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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

Hydrothermal synthesis of MWCNT/Ni-Mn-S composite derived from bimetallic MOF for high-performance electrochemical energy storage

Yanrui Hao,Hao Guo,Fan Yang,Junye Zhang,Ning Wu,Mingyue Wang,Cuiliu Li,Wu Yang

Multi-walled carbon nanotube (MWCNT)/Ni-Mn-S composites are derived from MWCNT/Ni/Mn bimetallic metal-organic framework (MOF) for supercapacitor electrodes. Electroconductive MWCNT is introduced into Ni-Mn-S to form a three-dimensional interconnected structure due to the covalent interaction between Ni atoms and C atoms. During energy storage, MWCNT serves as miniature current collector to shorten pathway of electron collection and transmission. In addition, S 2- etching agent with Kirkendall effect makes edges and surfaces of the resulted sulfide structures rougher provide more active sites and improves electrochemical performance compared with precursors. By finely adjusting Ni/Mn molar ratio, the prepared MWCNT/Ni-Mn-S composite achieves excellent properties. As-prepared MWCNT/Ni-Mn-S(3:2) exhibits high specific capacitance of 1041 mAh g −1 at 1 A g −1 and good cyclic stability. The capacitance retention reaches 83.3% after 10,000 cycles. The assembled MWCNT/Ni-Mn-S(3:2)//AC hybrid supercapacitor (HSC) also shows high energy density of 25.33 Wh Kg −1 at power density of 829 W Kg −1 and outstanding cycling stability (93.3% after 20,000 cycles), which illustrates MWCNT/Ni-Mn-S(3:2) has important potential in supercapacitor.

CAS / MDL: 308068-56-6
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BIOSENSORS & BIOELECTRONICS · 2022 · IF 12.545

The Mn-modified porphyrin metal-organic framework with enhanced oxidase-like activity for sensitively colorimetric detection of glutathione

Xiang Lai,Yue Shen,Shoubei Gao,Yajing Chen,Yanshuai Cui,Dongxue Ning,Xianbing Ji,Zhiwei Liu,Longgang Wang

The selective detection of glutathione (GSH) has been used as important colorimetric probe for human health. Herein, we used a facile method to synthesize manganese ions modified porphyrin metal-organic framework (PCN-224-Mn) with a size of 125.7 ± 14.2 nm and zeta potential of −3.9 ± 0.5 mV. We showed that PCN-224-Mn catalyzed oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in the absence of H 2 O 2 , resulting in a blue-colored oxidized TMB (oxTMB) that exhibits oxidase-like activity. Furthermore, a simple colorimetric detection method for GSH was developed based on the oxidase-like activity of PCN-224-Mn. This method shows wide linear detection range of 0.5–60 μM for GSH with a much lower detection limit of 0.233 μM. Finally, the recovery of colorimetric sensor of PCN-224-Mn suggests its great potential as a biosensor. As the catalytically active site, the manganese porphyrin unit plays a major role in the oxidase-like property and detection ability of PCN-224-Mn. Our data suggest that GSH detection method using PCN-224-Mn has great potential in multiple applications in the future.

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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2022 · IF 7.139

Self-template synthesis of lychee like Mn-doped Co2P yolk-shell spheres for enhanced hydrogen evolution reaction activity

Zhijie Zhang,Simin Chen,Sipeng Chen,Zeyu Yuan,Yanxiong Fang,Dai Dang,Yuying Zheng

Designing an electrocatalyst for hydrogen production from water splitting that is highly efficient, stable, and free of noble metals is necessary but challenging. The phosphorus compound is considered a viable candidate for producing hydrogen from water split, but its electrocatalytic performance needs further improvement. Herein, we present an easy and straightforward method for constructing Mn-doped Co 2 P yolk-shell lychee spheres. The Co nano prisms are used as a self-sacrificing template to conduct an ion exchange reaction with manganese ions, constructing Co oxide yolk-shell spheres with Mn–Co hydroxide nano-blocks. After in-suit phosphating at low temperature, Mn-doped Co 2 P with yolk-shell structure and lychee morphology is formed. The Mn-doped Co 2 P with an optimized Mn and Co molar ratio (0.125) exhibits excellent hydrogen evolution performance in alkaline and acidic electrolyte. The overpotentials can reach 10 mA cm −2 at 98 mV and 72 mV, respectively, and the Mn–Co 2 P-0.125 catalyst has faster electron transfer efficiency and larger electrochemically active surface area. The experimental results ascertain that doping an appropriate amount of Mn significantly changes the morphology and structure, thereby affecting the exposure of active sites, and modulating the electronic structure around Co 2 P. Under the dual regulation of morphology and electronic structure, the electrocatalytic process is accelerated, enhancing its catalytic activity .

