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Rational design of interfacial bonds within dual carbon-protected manganese oxide towards durable aqueous zinc ion battery

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Science China Chemistry 2023年第5期66卷 1406-1416页

作者： Xiuli Guo Chunguang Li Xiyang Wang Zhenhua Li Hui Zeng Pan Hou Minggang Xie Yuxin Li Zhan Shi Shouhua Feng State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of ChemistryJilin UniversityChangchun 130012China Department of Mechanical and Mechatronics Engineering Waterloo Institute for NanotechnologyMaterials Interface FoundryUniversity of WaterlooWaterlooOntario N2L 3G1Canada

manganese-based cathode materials are promising candidates for aqueous zinc ion batteries(AZIBs)by reason of their low cost and high energy density.However,their practical applicability is hampered by the intrinsic defects of poor electrical conductivity,sluggish reaction kinetics,and severe structural deterioration.Herein,we constructed a hierarchically porous structure composed of carbon-encapsulated Mn O nanoparticles(MOC)and three-dimensional(3D)nitrogen-doped graphene aerogel(NGA)(denoted as MOC@NGA).The hybrid was synthesized by a facile in-situ coprecipitation and annealing of manganesebased metal-organic framework(Mn-MOF74)and NGA composite(Mn-MOF74@NGA).Specifically,the carbon shells inherited from organic ligand of Mn-MOF74 could restrain the volume changes of Mn O,and the porous NGA prevented the agglomeration of MOC nanoparticles and enriched the types of interfacial chemical bonds.Profiting from the synergistic effect of rich interface chemical bonds and dual-carbon protection,the MOC@NGA hybrids exhibit fast interfacial electron/charge transfer and transport,and outstanding structural stability.Therefore,MOC@NGA cathode delivers an excellent rate performance(270 and 99.8 m Ah g^(-1)at 0.1 and 2.0 A g^(-1))and maintains an excellent specific capacity of 151.6 m Ah g^(-1)after 2,000cycles at 1.0 A g^(-1).Moreover,the fabricated MOC@NGA-based quasi-solid-state battery not only achieves outstanding flexibility but also displays impressive cycling stability,demonstrating a promising potential for portable and flexible equipment.This work provides a feasible strategy for the fabrication of the bridging structure of manganese-based oxides and porous carbon matrix for high-specific capacity and durable AZIBs cathodes.

关键词： manganese oxide interfacial chemical bonds carbon modification aqueous zinc ion batteries

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含双晶格氧的无定形锆掺杂锰氧化物选择性高效氧化5-羟甲基糠醛为2,5-呋喃二羧酸

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Science China Materials 2023年第5期66卷 1829-1836页

作者：温永霖贺来冉李虎韩昀晖张一鸣庄赞勇于岩 College of Materials Science and Engineering Fuzhou UniversityNew CampusFuzhou 350108China Key Laboratory of Advanced Materials Technologies Fuzhou UniversityFuzhou 350108China

晶格氧介导的氧化还原反应可以将有机物选择性氧化为高附加值产物,是实现生物质资源高值化利用的重要途径.其关键科学难题在于:如何使催化材料同时具有较低的晶格氧(O_(L))结合能以产生活性O_(L),以及较高的O_(L)结合能以保持其在催化... 详细信息

晶格氧介导的氧化还原反应可以将有机物选择性氧化为高附加值产物,是实现生物质资源高值化利用的重要途径.其关键科学难题在于:如何使催化材料同时具有较低的晶格氧(O_(L))结合能以产生活性O_(L),以及较高的O_(L)结合能以保持其在催化过程中的结构稳定性.在本工作中,我们制备了无定形锆掺杂的锰氧化物(amor-Zr:MnO_(x))催化材料,并证实其同时具有高活性的O_(L)以及高稳定性的O_(L).以5-羟甲基糠醛(HMF)的选择性氧化为反应模型,amor-Zr_(0.2)MnO_(x)催化剂实现了HMF的高效选择性氧化,产物中2,5-呋喃二甲酸(FDCA)的选择性高达99%,1小时内FDCA产率高达3600μmol_(FDCA)g_(cat)^(-1)h^(-1),在类似反应条件下其性能优于大多数Mn基和相关过渡金属氧化物基催化材料.实验和理论研究表明,amor-Zr:MnO_(x)的优异性能源于其同时含有两种O_(L).首先,锆提高了锰相邻的O_(L)的氧化活性,并促进了反应后氧空位对O_(2)的吸附/活化,获得活性O_(L)且同步促进催化反应中O_(L)的再生;锆相邻的O_(L)具有较低的反应活性,有利于催化材料保持结构稳定性.本工作有望为理解晶格氧的氧化机制以及高活性催化材料的设计提供思路.

