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A new insight into the promoting effects of transition metal phosphides in methanol electrooxidation

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Chinese Chemical Letters 2023年第6期34卷 200-205页

作者： Junjie Ding Shaojie Jing Changqing Yin Chaogang Ban Kaiwen Wang Xue Liu Youyu Duan Yuxin Zhang Guang Han Liyong Gan Jinsong Rao College of Physics and Center of Quantum Materials and Devices Chongqing UniversityChongqing 401331China College of Material Science and Engineering Chongqing UniversityChongqing 400044China Beijing Key Laboratory of Microstructure and Property of Advanced Materials Beijing University of TechnologyBeijing 100024China

The construction of highly active catalysts for methanol oxidation reaction(MOR)is central to direct methanol fuel *** progress has been made in transition metal phosphides(TMPs)based ***,TMPs would be partially damaged and transformed into new substances(e.g.,Pt-M-P composite,where M represents a second transition metal)during Pt deposition *** would pose a large obstacle to the cognition of the real promoting effects of TMPs in ***,Co_(2)P co-catalysts(Pt-P/Co_(2)P@NPC,where NPC stands for N and P co-doped carbon)and Pt-Co-P composite catalysts(Pt-CoP/NPC)were controllably *** tests show that the Pt-Co-P/NPC exhibits superior MOR activity as high as 1016 m A/mg_(Pt),significantly exceeding that of Pt-P/Co_(2)P@NPC(345 m A/mg_(Pt)).This result indicates that the promoting effect is ascribed primarily to the resultant Pt-Co-P composite,in sharply contrast to previous viewpoint that Co_(2)P itself improves the *** mechanistic studies reveal that Pt-Co-P/NPC exhibits much stronger electron interaction and thus manifesting a remarkably weaker CO absorption than Pt-P/Co_(2)P@NPC and Pt/***,Pt-Co-P is also more capable of producing oxygen-containing adsorbate and thus accelerating the removal of surface-bonded CO^(*),ultimately boosting the MOR performance.

关键词： Promoting effect transition metal phosphides Pt-Co-P composite Catalytic mechanisms Methanol oxidation reaction

Electronic modulation of sprout-shaped NiCoP nanoarrays by N and Ce doping for efficient overall water splitting

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Nano Research 2024年第1期17卷 282-289页

作者： Ting Zhao Guancheng Xu Bingbing Gong Jiahui Jiang Li Zhang State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources College of ChemistryXinjiang UniversityUrumqi 830017China College of Chemical Engineering Xinjiang UniversityUrumqi 830017China

Bifunctional catalysts for hydrogen/oxygen evolution reactions(HER/OER)are urgently needed given the bright future of water splitting hydrogen production ***,the self-supporting N and Ce dual-doped NiCoP nanoarrays(denoted N,Ce-NiCoP/NF)grown on Ni foam are successfully *** the N,Ce-NiCoP/NF simultaneously acts as the HER and OER electrodes,the voltages of 1.54 and 2.14 V are obtained for driving 10 and 500 mA·cm^(-2)with a robust durability,and demonstrate its significant potential for practical water *** to both experiments and calculations,the electronic structure of NiCoP may be significantly altered by strategically incorporating N and Ce into the lattice,which in turn optimizes the Gibbs free energy of HER/OER intermediates and speeds up the water splitting ***,the sprout-shaped morphology significantly increases the exposure of active sites and facilitates charge/mass transfer,thereby augmenting catalyst *** study offers a potentially effective approach involving the regulation of anion and cation double doping,as well as architectural engineering,for the purpose of designing and optimizing innovative electrocatalysts.

关键词： transition metal phosphides overall water splitting elements doping nanoarrays

Highly efficient and stable electrocatalyst for hydrogen evolution by molybdenum doped Ni-Co phosphide nanoneedles at high current density

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Nano Research 2024年第3期17卷 1066-1074页

作者： Chengyu Huang Zhonghong Xia Jing Wang Jing Zhang Chenfei Zhao Xingli Zou Shichun Mu Jiujun Zhang Xionggang Lu Hong Jin Fan Shengjuan Huo Yufeng Zhao College of Sciences&Institute for Sustainable Energy Shanghai UniversityShanghai 200444China State Key Laboratory of Metastable Materials Science and Technology Hebei Key Laboratory of Heavy Metal Deep-Remediation in Water and Resource ReuseYanshan UniversityQinhuangdao 066004China State Key Laboratory of Advanced Special Steel and Shanghai Key Laboratory of Advanced Ferrometallurgy School of Materials Science and EngineeringShanghai UniversityShanghai 200444China State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of TechnologyWuhan 430070China School of Physical and Mathematical Sciences Nanyang Technological UniversitySingapore639798

