Engineering topics

Knapp, Julia G.

Publications and source records attributed to Knapp, Julia G..

13 records

DOE OSTI2024

Uranyl uptake into metal–organic frameworks: a detailed X-ray structural analysis

Metal–organic frameworks (MOF) are a subclass of porous framework materials that have been used for a wide variety of applications in sensing, catalysis, and remediation. Among these myriad applications is their remarkable ability to capture substances in a variety of environments ranging from benign to extreme. Among the most common and problematic substances found throughout the world's oceans and water supplies is [UO 2 ] 2+ , a common mobile ion of uranium, which is found both naturally and as a result of anthropogenic activities, leading to problematic environmental contamination. While some MOFs possess high capability for the uptake of [UO 2 ] 2+ , many more of the thousands of MOFs and their modifications that have been produced over the years have yet to be studied for their ability to uptake [UO 2 ] 2+ . However, studying the thousands of MOFs and their modifications presents an incredibly difficult task. As such, a way to narrow down the numbers seems imperative. In this work, we evaluate the binding behaviors as well as identify the specific binding sites of [UO 2 ] 2+ incorporated into six different Zr MOFs to elucidate specific features that improve [UO 2 ] 2+ uptake. In doing so, we also present a method for the determination and verification of these binding sites by Anomalous wide-angle X-ray scattering, X-ray fluorescence, and X-ray absorption spectroscopy. This research not only presents a way for future research into the uptake of [UO 2 ] 2+ into MOFs to be conducted but also a means to evaluate MOFs more generally for the uptake of other compounds to be applied for environmental remediation and improvement of ecosystems globally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Influence of Linker Identity on the Photochemistry of Uranyl-Organic Frameworks

While uranyl-based metal–organic frameworks (MOFs) boast impressive photocatalytic abilities, significant questions remain regarding their excitation pathways and methods to fine-tune their performance due to the lack of information regarding heterogeneous uranyl catalysis. Herein, we investigated how linker identity and photoexcitation impact uranyl photocatalysis when the uranyl coordination environment remains constant. Toward this end, we prepared three uranyl-based MOFs (NU-1301, NU-1307, and ZnTCPP-U2) and then examined the structural and photochemical properties of each through X-ray diffraction, X-ray absorption, and photoluminescence. We then correlated our observations to the photocatalytic performance for fluorination of cyclooctane. The excitation profile from NU-1301 and NU-1307 exhibited spin-forbidden linker transitions and uranyl vibronic progressions, with uranyl excitation and emission being most dominant in NU-1301. Consequently, NU-1301 was a more active photocatalyst than NU-1307. In contrast, the excitation profile from ZnTCPP-U2 contained transitions associated with the porphyrin linker exclusively. Photocatalytic activity from ZnTCPP-U2 significantly underperformed in comparison to that of the other two MOFs. Furthermore, these data suggest that linkers’ photophysical properties can be used to predict the photocatalytic behavior of uranyl-containing MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Mapping the Complete Reaction Energy Landscape of a Metal–Organic Framework Phase Transformation

Crystalline materials undergo valuable phase transformations, and the energetic processes that underlie these transformations can be fully characterized through a combination of thermodynamic and kinetic studies. Here, we report the first complete reaction energy landscape of metal–organic framework (MOF) interpenetration, specifically in the phase transformation of NU-1200 to its doubly interpenetrated counterpart, STA-26. We characterized the thermodynamics of this phase transformation by pairing experiments with density functional theory (DFT) calculations. This analysis revealed that factors such as the increase in crystal density likely drive Zr- and Hf-NU-1200 to STA-26 interpenetration, while other chemical interactions such as steric repulsions prevent Th-NU-1200 from interpenetrating. Using time-resolved in situ X-ray diffraction, we monitored phase transformation reaction profiles and extracted quantitative kinetic information using the Avrami-Erofe’ev model. As a result, we obtained activation energies for the Zr- and Hf-NU-1200 transformations to Zr- and Hf-STA-26, respectively, revealing slower phase change kinetics for MOFs with stronger bonds. Finally, we paired the kinetic data with experimental observations to classify the mechanistic model of this phase transformation as partial dissolution. Here, we anticipate that this thermodynamic, kinetic, and mechanistic understanding will broadly inform further studies on the energetics of crystallization.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2023

Evidence of a Uranium‐Paddlewheel Node in a Catecholate‐Based Metal–Organic Framework

Abstract The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOF NU‐1700 , assembled from U 4+ ‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U 4+ ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.