关键词： dual lattice oxygens selective oxidation reaction biomass transformation amorphous catalyst manganese oxide

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manganese oxide and derivative-modified materials in advanced oxidation processes:A review of modification enhancement and activation mechanisms

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Chinese Chemical Letters 2024年第3期35卷 40-51页

作者： Si Sun Shuang Song Shuai Yang Yong-Li He Yang Shi Peng Zhou Zhao-kun Xiong Yang Liu Heng Zhang Ye Du Chuan-Shu He Bo Lai State Key Laboratory of Hydraulics and Mountain River Engineering College of Architecture and EnvironmentSichuan UniversityChengdu 610065China Sino-German Centre for Water and Health Research Sichuan UniversityChengdu 610065China Institute of Fundamental and Frontier Sciences University of Electronic Science and Technology of ChinaSichuanChengdu 610054China

manganese oxides(MNO_(x)),as low-toxicity and high-abundance catalysts,have been demonstrated to hold great promise for application in advanced oxidation processes(AOPs).However,further application of this material is restricted due to its unsatisfactory oxidant activation efficiency.Fortunately,recently remarkable research on deep activation mechanisms and modification of MNO_(x)have been undertaken to improve its reactivity.Herein,modification enhancement mechanisms of MNO_(x)to efficiently degrade various organic contaminants were discussed and highlighted,including metal doping,coupling with other metal oxides,composite with carbonaceous material,and compounding with other support.The activation mechanisms of different MNO_(x)and derivative-modified material(such as doped MNO_(x),metal oxide-MNO_(x)hybrids,and MNO_(x)-carbonaceous material hybrids)were summarized in great details,which was specifically categorized into both radical and non-radical pathways.The effects of pH,inorganic ions,and natural organic matter on degradation reactions are also discussed.Finally,future research directions and perspectives are presented to provide a clear interpretation on the MNO_(x)initiated AOPs.

关键词： manganese oxide Derivative-modified materials Modification enhancement mechanisms Advanced oxidation process Activation mechanism

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Temperature-controlled fabrication of hydrophilic manganese oxide microspheres as high-performance electrode materials for supercapacitors

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Chinese Chemical Letters 2023年第5期34卷 516-520页

作者： Yuchen Wang Yaoyu Liu Ahsan Ejaz Kai Yan Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology School of Environmental Science and EngineeringSun Yat-sen UniversityGuangzhou 510275China Department of Civil Engineering Mirpur University of Science and TechnologyAJKMirpur 10250Pakistan

The supercapacitive properties of manganese oxides(MnO_(x))are strongly affected by their crystal structure.Nevertheless,the relationship between the crystal structure and supercapacitive performance of Mn O_(x)is elusive.Herein,a temperature-controlled fabrication method was developed to achieve MnO_(2),Mn_(3)O_(4),MnO and Mn_(2)O_(3)microspheres with various crystal structure as electrode materials tunable for supercapacitors.The detailed material and electrochemical characterizations revealed the structureactivity relationship of Mn O_(x)microspheres by systematically investigating the effect of valence state,specific surface area,conductivity and morphology on supercapacitive performance.Among these MnO_(x)materials,nanoneedle-like Mn O_(2)delivered a relatively high specific capacitance of 274.1 F/g at 1 A/g due to a high Mn valence state of+4,a large specific surface area of 113.4 m^(2)/g and a desirable electronic conductivity of 1.73×10^(-5)S/cm.Furthermore,MnO_(2)presented a remarkable cycle stability with 115%capacitance retention after 10,000 cycles owing to the enhancement of wettability.This work not only provides a facile strategy to modulate MnO_(x)crystal structure,but also offers a deep understanding of structure-dependent supercapacitive performance of MnO_(x).

