MnVO OAT reaction pathway.

Influence of pH on properties of Mn-Zn ferrites synthesized from low-grade manganese ore

Mn-Zn ferrite powders were produced from low-grade manganese ore(LMO) via the chemical coprecipitation method combined with the ceramic method,after the LMO was leached in sulfuric acid and the obtained solution was purified.The effect of the pH on the magnetic properties of Mn-Zn ferrite was investigated by the varying pH of the co-precipitation system.The crystal structure and phases of the samples were characterized by X-ray diffraction and infrared spectrum,respectively.The magnetic measurements were carried out on a vibrating sample magnetometer.The optimal sample was obtained with a saturation magnetization of 55.02 emu/g,a coercivity of 8.20 G and a remanent magnetization of1.71 emu/g when pH is 7.5.

Deep removal of copper from nickel electrolyte using manganese sulfide

Copper is difficult to separate from nickel electrolyte due to low concentration of copper (0.53 g/L) with high concentration of nickel (75 g/L). Manganese sulfide (MnS) was used to deeply remove copper from the electrolyte. Experimental results show that the concentration of copper (ρ(Cu)) decreases from 530 to 3 mg/L and the mass ratio of copper to nickel (RCu/Ni) in the residue reaches above 15 when the MnS dosage is 1.4 times the theoretical valueDt,MnS (Dt,MnS=0.74 g) and the pH value of electrolyte is 4?5 with reaction time more than 60 min at temperatures above 60 °C. The concentration of newly generated Mn2+(ρ(Mn)) in the solution is also reduced to 3 mg/L by the oxidation reaction. The values ofρ(Cu),ρ(Mn)andRCu/Ni meet the requirements of copper removal from the electrolyte. It is shown that MnS can be considered a highly effective decoppering reagent.

Study of Manganese Promoter on a Precipitated Iron-Based Catalyst for Fischer-Tropsch Synthesis

The effects of Manganese （Mn） incorporation on a precipitated iron-based Fischer-Tropsch synthesis （FTS） catalyst were investigated using N2 physical adsorption, air differential thermal analysis （DTA）, H2 temperature-programmed reduction （TPR）, and Mǒssbauer spectroscopy. The FTS performances of the catalysts were tested in a slurry phase reactor. The characterization results indicated that Mn increased the surface area of the catalyst, and improved the dispersion of （α-Fe2O3 and reduced its crystallite size as a result of the high dispersion effect of Mn and the Fe-Mn interaction. The Fe-Mn interaction also suppressed the reduction of （α-Fe2O3 to Fe3O4, stabilized the FeO phase, and （or） decreased the carburization degree of the catalysts in the H2 and syngas reduction processes. In addition, incorporated Mn decreased the initial catalyst activity, but improved the catalyst stability because Mn restrained the reoxidation of iron carbides to Fe3O4, and improved further carburization of the catalysts. Manganese suppressed the formation of CH4 and increased the selectivity to light olefins （C2-4^=）, but it had little effect on the selectivities to heavy （C5＋） hydrocarbons. All these results indicated that the strong Fe-Mn interaction suppressed the chemisorptive effect of the Mn as an electronic promoter, to some extent, in the precipitated iron-manganese catalyst system.

Low temperature surface oxygen activation in crystalline MnO_(2) triggered by lattice confined Pd single atoms

Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as support. Compared with the Pd clusters anchored on the surface, the lattice confined Pd single atoms allows spontaneous exaction of surrounding lattice oxygen at room temperature when employed in CO oxidation. The MnO_(2) supported Pd SAC exhibited a high turnover frequency of 0.203 s^(−1) at low reaction temperature, which is higher than that of recently reported Pd SACs. Theoretical calculations also confirmed the confined monatomic Pd activate lattice oxygen with an ultralow energy barrier. Our results illustrate that the unique coordination environment of single atom provided by lattice confinement is promising to boost the activity of SACs.

不同Mn/Fe比例天然含铁锰矿的As(Ⅲ)吸附性能与机制

水体中的砷主要以亚砷酸(As(Ⅲ))形态存在.金属氧化物常用于水体砷的去除,但其对As(Ⅲ)的亲和力较弱,导致水体砷很难去除,因此,寻求高效、廉价、绿色的除As(Ⅲ)材料具有显著的环境意义.天然含铁锰矿是一种高效的砷吸附剂,由于自然形成条件复杂,其不同含铁锰矿对As(Ⅲ)的去除性能存在较大差异.本研究以两种不同Mn/Fe比例的天然含铁锰矿(NFM-L、NFM-H)为研究对象,评估其对As(Ⅲ)的吸附性能,并结合XPS、XRD等光谱学表征手段探究其砷的去除机制.实验结果表明,NFM-L的Fe含量是NFM-H的5.61倍,其As(Ⅲ)的最大吸附量(24.82 mg·g^(−1))与吸附速率亦显著高于NFM-H(18.94 mg·g^(−1)),NFM-L和NFM-H对As(Ⅲ)的等温吸附曲线更符合Freundlich模型.影响因子实验表明,溶液pH值对NFM-L的影响更大,共存离子H_(2)PO_(4)^(−)能够显著抑制两种材料对As(Ⅲ)的吸附,但是材料粒径对As(Ⅲ)去除的影响较小.光谱学表征发现,两种矿物吸附砷后结构并未发生明显变化,但锰氧化物能将As(Ⅲ)氧化为As(V),从而显著提高了铁锰矿对砷的吸附能力.

