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Journal of Energy Chemistry 2022年第8期31卷 580-587,I0016页

作者： Kahyun Ham Jaewon Lee Kiyoung Lee Jaeyoung Lee School of Earth Sciences and Environmental Engineering Gwangju Institute of Science and Technology(GIST)123 Cheomdangwagi-RoGwangju 61005South Korea International Future Research Center of Chemical Energy Storage and Conversion Processes GIST123 Cheomdangwagi-RoGwangju 61005South Korea Ertl Center for Electrochemical and Catalysis GIST123 Cheomdangwagi-RoGwangju 61005South Korea Department of Chemistry and Chemical Engineering Inha University100 Inha-RoIncheon 22212South Korea

Electrochemical water splitting is one of the most reliable approaches for environmental-friendly hydrogen production.Because of their stability and abundance,Mn-based materials have been studied as electrocatalysts for the oxygen evolution reaction(OER),which is a more sluggish reaction in the water splitting system.To increase the OER activity of Mn,it is imperative to facilitate the structural change of Mn oxide to the active phase with Mn_(3)+species,known as the active site.Here,we present the relationship between the electronic conductivity in the catalyst layer and the formation of the Mn active phase,δ-MnO_(2),from wrinkled Mn(OH)_(2).Mn(OH)_(2) has poor conductivity,and it disrupts the oxidation reaction toward MnOOH orδ-MnO_(2).Adjacent conductive carbon to Mn(OH)_(2) enabled Mn(OH)_(2) to be oxidized toδ-MnO_(2).Furthermore,after repetitive cyclic voltammetry activation,the more conductive environment resulted in a higher density ofδ-MnO_(2) through the irreversible phase transition,and thus it contributes to the improvement of the OER activity.

关键词： Hydrogen production oxygen evolution reaction Anion exchange membrane water electrolysis Anodization Manganese oxide

Anchoring Active Sites by Pt_(2)FeNi Alloy Nanoparticles on NiFe Layered Double Hydroxides for Efficient Electrocatalytic oxygen evolution reaction

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Energy & Environmental Materials 2022年第1期5卷 270-277页

作者： Zhicheng Zheng Yanru Guo Hao Wan Gen Chen Ning Zhang Wei Ma Xiaohe Liu Shuquan Liang Renzhi Ma School of Materials Science and Engineering Central South University College of Chemistry and Molecular Engineering Peking University School of Chemical Engineering Zhengzhou University International Center for Materials Nanoarchitectonics (WPI-MANA) National Institute for Materials Science (NIMS)

Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step hydrothermal coprecipitation method for essentially enhancing oxygen evolution reaction(OER)performance was proposed.The results of structural characterization indicate Pt_(2)FeNi alloy nanoparticles evenly distribute on the surface of DS^(-)-NiFe LDH.The sizes of the Pt_(2)FeNi nanoparticles,closely related to their OER performance,could be wellcontrolled by adjusting the amount of H;PtCl;addition.The composite structure of as-prepared product was stable during processes of synthesis,exfoliation,self-assembly,and subsequent electrocatalytic OER.Rigorous electrochemical test proving the contributing catalytic active sites was located at the interface between Pt_(2)FeNi and DS^(-)-NiFe LDH,and the Ni and Fe were the major active elements while O atoms are adsorption sites.The formation of Pt_(2)FeNi nanoparticles could greatly prompt the reduction of Tafel slope.The best-performing Pt_(2)FeNi/DS^(-)-NiFe LDH with a Pt content of 0.98 wt%achieved low overpotential of 204 mV at 10 mA cm^(-2)and 262 mV at 50 mA cm^(-2).This work provides a convenient and effective strategy to create additional active sites for enhancing OER performance of NiFe LDH and make contribution to its wide application.

关键词： electrocatalysis NiFe Layered double hydroxides oxygen evolution reaction Pt_(2)FeNi nanoparticles

Insight into sulfur and iron effect of binary nickel-iron sulfide on oxygen evolution reaction

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Nano Research 2022年第3期15卷 1901-1908页

作者： Qikang Wu Songrui Wang Jiahui Guo Xueqing Feng Han Li Shanshan Lv Yan Zhou Zheng Chen Key Laboratory of Functional Molecular Solids Ministry of EducationCollege of Chemistry and Materials ScienceAnhui Normal UniversityWuhu 241002China

