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. 2025 Sep 3;10(36):41890-41898.
doi: 10.1021/acsomega.5c06158. eCollection 2025 Sep 16.

Glyphosate Adsorption on Metal-Organic Framework M3(BTC)2: Mechanistic Insights and Descriptors for the Adsorption Energy from Density Functional Calculations

Araya Putthabal  1 , Siriya Sukhonthachat  1 , Michael Probst  2 , Anawat Thivasasith  3 , Jumras Limtrakul  4 , Thana Maihom  1   5
Affiliations

Glyphosate Adsorption on Metal-Organic Framework M3(BTC)2: Mechanistic Insights and Descriptors for the Adsorption Energy from Density Functional Calculations

Araya Putthabal et al. ACS Omega. .

Abstract

Adsorption-based removal has emerged as an effective strategy for mitigating the harmful impact of glyphosate. Here, the adsorption of glyphosate over the coordinatively unsaturated metal-organic framework (MOF) M3(BTC)2 (M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn) was investigated by means of density functional theory (DFT) calculations. Among the studied MOFs, Zn3(BTC)2 and Ni3(BTC)2 show the highest adsorption energy. The Lewis acidity of the MOFs, as determined by ammonia adsorption, is found to significantly influence glyphosate adsorption. Decomposing the adsorption free energy reveals that the adsorption is dominated by the bond energy. A moderately strong linear correlation between the adsorption energies of glyphosate and ammonia suggests that ammonia adsorption can serve as a descriptor for predicting the glyphosate adsorption energy. To enhance the predictive accuracy, we employed the sure independence screening and sparsifying operator (SISSO) method, which explores a large pool of mathematical combinations of DFT descriptors to identify the most relevant ones. The resulting models enable accurate and transferable prediction of glyphosate adsorption energy.

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Figures

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1
M3(BTC)2 unit cell (a) and cluster model used in this work (b).
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Optimized structures of glyphosate adsorbed on Cu3(BTC)2 and an orbital interaction analysis of the (a) O1, (b) O2, (c) O3, and (d) O4 adsorption modes. The isosurface value for the orbital visualization is set to ±0.03 au.
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Adsorption free energies of glyphosate on Cu3(BTC)2 for different modes.
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Temperature dependence of the equilibrium constants for the adsorption on the MOFs (a) and correlation between the adsorption energies of glyphosate (ΔG ads) and ammonia (ΔG NH3 ) on the MOFs (b).
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Contributions from the structural variation of M3(BTC)2 (ΔG strain) and bond energy (ΔG bond) to the overall adsorption energy (ΔG ads) (a), and the overall adsorption energy (ΔG ads) together with its two contributing components, ΔG strain and ΔG bond (b).
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Comparison of ΔG ads obtained from DFT and from SISSO in one-dimensional (1D) (a), two-dimensional (2D) (b), and three-dimensional (3D) (c) models, along with the corresponding RMSE and R 2 values (d).
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