Computational Screening of Bimetal-Functionalized Zr<sub>6</sub>O<sub>8</sub> MOF Nodes for Methane C–H Bond Activation

Pahls, Dale R.; Ortuño, Manuel Á.; Winegar, Peter H.; Cramer, Christopher J.; Gagliardi, Laura

doi:10.1021/acs.inorgchem.7b01334

Cited by 50 publications

(75 citation statements)

References 59 publications

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“…Two recent studies of computational screening of bimetallic MOFs will highlight this. First, Gagliardi et al 86 screened a series of homo-and heterobimetal-functionalized NU-1000 MOF nodes selected to computationally screen the effect of ancillary metals for C−H bond activation. Correlating activation free energies with various chemical descriptors of the cluster models studied, they showed that transition state C···H (and O···H) bond lengths were reasonable predictors, and that materials combining Cu and Lewis-acidic metals had encouraging properties.…”

Section: Catalytic Activity and Mechanismsmentioning

confidence: 99%

Mixed-metal metal–organic frameworks

et al. 2019

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Section: Catalytic Activity and Mechanismsmentioning

confidence: 99%

Mixed-metal metal–organic frameworks

et al. 2019

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“…[27] Computational studies have also shown the potentialo fs uch bimetallic MOFs for variousa pplications, such as CÀHb ond activation. [28] Generation of defects and the synergistic effect between the two metals in bimetallic MOFs could lead to enhanced catalytic activity.H ere, we report ao ne-pot method, eliminating the post synthetic process, for the partial substitution of Fe with Co in an amine-functionalized MOF [NH 2 -MIL-88B(Fe)]. [29] The effects of metal substitution on crystallinity,c rystal structure, stability, and catalytic activity were investigated.…”

Section: Introductionmentioning

confidence: 99%

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

Iqbal

Saleem

Arshad

et al. 2019

Chemistry A European J

118

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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).

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“…Though strictly speaking not a materials characterisation method, increasingly sophisticated systems increasingly rely on supporting understanding of characterisation techniques by computational modelling. This is none the least relevant for catalytic reactions, including single‐site catalysts, an area that has undergone a tremendous amount of progress thanks to method development, increased computational power . Computationally assessing catalytic activity by relating it to descriptors instead of calculating the activation energies of elementary reaction steps in heterogeneous catalytic reactions has been significantly relying on screening linear free energy relationships (LFERs), or linear scaling relations .…”

Section: Identification Of Fenx Single Sitesmentioning

confidence: 99%

“…This is none the least relevant for catalytic reactions, including single-site catalysts, an area that has undergone a tremendous amount of progress thanks to method development, increased computational power. [148][149][150][151][152][153][154][155][156][157][158][159][160] Computationally assessing catalytic activity by relating it to descriptors instead of calculating the activation energies of elementary reaction steps in heterogeneous catalytic reactions has been significantly relying on screening linear free energy relationships (LFERs), or linear scaling relations. [161][162][163][164][165][166][167][168][169] However, the direct transposition of LFER on the single-site systems is problematic as the simple models used for bulk metal systems are not satisfactory to describe directional metal-ligand bonds.…”

Section: Advanced Characterisation Of Fen X Single Site (Ssc) Catalystsmentioning

confidence: 99%

Homogenous Meets Heterogenous and Electro‐Catalysis: Iron‐Nitrogen Molecular Complexes within Carbon Materials for Catalytic Applications

Nicolae

Qiao

et al. 2019

ChemCatChem

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High activity, selectivity and recyclability are crucial parameters in the design of performant catalysts. Furthermore, depletion of platinum‐group metals (PGM) drives further research towards highly available metal‐based catalysts. In this framework, iron‐based active sites supported on nitrogen‐doped carbon materials (Fe/N@C) have been explored to tackle important applications in organic chemistry, for both oxidation and reduction of C−O/C−N bonds, as well as in electrocatalysis for energy applications. This versatile reactivity makes them ideal substitutes to PGM‐based catalysts, being based on abundant elements. Despite important advances in material science and characterisation techniques allowing the analysis of heterogeneous/electro‐ catalysts at the atomic scale, the nature of the catalytically active sites in Fe/N@C remains elusive. Most recent theoretical studies point at individual FeNx single sites as the origin of the catalytic activity. Although their identification is still challenging with current technology, establishing their real nature will foster further research on these PGM‐free and redox‐polyvalent catalysts. In this review, we provide an overview of their applications in both thermal and electrochemical processes. Throughout the review, we highlight the different characterisation techniques employed to gain insight into the catalyst's active sites.

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Computational Screening of Bimetal-Functionalized Zr₆O₈ MOF Nodes for Methane C–H Bond Activation

Cited by 50 publications

References 59 publications

Mixed-metal metal–organic frameworks

Mixed-metal metal–organic frameworks

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

Homogenous Meets Heterogenous and Electro‐Catalysis: Iron‐Nitrogen Molecular Complexes within Carbon Materials for Catalytic Applications

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Computational Screening of Bimetal-Functionalized Zr6O8 MOF Nodes for Methane C–H Bond Activation

Cited by 50 publications

References 59 publications

Mixed-metal metal–organic frameworks

Mixed-metal metal–organic frameworks

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

Homogenous Meets Heterogenous and Electro‐Catalysis: Iron‐Nitrogen Molecular Complexes within Carbon Materials for Catalytic Applications

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Computational Screening of Bimetal-Functionalized Zr₆O₈ MOF Nodes for Methane C–H Bond Activation