Nickel-iron sulfide has shown attractive activity in electrocatalytic oxygen evolution reaction(OER).However,the effects of low valence sulfur(S^(2−))and metal species on OER in binary nickel-iron sulfide have rarely been systematically studied.Works based on post-catalysis characterization have led to the assumption that the real active species are nickel-iron oxyhydroxide,and that nickel-iron sulfide acts only as a precatalyst.Therefore,to study the role of S,Ni,and Fe for the development of nickel-iron sulfide catalyst is of self-evident importance.Herein,a facile solvothermal method is used to synthesize acetylene black coated with nickel-iron sulfide nanosheets.Electrochemical tests show that the presence of low valence S species makes the catalyst have faster OER kinetics,larger active area,and intermediate active species adsorption area.Therefore,the present study reveals the enhancing effect of low valence sulfur species(S^(2−))on OER in binary nickel-iron sulfide.In situ Raman spectroscopy shows that the generation ofγ-NiOOH intermediate is essential and Fe does not directly participate in the oxygen production.Density functional theory(DFT)calculation shows that Ni-OH deprotonation is a rate-determining step for both binary nickel-iron sulfide and nickel sulfide.The addition of Fe into NiSx lightly increases the charge transfer of Ni atom to O atom,which makes deprotonation easier and thereby improves the OER performance.

关键词： oxygen evolution reaction nickel-iron sulfide electrocatalyst low valence S species in-situ Raman

Low-cost high entropy alloy(HEA)for high-efficiency oxygen evolution reaction(OER)

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Nano Research 2022年第6期15卷 4799-4806页

作者： Lalita Sharma Nirmal Kumar Katiyar Arko Parui Rakesh Das Ritesh Kumar Chandra Sekhar Tiwary Abhisek K.Singh Aditi Halder Krishanu Biswas School of Basic Sciences Advanced Materials Research Centre(AMRC)Indian Institute of Technology Mandi(H.P)KamandMandi 175005India Department of Materials Science and Engineering Indian Institute of Technology KanpurKanpur 208016India School of Engineering London South Bank UniversityLondonSE10 AAUK Materials Research Centre Indian Institute of ScienceBangalore 560012India Metallurgical and Materials Engineering Indian Institute of Technology KharagpurKharagpur 382355India

oxygen evolution reaction(OER)is the key step involved both in water splitting devices and rechargeable metal-air batteries,and hence,there is an urgent need for a stable and low-cost material for efficient OER.In the present investigation,Co-Fe-Ga-NiZn(CFGNZ)high entropy alloy(HEA)has been utilized as a low-cost electrocatalyst for OER.Herein,after cyclic voltammetry activation,CFGNZ-nanoparticles(NPs)are covered with oxidized surface and form high entropy(oxy)hydroxides(HEOs),exhibiting a low overpotential of 370 mV to achieve a current density of 10 mA/cm^(2)with a small Tafel slope of 71 mV/dec.CFGNZ alloy has higher electrochemical stability in comparison to state-of-the art RuO2 electrocatalyst as no degradation has been observed up to 10 h of chronoamperometry.Transmission electron microscopy(TEM)studies after 10 h of long-term chronoamperometry test showed no change in the crystal structure,which confirmed the high stability of CFGNZ.The density functional theory(DFT)based calculations show that the closeness of d(p)-band centers to the Fermi level(EF)plays a major role in determining active sites.This work highlights the tremendous potential of CFGNZ HEA for OER,which is the primary reaction involved in water splitting.

关键词： high entropy alloy cyclic voltammetry activation oxygen evolution reaction electrocatalyst nanocrystalline catalyst

Deep eutectic solvent strategy enables an octahedral Ni–Co precursor for creating high-performance NiCo_(2)O_(4) catalyst toward oxygen evolution reaction

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Green Energy & Environment 2022年第6期7卷 1217-1227页

作者： Chenyun Zhang Bingwei Xin Tingting Chen Hao Ying Zhonghao Li Jingcheng Hao Key Laboratory of Colloid and Interface Chemistry Ministry of EducationShandong UniversityJinan250100China College of Chemistry and Chemical Engineering Dezhou UniversityDezhou253023China

Deep eutectic solvents(DESs)have gained much attention in the fabrication of advanced nanoelectrocatalysts due to their amazing template function.However,their stabilizing function for easily hydrolyzed inorganic nanomaterials is rarely studied.Here,a DES-mediated strategy was reported to synthesize octahedral Ni–Co precursor(NiCo–NH_(3) complex),which could be directly transformed into NiCo_(2)O_(4) nanooctahedrons after thermal decomposition.The NiCo–NH_(3) precursor in octahedral shape was achieved with the DES-mediated crystallization in the choline chloride(ChCl)/glycerol.The ChCl/glycerol DES not only tailored the morphology of the as-prepared precursor by template effect but also inhibited its hydrolysis,ensuring the successful fabrication of octahedral NiCo–NH_(3) complex precursor with high yield.The NiCo–NH_(3) complex precursor was converted to well-defined NiCo_(2)O_(4) nanooctahedrons,where the calcination temperature and time were explored in detail.It revealed that DES could participate in the conversion process to control the morphology of calcination product.The resultant NiCo_(2)O_(4) nanooctahedrons demonstrated excellent electroactivity and remarkable durability for oxygen evolution reaction(OER).The present strategy not only offers an efficient OER electrocatalyst but also enriches the approaches of DESs in designing advanced nanocatalysts.

