Flower-like hierarchical three-dimensional Ni Fe layered double hydroxides hollow microspheres(3D NiFe-LDH HMS),as one kind of novel non-noble metal electrocatalysts,have been fabricated in a templatefree route for wa...Flower-like hierarchical three-dimensional Ni Fe layered double hydroxides hollow microspheres(3D NiFe-LDH HMS),as one kind of novel non-noble metal electrocatalysts,have been fabricated in a templatefree route for water oxidation.Both of the concentration of ammonium fluoride and the reaction time are adjusted to obtain a series of Ni Fe-LDH microspheres,with different internal structures from massive to hollow generated during the hydrothermal treatment,which improve the electrocatalytic activity of the Ni Fe-LDH catalysts towards the evolution reaction of oxygen.The optimized Ni Fe-LDH-0.4M HMS show the excellent OER performance in alkaline electrolyte withη=290 mV@10 mA cm^-2,and a Tafel slope of 51 mV dec-1,which outperforms the benchmark RuO2 catalyst.The possible reason is attributed to the more exposure of active sites,and fast ion transport resulting from the hierarchical hollow structure.展开更多
Carbon-based N-coordinated Mn(Mn-N_(x)/C)single-atom electrocatalysts are considered as one of the most desirable non-precious oxygen reduction reaction(ORR)candidates due to their insignificant Fenton reactivity,high...Carbon-based N-coordinated Mn(Mn-N_(x)/C)single-atom electrocatalysts are considered as one of the most desirable non-precious oxygen reduction reaction(ORR)candidates due to their insignificant Fenton reactivity,high abundance,and intriguing electrocatalytic performance.However,current MnN_(x)/C single-atom electrocatalysts suffer from high overpotentials because of their low intrinsic activity and unsatisfactory chemical stability.Herein,through an in-situ polymerization-assisted pyrolysis,the Co as a second metal is introduced into the Mn-N_(x)/C system to construct Co,Mn-N_(x)dual-metallic sites,which atomically disperse in N-doped 1D carbon nanorods,denoted as Co,Mn-N/CNR and hereafter.Using electron microscopy and X-ray absorption spectroscopy(XAS)techniques,we verify the uniform dispersion of CoN4and MnN4atomic sites and confirm the effect of Co doping on the MnN_(4) electronic structure.Density functional theory(DFT)calculations further elucidate that the energy barrier of ratedetermining step(^(*)OH desorption)decreases over the 2 N-bridged MnCoN_(6) moieties related to the pure MnN_(4).This work provides an effective strategy to modulate the local coordination environment and electronic structure of MnN_(4) active sites for improving their ORR activity and stability.展开更多
Incorporation of anions of Acid Red 114 dye （1,3-naphthalenedisulfonic acid, 8-[2-[3,3＇-dimethyl-4＇-[2-[4- [l（4-methylphenyl）sulfonyl]oxy] phenyl]diazenyl] [1,1＇-biphenyl]-4-yl]diazenyl]-7-hydroxy-, disodium sal...Incorporation of anions of Acid Red 114 dye （1,3-naphthalenedisulfonic acid, 8-[2-[3,3＇-dimethyl-4＇-[2-[4- [l（4-methylphenyl）sulfonyl]oxy] phenyl]diazenyl] [1,1＇-biphenyl]-4-yl]diazenyl]-7-hydroxy-, disodium salt） （denoted as NPDA） into ZnAl-layered double hydroxides （LDHs） has been carried out by an anion- exchange method in an effort to improve their thermal stability and light fastness. After intercalation of NPDA anions, the interlayer distance of the LDHs increases from 0.87 to 2.18 nm, confirming their incorporation into the interlayer galleries of the LDHs host. Infrared spectroscopy and thermogravimetric analysis revealed the presence of host-vip interactions between LDHs layers and NPDA anions. The thermal stability of NPDA and ZnAI-NPDA-LDHs was compared by thermogravimetric-differential ther- mal analysis, UV-visible spectroscopy and infrared spectroscopy. It was found that the thermal stability of NPDA anions was markedly improved by incorporation into the ZnA1-LDHs matrix, while the light fastness was also enhanced.展开更多
