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<p>While the dynamic restructuring of Cu-metalated metal-organic frameworks for photocatalysis has recently been explored, its effect on electronic excitation remains under-investigated. For better mechanistic understanding, we study the light-induced activity of Cu-metalated UiO-66(COOH)<sub>2</sub> metal-organic framework, known as UiO-66(COOH)<sub>2</sub>-Cu under varied irradiations, using gas-phase formic acid dehydrogenation at ambient conditions as a model reaction. A photocatalytic logic gate behavior is observed. The UiO-66(COOH)<sub>2</sub>-Cu remains photo-catalytically <i>OFF</i> under visible (&gt;390-720 nm) or near-infrared (&gt;700 nm) light alone, but shows high H<sub>2</sub> production of 6.1 mmol·g⁻¹·h⁻¹ (<i>ON</i> state) when both are applied (≥390 nm). <i>Operando</i> Fourier transform infrared spectroscopy and X-ray absorption spectroscopy demonstrate that both visible and near-infrared irradiations are required for metalated Cu<sup>2+/1+</sup> restructuring inside the framework to form photoactive Cu<sup>0</sup>/Cu<sup>+</sup> binary center, and thereafter for the photocatalytic dehydration of formic acid. X-ray absorption spectroscopic analysis suggests a distinct initiation behavior of Cu<sup>+</sup> and Cu<sup>0</sup> species under visible and near-infrared irradiation, respectively. However, <i>operando</i> Fourier-transform infrared spectroscopy reveals a cascade mechanism requiring both irradiations to progress the catalytic reaction. This photocatalytic logic gate behavior also appears in bare Cu<sup>0</sup>/Cu<sub>2</sub>O system used as reference. These findings provide insights into dual-photon-driven photocatalysis and aid advanced hydrogen catalyst design.</p>

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Dual-photon–driven hydrogen evolution in copper-based photocatalysts under near-infrared and visible light

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月9日

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  • Zahraa Abou Khalil,
  • Akashdeep Nath,
  • Karen Hannouche,
  • Nisrine Assaad,
  • Georges Mouchaham,
  • Antony Beauvois,
  • Valerie Briois,
  • Christian Serre,
  • Mohamad Hmadeh,
  • Marco Daturi,
  • Mohamad El-Roz

摘要

While the dynamic restructuring of Cu-metalated metal-organic frameworks for photocatalysis has recently been explored, its effect on electronic excitation remains under-investigated. For better mechanistic understanding, we study the light-induced activity of Cu-metalated UiO-66(COOH)2 metal-organic framework, known as UiO-66(COOH)2-Cu under varied irradiations, using gas-phase formic acid dehydrogenation at ambient conditions as a model reaction. A photocatalytic logic gate behavior is observed. The UiO-66(COOH)2-Cu remains photo-catalytically OFF under visible (>390-720 nm) or near-infrared (>700 nm) light alone, but shows high H2 production of 6.1 mmol·g⁻¹·h⁻¹ (ON state) when both are applied (≥390 nm). Operando Fourier transform infrared spectroscopy and X-ray absorption spectroscopy demonstrate that both visible and near-infrared irradiations are required for metalated Cu2+/1+ restructuring inside the framework to form photoactive Cu0/Cu+ binary center, and thereafter for the photocatalytic dehydration of formic acid. X-ray absorption spectroscopic analysis suggests a distinct initiation behavior of Cu+ and Cu0 species under visible and near-infrared irradiation, respectively. However, operando Fourier-transform infrared spectroscopy reveals a cascade mechanism requiring both irradiations to progress the catalytic reaction. This photocatalytic logic gate behavior also appears in bare Cu0/Cu2O system used as reference. These findings provide insights into dual-photon-driven photocatalysis and aid advanced hydrogen catalyst design.