Knapp, Julia G.↗

DOE OSTI2023

Evidence of a Uranium‐Paddlewheel Node in a Catecholate‐Based Metal–Organic Framework

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Mechanistic Investigation of Enhanced Catalytic Selectivity toward Alcohol Oxidation with Ce Oxysulfate Clusters

Ceria-based materials have been highly desired in photocatalytic reactions due to their easily redox property and strong oxygen storage and transfer ability. Herein, we report the structures of one CeCe 70 oxysulfate cluster and four MCe 70 clusters (M = Cu, Ni, Co, Fe) with the same Ce 70 core. As noted, single crystal X-ray diffraction confirmed the structures of CeCe 70 and the MCe 70 series, while Raman spectroscopy indicated an increase in oxygen defects upon the introduction of Cu and Fe ions. The clusters catalyzed the oxidation of 4-methoxybenzyl alcohol under ultraviolet light. CuCe 70 and FeCe 70 exhibited enhanced reactivity compared to CeCe 70 and improved aldehyde selectivity compared to control experiments. In comparison with their homogeneous congeners, the CeCe 70 /MCe 70 clusters altered the location of radical generation from the bulk solution to the clusters’ surfaces. Mechanistic studies highlight the role of oxygen defects and specific transition metal introduction for efficient photocatalysis. Furthermore, the mechanistic pathway in this study provides insight on how to select or design a highly selective catalyst for photocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Ethylene polymerization with a crystallographically well-defined metal–organic framework supported catalyst

The inherent crystallinity of metal–organic framework (MOF) catalysts offers the possibility to understand the structure of the active site at the molecular level. This property is often lacking in traditional amorphous supports. Cr-SIM-NU-1000, a MOF-supported Cr 3+ heterogeneous catalyst, is shown to be competent for ethylene polymerization after activation with AlEt 2 Cl (DEAC), producing crystalline linear polyethylene (PE). The polymer produced has a low polydispersity (D = 2.0), in marked contrast to the Phillips supported chromium catalyst, Cr@SiO 2 (D ~ 8–65). Cr-SIM-NU-1000 achieves a turnover frequency of 2.6 × 10 3 h –1 under 40 bar ethylene pressure at room temperature, with corresponding PE productivity of 1.3 × 10 5 g PE mol –1 Cr per h. Single crystal X-ray diffraction (SC-XRD) of the pre-catalyst was conducted by collecting a structure of alkyl aluminum (DEAC) co-catalyst treated Cr-SIM-NU-1000. This crystal structure provides insight into the interactions between DEAC co-catalyst and Cr active site, revealing a Cr–C bond after treatment with DEAC. Furthermore, DEAC is crystallographically resolved at the terminal oxy-ligands of the node and likely also exists within the window pores of the framework between nodes, based on electron density mapping. Cr-SIM-NU-1000 offers the opportunity to study a structurally well-defined olefin polymerization system, with atomically precise characterization of the pre-catalyst structure. Furthermore, this allows the proposal of a mechanism and feeds into future development of next-generation heterogeneous catalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity vs. flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour. Here, this review focuses on how porous, catalyst-containing MOFs capitalize on molecular-scale confinement, containment, isolation, environment modulation, energy delivery, and mobility to accomplish desired chemical transformations with potentially superior selectivity or other efficacy, especially in comparison to catalysts in homogeneous solution environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Electron transitions in a Ce(iii)-catecholate metal–organic framework

A rare three-dimensional catecholate-based Ce(III) metal–organic framework (MOF), denoted as NU-1701, has been synthesized and crystallographically characterized. Density functional theory calculations highlight various possible electronic transitions that may present in NU-1701. These transitions are competitive and indicate increased lanthanide character of Ce(III).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Linker Contribution toward Stability of Metal–Organic Frameworks under Ionizing Radiation