There is an increasingly urgent need to develop cost-effective electrocatalysts with high catalytic activity and stability as alternatives to the traditional Pt/C in catalysts in water *** this study,microspheres composed of Mo-doped NiCoP nanoneedles supported on nickel foam were prepared to address this *** results show that the nanoneedles provide sufficient active sites for efficient electron transfer;the small-sized effect and the micro-scale roughness enhance the entry of reactants and the release of hydrogen bubbles;the Mo doping effectively improves the electrocatalytic performance of NiCoP in alkaline *** catalyst exhibits low hydrogen evolution overpotentials of 38.5 and 217.5 mV at a current density of 10 mA·cm^(-2) and high current density of 500 mA·cm^(-2),respectively,and only 1.978 V is required to achieve a current density of 1000 mA·cm^(-2) for overall water *** functional theory(DFT)calculations show that the improved hydrogen evolution performance can be explained as a result of the Mo doping,which serves to reduce the interaction between NiCoP and intermediates,optimize the Gibbs free energy of hydrogen adsorption(△G_(*H)),and accelerate the desorption rate of **** study provides a promising solution to the ongoing challenge of designing efficient electrocatalysts for high-current-density hydrogen production.

关键词： transition metal phosphides Mo-doped NiCoP hydrogen evolution reaction gradient hydrothermal water splitting

B and Fe co-doped Co_(2)P hollow nanocubes for nitrate electroreduction to ammonia

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Chinese Chemical Letters 2024年第2期35卷 278-282页

作者： Jing Miao Qingling Hong Liping Liang Guomin Li Zhihong Liu Shibin Yin Yu Chen School of Materials Science and Engineering Taiyuan University of Science and TechnologyTaiyuan 030024China School of Materials Science and Engineering Shaanxi Normal UniversityXi'an 710062China School of Chemistry and Chemical Engineering Shaanxi Normal UniversityXi'an 710062China Guangxi Key Laboratory of Electrochemical Energy Materials School of Chemistry and Chemical EngineeringGuangxi UniversityNanning 530004China

Nitrate(NO_(3)^(−))electroreduction reaction(NO_(3)^(−)RR)provides an attractive and sustainable route for NO_(3)^(−)pollution mitigation or energy-saved ammonia(NH3)*** this work,high-quality B and Fe co-doped Co_(2) P hollow nanocubes(B/Fe-Co_(2) P HNCs)are successfully synthesized though simultaneous boronation-phosphorization treatment,which reveal outstanding selectivity,activity,stability for the NO_(3)^(−)to NH_(3) conversion in neutral electrolyte because of big surface area,fast mass transport,superhydrophilic surface,and optimized electronic structure.B/Fe-Co_(2) P HNCs can achieve the high NH3 yield rate(22.67 mg h^(−1) mg_(cat)^(−1))as well as Faradaic efficiency(97.54%)for NO_(3)^(−)RR,greatly outperforming most of non-precious metal based NO_(3)^(−)RR electrocatalysts.

关键词： Nitrate electroreduction reaction Ammonia synthesis transition metal phosphides Hollow nanocubes

Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

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Nano Materials Science 2024年第2期6卷 174-192页

作者： Ge Li Yu Feng Yi Yang Xiaoliang Wu Xiumei Song Lichao Tan College of Chemistry Chemical Engineering and Resource UtilizationNortheast Forestry University26 Hexing RoadHarbin150040PR China Institute of Carbon Neutrality Zhejiang Wanli UniversityNingbo315100PR China School of Materials Science and Chemical Engineering Harbin University of Science and TechnologyHarbin150040PR China

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling *** exploitation of cheap and efficient electrode materials is the key to improve the performance of *** the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for *** this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of *** the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

关键词： transition metal phosphides Cobalt phosphide Nickel phosphides Electrode materials Supercapacitor

Growth of 2D MoP single crystals on liquid metals by chemical vapor deposition

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Science China Materials 2021年第5期64卷 1182-1188页

作者： Feifei Cao Shuting Zheng Jingjing Liang Zhi Li Bin Wei Yiran Ding Zhongchang Wang Mengqi Zeng Nan Xu Lei Fu Institute for Advanced Studies(IAS) Wuhan UniversityWuhan 430072China College of Chemistry and Molecular Sciences Wuhan UniversityWuhan 430072China MIIT Key Laboratory of Advanced Display Materials and Devices Ministry of Industry and Information TechnologyInstitute of Optoelectronics&NanomaterialsNanjing University of Science and TechnologyNanjing 210094China Department of Quantum and Energy Materials International Iberian Nanotechnology Laboratory(INL)4715-330 BragaPortugal

Two-dimensional(2 D) transition metal phosphides(TMPs) are predicted with many novel properties and various applications. As a member of TMPs family, molybdenum phosphide(MoP) exhibits many exotic physicochemical properties. However, the synthesis of high-quality2 D MoP single crystals is not reported due to the lack of reliable fabrication method, which limits the exploration of 2 D MoP. Here, we report the growth of high-quality ultrathin MoP single crystals with thickness down to 10 nm on liquid metals via chemical vapor deposition(CVD). The smooth surface of liquid Ga is regarded as a suitable growth substrate for producing 2 D MoP single crystals. The Mo source diffuses toward the Ga surface due to the high surface energy to react with phosphorus source, thus to fabricate ultrathin MoP single crystals. Then, we study the second harmonic generation(SHG) of 2 D MoP for the first time due to its intrinsic noncentrosymmetric structure. Our study provides an new approach to synthesize and explore other 2 D TMPs for future applications.

