Using Predefined M 3 (μ 3 -O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

118

Ao ne-pot synthesis of bimetallic metal-organic frameworks( Co/Fe-MOFs)w as achieved by treating stoichiometric amounts of Fe and Co salts with 2-aminoterephthalic acid (NH 2 -BDC). Monometallic Fe (catalystA )and Co (catalyst F) were also prepared along with mixed-metal Fe/Co catalysts (B-E) by changing the Fe/Co ratio. For mixed-metal catalysts (B-E) SEM energy-dispersive X-ray (EDX) analysisc onfirmed the incorporation of both Fe and Co in the catalysts. However,aspindle-shaped morphology,t ypicallyk nown for the Fe-MIL-88Bs tructure and confirmed by PXRD analysis, was only observed for catalysts A-D. To test the catalytic potential of mixed-metal MOFs, reduction of nitroarenes was selected as ab enchmark reaction. Incorporation of Co enhanced the activity of the catalysts compared with the parentN H 2 -BDC-Fe catalyst. These MOFs werea lso testeda s electrocatalysts for the oxygen evolution reaction( OER) and the best activity was exhibited by mixed-metal Fe/Co-MOF (Fe/Cob atch ratio = 1). The catalystp rovided ac urrent density of 10 mA cm À2 at 410 mV overpotential, whichi sc omparable to the benchmarkO ER catalyst (i.e.,R uO 2 ). Moreover,i t showedl ong-term stability in 1 m KOH. In at hird catalytic test, dehydrogenation of sodium borohydride showedh igh activity (turnover frequency = 87 min À1 )a nd hydrogen generation rate (67 Lmin À1 g À1 catalyst). This is the first example of the synthesis of bimetallic MOFs as multifunctional catalysts particularly for catalytic reductiono fn itroarenes and dehydrogenation reactions. Figure 7. Catalytichydrolysis of NaBH 4 .a )Effect of monometallic and bimetallic catalysts on the dehydrogenation reaction;b )effect of temperature; c) Arrhenius plot (see Table S6 in the SupportingI nformation).

Section: Resultsmentioning

confidence: 99%

One‐Pot Synthesis of Heterobimetallic Metal–Organic Frameworks (MOFs) for Multifunctional Catalysis

Iqbal

Saleem

Arshad

et al. 2019

118

“…These properties endow MOFs with great promise in applications coupled to catalysis, gas adsorption/separation, chemical sensing and so on . For example, the organic ligands in MOFs, promote the formation of frameworks that have highly dispersed metal ions and clusters . Further, these ligands can be pre‐designed to afford additional coordination sites for metals .…”

Section: Methodsmentioning

confidence: 99%

“…[2] For example, the organic ligands in MOFs, promote the formation of frameworks that have highly dispersed metal ions and clusters. [3] Further, these ligands can be pre-designed to afford additional coordination sites for metals. [4] These structural features can aid the formation of MOFs and MOF-derived materials with very small and highly dispersed nanoparticles, clusters, and even single atoms as catalyticallya ctive sites.…”

mentioning

confidence: 99%

MOF‐Derived Cobalt Phosphide/Carbon Nanocubes for Selective Hydrogenation of Nitroarenes to Anilines

Yang

Oveisi

et al. 2018

Self Cite

Transition-metal phosphides have received tremendous attention during the past few years because they are earth-abundant, cost-effective, and show outstanding catalytic performance in several electrochemically driven conversions including hydrogen evolution, oxygen evolution, and water splitting. As one member of the transition-metal phosphides, Co P-based materials have been widely explored as electrocatalyts; however, their application in the traditional thermal catalysis are rarely reported. In this work, cobalt phosphide/carbon nanocubes are designed and their catalytic activity for the selective hydrogenation of nitroarenes to anilines is studied. A high surface area metal-organic framework (MOF), ZIF-67, is infused with red phosphorous, and then pyrolysis promotes the facile production of the phosphide-based catalysts. The resulting composite, consisting of Co P/CN nanocubes, is shown to exhibit excellent catalytic performance in the selective hydrogenation of nitroarenes to anilines. To the best of our knowledge, this is the first report showing catalytic activity of a cobalt phosphide in nitroarenes hydrogenation.

“…Since the trimeric building blocks are stable under the applied reaction conditions, each building blocks maintained the 2:1 ratio of the metals, which is characteristic for the site‐specific incorporation. In combination with the report of Peng et al . this approach has been shown to work for a large range of linker molecules and several metal combinations within the trimeric building block.…”

Section: Mixed‐metal Metal–organic Frameworkmentioning

confidence: 99%

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

Bitzer

Kleist

2019

In recent years, the synthesis of mixed‐metal and mixed‐linker metal–organic frameworks with multiple metals and/or linker molecules combined in one framework has become a growing field of interest. These mixed‐component or multivariate metal–organic framework materials provide the possibility to introduce multiple functionalities inside one framework. The interaction of guest molecules with different functionalities in the same material is a promising approach in the fields of gas storage, separation, catalysis and drug delivery. Furthermore, the combination of different components may lead to synergistic effects that cannot be achieved otherwise. These mixed‐component approaches open up new pathways to an even larger range of possible customizations in the field of metal–organic frameworks.