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Fabrication and dealloying Behavior of Monolithic Nanoporous Copper Ribbons with Bimodal Channel Size Distributions

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Journal of Materials Science & Technology 2012年第8期28卷 693-699页

作者： Wenbo Liu Shichao Zhang Ning Li Jiwei Zheng Yalan Xing School of Materials Science and Engineering Beihang UniversityBeijing 100191China School of Manufacturing Science and Engineering Sichuan UniversityChengduSichuan 610065China

Monolithic nanoporous copper （NPC） ribbons with bimodal channel size distributions can be fabricated through chemical dealloying of Mg-32 Cu alloy in an acidic solution at room temperature. The microstructure of the as- dealloyed samples was characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. These NPC ribbons are composed of interconnected large-sized channels （hundreds of nm） with highly porous channel walls （tens of nm）. Both large- and small-sized channels are open, bicontinuous, and interpenetrating. Additionally, it is the first time to find that the evolution process of porous structure along the thickness direction of samples during the dealloying is from the interior to exterior, which is just contrary to the coarsening process along the thickness direction during the post-dealloying. Meanwhile, the corresponding mechanism is discussed in detail.

关键词： Nanoporous copper dealloying Bimodal channel size distribution Microstructure Electron microscopy

dealloying-constructed hierarchical nanoporous bismuth-antimony anode for potassium ion batteries

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Fundamental Research 2021年第4期1卷 408-417页

作者： Hui Gao Kuibo Yin Zhiyuan Guo Ying Zhang Wensheng Ma Wanfeng Yang Ke Sun Zhangquan Peng Zhonghua Zhang Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJingshi Road 17923Jinan 250061China SEU-FEI Nano-Pico Center Key Lab of MEMS of Ministry of EducationSoutheast UniversityNanjing 210096China Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China

Bi-Sb alloys are appealing anode materials for potassium ion batteries(PIBs)but challenged by their enormous volumetric variation during operation.Herein,a facile one-step dealloying protocol was devised and utilized to prepare the Bi-Sb alloys that manifest an exotic bicontinuous hierarchical nanoporous(np)microstructure ideal for volume-change mitigation and K+transport percolation.The growth mechanism fostering the peculiar morphology of the np-(Bi,Sb)alloys was investigated and clarified via operando X-ray(XRD)and ex-situ scanning electron microscopy(SEM).In particular,the np-Bi6Sb2 electrode,optimized for comprehensive electrochemical performance,achieves decent reversible capacities and a superior lifespan,as benchmarked with the monometallic references and other Bi-Sb alloy electrodes.The(de)potassiation mechanism of the np-(Bi,Sb)alloys was studied by operando XRD and further rationalized by density functional theory(DFT)calculations,whereby a homogeneous(segregation-free)and robust two-step electrochemically-driven phase transformations’catenation of(Bi,Sb)↔K(Bi,Sb)2↔K3(Bi,Sb)was reliably established to substantiate the outstanding reversibility of the np-(Bi,Sb)anodes in PIBs.

关键词： Potassium ion battery Bismuth-antimony anodes Density functional theory dealloying Operando X-ray diffraction

Alloying and dealloying of CuPt bimetallic nanocrystals

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Progress in Natural Science:Materials International 2013年第3期23卷 331-337页

作者： Fengjiao Yu Wuzong Zhou School of Chemistry University of St AndrewsSt Andrews KY16 9STUnited Kingdom

Bimetallic CuPt nanocrystals with size ranging from 3 to 30 nm were synthesized in the presence of either hexadecylamine or poly(vinylpyrrolidone) as a capping agent.Different growth stages of CuPt nanoparticles prepared with hexadecylamine have been investigated and a non-classic mechanism governing the formation of the metal alloy was revealed.It was found that the precursor molecules aggregate into amorphous spheres at a very early stage,followed by surface multiple nucleation,formation and combination of crystalline islands to produce a core-shell structure with surface-to-core extension of the crystallization to achieve single crystals.CuPt nanocrystals synthesized with poly(vinylpyrrolidone) grew via the classic route.dealloying treatment was applied on these CuPt nanoalloys to selectively remove Cu.Large particles(30 nm) with Cu-rich cores exhibited hollow structures after dealloying while 3 nm particles remained solid,demonstrating that particle size and composition have a great influence on the final morphology of dealloyed particles.