关键词： Temperature-controlled manganese oxide Microsphere Supercapacitors Hydrophilic

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Recent advances in water-splitting electrocatalysts based on manganese oxide

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Carbon Resources Conversion 2019年第3期2卷 242-255页

作者： Vijay SKumbhar Hyeonkwon Lee Jaeyoung Lee Kiyoung Lee School of Nano&Materials Science and Engineering Kyungpook National University2559 Gyeongsang-daeroSangjuGyeongbukSouth Korea Research Institute of Environmental Science&Technology Kyungpook National University80 Daehak-roBuk-guDaeguSouth Korea School of Earth Sciences and Environmental Engineering Ertl Center for Electrochemistry and CatalysisGwangju Institute of Science and Technology(GIST)Gwangju 61005South Korea

The oxygen evolution reaction(OER)of electrochemical water splitting represents a source of hydrogen(H_(2))energy.Precious-metal-based RuO_(x)and IrO_(x)are expensive and degrade in the presence of electrolyte;thus,the development of low-cost and eco-friendly OER electrocatalysts is needed.This review summarizes the recent status of the nonprecious manganese metal-oxide-based electrocatalysts with reference to nanostructure,defect engineering,hybrid composite formation,and core-shell formation to achieve efficient OER performance.In particular,we focus on the strategies used to lower the onset potential and the Tafel slope of the water oxidation process.Future prospects for the development of manganese-oxide-based electrocatalysts are discussed.

关键词： Hydrogen energy manganese oxide Oxygen evolution reaction Nanostructures,Core-shell

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Supported manganese oxide on Graphite oxide: Catalytic Oxidation of Nitrogen oxide in Waste Gas

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Journal of Donghua University(English Edition) 2015年第1期32卷 103-108页

作者：吕伟段元东孙秀枝李登新 College of Environmental Science and Engineering Donghua University

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.

关键词： peroxymonosulfate(PMS) manganese oxide graphite oxide nitrogen oxide(NO)

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Encapsulating manganese oxide nanoparticles within conducting polypyrrole via in situ redox reaction and oxidative polymerization for long-life lithium-ion batteries

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Rare Metals 2021年第9期40卷 2415-2423页

作者： He-Liang Yao Shan-Shan Gao Zheng-Qian Fu Wei-Chao Bao Zhong-Hui Cui Yi-Qiu Li Fang-Fang Xu State Key Laboratory of High Performance Ceramics and Superﬁne Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China

manganese oxides(MnO_(x)) have been extensively investigated due to their extremely high theoretical capacities for application as conversion anodes in lithiumion batteries. However, fully performing their theoretical performance still faces poor electric conductivity and serious volume change upon lithium insertion/extraction.Herein, we demonstrate encapsulating manganese oxide nanoparticles within a conducting polymer polypyrrole(PPy) shell as a facile strategy to overcome such flaws through in situ redox reaction and oxidative polymerization process. Such an in situ method combines the redox reaction between potassium permanganate and tetrahydrofuran to form MnO_(x)nanoparticles and the subsequent oxidative polymerization of pyrrole to form a conductive polypyrrole coating shell by the oxidant KMnO_(4) into one step. For the as-fabricated products(MnO_(x)@PPy), this tenderly introduced conductive PPy shell highly favors the fast electron transfer and preserves the electrode structure integrity upon repeated cycling. As the anode for LIBs, MnO_(x)@PPy exhibits superior lithium storage performance with a high reversible capacity(1538 mAh·g^(-1)), long-life cyclability(747 mAh·g^(-1) after 1000 cycles at 1.0 C) and durable ratability(574 mAh·g^(-1) at 2.0 C). This work demonstrates that the convenient in situ strategy to form conductive polymer coating shell is effective to improve the performance of conversion anodes and can be extended to other materials for energy storage applications.