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JOURNAL OF THE AMERICAN CERAMIC SOCIETY · 2022 ·Vol. 106 ·期 1 ·513-526 · IF 4.186

Mn ions-activated Gd3(Al,Ga)5O12 garnet solid-solution ceramics: Cation substitution for dual wavelength red-emission

Bingheng Sun,Benxue Jiang,Jintai Fan,Le Zhang,Long Zhang

Red-emitting color-convertors have attracted considerable attention for promising applications in solid-state lighting (SSL) to improve color rendition. However, the current nitride and fluoride phosphor powders have encountered several challenges, such as high cost, narrow emission bands, and insufficient stability during operation, which limit the development of high-power full-spectrum SSL. In this study, thermally robust Gd 3 (Al,Ga) 5 O 12 :Mn (GAGG:Mn) solid-solution ceramics (SSCs) with dual wavelength red-emission bands were prepared via an oxygen solid-state sintering reaction. The doped Mn ions occupied octahedral Al 3+ and Ga 3+ sites to generate Mn 4+ luminescent centers with pronounced deep-red emissions peaking at 698 nm ( 2 E → 4 A 2 ), and Mn 2+ luminescent centers with broad red emissions at 628 nm ( 4 T 1 → 6 A 1 ). Because the cationic radius matching effect induced the regulation of valence state of Mn, the photoluminescence of the GAGG:Mn SSCs can be tailored by the substitution of Al 3+ with Ga 3+ . Moreover, the Mn 3+ also existed in the GAGG lattice host, and their concentration decreased with increasing Ga 3+ contents owing to the mismatch of ionic radius between Mn 3+ and Ga 3+ ions. With the optimization of Al/Ga ratio and concentration of Mn ions, a broad emission band ranging from 550 to 800 nm (bandwidth = 250 nm) was achieved from Gd 3 Al 3 Ga 2 O 12 :0.3%Mn SSCs upon 465-nm excitation. Moreover, the GAGG:Mn SSC has over 17-fold enhanced thermal conductivity compared with the corresponding phosphor powder. This paper opens a door of regulating the valence state of luminescence centers with cation substitution and the application of oxide red-emitting color-convertors.

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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2022 · IF 7.139

In-situ construction of Mn–Fe mixed oxides nanoparticles on reduced graphene oxide with superior lithium storage property

Huaiyang Chen,Xiaoping Shen,Zhenyuan Ji,Jia Cheng,Guangxiang Liu,Leiming Lang,Yao Chen

In this paper, porous Mn 3 O 4 –Fe 3 O 4 nanoparticles with highly uniform composition are in-situ anchored on reduced graphene oxide (rGO) nanosheets by a simple cyanometallic framework template method . Thanks to the synergistic effects between the porous Mn 3 O 4 –Fe 3 O 4 nanoparticles and the well-conductive rGO nanosheets, the Mn 3 O 4 –Fe 3 O 4 /rGO composites present superior electrochemical lithium storage performances with a great reversible capacity of 1013 mAh g −1 after 100 cycles at 0.1 A g −1 , satisfactory rate capability of 510 mAh g −1 at 3.0 A g −1 , and eminent long-term cycle stability of 804 mAh g −1 after 500 cycles at 0.5 A g −1 . It is demonstrated that the rGO can not only act as a conducting matrix, but also buffer the volume expansion and avoid the aggregation of the Mn 3 O 4 –Fe 3 O 4 nanoparticles during charging-discharging. The work provides a simple strategy for designing and fabricating advanced multi-component metal oxide-based anodes for high-performance lithium-ion battery.

CAS / MDL: 7782-42-5
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ADVANCED FUNCTIONAL MATERIALS · 2022 ·Vol. 32 ·期 34 ·2204499 · IF 19.924

Oxygen Vacancy-Induced Dielectric Polarization Prevails in the Electromagnetic Wave-Absorbing Mechanism for Mn-Based MOFs-Derived Composites

Yue Liu,Xinfeng Zhou,Zirui Jia,Hongjing Wu,Guanglei Wu

Polymeric metal-organic framework (MOF)-derived composites are promising functional materials because of their exceptional chemical homogeneity, designable components, and adjustable pore size. The modulation of oxygen and Mn vacancies via the introduction of heteroatoms and changes in the annealing temperature in MOFs-derived composites can be a possible solution to investigate the polarization loss mechanism, which facilitates the improvement of electromagnetic loss capacity. Herein, the design of laminate-stacked sphere-shaped trimetallic CoNiMn-MOFs is presented. The derived CoNi/MnO@C composites retain the original topography of the MOFs. The concentration of oxygen vacancies increases with the incorporation of heteroatoms, but decreases with annealing temperature, which prevails in the polarization loss mechanism rather than the contribution of Mn 2+ vacancies and heterogeneous interfaces. Therefore, the minimum reflection loss of the CoNi/MnO@C sample demonstrates −55.2 dB at 2.6 mm and the broad effective absorption bandwidth reaches 8.0 GHz at 2.1 mm. This work is expected to provide meaningful insights into the significant effect of ion vacancy modulation on the EM wave-absorbing performance of Mn-based MOFs-derived composites.