关键词： CuPt alloy dealloying Nanocrystal Electron microscopy Crystal growth

Comparison of microstructure,mechanical property,and degradation rate of Mg-1Li-1Ca and Mg-4Li-1Ca alloys

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Bioactive Materials 2023年第8期26卷 279-291页

作者： Li-Xin Long Fen-Fen Chen Lan-Yue Cui Ze-Song Wei Hai-Tao Wang Rong-Chang Zeng Yu-Feng Zheng College of Materials Science and Engineering Shandong University of Science and TechnologyQingdao266590China Institute of Corrosion Science and Technology Guangzhou510530China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou450002China School of Materials Science and Engineering Peking UniversityBeijing100871China International Research Organization for Advanced Science and Technology(IROAST) Kumamoto University2-39-2 Kumamoto860-8555Japan

Mg-1 wt.%Li-1 wt.%Ca(LX11)and Mg-4 wt.%Li-1 wt.%Ca(LX41)alloys share the same hexagonal closed-packed crystalline structure.However,the differences in microstructure,mechanical properties,and degradation rates between the two alloys are not well understood.Hereby,the above three aspects of LX11 and LX41 alloys were studied via optical microscopy,tensile tests,and electrochemical polarization and electrochemical impedance spectroscopy,together with hydrogen evolution.The concentration of the released Mg^(2+),Ca^(2+),and Li+ions was analyzed using a flame atomic absorption spectrophotometer.Results demonstrated that the LX11 alloy was composed of finerα-Mg grains,fewer twins,and smaller volume fractions of the intermetallic phases Mg_(2)Ca than the LX41 alloy.The increasing Li concentration generated a weak decrease in the yield strength of the Mg-Li-Ca alloys,a remarkable increase in elongation to failure,and a stable ultimate tensile strength.The LX11 alloy had better corrosion resistance than the LX41 alloy.The release rate of the cations(Mg^(2+),Ca^(2+),and Li+)varied significantly with time.The release rate of metallic ions in Hank’s solution cannot reflect the true corrosion rate of Mg-Li-Ca alloys due to the formation of the precipitated corrosion products and their difference in solubility.The dealloying corrosion mechanism of the Mg_(2)Ca phase in Mg-Li-Ca alloys was proposed.

关键词： Magnesium alloys dealloying Intermetallic compound Biomaterial Ionic release

Self-Supporting Nanoporous Copper Film with High Porosity and Broadband Light Absorption for Efficient Solar Steam Generation

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Nano-Micro Letters 2023年第7期15卷 57-71页

作者： Bin Yu Yan Wang Ying Zhang Zhonghua Zhang Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJingshi Road 17923Jinan 250061People’s Republic of China School of Materials Science and Engineering University of JinanWest Road of Nan Xinzhuang 336Jinan 250022People’s Republic of China

Solar steam generation(SSG)is a potential technology for freshwater production,which is expected to address the global water shortage problem.Some noble metals with good photothermal conversion performance have received wide concerns in SSG,while high cost limits their practical applications for water purification.Herein,a self-supporting nanoporous copper(NP-Cu)film was fabricated by one-step dealloying of a specially designed Al_(98)Cu_(2)precursor with a dilute solid solution structure.In-situ and ex-situ characterizations were performed to reveal the phase and microstructure evolutions during dealloying.The NP-Cu film shows a unique three-dimensional bicontinuous ligament-channel structure with high porosity(94.8%),multi scale-channels and nanoscale ligaments(24.2±4.4nm),leading to its strong broadband absorption over the 200–2500 nm wavelength More importantly,the NP-Cu film exhibits excellent SSG performance with high evaporation rate,superior efficiency and good stability.The strong desalination ability of NP-Cu also manifests its potential applications in seawater desalination.The related mechanism has been rationalized based upon the nanoporous network,localized surface plasmon resonance effect and hydrophilicity.

