Molten salt synthesis of α-MnO2/Mn2O3 nanocomposite as a high-performance cathode material for aqueous zinc-ion batteries

Thanks to low cost,high safety,and large energy density,aqueous zinc-ion batteries have attracted tremendous interest worldwide.However,it remains a challenge to develop high-performance cathode materials with an appropriate method that is easy to realize massive production.Herein,we use a molten salt method to synthesize nanostructured manganese oxides.The crystalline phases of the manganese oxides can be tuned by changing the amount of reduced graphene oxide added to the reactant mixture.It is found that the α-MnO₂/Mn₂O₃ nanocomposite with the largest mass ratio of Mn₂O₃ delivers the best electrochemical performances among all the products.And its rate capability and cyclability can be significantly improved by modifying the Zn anode with carbon black coating and nanocellulose binder.In this situation,the nanocomposite can deliver high discharging capacities of 322.1 and 213.6 mAh g^-1 at 0.2 and 3 Ag^-1,respectively.After 1000 cycles,it can retain 86.2% of the capacity at the 2 nd cycle.Thus,this nanocomposite holds great promise for practical applications.     

Synthesis of high-performance nickel hydroxide nanosheets/gadolinium doped-α-MnO2 composite nanorods as cathode and Fe3O4/GO nanospheres as anode for an all-solid-state asymmetric supercapacitor

The wide use of manganese dioxide(MnO₂)as an electrode in all-solid-state asymmetric supercapacitors(ASCs)remains challenging because of its low electrical conductivity.This complication can be circumvented by introducing trivalent gadolinium(Gd)ions into the MnO₂.Herein,we describe the successful hydrothermal synthesis of crystalline Gd-doped MnO₂ nanorods with Ni(OH)₂ nanosheets as cathode,which we combined with Fe₃O₄/GO nanospheres as anode for all-solid-state ASCs.Electrochemical tests dem on strate that Gd dopi ng sign ifica ntly affected the electrochemical activities of the MnO₂,which was further enhanced by introducing Ni(OH)₂.The GdMnO₂/Ni(OH)₂ electrode offers sufficient surface electrochemical activity and exhibits excellent specific capacity of 121.8 mA h g^-1,at 1A g^-1,appealing rate performance,and ultralong lifetime stability(99.3%retention after 10,000 discharge tests).Furthermore,the GdMnO₂/Ni(OH)₂//PVA/KOH//Fe₃O₄/GO solid-state ASC device offers an impressive specific energy density(60.25 W h kg^-1)at a high power density(2332 W kg^-1).This investigation thus shows its large potential in developing novel approaches to energy storage devices.     

α-MnO2和β-MnO2纳米棒的制备和催化性能研究

α-MnO₂ and β-MnO₂ nanorods were prepared directly by facile hydrothermal process at 150 ℃ and 220 ℃, respectively. The as-prepared α-MnO₂ and β-MnO₂ nanorods were shown to be phase-pure single crystallites as evidenced by XRD, TEM and SEM results. Further experiments show that the as-prepared α-MnO₂ and β-MnO₂ nanorods have catalytic effect on the oxidation and decomposition of the methylene blue(MB) dye with H₂O₂. The catalytic activity of β-MnO₂ is much higher than that of α-MnO₂.     

Tuning electronic structure ofδ-MnO2 by the alkali-ion(K,Na,Li)associated manganese vacancies for high-rate supercapacitors

Cation vacancies can bring numerous surprising characters due to its multifarious electron and orbit distribution.In this work,d-MnO₂ with alkali-ion(K,Na,Li)associated manganese(Mn)vacancies is fabricated by a simple hydrothermal reaction,and the correlation between their electronic structure and pseudocapacitance are systematically investigated.FESEM/TEM images have shown that the morphology of MnO₂ is obviously changed after the introducing of cation vacancies.The position of alkali-ion in MnO₂ structure can be controlled by adjusting the ion concentration.XRD patterns and Raman spectra demonstrate that the alkali-ion is embedded in Mn vacancies at low concentration,while entered the interlayer of MnO₂ at high concentration.The existence of Mn vacancies will resulting in the distortion of neighboring atoms,leading to the electronic delocalization,and thus enhancing the conductivity,pseudocapacitance and rate capability of MnO₂.Accordingly,the specific capacitances of optimized 0.4 KMO,0.4 NaMO and 0.4 LiMO samples are enhanced about 1.9,1.6 and 1.6 times compared to pure MnO₂.Meanwhile,the rate performance has also been improved about 76%,46%and 42%,respectively.Theoretical calculations further confirm that the Mn vacancies can generate additional occupancy states and cause an increase in carrier concentration,which will improve the conductivity and further boost the pseudocapacitance of MnO₂.This result open up a promising approach to explore active and durable electrode materials.     

