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Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Journal of Energy Chemistry 2024年第2期89卷 646-669,I0014页

作者： Rose Anne Acedera Alicia Theresse Dumlao DJ Donn Matienzo Maricor Divinagracia Julie Anne del Rosario Paraggua Po-Ya Abel Chuang Joey Ocon Laboratory of Electrochemical Engineering(LEE) Department of Chemical EngineeringUniversity of the PhilippinesDilimanQuezon City 1101Philippines Mechanical Engineering University of CaliforniaMercedCA 95343USA Energy Engineering Program College of EngineeringUniversity of the PhilippinesDilimanQuezon City 1101Philippines

transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

关键词： OER HER transition metal phosphide Templated synthesis Electrocatalysts

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A revisiting of transition metal phosphide(Cu_(3)P and FeP)nanozymes for two sugar-related reactions

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Nano Research 2023年第1期16卷 189-194页

作者： Daiyong Chao Zhixuan Yu Jinxing Chen Qing Dong Weiwei Wu Youxing Fang Ling Liu Shaojun Dong College of Chemistry Jilin UniversityChangchun 130012China State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China

transition metal phosphides(TMPs)are essential catalysts for some general catalytic reactions.However,their potentials for biological catalysis have seldom been explored.Herein,we investigated the enzyme-like properties of four TMPs(FeP,CoP,Ni_(2)P,and Cu_(3)P)towards two sugar-related reactions.Among the four TMPs,Cu_(3)P nanoparticles(NPs)efficiently catalyzed the hydrolysis of glycosidic bonds as glycoside hydrolase mimics,and FeP NPs possessed both glucose oxidase-like(GOx-like)and peroxidase-like activities,which combined into a cascade reaction for glucose’s simple and one-step colorimetric biosensor without GOx.Cu_(3)P and FeP NPs with distinctive enzyme-like activities have shown unique biological catalysis potentials for further applications with an attractive and challenging goal of developing nanomaterials to mimic natural enzymes,which encourages more efforts to reveal TMP’s capabilities towards biocatalysis.

关键词： transition metal phosphide glycoside hydrolase mimic glucose oxidase-like activity peroxidase-like activity cascade reaction

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Self-supported transition metal phosphide based electrodes as high-efficient water splitting cathodes

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Frontiers of Chemical Science and Engineering 2018年第3期12卷 494-508页

作者： Yan Zhang Jian Xiao Qiying Lv Shuai Wang State Key Laboratory of Digital Manufacturing Equipment and Technology Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education) School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan 430074 China Flexible Electronics Research Center (FERC) School of Mechanical Science and Engineering Huazhong University of Science and Technology Wuhan 430074 China

Electrolytic water splitting has been considered as a promising technology to produce highly pure H2 by using electrical power produced from wind, solar energy or other fitful renewable energy resources. Combining novel self-supporting structure and high-performance transition metal phosphides （TMP） shows substantial promise for practical application in water splitting. In this review, we try to provide a comprehensive analysis of the design and fabrication of various self-supported TMP electrodes for hydrogen evolution reaction, which are divided into three categories： catalysts growing on carbon-based substrates, catalysts growing on metal-based substrates and free- standing catalyst films. The material structures together with catalytic performances of self-supported electrodes are presented and discussed. We also show the specific strategies to further improve the catalytic performance by elemental doping or incorporation of nanocarbons. The simple and one-step methods to fabricate self-supported TMP electrodes are also highlighted. Finally, the chal- lenges and perspectives for self-supported TMP electrodes in water splitting application are briefly discussed.