Direct and Simultaneous Determination of Several Impurity Elements in Manganese Tetroxide using ICP-AES

A rapid method for the determination of impurity elements, such as Zn, Ni, Co, Cr, Cu, Cd and Pb in manganese tetroxide was developed, using inductively coupled plasma atomic emission spectrometry （ICP-AES）. The critical instrumental parameters such as sample flow rate and radio frequency incident were thoroughly optimized. The effect of matrix was also examined. The sensitivity was investigated using calibration curves obtained in presence of the matrix. The obtained recoveries for Ni, Co, Cr, Cu, and Cd at the μg· g^ -1 level were satisfactory and practically independent of the matrix used for the calibration standards. The recoveries of Pb and Zn were less suffwient. The method can be applied for routine analysis and quality control purposes at μg· g^-1 level of concentration.

Reductive recovery of manganese from low-grade manganese dioxide ore using toxic nitrocellulose acid wastewater as reductant

The hydrometallurgical strategy of extracting Mn from low-grade Mn ores has attracted attention for the production of electrolytic manganese metal(EMM). In this work, the reductive dissolution of low-grade Mn O2 ores using toxic nitrocellulose acidic wastewater(NAW) as a reductant was investigated for the first time. Under the optimized conditions of an Mn O2 ore dosage of 100 g·L-1, an ore particle size of-200 mesh, concentrated H2 SO4-to-NAW volume ratio of 0.12, reaction temperature of 90°C, stirring speed at 160 r·min-1, and a contact time of 120 min, the reductive leaching efficiency of Mn and the total organic carbon(TOC) removal efficiency of NAW reached 97.4% and 98.5%, respectively. The residual TOC of 31.6 mg·L-1 did not adversely affect the preparation of EMM. The current process offers a feasible route for the concurrent realization of the reductive leaching of Mn and the treatment of toxic wastewater via a simple one-step process.

Ultrafine ordered L1_(2)-Pt-Co-Mn ternary intermetallic nanoparticles as high-performance oxygen-reduction electrocatalysts for practical fuel cells

The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.

Evaluating the Stability of Active Manganese Sites During Electrochemical Reactions by Cyclic Voltammetry

Manganese oxides are a promising class of electrocatalysts for renewable energy devices,such as fuel cells.Mn(Ⅲ) ions with e_(g) electron filling of-1 are the active sites for manganese-based electrocatalysts.However,Mn(Ⅲ) sites may be disproportionated during electrochemical reactions,thus reducing the number of Mn(Ⅲ) active sites and decreasing the catalytic activity of manganese oxides.In this work,we developed a facile cyclic voltammetry method to monitor the evolution of Mn(Ⅲ) sites on a series of manganese oxides under "working" conditions.We proposed a descriptor S_(Mn(Ⅲ)) to describe the stability of Mn(Ⅲ).Our simulated and experimental results show that the higher is S_(Mn(Ⅲ)),the higher the active Mn(Ⅲ)density,and the higher the electrocatalytic activity of the manganese oxide electrocatalyst.

Achieving 20% photovoltaic efficiency by manganese doped methylammonium lead halide perovskites

We report a transition metal such as manganese doped methylammonium lead halide perovskite(MA(Pb:Mn)I_(3)) solar cell with an power conversion efficiency(PCE) over 20%. The rational design and fabrication of MA(Pb:Mn)I3 lead to the enhancements of all the photovoltaic parameters. To incorporate Mn can effectively eliminate the trap-assist and bi-molecular recombination. The photo-absorption ability at shorter wavelengths(i.e., less than 500 nm) and charge carrier lifetime can be elaborated. More importantly, the existence of the Mn^(2+)-I~--Mn^(3+)motif contributes for the double exchange effect, giving rise to the charge/spin transport. By a combination of linearly and circularly polarized photo-excitations, we have explicitly determined the role of intrinsic spin–orbit coupling(SOC) in MA(Pb:Mn)I_(3). More dark states are expected to be available for the photocurrent generation. This study may pave the way for deep understandings of transition metals doped hybrid perovskites for highly efficient solar cell applications.

Marsh Spot Disease and Its Causal Factor, Manganese Deficiency in Plants: A Historical and Prospective Review

This review provides an examination of the marsh spot disease in beans and the roles played by its causal factor, manganese (Mn) deficiency. The discovery of the marsh spot disease, its relation with Mn deficiency, and how it can be treated are discussed. Mn serves as a cofactor and a catalyst in various metabolic processes in different cell compartments, such as the oxygen-evolving complex of photosystem II (PSII) or reactive oxygen species scavenging. Some major quantitative trait loci (QTL) and putative candidate genes associated with Mn content in plants, especially in plant seeds, have been identified. Marsh spot disease in cranberry common bean is controlled by several major genes with significant additive and epistatic effects. They provide valuable clues for QTL candidate gene prediction and an improved understanding of the genetic mechanisms responsible for marsh spot resistance in plants.