β-MnO2纳米棒的电磁特性和多极化驰豫损耗

采用低温水热合成法,以(NH₄)₂S₂O₈作氧化剂,以MnSO₄·H₂O为锰源,在高压反应釜中加热120 ℃并保压48 h制备了β-MnO₂纳米棒。利XRD,SEM,TEM和振动样品磁强计(VSM)对产物进行表征,并就产物的电磁特性和多极化损耗机制进行研究。结果表明,纳米粉体产物是直径为50～70 nm,长度约为几个微米并具有四方晶体结构的β-MnO₂纳米棒,同时产物表现出超顺磁性特征。β-MnO₂纳米棒具有优异的电磁波损耗特性,厚度为1 mm的试样其最大反射损耗在18 GHz能达到-8.1 dB,优于-5 dB的有效吸收带处于15.7～18 GHz宽频段内;2 mm厚的试样在9.8 GHz其反射损耗达到-25 dB,并且优于-5 dB的有效吸收带处于8～12.8 GHz。     

Porous core–shell CoMn_2O_4 microspheres as anode of lithium ion battery with excellent performances and their conversion reaction mechanism investigated by XAFS

Porous core–shell CoMn_2O_4 microspheres of ca. 3–5 μm in diameter were synthesized and served as anode of lithium ion battery. Results demonstrate that the as-synthesized CoMn_2O_4 materials exhibit excellent electrochemical properties. The CoMn_2O_4 anode can deliver a large capacity of 1070 mAh g~(–1) in the first discharge, a reversible capacity of 500 mAh g~(–1) after 100 cycles with a coulombic efficiency of 98.5%at a charge–discharge current density of 200 mA g~(–1), and a specific capacity of 385 mAh g~(–1) at a much higher charge-discharge current density of 1600 mA g~(–1). Synchrotron X–ray absorption fine structure(XAFS) techniques were applied to investigate the conversion reaction mechanism of the CoMn_2O_4 anode.The X–ray absorption near edge structure(XANES) spectra revealed that, in the first discharge–charge cycle, Co and Mn in CoMn_2O_4 were reduced to metallic Co and Mn when the electrode was discharged to 0.01 V, while they were oxidized respectively to CoO and MnO when the electrode was charged to 3.0 V.Experiments of both XANES and extended X–ray absorption fine structure(EXAFS) revealed that neither valence evolution nor phase transition of the porous core–shell CoMn_2O_4 microspheres could happen in the discharge plateau from 0.8 to 0.6 V, which demonstrates the formation of solid electrolyte interface(SEI) on the anode.     

超声辐射沉淀法制备纳米γ -MnO2的研究

以KMnO₄和MnSO₄·H₂O为原料，采用超声辐射沉淀法制备出纳米γ-MnO₂粉体，研究了反应物浓度、滴速、超声时间及超声功率等合成条件对粉体的影响，得出了最佳工艺条件。ICP、XRD和TEM分析表明, 施加超声辐射对反应体系有显著影响，超声辐射沉淀法获得了含K量极低，分布均匀，平均晶粒尺寸约10 nm的近球形γ-MnO₂粉体，而未施加超声辐射的普通沉淀法却得到了棒状KMn₈O₁₆粉体。XPS与IR分析表明，两种方法所得粉体中Mn主要以+4价形式存在，而前者具有较多的氧缺位，由于K⁺进入了确定的晶格位置使后者的Mn-O键红外吸收峰明显不同于前者。     

