Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly...Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly efficient Fe-N-C porous ORR electrocatalyst with FeNx moieties promoted by Fe2N nanoparticles derived from Fe-doped zeolitic imidazolate framework.The best-performing Fe-N-C/HPC-NH3 catalyst exhibits a superior ORR activity with an onset (E0) and half-wave (E1/2) potential of 0.945 and 0.803 V (RHE),respectively,which is comparable to those of the commercial Pt/C in acidic media.Probing and acid-leaching experiments prove that FeNx moieties play an important role in the ORR and the Fe2N can further improve the ORR activity.Density functional theory calculation reveals a synergistic effect that the existence of Fe2N weakens the adsorption of ORR intermediates on active sites and lowers the reaction free energy of the potential limiting step,thus facilitating the ORR.Both experimental evidence and theoretical analysis for the enhancement of ORR activity by Fe2N decoration in Fe-N-C catalyst might inspire a new strategy for rational design of high performance non-precious metal catalysts.展开更多
Co-based metal-organic framework(MOF),a kind of porous crystal material composed of Co ions and organic linkers,is a common type of MOF.It not only has the intrinsic properties of MOF,such as structural diversity,func...Co-based metal-organic framework(MOF),a kind of porous crystal material composed of Co ions and organic linkers,is a common type of MOF.It not only has the intrinsic properties of MOF,such as structural diversity,functional adjustability,and high surface area,but more importantly,it contains Co metal species,which are considered by many reports to be active catalytic centers for many reactions.Meanwhile,metal catalysts always received wide and sustained attention.The combi-nation of the two types of catalysts can enhance the catalytic performance and achieve the"1+1>2"effect.In this review,we mainly overview the synthesis methods of Co-based MOF-derived metal catalysts from nano-to atom-level and their applications in the catalysis field in recent years and put forward our own views and prospects for this research direction.展开更多
Wide-angle light scattering(WALS)was used for in situ measurements of droplet and nanoparticle size distributions during the synthesis of titania and iron oxide particles from liquid precursor solutions in the standar...Wide-angle light scattering(WALS)was used for in situ measurements of droplet and nanoparticle size distributions during the synthesis of titania and iron oxide particles from liquid precursor solutions in the standardized SpraySyn burner for spray flame synthesis.Titania was synthesized from titanium tetraisopropoxide(TTIP)and iron oxide from iron(II)nitrate nonahydrate(INN)using ethanol(EtOH)as solvent.Scattering images were taken at heights up to 120 mm above the burner surface and classified into droplet and particle scattering.Droplet size distributions were derived from a sequential analysis of scattering data containing the oscillating Mie pattern,the lognormal size distribution parameters for spherical and fractal particle fractions from a multivariate approach on averaged particle scattering data.The results show that the precursor addition leads to altered evaporation behavior and even droplet disruption probably induced by puffing or micro-explosions compared to pure EtOH.In the case of TTIP(a hygroscopic alkoxide),the synthesis of a large fraction of spheres was observed,while the nitrate INN leads to the formation of mostly fractal aggregates.展开更多
基金the National Key Research and Development Program of China (No.2017YFA0206500)the National Natural Science Foundation of China (Nos.21802161,21673275,and 21533005).
文摘Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly efficient Fe-N-C porous ORR electrocatalyst with FeNx moieties promoted by Fe2N nanoparticles derived from Fe-doped zeolitic imidazolate framework.The best-performing Fe-N-C/HPC-NH3 catalyst exhibits a superior ORR activity with an onset (E0) and half-wave (E1/2) potential of 0.945 and 0.803 V (RHE),respectively,which is comparable to those of the commercial Pt/C in acidic media.Probing and acid-leaching experiments prove that FeNx moieties play an important role in the ORR and the Fe2N can further improve the ORR activity.Density functional theory calculation reveals a synergistic effect that the existence of Fe2N weakens the adsorption of ORR intermediates on active sites and lowers the reaction free energy of the potential limiting step,thus facilitating the ORR.Both experimental evidence and theoretical analysis for the enhancement of ORR activity by Fe2N decoration in Fe-N-C catalyst might inspire a new strategy for rational design of high performance non-precious metal catalysts.
基金The authors gratefully acknowledge the financial support from the Natural Science research project of Universities in Anhui Province(KJ2021ZD0001)the Natural Science Foundation of AnhuiProvince(2208085MB20).
文摘Co-based metal-organic framework(MOF),a kind of porous crystal material composed of Co ions and organic linkers,is a common type of MOF.It not only has the intrinsic properties of MOF,such as structural diversity,functional adjustability,and high surface area,but more importantly,it contains Co metal species,which are considered by many reports to be active catalytic centers for many reactions.Meanwhile,metal catalysts always received wide and sustained attention.The combi-nation of the two types of catalysts can enhance the catalytic performance and achieve the"1+1>2"effect.In this review,we mainly overview the synthesis methods of Co-based MOF-derived metal catalysts from nano-to atom-level and their applications in the catalysis field in recent years and put forward our own views and prospects for this research direction.
基金funded by the German Research Foundation DFG under grants WI1602/16-1 and WI1602/16-2.
文摘Wide-angle light scattering(WALS)was used for in situ measurements of droplet and nanoparticle size distributions during the synthesis of titania and iron oxide particles from liquid precursor solutions in the standardized SpraySyn burner for spray flame synthesis.Titania was synthesized from titanium tetraisopropoxide(TTIP)and iron oxide from iron(II)nitrate nonahydrate(INN)using ethanol(EtOH)as solvent.Scattering images were taken at heights up to 120 mm above the burner surface and classified into droplet and particle scattering.Droplet size distributions were derived from a sequential analysis of scattering data containing the oscillating Mie pattern,the lognormal size distribution parameters for spherical and fractal particle fractions from a multivariate approach on averaged particle scattering data.The results show that the precursor addition leads to altered evaporation behavior and even droplet disruption probably induced by puffing or micro-explosions compared to pure EtOH.In the case of TTIP(a hygroscopic alkoxide),the synthesis of a large fraction of spheres was observed,while the nitrate INN leads to the formation of mostly fractal aggregates.
