Work

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

Year: 2025

Type: article

Abstract: 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. Cu-based photocatalysts usually show wavelength-dependent activity. Here, UiO-66(COOH)2-Cu exhibits dual-light “logic gate” behavior, where visible and near-infrared synergy drives in-situ Cu restructuring for exceptional hydrogen production.

Source: Nature Communications

DOI: 10.1038/s41467-025-67014-x