Doping strategy to boost electromagnetic property and gigahertz tunable electromagnetic attenuation of hetero-structured manganese dioxide.

A facile and simple chemical route has been used to synthesize novel three-dimensional (3D) architectures of nickel-doped ε-MnO2 without the addition of any surfactant or organic template. Nickel salt is used directly as the reagent rather than as an additive to produce doped manganese dioxide, which is different from the overwhelming majority of previous synthetic methods for doped MnO2 for use as an electromagnetic wave absorption material. This method overcomes the shortcomings of the previously reported approaches of doping with a slight amount of metallic ion, which is sometimes hard to detect. The chemical composition of the samples is analyzed by electron-probe micro-analysis (EPMA) and energy dispersive spectroscopy (EDS). The chemical state of the elements in the composites is demonstrated with X-ray photoelectron spectroscopy (XPS). The structures of the micro-spheres are detected by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the self-organized crystals are made up of walnut-like spheres and are arrays of polycrystals. The nickel ion is certified to have been successfully doped into the crystal based on the results of EPMA, EDS, and XPS as well as dark field scanning TEM. Thus, a multiple heterojunction structure is constructed. After nickel doping, the crystalline phase remains ε type and the morphology turns into a walnut-like structure. Electromagnetic performances also exhibit significant variation with the introduction of nickel ions. Nickel-doped MnO2 has a decreased dielectric constant compared with that of commercial MnO2, while the nickel-doped MnO2 appears to have fascinating magnetic properties with a maximum magnetic loss tangent value of 0.37, which is 7 times greater than that of the dielectric loss tangent. Likewise, it is further presented that the optimized electromagnetic capacities are related to the mass fraction of the walnut-like MnO2 spheres in the composite. When the mass fraction is as high as 50%, the magnetic loss tangent goes up with a distinct increase in mutations as well as in relaxation times and in the real part and the imaginary part of the relative complex permeability. Furthermore, the mechanisms of the highlighted electromagnetic attenuation are explored in detail.

[1]  Zhihong Yang,et al.  Encapsulating metal nanoparticles inside carbon nanoflakes: a stable absorbent designed from free-standing sandwiched composites. , 2018, Dalton transactions.

[2]  Yingshuo Yu,et al.  Rational design of CNTs with encapsulated Co nanospheres as superior acid- and base-resistant microwave absorbers. , 2018, Dalton transactions.

[3]  Zhihong Yang,et al.  Extended Working Frequency of Ferrites by Synergistic Attenuation through a Controllable Carbothermal Route Based on Prussian Blue Shell. , 2018, ACS applied materials & interfaces.

[4]  Xiaohui Liang,et al.  Laminated graphene oxide-supported high-efficiency microwave absorber fabricated by an in situ growth approach , 2018 .

[5]  Jian Sun,et al.  Enhanced High-Temperature Cyclic Stability of Al-Doped Manganese Dioxide and Morphology Evolution Study Through in situ NMR under High Magnetic Field. , 2018, ACS applied materials & interfaces.

[6]  Yanglong Hou,et al.  A Versatile Route toward the Electromagnetic Functionalization of Metal-Organic Framework-Derived Three-Dimensional Nanoporous Carbon Composites. , 2018, ACS applied materials & interfaces.

[7]  Youwei Du,et al.  Rationally regulating complex dielectric parameters of mesoporous carbon hollow spheres to carry out efficient microwave absorption , 2018 .

[8]  Guangyao Ma,et al.  Metal‐Ion (Fe, V, Co, and Ni)‐Doped MnO2 Ultrathin Nanosheets Supported on Carbon Fiber Paper for the Oxygen Evolution Reaction , 2017 .

[9]  M. Tagawa,et al.  Plasmonic Heating-Assisted Laser-Induced Crystallization from a NaClO3 Unsaturated Mother Solution , 2017 .

[10]  Z. Li,et al.  Tunable high-performance microwave absorption for manganese dioxides by one-step Co doping modification , 2016, Scientific Reports.

[11]  Huijun Zhao,et al.  Fabrication of hierarchical iron-containing MnO2 hollow microspheres assembled by thickness-tunable nanosheets for efficient phosphate removal , 2016 .

[12]  Dongyang Deng,et al.  Enhanced microwave absorption properties of MnO2 hollow microspheres consisted of MnO2 nanoribbons synthesized by a facile hydrothermal method , 2016 .

[13]  Z. Li,et al.  Controllable adjustment of the crystal symmetry of K–MnO2 and its influence on the frequency of microwave absorption , 2016 .

