| 1. |
- Howe, Andrew, et al.
(författare)
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Electrocatalytic water oxidation from a mixed linker MOF based on NU-1000 with an integrated ruthenium-based metallo-linker
- 2022
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Ingår i: Materials Advances. - : Royal Society of Chemistry (RSC). - 2633-5409. ; 3:10, s. 4227-4234
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Tidskriftsartikel (refereegranskat)abstract
- A novel tetratopic metallo-linker, [Ru(tda)(py(PhCOOH)2)2], 1, (tda = 2,2′:6′,2′′-terpyridine-6,6′′-dicarboxylate; py(PhCOOH)2 = (4,4′-(pyridine-3,5-diyl)dibenzoic acid), that is structurally based on one of the most active molecular water oxidation catalysts has been prepared and fully characterized, including single crystal X-ray diffraction. 1 bears geometric similarities to H4TBAPy (H4TBAPy = 4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid), i.e. the native linker in NU-1000, which offers the possibility to synthesize NU-1000-Ru mixed linker MOFs solvothermally. Mixed linker MOF formation was demonstrated by powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM), and Ru linker incorporation confirmed by FT-IR, energy-dispersive X-ray (EDX) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES). It was found that the Ru contents in the final mixed linker MOFs correlate with the amount of Ru linker present during solvothermal synthesis, albeit not in a linear fashion. The cyclic voltammograms (CV) of the mixed linker MOFs are largely dominated by TBAPy-based oxidations with features attributed to 1. Interestingly, Ru linkers near the crystal surface are oxidized directly by interfacial hole transfer form the electrode, while those in the crystal interior can be oxidized indirectly from oxidized TBAPy linkers at more anodic potential. Upon repeated scanning, the CVs show the appearance of new waves that arise from irreversible TBAPy oxidation, as well as from the activation of the Ru-based water oxidation catalyst. Of the materials prepared, the one with the highest Ru content, NU-1000-Ruhigh, was shown to catalyze the electrochemical oxidation of water to dioxygen. The Faradaic efficiency (FE) of the construct is 37%, due to water oxidation being accompanied by oxidative transformations of the TBAPy linkers. Despite the low FE, NU-1000-Ruhigh is still among the best MOF-based water oxidation catalysts, operating by a unique co-linker mediated hole-transport mechanism to supply oxidizing equivalents also to catalysts in the crystal interior.
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| 2. |
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| 3. |
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| 4. |
- Liseev, Timofey, et al.
(författare)
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Synthetic strategies to incorporate Ru-terpyridyl water oxidation catalysts into MOFs : direct synthesis vs. post-synthetic approach
- 2020
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Ingår i: Dalton Transactions. - : ROYAL SOC CHEMISTRY. - 1477-9226 .- 1477-9234. ; 49:39, s. 13753-13759
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Tidskriftsartikel (refereegranskat)abstract
- Incorporating molecular catalysts into metal-organic frameworks (MOFs) is a promising strategy for improving their catalytic longevity and recyclability. In this article, we investigate and compare synthetic routes for the incorporation of the potent water oxidation catalyst Ru(tda)(pyCO(2)H)(2) (tda = 2,2':6',2 ''-terpyridine-6,6 ''-dicarboxylic acid, pyCO(2)H = iso-nicotinic acid) as a structural linker into a Zr-based UiO-type MOF. The task is challenging with this particular metallo-linker because of the equatorial dangling carboxylates that can potentially compete for Zr-coordination, as well as free rotation of the pyCO(2)H groups around the HO(2)Cpy center dot center dot center dot Ru center dot center dot center dot pyCO(2)H axis. As a consequence, all attempts to synthesize a MOF with the metallo-linker directly under solvothermal conditions led to amorphous materials with the Ru(tda) (pyCO(2)H)(2) linker coordinating to the Zr nodes in ill-defined ways, resulting in multiple waves in the cyclic voltammograms of the solvothermally obtained materials. On the other hand, an indirect post-synthetic approach in which the Ru(tda)(pyCO(2)H)(2) linker is introduced into a preformed edba-MOF (edba = ethyne dibenzoic acid) of UiO topology results in the formation of the desired material. Interestingly, two distinctly different morphologies of the parent edba-MOF have been discovered, and the impact that the morphological difference has on linker incorporation is investigated.
