Issue 6, 2024

Deciphering structural evolution of adsorbed ˙OH species on Zr-oxo nodes of UiO-66 to modulate methane hydroxylation

Abstract

Direct selective oxidation of methane (DSOM) to oxygenates under mild conditions is garnering increasing interest. UiO-66-H MOFs are effective for this reaction, while the active configuration of Zr-oxo nodes with adsorbed ˙OH species need further clarification from the atomic/molecular viewpoint. Here, we detect the evolution of the geometric and electronic structures of adsorbed oxygenic species on Zr-oxo nodes of UiO-66-H via the controlled ˙OH species. DFT calculations reveal a volcano-like curve relationship between the quantity of ˙OH species and the DSOM performance, which is further corroborated by experimental tests. Zroxo-˙OH is the main active configuration on Zr-oxo nodes of UiO-66-H at low ˙OH concentration, while it evolves to other oxygenic species (˙OOH, O2, and H2O) due to the self-reaction with the increase of ˙OH concentration, which leads to performance decrease. Furthermore, a critical descriptor of the p-band centers of O atoms in these oxygenic species on the Zr-oxo nodes is established, which can well represent the catalytic activity for the DSOM reaction.

Graphical abstract: Deciphering structural evolution of adsorbed ˙OH species on Zr-oxo nodes of UiO-66 to modulate methane hydroxylation

Supplementary files

Article information

Article type
Paper
Submitted
26 Sep 2023
Accepted
28 Dec 2023
First published
29 Dec 2023

J. Mater. Chem. A, 2024,12, 3565-3574

Deciphering structural evolution of adsorbed ˙OH species on Zr-oxo nodes of UiO-66 to modulate methane hydroxylation

L. Tian, G. Fang, Y. Zhou, W. Yu, L. Li, J. Hu, H. Wang, J. Liang, C. Zhu, X. Wang and J. Lin, J. Mater. Chem. A, 2024, 12, 3565 DOI: 10.1039/D3TA05851D

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