关键词： manganese oxide Polypyrrole High cycling performance Lithium-ion battery

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Introduction of manganese oxide into Carbon Nanotubes for the Potential Applications as a Contrast Medium

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沈阳建筑大学学报（自然科学版） 2010年第6期26卷 1151-1154页

作者：佟钰 School of Materials Science and Engineering Shenyang Jianzhu University

manganese compound with evident toxicity is widely employed as the contrast medium for clinicalexaminations such as magnetic resonance imaging(MRI).In the present work,a feasible way with the applica-tion of vacuum impregnation and rotary evaporation was proposed to introduce manganese chloride hydrate intothe inner cavities of template - synthesized carbon nanotubes(CNTs),and then a process of alkali treatmentwas used to liberate the loaded CNTs from the template.It is notable that the alkali attack in the presence ofresidual oxygen also resulted in a series of changes in chemical compositions of guest substances,and the ulti-mate compound of manganese was found to be manganese oxide(Mn3O4) by X-ray diffraction and transmissionelectron microscopy.Determinations of energy dispersive spectrum under scanning electron microscopy showeda high-content filling(more than 50 wt%) of Mn3O4 in the loaded CNTs.This work developed a feasible andconvenient way for the encapsulation of guest substances to reduce bio-toxic effects.

关键词： carbon nanotube(CNT) manganese oxide template synthesis filling contrast medium

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Carbon-spheres-supported manganese oxide as highly efficient electrocatalyst for oxygen reduction reaction in alkaline fuel cell

Carbon-spheres-supported manganese oxide as highly efficient...

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第30届全国化学与物理电源学术年会

作者：高海玲秦学天津大学理学院化学系

Carbon spheres which own excellent activity are considered to be one of the most ideal catalyst support and have been widely used in alkaline fuel cell.In this paper,carbon spheres(CS) with BET surface area 1110 mg have been synthesized from sucrose in HSO solution by reflux-calcinations method.Hydrothermally-synthesized carbon spheres(HCS) are prepared by autoclave method.manganese oxide supported on those carbon spheres via impregnation method and denoted as MnO/CS and MnO/HCS respectively.

关键词： Carbon spheres manganese oxide oxygen reduction reaction alkaline fuel cell

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Development of LnMnO_(3+σ) perovskite on low temperature Hg0 removal

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Journal of Environmental Sciences 2022年第3期34卷 141-151页

作者： Qicheng Shen Jiacheng Zhou Chenglong Ma Jie Yang Limei Cao Ji Yang School of Resources and Environmental Engineering State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical ProcessEast China University of Science and TechnologyShanghai 200237China Shanghai Institute of Pollution Control and Ecological Security Shanghai 200092China

LnMnO_(3+σ)(Ln=La,Pr,Nd,Sm,Eu,Gd or Dy)perovskites synthesized by sol-gel method were employed for gaseous elemental mercury(Hg^(0))removal from coal-fired flue gas.Characterization results revealed the structure of the perovskites presented a phase transition process from rhombohedral system to O-and O'-orthorhombic structure with the change of A-site rare earth elements.The perovskites showed satisfactory Hg^(0) removal capacity in a narrow temperature range of 100-150℃.NdMnO_(3+σ) with an O-O'orthorhombic structure presented the best Hg^(0) removal performance,which markedly depends on four factors:crystal structure,oxygen vacancy density,Mn^(4+)/Mn^(3+) ratio and surface element segregation.The Hg^(0) removal mechanism was illustrated based on the mercury temperature programmed desorption experiment and X-ray photoelectron spectroscopy characterization.Both chemisorption and catalytic oxidation played a role in the Hg^(0) removal process.Chemisorption dominated the Hg^(0) removal,due to the slow catalytic oxidation rate at low temperature.This work preliminarily established the relation between the structure of rare earth manganese perovskite and Hg^(0) removal performance.

关键词： Hg^(0)removal manganese oxide Perovskite Rare earth element

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