Loading across the Periodic Table: Introducing 14 Different Metal Ions To Enhance Metal–Organic Framework Performance

Chen, Shoushun; Lucier, Bryan E. G.; Luo, Wilson; Xie, Xinkai; Feng, Kun; Chan, Hendrick; Terskikh, Victor V.; Sun, Xuhui; Sham, Tsun‐Kong; Workentin, Mark S.; Huang, Yining

doi:10.1021/acsami.8b08496

Cited by 21 publications

(119 citation statements)

References 74 publications

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“…8 ppm arises from phenyl hydrogen, and the H3 resonance at ca. 3 ppm corresponds to the bridging hydroxyl group that connects adjacent Al atoms. , With basic spectral assignments given, we now discuss how the 13 C and 1 H NMR spectra in Figure and Figure S5 evolve with increasing thermal treatment temperatures and times, relating spectral changes to structural features.…”

Section: Resultsmentioning

confidence: 99%

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Cleaving Carboxyls: Understanding Thermally Triggered Hierarchical Pores in the Metal–Organic Framework MIL-121

et al. 2019

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Carboxylic acid linker ligands are known to form strong metal−carboxylate bonds to afford many different variations of permanently microporous metal−organic frameworks (MOFs). A controlled approach to decarboxylation of the ligands in carboxylate-based MOFs could result in structural modifications, offering scope to improve existing properties or to unlock entirely new properties. In this work, we demonstrate that the microporous MOF MIL-121 is transformed to a hierarchically porous MOF via thermally triggered decarboxylation of its linker. Decarboxylation and the introduction of hierarchical porosity increases the surface area of this material from 13 to 908 m 2 /g and enhances gas adsorption uptake for industrially relevant gases (i.e., CO 2 , C 2 H 2 , C 2 H 4 , and CH 4 ). For example, CO 2 uptake in hierarchically porous MIL-121 is improved 8.5 times over MIL-121, reaching 215.7 cm 3 /g at 195 K and 1 bar; CH 4 uptake is 132.3 cm 3 /g at 298 K and 80 bar in hierarchically porous MIL-121 versus zero in unmodified MIL-121. The approach taken was validated using a related aluminum-based MOF, ISOMIL-53. However, many specifics of the decarboxylation procedure in MOFs have yet to be unraveled and demand prompt examination. Decarboxylation, the formation of heterogeneous hierarchical pores, gas uptakes, and host−guest interactions are comprehensively investigated using variable-temperature multinuclear solid-state NMR spectroscopy, X-ray diffraction, electron microscopy, and gas adsorption; we propose a mechanism for how decarboxylation proceeds and which local structural features are involved. Understanding the complex relationship among the molecular-level MOF structure, thermal stability, and the decarboxylation process is essential to fine-tune MOF porosity, thus offering a systematic approach to the design of hierarchically porous, custom-built MOFs suited for targeted applications.

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Section: Resultsmentioning

confidence: 99%

“…The overlapping C1 and C2 resonances at ca. 172 ppm originate from free (C2) and Al-coordinated (C1) carboxyl carbon sites, , while the 13 C resonances at ca. 135 and 130 ppm are assigned to the unsubstituted C3 phenyl carbon site and the carboxyl-substituted C4/C5 phenyl carbon sites, respectively.…”

Section: Resultsmentioning

confidence: 99%

Cleaving Carboxyls: Understanding Thermally Triggered Hierarchical Pores in the Metal–Organic Framework MIL-121

et al. 2019

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“…The resonances at ca. 134.9 and 130.0 ppm originate from the C3, C4, and C5 sites of phenyl carbons (Figure b). , The less intense signals at ca. 50 ppm belong to residual guest methanol molecules which were subsequently removed during thermal treatment.…”

Section: Resultsmentioning

confidence: 99%

“…As mentioned earlier, the signal at 172 ppm in the 13 C spectrum of MIL-121 originates from two overlapping resonances: C1 from the Al-coordinated carbon atom and C2 from the free carboxylate groups. Our previous study showed that, once the free carboxylate groups are doped with extra-framework metal ions, new signals often appear on the lower-field side of the peak at 172 ppm, which is due to the C2 site of the free COO – group interacting with the newly introduced metal ions. In the 13 C spectrum of Pt-HMIL-121, an extra peak indeed appears at ca.…”

