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Atomically dispersed Fe sites on hierarchically porous carbon nanoplates for oxygen reduction reaction
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作者 Ruixue Zheng Qinglei Meng +9 位作者 Hao Zhang Teng Li Di Yang Li Zhang Xiaolong Jia Changpeng Liu Jianbing Zhu Xiaozheng Duan Meiling Xiao Wei Xing 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第3期7-15,I0002,共10页
Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air bat... Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties. 展开更多
关键词 fe single atom catalysts Oxygen reduction reaction Mesoporous structure Active sites Zinc-air battery
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Boron modulating electronic structure of FeN4C to initiate high-efficiency oxygen reduction reaction and high-performance zinc-air battery 被引量:7
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作者 Xue Zhao Xue Li +7 位作者 Zenghui Bi Yuwen Wang Haibo Zhang Xiaohai Zhou Quan Wang Yingtang Zhou Huaisheng Wang Guangzhi Hu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第3期514-524,I0014,共12页
The biggest challenge is to develop a low cost and readily available catalyst to replace expensive commercial Pt/C for efficient electrochemical oxygen reduction reaction(ORR).In this research,closo-[B_(12)H_(12)]^(2−... The biggest challenge is to develop a low cost and readily available catalyst to replace expensive commercial Pt/C for efficient electrochemical oxygen reduction reaction(ORR).In this research,closo-[B_(12)H_(12)]^(2−)and 1,10-phenanthroline-iron complexes were introduced into the porous metal-organic framework by impregnation method,and further annealing treatment achieved the successful anchoring of single-atom-Fe in B-doped CN Matrix(FeN4CB).The ORR activity of FeN4CB is comparable to the widely used commercial 20 wt%Pt/C.Where the half-wave potential(E_(1/2))in alkaline medium up to 0.84 V,and even in the face of challenging ORR in acidic medium,the E_(1/2)of ORR driven by FeN4CB is still as high as 0.81 V.When FeN4CB was used as air cathode,the open circuit voltage of Zn-air battery reaches 1.435 V,and the power density and specific capacity are as high as 177 mW cm^(−2)and 800 mAh g_(Zn)^(−1)(theoretical value:820 mAh g_(Zn)^(−1)),respectively.The dazzling point of FeN4CB also appears in the high ORR stability,whether in alkaline or acidic media,E_(1/2)and limiting current density are still close to the initial value after 5000 times cycles.After continuously running the charge-discharge test for 220 h,the charge voltage and discharge voltage of the rechargeable zinc-air battery with FeN4CB as the air cathode maintained the initial state.Density functional theory calculations reveals that introducing B atom to Fe–N4–C can adjust the electronic structure to easily break O=O bond and significantly reduce the energy barrier of the rate-determining step resulting in an improved ORR activity. 展开更多
关键词 Single-atom fe B-doped CN Oxygen reduction reaction Zn-air battery Electronic modulation
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Inducing Fe 3d Electron Delocalization and Spin‑State Transition of FeN_(4) Species Boosts Oxygen Reduction Reaction for Wearable Zinc–Air Battery 被引量:3
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作者 Shengmei Chen Xiongyi Liang +7 位作者 Sixia Hu Xinliang Li Guobin Zhang Shuyun Wang Longtao Ma Chi‑Man Lawrence Wu Chunyi Zhi Juan Antonio Zapien 《Nano-Micro Letters》 SCIE EI CAS CSCD 2023年第4期23-39,共17页
Transition metal-nitrogen-carbon materials(M-N-Cs),particularly Fe-N-Cs,have been found to be electroactive for accelerating oxygen reduction reaction(ORR)kinetics.Although substantial efforts have been devoted to des... Transition metal-nitrogen-carbon materials(M-N-Cs),particularly Fe-N-Cs,have been found to be electroactive for accelerating oxygen reduction reaction(ORR)kinetics.Although substantial efforts have been devoted to design Fe-N-Cs with increased active species content,surface area,and electronic conductivity,their performance is still far from satisfactory.Hitherto,there is limited research about regulation on the electronic spin states of Fe centers for Fe-N-Cs electrocatalysts to improve their catalytic performance.Here,we introduce Ti_(3)C_(2) MXene with sulfur terminals to regulate the electronic configuration of FeN_(4) species and dramatically enhance catalytic activity toward ORR.The MXene with sulfur terminals induce the spin-state transition of FeN_(4) species and Fe 3d electron delocalization with d band center upshift,enabling the Fe(II)ions to bind oxygen in the end-on adsorption mode favorable to initiate the reduction of oxygen and boosting oxygen-containing groups adsorption on FeN_(4) species and ORR kinetics.The resulting FeN_(4)-Ti_(3)C_(2)Sx exhibits comparable catalytic performance to those of commercial Pt-C.The developed wearable ZABs using FeN_(4)-Ti_(3)C_(2)Sx also exhibit fast kinetics and excellent stability.This study confirms that regulation of the electronic structure of active species via coupling with their support can be a major contributor to enhance their catalytic activity. 展开更多
关键词 fe 3d electron delocalization Spin-state transition Oxygen reduction reaction Wearable zinc-air batteries
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Addition Reaction of Fe(CO)_n (n = 3~5) on Fullerene C_(50), C_(60), and C_(70): A Density Functional Theory Study 被引量:1
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作者 陈林刚 陈勇 +2 位作者 肖河阳 李浩宏 李俊篯 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2011年第8期1161-1167,共7页
The electronic structure and reactivities of Fe(CO)n (n = 3~5) addition to different fullerenes have been investigated through the first-principles calculations, and the results indicate that Fe(CO)3 and Fe(CO... The electronic structure and reactivities of Fe(CO)n (n = 3~5) addition to different fullerenes have been investigated through the first-principles calculations, and the results indicate that Fe(CO)3 and Fe(CO)4 can be adsorbed to the outside network of fullerene via hollow and bridge sites, respectively. Both of them have larger binding energy, but when Fe(CO)5 is adsorbed via the top site, the binding energy is relatively smaller. According to the directional curvature theory, the reactivities of Fe(CO)3 addition to the fullerenes are determined by KM of the ring center, and those of Fe(CO)4 addition by KD of the C–C bond curvature; while for Fe(CO)5, it presents weak reactivities in the addition reaction because of the larger volume effect. No matter whether the addition reaction takes place on the hollow or bridge site, the binding energies show a linear relationship with KD. This work further enriched the directional curvature theory and applied the isolobel analogy theory in the fullerene addition reactions. 展开更多
关键词 FULLERENE density functional theory addition reaction fe(CO)n directional curvature
