A5030036897- Metal-Organic Frameworks: Synthesis and Applications
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Catalytic Processes in Materials Science
- Covalent Organic Framework Applications
- Catalysis and Oxidation Reactions
- Magnetism in coordination complexes
- Polyoxometalates: Synthesis and Applications
- Machine Learning in Materials Science
- Catalysis and Hydrodesulfurization Studies
- Carbon Dioxide Capture Technologies
- Nanocluster Synthesis and Applications
- Chemical Synthesis and Characterization
- Crystallography and molecular interactions
- Radioactive element chemistry and processing
- Organometallic Complex Synthesis and Catalysis
- Zeolite Catalysis and Synthesis
- Organoboron and organosilicon chemistry
- Advanced NMR Techniques and Applications
- Ammonia Synthesis and Nitrogen Reduction
- Electrocatalysts for Energy Conversion
- Chemical Synthesis and Reactions
- Magnesium Oxide Properties and Applications
- Mesoporous Materials and Catalysis
- Carbon dioxide utilization in catalysis
Argonne National Laboratory
2019-2024
Northwestern University
2019-2024
Metal-organic frameworks (MOFs) are promising candidates for the catalytic hydrolysis of nerve agents and their simulants. Though highly efficient, bulk water volatile bases often required with these MOF catalysts, preventing real-world implementation. Herein we report a generalizable scalable approach integrating MOFs non-volatile polymeric onto textile fibers agent hydrolysis. Notably, composite material showed similar reactivity under ambient conditions compared to powder in aqueous...
A desirable feature of metal–organic frameworks (MOFs) is their well-defined structural periodicity and the presence catalyst grafting sites (e.g., reactive −OH −OH2 groups) that can support single-site heterogeneous catalysts. However, one should not overlook potential role residual organic moieties, specifically formate ions occupy anchoring during MOF synthesis. Here we show how these species in a Zr-based MOF, NU-1000, critically alter structure, redox capability, catalytic activity...
The efficient removal, capture, and recycling of ammonia (NH3) constitutes a demanding process; thus, the development competent adsorbent materials is highly desirable. implementation metal–organic frameworks (MOFs), known for their tunability high porosity, has attracted much attention NH3 adsorption studies. Here, we report three isoreticular porphyrin-based MOFs containing aluminum (Al-PMOF), gallium (Ga-PMOF), indium (In-PMOF) rod secondary building units with Brønsted acidic bridging...
Catalysis is a ubiquitous element of the modern economy, representing cornerstone many sectors including energy, materials, and pharmaceuticals. Within this realm, 80% reactions are carried out by heterogeneous catalysts due to their advantageous physical chemical characteristics. In some systems, reaction rate can be optimized through rational catalyst design, in which support materials tailored structurally stereoelectronically for targeted purposes better facilitate catalytic reaction. To...
Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique a variety of fields. When incorporated solid state materials, generation organic radicals proves challenging due aggregation. Metal-organic frameworks (MOFs) are promising candidates for immobilization stabilization because the tunable spatial arrangement linkers metal nodes, which sequesters reactive species. Herein, flexible, redox-active...
The local environment of a metal active site plays an important role in affecting the catalytic activity and selectivity. In recent studies, tailoring behavior molybdenum-based via modulation first coordination sphere has led to improved thioanisole oxidation performance, but disentangling electronic effects from steric influences that arise these modifications is nontrivial, especially heterogeneous systems. To this end, tunability metal–organic frameworks (MOFs) makes them promising...
Single-site supported organometallic catalysts bring together the favorable aspects of homogeneous and heterogeneous catalysis while offering opportunities to investigate impact metal–support interactions on reactivity. We report a (dmPhebox)Ir(III) (dmPhebox = 2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl) complex chemisorbed sulfated zirconia, molecular precursor for which was previously applied hydrocarbon functionalization. Spectroscopic methods such as diffuse reflectance infrared...
Interpenetration of two or more sublattices is common among many metal–organic frameworks (MOFs). Herein, we study the evolution one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, directly, high-resolution transmission electron microscopy. The approach detailed here will serve a template for...
Polyoxometalates (POMs) are versatile materials for chemical catalysis due to their tunable acidity and rich redox properties. While POMs have attracted significant attention in homogeneous catalysis, challenges regarding aggregation instability solvents often prevent the wide implementation of as heterogeneous catalysts. Therefore, successful incorporation a POM into solid support, such polymer, is desirable practical applications where unique functionalities combine with advantages...
Understanding heterogeneous catalysts is a challenging pursuit due to surface site nonuniformity and aperiodicity in traditionally used materials. One example sulfated metal oxides, which function as highly active supports for organometallic complexes. These applications are traits such acidity, ability act weakly coordinating ligand, aptitude promoting transformations via radical cation intermediates. Research ongoing about the structural features of oxides that imbue aforementioned...
