Hai-Bo Huang, Fang-Long Sun, Ze Luo, Meng-Yu Sun, Ben-Hao Liu, Xu-Sheng Wang, Hua Tang*

Cite this article: Chin. J. Struct. Chem., 2025, 44(11), 100717. DOI: 10.1016/j.cjsc.2025.100717

Publication date: November 1, 2025

Keywords: MOF@MOF; Hierarchical structure; Photocatalytic; Hydrogen peroxide; Furfuryl alcohol oxidation

ABSTRACT

By integrating photocatalytic H2O2 production with furfuryl alcohol (FAL) oxidation, this coupled process establishes an atom-economical pathway for sustainable chemical synthesis, simultaneously achieving energy storage and biomass valorization. This study introduces a meticulously engineered MOF@MOF hierarchical photocatalytic architecture, specifically the PCN-134@MOF-525 (PM-X series) composite, designed for synergistic catalysis of these processes. By strategically integrating two distinct MOF materials, we circumvent the limitations of single-component systems, such as facile charge carrier recombination, and establish a redox dual-active site catalytic system. This rational design transcends simple additivity, yielding emergent catalytic behaviors driven by precise control over interfacial electric fields and dynamic structural modulation. The resultant hierarchical organization enhances light harvesting, promotes efficient charge separation, and accelerates charge transfer kinetics. Mechanistic insights, derived from photoelectrochemical, spectroscopic, and in-situ IR analyses, reveal a synergistic interplay that suppresses electron-hole recombination and spatially segregates redox processes. PM-3 demonstrates a significant enhancement in catalytic efficiency (highest value reported) , exhibiting a 4.5-fold increase in both H2O2 production and FAL oxidation rates compared to the individual MOF components, achieving near-quantitative FAL conversion and exceptional selectivity. This work provides a potent design blueprint, emphasizing interfacial engineering and structural synergy for unprecedented efficiency and selectivity in sustainable chemical transformations.