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Research progress of transition metal compounds as bifunctional catalysts for zinc-air batteries

Nano Research Energy 2024年第1期3卷 78-100页

作者： Yan Ran Changfan Xu Deyang Ji Huaping Zhao Liqiang Li Yong Lei Fachgebiet Angewandte Nanophysik Institut für Physik&IMN MacroNanoTechnische Universität IlmenauIlmenau 98693Germany Tianjin Key Laboratory of Molecular Optoelectronic Sciences Department of ChemistryInstitute of Molecular Aggregation ScienceTianjin UniversityTianjin 300072China

Zinc-air batteries(ZABs)are widely studied because of their high theoretical energy density,high battery voltage,environmental protection,and low price.However,the slow kinetics of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)on the air electrode limits the further application of ZABs,so that how to develop a cheap,efficient,and stable catalyst with bifunctional catalytic activity is the key to solving the development of ZABs.transition metal compounds are widely used as cathode materials for ZABs due to their low cost,high electrocatalytic activity,and stable structure.This review summarizes the research progress of transition metal compounds as bifunctional catalysts for ZABs.The development history,operation principle,and mechanism of ORR and OER reactions are introduced first.The application and development of transition metal compounds as bifunctional catalysts for ZABs in recent years are systematically introduced,including transition metal oxides(TMOs),transition metal nitrides(TMNs),transition metal sulfides(TMSs),transition metal carbides(TMCs),transition metal phosphates(TMPs),and others.In addition,the shortcomings of transition metal compounds as bifunctional catalysts for ZABs were summarized and reasonable design strategies and improvement measures were put forward,aiming at providing a reference for the design and construction of high-performance ZABs cathode materials.Finally,the challenges and future in this field are discussed and prospected.

关键词： transition metal compounds zinc-air batteries bifunctional catalysts electrochemical air electrode

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Physical and chemical origin of transition metal compounds counter electrode catalysts for dye-sensitized solar cells

Physical and chemical origin of transition metal compounds c...

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第三届新型太阳能电池学术研讨会

作者：云斯宁张太宏刘行刘艳芳孟胜西安建筑科技大学材料与矿资学院功能材料研究所中国科学院物理研究所北京凝聚态物理国家实验室

Up to now,almost all early transition metal compounds(TMCs) have been developed as counter electrodes(CEs) in dye-sensitized solar cells(DSSCs).Catalytic activity is determined by the electronic structure of the catalysts,however,the accurate relationship between the electronic structure and the catalytic activity remains unknown.Moreover,the superior catalytic activity of TMCs hybrids can be attributed to the synergistic effect.However,the function of each component in the hybrids remains unclear.It is difficult to predict the catalytic activity of different materials,and also no one knows which electronic structure of CE materials can make them exhibit superior catalytic performance.To overcome these challenges,we performed First-principle density functional theory(DFT) calculations,combined Car-Parrinello molecular dynamics(CPMD) simulations,which can explain why carbides have higher catalytic activity than oxides and nitrides,and why oxide-based hybrids is more efficient than carbide-based hybrids in DSSCs.These results are helpful to clarify the catalytic mechanism of TMCs as CE catalysts in DSSCs.

关键词： dye-sensitized solar cells transition metal compounds first-principle DFT calculations ab-initio Car-Parrinello molecular dynamics simulations

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First-principle calculations and molecular dynamics simulations of transition metal compounds catalysts for counter electrode of dye-sensitized solar cells

First-principle calculations and molecular dynamics simulati...

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第二届新型太阳能电池学术研讨会

作者：刘艳芳 Taihong Zhang Xiao Zhou Yuzhi Hou Wen Fang Jing Li 云斯宁西安建筑科技大学材料与矿资学院功能材料研究所

Recently, considerable attention have been paid to the novel dye-sensitized solar cells(DSSCs), which are based on transition metal compounds(TMCs) catalysts. TMCs catalysts exhibiting Pt-like catalytic activity showed a great development potential of the novel DSSCs. To clarify the mechanism of the catalytic performance in novel DSSCs, the first-principle density functional theory calculations(DFT) and the ab-initio Car-Parrinello molecular dynamics(CPMD) simulations were performed. The DFT-CPMD calculation provides a better understanding of the prominent catalytic properties of TMCs catalysts in novel DSSCs.