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Boost oxygen reduction reaction performance by tuning the active sites in Fe-N-P-C catalysts 被引量:2
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作者 Yahao Li Ketao Zang +2 位作者 Xuezhi Duan Jun Luo De Chen 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2021年第4期572-579,共8页
Cost-effective atomically dispersed Fe-N-P-C complex catalysts are promising to catalyze the oxygen reduction reaction(ORR)and replace Pt catalysts in fuel cells and metal-air batteries.However,it remains a challenge ... Cost-effective atomically dispersed Fe-N-P-C complex catalysts are promising to catalyze the oxygen reduction reaction(ORR)and replace Pt catalysts in fuel cells and metal-air batteries.However,it remains a challenge to increase the number of atomically dispersed active sites on these catalysts.Here we report a highly efficient impregnation-pyrolysis method to prepare effective ORR electrocatalysts with large amount of atomically dispersed Fe active sites from biomass.Two types of active catalyst centers were identified,namely atomically dispersed Fe sites and Fe_(x)P particles.The ORR rate of the atomically dispersed Fe sites is three orders of magnitude higher than it of Fe_(x)P particles.A linear correlation between the amount of the atomically dispersed Fe and the ORR activity was obtained,revealing the major contribution of the atomically dispersed Fe to the ORR activity.The number of atomically dispersed Fe increases as the Fe loading increased and reaching the maximum at 1.86 wt%Fe,resulting in the maximum ORR rate.Optimized Fe-N-P-C complex catalyst was used as the cathode catalyst in a homemade Zn-air battery and good performance of an energy density of 771 Wh kgZn^(-1),a power density of 92.9 m W cm^(-2) at 137 m A cm^(-2) and an excellent durability were exhibited. 展开更多
关键词 Oxygen reduction reaction fe electrocatalyst Atomically dispersed active center Activity tuning Zn-air battery
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Preparation of Fe_2P/Al_2O_3 and FeP/Al_2O_3 catalysts for the hydrotreating reactions 被引量:3
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作者 Yamei Yuan Jiayou Zhang +2 位作者 Hui Chen Qiumei Hou Jianyi Shen 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2019年第2期116-121,共6页
A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in... A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in liquid phases to Fe2 P and Fe P.It was found that the iron sulfides(Fe0.96 S and Fe_3S_4) exhibited the low activity for the hydrodesulfurization(HDS) reactions.The HDS activity was also low on the Fe(metal)/Al_2O_3 and Fe_2 P/Al_2O_3 catalysts since they were converted into Fe0.96 S and Fe_3S_4 during the HDS reactions.In contrast,the FeP/Al_2O_3 was found to be stable and active for the HDS reactions.In particular,Fe P/Al_2O_3 possessed significantly smaller Fe P particles than Fe P/C,leading to the significant higher HDS activity of FeP/Al_2O_3 than Fe P/C. 展开更多
关键词 fe2P/Al2O3 CATALYST feP/Al2O3 CATALYST Liquid phase phosphidation PPh3 HYDROTREATING reactionS
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Influence of different Fe doping strategies on modulating active sites and oxygen reduction reaction performance of Fe, N-doped carbonaceous catalysts 被引量:1
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作者 Yang Liu Suqiong He +2 位作者 Bing Huang Ziyan Kong Lunhui Guan 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第7期511-520,I0013,共11页
Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity i... Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries. 展开更多
关键词 Mg-air battery Oxygen reduction reaction Single-atom fe/N/C catalysts fe doping strategies Zeolitic imidazole frameworks
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Fe,N,S-doped porous carbon as oxygen reduction reaction catalyst in acidic medium with high activity and durability synthesized using CaCl_2 as template 被引量:3
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作者 Chi Chen Zhiyou Zhou +4 位作者 Yucheng Wang Xue Zhang Xiaodong Yang Xinsheng Zhang Shigang Sun 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2017年第4期673-682,共10页
Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped p... Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped porous carbon(FeNS‐PC)was synthesized using melamine formaldehyderesin as C and N precursors,Fe(SCN)3as Fe and S precursors,and CaCl2as a template via a two‐stepheat treatment without a harsh template removal step.The results show that the catalyst treated at900℃(FeNS‐PC‐900)had a high surface area of775m2/g,a high mass activity of10.2A/g in anacidic medium,and excellent durability;the half‐wave potential decreased by only20mV after10000potential cycles.The FeNS‐PC‐900catalyst was used as the cathode in a proton exchangemembrane fuel cell and delivered a peak power density of0.49W/cm2.FeNS‐PC‐900therefore hasgood potential for use in practical applications. 展开更多
关键词 Non‐precious metal catalyst Oxygen reduction reaction Proton exchange membrane fuel cell fe N S‐doped porous carbon Melamine formaldehyde resin
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Measurement of absolute reaction rates in Be, Pb and Fe spherical systems 被引量:2
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作者 Liu Rong Chen Yuan +2 位作者 Guo Hai-Ping Shen Jian Liu Yuan and Jiang Wen-Mian (Institute of Nuclear Physics and Chemistry of CAEP, Chengdu 610003) 《Nuclear Science and Techniques》 SCIE CAS CSCD 1998年第2期82-85,共4页
The absolute reaction rates in Be,Pb and Fe have been measured by using the activation foil technique with different reaction energy thresholds.Thicknesses of Be,Pb and Fe spheres were 5.3,19.1 and 31.9cm.respectively... The absolute reaction rates in Be,Pb and Fe have been measured by using the activation foil technique with different reaction energy thresholds.Thicknesses of Be,Pb and Fe spheres were 5.3,19.1 and 31.9cm.respectively,Eight kinds of activation folis were used for Fe,and four kinds each for Be and Pb,The total experimental er5ror was about 5-7%.The measured results were compared to the values calculated with the 1-D ANISN code and the ENDF/B-VI library data.The average ratio of the experimental to the calculational is less than 7% for Be and Pb,about 5-30% for Fe. 展开更多
关键词 核聚变反应堆 BE PB fe 反应速率测量
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Fine-tuning electronic structure of N-doped graphitic carbon-supported Co-and Fe-incorporated Mo_(2)C to achieve ultrahigh electrochemical water oxidation activity 被引量:2
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作者 Md.Selim Arif Sher Shah Hyeonjung Jung +3 位作者 Vinod K.Paidi Kug-Seung Lee Jeong Woo Han Jong Hyeok Park 《Carbon Energy》 SCIE EI CAS CSCD 2024年第7期134-149,共16页
