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Intermetallic-driven highly reversible electrocatalysis in Li–CO_(2) battery over nanoporous Ni_(3)Al/Ni heterostructure

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eScience 2023年第3期3卷 79-88页

作者： Tianzhen Jian Wenqing Ma Caixia Xu Hong Liu John Wang Institute for Advanced Interdisciplinary Research(iAIR) School of Chemistry and Chemical EngineeringCollaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of ShandongUniversity of JinanJinan250022China Department of Materials Science and Engineering National University of SingaporeSingapore117574Singapore Institute of Materials Research and Engineering A*StarSingapore138634Singapore

Li–CO_(2) batteries,which integrate CO_(2) utilization and electrochemical energy storage,offer the prospect of utilizing a greenhouse gas and providing an alternative to the well-established lithium-ion batteries.However,they still suffer from rather limited reversibility,low energy efficiency,and sluggish CO_(2) redox reaction kinetics.To address these key issues,a nanoporous Ni_(3)Al intermetallic/Ni heterojunction(NP–Ni_(3) Al/Ni)is purposely engi-neered here via an alloying–etching protocol,whereby the unique interactions between Al and Ni in Ni_(3)Al endow NP-Ni_(3)Al/Ni with optimum reactant/product adsorption and thus unique catalytic performance for the CO_(2) redox reaction.Furthermore,the nanoporous spongy structure benefits mass transport as well as discharge product storage and enables a rich multiphase reaction interface.In situ Raman studies and theoretical simulations reveal that both CO_(2) reduction and the co-decomposition of Li_(2)CO_(3) and C are distinctly promoted by NP-Ni_(3)Al/Ni,thereby greatly improving catalytic activity and stability.NP-Ni_(3)Al/Ni offers promising application potential in Li–CO_(2) batteries,with its scalable fabrication,low production cost,and superior catalytic performance.

关键词： Ni_(3)Al intermetallic Nanoporous Li-CO_(2)batteries dealloying

简单易得的自氧化纳米泡沫镍用于高性能析氢和析氧催化

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Science China Materials 2023年第10期66卷 3855-3864页

作者：徐洪杰王新朝赵威郭瑞娟薛志勇张涛邵洋姚可夫 Institute for Advanced Materials North China Electric Power UniversityBeijing 102206China Key Laboratory of Aerospace Materials and Performance(Ministry of Education) School of Materials Science and EngineeringBeihang UniversityBeijing 100191China Key Laboratory for Advanced Materials Processing Technology Ministry of EducationSchool of Materials Science and EngineeringTsinghua UniversityBeijing 100084China Center for Advanced Analysis and Computational Science Zhengzhou UniversityZhengzhou 450001China

开发组成简单、无贵金属、制备简洁的自支撑析氢、析氧催化反应(HER和OER)催化剂是电解水的关键需求之一.本文以Mg_(80)Ni_(20)非晶合金薄带为前驱体,采用一步脱合金法制备了具有自支撑结构的自氧化纳米泡沫镍,在电流密度为10 mA cm^(-2... 详细信息

开发组成简单、无贵金属、制备简洁的自支撑析氢、析氧催化反应(HER和OER)催化剂是电解水的关键需求之一.本文以Mg_(80)Ni_(20)非晶合金薄带为前驱体,采用一步脱合金法制备了具有自支撑结构的自氧化纳米泡沫镍,在电流密度为10 mA cm^(-2)时HER和OER的过电位仅分别为33.1和330 mV,且均具有长达100 h的长期稳定性.基于纳米泡沫镍的水电解槽达到10 mA cm^(-2)的外加电压仅为1.58 V.纳米泡沫镍独特的三维超细多孔结构显著促进了其表观活性,同时其Ni/NiO复合结构显著提高了本征HER活性.本工作验证了纳米泡沫金属是一种有潜力的高性能催化材料.

