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
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
By using the first-principles calculations, the electronic Structure and quantum transport properties of metallic carbon nanotubes with B/N pairs co-doping have been investigated. It is shown that the total energies o...By using the first-principles calculations, the electronic Structure and quantum transport properties of metallic carbon nanotubes with B/N pairs co-doping have been investigated. It is shown that the total energies of metallic carbon nanotubes are sensitive to the doping sites of the B/N pairs. The energy gaps of the doped metallic carbon nanotubes decrease with decreasing the concentration of the B/N pair not only along the tube axis but also around the tube. Moreover, the I-V characteristics and transmissions of the doped tubes are studied. Our results reveal that the conducting ability of the doped tube decreases with increasing the concentrations of the B/N pairs due to symmetry breaking of the system. This fact opens a new way to modulate band structures of metallic carbon nanotubes by doping B/N pair with suitable concentration and the novel characteristics are potentially useful in future applications.展开更多
Using the first-principles calculations, we investigate the electronic band structure and the quantum transport properties of metallic carbon nanotubes （MCNTs） with B/N pair co-doping. The results about formation en...Using the first-principles calculations, we investigate the electronic band structure and the quantum transport properties of metallic carbon nanotubes （MCNTs） with B/N pair co-doping. The results about formation energy show that the B/N pair co-doping configuration is a most stable structure. We find that the electronic structure and the transport properties are very sensitive to the doping concentration of the B/N pairs in MCNTs, where the energy gaps increase with doping concentration increasing both along the tube axis and around the tube, because the mirror symmetry of MCNT is broken by doping B/N pairs. In addition, we discuss conductance dips of the transmission spectrum of doped MCNTs. These unconventional doping effects could be used to design novel nanoelectronic devices.展开更多
The saturated solubility of carbon and nitrogen in Fe-C-N and Fe-C-B-N melts was measured experimentally at 1 485℃ to obtain the activity interaction coefficients between components in these melts. A new method was u...The saturated solubility of carbon and nitrogen in Fe-C-N and Fe-C-B-N melts was measured experimentally at 1 485℃ to obtain the activity interaction coefficients between components in these melts. A new method was used to treat experimental results. Using thermodynamic derivation and calculation, some important interac- tion coefficients between components in these melts were obtained.展开更多
Electrocatalytic N2 reduction to ammonia is a fascinating alternative to Haber-Bosch process and also considered as an energy sto rage method.This work,Fe doped MoS2/carbon cloth(CC) has been studied on the electro-ca...Electrocatalytic N2 reduction to ammonia is a fascinating alternative to Haber-Bosch process and also considered as an energy sto rage method.This work,Fe doped MoS2/carbon cloth(CC) has been studied on the electro-catalysis fix nitrogen indicating the doped Fe can indeed enhance the MoS2 material ability.Compared with MoS2/CC,Fe-Mo-S-3/CC not only increases 10 times in the rate of production ammonia,but also 5 times in Faraday efficiency.展开更多
We investigate the effect of the optimized aging processing on magnetism and mechanical property of the sintered Dydoped Nd–Fe–B permanent magnet. The experimental results show that the magnetism, especially intrins...We investigate the effect of the optimized aging processing on magnetism and mechanical property of the sintered Dydoped Nd–Fe–B permanent magnet. The experimental results show that the magnetism, especially intrinsic coercivity, of the optimized aged Dy-doped Nd–Fe–B magnet is more excellent than that of the sintered one, but the former＇s strength and hardness are lower than that of the latter. It was observed that the optimized aged Dy-doped Nd–Fe–B magnet have more uniform grain size, thinner（Nd, Dy）-rich boundary phase. By means of the EBSD technology, the number of larger angle grain boundaries in the optimized aged Dy-doped Nd–Fe–B magnet is more than that of the sintered one. The reasons for the increased intrinsic coercivity and decreased mechanical properties of the optimized aged Dy-doped Nd–Fe–B magnet are also discussed.展开更多
基金supported by the National Natural Science Foundation of China(22171266)the FJIRSM&IUE Joint Research Fund(RHZX-2019-002)+2 种基金the STS Project(KFJ-STS-QYZD-2021-09002)the National Key Basic Research Program of China(2017YFA0403402)the Project of the National Natural Science Foundation of China(U1932119)。
文摘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.