Mo_(2)C is an excellent electrocatalyst for hydrogen evolution reaction(HER).However,Mo_(2)C is a poor electrocatalyst for oxygen evolution reaction(OER).Herein,two different elements,namely Co and Fe,are incorporated... Mo_(2)C is an excellent electrocatalyst for hydrogen evolution reaction(HER).However,Mo_(2)C is a poor electrocatalyst for oxygen evolution reaction(OER).Herein,two different elements,namely Co and Fe,are incorporated in Mo_(2)C that,therefore,has a finely tuned electronic structure,which is not achievable by incorporation of any one of the metals.Consequently,the resulting electrocatalyst Co_(0.8)Fe_(0.2)-Mo_(2)C-80 displayed excellent OER catalytic performance,which is evidenced by a low overpotential of 214.0(and 246.5)mV to attain a current density of 10(and 50)mA cm^(-2),an ultralow Tafel slope of 38.4 mV dec^(-1),and longterm stability in alkaline medium.Theoretical data demonstrates that Co_(0.8)Fe_(0.2)-Mo_(2)C-80 requires the lowest overpotential(1.00 V)for OER and Co centers to be the active sites.The ultrahigh catalytic performance of the electrocatalyst is attributed to the excellent intrinsic catalytic activity due to high Brunauer-Emmett-Teller specific surface area,large electrochemically active surface area,small Tafel slope,and low chargetransfer resistance. 展开更多
关键词 fine-tuning electronic structures heteronanostructures Mo_(2)C multimetal(Co/fe) oxygen evolution reaction
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EFFECT OF Fe ON SURFACE REACTION OF Co_(3)Ti WITH WATER VAPOR
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作者 Y.X.Chen X.J.Wan W.X.Xu 《中国有色金属学会会刊:英文版》 CSCD 1999年第S1期142-145,共4页
The surface reaction of Co 3Ti alloys (with and without Fe) with water vapor was investigated by using Auger electron spectroscopy (AES). The results showed that the rate of the surface reaction is much lower in Co 21... The surface reaction of Co 3Ti alloys (with and without Fe) with water vapor was investigated by using Auger electron spectroscopy (AES). The results showed that the rate of the surface reaction is much lower in Co 21 5Ti 3Fe alloy as compared with Co 3Ti (Co 23Ti) alloy. The surface reaction of Co 21 5Ti 3Fe alloy with water vapor saturates at exposure of 2×10 -3 Pa·s, but it does not saturate even at 0 1 Pa·s exposure for Co 3Ti alloy without Fe. The results also indicated that the kinetic of the surface reaction of Co 21 5Ti 3Fe with water vapor is much smaller than that of Co 3Ti at the same exposure. All the above results illustrate that the suppression of environmental embrittlement by addition of Fe to Co 3Ti alloy is attributed to its reduction of the surface reaction kinetics with water vapor. 展开更多
关键词 Co_(3)Ti surface reaction water vapor fe doping
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REACTION OF FERROCENOYL CHLORIDE WITH [Et_(?)NH] [μ-CO)(μ-RS)Fe_2(CO)_6]COMPLEXES SYNTHESIS AND STRUCTURE OF Fe_2(CO)_6COMPLEXES WITH BRIDGING FERROCENOYL LIGAND
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作者 Jin Ting LIU Xin SHENG Xia ZHONG Department of Chemistry, Shandong University, Jinan, 250100 《Chinese Chemical Letters》 SCIE CAS CSCD 1993年第11期1025-1028,共4页
Reaction of ferrocenoyl chloride with [Et;NH] [(μ-CO)(μ-RS) Fe;=(CO);] complexes gave bridging ferrocenoyl complexes(μ-FcCO)(μ-RS)Fe;(CO);(Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph).The structures of all... Reaction of ferrocenoyl chloride with [Et;NH] [(μ-CO)(μ-RS) Fe;=(CO);] complexes gave bridging ferrocenoyl complexes(μ-FcCO)(μ-RS)Fe;(CO);(Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph).The structures of all new complexes were characterised by;HNMR, IR and MS. 展开更多
