Elucidating the Acidic and Textural Properties of ZMQ-1, a 28-membered Ring Mesoporous Aluminosilicate Zeolite

Abstract

ZMQ-1 is a recently discovered aluminosilicate zeolite featuring atomically ordered mesopores (28 × 10-membered rings), providing a unique, intrinsically bimodal micro/mesoporous framework. This study systematically investigates how residual inorganic phosphate species, derived from the biphosphonium organic structure-directing agent, influence the textural and acidic properties of the material. Using argon physisorption, solid-state NMR, in situ FTIR, and DFT calculations, we demonstrate that vacuum calcination or targeted postsynthetic washing (NH4Cl, CsNO3) removes ∼90% of residual phosphorus species, which otherwise severely diminishes Brønsted acid sites density and accessibility. Crucially, the determination of accurate molar extinction coefficients for pyridine and 2,6-di-tert-butylpyridine revealed that residual phosphorus markedly hinders probe molecule accessibility and diminishes acid strength. DFT modeling identifies preferred Al substitution sites that orient Brønsted protons toward the 28-MR mesoporous channels. The catalytic potential of this architecture was interrogated via the sterically demanding alkylation of 2,4-di-tert-butylphenol with tert-butyl alcohol. Phosphorus-free ZMQ-1 achieves a 15.5% yield of the bulky target, 2,4,6-tri-tert-butylphenola 31-fold increase over hierarchical USY (0.5%) and vastly outperforming amorphous-walled Al-MCM-41. These findings establish ZMQ-1 as a landmark catalyst bridging the gap between zeolitic acidity and mesoporous accessibility and further push the catalytic operating boundaries of nanoporous solid acid catalysts.

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BibTeX RIS

BibTeX

@article{fahda2026elucidating,
  title = {{Elucidating the Acidic and Textural Properties of ZMQ-1, a 28-membered Ring Mesoporous Aluminosilicate Zeolite}},
  author = {Mohammad Fahda and Yiqing Sun and Petko Petkov and Eddy Dib and Nourrdine Chaouati and Ali Youssef and Rémy Guillet-Nicolas and Mathias Barreau and Ludovic Pinard and Svetlana Mintova and Peng Lu and Georgi Vayssilov and Valentin Valtchev},
  journal = {Journal of the American Chemical Society},
  year = {2026},
  month = oct,
  doi = {10.1021/jacs.5c21600},
  url = {https://hal.science/hal-05638651v1},
  note = {CC BY 4.0},
}

RIS

TY  - JOUR
TI  - Elucidating the Acidic and Textural Properties of ZMQ-1, a 28-membered Ring Mesoporous Aluminosilicate Zeolite
AU  - Mohammad Fahda
AU  - Yiqing Sun
AU  - Petko Petkov
AU  - Eddy Dib
AU  - Nourrdine Chaouati
AU  - Ali Youssef
AU  - Rémy Guillet-Nicolas
AU  - Mathias Barreau
AU  - Ludovic Pinard
AU  - Svetlana Mintova
AU  - Peng Lu
AU  - Georgi Vayssilov
AU  - Valentin Valtchev
PY  - 2026
DA  - 2026/10/15
JO  - Journal of the American Chemical Society
DO  - 10.1021/jacs.5c21600
UR  - https://hal.science/hal-05638651v1
AB  - ZMQ-1 is a recently discovered aluminosilicate zeolite featuring atomically ordered mesopores (28 × 10-membered rings), providing a unique, intrinsically bimodal micro/mesoporous framework. This study systematically investigates how residual inorganic phosphate species, derived from the biphosphonium organic structure-directing agent, influence the textural and acidic properties of the material. Using argon physisorption, solid-state NMR, in situ FTIR, and DFT calculations, we demonstrate that vacuum calcination or targeted postsynthetic washing (NH4Cl, CsNO3) removes ∼90% of residual phosphorus species, which otherwise severely diminishes Brønsted acid sites density and accessibility. Crucially, the determination of accurate molar extinction coefficients for pyridine and 2,6-di-tert-butylpyridine revealed that residual phosphorus markedly hinders probe molecule accessibility and diminishes acid strength. DFT modeling identifies preferred Al substitution sites that orient Brønsted protons toward the 28-MR mesoporous channels. The catalytic potential of this architecture was interrogated via the sterically demanding alkylation of 2,4-di-tert-butylphenol with tert-butyl alcohol. Phosphorus-free ZMQ-1 achieves a 15.5% yield of the bulky target, 2,4,6-tri-tert-butylphenola 31-fold increase over hierarchical USY (0.5%) and vastly outperforming amorphous-walled Al-MCM-41. These findings establish ZMQ-1 as a landmark catalyst bridging the gap between zeolitic acidity and mesoporous accessibility and further push the catalytic operating boundaries of nanoporous solid acid catalysts.
SN  - 0002-7863
SN  - 1520-5126
ER  -

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