关键词： Dye-sensitized solar cells transition metal compounds first-principle density functional theory calculations ab-initio Car-Parrinello molecular dynamics

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Nucleation growth quenching for superior cluster catalysts

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Nano Research 2022年第9期15卷 7933-7939页

作者： Ruyue Wang Feng Cheng Yonggang Wang Dongyu Fan Bohan Deng Yuanzheng Long Haolin Tang Kai Huang Zhaowei Qu Ming Lei Binghui Ge Hui Wu State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of TechnologyWuhan 430070China State Key Laboratory of Information Photonics and Optical Communications School of ScienceBeijing University of Posts and TelecommunicationsBeijing 100876China State Key Laboratory of New Ceramics and Fine Processing School of Materials Science and EngineeringTsinghua UniversityBeijing 100084China Beijing Key Laboratory of Space-ground Interconnection and Convergence Beijing University of Posts and Telecommunications(BUPT)Beijing 100876China Information Materials and Intelligent Sensing Laboratory of Anhui Province Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of EducationInstitutes of Physical Science and Information TechnologyAnhui UniversityHefei 230601China

Cluster catalysts are rapidly growing into an important sub-field in heterogeneous catalysis,owing to their distinct geometric structure,neighboring metal sites,and unique electronic structure.Although the thermodynamics and kinetics of the formation of nanoparticles have been largely investigated,the precise synthesis of clusters in wet chemical methods still faces great challenges.In the study,a quenching strategy of asymmetric temperature in solution for the rapid generation of vacancy-defect rich clusters is reported.The quenching process can be used to synthesize multitudinous metal compound clusters,including metal oxides,fluorides,oxygen-sulfur compounds,and tungstate.For oxygen evolution reaction(OER),IrO_(2)clusters with abundant oxygen vacancies were obtained and uniformly dispersed in the solution.Compared to commercial IrO_(2),the prepared IrO_(2)cluster can be directly loaded on carbon paper and used as binder-free electrodes,which exhibit higher OER activity and long-term operational stability in alkaline electrolytes.The quenching strategy provides a simple and efficient method for the synthesis of clusters,which has tremendous potential for industrial-scale preparation and application,especially can be further applied to flow electrochemical generators.

关键词： rapid-chilling cluster structure transition metal compounds binder-free electrode oxygen evolution reaction

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Optimizing the electronic spin state and delocalized electron of NiCo_(2)(OH)_(x)/MXene composite by interface engineering and plasma boosting oxygen evolution reaction

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Journal of Energy Chemistry 2022年第8期31卷 129-140,I0004页

作者： Jingyao Xu Xia Zhong Xiaofeng Wu Ying Wang Shouhua Feng State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of ChemistryJilin UniversityChangchun 130012JilinChina Chinese Acad Sci Inst Met ResShenyang Natl Lab Mat SciShenyang 110016LiaoningChina Univ Sci&Technol China Sch Mat Sci&EngnShenyang 110016LiaoningChina State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022JilinChina

The electrocatalytic activity of transition-metal-based compounds is closely related to the electronic configuration.However,optimizing the surface electron spin state of catalysts remains a challenge.Here,we developed a spin-state and delocalized electron regulation method to optimize oxygen evolution reaction(OER)performance by in-situ growth of NiCo_(2)(OH)_(x) using Oswald ripening and coordinating etching process on MXene and plasma treatment.X-ray absorption spectroscopy,magnetic tests and electron paramagnetic resonance reveal that the coupling of NiCo_(2)(OH)_(x) and MXene can induce remarkable spin-state transition of Co^(3+)and transition metal ions electron delocalization,plasma treatment further optimizes the 3 d orbital structure and delocalized electron density.The unique Jahn-Teller phenomenon can be brought by the intermediate spin state(t2 _(g)^(5) e_(g)^(1))of Co^(3+),which benefits from the partial electron occupied egorbitals.This distinct electron configuration(t2_(g)^(5) e_(g)^(1))with unpaired electrons leads to orbital degeneracy,that the adsorption free energy of intermediate species and conductivity were further optimized.The optimized electrocatalyst exhibits excellent OER activity with an overpotential of 268 m V at 10 m A cm^(-2).DFT calculations show that plasma treatment can effectively regulate the d-band center of TMs to optimize the adsorption and improve the OER activity.This approach could guide the rational design and discovery of electrocatalysts with ideal electron configurations in the future.

