Thermodynamics of the oxygen evolution electrocatalysis in a functionalized UiO‐66 metal‐organic frameworks |
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| Authors: | Terence Musho Jiangtian Li Nianqiang Wu |
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| Affiliation: | Department of Mechanical and Aerospace Engineering, West Virginia University, Morgantown, West Virginia |
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| Abstract: | A density functional theory (DFT) approach was used to predict the thermodynamic energy barriers of the oxygen evolution reaction (OER) for three functionalized Metal‐organic Frameworks (MOFs). A UiO‐66(Zr) MOF design was selected for this study that incorporates three linker designs, a 1,4‐benzenedicarboxylate (BDC), BDC functionalized with an amino group (BDC + NH2), and BDC functionalized with nitro group (BDC + NO2). The study found several key differences between homogeneous planar catalyst thermodynamics and MOF‐based thermodynamics, the most significant being the non‐unique or heterogeneity of reaction sites. Additionally, the functionalization of the MOF was found to significantly influence the hydroperoxyl binding energy, which proves to be the largest hurdle for both oxide and MOF‐based catalyst. Both of these findings provide evidence that many of the limitations precluding planar homogeneous catalysts can be surpassed with a MOF‐based catalyst. The BDC + NH2 proved to be the best performing catalyst with a predicted over‐potential for spontaneous OER evolution to be 3.03eV. © 2016 Wiley Periodicals, Inc. |
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| Keywords: | metal‐organic framework thermodynamics density functional theory electrolysis water‐splitting |
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