关键词： transition metal phosphide self-supported electrode electrocatalysis hydrogen evolution reaction

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Electron engineering of nickel phosphide for Ni^(δ+) in electrochemical nitrate reduction to ammonia

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Nano Research 2024年第6期17卷 4864-4871页

作者： Jie Hu Hao Huang Miao Yu Shuang Wang Jinping Li College of Environmental Science and Engineering Taiyuan University of TechnologyJinzhong 030600China School of Sustainable Energy Materials and Science Jinhua Advanced Research InstituteJinhua 321000China Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization Taiyuan University of TechnologyTaiyuan 030024China

The electrochemical reduction of nitrate to ammonia(ENRA)provides an efficient approach to remove nitrate pollution and achieve ammonia production simultaneously.Herein,inspired by bio-enzyme in denitrifying bacteria,a carbon-coated nickel phosphide(NiPC)nanosheet derived from metal-organic frameworks(MOFs)is proposed as an efficient catalyst for ENRA.Through electron engineering,controllable Ni^(δ+)in nickel phosphide is achieved by regulating the degree of phosphating,which enhances its activity for the hydrogenation of nitrate.As the result,Niδ+becomes one of dominating factors determining the efficiency of the ENRA reaction in nickel phosphide.The optimal NiPC catalyst exhibits impressive property toward ENRA:NH_(4)^(+)Faraday efficiency of 96.68%,NH4+selectivity of 99.04%,and nitrate conversion rate of 90.43%under low nitrate concentration(200 mg·L^(−1)).This work opens a new avenue for the design of next-generation catalysts through electron engineering for ENRA.

关键词： electron engineering transition metal phosphide nitrate reduction ammonia production metal-organic frameworks

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metal-organic frameworks derived transition metal phosphides for electrocatalytic water splitting

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Journal of Energy Chemistry 2022年第5期31卷 494-520页

作者： Li-Ming Cao Jia Zhang Li-Wen Ding Zi-Yi Du Chun-Ting He Key Laboratory of Functional Small Molecules for Ministry of Education College of Chemistry and Chemical EngineeringJiangxi Normal UniversityNanchang 330022JiangxiChina Key Laboratory for Green Chemistry of Jiangxi Province Nanchang 330022JiangxiChina

It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. metal-organic frameworks(MOFs) can function as ideal molecular platforms for the design of highly reactive transition metal phosphides(TMPs), a kind of candidates for high-efficiently electrocatalytic water splitting. The intrinsic activity of the electrocatalysts can be greatly improved via modulating the electronic structure of the catalytic center through the MOF precursors/templates. Moreover, the carbon layer converted in-situ by the organic ligands can not only protect the TMPs from being degraded in the harsh electrochemical environments, but also avoid agglomeration of the catalysts, thereby promoting their activities and stabilities. Furthermore,heteroatom-containing ligands can incorporate N, S or P, etc. atoms into the carbon matrixes after conversion, regulating the coordination microenvironments of the active centers as well as their electronic structures. In this review, we first summarized the latest developments in MOF-derived TMPs by the unique advantages in metal, organic ligand, and morphology regulations for electrocatalytic water splitting. Secondly, we concluded the critical scientific issues currently facing for designing state-of-the-art TMP-based electrocatalysts. Finally, we presented an outlook on this research area, encompassing electrocatalyst construction, catalytic mechanism research, etc.

关键词： metal-organic framework transition metal phosphide Water splitting Electrocatalyst Electronic structure

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Heterostructured bimetallic phosphide nanowire arrays with latticetorsion interfaces for efficient overall water splitting

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Journal of Energy Chemistry 2023年第2期77卷 420-427,I0011页

作者： Hua Zhang Hongyi Li Yintang Zhou Fang Tan Ruijie Dai Xijun Liu Guangzhi Hu Laiming Jiang Anran Chen Renbing Wu School of Materials and Energy Institute for Ecological Research and Pollution Control of Plateau LakesSchool of Ecology and Environmental ScienceYunnan UniversityKunming 650091YunnanChina Department of Materials Science Fudan UniversityShanghai 200433China Guangzhou Panyu Polytechnic Guangzhou 511483GuangdongChina National Engineering Research Center for Marine Aquaculture Marine Science and Technology CollegeZhejiang Ocean UniversityZhoushan 316004ZhejiangChina MOE Key Laboratory of New Processing Technology for Non-ferrous metals and Materials Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured MaterialsGuangxi UniversityNanning 530004GuangxiChina Engineering Research Center of Alternative Energy Materials&Devices Ministry of EducationSichuan UniversityChengdu 610065SichuanChina

