Benchmarking of Oxygen Adsorption using TPD Spectroscopy for Accurate DFT Prediction of ORR on Anatase Titanium Dioxide (101)
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| Autores principales: | , , , |
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| Formato: | Preprint |
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2025
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| _version_ | 1866915585969881088 |
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| author | Muhammady, Shibghatullah Haruyama, Jun Kasamatsu, Shusuke Sugino, Osamu |
| author_facet | Muhammady, Shibghatullah Haruyama, Jun Kasamatsu, Shusuke Sugino, Osamu |
| contents | Despite the wide use of first-principles calculations to elucidate catalytic reaction mechanisms, the reliability of the theory remains unknown for reactions that initiate with O$_2$ adsorption, as few papers in the literature have systematically verified the accuracy of the calculations. Here, we have overcome this issue by comparing calculated O$_2$ adsorption energy ($E_{\text{ads}}$) to simulated $E_{\text{ads}}$ distribution from experimental temperature-programmed desorption (TPD) spectrum. The distribution obtained based on equilibrium thermodynamic arguments is in good agreement with the calculated $E_{\text{ads}}$ from modelling O$_2$ adsorption on anatase-TiO$_2$(101) using the generalized gradient approximation and van der Waals density functionals (vdW-DFs) with Hubbard correction, which is particularly the case when vdW-DF3-opt2 is used. On this basis, we concluded that the oxygen reduction reaction (ORR) initiates from a physisorbed O$_2$ thermodynamically as stable as that in the gas phase. In contrast, the calculated $E_{\text{ads}}$ for Pt(111) exhibit a significant overestimation of the O$_2$ adsorption due to excessive vdW correction. Therefore, a systematic investigation based on TPD spectroscopy can be used to diagnose the reliability of theoretical predictions of ORR and is expected to lead to improvements in exchange-correlation functionals for catalysts. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2506_18225 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Benchmarking of Oxygen Adsorption using TPD Spectroscopy for Accurate DFT Prediction of ORR on Anatase Titanium Dioxide (101) Muhammady, Shibghatullah Haruyama, Jun Kasamatsu, Shusuke Sugino, Osamu Chemical Physics Despite the wide use of first-principles calculations to elucidate catalytic reaction mechanisms, the reliability of the theory remains unknown for reactions that initiate with O$_2$ adsorption, as few papers in the literature have systematically verified the accuracy of the calculations. Here, we have overcome this issue by comparing calculated O$_2$ adsorption energy ($E_{\text{ads}}$) to simulated $E_{\text{ads}}$ distribution from experimental temperature-programmed desorption (TPD) spectrum. The distribution obtained based on equilibrium thermodynamic arguments is in good agreement with the calculated $E_{\text{ads}}$ from modelling O$_2$ adsorption on anatase-TiO$_2$(101) using the generalized gradient approximation and van der Waals density functionals (vdW-DFs) with Hubbard correction, which is particularly the case when vdW-DF3-opt2 is used. On this basis, we concluded that the oxygen reduction reaction (ORR) initiates from a physisorbed O$_2$ thermodynamically as stable as that in the gas phase. In contrast, the calculated $E_{\text{ads}}$ for Pt(111) exhibit a significant overestimation of the O$_2$ adsorption due to excessive vdW correction. Therefore, a systematic investigation based on TPD spectroscopy can be used to diagnose the reliability of theoretical predictions of ORR and is expected to lead to improvements in exchange-correlation functionals for catalysts. |
| title | Benchmarking of Oxygen Adsorption using TPD Spectroscopy for Accurate DFT Prediction of ORR on Anatase Titanium Dioxide (101) |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.18225 |