关键词： metallic glass dealloying Ni nano-foam hydrogen evolution oxygen evolution

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Ternary mesoporous cobalt-iron-nickel oxide efficiently catalyzing oxygen/hydrogen evolution reactions and overall water splitting

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Nano Research 2019年第9期12卷 2281-2287页

作者： Lulu Han Limin Guo Chaoqun Dong Chi Zhang Hui Gao Jiazheng Niu 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 Jilin Engineering Normal University Changchun 130052China State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China School of Applied Physics and Materials Wuyi University22 Dongcheng VillageJiangmen 529020China

Among various efficient electrocatalysts for water splitting,CoFe and NiFe-based oxides/hydroxides are typically promising candidates thanks to their extraordinary activities towards oxygen evolution reaction (OER).However,the endeavor to advance their performance towards overall water splitting has been largely impeded by the limited activities for hydrogen evolution reaction (HER).Herein,we present a CoFeNi ternary metal-based oxide (CoFeNi-O) with impressive hierarchical bimodal channel nanostructures,which was synthesized via a facile one-step dealloying strategy.The oxide shows superior catalytic activities towards both HER and OER in alkaline solution due to the alloying effect and the intrinsic hierarchical porous structure.CoFeNi-O loaded on glass carbon electrodes only requires the overpotentials as low as 230 and 278 mV to achieve the OER current densities of 10 and 100 mA·cm-2,respectively.In particular,extremely low overpotentials of 200 and 57.9 mV are sufficient enough for Ni foam-supported CoFeNi-O to drive the current density of 10 mA·cm-2 towards OER and HER respectively,which is comparable with or even better than the already-developed state-of-the-art non-noble metal oxide based catalysts.Benefiting from the bifunctionalities of CoFeNi-O,an alkaline electrolyzer constructed by the Ni foam-supported CoFeNi-O electrodes as both the anode and the cathode can deliver a current density of 10 mA·cm-2 at a fairly low cell-voltage of 1.558 V.In view of its electrocatalytic merits together with the facile and cost-effective dealloying route,CoFeNi-O is envisioned as a promising catalyst for future production of sustainable energy resources.

关键词： electrocatalysts hydrogen evolution reaction oxygen evolution reaction water splitting dealloying

Highly efficient nanoporous CoBP electrocatalyst for hydrogen evolution reaction

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Rare Metals 2021年第5期40卷 1031-1039页

作者： Hui-Lan Guang Sheng-Li Zhu Yan-Qin Liang Shui-Lin Wu Zhao-Yang Li Shui-Yuan Luo Zhen-Duo Cui Akihisa Inoue School of Materials Science and Engineering Tianjin UniversityTianjin 300350China School of Materials Science and Engineering Lanzhou Jiaotong UniversityLanzhou 730070China College of Chemistry Engineering and Materials Science Quanzhou Normal UniversityQuanzhou 362000China International Institute of Green Materials Josai International UniversityTogane 283-8555Japan Department of Physics King Abdulaziz UniversityJeddah 22254Saudi Arabia

Water splitting is an environment friendly and efficient way to produce hydrogen.Highly efficient and low-cost non-noble metal catalysts play an important role in hydrogen evolution reaction(HER).dealloying is a simple method to prepare three-dimensional self-supporting nanoporous materials without conductive supports and binders.In this work,we prepared self-supporting nanoporous CoBP electrocatalyst by dealloying method.The influence of the synergistic effect of nonmetallic elements on catalytic activity was investigated.The synergistic electronic effect of Co,B and P atoms on the surface optimizes the H atoms desorption and results in superior HER activity.The bi-continuous structure of nanoporous CoBP provides more active area and favors of electron and electrolyte transfer.The nanoporous CoBP with the B/P atomic ratio of 1/3 exhibits low overpotential of 42 mV at 10 mA·cm^(-2),small Tafel slope of 39.8 mV·dec-1 and good long-term stability with no performance decrease for 20 h in alkaline solution.

关键词： Hydrogen evolution reaction Nanoporous Self-supporting electrocatalyst Co-B-P alloy dealloying

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Self-supporting Co_(0.85)Se nanosheets anchored on Co plate as highly efficient electrocatalyst for hydrogen evolution reaction in both acidic and alkaline media

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Nano Research 2020年第11期13卷 2950-2957页

作者： Rong Qin Jiagang Hou Caixia Xu Hongxiao Yang Qiuxia Zhou Zizhong Chen Hong Liu Institute for Advanced Interdisciplinary Research(iAIR) Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of ShandongUniversity of JinanJinan250022China Qilu University of Technology(Shandong Academy of Sciences) Jinan250353China State Key Laboratory of Crystal Materials Shandong UniversityJinan250100China

Electrocatalytic water splitting via hydrogen evolution reaction(HER)represents one of promising strategies to gain hydrogen energy.In current work,self-supporting Co_(0.85)Se nanosheets network anchored on Co plate(Co_(0.85)Se NSs@Co)is fabricated by employing easily tailorable Co metal plate as the source conductive substrate.The scalable dealloying and hydrothermal selenization strategy was employed to build one layer of three dimensional interlinking Co_(0.85)Se nanosheets network on the surface of Co plate.Benefiting from bulky integrated architecture and rich active sites,the as-made Co_(0.85)Se NSs@Co exhibits superior electrocatalytic activity and long-term catalytic durability toward HER.It only requires lower overpotentials of 121 and 162 mV to drive the current density of 10 mA·cm^(−2)for hydrogen evolution in 0.5 M H_(2)SO_(4)and 1 M KOH solution.Especially,no evident activity decay occurs upon 1,500 cycles or continuous test for 20 h at 10 mA·cm^(−2)in both acidic and alkaline electrolytes.With the merits of exceptional performances,scalable production,and low cost,the self-supporting Co0.85Se NSs@Co holds prospective application potential as stable and binder-free electrocatalysts for hydrogen generation in a wide range of electrolyte.

关键词： hydrogen evolution reaction Co_(0.85)Se electrocatalyst dealloying hydrothermal selenization

Facile synthesis and enhanced catalytic activity of electrochemically dealloyed platinum–nickel nanoparticles towards formic acid electro-oxidation

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Journal of Energy Chemistry 2019年第8期28卷 9-16,I0001页

作者： Maryam Kiani Jie Zhang Yan Luo Yihan Chen Jinwei Chen Jinlong Fan Gang Wang Ruilin Wang College of Materials Science and Engineering Sichuan University

To obtain the electrocatalyst with an improved electrocatalytic performance towards formic acid electrooxidation(FAEO), a simple impregnation method is used to prepare Pt3Ni nanoparticles loaded on carbon black, assisted with electrochemically dealloying process. The X-ray powder diffraction(XRD) results as well as transmission electron microscopy(TEM) analysis of as-synthesized electrocatalyst demonstrates that the reduction temperature has a great influence on the FAEO activity of the dealloyed Pt3Ni nanoparticles. X-ray photoelectron spectroscopy(XPS) analyses confirm the variation in the electronic structure of platinum by incorporation of nickel atoms which reduces chemisorption of toxic carbon monoxide and promotes the dehydrogenation pathway of FAEO. The size of the dealloyed Pt3Ni nanoparticles remains within the range of about 2.7 nm. All electrochemical results illustrate that the performance of the asobtained electrocatalyst towards the FAEO is significantly enhanced. Moreover, the carbon black content,incorporation of Ni atoms, and reduction temperature conditions have been proven to be the key factors for modification of the crystal structure and morphology which leads to enhanced catalytic performance.