Designing cost-effective and high-efficiency electrocatalysts is critical to the water splitting performance during hydrogen generation.Herein,we have developed Fe_(2)P-Co_(2)P heterostructure nanowire arrays with excellent lattice torsions and grain boundaries for highly efficient water splitting.According to the microstructural investigations and theoretical calculations,the lattice torsion interface not only contributes to the exposure of more active sites but also effectively tunes the adsorption energy of hydrogen/oxygen intermediates via the accumulation of charge redistribution.As a result,the Fe_(2)P-Co_(2)P heterostructure nanowire array exhibits exceptional bifunctional catalytic activity with overpotentials of 65 and 198 mV at 10 mA cm^(-2) for hydrogen and oxygen evolution reactions,respectively.Moreover,the Fe_(2)P-Co_(2)P/NF-assembled electrolyzer can deliver 10 mA cm^(-2) at an ultralow voltage of1.51 V while resulting in a high solar-to-hydrogen conversion efficiency of 19.8%in the solar-driven water electrolysis cell.

关键词： transition metal phosphide Lattice torsion Heterogeneous interfaces Water splitting Theoretical calculation

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Synergistic phosphorized NiFeCo and MXene interaction inspired the formation of high-valence metal sites for efficient oxygen evolution

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Journal of Materials Science & Technology 2022年第11期106卷 90-97页

作者： Ning Li Jingrui Han Kaili Yao Mei Han Zumin Wang Yongchang Liu Lihua Liu Hongyan Liang School of Materials Science and Engineering Tianjin UniversityTianjin 300350China Key Laboratory of Efficient Utilization of Low and Medium Grade Energy Ministry of EducationTianjin UniversityTianjin 300350China College of Innovation and Entrepreneurship Shanghai Jianqiao UniversityShanghai 201306China State Key Lab of Hydraulic Engineering Simulation and Safety School of Materials Science and EngineeringTianjin UniversityTianjin 300354China

Exploring low-cost,high-performance,and stable electrocatalysts toward the oxygen evolution reaction(OER)is highly desired but remains challenging.transition metal hydroxide has been wildly utilized as a promising candidate,but practical implementation is impeded by insufficient catalytic activity,easy agglomeration,and poor conductivity.Here,we report that both phosphorization and combination with MXnene can improve the catalysts’intrinsic activity and conductivity.Besides,MXene also prevents the agglomeration of the nanoparticles,resulting in the enhanced exposure of active sites.Experimental char-acterizing and density functional theory simulations revealed that P species can attract electrons to pro-mote the formation of high-valence states of adjacent metal atoms,and coupling MXene support can effectively modulate the electronic structure and optimize the d-band center,which boosts the OER per-formance.Consequently,the optimized NiFeCoP/Mxene catalyst exhibits a low overpotential of 240 mV at a current density of 10 mA cm^(−2),a small Tafel slope of 55 mV dec^(−1),and superior long-term stability of 40 h in 1 M KOH electrolyte,which is superior to other counterparts.

关键词： transition metal phosphide Ti3C2Tx MXene Electrocatalyst Oxygen evolution

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Unveiling the role of Zn dopants in NiFe phosphide nanosheet for oxygen evolution reaction

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Progress in Natural Science:Materials International 2023年第1期33卷 74-82页

作者： Chendong Kou Jingrui Han Haibin Wang Mei Han Hongyan Liang School of Materials Science and Engineering Tianjin University Key Laboratory of Efficient Utilization of Low and Medium Grade Energy Tianjin University

transition metal phosphides have been recognized as promising electrocatalysts for oxygen evolution reaction(OER) due to their low cost and high activity. However, the insufficient exposed active region limited the OER performance. Recently, the introduction of sacrificial dopants has been considered an effective strategy to enlarge the surface area. Herein, the Zn dopants are introduced in NiFe phosphide(NiFeZnP) nanosheet, which work as the sacrificial dopants to generate more exposed active NiFe sites and promote the formation of the NiFeOOH active phase during OER process. The optimized Zn-doped NiFeP catalyst shows an overpotential of ≈203 mV to reach a current density of 10 mA cm-2in 1 M KOH, and a stability of 100 h at 1000 mA cm-2. Overall, this work provides a sacrificial Zn doping strategy to prepare highly efficient OER electrocatalysts.