水热法合成α-MnO2纳米棒及其电化学性能

以KMnO4、氧化石墨(GO)和硫酸为原料,在120℃水热条件下3 h成功合成了直径为10~20 nm,长度为300~400 nm的α-MnO2纳米棒。研究发现GO的引入降低了纳米棒的制备温度,缩短了反应时间。电化学测试结果表明,在1 mol.L-1Na2SO4中性水系电解液中,该纳米棒表现出良好的电容性能,当扫描速率分别为2 mV.s-1和5 mV.s-1时,比电容分别为276 F.g-1和240F.g-1;该纳米材料是一种潜在的电化学电容器电极材料。     

CoS2-碳(C60,石墨,碳纳米管)/TiO2复合光敏剂光降解有机染料（英文）

CoS2,CoS 2-C60 /TiO2,CoS2-CNT/TiO2,and CoS2-Graphene/TiO2 were prepared.The TiO2 products had the anatase phase structure and interesting surface compositions.X-ray diffraction patterns of the CoS2-carbon/TiO2 composites showed a single and clear anatase phase and the CoS2 structure.Scanning electron microscopy characterization of the texture on the CoS 2-carbon/TiO2 composites showed a homogenous composition.Energy-dispersive X-ray spectra for elemental identification showed the presence of C and Ti with strong Co and S peaks from the CoS2-carbon/TiO2 composites.The composites obtained were also characterized by transmission electron microscopy and UV-Vis spectroscopy.CoS2-carbon/TiO2 composites showed excellent photocatalytic activity for the degradation of methylene blue under visible light irradiation.This was attributed to both photocatalysis on the TiO2 support and charge transfer by the carbon nanomaterial,and the introduction of CoS2 to enhance transfer of photogenerated electrons.     

Au/γ-MnO2催化剂催化无溶剂条件下甲苯氧化反应

采用氧化还原法制备了α, δ, γ-MnO₂载体, 采用原位还原法制备了Au负载量为0.5%-3.0%的Au/γ-MnO₂催化剂, 并采用X射线衍射、扫描电镜、透射电镜和N₂物理吸附等手段对其进行了表征. 透射电镜照片表明Au/γ-MnO₂催化剂中Au颗粒的大小约为10 nm. 采用无溶剂存在下的甲苯氧化反应测试所制备样品的催化活性. 结果表明, 甲苯转化率随着Au负载量的增加而增大. 这是由于Au颗粒数量增多, 尺寸减小的缘故. 同时, 负载Au颗粒对苯甲醛具有较高的选择性. Au/γ-MnO₂催化剂具有良好的重复使用性.     

Synthesis and electrochemical properties of nonstoichiometric LiAlxMn2−xO4−δ as cathode materials for rechargeable lithium ion battery

Nonstoichiometric spinel oxides, LiAl_xMn_2−xO_4−δ (x=0.1,0.2), were synthesized under controlled partial pressure of oxygen, and their elecrochemical performances were investigated. As an Al content increases, solubility limit of the oxygen nonstoichiometry, δ, increased, while partial molar enthalpy of the formation of oxygen nonstoichiometry decreased.Cycle performance of LiAl_xMn_2−xO₄ showed significant improvement comparing with that of LiMn₂O₄ cathode. However, the decrease of theoretical capacity was accompanied with Al doping. Nonstoichiometric LiAl_xMn_2−xO_4−δ showed the increase in capacity with keeping good cycle performances as well as stoichiometric LiAl_xMn_2−xO₄. Although the introduction of oxygen nonstoichiometry leads to the increase of Mn³⁺ which is known as Jahn-Teller ion, DSC curves for LiAl_xMn_2−xO_4−δ showed no exothermic peak due to phase transition arising from Jahn-Teller distortion around room temperature.     

Al3+离子掺杂δ-MnO2的制备和电化学性能

采用水热法合成了不同比例Al³⁺离子掺杂的δ-MnO₂纳米粉体.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线光电子能谱(XPS)、循环伏安(CV)曲线、电化学阻抗谱(EIS)和恒电流充放电(GCD)曲线等手段对材料的结构和电化学性能进行了表征.结果表明, Al³⁺离子进入δ-MnO₂的晶格替代部分Mn³⁺和Mn⁴⁺离子,使得δ-MnO₂电极的性能明显提升.当反应物中Al³⁺/Mn²⁺摩尔比为0.45时,所得样品(A0.45M)的性能最好;其在1 A/g电流密度下的比电容为207.61 F/g,是纯相δ-MnO₂(A0M)的2.4倍;其在10 A/g电流密度下循环10000次后的比电容为100.81 F/g,容量保持率为81.33%.     

