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Revealing the role of mo doping in promoting oxygen reduction reaction performance of Pt_(3)Co nanowires

Journal of Energy Chemistry 2022年第3期31卷 16-23,I0002页

作者： Zhiping Deng Wanying Pang Mingxing Gong Zhehui Jin Xiaolei Wang Department of Chemical and Materials Engineering University of AlbertaAlberta T6G 1H9Canada Department of Civil and Environmental Engineering University of AlbertaEdmontonAlberta T6G 1H9Canada Engineering Research Center of Nano-Geomaterials of Ministry of Education Faculty of Materials Science and ChemistryChina University of GeosciencesWuhan 430078HubeiChina

Highly active and durable electrocatalysts towards oxygen reduction reaction(ORR)are imperative for the commercialization application of proton exchange membrane fuel cells.By manipulating ligand effect,structural control,and strain effect,we report here the precise preparation of mo-doped Pt_(3)Co alloy nanowires(Pt_(3)Co-mo NWs)as the efficient catalyst towards ORR with high specific activity(0.596 mA cm^(−2))and mass activity(MA,0.84 A mg^(−1)_(Pt)),much higher than those of undoped counterparts.Besides activity,Pt_(3)Co-mo NWs also demonstrate excellent structural stability and cyclic durability even after 50,000 cycles,again surpassing control samples without mo dopants.According to the strain maps and DFT calculations,mo dopants could modify the electronic structure of both Pt and Co to achieve not only optimized oxygen-intermediate binding energy on the interface but also increased the vacancy formation energy of Co,together leading to enhanced activity and durability.This work provides not only a facile methodology but also an in-depth investigation of the relationship between structure and properties to provide general guidance for future design and optimization.

关键词： Pt-Co alloy Ultrafine nanowires Oxygen reduction reaction mo doping Vacancy formation energy

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mo-doped CoP nanoparticles anchored on porous Co-N-C framework as an efficient bifunctional electrocatalyst for pH-universal water splitting

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Journal of Materials Science & Technology 2023年第35期166卷 58-66页

作者： Guohua Li Fan Yang Sai Che Hongchen Liu Neng Chen Jinxiu Qian Chunhui Yu Bo Jiang Mengxi Liu Yongfeng Li State Key Laboratory of Heavy Oil Processing China University of PetroleumBeijing 102249China

Designing highly active and stable noble-metal-free electrocatalysts for water splitting over a wide pH range is critical yet remains significantly challenging.In this work,mo-doped CoP nanoparticles(mo-CoP)supported and enwrapped by porous single-atomic-Co doped carbon framework(Co-N-C)were designed and prepared by a simple one-pot pyrolysis method.The mo-CoP/Co-N-C electrocatalyst exhibits superior performance with low overpotentials of only 45 mV for hydrogen evolution reaction(HER)and 201 mV for oxygen evolution reaction(OER)in 1 M KOH at 10 mA cm^(-2)current density.Such excellent catalytic activity can be ascribed to enhanced intrinsic activity,large surface area,and highly exposed active sites.Meanwhile,an extremely small overpotential of only 250 mV is required for a large current density of 500 mA cm^(-2)in HER,which exceeds the performance of benchmark 10%Pt/C.Besides,mo-CoP/Co-N-C also exhibits superior HER performance in acidic and neutral mediums,with overpotentials of only 41 and 98 mV in 0.5 M H_(2)SO_(4),and 1 M PBS,respectively,thus achieving efficient water splitting at a wide pH range.The long-term stabilities are guaranteed with no significant decline of catalytic activities for more than 24 h in all electrolytes,which can be ascribed to the carbon layer encapsulation structure.Addition-ally,in overall water splitting,the electrocatalytic cell consisting of the as-synthesized mo-CoP/Co-N-C only requires a cell voltage of 1.611 V at 100 mA cm^(-2)with excellent stability,exceeding that of the benchmark Pt/C||RuO(2) couple(1.645 V at 100 mA cm^(-2)).This work not only presents a highly efficient electrocatalyst for pH-universal water splitting but also provides a new perspective for the design and construction of transition metal catalysts with excellent stability.

关键词： Cobalt phosphide mo doping Single atomic catalyst Water splitting pH-universal

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Engineering layered/spinel heterostructure via molybdenum doping towards highly stable Li-rich cathodes

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Tungsten 2022年第4期4卷 323-335页

作者： Kun-Qi Geng Meng-Qian Yang Jun-Xia Meng Ling-Fei Zhou Yu-Qin Wang Sydorov Dmytro Qian Zhang Sheng-Wen Zhong Quan-Xin Ma Key Laboratory of Power Battery and Materials Faculty of Materials Metallurgy and ChemistryJiangxi University of Science and TechnologyGanzhou341000China School of Physics and Electronics Gannan Normal UniversityGanzhou341000China

Li-rich layered oxide(LLO),e.g.,Li_(1.12)[Mn_(0.56)Ni_(0.16)Co_(0.08)]O_(2)(LRmo),is considered as a promising cathode material due to its superior Li-storage capability.However,the poor cycling stability and large voltage decay,which are related to the phase transition,limit its industrialization process.Herein,a mo-doped LRmo(Li_(1.12)[Mn_(0.56)Ni_(0.16)Co_(0.08)]_(0.98)mo_(0.02)O_(2),LRmo-mo2.0%)was successfully synthesized via a simple combination of co-precipitation with high-temperature calcination for solving the mentioned above-disadvantages.Compared with the pristine counterpart,the as-prepared LRmo-mo2.0%shows more excellent electrochemical performance in terms of rate capability(reversible capacity of 118 mA·h·g^(−1) at 5 C),cyclic ability(94.3%capacity retention after 100 cycles at 0.2 C)and discharge midpoint voltage decay(0.11 V after 100 cycles).Systematic investigation of structural evolution and electrochemical kinetics elucidate that the synergic effect of robust oxygen framework and layered/spinel heterostructure is the key to its performance improvement.Such synergy helps to stabilize the layered structure by curbing the structural transformation and oxygen escaping during the electrochemical cycling.This work paved the way for the simple and efficient preparation of highly stable LLO cathode materials.

关键词： Li-rich layered oxide mo doping Layered/spinel heterostructure High rate performance Cycling stability

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Fabrication of C@moxTi1-xO2-δ nanocrystalline with functionalized interface as efficient and robust PtRu catalyst support for methanol electrooxidation

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Journal of Energy Chemistry 2020年第1期29卷 7-14,I0001页

作者： Jialong Li Lei Zhao Xifei Li Sue Hao Zhenbo Wang MIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage School of Chemistry and Chemical EngineeringHarbin Institute of TechnologyNo.92 West-Da Zhi StreetHarbin 150001HeilongjiangChina Institute of Advanced Electrochemical Energy&School of Materials Science and Engineering Xi'an University of TechnologyXi'an 710048ShaanxiChina

A core shell structured C@moxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.

关键词： Interface functionalization TiO2 Nanocrystalline mo doping Core–shell PtRu catalyst Methanol electrooxidation

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