关键词 fe COMPLEXES SYNTHESIS AND STRUCTURE OF fe2 RS)fe2 Et reaction OF feRROCENOYL CHLORIDE WITH NH
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Solid-State Reaction and Vacancy-Type Defects in Bilayer Fe/Hf Studied by the Slow Positron Beam
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作者 K. Yamada T. Sasaki +5 位作者 T. Nagata I. Kanazawa R. Suzuki T. Ohdaira K. Nozawa F. Komori 《Journal of Applied Mathematics and Physics》 2015年第2期233-239,共7页
The positron annihilation lifetimes and the Doppler broadening by slow positron beam are measured in thin Fe films with thickness 500 nm, a thin Hf film with thickness 100 nm, and the bilayer Fe (50 nm)/Hf (50 nm) on ... The positron annihilation lifetimes and the Doppler broadening by slow positron beam are measured in thin Fe films with thickness 500 nm, a thin Hf film with thickness 100 nm, and the bilayer Fe (50 nm)/Hf (50 nm) on quartz glass substrate. We have analyzed the behavior in vacancy-type defects in each layer through some deposition temperatures and annealing. It is observed that the thin Fe film, the thin Hf film, and the bilayer Fe (50 nm)/Hf (50 nm) already contain many vacancy-type defects. We have investigated the change of densities of the vacancy-carbon complex and the small vacancy-cluster with carbons, through solid-state amorphization of Fe (50 nm)/Hf (50 nm) bilayer. 展开更多
关键词 Metallic Films POSITRON ANNIHILATION Measurement SOLID-STATE reaction fe Film Diffusion Vacancy-Type Defects
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Fe稳固的FeOOH@NiOOH电催化剂的大电流极化设计与析氧研究
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作者 吕青芸 张伟伟 +8 位作者 龙志鹏 王建涛 邹星礼 任伟 侯龙 鲁雄刚 赵玉峰 余兴 李喜 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第7期254-264,共11页
电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍... 电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍铁羟基/氢氧化物(NiFe(oxy)hydroxides)是近期研究的热点,其在碱性条件下具有极低的OER过电位,部分材料性能甚至超过了贵金属基催化剂,如IrO_(2)和RuO_(2).然而,NiFe(oxy)hydroxides的长期催化稳定性,尤其是在大电流下的长期催化稳定性,成为限制其实际应用的主要问题,这主要是由于铁元素的严重流失导致的.因此,如何有效控制和利用电化学溶解/沉积动力学成为稳定铁位点的关键.为克服该挑战,本文提出了一种大电流极化重构方法来固定活性铁位点.通过在大电流(1.5 A cm^(-2))下对材料进行表面快速极化重构,成功制备了FeOOH@NiOOH(eFNO_(L))电催化剂.eFNO_(L)不仅具有稳定的铁位点,还暴露出高指数晶面,因此eFNO_(L)同时展现出较好的OER催化活性和稳定性.同时,密度泛函理论计算结果表明,与具有低指数晶面的FeNiOOH相比,大电流极化工程制备的分相eFNO_(L)对铁位点表现出更高的结合能,可以有效抑制OER过程中的铁流失,且高指数晶面在改变速率决定步骤和减少吸附能垒上具有更大的优势.电化学测试结果表明,经过优化后的eFNO_(L)催化剂在产生100和500 mA cm^(-2)大电流密度仅需234和27 mV的过电位,并且具有较小的Tafel斜率(35.2 mV dec^(-1)).由于铁位点结合能的提高,eFNO_(L)催化剂在500 mA cm^(-2)的电流密度下能够稳定催化超过100 h,且仅有1.5%的性能衰减,优于近期报道的大多数镍铁基OER催化剂.综上,本文为开发高活性和高稳定性能的催化剂提供了一种有效的大电流电化学重构策略,在电解水制氢领域实现其工业化的大规模应用方面显示出巨大潜力,有望降低可持续电解水制氢成本. 展开更多
关键词 析氧反应 feOOH@NiOOH 大电流极化重构 高指数晶面 铁位点固定
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Ti/Fe EUTECTIC REACTION PROCESS
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作者 WU Mingfang MA Cheng YANG Min 《Chinese Journal of Mechanical Engineering》 SCIE EI CAS CSCD 2006年第4期614-617,共4页