Toluene-solvated zinc dimethyldithiocarbamate adduct with piperidine [Zn{NH(CH2)5}{S2CN(CH3)2}2] · 2C6H5CH3: Synthesis, structure, and thermal properties

A solvated form of zinc dimethyldithiocarbamate adduct with piperidine of the composition [Zn{NH(CH₂)₅}{S₂CN(CH₃)₂}2] · 2C₆H₅CH₃ (I) was synthesized. The structure and thermal properties of the adduct were studied by X-ray crystallography and simultaneous thermal analysis (STA). The structure of compound I is characterized by the presence of a system of channels populated by solvating toluene molecules (structural type of lattice clathrates). The central zinc atom coordinates two dithiocarbamate ligands and a piperidine molecule (zinc coordination number CN_Zn = 5). The zinc polyhedron geometry is intermediate between a tetragonal pyramid (TP) and trigonal bipyramid (TBP); the contributions of the TP and TBP components were evaluated from the X-ray diffraction data. The STA study of the thermal properties of I has shown that the weight loss occurs in three steps and includes desorption of solvating toluene molecules, then, desorption of coordinated piperidine molecules, and thermolysis of the dithiocarbamate moiety of the complex with formation of a zinc sulfate powder.     

xAu/α-MnO2催化剂的结构及催化氧化VOCs气体性能

以NaOH为沉淀剂,采用沉积-沉淀法制备了α-MnO2负载Au催化剂xAu/α-MnO2(x=1.0%～7.0%,质量分数),利用X射线衍射(XRD)、N2吸附-脱附、H2程序升温还原(H2-TPR)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等技术对所得样品进行了表征,并对其催化氧化挥发性有机化合物(VOCs,苯和甲苯)的性能进行了研究.XRD结果表明,负载Au对α-MnO2载体结构影响不大,但对其晶粒大小和比表面积略有影响.随着Au含量的增加,α-MnO2结晶度增强,颗粒增大,Au粒径明显增大.XPS结果表明,随着Au负载量的增加,xAu/α-MnO2的晶格氧(O2-),Mn4+和Au3+的浓度增加.H2-TPR结果表明,由于贵金属的溢氢作用,Au明显提升了xAu/α-MnO2的还原能力,其中3%Au/α-MnO2的还原能力最强.负载Au明显影响xAu/α-MnO2的催化性能,xAu/α-MnO2的催化性能与Au的颗粒分散性、低温还原性能及表面氧物种密切相关,其中3%Au/α-MnO2显示出最佳活性,其催化氧化苯和甲苯的T100分别为280和250℃.     

Noncentrosymmetric K2Mn3(SO4)3F2·4H2O and Rb2Mn3(SO4)3F2·2H2O with pseudo-KTP structures

Two fluoride sulfates,K₂Mn₃(SO₄)₃F₂·4H₂O(Ⅰ) and Rb₂Mn₃(SO₄)₃F₂·2H₂O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_1.Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn₃(SO₄)3F₂(H₂O)2]_∞ layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH₂PO₄.     

Removal of bisphenol A via a hybrid process combining oxidation on β-MnO2 nanowires with microfiltration

A novel hybrid process combining β-MnO₂ nanowires oxidation and microfiltration was adopted to remove bisphenol A (BPA), an endocrine disrupting chemical (EDC) in the aquatic environment. The β-MnO₂ nanowires synthesized via a facile hydrothermal method were characterized by X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscope, and nitrogen sorption. It was demonstrated that β-MnO₂ nanowires can degrade BPA effectively. Investigation on operation parameters indicated that oxidation of BPA using β-MnO₂ nanowires was evidently dependent on pH, while humic acid and coexisting metal ions such as Ca²⁺, Mg²⁺, and Mn²⁺ induced suppressive effects. After oxidation, a crossflow microfiltration process was conducted to efficiently separate and recover the β-MnO₂ nanowires from treated water. Membrane fouling study showed that the as-synthesized β-MnO₂ nanowires possess excellent mechanical stability and was able to retain the 1D structure with high aspect ratios after reaction, thus significantly reducing membrane pore blocking in the microfiltration process.     