Section: Resultsmentioning

confidence: 99%

Anhydride Post-Synthetic Modification in a Hierarchical Metal–Organic Framework

et al. 2020

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Metal–organic frameworks (MOFs) are important porous materials. Post-synthetic modification (PSM) of MOFs via the pendant groups or secondary functional groups of organic linkers has been widely used to introduce new or enhance existing properties of MOFs for various practical applications. In this work, we have constructed, for the first time, a novel platform for PSM of MOFs by introducing an anhydride functional group into a hierarchically porous MOF (MIL-121) as an effective anchor. We have demonstrated that the combination of the high reactivity of anhydride and hierarchical porosity makes this protocol particularly novel and important, as it led to excellent opportunities of incorporating not only a wide variety of organic molecules with different sizes and chemical nature but also the noble metal complexes in MOFs. Specifically, we show that the anhydride group decorated in the MOF exhibits a high reactivity toward covalently binding 10 different guest molecules including alcohols, amines, thiols, and noble metal (Pt(II)/Pt(IV)) complexes, whereas the hierarchical pores created in the MOF allow the incorporation of guest species varying in size from methanol to larger molecules such as polyaromatic amines. This novel approach provides the community with a new avenue to prepare MOF-based materials for targeted applications. To illustrate this point, we furnish an example of using this new platform to prepare a Pt-based electrocatalyst which shows excellent catalytic activity toward the oxygen reduction reaction (ORR), a pivotal half-reaction in hydrogen–oxygen fuel cells and other energy storage and conversion devices.

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“…In the particular case of MIL-121 and loading with Ca 2+ , detailed characterization was performed by 43 Ca NMR. [20] (iii) The study by natural abundance 43 Ca NMR of bioceramic materials based on silico-carnotite, Ca 5 (PO 4 ) 2 SiO 4 , synthesized mechanochemically: calculated δ iso ( 43 Ca) were used to analyze carefully the experimentally determined results. [21] 43…”

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A ⁴³Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives

Laurencin

Duer

et al. 2021

Magnetic Reson in Chemistry

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Ca nuclear magnetic resonance (NMR) spectroscopy has been extensively applied to the detailed study of octacalcium phosphate (OCP), Ca 8 (HPO 4 ) 2 (PO 4 ) 4 .5H 2 O, and hybrid derivatives involving intercalated metabolic acids (viz., citrate, succinate, formate, and adipate). Such phases are of importance in the development of a better understanding of bone structure. High-resolution 43 Ca magic angle spinning (MAS) experiments, including double-rotation (DOR) 43 Ca NMR, as well as 43 Ca{ 1 H} rotational echo DOR (REDOR) and 31 P{ 43 Ca} REAPDOR NMR spectra, were recorded on a 43 Calabeled OCP phase at very high magnetic field (20 T), and complemented by ab initio calculations of NMR parameters using the Gauge-Including Projector Augmented Wave-density functional theory (GIPAW-DFT) method. This enabled a partial assignment of the eight inequivalent Ca 2+ sites of OCP.Natural-abundance 43 Ca MAS NMR spectra were then recorded for the hybrid organic-inorganic derivatives, revealing changes in the 43 Ca lineshape. In the case of the citrate derivative, these could be interpreted on the basis of computational models of the structure. Overall, this study highlights the advantages of combining high-resolution 43 Ca NMR experiments and computational modeling for studying complex hybrid biomaterials.

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Loading across the Periodic Table: Introducing 14 Different Metal Ions To Enhance Metal–Organic Framework Performance

Cited by 21 publications

References 74 publications

Cleaving Carboxyls: Understanding Thermally Triggered Hierarchical Pores in the Metal–Organic Framework MIL-121

Cleaving Carboxyls: Understanding Thermally Triggered Hierarchical Pores in the Metal–Organic Framework MIL-121

Anhydride Post-Synthetic Modification in a Hierarchical Metal–Organic Framework

A ⁴³Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives

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Loading across the Periodic Table: Introducing 14 Different Metal Ions To Enhance Metal–Organic Framework Performance

Cited by 21 publications

References 74 publications

Cleaving Carboxyls: Understanding Thermally Triggered Hierarchical Pores in the Metal–Organic Framework MIL-121

Cleaving Carboxyls: Understanding Thermally Triggered Hierarchical Pores in the Metal–Organic Framework MIL-121

Anhydride Post-Synthetic Modification in a Hierarchical Metal–Organic Framework

A 43Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives

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A ⁴³Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives