Scholarlink

<p>Amorphous metal-organic frameworks (aMOFs), owing to their abundant defects and unsaturated coordination sites, have emerged as ideal precursors for investigating electrocatalytic reconstruction mechanisms. However, a systematic understanding of how different modulation strategies affect the reconstruction pathways of amorphous MOFs and thereby determine the nature of the final active species remains lacking. In this study, an amorphous MOF constructed from 3,4,9,10-pyrene-tetracarboxylic acid (PTA) was employed as a controllable precursor platform to systematically compare two classical strategies (doping and alloying) in terms of their effects on structural reconstruction and oxygen evolution reaction (OER) performance. The results reveal that doping promotes preferential reconstruction into Fe-rich (oxy)hydroxides with more exposed active sites, whereas alloying tends to yield Fe-Co mixed (oxy)hydroxides with limited site exposure. Benefiting from this difference, the doped system FeCo<sub>0.05</sub>-PTA exhibits outstanding OER activity under alkaline conditions, with overpotentials of only 208 and 248 mV at 50 and 100 mA cm<sup>−2</sup>, respectively, and a low Tafel slope of 36.2 mV dec<sup>−1</sup>. <i>In situ</i> Fourier transform infrared spectroscopy (FTIR) captures the OOH* intermediate, confirming that the reaction follows the adsorbate evolution mechanism; density functional theory (DFT) calculations further demonstrate that the doped system possesses the lowest free-energy barrier (Δ<i>G</i> = 0.59 eV) at the rate-determining step. This study underscores the decisive role of precursor design in this system, elucidates the distinct effects of doping and alloying on the reconstruction pathways and final properties of amorphous MOF-derived (oxy)hydroxides, and provides valuable insights for the design and mechanistic understanding of related electrocatalysts.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Elucidating the distinct roles of metal ion doping and alloying in MOF reconstruction toward enhanced oxygen evolution reaction

  • 期刊论文

  • 发表日期：

    2026年2月3日

查看全文
  • Ruize Yin,
  • Juan Liu,
  • Xiaohui Zhang,
  • Peinan Wang,
  • Jiajie Lu,
  • Weiwei Xiong,
  • Saisai Yuan,
  • Fenfen Zheng,
  • Junhao Zhang,
  • Wenlei Zhu

摘要

Amorphous metal-organic frameworks (aMOFs), owing to their abundant defects and unsaturated coordination sites, have emerged as ideal precursors for investigating electrocatalytic reconstruction mechanisms. However, a systematic understanding of how different modulation strategies affect the reconstruction pathways of amorphous MOFs and thereby determine the nature of the final active species remains lacking. In this study, an amorphous MOF constructed from 3,4,9,10-pyrene-tetracarboxylic acid (PTA) was employed as a controllable precursor platform to systematically compare two classical strategies (doping and alloying) in terms of their effects on structural reconstruction and oxygen evolution reaction (OER) performance. The results reveal that doping promotes preferential reconstruction into Fe-rich (oxy)hydroxides with more exposed active sites, whereas alloying tends to yield Fe-Co mixed (oxy)hydroxides with limited site exposure. Benefiting from this difference, the doped system FeCo0.05-PTA exhibits outstanding OER activity under alkaline conditions, with overpotentials of only 208 and 248 mV at 50 and 100 mA cm−2, respectively, and a low Tafel slope of 36.2 mV dec−1. In situ Fourier transform infrared spectroscopy (FTIR) captures the OOH* intermediate, confirming that the reaction follows the adsorbate evolution mechanism; density functional theory (DFT) calculations further demonstrate that the doped system possesses the lowest free-energy barrier (ΔG = 0.59 eV) at the rate-determining step. This study underscores the decisive role of precursor design in this system, elucidates the distinct effects of doping and alloying on the reconstruction pathways and final properties of amorphous MOF-derived (oxy)hydroxides, and provides valuable insights for the design and mechanistic understanding of related electrocatalysts.