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ACS Applied Energy Materials · 2021 · IF 6.024

Particle Size and Particle-Size Distribution Effects on Li+ Extraction/Insertion Kinetics for Li-Rich Mn-Based Oxides

Zhitang Fang,Wanyun Li,Bangchuan Zhao,Jin Bai,Kunzhen Li,Hongyang Ma,Xuebin Zhu,Yuping Sun

A series of Li-rich Mn-based layered material Li1.2Ni0.13Co0.13Mn0.54O2 (LMR) with different particle sizes and particle-size distributions (PSDs) have been successfully synthesized via a combustion method using different manganese sources. The particle size of the N-LMR material prepared using Mn(NO3)2·4H2O as the manganese source is the smallest, and its PSD range is the narrowest among all of the samples. The unique particle size and PSD have a great influence on the electrochemical kinetics of Li-ion extraction/insertion reactions, leading to enhanced electrochemical performance when used as a cathode material for both the half and full Li-ion cells, especially the specific charge capacity at high current rates. The value of the charge specific capacity will determine the state of charge at the initial discharge stage and then influence the discharge process of these Li-rich Mn-based oxides. The N-LMR electrode delivers an initial discharge capacity of 309.2 mA h g–1 at 0.1C, and the specific capacity can reach up to 208.1 mA h g–1 at 1C. After 140 cycles, the electrode can still maintain 95.6% of its initial specific capacity at 1C. Moreover, the material displays a superior high-temperature lithium storage property at 55 °C and the full cells using N-LMR as the cathode material also show a much better electrochemical performance.

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ELECTROCHIMICA ACTA · 2021 · IF 6.901

Elucidating the effect of Nb doping on the electrochemical performance of Fe–Mn based Li-rich cathode materials

Chen Hou,Yi-Ran Xing,Le-Le Yu,Yong-Heng Si,Han Lu,Yu-Juan Zhao

Fe–Mn based Li-rich cathode materials are regarded as one of the most promising cathode materials for their low cost and high energy density but possess drawbacks such as high oxygen release, low conductivity, and slow kinetics for lithium-ion transport. To address these issues, herein, we proposed a high-valance cations Nb 5+ doping strategy and synthesized a series of Li 1.26 [Fe 0.22 Mn 0.52 ] 1−x Nb 0.74x O 2 ( x  = 0, 0.02, 0.03, 0.04) cathode materials. Using a combination of experimental approaches and density functional theory (DFT) calculations, we found that the doped samples presented expanded interlayer spacing for Li-ion migration and better structural stability due to the large ionic radius of Nb 5+ and the strengthened Nb–O bond. Moreover, Nb doping could not only decrease the band gap and the density of states of the O 2p band but also contribute extra electrons to surrounding O atoms, thereby enhancing electronic conductivity and stabilizing lattice oxygen. Benefit from the underlying mechanisms mentioned above, the Nb 0.022 sample possessed a higher Coulombic efficiency (71.1 vs 65.0%) at 0.2 C, showing more stable cycling performance (90.4 vs 67.7 mAh g −1 ) at 0.5 C and rate capability. These favorable results can assist in the development of Fe–Mn based Li-rich cathode materials with excellent electrochemical properties.

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Biomaterials Science · 2021 ·Vol. 9 ·期 20 ·6830-6841 · IF 6.843

Transdermal delivery of multifunctional CaO2@Mn-PDA nanoformulations by microneedles for NIR-induced synergistic therapy against skin melanoma

Liming Ruan,Gao Song,Xueya Zhang,Tianqi Liu,Yanfang Sun,Junlan Zhu,Zhiyong Zeng,Guohua Jiang

The development of multifunctional nanoformulations (NFs) include several features in a single nanosystem for these devices to overcome the disadvantages of inefficiency and undesirable toxicity of traditional therapies and provide new opportunities in the management of tumors. Herein, multifunctional CaO2@Mn-PDA NFs with a core–shell structure, integrating the photothermal conversion properties of Mn-PDA, the chemodynamic properties of doped Mn ions, and relieving hypoxia in the tumor microenvironment (TME) were developed. The as-fabricated CaO2@Mn-PDA NFs were embedded in microneedles (MNs) for transdermal delivery into tumor sites, leading to the generation of a new minimally invasive and synergistic therapeutic strategy against skin melanoma. Under near-infrared (NIR) light irradiation, the CaO2@Mn-PDA NFs exhibited a synergistic therapeutic effect, including photothermal therapy (PTT), chemodynamic therapy (CDT), and modulating hypoxia due to their high photothermal conversion efficiency, boosted intracellular production of reactive oxygen species, excellent chemodynamic reactions, etc. Therefore, the developed MN platform, which can build implanted multifunctional characteristics for on-demand NIR-induced synergistic therapy, have a bright future in tumor suppression.

