Redox property switching in MOFs with open metal sites for improved catalytic hydrogenation performance

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.

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Nanometer Scale Spectroscopic Visualization of Catalytic Sites During a Hydrogenation Reaction on a Pd/Au Bimetallic Catalyst

10.26434/chemrxiv.12346823.v3 ◽

2020 ◽

Author(s):

hao yin ◽

Liqing Zheng ◽

Wei Fang ◽

Yin-Hung Lai ◽

Nikolaus Porenta ◽

...

Keyword(s):

Catalytic Hydrogenation ◽

Density Functional ◽

Hydrogen Transfer ◽

Bimetallic Catalyst ◽

Local Environment ◽

Hydrogenation Reaction ◽

Boundary Density ◽

Catalytic Sites ◽

Powerful Analytical Tool ◽

Tip Enhanced Raman Spectroscopy

Understanding the mechanism of catalytic hydrogenation at the local environment requires chemical and topographic information involving catalytic sites, active hydrogen species and their spatial distribution. Here, tip-enhanced Raman spectroscopy (TERS) was employed to study the catalytic hydrogenation of chloro-nitrobenzenethiol on a well-defined Pd(sub-monolayer)/Au(111) bimetallic catalyst (pH2=1.5 bar, 298 K), where the surface topography and chemical fingerprint information were simultaneously mapped with nanoscale resolution (≈10 nm). TERS imaging of the surface after catalytic hydrogenation confirms that the reaction occurs beyond the location of Pd sites. The results demonstrate that hydrogen spillover accelerates hydrogenation at the Au sites within 20 nm from the bimetallic Pd/Au boundary. Density functional theory was used to elucidate the thermodynamics of interfacial hydrogen transfer. We demonstrate that TERS as a powerful analytical tool provides a unique approach to spatially investigate the local structure-reactivity relationship in catalysis.

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Nanometer Scale Spectroscopic Visualization of Catalytic Sites During a Hydrogenation Reaction on a Pd/Au Bimetallic Catalyst

10.26434/chemrxiv.12346823.v1 ◽

2020 ◽

Author(s):

Hao Yin ◽

Liqing Zheng ◽

Wei Fang ◽

Yin-Hung Lai ◽

Nikolaus Porenta ◽

...

Keyword(s):

Catalytic Hydrogenation ◽

Density Functional ◽

Hydrogen Transfer ◽

Bimetallic Catalyst ◽

Local Environment ◽

Hydrogenation Reaction ◽

Boundary Density ◽

Catalytic Sites ◽

Powerful Analytical Tool ◽

Tip Enhanced Raman Spectroscopy

Understanding the mechanism of catalytic hydrogenation at the local environment requires chemical and topographic information involving catalytic sites, active hydrogen species and their spatial distribution. Here, tip-enhanced Raman spectroscopy (TERS) was employed to study the catalytic hydrogenation of chloro-nitrobenzenethiol on a well-defined Pd(sub-monolayer)/Au(111) bimetallic catalyst (pH2=1.5 bar, 298 K), where the surface topography and chemical fingerprint information were simultaneously mapped with nanoscale resolution (≈10 nm). TERS imaging of the surface after catalytic hydrogenation confirms that the reaction occurs beyond the location of Pd sites. The results demonstrate that hydrogen spillover accelerates hydrogenation at the Au sites within 20 nm from the bimetallic Pd/Au boundary. Density functional theory was used to elucidate the thermodynamics of interfacial hydrogen transfer. We demonstrate that TERS as a powerful analytical tool provides a unique approach to spatially investigate the local structure-reactivity relationship in catalysis.

Download Full-text