To obtain satisfactory joining between titanium alloys end stainless steel, it is of great significance to study the process of Ti-Fe eutectic reaction. The preliminary studies about the liquid forming, spreading end ... To obtain satisfactory joining between titanium alloys end stainless steel, it is of great significance to study the process of Ti-Fe eutectic reaction. The preliminary studies about the liquid forming, spreading end the structure of the contact reaction between pure Ti and pure Fe are carried out at 1 120℃ for different holding times in high-frequency induction heated vacuum furnace. The results show that for Fe(particle-like)/Ti(plate-like) contact reaction couples, owing to Fe's higher density then titanium's, the Fe/Ti eutectic reaction develops in the thickness direction of plate-like Ti, named "deposition effect". Then the eutectic reaction can be realized without the inter-diffusion between Ti end Fe atoms, so the formation rate of the liquid phase is very quick. For Ti (particle-like)/ Fe (plate-like) contact reaction couples, the eutectic reaction has a strong direction, i.e. the eutectic liquid is formed mostly at the Ti side, which leads to much dissolution of Ti particle end very little dissolution of the Fe base metal. It can be seen that the diffusion rate of Fe in Ti determines the whole process of the eutectic reaction, behaved as that the dissolution rate of Ti (particle-like)/ Fe (plate-like) is much lower then that of Fe(particle-like)/Ti(plate-like), end the dissolution rate of Ti obeys the square root law. Whatever means the Ti, Fe are assembled by, only dissolution process can be founded, the spread phenomena is unobvious, which is concerned with the formation of the inter- metallic compounds end the "deposition effect" of Fe. 展开更多
关键词 Ti fe Eutectic reaction Dissolution Spread
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Atomically dispersed Fe atoms anchored on N-doped carbon hollow nanospheres boost the electrocatalytic performance for oxygen reduction reaction
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作者 Danye Liu Dong Chen Jun Yang 《Green Energy & Environment》 SCIE CSCD 2019年第3期208-209,共2页
Oxygen reduction reaction(ORR)is the key reaction at the cathode of proton exchange membrane fuel cells(PEMFCs)and metal-air batteries(1)To address the challenges associated with Pt-based electrocatalysts having promi... Oxygen reduction reaction(ORR)is the key reaction at the cathode of proton exchange membrane fuel cells(PEMFCs)and metal-air batteries(1)To address the challenges associated with Pt-based electrocatalysts having prominent activity for ORR,e.g.scarce abundance,prohibitive cost,poor stability,and vulnerability to reaction intermediates,it is necessary to explore other cost-effective ORR electrocatalysts with competitive or even superior performance to promote the commercialization of the energy conversion devices. 展开更多
关键词 Atomically dispersed fe ATOMS anchored on N-DOPED CARBON hollow NANOSPHERES BOOST the electrocatalytic performance for oxygen reduction reaction SiO BOOST
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Fe/N/C材料在质子交换膜燃料电池中阴极催化剂的研究进展
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作者 李宬志 冯骞 +1 位作者 李超 刘伟京 《应用化工》 CAS CSCD 北大核心 2024年第4期991-995,共5页
从ORR反应的机理出发,结合Fe/N/C材料的制备方式,从活性位点角度分析了Fe/N/C材料高效氧还原电催化的机制,并针对在高性能Fe/N/C材料开发过程中存在的各种稳定性问题进行阐述。对于Fe/N/C催化剂在燃料电池中的应用前景提出建议和展望,... 从ORR反应的机理出发,结合Fe/N/C材料的制备方式,从活性位点角度分析了Fe/N/C材料高效氧还原电催化的机制,并针对在高性能Fe/N/C材料开发过程中存在的各种稳定性问题进行阐述。对于Fe/N/C催化剂在燃料电池中的应用前景提出建议和展望,为今后Fe/N/C材料的发展提供了参考。 展开更多
关键词 fe/N/C材料 氧还原反应 质子交换膜燃料电池 活性位点 电催化
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Ti-Si-Fe合金添加量对Si_(3)N_(4)结合SiC材料结构与性能的影响
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作者 姚路炎 韩兵强 +1 位作者 张锦化 柯昌明 《耐火材料》 CAS 北大核心 2024年第4期277-283,共7页