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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

SiC/Mn co-doped CaO pellets with enhanced optical and thermal properties for calcium looping thermochemical heat storage

Boyu Li,Yingjie Li,Yehui Dou,Yuzhuo Wang,Jianli Zhao,Tao Wang

To achieve high heat storage capacity, excellent mechanical, optical and thermal properties in calcium looping thermochemical heat storage, the novel SiC/Mn co-doped CaO pellets were fabricated by the extrusion-spheronization method. The heat storage performances of the novel CaO pellets were studied under harsh calcination (pure CO 2 , 950 °C) and pressurized carbonation (pure CO 2 , 13 bar, 800 °C) conditions in a dual fixed-bed reactor system. The additions of SiC and Mn enhance the cyclic stability of CaO pellets during the multiple heat storage cycles. When the mass ratio of CaO:SiC:MnO 2 is 100:5:5, the co-doped CaO pellets exhibit an excellent heat storage performance. The effective conversion and heat storage density of the co-doped CaO pellets are 41.5% higher than those of original CaO pellets, respectively. Meanwhile, the co-doped CaO pellets possess a good optical absorption capacity and a high thermal conductivity , which are 17.6 and 3.2 times as high as those of original CaO pellets, respectively. In addition, the co-doped CaO pellets show much higher crushing strength and lower weight loss during the attrition test. The stronger interaction between SiC and CaO cluster mitigates the movement of CaO, which is determined by density functional theory simulation. The adsorption of CO 2 onto the CaO surface is enhanced by the addition of Mn. Therefore, SiC/Mn co-doped CaO pellets used in the calcium looping thermochemical heat storage process appear promising.

CAS / MDL: 6156-78-1 409-21-2
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Simultaneous adsorption and oxidation of para arsanilic acid by a highly efficient nanostructured Fe-Ti-Mn composite oxide

Wei Zhang,Wei Liu,Guoliang Li,Wei Du,Jianbo Lu,Jianguo Song,Qixia Yang,Xiangming Li,Huizhong Xu,Xu He,Jun Ma

The para arsanilic acid ( p -ASA) used as feed additive in the poultry and swine industries tends to transform into more toxic inorganic arsenic (As(V) and As(III)), leading to a greater risk to human health and environmental system. In this study, simultaneous adsorption and oxidation of p -ASA was achieved by a synthesized highly efficient nanostructured Fe-Ti-Mn composite oxide (FTMO), with a high specific surface area of 424.7 m 2 /g. The maximum adsorption capacity for p -ASA could be as high as 45.6 mg/g, meanwhile the combined oxidation/photo-oxidation processes led to the formation of intermediate containing hydrazine group, however, without release of toxic inorganic As(III) and As(V). The p -ASA adsorption by FTMO was verified as the chemisorption process with the formation of inner-sphere complexes at the solid/water interface, which was prominently influenced by solution pH, coexisting ions and humic acid, however relatively insensitive to ionic strength. The systematic characterization by FTIR, XPS, EPR and XANES revealed that Fe phase of FTMO played the dominant role for p -ASA adsorption, while Mn and Ti phases were responsible for the oxidation and photo-oxidation of p -ASA, respectively.

CAS / MDL: 3317-61-1 2564-83-2
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Metals · 2020 ·Vol. 10 ·期 12 ·1574 · IF 2.117

Effect of Mischmetal Introduction on Hydrogen Storage Properties in Impure Hydrogen Gas of Ti-Fe-Mn-Co Alloys

Ruochen Shen,Chaohui Pu,Xiaoou Xu,Youpeng Xu,Zhilin Li,Zhu Wu

The research aims to study the effect of adding mischmetal (Mm) to the TiFe0.86Mn0.07Co0.07alloy on its hydrogen storage performance and cyclic stability. The results show that TiFe0.86Mn0.07Co0.07+ x% Mm (x = 0,4,6,8) alloys can be easily activated. The hydrogen absorption capacity of TiFe0.86Mn0.07Co0.07+ 4% Mm reaches 1.76 wt% (mass fraction) at 298 K. With the increase of Mm addition, the hydrogen storage capacity decreases slightly. Furthermore, after 40 absorption and desorption cycles in hydrogen containing 250 ppm O2, the alloy still has 36% of its initial hydrogen storage capacity, and the alloy can recover 93% of its hydrogen storage capacity through heat treatment.Keywords:TiFe hydrogen storage alloys;life test;impure hydrogen gas;cyclic stability

CAS / MDL: 103060-53-3 57-09-0
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