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<p>According to Le Chatelier’s principle, increasing the reaction pressure of O<sub>2</sub> is expected to significantly enhance H<sub>2</sub>O<sub>2</sub> electrosynthesis performance, but this effect remains unexplored. By comparing various catalysts under different pressures, we uncover an intriguing phenomenon. Namely, in a pressurized electrolyzer (2.0 V, 30 bar O<sub>2</sub>), a microporous metal-organic framework (MAF-2) with enzyme-mimicking dicopper(I) active sites on its pore surface achieved a current density of 90 mA cm<sup>−2</sup>, Faradaic efficiency of ∼95%, a record yield rate of 4.2 mol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup>, and record energy conversion efficiency of 27% for H<sub>2</sub>O<sub>2</sub> production, generating pure and salt-free H<sub>2</sub>O<sub>2</sub> at medical-grade concentration (3.3 wt%). Notably, this performance at 30 bar O<sub>2</sub> is seven times higher than at 1 bar O<sub>2</sub>. The performance increase caused by this pressurization far exceeds those of other types of catalysts (<i>e.g.</i>, carbon black and BBL-PcNi covalent framework), which rely solely on particle-surface active sites and exhibit &lt;10% pressure response. Mechanism studies reveal that while O<sub>2</sub> struggles to enter MAF-2 pores at 1 bar (uptake &lt; 2 cm<sup>3</sup> g<sup>−1</sup>), pressurization facilitates oxygen entering the pores (adsorption enthalpy = −45 kJ mol<sup>−1</sup>, uptake = 40 cm<sup>3</sup> g<sup>−1</sup> at 30 bar) and contact with abundant highly active dicopper(I) sites on the pore surface, thereby significantly enhancing its high-pressure performance. This study highlights the synergistic advantages of dual active sites and MOF porosities in electrocatalytic gas molecule conversion, providing critical insights for designing high performance catalysts under high pressure.</p>

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Efficient capture and conversion of O2 into salt-free medical-grade H2O2 via a metal-organic framework with enzyme-mimicking dicopper sites in a pressurized electrolyzer

  • 期刊论文

  • 发表日期：

    2025年8月5日

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  • Ze-Wei Chai,
  • Jia-Run Huang,
  • Meng-Di Zhang,
  • Xiao-Ming Chen,
  • Pei-Qin Liao

摘要

According to Le Chatelier’s principle, increasing the reaction pressure of O2 is expected to significantly enhance H2O2 electrosynthesis performance, but this effect remains unexplored. By comparing various catalysts under different pressures, we uncover an intriguing phenomenon. Namely, in a pressurized electrolyzer (2.0 V, 30 bar O2), a microporous metal-organic framework (MAF-2) with enzyme-mimicking dicopper(I) active sites on its pore surface achieved a current density of 90 mA cm−2, Faradaic efficiency of ∼95%, a record yield rate of 4.2 mol gcat−1 h−1, and record energy conversion efficiency of 27% for H2O2 production, generating pure and salt-free H2O2 at medical-grade concentration (3.3 wt%). Notably, this performance at 30 bar O2 is seven times higher than at 1 bar O2. The performance increase caused by this pressurization far exceeds those of other types of catalysts (e.g., carbon black and BBL-PcNi covalent framework), which rely solely on particle-surface active sites and exhibit <10% pressure response. Mechanism studies reveal that while O2 struggles to enter MAF-2 pores at 1 bar (uptake < 2 cm3 g−1), pressurization facilitates oxygen entering the pores (adsorption enthalpy = −45 kJ mol−1, uptake = 40 cm3 g−1 at 30 bar) and contact with abundant highly active dicopper(I) sites on the pore surface, thereby significantly enhancing its high-pressure performance. This study highlights the synergistic advantages of dual active sites and MOF porosities in electrocatalytic gas molecule conversion, providing critical insights for designing high performance catalysts under high pressure.