An In(III) based metal-organic framework (MOF), In-pbpta, with topology was constructed from the trigonal prismatic [In(μ-O)(HO)(OC-)] secondary building unit (SBU) and a custom-designed tetratopic linker Hpbpta (pbpta = 4,4',4″,4‴-(1,4-phenylenbis(pyridine-4,2,6-triyl))-tetrabenzoic acid)). The obtained MOF shows a Brunauer-Emmett-Teller surface area of 1341 m/g with a pore volume of 0.64 cm/g, which is the highest among the scarcely reported In--MOFs. The constructed MOF demonstrates excellent performance as a heterogeneous Lewis acid catalyst for highly efficient conversion in a one-pot multicomponent Strecker reaction for the preparation of α-aminonitriles under solvent-free conditions, which can be easy to separate and recycle without significant loss of activity for up to seven cycles. The computational modeling studies suggest the presence of the three substrates in close vicinity to the In-oxo cluster. The strong interactions of the aldehyde/ketone and the amine with the In-oxo cluster together with the readily available cyanide ion around the In-oxo cluster lead to high catalytic conversion within a short period of time for the MOF catalyst. Our work therefore lays a foundation to develop MOF as a new class of efficient heterogeneous catalyst for one-pot Strecker reaction.
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http://dx.doi.org/10.1021/acsami.1c09074 | DOI Listing |
Phys Chem Chem Phys
April 2023
School of Advanced Engineering, Kogakuin University, 2665-1, Nakano-cho, Hachioji, 192-0015, Japan.
Metal-exchanged zeolites have great potential to form unique active metal species and develop their catalysis by promoting small molecules such as light alkanes. Ga-exchanged zeolites have attracted attention as promising heterogeneous catalysts for dehydrogenative light-alkane transformations. The speciation of active Ga species in reduced and oxidized Ga-exchanged zeolites and their reaction mechanisms have been discussed in several studies based on experimental and theoretical investigations.
View Article and Find Full Text PDFACS Appl Mater Interfaces
November 2021
Department of Chemistry, University of North Texas, 1508 West Mulberry Street, Denton, Texas 76201, United States.
An In(III) based metal-organic framework (MOF), In-pbpta, with topology was constructed from the trigonal prismatic [In(μ-O)(HO)(OC-)] secondary building unit (SBU) and a custom-designed tetratopic linker Hpbpta (pbpta = 4,4',4″,4‴-(1,4-phenylenbis(pyridine-4,2,6-triyl))-tetrabenzoic acid)). The obtained MOF shows a Brunauer-Emmett-Teller surface area of 1341 m/g with a pore volume of 0.64 cm/g, which is the highest among the scarcely reported In--MOFs.
View Article and Find Full Text PDFPhys Chem Chem Phys
June 2019
Institute for Catalysis, Hokkaido University, N-21, W-10, Sapporo 001-0021, Japan.
We have carried out an experimental and theoretical study of CHA-zeolite supported indium (In)-oxo clusters that promote CH4 activation at room temperature. X-ray absorption fine structure (XAFS) measurements indicate the formation of multinuclear In-oxo clusters by the O2 activation of the In(i)-exchanged CHA zeolite prepared through reductive solid-state ion exchange (RSSIE). The structure of the In-oxo clusters and their locations were investigated in detail using ab initio thermodynamic analysis.
View Article and Find Full Text PDFAcc Chem Res
November 2018
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering , Beijing Institute of Technology, Beijing 102488 , China.
Developments in strategies for the synthesis of oxo-hydroxo lanthanide (Ln) clusters during the past few decades have resulted in abundant relevant crystalline materials that exhibit attractive structures and interesting properties. The combination of these oxo-hydroxo Ln clusters and organic ligands has led to the formation of new extended arrays of Ln cluster organic frameworks (LnCOFs). In contrast to metal-organic frameworks, the incorporation of particular characteristics of clusters provides the opportunity to develop performances not available in single-metal compounds.
View Article and Find Full Text PDFInorg Chem
November 2013
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley , California 94720, United States.
The protonation state of oxo bridges in nature is of profound importance for a variety of enzymes, including the Mn4CaO5 cluster of photosystem II and the Mn2O2 cluster in Mn catalase. A set of dinuclear bis-μ-oxo-bridged Mn(IV) complexes in different protonation states was studied by Kβ emission spectroscopy to form the foundation for unraveling the protonation states in the native complex. The valence-to-core regions (valence-to-core XES) of the spectra show significant changes in intensity and peak position upon protonation.
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