Ni-Fe-based catalysts are considered to be among the most active catalysts for the oxygen evolution reaction(OER)under alkaline conditions,with Fe playing a crucial role.However,Fe leaching occurs during the reaction ...Ni-Fe-based catalysts are considered to be among the most active catalysts for the oxygen evolution reaction(OER)under alkaline conditions,with Fe playing a crucial role.However,Fe leaching occurs during the reaction due to thermodynamic instability,which has resulted in conflicting reports within the literature regarding its role.To clarify this point,we propose a strategy consisting of modulating the electronic orbital occupancy to suppress the extensive loss of Fe atoms during the OER process.Theoretical calculations,in-situ X-ray photoelectron spectroscopy,molecular dynamics simulations,and a series of characterization showed that the stable presence of Fe not only accelerates the electron transfer process but also optimizes the reaction barriers of the oxygen evolution intermediates,promoting the phase transition of Fe_(5)Ni_(4)S_(8)to highly active catalytic species.The modulated Fe_(5)Ni_(4)S_(8)-based pre-catalysts exhibit improved OER activity and long-term durability.This study provides a novel perspective for understanding the role of Fe in the OER process.展开更多
钠离子电池(SIBs)的阳极材料一直备受研究关注,但缓慢的动力学行为和较大的体积变化限制了其在实际应用中的推广。为了克服这些问题,本研究利用金属有机框架和MoS_(2)的优异性能,设计并制备了具有稳定骨架结构的复合材料。以Co-ZIF为前...钠离子电池(SIBs)的阳极材料一直备受研究关注,但缓慢的动力学行为和较大的体积变化限制了其在实际应用中的推广。为了克服这些问题,本研究利用金属有机框架和MoS_(2)的优异性能,设计并制备了具有稳定骨架结构的复合材料。以Co-ZIF为前驱体,添加Mo源材料,在高温硫化烧结的过程中,构建了花状的Co_(9)S_(8)/MoS_(2)/C复合材料,探究其在不同温度条件下的结构和电化学性能。此外,通过密度泛函理论(DFT)分析了Co9S8(001)/MoS2异质结对扩散动力学的影响。结果表明,电子结构在异质结构的界面处发生了重塑,Co_(9)S_(8)/MoS_(2)表现出典型的金属性和显著增强的电子导电性。在所有样品中,700℃合成的阳极材料Co_(9)S_(8)/MoS_(2)/C具有更稳定的结构和优异的电化学性能。当电流密度从4000恢复到40 mA g^(-1)时,Co_(9)S_(8)/MoS_(2)/C-700的放电容量可以从368 mAh g^(-1)完全恢复到571 mAh g^(-1),并稳定在543 mAh g^(-1)。综上所述,本研究提供了一些关于异质结材料合理制备的思路,有助于设计高性能的金属钠离子电池负极复合材料。展开更多
以四水合钼酸铵、六水合硝酸钴和硫脲为原料,采用一步水热法在钛网(TM)上原位构筑了不同阵列结构Co_(9)S_(8)/MoS_(2)@TM催化电极。通过改变原料中钴、钼、硫的物质的量之比来调控Co_(9)S_(8)/MoS_(2)@TM电极的结构。采用SEM、XRD和XPS...以四水合钼酸铵、六水合硝酸钴和硫脲为原料,采用一步水热法在钛网(TM)上原位构筑了不同阵列结构Co_(9)S_(8)/MoS_(2)@TM催化电极。通过改变原料中钴、钼、硫的物质的量之比来调控Co_(9)S_(8)/MoS_(2)@TM电极的结构。采用SEM、XRD和XPS对Co_(9)S_(8)/MoS_(2)@TM进行物相分析和形貌表征,并在1 mol/L KOH电解液中对Co_(9)S_(8)/MoS_(2)@TM的电催化析氧性能进行了研究。结果表明,钴、钼、硫的物质的量之比为10∶14∶600时,制备的Co_(9)S_(8)/MoS_(2)@TM为3D花瓣状阵列结构,且在10 m A/cm^(2)电流密度下过电势为271 m V,塔菲尔斜率为88.5 m V/dec,具有良好的析氧稳定性和耐久性,展现了优异的电化学性能。展开更多
