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Abstract Traditional MOF e‐CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi‐electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e‐CRR systems, CoPc@NU‐1000 and TPP(Co)@NU‐1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU‐1000 MOF. For CoPc@NU‐1000, the e‐CRR responsive CoI/0potential is close to that of NU‐1000 reduction compared to the TPP(Co)@NU‐1000. Efficient charge delivery, defined by a higher diffusion (Dhop=4.1×10−12 cm2 s−1) and low charge‐transport resistance (=59.5 Ω) in CoPC@NU‐1000 led FECO=80 %. In contrast, TPP(Co)@NU‐1000 fared a poor FECO=24 % (Dhop=1.4×10−12 cm2 s−1and=91.4 Ω). For such a decoupling strategy, careful choice of the host framework is critical in pairing up with the underlying electrochemical properties of the catalysts to facilitate the charge delivery for its activation.
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Homogeneous versus MOF-supported catalysis: A direct comparison of catalytic hydroboration at Ni tripodal P 3 E (E = Si, Ge) complexes
MOF NU-1000 was employed to host Ni tripodal complexes prepared from new organometallic precursors [HNi(κ4(E,P,P,P)-E(o-C 6 H 4 CH 2 PPh 2 ) 3 ], E = Si (Ni-1), Ge (Ni-2). The new heterogenous catalytic materials, Ni-1@NU-1000 and Ni-2@NU-1000 show the advantages of both homogenous and heterogeneous catalysts. They catalyze the hydroboration of aldehydes and ketones more efficiently than the homogenous Ni-1 and Ni-2, under aerobic conditions, and allowing recyclability of the catalyst.
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- Award ID(s):
- 2102689
- PAR ID:
- 10417103
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Dalton Transactions
- Volume:
- 52
- Issue:
- 26
- ISSN:
- 1477-9226
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The new material [RuGa]@NU-1000 incorporates Ru and Ga in 1.2 and 1.8 wt% respectively (molar ratio 1 : 2). It stems from the grafting of the heterobimetallic ruthenium gallate complex, [MeRu(η 6 -C 6 H 6 )(PPh 3 ) 2 ][GaMe 2 Cl 2 ] into the MOF material NU-1000. [RuGa]@NU-1000 shows enhanced adsorption of SO 2 , specially at low pressures (10 −3 bar) even when compared with other materials employing more expensive precious metals. Additionally, [RuGa]@NU-1000 samples need not be exposed to such harsh conditions for reactivation as they retain their adsorption properties after several cycles and preserve their porosity and structure. Thus, [RuGa]@NU-1000 is an excellent, selective material suitable for detection and precise quantification of SO 2 , with a lower cost compared to other MOFs incorporating precious metals.more » « less
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The stability of metal–organic frameworks (MOFs) in water affects their ability to function as chemical catalysts, their capacity as adsorbents for separations in water vapor presence, and their usefulness as recyclable water harvesters. Here, we have examined water stability of four node-modified variants of the mesoporous MOF, NU-1000, namely formate-, Acac-, TFacac-, and Facac-NU-1000, comparing these with node-accessible NU-1000. These NU-1000 variants present ligands grafted to NU-1000's hexa-Zr( iv )-oxy nodes by displacing terminal aqua and hydroxo ligands. Facac-NU-1000, containing the most hydrophobic ligands, showed the greatest water stability, being able to undergo at least 20 water adsorption/desorption cycles without loss of water uptake capacity. Computational studies revealed dual salutary functions of installed Facac ligands: (1) enhancement of framework mechanical stability due to electrostatic interactions; and (2) transformation and shielding of the otherwise highly hydrophilic nodes from H-bonding interactions with free water, presumably leading to weaker channel-stressing capillary forces during water evacuation – consistent with trends in free energies of dehydration across the NU-1000 variants. Water harvesting and hydrolysis of chemical warfare agent simulants were examined to gauge the functional consequences of modification and mechanical stabilization of NU-1000 by Facac ligands. The studies revealed a harvesting capacity of ∼1.1 L of water vapor per gram of Facac-NU-1000 per sorption cycle. They also revealed retention of catalytic MOF activity following 20 water uptake and release cycles. This study provides insights into the basis for node-ligand-engendered stabilization of wide-channel MOFs against collapse during water removal.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3DT01328F