关键词： Deep eutectic solvents Choline chloride Glycerol oxygen evolution reaction

Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction:a density functional theory study

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Frontiers of Chemical Science and Engineering 2023年第5期17卷 570-580页

作者： Xin Chen Liang Luo Shihong Huang Xingbo Ge Xiuyun Zhao Center for Computational Chemistry and Molecular Simulation College of Chemistry and Chemical EngineeringSouthwest Petroleum UniversityChengdu 610500China State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation Southwest Petroleum UniversityChengdu 610500China Oil&Gas Field Applied Chemistry Key Laboratory of Sichuan Province College of Chemistry and Chemical EngineeringSouthwest Petroleum UniversityChengdu 610500China Department of Applied Physics University of Eastern FinlandKuopio 70211Finland

Recently,metal–organic frameworks are one of the potential catalytic materials for electrocatalytic applications.The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory.Firstly,the catalytic activities of heterometallic clusters are investigated.Among all heterometallic clusters,Fe_(2)Mn–Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction,and Fe_(2)Co–Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction,respectively 100 and 50 mV lower than those of Pt(111)and RuO_(2)(110)catalysts.The analysis of the potential gap of Fe_(2)M clusters indicates that Fe_(2)Mn,Fe_(2)Co,and Fe_(2)Ni clusters possess good bifunctional catalytic activity.Additionally,the catalytic activity of Fe_(2)Mn and Fe_(2)Co connected through 3,3′,5,5′-azobenzenetetracarboxylate linker to form Fe_(2)M–PCN–Fe_(2)M is explored.Compared with Fe_(2)Mn–PCN–Fe_(2)Mn,Fe_(2)Co–PCN–Fe_(2)Co,and isolated Fe_(2)M clusters,the mixed-metal Fe_(2)Co–PCN–Fe_(2)Mn possesses excellent bifunctional catalytic activity,and the values of potential gap on the Mn and Co sites of Fe_(2)Co–PCN–Fe_(2)Mn are 0.69 and 0.70 V,respectively.Furthermore,the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst.In conclusion,the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.

关键词： bimetallic metal–organic frameworks bifunctional electrocatalyst density functional theory oxygen reduction reaction oxygen evolution reaction

Ultrafine Fe-modulated Ni nanoparticles embedded within nitrogen-doped carbon from Zr-MOFs-confined conversion for efficient oxygen evolution reaction

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Frontiers of Chemical Science and Engineering 2022年第7期16卷 1114-1124页

作者： Lingtao Kong Zhouxun Li Hui Zhang Mengmeng Zhang Jiaxing Zhu Mingli Deng Zhenxia Chen Yun Ling Yaming Zhou Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Department of ChemistryFudan UniversityShanghai 200433China

Improvement of the low-cost transition metal electrocatalyst used in sluggish oxygen evolution reaction is a significant but challenging problem. In this study, ultrafine Fe-modulated Ni nanoparticles embedded in a porous Ni-doped carbon matrix were produced by the pyrolysis of zirconium metal–organic–frameworks, in which 2,2′-bipyridine-5,5′-dicarboxylate operating as a ligand can coordinate with Ni^(2+) and Fe^(3+). This strategy allows formation of Fe-modulated Ni nanoparticles with a uniform dimension of about 2 nm which can be ascribed to the spatial blocking effect of ZrO_(2). This unique catalyst displays an efficient oxygen evolution reaction electrocatalytic activity with a low overpotential of 372 mV at 10 mA·cm^(–2) and a small Tafel slope of 84.4 mV·dec^(–1) in alkaline media. More importantly, it shows superior durability and structural stability after 43 h in a chronoamperometry test. Meanwhile, it shows excellent cycling stability during 4000 cyclic voltammetry cycles. This research offers a new insight into the construction of uniform nanoscale transition metals and their alloys as highly efficient and durable electrocatalysts.

