Benchmarking of Oxygen Adsorption using TPD Spectroscopy for Accurate DFT Prediction of ORR on Anatase Titanium Dioxide (101)

Abstract

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.

References in corpus (14)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Advanced capabilities for materials modelling with Quantum ESPRESSO
• Van der Waals Density Functional for General Geometries
• Van der Waals density functionals applied to solids
• A Higher-Accuracy van der Waals Density Functional
• Quantum ESPRESSO toward the exascale
• Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
• Spin signature of nonlocal-correlation binding in metal organic frameworks
• Tractable non-local correlation density functionals for flat surfaces and slabs
• Next-generation non-local van der Waals density functional
• Improving the Description of Nonmagnetic and Magnetic Molecular Crystals via the van der Waals Density Functional
• Diffusion Monte Carlo Study of the O${}_2$ Adsorption on a Single Layer Graphene
• First-principles description of van der Waals-bonded spin-polarized systems using vdW-DF$+U$ method---application to solid oxygen at low pressure
• Theoretical analysis of zirconium oxynitride/water interface using neural network potential