关键词： Solar steam generation Nanoporous copper Broadband solar absorption Localized surface plasmon resonance Seawater desalination dealloying

Duplex Interpenetrating-Phase FeNiZn and FeNi_(3)Heterostructure with Low-Gibbs Free Energy Interface Coupling for Highly Efficient Overall Water Splitting

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Nano-Micro Letters 2023年第7期15卷 72-89页

作者： Qiuxia Zhou Caixia Xu Jiagang Hou Wenqing Ma Tianzhen Jian Shishen Yan Hong Liu Institute for Advanced Interdisciplinary Research(iAIR) Spintronics InstituteCollaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of ShandongSchool of Chemistry and Chemical EngineeringUniversity of JinanJinan 250022People’s Republic of China School of Medical Information and Engineering Southwest Medical UniversityLuzhou 646000People’s Republic of China Kyiv College at Qilu University of Technology Qilu University of TechnologyShandong Academy of SciencesJinan 250353People’s Republic of China State Key Laboratory of Crystal Materials Shandong UniversityJinan 250100People’s Republic of China

The sluggish kinetics of both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)generate the large overpotential in water electrolysis and thus high-cost hydrogen production.Here,multidimensional nanoporous interpenetrating-phase FeNiZn alloy and FeNi_(3)intermetallic heterostructure is in situ constructed on NiFe foam(FeNiZn/FeNi_(3)@NiFe)by dealloying protocol.Coupling with the eminent synergism among specific constituents and the highly efficient mass transport from integrated porous backbone,FeNiZn/FeNi_(3)@NiFe depicts exceptional bifunctional activities for water splitting with extremely low overpotentials toward OER and HER(η_(1000)=367/245 mV)as well as the robust durability during the 400 h testing in alkaline solution.The as-built water electrolyzer with FeNiZn/FeNi_(3)@NiFe as both anode and cathode exhibits record-high performances for sustainable hydrogen output in terms of much lower cell voltage of 1.759 and 1.919 V to deliver the current density of 500 and 1000 mA cm^(-2)as well long working lives.Density functional theory calculations disclose that the interface interaction between FeNiZn alloy and FeNi_(3)intermetallic generates the modulated electron structure state and optimized intermediate chemisorption,thus diminishing the energy barriers for hydrogen production in water splitting.With the merits of fine performances,scalable fabrication,and low cost,FeNiZn/FeNi_(3)@NiFe holds prospective application potential as the bifunctional electrocatalyst for water splitting.

关键词： Heterostructure Interface effect dealloying Bifunctional electrocatalyst Overall water splitting

Phosphorus-doped NiS_(2)electrocatalyst with a hybrid structure for hydrogen evolution

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Science China(Technological Sciences) 2022年第7期65卷 1506-1512页

作者： ZHOU Qi LIU HaoRui JIAO SunZhi FENG ChenChen State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals Lanzhou University of TechnologyLanzhou 730050China School of Materials Science and Engineering Lanzhou University of TechnologyLanzhou 730050China College of Mechanical Engineering Longdong UniversityQingyang 745000China

In this article,P-NiS_(2)/Ni_(x)P electrocatalysts were synthesized by dealloying the Ni-Al precursor followed by phosphosulfide treatment.We found that the hybrid structure of P-NiS_(2)/Ni_(x)P provides rich active sites for the surface hydrogen evolution reaction (HER),and the doping of P enhances the electronic conductivity of electrodes.In particular,the obtained electrode shows a low overpotential of 196 mV at 10 mA cm^(-2)and a small Tafel slope of only 110 mV dec^(-1)in the HER.Meanwhile,longterm constant current electrolysis test experiments indicate that P-NiS_(2)/Ni_(x)P has good service stability.This research will help to open a new window on the design and fabrication of HER electrocatalysts.