基金supported by the National Natural Science Foundation of ChinaProgramme XU GuangqiProgram for Changjiang Scholars and Innovative Research Team in University (No. IRT1205)
文摘Flower-like hierarchical three-dimensional Ni Fe layered double hydroxides hollow microspheres(3D NiFe-LDH HMS),as one kind of novel non-noble metal electrocatalysts,have been fabricated in a templatefree route for water oxidation.Both of the concentration of ammonium fluoride and the reaction time are adjusted to obtain a series of Ni Fe-LDH microspheres,with different internal structures from massive to hollow generated during the hydrothermal treatment,which improve the electrocatalytic activity of the Ni Fe-LDH catalysts towards the evolution reaction of oxygen.The optimized Ni Fe-LDH-0.4M HMS show the excellent OER performance in alkaline electrolyte withη=290 mV@10 mA cm^-2,and a Tafel slope of 51 mV dec-1,which outperforms the benchmark RuO2 catalyst.The possible reason is attributed to the more exposure of active sites,and fast ion transport resulting from the hierarchical hollow structure.
基金the financial support from the Research Foundation for Talented Scholars of Hainan University(YEAZ22091)the financial supports from the Joint Funds of the National Natural Science Foundation of China(ZK20180055)+1 种基金the Programs for Foreign Talent(G2021106012L)the National Natural Science Foundation of China(22075290)。
文摘Carbon-based N-coordinated Mn(Mn-N_(x)/C)single-atom electrocatalysts are considered as one of the most desirable non-precious oxygen reduction reaction(ORR)candidates due to their insignificant Fenton reactivity,high abundance,and intriguing electrocatalytic performance.However,current MnN_(x)/C single-atom electrocatalysts suffer from high overpotentials because of their low intrinsic activity and unsatisfactory chemical stability.Herein,through an in-situ polymerization-assisted pyrolysis,the Co as a second metal is introduced into the Mn-N_(x)/C system to construct Co,Mn-N_(x)dual-metallic sites,which atomically disperse in N-doped 1D carbon nanorods,denoted as Co,Mn-N/CNR and hereafter.Using electron microscopy and X-ray absorption spectroscopy(XAS)techniques,we verify the uniform dispersion of CoN4and MnN4atomic sites and confirm the effect of Co doping on the MnN_(4) electronic structure.Density functional theory(DFT)calculations further elucidate that the energy barrier of ratedetermining step(^(*)OH desorption)decreases over the 2 N-bridged MnCoN_(6) moieties related to the pure MnN_(4).This work provides an effective strategy to modulate the local coordination environment and electronic structure of MnN_(4) active sites for improving their ORR activity and stability.
基金supported by National Natural Science Foundation of China
文摘Incorporation of anions of Acid Red 114 dye （1,3-naphthalenedisulfonic acid, 8-[2-[3,3＇-dimethyl-4＇-[2-[4- [l（4-methylphenyl）sulfonyl]oxy] phenyl]diazenyl] [1,1＇-biphenyl]-4-yl]diazenyl]-7-hydroxy-, disodium salt） （denoted as NPDA） into ZnAl-layered double hydroxides （LDHs） has been carried out by an anion- exchange method in an effort to improve their thermal stability and light fastness. After intercalation of NPDA anions, the interlayer distance of the LDHs increases from 0.87 to 2.18 nm, confirming their incorporation into the interlayer galleries of the LDHs host. Infrared spectroscopy and thermogravimetric analysis revealed the presence of host-vip interactions between LDHs layers and NPDA anions. The thermal stability of NPDA and ZnAI-NPDA-LDHs was compared by thermogravimetric-differential ther- mal analysis, UV-visible spectroscopy and infrared spectroscopy. It was found that the thermal stability of NPDA anions was markedly improved by incorporation into the ZnA1-LDHs matrix, while the light fastness was also enhanced.