We have screened an array of 23 metals deposited onto the metal–organic framework (MOF) NU-1000 for propyne dimerization to hexadienes. By a first-of-its-kind study utilizing data-driven algorithms and high-throughput experimentation (HTE) in MOF catalysis, yields on Cu-deposited were improved from 0.4 24.4%. Characterization best-performing catalysts reveal conversion hexadiene be due formation large Cu nanoparticles, which is further supported by reaction mechanisms calculated with density...
Zirconium-based metal–organic frameworks (Zr-MOFs) have been increasingly studied over the past two decades as heterogeneous catalysts due to their synthetic tunability, well-defined nature, and chemical stability. In contrast traditional zirconia-based catalysts, community has assumed that Zr-MOFs are inert catalyst supports do not participate directly in hydrocarbon transformations, such olefin hydrogenation isomerization. Here, we report Zr-MOF NU-1000 is capable of catalyzing...
Organometallic iridium catalysts can be used in conjunction with bispinacolatodiboron (B2Pin2) to effect the borylation of a variety substrates such as arenes, alkanes, heteroarenes, and oxygenates. Recently, efforts have also focused on integrating these into porous supports, metal–organic frameworks (MOFs). While mechanism homogeneous systems has been thoroughly investigated experimentally computationally, analogous studies MOF-supported not conducted. Herein, we report mechanistic...
Mesoporous silicon nitride (Si3N4) is a nontraditional support for the chemisorption of organometallic complexes with potential enhancing catalytic activity through features such as increased Lewis basicity nitrogen heterolytic bond activation, ligand donor strength, and metal-ligand orbital overlap. Here, tetrabenzyl zirconium (ZrBn4) was chemisorbed on Si3N4, resulting supported species characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Dynamic Nuclear...
Although single-site, supported organometallic catalysts were designed with homogeneity in mind, little is strictly known about their atomic-level structure and uniformity. This large part due to the inability of conventional characterization tools provide structural information adequate resolution range for this purpose. Here, we show that dynamic nuclear polarization (DNP)-enhanced solid-state magnetic resonance (NMR) enables measurement distances between surface individual carbons, making...
Abstract Synthesis of single‐site catalysts, whereby the local structure and surrounding chemical environments are identical, has been challenging, particularly in heterogeneous catalysis, as support often presents spectrum chemically distinct binding sites. Yet, above criteria crucial attributing apparent catalytic performance to structural motif. The presented work augments on our previous using monometallic molybdenum sulfide tethered within a zirconium‐based metal‐organic framework...
Crystallographic characterization of a heterogeneous ethylene polymerization catalyst elucidates chromium–carbon bond after alkyl aluminum activation and provides mechanistic insights.
The development of new methods catalyst synthesis with the potential to generate active site structures orthogonal those accessible by traditional protocols is great importance for discovering materials addressing challenges in evolving energy and chemical economy. In this work, generality oxidative grafting organometallic well-defined molecular metal precursors onto redox-active surfaces such as manganese dioxide (MnO2) lithium oxide (LiMn2O4) investigated. Nine are explored, spanning...
Identifying the relationship between structure and energetics in a uranium MOF isomer system reveals how non-equilibrium synthetic conditions can be used as strategy to target metastable MOFs.
To increase catalytic efficiency, mesoporous supports have been widely applied to immobilize well-defined metal oxide clusters due their ability stabilize highly dispersed clusters. Herein, a redox-active heterometallic Ce12V6-oxo cluster (CeV) was first presynthesized and then incorporated into silica, SBA-15, via straightforward impregnation method. Scanning transmission electron microscopy (STEM) Fourier transform infrared spectroscopy (FTIR), in concert with scanning energy-dispersive...
The efficient removal, capture, and recycling of ammonia (NH 3 ) constitutes a demanding process, thus the development competent adsorbent materials is highly desirable. implementation metal-organic frameworks (MOFs), known for their tunability high porosity, has attracted much attention NH adsorption studies. Here, we report three isoreticular porphyrin-based MOFs containing aluminum ( Al-PMOF ), gallium Ga-PMOF indium In-PMOF rod secondary building units with Brønsted acidic bridging...
We have screened an array of 23 metals deposited onto the metal–organic framework (MOF) NU-1000 for propyne dimerization to hexadienes under different reaction conditions a total ~1400 experiments. By first-of-its-kind study utilizing data-driven algorithms and high-throughput experimentation (HTE) in MOF catalysis, yields on Cu-deposited were improved from 4.2% 24.4%. Characterization most-performant catalysts reveal conversion hexadiene be due formation large Cu nanoparticles, which is...
The efficient removal, capture, and recycling of ammonia (NH<sub>3</sub>) constitutes a demanding process, thus the development competent adsorbent materials is highly desirable. implementation metal-organic frameworks (MOFs), known for their tunability high porosity, has attracted much attention NH<sub>3</sub> adsorption studies. Here, we report three isoreticular porphyrin-based MOFs containing aluminum (<b>Al-PMOF</b>), gallium...