为促进Si_(3)N_(4)结合SiC耐火材料的致密化,降低Si粉氮化温度,以SiC颗粒和细粉、Si粉为主要原料,利用从高钛型高炉渣提取的Ti-Si-Fe合金部分取代Si粉,在埋碳气氛下于1350℃反应烧结5 h,制备了Si_(3)N_(4)结合SiC耐火材料。研究了Ti-Si... 为促进Si_(3)N_(4)结合SiC耐火材料的致密化,降低Si粉氮化温度,以SiC颗粒和细粉、Si粉为主要原料,利用从高钛型高炉渣提取的Ti-Si-Fe合金部分取代Si粉,在埋碳气氛下于1350℃反应烧结5 h,制备了Si_(3)N_(4)结合SiC耐火材料。研究了Ti-Si-Fe合金添加量(加入质量分数分别为0、1.8%、3.6%、5.4%、7.2%)对Si粉的氮化行为、材料力学性能和显微结构的影响,并探讨了氮化反应烧结机制。结果表明:1)随着Ti-Si-Fe合金添加量的增加,材料的常温力学性能和高温抗折强度明显改善,荷重软化温度均超过1700℃,Ti-Si-Fe合金添加量超过3.6%(w)后材料性能的增幅变缓;2)Ti-Si-Fe合金促进了Si粉在较低温度下的完全氮化和材料的反应烧结,Ti-Si-Fe合金中各物相及Si粉氮化反应的体积增加能够充填气孔,氮化产物改善骨料与基质、基质内部的结合状态,从而提高材料的致密化程度,改善力学性能;3)引入Ti-Si-Fe合金后,反应体系中形成了富含Ti、Si、N、Fe成分的液相,氮化物的形成除传统的VS、VLS机制外,溶解-沉淀机制在短柱状β-Si_(3)N_(4)、粒状TiN的形成中起到主导作用,交错连结的α-Si_(3)N_(4)晶须、短柱状β-Si_(3)N_(4)、粒状TiN对材料的力学性能起到增强作用。 展开更多
关键词 Ti-Si-fe合金 反应烧结 Si_(3)N_(4)结合SiC耐火材料 致密化 溶解-沉淀
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Effect of particle size of iron on reaction velocity of combustion synthesis of Ti-C-Fe system
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作者 范群成 柴惠芬 金志浩 《中国有色金属学会会刊:英文版》 CSCD 2002年第2期266-268,共3页
Four Ti C Fe powder mixtures, with a same molar ratio but different particle sizes of Fe and Ti, were used to measure the reaction velocity of the combustion synthesis. The results show that in the case of the finer T... Four Ti C Fe powder mixtures, with a same molar ratio but different particle sizes of Fe and Ti, were used to measure the reaction velocity of the combustion synthesis. The results show that in the case of the finer Ti powder used, the reaction velocity of mixture with the finer Fe powder is higher than that with the coarser Fe powder. However, in the case of the coarser Ti powder used, the reaction velocity of mixture with the finer Fe powder is lower than that with the coarser Fe powder. The effect of particle size of Fe powder on reaction velocity can be explained with the previously proposed mechanisms of the combustion synthesis of Ti C Fe system. 展开更多
关键词 Ti-C-fe粉末混合物 燃烧合成 反应速度 微粒尺寸 金属陶瓷
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铋牺牲法制备石墨烯负载Fe-N单原子位点增效氧还原催化和锌-空气电池性能
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作者 杨志远 张燕 +2 位作者 肖娟定 王俊英 王俊中 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第4期272-281,共10页
催化氧反应(ORR)是锌空电池和氢燃料电池能量转化的关键过程,然而其反应速率往往较低,因此开发高活性且耐久的催化材料至关重要.当前,研发低成本、高效率且稳定的氧还原催化剂已成为国内外的研究热点.其中,富含金属-氮-碳活性位点的低成... 催化氧反应(ORR)是锌空电池和氢燃料电池能量转化的关键过程,然而其反应速率往往较低,因此开发高活性且耐久的催化材料至关重要.当前,研发低成本、高效率且稳定的氧还原催化剂已成为国内外的研究热点.其中,富含金属-氮-碳活性位点的低成本ORR催化材料,因其具有替代贵金属的潜力,成为重要的候选材料.然而,在制备这类催化剂时,所用分子前驱体在热解过程中易团聚形成金属基硬颗粒,如何减少热解过程中金属成分的自发聚集和不良副产物的生成,提高活性单原子的利用率,特别是在使用廉价分子前驱体(如三聚氰胺和铁盐)时,仍面临挑战.本研究旨在探索有效的制备策略,以优化催化剂性能,推动其在能源转换领域的应用.本文报道了一种以硝酸铋为牺牲剂,石墨烯为导电载体,通过热解廉价的三聚氰胺和铁盐,合成石墨烯负载丰富Fe-N-C活性位点催化剂的新方法.该方法中硝酸铋前驱体高温热解生成的铋铁合金或氧化铋因表面没有碳层,而容易被热酸除去,形成更多的可接近的FeNx活性位点,从而有效地抑制铁基颗粒和管状碳结构的形成,实现了催化剂的高效合成.双球差矫正电镜、X-射线光电子能谱和X-射线吸收结构光谱等表征证明,铋化合物去除后留下空位被铁原子取代,增加了Fe-N-C位点密度,并且铁以单原子活性位形式存在.实验结果表明,所制备的催化剂表现出高氧还原性能,在碱性和酸性条件下的半波电位分别为0.916和0.784 V.石墨烯基催化剂的动力学电流密度(0.9 V vs.RHE)达到10.41 mA cm^(-2),是不加铋化合物样品的6倍,贵金属Pt/C催化剂的4倍.此外,催化剂的塔菲尔斜率为59 mV dec^(-1),低于不加铋化合物样品(80 mV dec^(-1))、不加石墨烯样品(93 mV dec^(-1))、无金属样品(88 mV dec^(-1))和Pt/C(80 mV dec^(-1)).在0.1 mol L^(-1) KOH条件下,催化剂循环10000圈后,半波电位仅衰减15 mV,低于Pt/C(36 mV)和无铋对照样(20 mV),表明催化剂具有较好的稳定性.由于电化学法制备的石墨烯比热解法制备的非晶碳具有更好的耐腐蚀性,从而可以提高阴极氧还原的稳定性.另外,所制备的催化剂应用在锌-空气电池中时,最大功率密度可达201.4 mW cm-2,且循环1000次后电池电压几乎没有衰减.综上,本研究通过引入铋化合物,显著提升了廉价前驱物铁-三聚氰胺的金属单原子化效率.利用电化学法合成了石墨烯负载的Fe-N-C催化活性位,制备出高活性、高稳定的催化剂.将该低成本催化剂应用于锌-空气电池的阴极,其表现出良好的长循环性能.本研究为制备低成本、高性能的金属-氮-碳基电催化剂提供了新思路. 展开更多
关键词 氧还原反应 石墨烯 锌-空气电池 fe-N-C
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