[14]  Dongyan Li,et al.  Effective Ti Doping of δ-MnO2 via Anion Route for Highly Active Catalytic Combustion of Benzene , 2016 .

[15]  L. Zhuang,et al.  Large-Scale Synthesis of Metal-Ion-Doped Manganese Dioxide for Enhanced Electrochemical Performance. , 2016, ACS applied materials & interfaces.

[16]  Youwei Du,et al.  A novel Co/TiO2 nanocomposite derived from a metal–organic framework: synthesis and efficient microwave absorption , 2016 .

[17]  Shuoqing Zhao,et al.  Facile synthesis of nickel doped walnut-like MnO2 nanoflowers and their application in supercapacitor , 2016, Journal of Materials Science: Materials in Electronics.

[18]  Jianping Wang,et al.  Biocompatible Fe-Si Nanoparticles with Adjustable Self-Regulation of Temperature for Medical Applications. , 2015, ACS applied materials & interfaces.

[19]  S. Hyun,et al.  Adsorption properties of transition metal atoms on strongly correlated NiO(001) surfaces with surface oxygen vacancies , 2015 .

[20]  A. Senthilkumar,et al.  Influence of Zn doping on the electrochemical capacitor behavior of MnO2 nanocrystals , 2015 .

[21]  Tongmin Wang,et al.  Frequency response of microwave dielectric based on tunable crystallographic defects of β-MnO2 , 2015 .

[22]  B. Fan,et al.  Facile preparation and enhanced microwave absorption properties of core-shell composite spheres composited of Ni cores and TiO2 shells. , 2015, Physical chemistry chemical physics : PCCP.

[23]  Lei Zhang,et al.  Controllable hydrothermal synthesis of Cu-doped δ-MnO2 films with different morphologies for energy storage and conversion using supercapacitors , 2014 .

[24]  M. Zhang,et al.  Electromagnetic characteristics and microwave absorption properties of carbon-encapsulated cobalt nanoparticles in 2–18-GHz frequency range , 2014 .

[25]  Wenyao Li,et al.  Magnetic-field-assisted hydrothermal synthesis of 2 × 2 tunnels of MnO2 nanostructures with enhanced supercapacitor performance , 2014 .

[26]  Hong Bi,et al.  Enhanced interfacial polarization relaxation effect on microwave absorption properties of submicron-sized hollow Fe3O4 hemispheres , 2014 .

[27]  Tongmin Wang,et al.  Structure, Morphology, and Electromagnetic Properties of Manganese Dioxide with Ni Doping , 2014 .

[28]  M. Cao,et al.  Enhanced Dielectric Properties and Excellent Microwave Absorption of SiC Powders Driven with NiO Nanorings , 2014 .

[29]  Yan Wang,et al.  Synthesis and microwave absorption enhancement of graphene@Fe3O4@SiO2@NiO nanosheet hierarchical structures. , 2014, Nanoscale.

[30]  Shengping Wang,et al.  Al and/or Ni-doped nanomanganese dioxide with anisotropic expansion and their electrochemical characterisation in primary Li–MnO2 batteries , 2014, Journal of Solid State Electrochemistry.

[31]  Xiaobo Chen,et al.  Hydrogenated TiO2 Nanocrystals: A Novel Microwave Absorbing Material , 2013, Advanced materials.

[32]  T. Pal,et al.  Morphological Evolution of Two-Dimensional MnO2 Nanosheets and Their Shape Transformation to One-Dimensional Ultralong MnO2 Nanowires for Robust Catalytic Activity , 2013 .

[33]  Wei Lv,et al.  Porous MnO2 for use in a high performance supercapacitor: replication of a 3D graphene network as a reactive template. , 2013, Chemical communications.

[34]  Siwen Wang,et al.  Catalytic removal of gaseous unintentional POPs on manganese oxide octahedral molecular sieves , 2013 .

[35]  B. Wen,et al.  Synthesis and growth mechanism of 3D α-MnO2 clusters and their application in polymer composites with enhanced microwave absorption properties , 2013 .

[36]  M. Tadé,et al.  Different crystallographic one-dimensional MnO2 nanomaterials and their superior performance in catalytic phenol degradation. , 2013, Environmental science & technology.

[37]  Dongyan Li,et al.  Synthesis of Hierarchical Hollow MnO2 Microspheres and Potential Application in Abatement of VOCs , 2013 .

[38]  F. Tao,et al.  Catalytic Performance and in Situ Surface Chemistry of Pure α-MnO2 Nanorods in Selective Reduction of NO and N2O with CO , 2013 .