基金financially supported by the Scientific and Technological Development Program of Jilin Province(20220201138GX)the support of the National Key R&D Program of China(No.2022YFA1503801)+1 种基金CAS Project for Young Scientists in Basic Research(No.YSBR-022)the Young Cross Team Project of CAS(No.JCTD-2021-14)。
文摘Ni-Fe-based catalysts are considered to be among the most active catalysts for the oxygen evolution reaction(OER)under alkaline conditions,with Fe playing a crucial role.However,Fe leaching occurs during the reaction due to thermodynamic instability,which has resulted in conflicting reports within the literature regarding its role.To clarify this point,we propose a strategy consisting of modulating the electronic orbital occupancy to suppress the extensive loss of Fe atoms during the OER process.Theoretical calculations,in-situ X-ray photoelectron spectroscopy,molecular dynamics simulations,and a series of characterization showed that the stable presence of Fe not only accelerates the electron transfer process but also optimizes the reaction barriers of the oxygen evolution intermediates,promoting the phase transition of Fe_(5)Ni_(4)S_(8)to highly active catalytic species.The modulated Fe_(5)Ni_(4)S_(8)-based pre-catalysts exhibit improved OER activity and long-term durability.This study provides a novel perspective for understanding the role of Fe in the OER process.
文摘钠离子电池(SIBs)的阳极材料一直备受研究关注,但缓慢的动力学行为和较大的体积变化限制了其在实际应用中的推广。为了克服这些问题,本研究利用金属有机框架和MoS_(2)的优异性能,设计并制备了具有稳定骨架结构的复合材料。以Co-ZIF为前驱体,添加Mo源材料,在高温硫化烧结的过程中,构建了花状的Co_(9)S_(8)/MoS_(2)/C复合材料,探究其在不同温度条件下的结构和电化学性能。此外,通过密度泛函理论(DFT)分析了Co9S8(001)/MoS2异质结对扩散动力学的影响。结果表明,电子结构在异质结构的界面处发生了重塑,Co_(9)S_(8)/MoS_(2)表现出典型的金属性和显著增强的电子导电性。在所有样品中,700℃合成的阳极材料Co_(9)S_(8)/MoS_(2)/C具有更稳定的结构和优异的电化学性能。当电流密度从4000恢复到40 mA g^(-1)时,Co_(9)S_(8)/MoS_(2)/C-700的放电容量可以从368 mAh g^(-1)完全恢复到571 mAh g^(-1),并稳定在543 mAh g^(-1)。综上所述,本研究提供了一些关于异质结材料合理制备的思路,有助于设计高性能的金属钠离子电池负极复合材料。
文摘以四水合钼酸铵、六水合硝酸钴和硫脲为原料,采用一步水热法在钛网(TM)上原位构筑了不同阵列结构Co_(9)S_(8)/MoS_(2)@TM催化电极。通过改变原料中钴、钼、硫的物质的量之比来调控Co_(9)S_(8)/MoS_(2)@TM电极的结构。采用SEM、XRD和XPS对Co_(9)S_(8)/MoS_(2)@TM进行物相分析和形貌表征,并在1 mol/L KOH电解液中对Co_(9)S_(8)/MoS_(2)@TM的电催化析氧性能进行了研究。结果表明,钴、钼、硫的物质的量之比为10∶14∶600时,制备的Co_(9)S_(8)/MoS_(2)@TM为3D花瓣状阵列结构,且在10 m A/cm^(2)电流密度下过电势为271 m V,塔菲尔斜率为88.5 m V/dec,具有良好的析氧稳定性和耐久性,展现了优异的电化学性能。