关键词： Formic acid electro-oxidation Electrocatalysis Pt3Ni nanoparticles dealloying Dehydrogenation pathway

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Self-supported amorphous nanoporous nickel-cobalt phosphide catalyst for hydrogen evolution reaction

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Progress in Natural Science:Materials International 2021年第2期31卷 201-206页

作者： Yao Pang Shengli Zhu Zhenduo Cui Yanqin Liang Zhaoyang Li Shuilin Wu School of Materials Science and Engineering Tianjin University School of Materials Science and Engineering Lanzhou Jiaotong University

Hydrogen evolution reaction(HER) through electrocatalysis using cost-efficient and long-term stable bimetallic phosphide as electrocatalyst holds a great promise for sustainable clean energy technologies. In this study, self-supported nanoporous Ni-Co-P(np-Ni-Co-P) catalyst with amorphous structure was synthesized by utilizing a facile electrochemical dealloying strategy. The results showed that due to the nanoporous structure, disorder atomic arrangement and alloying effect, the np-Ni-Co-P exhibited outstanding electrocatalytic performance for HER with low overpotential of 114 m V at a current density of 10 mA cm~2, small Tafel slope(57.3 mV dec-1) and good long-term durability in 1 M KOH. The synergetic effect of Ni and Co elements improves the intrinsic activity of the active sites. This research provides a direction for the exploration of bimetallic phosphides toward HER in the water splitting process.

关键词： Hydrogen evolution reaction Metal phosphide Electrocatalyst dealloying Amorphous alloys

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Nanoporous magnesium

Nano Research 2018年第12期11卷 6428-6435页

作者： Ilya Vladimirovich Okulov Sviatlana V.Lamaka Takeshi Wada Kunio Yubuta Mikhail L.Zheludkevich Jorg Weissmuller Jurgen Markmann Hidemi Kato Institute for Materials Research Tohoku UniversityKatahira 2-1-1Sendai980-8577Japan Institute of Materials Research Materials MechanicsHelmholtz-Zentrum Geesthacht21502GeesthachtGermany MagiC-Magnesium Innovation Centre Helmholtz-Zentrum Geesthacht21502GeesthachtGermany Faculty of Engineering University of Kiel24118KielGermany Institute of Materials Physics and Technology Hamburg University of Technology21073HamburgGermany

In this study, we present freestanding nanoporous magnesium as a novel lightweight material with high potential for structural and functional applications. Thus far, the high reactivity of Mg with oxygen and aqueous media prevented the fabrication of nanoporous Mg. First, in order to synthesize nanoporous Mg, we fabricated a bicontinuous nanocomposite consisting of interpenetrating Mg and non-Mg phases by liquid metal dealloying. The non-Mg phases in the nanocomposite protect Mg against corrosion. Second, we etched the non-Mg phases from the nanocomposite, leaving nanoporous Mg, using HF solution. This process is advantageous because the nanoporous Mg was passivated by a MgF2 layer during the etching. Our approach is very flexible, and we demonstrate that versatile microstructures of the nanoporous Mg—e.g., nanoscale bicontinuous network, hierarchical, or plate-like structures—can be designed for the given needs. More importantly, these nanoporous Mg samples can readily be exposed to air without being harmed by corrosion.

关键词： dealloying nanoporous magnesium

Fabrication of fine spongy nanoporous Ag-Au alloys with improved catalysis properties

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Progress in Natural Science:Materials International 2017年第6期27卷 658-663页

作者： Cuiting Li Tao Zhang Min Zhang Yu Jin Lei Zuo Hongjie Xu Ran Li Key Laboratory of Aerospace Materials and Performance (Ministry of Education) School of Materials Science and Engineering Beihang University Materials Science and Engineering Research Center School of Mechanical Electronic and Control Engineering Beijing Jiaotong University

Fine NP-AgAu（nanoporous AgAu） alloys with spongy structure was fabricated by chemical dealloying from rapidly solidified amorphous precursors Ag;Cu;Si;Au;（x=0, 0.5, 1 and 5）. The results indicate that the addition of small content Au in precursor can refine both the ligaments and pores obviously. Among the present components of the precursors, NP-AgAu alloys dealloying from Ag;Cu;Si;Au;had the finest spongy structure. The size of pores was 5–10 nm and the grain size of ligaments was 10–20 nm. It also had the highest surface area of 106.83 m;g;and the best catalytic activity towards electro-oxidation of formaldehyde with the peak current of 665 mA mg;.

关键词： Nanoporous Ag-Au dealloying Formaldehyde electro-oxidation Catalysis Amorphous