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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
基金financially supported by the National Key R&D Program of China(2022YFB4004100)the National Natural Science Foundation of China(22272161)+6 种基金the Jilin Province Science and Technology Development Program(20230101367JC)financially supported by the National Natural Science Foundation of China(22073094)the Science and Technology Development Program of Jilin Province(20210402059GH)the Science and Technology Plan Projects of Yunnan Province(202101BC070001–007)the Major Science and Technology Projects for Independent Innovation of China FAW Group Co.,Ltd(20220301018GX)the essential support of the Network and Computing Center,CIAC,CASthe Computing Center of Jilin Province。
文摘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.
基金financially supported by the NSFC-Yunnan Joint Foundation(U2002213)the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University(2019FY003025)the‘Double-First Class’University Construction Project(C176220100042 and CZ21623201)。
文摘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.
基金supported by a Grant of the Innovation and Technology Commission of Hong Kong(Project number:ITS/461/18)City University of Hong Kong(Project number:9678179).
文摘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.
基金Supported by the National Natural Science Foundation of China (No. 21073034)the State Key Laboratory of Structural Chemistry (No. 20090060)
文摘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.
基金The financial supports from Department of Chemical Engineeringthe support from China Scholarship Council(CSC)for his study at NTNU。
文摘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.
基金Financial supports from the NSFC-DFG (21761132006),NSFC (21773108)fundamental research funds for central universities are acknowledged
文摘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.
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.
文摘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.
基金financial support from the SERB-SURE under file number of SUR/2022/003129Jong Hyeok Park acknowledges the support of the National Research Foundation of Korea (NRF)funded by the Ministry of Science and ICT (RS-2023-00302697,RS-2023-00268523).
文摘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.
文摘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.
基金The project was supported by Youth Science Foundation of Shandong University
文摘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.
文摘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.
文摘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.
文摘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.
文摘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.
文摘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.