Enlightening the journey of metal-organic framework (derived) catalysts during the oxygen evolution reaction in alkaline media via operando X-ray absorption spectroscopy

Linke, J.; Rohrbach, Thomas; Ranocchiari, Marco; Schmidt, Thomas J.; Fabbri, Emiliana

doi:10.1016/j.coelec.2021.100845

Cited by 7 publications

(7 citation statements)

References 37 publications

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“…The structure of defects and thus their contribution to catalysis can also vary over the course of a reaction. Hence, computational and mechanistic studies guided by ex situ and operando/in situ ,,, characterization of defects, catalytic sites, and reaction intermediates are necessary to clarify the origin of catalytic activity and inform rational catalyst design.…”

Section: Discussionmentioning

confidence: 99%

“…Researchers have leveraged confinement effects, such as pore size, neighboring group interactions, and the regular arrangement of active sites, to unlock new reactivity and selectivity patterns within MOFs. Furthermore, the periodic architecture of MOFs offers an exceptional platform to determine the location of catalytically active sites and characterize pore microenvironments using computational − and spectroscopic ,− techniques. For example, substantial insight into catalyst–substrate interactions can be gained via single crystal-to-single crystal chemical transformations during a catalytic cycle. , Detailed mechanistic investigations are critical to understanding reactivity and facilitating the development of new and reliable transformations.…”

Section: Unique Reactivity Within Mofsmentioning

confidence: 99%

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MOFganic Chemistry: Challenges and Opportunities for Metal–Organic Frameworks in Synthetic Organic Chemistry

et al. 2023

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Metal–organic frameworks (MOFs) are porous crystalline solids constructed from organic linkers and inorganic nodes that have been widely studied for applications in gas storage, chemical separations, and drug delivery. Owing to their highly modular structures and tunable pore environments, we propose that MOFs have significant untapped potential as catalysts and reagents relevant to the synthesis of next-generation therapeutics. Herein, we outline the properties of MOFs that make them promising for applications in synthetic organic chemistry, including new reactivity and selectivity, enhanced robustness, and user-friendly preparation. In addition, we outline the challenges facing the field and propose new directions to maximize the utility of MOFs in drug synthesis. This Perspective aims to bring together the organic and MOF communities to develop new heterogeneous platforms capable of achieving synthetic transformations that cannot be replicated by homogeneous systems.

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Section: Discussionmentioning

confidence: 99%

Section: Unique Reactivity Within Mofsmentioning

confidence: 99%

MOFganic Chemistry: Challenges and Opportunities for Metal–Organic Frameworks in Synthetic Organic Chemistry

et al. 2023

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“…The structure of defects-and thus their contribution to catalysis-can also vary over the course of a reaction. Hence, computational and mechanistic studies guided by ex situ and operando/in situ 49,50,54,157 characterization of defects, catalytic sites, and reaction intermediates are necessary to clarify the origin of catalytic activity and inform rational catalyst design.…”

Section: Discussionmentioning

confidence: 99%

“…Researchers have leveraged confinement effects such as pore size, neighboring group interactions, and the regular arrangement of active sites to unlock new reactivity and selectivity within MOFs. Furthermore, the periodic architecture of MOFs offers an exceptional platform to determine the location of catalytically active sites and characterize pore microenvironments using computational [42][43][44][45][46][47][48] and spectroscopic 47,[49][50][51][52][53] techniques. For example, substantial insight into catalystsubstrate interactions can be gained via single-crystal-tosingle-crystal chemical transformations during a catalytic cycle.…”

Section: Introductionmentioning

confidence: 99%

MOFganic Chemistry: Challenges and Opportunities for Metal-Organic Frameworks in Synthetic Organic Chemistry

Ahmad

Keasler

Stacy

et al. 2023

Preprint

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Metal-organic frameworks (MOFs) are porous, crystalline solids constructed from organic linkers and inorganic nodes that have been widely studied for applications in gas storage, chemical separations, and drug delivery. Owing to their highly modular structures and tunable pore environments, we propose that MOFs have significant untapped potential as catalysts and reagents relevant to the synthesis of next-generation therapeutics. Herein, we outline the properties of MOFs that make them promising for applications in synthetic and organic chemistry, including new reactivity and selectivity, enhanced robustness, and user-friendly preparation. In addition, we outline the challenges facing the field and propose new directions to maximize the utility of MOFs for drug synthesis. This perspective aims to bring together the organic and MOF communities to develop new heterogeneous platforms capable of achieving synthetic transformations that can-not be replicated by homogeneous systems.

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“…MOFs and MOF-derived catalysts have been studied for many electrochemical reactions, including hydrogen evolution, oxygen reduction, , and oxygen evolution reaction. − Unfortunately, MOFs can be unstable during electrochemical reactions such as the OER and may convert to (oxy)hydroxides. − For example, Zhao et al demonstrated the structural transformations of Ni 0.5 Co 0.5 -MOF-74 to Ni 0.5 Co 0.5 OOH during OER using operando X-ray absorption spectroscopy (XAS) . Recently, Yuan et al have designed metal-hydroxide organic frameworks (MHOFs) that are composed of edge-sharing metal-hydroxide octahedral sheets cross-linked with organic linkers, which show tunable metal redox potential and electrochemical OER activity via metal substitution .…”

Section: Introductionmentioning

confidence: 99%

Linker-Dependent Stability of Metal-Hydroxide Organic Frameworks for Oxygen Evolution

et al. 2023

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Metal–organic frameworks (MOFs) are periodic organic–inorganic materials that have garnered considerable attention for electrocatalytic applications due to their wide tunability. Metal-hydroxide organic frameworks (MHOFs), a subset of MOFs that combine layered metal hydroxides with organic ligands of various π–π stacking energy, have shown promising catalytic functions, such as for the oxygen evolution reaction (OER). The long-term electrochemical stability of these materials for the OER is unfortunately not well understood, which is critical to design practical devices. In this study, we investigated how Ni-based MHOFs composed of two linkers with different π–π interaction strength (terephthalate; L1 and azobenzene-4,4′-dicarboxylate; L4) change as a function of cycle number and potential for the OER. All MHOFs tested showed significant increases in the number of electrochemically active Ni sites and OER activity when cycled. MHOFs constructed using the linkers with stronger π–π stacking energy (L4) were observed to remain intact in bulk with only near-surface transformations to NiOOH2–x -like phases, whereas MHOFs with linkers of weaker π–π stacking energy (L1) showed complete reconstruction to NiOOH2–x -like phases. This was confirmed using X-ray diffraction, X-ray absorption spectroscopy, and electron microscopy. Further, in situ characterization using Raman and UV–vis revealed that the presence of stable linkers within the MHOF structure suppresses the Ni2+/Ni(3+δ)+ redox process. We further identify NiOOH2–x as the OER active phase, while the MHOF phase serves as a precatalyst. We further propose a detailed mechanism for the phase transformation, which provides valuable insights into the future challenges for the design of both stable and catalytically active MOF-based materials for water oxidation.

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Enlightening the journey of metal-organic framework (derived) catalysts during the oxygen evolution reaction in alkaline media via operando X-ray absorption spectroscopy

Cited by 7 publications

References 37 publications

MOFganic Chemistry: Challenges and Opportunities for Metal–Organic Frameworks in Synthetic Organic Chemistry

MOFganic Chemistry: Challenges and Opportunities for Metal–Organic Frameworks in Synthetic Organic Chemistry

MOFganic Chemistry: Challenges and Opportunities for Metal-Organic Frameworks in Synthetic Organic Chemistry

Linker-Dependent Stability of Metal-Hydroxide Organic Frameworks for Oxygen Evolution

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