关键词： transition metal phosphide Sacrificial dopant Self-supported electrode Oxygen evolution reaction

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Rational construction of CoP@C hollow structure for ultrafast and stable sodium energy storage

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Rare metals 2022年第6期41卷 1859-1869页

作者： Ling-BoRen Wei Hua Zhi-Dong Hou Jian-Gan Wang State Key Laboratory of Solidification Processing Center for Nano Energy MaterialsSchool of Materials Science andEngineeringNorthwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene(NPU)Xi'an 710072China

The development of transition metal phosphides as potential anode materials of sodium-ion batteries has been substantially hindered by their sluggish kinetics and significant volume change during the sodiation/desodiation process.In this work,we put forward a rational design strategy to construct a hollow-structured CoP@C com-posite to achieve ultrafast and durable sodium energy storage.The CoP@C composite with a well-defined hollow dodecahedron architecture has been synthesized via a stepwise treatment of carbonization and pohsphorization on ZIF-67.The unique hollow carbon framework not only provides high-speed electron/ion transportation pathways for CoP to enable fast sodiation kinetics,but also accom-modates large volume change to stabilize the electrode structure.As a consequence,the CoP@C composite could exhibit an ultra-high rate capability of 105 mAh·g^(-1)at a current density of 30 A·g^(-1),and a long-term cycling life-time.The present study will pave a fresh strategy for exploring advanced high-power anode materials for sodium ion batteries.

关键词： transition metal phosphide Hollow structure Anode:High-rate capability Sodium ion battery

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Polydopamine-derived carbon layer anchoring NiCo-P nanowire arrays for high-performance binder-free supercapacitor and electrocatalytic hydrogen evolution

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SusMat 2022年第5期2卷 646-657页

作者： Zhenyuan Zhang Na Song Jian Wang Yingqi Liu Zhang Dai Guangdi Nie Industrial Research Institute of Nonwovens&Technical Textiles(Shandong Center for Engineered Nonwovens) and Collaborative Innovation Center for Eco-Textiles of Shandong ProvinceCollege of Textiles and ClothingQingdao UniversityQingdaoP.R.China Alan G.MacDiarmid Institute College of ChemistryJilin UniversityChangchunP.R.China College of Textile and Clothing Xinjiang UniversityUrumchiP.R.China

transition metal phosphides(TMPs)have been extensively and deeply researched as electrode materials for energy-related applications.However,the inferior stability is still a bottleneck restricting their substantive development.Herein,a freestanding three-dimensional hierarchical nanostructure(marked as CC@NC/NiCo-P)is delicately designed for high-performance supercapacitors and electrocatalytic hydrogen evolution,where the nitrogen-doped carbon(NC)layer derived from polydopamine serves as an interface coupling bridge for anchoring electroactive nickel cobalt phosphide(NiCo-P)nanowire arrays on flexible carbon cloth(CC)substrate.Thanks to the robust interaction between the conductive carbon support and NiCo-P nanowires,the resultant CC@NC/NiCo-P electrode delivers an ultrahigh capacitance(2175.5 F/g at 1 A/g)and a distinguished rate capability with a capacity retention of 85.8%.The assembled asymmetric supercapacitor can achieve a superior energy density of 28.47 Wh/kg and an ultralong lifespan of 10000 cycles.In addition,the CC@NC/NiCo-P electrode shows favorable electrocatalytic activity toward the hydrogen evolution reaction.These results indicate that the strong binding between the NC layer and metal species in TMPs notably improves the stability and electrochemical activity of CC@NC/NiCo-P.It is expected that this effective strategy to design innovative electrode materials may be promising for the applications in energy-related fields.

关键词： hydrogen evolution reaction nanowires rate capability supercapacitors transition metal phosphide

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