基金supported by the National Basic Research Program of China (973 Program,2015CB932303)the National Natural Science Founda-tion of China (21373175,21621091)~~
文摘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.
基金supported by the Major Research Plan from the Ministry of Science and Technology of China (Grant No. 2011CB921900)the China Postdoctoral Science Special Foundation (Grant No. 201003009)+2 种基金the China Postdoctoral Science Foundation (GrantNo. 20090460145)the Fundamental Research Funds for the Central Universities (Grant No. 201012200053)the Science and Technology Program of Hunan Province of China (Grant No. 2010DFJ411)
文摘By using the first-principles calculations, the electronic Structure and quantum transport properties of metallic carbon nanotubes with B/N pairs co-doping have been investigated. It is shown that the total energies of metallic carbon nanotubes are sensitive to the doping sites of the B/N pairs. The energy gaps of the doped metallic carbon nanotubes decrease with decreasing the concentration of the B/N pair not only along the tube axis but also around the tube. Moreover, the I-V characteristics and transmissions of the doped tubes are studied. Our results reveal that the conducting ability of the doped tube decreases with increasing the concentrations of the B/N pairs due to symmetry breaking of the system. This fact opens a new way to modulate band structures of metallic carbon nanotubes by doping B/N pair with suitable concentration and the novel characteristics are potentially useful in future applications.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.10325415 and 50504017)the Natural Science Foundation of Hunan Province,China(Grant No.07JJ3102)+1 种基金the Scientific Research Fund of Hunan Provincial Education Department,China(Grant No.10C1171)the Science Development Foundation of Central South University,China(Grant Nos.08SDF02 and 09SDF09)
文摘Using the first-principles calculations, we investigate the electronic band structure and the quantum transport properties of metallic carbon nanotubes （MCNTs） with B/N pair co-doping. The results about formation energy show that the B/N pair co-doping configuration is a most stable structure. We find that the electronic structure and the transport properties are very sensitive to the doping concentration of the B/N pairs in MCNTs, where the energy gaps increase with doping concentration increasing both along the tube axis and around the tube, because the mirror symmetry of MCNT is broken by doping B/N pairs. In addition, we discuss conductance dips of the transmission spectrum of doped MCNTs. These unconventional doping effects could be used to design novel nanoelectronic devices.
基金Item Sponsored by National Natural Science Foundation of China (50374002)
文摘The saturated solubility of carbon and nitrogen in Fe-C-N and Fe-C-B-N melts was measured experimentally at 1 485℃ to obtain the activity interaction coefficients between components in these melts. A new method was used to treat experimental results. Using thermodynamic derivation and calculation, some important interac- tion coefficients between components in these melts were obtained.
基金supported by Science and Technology Commission of Shanghai Municipality(Nos.17ZR1441200,18QA1402400 and 18230743400)National Natural Science Foundation of China(Nos.21771124,21901156)。
文摘Electrocatalytic N2 reduction to ammonia is a fascinating alternative to Haber-Bosch process and also considered as an energy sto rage method.This work,Fe doped MoS2/carbon cloth(CC) has been studied on the electro-catalysis fix nitrogen indicating the doped Fe can indeed enhance the MoS2 material ability.Compared with MoS2/CC,Fe-Mo-S-3/CC not only increases 10 times in the rate of production ammonia,but also 5 times in Faraday efficiency.
基金supported by the Chinese National Major Special Project for the Rare Earth and Rare Metallic Materials(Grant No.(2012)1743)
文摘We investigate the effect of the optimized aging processing on magnetism and mechanical property of the sintered Dydoped Nd–Fe–B permanent magnet. The experimental results show that the magnetism, especially intrinsic coercivity, of the optimized aged Dy-doped Nd–Fe–B magnet is more excellent than that of the sintered one, but the former＇s strength and hardness are lower than that of the latter. It was observed that the optimized aged Dy-doped Nd–Fe–B magnet have more uniform grain size, thinner（Nd, Dy）-rich boundary phase. By means of the EBSD technology, the number of larger angle grain boundaries in the optimized aged Dy-doped Nd–Fe–B magnet is more than that of the sintered one. The reasons for the increased intrinsic coercivity and decreased mechanical properties of the optimized aged Dy-doped Nd–Fe–B magnet are also discussed.
