Thermodynamics of the oxygen evolution electrocatalysis in a functionalized UiO‐66 metal‐organic frameworks. Issue 15 (5th May 2016)

• Record Type: Journal Article
• Authors: Musho, Terence; Li, Jiangtian; Wu, Nianqiang
• Is Part Of: International journal of quantum chemistry. Volume 116:Issue 15(2016)
• Page Start: 1153
• Page End: 1159
• Publication Date: 2016-05-05
• Subjects: metal‐organic framework -- thermodynamics -- density functional theory -- electrolysis -- water‐splitting; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.25149
• Languages: English
• ISSNs: 0020-7608

Abstract

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. Abstract : Metal‐organic frameworks (MOFs) embody several tailorable material attributes that lend themselves well to sustainable water‐splitting through photocatalysis. This study theoretically investigates the oxygen evolution reaction (OER) within a functionalized MOF pore. Findings include high heterogeneous reaction site affinity that surpassing physical limitation of planar catalyst. A 3.03 V OER over‐potential was predicted for a UiO‐66(Zr)‐NH2 functionalized MOF.