Scholarlink

<p>Reconstruction of metal-organic frameworks often occurs under reaction conditions, thereby impeding true active species identification and hindering mechanism understanding. Herein, we present the mechanistic insight underlying the electrochemical synthesis of deprotonated anion of H<sub>2</sub>O<sub>2</sub> (HO<sub>2</sub><sup>−</sup>) via 2e<sup>−</sup> oxygen reduction by ultrathin Ni-benzenedicarboxylic acid (NiBDC), guided by its thickness-dependent performance and pH-induced reconstruction behavior. The real active species are identified as alkaline-reconstructed β-Ni(OH)<sub>2</sub> that is chemically coupled with 1,4-benzenedicarboxylic acid residual ligand. The hybrid catalyst is characterized to exhibit an optimized surface electronic structure, which improves the intrinsic activity and selectivity. <i>Operando</i> characterization and theoretical simulations further reveal that the residual ligand functionalization significantly boosts the formation and facilitates the adequate binding of *OOH intermediates. Thus, the ligand-functionalized Ni(OH)<sub>2</sub> exhibits high HO<sub>2</sub><sup>−</sup> selectivity (&gt;90%) in 0.1 M KOH across a broad current density up to 200 mA cm<sup>−2</sup>. Moreover, high HO<sub>2</sub><sup>−</sup> production rate of 13.7 mol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup> with significant accumulation of 2.0 wt.% HO<sub>2</sub><sup>−</sup> under alkaline conditions is achieved at 200 mA cm<sup>−2</sup> over 100 h, suggesting the promising potential for large-scale electrosynthesis of HO<sub>2</sub><sup>−</sup> in industrial applications.</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

Residual ligand-functionalized ultrathin Ni(OH)2 via reconstruction for high-rate HO2− electrosynthesis

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年6月5日

查看全文
  • Tianyu Zhang,
  • Weibo Wang,
  • Wenxian Liu,
  • Zhengxiao Guo,
  • Junfeng Liu

摘要

Reconstruction of metal-organic frameworks often occurs under reaction conditions, thereby impeding true active species identification and hindering mechanism understanding. Herein, we present the mechanistic insight underlying the electrochemical synthesis of deprotonated anion of H2O2 (HO2−) via 2e− oxygen reduction by ultrathin Ni-benzenedicarboxylic acid (NiBDC), guided by its thickness-dependent performance and pH-induced reconstruction behavior. The real active species are identified as alkaline-reconstructed β-Ni(OH)2 that is chemically coupled with 1,4-benzenedicarboxylic acid residual ligand. The hybrid catalyst is characterized to exhibit an optimized surface electronic structure, which improves the intrinsic activity and selectivity. Operando characterization and theoretical simulations further reveal that the residual ligand functionalization significantly boosts the formation and facilitates the adequate binding of *OOH intermediates. Thus, the ligand-functionalized Ni(OH)2 exhibits high HO2− selectivity (>90%) in 0.1 M KOH across a broad current density up to 200 mA cm−2. Moreover, high HO2− production rate of 13.7 mol gcat−1 h−1 with significant accumulation of 2.0 wt.% HO2− under alkaline conditions is achieved at 200 mA cm−2 over 100 h, suggesting the promising potential for large-scale electrosynthesis of HO2− in industrial applications.