Structural Single Fe(II) Sites in MIL-Type Metal Or-Ganic Frameworks for Oxidation of Methane to Methanol and Ethane to Ethanol

Single non-heme Fe(II) ions present as structural metals in several metal organic frameworks (e.g. MIL-100, MIL-101, MIL-808) are identified by Kohn-Sham density functional calculations as promising catalysts for C-H bond activation, with energetic barriers as low as 40 kJ mol-1 for ethane and 60 kJ mol-1 for methane following oxidative activation of iron. Through consideration of the full reaction profile leading to the corresponding alcohols ethanol and methanol, we have identified key changes in the chemical composition of the node that would modulate catalytic activity. The thermal and chemical stability of these MOFs together with the scalability of their syntheses make them attractive catalysts for the selective low temperature conversion of light alkanes to higher-value oxygenates.

Download Full-text

Ethane C–H bond activation on the Fe(iv)–oxo species in a Zn-based cluster of metal–organic frameworks: a density functional theory study

Physical Chemistry Chemical Physics ◽

10.1039/c6cp07771d ◽

2017 ◽

Vol 19 (5) ◽

pp. 3782-3791 ◽

Cited By ~ 8

Author(s):

Sarawoot Impeng ◽

Siwarut Siwaipram ◽

Sareeya Bureekaew ◽

Michael Probst

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Bond Activation ◽

Metal Organic Frameworks ◽

Density Functional Theory Study ◽

Functional Theory ◽

Metal Organic

The generation of a Fe(iv)–oxo complex and its reactivity for C–H bond activation of ethane have been theoretically unraveled.

Download Full-text

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

10.26434/chemrxiv.10316681.v1 ◽

2019 ◽

Author(s):

Andrew Rosen ◽

M. Rasel Mian ◽

Timur Islamoglu ◽

Haoyuan Chen ◽

Omar Farha ◽

...

Keyword(s):

Density Functional ◽

Metal Organic Frameworks ◽

Redox Activity ◽

Screening Methods ◽

Bridging Ligands ◽

Metal Centers ◽

Computational Screening ◽

Open Metal Sites ◽

Metal Organic ◽

Unsaturated Metal Sites

Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O2 and N2 adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O2 at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the O2 adsorbate.

Download Full-text

Modulating electronic structure of metal-organic frameworks by introducing atomically dispersed Ru for efficient hydrogen evolution

Nature Communications ◽

10.1038/s41467-021-21595-5 ◽

2021 ◽

Vol 12 (1) ◽

Cited By ~ 1

Author(s):

Yamei Sun ◽

Ziqian Xue ◽

Qinglin Liu ◽

Yaling Jia ◽

Yinle Li ◽

...

Keyword(s):

Electronic Structure ◽

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Density Functional ◽

Metal Organic Frameworks ◽

Catalyst Design ◽

Single Atom ◽

Hydrogen Energy ◽

Structure Of Metal ◽

Metal Organic

AbstractDeveloping high-performance electrocatalysts toward hydrogen evolution reaction is important for clean and sustainable hydrogen energy, yet still challenging. Herein, we report a single-atom strategy to construct excellent metal-organic frameworks (MOFs) hydrogen evolution reaction electrocatalyst (NiRu0.13-BDC) by introducing atomically dispersed Ru. Significantly, the obtained NiRu0.13-BDC exhibits outstanding hydrogen evolution activity in all pH, especially with a low overpotential of 36 mV at a current density of 10 mA cm−2 in 1 M phosphate buffered saline solution, which is comparable to commercial Pt/C. X-ray absorption fine structures and the density functional theory calculations reveal that introducing Ru single-atom can modulate electronic structure of metal center in the MOF, leading to the optimization of binding strength for H2O and H*, and the enhancement of HER performance. This work establishes single-atom strategy as an efficient approach to modulate electronic structure of MOFs for catalyst design.

Download Full-text

Modeling flexibility in metal–organic frameworks: Comparison between Density-Functional Tight-Binding and Universal Force Field approaches for bonded interactions

Microporous and Mesoporous Materials ◽

10.1016/j.micromeso.2012.07.026 ◽

2012 ◽

Vol 163 ◽

pp. 215-220 ◽

Cited By ~ 25

Author(s):

Giovanni Garberoglio ◽

Simone Taioli

Keyword(s):

Force Field ◽

Density Functional ◽

Metal Organic Frameworks ◽

Tight Binding ◽

Universal Force Field ◽

Metal Organic ◽

Field Approaches

Download Full-text

Two-dimensional metal-organic frameworks Mo3(C2O)12 as promising single-atom catalysts for selective nitrogen-to-ammonia

Journal of Materials Chemistry A ◽

10.1039/d1ta07613b ◽

2022 ◽

Author(s):

Zhen Feng ◽

Zelin Yang ◽

Xiaowen Meng ◽

Fachuang Li ◽

Zhanyong Guo ◽

...

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Metal Organic Frameworks ◽

Density Functional Theory Calculations ◽

Reduction Reaction ◽

Single Atom ◽

Two Dimensional ◽

Functional Theory ◽

New Family ◽

Metal Organic

The development of single-atom catalysts (SACs) for electrocatalytic nitrogen reduction reaction (NRR) remains a great challenge. Using density functional theory calculations, we design a new family of two-dimensional metal-organic frameworks...

Download Full-text

Including dispersion in density functional theory for adsorption on flat oxide surfaces, in metal–organic frameworks and in acidic zeolites

Physical Chemistry Chemical Physics ◽

10.1039/d0cp00394h ◽

2020 ◽

Vol 22 (14) ◽

pp. 7577-7585 ◽

Cited By ~ 2

Author(s):

Florian R. Rehak ◽

GiovanniMaria Piccini ◽

Maristella Alessio ◽

Joachim Sauer

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Van Der Waals ◽

Metal Organic Frameworks ◽

Many Body ◽

Functional Theory ◽

Metal Organic ◽

The Many ◽

Acidic Zeolites ◽

Better Than

Contrary to common believe, for eight adsorption cases, neither D3 or TS are an improvement compared to D2 nor van der Waals functionals or dDsC. Only the many body approaches are slightly better than D2(Ne) which uses Ne parameters for Mg2+ ions.

Download Full-text