关键词： nickle phosphosulfides hybrid structure hydrogen evolution reaction dealloying

Eutectic-derived high-entropy nanoporous nanowires for efficient and stable water-to-hydrogen conversion

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Nano Research 2022年第6期15卷 4820-4826页

作者： Ying Wang Bin Yu Ming He Zhihua Zhai Kuibo Yin Fangong Kong Zhonghua Zhang State Key Laboratory of Biobased Material and Green Papermaking Qilu University of Technology(Shandong Academy of Sciences)Jinan 250353China Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061China SEU-FEI Nano-Pico Center Key Lab of MEMS of Ministry of EducationSoutheast UniversityNanjing 210096China

Combining multiple metal elements into one nanostructure merits untold application potential but is still a challenge for the traditional bottom-up synthesis method.Herein,we propose a eutectic-directed self-templating strategy to prepare two multicomponent nanostructured alloys(PtPdRhIrNi(D-SN)and NiPtPdRhIrAl(D-SS))through the combination of rapid solidification with dealloying.The PtPdRhIrNi nanoporous nanowires(NPNWs)represent a new family of high-entropy alloys(HEAs)containing delicate hierarchical nanostructure with ultrafine ligament sizes of~2 nm in addition to one-dimensional(1D)morphology.Moreover,the PtPdRhIrNi NPNWs display excellent electrocatalytic activity and stability toward hydrogen evolution reaction,with the low overpotential of 22 and 55 mV to afford a current density of 10 mA·cm^(−2)in 0.5 M H_(2)SO_(4)and 1.0 M KOH electrolytes,respectively.The enhanced electrocatalytic performance can be attributed to the high-entropy effect favoring the surface electronic structure for the optimized activity,the promotion impact of Ni,1D morphology facilitating the electron transport,and the nanoporous structure promoting the electrolyte diffusion.

关键词： high-entropy alloy nanoporous nanowires dealloying electrocatalyst hydrogen evolution reaction

Self-templating synthesis and structural regulation of nanoporous rhodium-nickel alloy nanowires efficiently catalyzing hydrogen evolution reaction in both acidic and alkaline electrolytes

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Nano Research 2023年第2期16卷 2026-2034页

作者： Zhihua Zhai Yan Wang Conghui Si Pan Liu Wanfeng Yang Guanhua Cheng Zhonghua Zhang Key Laboratory for Liquid–Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061China School of Materials Science and Engineering University of JinanJinan 250022China Shandong Provincial Key Laboratory of Processing and Testing Technology of Glass&Functional Ceramics School of Materials Science and EngineeringQilu University of Technology(Shandong Academy of Sciences)Jinan 250353China Shanghai Key Laboratory of Advanced High Temperature Materials and Precision Forming School of Materials Science and EngineeringShanghai Jiao Tong UniversityShanghai 200240China

Highly active and stable electrocatalysts to produce hydrogen through water splitting are crucial for clean energy systems but are still challenging.Herein,a novel self-templating strategy was proposed to synthesize one-dimensional nanoporous RhNi alloy nanowires through combining metallurgical eutectic solidification and microalloying with chemical dealloying.In-situ X-ray diffraction and ex-situ characterizations reveal that the Al matrix served as a template to guide the growth of the Al3(Ni,Rh)nanowires during eutectic solidification of Al-Ni-Rh precursor and was completely removed in the dealloying process.Meanwhile,the nanowire morphology could be well retained and the dealloying of Al_(3)(Ni,Rh)led to the formation of nanoporous RhNi alloy nanowires.The length scale of the RhNi nanowires could be facilely regulated by changing the solidification conditions.More importantly,the RhNi catalysts show excellent electrocatalytic activity and stability towards hydrogen evolution reaction in both acidic and alkaline media,which has been rationalized by density functional theory calculations.

关键词： nanoporous alloys nanowires hydrogen evolution reaction density functional theory dealloying