关键词： metal–organic framework pyrolysis ultrafine Fe-modulated Ni nanoparticles oxygen evolution reaction

Iron adsorption engineering facilitated by Cu doping on cobalt hydroxide host with enhanced oxygen evolution reaction

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Nano Research 2023年第2期16卷 2111-2118页

作者： Xinyu Zhang Yiwen Dong Huiying Wang Ziyi Zhao Wenchun Jiang Bin Dong Han Hu Chenguang Liu Yongming Chai State Key Laboratory of Heavy Oil Processing College of Chemistry and Chemical EngineeringChina University of Petroleum(East China)Qingdao 266580China College of New Energy China University of Petroleum(East China)Qingdao 266580China

Iron plays a crucial role in improving the oxygen evolution reaction(OER)activity of hydroxide materials.Increasing the number of iron active sites at the solid–liquid interface is beneficial to enhancing the OER performance of catalysts but still challenging.Here,by systematic exploring the activity trends of M(OH)_(x)and Cu-M(OH)_(x)(M=Mn,Cu,Ni,Fe,and Co),we discover that the Cu doping can promote the deposition of Fe active sites on metal hydroxide and Cu-Co(OH)2 shows the most favorable iron adsorption capacity.When loaded on a conductive substrate(cobalt foam(CF),the M-Cu-Co(OH)2/CF(Co(OH)_(2))prepared by molten salt method)exhibits an attractive low overpotential of 337 mV at 1,000 mA·cm^(−2).Using in anion exchange membrane(AEM)water electrolyzer,the single cell with M-Cu-Co(OH)_(2)/CF as anode catalyst performs a stable cell voltage of 2.02 V to reach 1,000 mA·cm^(−2)over 24 h,indicating a great application potential for actual electrolytic water.Therefore,the promoted adsorption of copper on iron provides a new perspective for further enhancing the OER activity of other metal hydroxides.

关键词： copper doping promoted Fe adsorption industrial-level current density anion exchange membrane water electrolyzer oxygen evolution reaction

An amorphous FeMoO_(4) nanorod array enabled high-efficiency oxygen evolution electrocatalysis in alkaline seawater

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Nano Research 2024年第4期17卷 2270-2275页

作者： Jie Tang Shengjun Sun Xun He Hui Zhang Chaoxin Yang Min Zhang Meng Yue Hefeng Wang Yuntong Sun Yonglan Luo Sulaiman Alfaifi Asmaa Farouk Mohamed S.Hamdy Xuping Sun Huiqing Wang Binwu Ying Department of Laboratory Medicine West China HospitalSichuan UniversityChengdu 610041China College of Chemistry Chemical Engineering and Materials ScienceShandong Normal UniversityJinan 250014China Institute of Fundamental and Frontier Sciences University of Electronic Science and Technology of ChinaChengdu 610054China Chemistry Department Faculty of ScienceKing Abdulaziz UniversityJeddah 21589Saudi Arabia Department of Chemistry College of ScienceKing Khalid UniversityAbha 61413Saudi Arabia Medical Simulation Centre West China Second University HospitalSichuan UniversityChengdu 610041China

The development of highly efficient and durable oxygen evolution reaction(OER)catalysts for seawater electrolysis is of great importance for applications.Here,an amorphous FeMoO_(4) nanorod array on Ni foam is reported as a highly active OER electrocatalyst in alkaline seawater,requiring only overpotentials of 303 and 332 mV to achieve 100 and 300 mA·cm^(-2),respectively.Moreover,it shows strong long-term electrochemical durability for at least 50 h.

关键词： amorphous material FeMoO_(4) nanorod array electrocatalyst seawater electrolysis oxygen evolution reaction

CeO_(2)nanoparticles-decorated CoP nanocubes for accelerating alkaline electrocatalytic oxygen evolution reaction

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Particuology 2023年第10期81卷 38-44页

作者： Xueda Ding Yuxin Huang Dongyang Chen Zailai Xie College of Chemistry Fuzhou UniversityFuzhou350116China College of Materials Science and Engineering Fuzhou UniversityFuzhou350116China

Constructing heterojunction interface as an active catalyst is an effective strategy to boost electrocatalytic activity of oxygen evolution reaction(OER).Herein,we report an interfacial CoP/CeO_(2)heterostructure catalyst constructed by interface engineering and selective phosphorization procedure.X-ray photoelectron spectroscopy(XPS)suggests that coupling CeO_(2)nanoparticles on the surface of CoP will generate interfacial interaction at the two-phase interface,resulting in electron transfer between CoP and CeO_(2)components at the interface.Benefitting from the interfacial interaction,large exposed interface area,and luxuriant mesopores structure,CoP/CeO_(2)shows fascinating alkaline OER performance.At the current densities of 10 and 50 mA cm^(−2),the optimal CoP/CeO_(2)heterojunction exhibits lower overpotential(257 and 298 mV)than either CoP(288 and 354 mV)or RuO_(2)(305 and 409 mV).This work provides a facile synthetic protocol for constructing heterostructure interfaces to improve OER performance.

关键词： Prussian blue analogue CeO_(2)nanoparticles CoP/CeO_(2) oxygen evolution reaction