Here, the effects of radiation on a series of UiO derivative metal–organic frameworks (MOFs) that contain the same zirconium hexamer node and similar organic linkers, UiO-66, UiO-66–NH 2 , UiO-66–OH, and NU-403, were examined using γ-rays and 5 MeV He ions. UiO-66, UiO-66–NH2, and UiO-66–OH contain aromatic linkers and are significantly more stable to radiation than NU-403. Of these, UiO-66 is the most radiation resistant, displaying crystalline features up to 47 MGy of He-ion irradiation. MOFs containing aromatic linkers functionalized by electron-donating groups, UiO-66–NH 2 and UiO-66–OH, retained crystalline features up to 19 MGy. NU-403 contains aliphatic rings and is the least radiation-resistant MOF studied here. NU-403 exhibits small changes in infrared spectra upon 3 MGy of γ-irradiation and significant damage upon 10 MGy of He-ion irradiation. Diffraction data revealed radiation-induced defect formation. Structural locations of radiation-induced breakdown were interrogated experimentally and via density functional theory. The results indicated changes in the carboxylate (-OCO) of the linker and μ 3 -OH vibrational modes, suggesting that introduction of an aliphatic linker into the MOF renders the connection between the linker and metal node most susceptible to radiation damage. This study reveals that the choice of the linker is crucial in designing a radiation-resistant MOF.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Discovery of spontaneous de-interpenetration through charged point-point repulsions

Entanglement is an energetically favorable occurrence, pervasive in both nature and synthetic systems, where networks prefer to entwine with one another rather than remain open and accessible. As a result of entanglement, valuable internal pore space, useful for applications such as catalysis, storage, and sensing, is lost. Here, we detail our discovery of a phenomenon termed “charged point-point repulsion,” which energetically favors dis-entanglement, transforming a densely packed uranium-based framework with 14.2 and 19.8 Å pores into an open material with 40.7 Å pores and record-high void fraction and pore volume. We anticipate that the phenomenon described in this work could be widely generalized for the direct and systematic production of non-entangled structures with an abundance of valuable pore space and far-reaching practical importance. More fundamentally, this study compels a re-evaluation of the thermodynamics of porosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Coordination Chemistry in the Structural and Functional Exploration of Actinide-Based Metal-Organic Frameworks

The coordination chemistry between inorganic and organic species can be optimally exemplified by metal–organic frameworks (MOFs), whose structures and functionalities can be rationally designed from these highly tunable building blocks. The high porosity, stability, and versatile functionalities of MOFs have attracted wide-spread attention from energy-related research and pollution remediation to biomedical applications. A unique and underexplored subset of these materials are MOFs based on actinide nodes; these MOFs have distinguished themselves as a unique platform for investigating the versatile oxidation states, reactivity, and coordination chemistry of actinides. Herein, we will focus on the rational design and synthesis of actinide-based MOFs under the general guidelines of coordination chemistry for their structural and functional explorations. The dimensionality, topology, and structures of actinide-based MOFs can be controlled by selecting pre-designed building blocks of actinide-based nodes and organic linkers with certain desired coordination geometries and functionalities. Furthermore, these unique actinide-based MOFs have shown promise for applications in nuclear waste mitigation, pollution control, and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Single crystal structure and photocatalytic behavior of grafted uranyl on the Zr-node of a pyrene-based metal–organic framework

Accurately characterizing actinide oxides bound to metal–organic frameworks (MOFs) is important for designing MOFs as radioactive waste sorbents and catalytic supports. Here, the zirconium MOF NU-1000 was post-synthetically modified through solvothermal deposition to include the uranyl (UO 2 2+ ) ion and characterized via single-crystal X-ray diffraction. Additonally, bond lengths derived from the diffraction pattern and Raman spectroscopy indicate that UO 2 2+ maintains its chemical properties upon deposition, while alcohol oxidation photocatalysis reveals photo-interactions between the pyrene linkers and the UO 2 2+ ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