关键词： transition metal compounds Electronic state control of surface/interface Electron spin state Delocalized electron Electrocatalytic material

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Doping transition metal ions as a method for enhancement of ablation rate in femtosecond laser irradiation of silicate glass

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Chinese Optics Letters 2014年第12期12卷 78-82页

作者：房巨强姜澜曹强袁艳萍曲良体段吉安陆永枫 Nano Manufacturing Fundamental Research Joint Laboratory of National Science Foundation of China School of Mechanical EngineeringBeijing Institute of Technology Institute of Laser Engineering Beijing University of Technology Key Laboratory of Cluster Science Ministry of Education School of ChemistryBeijing Institute of Technology State Key Laboratory of High Performance Complex Manufacturing Central South University Department of Electrical Engineering University of Nebraska-LincolnLincoln NE 68588-0511 USA

We present a doping method to improve the femtosecond laser ablation rate and promote ablation selectivity. Doping transition metal ions, Co2＋ or Cu2＋, in silicate glass apparently change absorption spectroscopy and induce resonant absorption at wavelengths of 600 and 800 nm, respectively. Comparing with femtosecond laser processing of the same glass without doping, we find that the threshold fiuenee decreases and the ablation rate increases in resonant absorption in doped silicate glass. Resonant absorption effectively increases multiphoton ionization for seed-free electron generation, which in turn enhances avalanche ionization.

关键词： Absorption spectroscopy Electrons Glass Glass transition Ionization Laser ablation metal ions Multiphoton processes Photoionization Silicates transition metal compounds transition metals Ultrashort pulses

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Structure and Magnetocaloric Effect in Tb(Co_(1-x)Sn_x)_2 Alloys

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Journal of Rare Earths 2006年第3期24卷 337-340页

作者：庄应烘邓健秋李均钦周开文朱其明 Institute of Materials Science Guangxi University Nanning 530004 China Department of Materials Science and Engineering Shenzhen University Shenzhen Key Laboratory of Special Functional Materials Shenzhen 518060 China

The phases and magnetocaloric effect in the alloys Tb（Co1-xSnx）2 with x = 0, 0.025, 0.050, 0.075, 0. 100 were investigated by X-ray diffraction analysis and magnetization measurement. The substitution of Sn in TbCo2 was limited. The cubic MgCu2-type structure for the sample of TbCo2 was confirmed by the results of X-ray powder diffraction and the rest samples consist of the TbCo2 phase mainly, together with some TbCo3 and Tb5Sn3 impurity phases. The impurity phases increase with the increase of Sn contents. The magnetic phase transition in all samples keeps second-order transition. Tc increases slightly by Sn substitution from 230 K of the alloy with x = 0 to 233 K of the alloy with x = 0.050 and then a slight decrease for higher concentration of x. The maximum magnetic entropy change in the samples Tb （Co1- x Snx）2 with x =0, 0.025, 0.050, 0.075 are 3.44, 2.29, 1.64, 1.16 J·kg^-1·K^-1, respectively, with the applied field change from 0 to 2.0 T.

关键词： transition metal compounds magnetocaloric materials rare earths

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Magnetocaloric Effect in MnCo_(1-x)Al_xGe compounds

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Journal of Materials Science & Technology 2009年第6期25卷 781-784页

作者： O. Tegus Yirgeltu Inner Mongolia Key Laboratory for Physics and Chemistry of Functional Materials Inner Mongolia Normal University

The effects of substitution of AI for Co on magnetic and magnetocaloric properties of MnCo1-xAlxGe （x=0.00, 0.03, 0.05, 0.08, 0.10, 0.13, 0.15, and 0.20） compounds have been investigated by X-ray diffraction （XRD） and magnetization measurements. XRD exhibits that MnCo1-xAlxGe compounds crystallize in the orthorhombic TiNiSi-type structure for x〈0.03 and in the hexagonal Ni2In-type crystal structure for x〉0.03. Magnetic measurements show that the Curie temperature can be tuned between 286 and 347 K by changing the Co/Al ratio. The maximum magnetic entropy change determined from the isothermal magnetization measurement by Maxwell relation reaches 1.52 J/（kgK） for x=0.08 in a field change from 0 to 1.5 T around 310 K.

关键词： transition metal compounds Magnetic entropy change Magnetic refrigeration

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