关键词： 2D materials transition metal phosphides molybdenum phosphides liquid metals chemical vapor deposition

Tuning the electronic structure of NiCoP arrays through V doping for pH-universal hydrogen evolution reaction electrocatalyst

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Frontiers of Chemical Science and Engineering 2021年第5期15卷 1134-1146页

作者： Yu Lin Jinlei Wang Duanlin Cao Yaqiong Gong School of Chemical Engineering and Technology North University of ChinaTaiyuan030051China

The exploration of cost-effective,high-performance,and stable electrocatalysts for the hydrogen evolution reaction(HER)over wide pH range(0–14)is of paramount importance for future renewable energy conversion *** of electronic structure through doping vanadium atoms is a feasible construction strategy to enhance catalytic activities,electron transfer capability,and stability of the HER ***,V-doped NiCoP nanosheets on carbon fiber paper(CFP)(denoted as Vx-NiCoP/CFP)were constructed by doping V modulation on NiCoP nanosheets on CFP and used for pH-universal *** from the abundant catalytic sites and optimized hydrogen binding thermodynamics,the resultant V15-NiCoP/CFP demonstrates a significantly improved HER catalytic activity,requiring overpotentials of 46.5,52.4,and 85.3 mV to reach a current density of 10 mA·cm^(−2)in 1 mol·L^(−1) KOH,0.5 mol·L^(−1) H_(2)SO_(4),and 1 mol·L^(−1) phosphate buffer solution(PBS)electrolytes,*** proposed cation-doping strategy provides a new inspiration to rationally enhance or design new-type nonprecious metal-based,highly efficient,and pH-universal electrocatalysts for various energy conversion systems.

关键词： hydrogen evolution reaction transition metal phosphides pH-universal vanadium doping carbon fiber paper

5 nm NiCoP nanoparticles coupled with g-C3N4 as high-performance photocatalyst for hydrogen evolution

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Science China Materials 2020年第2期63卷 258-266页

作者： Bo Ma Jinping Zhao Zhenhua Ge Yantao Chen Zhihao Yuan Tianjin Key Laboratory for Photoelectric Materials and Devices School of Materials Science and EngineeringTianjin University of TechnologyTianjin 300384China

Graphitic carbon nitride(g-C3N4) coupled with NiCoP nanoparticles with sizes around 5 nm have been fabricated via a controllable alcohothermal process. NiCoP is an excellent electron conductor and cocatalyst in photocatalytic reactions. The coupling between tiny NiCoP nanoparticles and g-C3N4 through in-situ fabrication strategy could be a promising way to eliminate the light screening effect, hinder the recombination of photo-induced charge carriers, and improve the charge transfer. The NiCoP/g-C3N4 nanohybrids exhibit an excellent photocatalytic activity in the hydrogen generation, with a significantly improved performance compared with original g-C3N4, CoP/g-C3N4 and Ni2P/g-C3N4, respectively. This study paves a new way to design transition metal phosphides-based photocatalysts for hydrogen production.

关键词： transition metal phosphides photocatalytic hydrogen generation carbon nitride nanohybrids

Rational design of three-dimensional branched NiCo-P@CoNiMo-P core/shell nanowire heterostructures for high-performance hybrid supercapacitor

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Journal of Energy Chemistry 2021年第10期30卷 489-496,I0013页

作者： Yijing Huang Chong Luo Qiaobao Zhang Hehe Zhang Ming-Sheng Wang State Key Lab of Physical Chemistry of Solid Surfaces College of MaterialsXiamen UniversityXiamen 361005FujianChina

Owing to the dramatically enhanced charge-mass transport and abundant electrochemically active sites,transition metal compound electrodes are increasingly attractive for achieving high-performance supercapacitors(SCs).Here,we report the fabrication of nickel foam supported three-dimensional(3 D)branched nickel-cobalt phosphides@tri-metal cobalt-nickel-molybdenum phosphides core/shell nanowire heterostructures(denoted as NiCo-P@CoNiMo-P)as high-performance electrode materials for hybrid *** presence of multiple valences of the cations in such NiCo-P@CoNiMo-P enables rich redox reactions and promoted synergy *** from their collective effects,the resulting electrode demonstrates high specific capacity of 1366 C g^(-1) at 2 A g^(-1)(2.03 C cm^(-2) at2 mA cm^(-2))and 922 C g^(-1) at 10 A g^(-1),as well as good cycling stability(retaining~94%of the initial capacity after 6000 cycles at 15 A g^(-1)).A hybrid SC using the NiCo-P@CoNiMo-P as the positive electrode and N-doped rGOs as the negative electrode exhibits a high energy density of 81.4 Wh kg^(-1) at a power density of 1213 W kg^(-1) and a capacity retention of 132%even after 6000 cycles at 10 A g^(-1).Our findings can facilitate the material design for boosting the performance of transition metal compounds based materials for fast energy storage.

关键词： transition metal phosphides Branched nanowire heterostructures Electrode materials Hybird supercapacitors