[39]  Yuying Zheng,et al.  Transition metal doped cryptomelane-type manganese oxide for low-temperature catalytic combustion of dimethyl ether , 2013 .

[40]  Yuping Duan,et al.  A theoretical study of the dielectric and magnetic responses of Fe-doped α-MnO2 based on quantum mechanical calculations , 2013 .

[41]  A. Hirata,et al.  Enhanced supercapacitor performance of MnO2 by atomic doping. , 2013, Angewandte Chemie.

[42]  Biao Zhang,et al.  Mechanisms of capacity degradation in reduced graphene oxide/α-MnO2 nanorod composite cathodes of Li–air batteries , 2013 .

[43]  Shuqing Li,et al.  Novel microwave dielectric response of Ni/Co-doped manganese dioxides and their microwave absorbing properties , 2012 .

[44]  Y. Matsushita,et al.  High-pressure synthesis, crystal structure, and electromagnetic properties of CdRh2O4: an analogous oxide of the postspinel mineral MgAl2O4. , 2012, Inorganic chemistry.

[45]  H. Hng,et al.  Oxidation-etching preparation of MnO2 tubular nanostructures for high-performance supercapacitors. , 2012, ACS applied materials & interfaces.

[46]  P. Smirniotis,et al.  Nickel-doped Mn/TiO2 as an efficient catalyst for the low-temperature SCR of NO with NH3: Catalytic evaluation and characterizations , 2012 .

[47]  Z. Jia,et al.  Influence of Fe-doping on the microstructure and electromagnetic performance of manganese oxides , 2012 .

[48]  Li Lu,et al.  Hydrothermal synthesis of MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath hierarchy architecture for supercapacitors , 2012, Nanoscale Research Letters.

[49]  Aimee M. Morey,et al.  Characterization of the Fe-Doped Mixed-Valent Tunnel Structure Manganese Oxide KOMS-2 , 2011 .

[50]  Yitai Qian,et al.  Fabrication of γ-MnO2/α-MnO2 hollow core/shell structures and their application to water treatment , 2011 .

[51]  Xin Zhang,et al.  Morphology-Controlled Synthesis and Novel Microwave Absorption Properties of Hollow Urchinlike α-MnO2 Nanostructures , 2011 .

[52]  Kuei-Hsien Chen,et al.  Reversible phase transformation of MnO2 nanosheets in an electrochemical capacitor investigated by in situ Raman spectroscopy. , 2011, Chemical communications.

[53]  Lei Jin,et al.  Titanium Containing γ‐MnO2 (TM) Hollow Spheres: One‐Step Synthesis and Catalytic Activities in Li/Air Batteries and Oxidative Chemical Reactions , 2010 .

[54]  Xiong Zhang,et al.  Solution-combustion synthesis of ε-MnO2 for supercapacitors , 2010 .

[55]  Jie Yuan,et al.  Dual nonlinear dielectric resonance and nesting microwave absorption peaks of hollow cobalt nanochains composites with negative permeability , 2009 .

[56]  Youzhong Dong,et al.  Preparation and electrochemical performance studies on Cr-doped Li3V2(PO4)3 as cathode materials for lithium-ion batteries , 2009 .

[57]  Shuang Cheng,et al.  Nanoparticles and 3D sponge-like porous networks of manganese oxides and their microwave absorption properties , 2009, Nanotechnology.

[58]  T. Pal,et al.  A Green Chemistry Approach for the Synthesis of Flower-like Ag-Doped MnO2 Nanostructures Probed by Surface-Enhanced Raman Spectroscopy , 2009 .

[59]  Fei Teng,et al.  Effect of Phase Structure of MnO2 Nanorod Catalyst on the Activity for CO Oxidation , 2008 .

[60]  J. Pereira‐Ramos,et al.  Doping effects on structure and electrode performance of K-birnessite-type manganese dioxides for rechargeable lithium battery , 2008 .

[61]  Wensheng Yang,et al.  Synthesis and characterization of α-MnO2 nanowires: Self-assembly and phase transformation to β-MnO2 microcrystals , 2008 .

[62]  L. Zhen,et al.  Resonance-antiresonance electromagnetic behavior in a disordered dielectric composite , 2007 .

[63]  M. Iliev,et al.  Structural, transport, magnetic properties and Raman spectroscopy of orthorhombic Y1−xCaxMnO3 (0≤x≤0.5) , 2004, cond-mat/0408360.

[64]  Liangbing Hu,et al.  The effects of Jahn–Teller distortion changes on transport properties in LaMn1−xZnxO3 , 2003 .

[65]  A. Aharoni Exchange resonance modes in a ferromagnetic sphere , 1991 .