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| 5. |
- Liseev, Timofey, 1991-
(författare)
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Toward functional Metal-Organic Frameworks: molecular doping, depth profiling, and surface growth
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis, selected synthetic aspects of functional Metal-Organic Frameworks (MOFs) are considered. More specifically, the work is focused on MOFs doped with functional molecules in the role of structural linkers. In the first part, preparation of such MOF/molecular catalyst hybrid materials of two topologies UiO (UiO = Universitet i Oslo) and NU-1000 (NU = Northwestern University) – is investigated and three different synthetic pathways to these materials are studied. In the second part, a novel MOF depth profiling technique – Rutherford Backscattering Spectrometry – is introduced and then used to elucidate depth distribution of molecules post-synthetically introduced into a MOF. In the last part, efficient interfacing of MOFs with electrodes is considered and a methodology for growing surface-mounted layer-pillar-type M2L2P MOFs (SURMOFs, M = metal, L = layer linker, P = pillar linker) with high degree of orientation and thickness control on bare Si substrates is developed.
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| 6. |
- McCarthy, Brian D., et al.
(författare)
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Analysis of electrocatalytic metal-organic frameworks
- 2020
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Ingår i: Coordination chemistry reviews. - : ELSEVIER SCIENCE SA. - 0010-8545 .- 1873-3840. ; 406
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Forskningsöversikt (refereegranskat)abstract
- The electrochemical analysis of molecular catalysts for the conversion of bulk feedstocks into energy-rich clean fuels has seen dramatic advances in the last decade. More recently, increased attention has focused on the characterization of metal-organic frameworks (MOFs) containing well-defined redox and catalytically active sites, with the overall goal to develop structurally stable materials that are industrially relevant for large-scale solar fuel syntheses. Successful electrochemical analysis of such materials draws heavily on well-established homogeneous techniques, yet the nature of solid materials presents additional challenges. In this tutorial-style review, we cover the basics of electrochemical analysis of electroactive MOFs, including considerations of bulk stability, methods of attaching MOFs to electrodes, interpreting fundamental electrochemical data, and finally electrocatalytic kinetic characterization. We conclude with a perspective of some of the prospects and challenges in the field of electrocatalytic MOFs.
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| 7. |
- McCarthy, Brian D., et al.
(författare)
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Elemental Depth Profiling of Intact Metal-Organic Framework Single Crystals by Scanning Nuclear Microprobe
- 2021
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 143:44, s. 18626-18634
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Tidskriftsartikel (refereegranskat)abstract
- The growing field of MOF-catalyst composites often relies on postsynthetic modifications for the installation of active sites. In the resulting MOFs, the spatial distribution of the inserted catalysts has far-reaching ramifications for the performance of the system and thus needs to be precisely determined. Herein, we report the application of a scanning nuclear microprobe for accurate and nondestructive depth profiling of individual UiO-66 and UiO-67 (UiO = Universitetet i Oslo) single crystals. Initial optimization work using native UiO-66 crystals yielded a microbeam method which avoided beam damage,y while subsequent analysis of Zr/Hf mixed-metal UiO-66 crystals demonstrated the potential of the method to obtain high-resolution depth profiles. The microbeam method was further used to analyze the depth distribution of postsynthetically introduced organic moieties, revealing either core-shell or uniform incorporation can be obtained depending on the size of the introduced molecule, as well as the number of carboxylate binding groups. Finally, the spatial distribution of platinum centers that were postsynthetically installed in the bpy binding pockets of UiO-67-bpy (bpy = 5,5'dicarboxyy-2,2'-bipyridine) was analyzed by microbeam and contextualized. We expect that the method presented herein will be applicable for characterizing a wide variety of MOFs subjected to postsynthetic modifications and provide information crucial for their optimization as functional materials.
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| 8. |
- McCarthy, Brian D., et al.
(författare)
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Facile Orientational Control of M2L2P SURMOFs on < 100 > Silicon Substrates and Growth Mechanism Insights for Defective MOFs
- 2019
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 11:41, s. 38294-38302
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Tidskriftsartikel (refereegranskat)abstract
- Layer-by-layer growth of Cu-2(bdc)(2)(dabco) surface-mounted metal organic frameworks (SURMOFs) was investigated on silicon wafers treated with different surface anchoring molecules. Well-oriented growth along the [100] and [001] directions could be achieved with simple protocols: growth along the [100] direction was achieved by substrate pretreatment with 80 degrees C piranha, while growth along the [001] direction was enabled by only rinsing silicon with absolute ethanol. Growth along the [001] direction produced more homogeneous SURMOF films. Optimization to enhance [001]-preferred orientation growth revealed that small changes in the SURMOF growth sequence (the number of rinse steps and linker concentrations) have a noticeable impact on the final film quality and the number of misaligned crystals. This new straightforward protocol was used to successfully grow other layer pillar-type SURMOFs, including the growth of Cu-2(bdc)(2)(bipy) with simultaneous suppression of framework interpenetration.
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