ZnSe-石墨烯/TiO2声催化剂上罗丹明B降解与反应氧物种生成（英文）

Nanostructured ZnSe-graphene/TiO2 was synthesized by a hydrothermal-assisted approach. ZnSe-graphene/TiO2 exhibited favorable adsorption of rhodamine B, a wide wavelength absorption range, and efficient charge separation. Reactive oxygen species were generated by the oxidation of 1,5-diphenyl carbazide to 1,5-diphenyl carbazone. The sonocatalytic reaction mechanism was pro-posed. These findings potentially broaden the applications of sonocatalytic technologies.     

Conversion efficiency of γ/β-MnO2 in composites with natural graphite and carbon nanotubes in a prototype lithium battery

Chemically synthesized manganese dioxide γ/β-MnO₂ was studied in composites with multi-walled carbon nanotubes and natural graphite of EUZ-M brand was studied in the redox reaction with lithium. It was shown that nanometer carbon electron-conducting filler is advantageous over the micrometer filler (EUZ-M) in the efficiency of influence exerted on power characteristics and cycling capacity of a prototype lithium battery with a cathode based on γ/β-MnO₂. The effective chemical diffusion coefficient of lithium ions in MnO₂ composites with multi-walled carbon nanotubes and EUZ-M was estimated and hodographs of electrodes based on γ/β-MnO₂ without a carbon additive and with EUZ-M, brought in contact with an electrolyte, were analyzed.     

The preparation of terephthalic acid by solvent-free oxidation of p-xylene with air over T（p-C1）PPMnC1 and Co（OAc）2

An attempt has been made to prepare terephthalic acid（TPA） by solvent-free oxidation of p-xylene（PX） with air over tetra（pchlorophenylporphinato） manganese chloride（T（p-Cl）PPMnCl） and cobalt acetate.The co-catalysis between T（p-Cl）PPMnCl and Co（OAc）₂ has been discovered under solvent-free conditions.TPA yield could be increased significantly when T（p-Cl）PPMnCl and Co（OAc）₂ were used together.The addition of T（p-Cl）PPMnCl into the reaction mixture over Co（OAc）₂ significantly accelerated the rate-determining step of the oxidation process of PX to TPA.The effect of temperature on reaction was also investigated.     

A 4D Structural Study of a Ca-Rich Composite-Type Crystal [A2Cu2O3]7+δ [CuO2]10 with Disorder Phenomena in CuO2 Sublattice

The structure of a Ca-rich composite-type crystal [A₂Cu₂O₃]_7+δ [CuO₂]₁₀ with A=Sr_0.43Ca_0.55Bi_0.03 and δ=0.04 was determined by single-crystal X-ray diffraction using the 4D superspace group formalism. Thanks to the existence of a significant number of first-order satellite reflections, reliable results were obtained concerning the displacive modulation within each subsystem. A comparison is made with the accurate structural results obtained by Frost Jensen on similar composite crystals containing less calcium. A larger modulation amplitude is observed in our crystal. Weak interactions (Cu-O?2.72 Å) are involved locally between the copper atoms of a [Cu₂O₃] layer and one oxygen atom of a [CuO₂] layer, leading in some unit cells to a pyramidal coordination of copper. Such an interaction is not observed in the Ca-less-containing crystal of Frost-Jensen. However, the most important point of this study concerns the evidence for the first time of disorder phenomena inside the [CuO₂] subsystem; this disorder was modeled with both Cu and O splitted sites. Two main configurations with realistic Cu-O bonds are privileged for the CuO₄ squares inside the [CuO₂] sublattice. The refinement results and the bond valence formalism give strong evidence that the A sites are occupied at random by Sr and Ca atoms, which display two types of coordination, 7 and 8, in the crystal.