169 Search Results

This project was originally headed by Dr. Abraham Clearfield (Texas A&M University, ret.) and focused on developing structural models of zirconium phosphate (ZrP) based materials at different stages of crystalline order using PDF techniques developed by co-PI Dr. Simon Billinge (Columbia University). When Dr. Clearfield retired, the project was taken over by Dr. Hong-Cai Zhou (Texas A&M University). The project proposed looking at defective metal-organic frameworks (MOFs) supported on the surface of the ZrP materials. During the project, the personnel conducted studies of the dispersion of different phosphate ligands in mixed organic phosphonates, and how they could be utilized tomore » incorporate different metals within the ZrP interlayer spacing.« less

Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Here, using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O₂ from air, chemically oxidizing the ironmore » from Fe(II) to Fe(III). We also show that the binding of oxygen is reversible through temperature swing experiments. Our analysis is based on combining Mößbauer spectroscopy, extended X-ray absorption fine structure, in situ infrared, SQUID, thermal gravimetric analysis, and energy dispersive X-ray fluorescence spectroscopy measurements with ab initio modeling.« less

To precisely evaluate the potential of metal-organic frameworks (MOFs) for gas separation and purification applications, it is crucial to understand how various molecules competitively adsorb inside MOFs. In this paper, we combine in situ infrared spectroscopy with ab initio calculations to investigate the mechanisms associated with co-adsorption of a number of small molecules including CO, NO, and CO₂ inside the prototypical framework Ni-MOF-74. Surprisingly, we find that the displacement of CO bound inside Ni-MOF-74 (binding energy of 53 kJ/mol) is readily driven by CO₂ exposure, even though CO₂ has a noticeably weaker binding energy of only 41 kJ/mol; meanwhile, themore » significantly more strongly binding NO molecule (90 kJ/mol) is not able to easily displace bound CO inside Ni-MOF74. These results show that single-phase binding energies of a molecule inside the MOF cannot completely describe their interaction with the MOF in the presence of other guest molecules. Here, we unveil a number of crucial factors such as the kinetic barrier, partial pressure, secondary binding sites, and guest-host/lateral interactions that control the co-adsorption process and combined with the binding energy are better descriptors of the behavior and adsorption of gas mixtures inside MOFs.« less

While trinuclear [Fe_xM_3–x(μ₃-O)] cluster-based metal–organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [Fe_xM_3–x(μ₃-O)]-based MOFs (PCN-250, M = Ni²⁺, Co²⁺, Zn²⁺, Mg²⁺) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe³⁺ sites was observed along with the transformation of Fe³⁺ coordination geometries from octahedron to square pyramid.more » Furthermore, the effect of divalent metals in heterometallic PCN-250 was studied for the purpose of reducing the activation temperature and increasing the number of open metal sites. The metal site structures were corroborated by X-ray absorption and infrared spectroscopy. These results will not only guide the pretreatment of [Fe_xM_3–x(μ₃-O)]-based MOFs but also corroborate spectral and computational studies on these materials.« less

Elucidating the interaction between coadsorbed H₂O and NH₃ in metal–organic frameworks (MOFs) is of paramount importance to uncover mechanistic details of their competitive coadsorption behavior as well as to guide the design of new materials for enhanced NH₃ adsorption in humid environments. Nevertheless, molecular competition between NH₃ and H₂O within the confined nanopores of MOFs was rarely explored and is poorly understood due to challenges in characterization. Here, we combine in situ infrared spectroscopy with ab initio calculations to unveil the competition of NH₃ and H₂O for occupying active adsorption sites in the representative MOF-74 material by analyzing the kineticsmore » and energetics of the molecular exchange process. We find that at a high NH₃/H₂O ratio, the incoming NH₃ is capable of displacing metal-bound H₂O and moving it to secondary adsorption sites due to the stronger binding of NH₃ compared with H₂O. Interestingly, the reverse process of H₂O displacing metal-bound NH₃ is also possible upon increasing water concentration. Our calculations show that H₂O exchanging the preabsorbed NH₃ at the metal site is driven not only by a reduced kinetic barrier but also by a favorable energetical state resulting from the formation of water clusters at metal sites and intermolecular H-bonding between the metal-coordinated H₂O and displaced NH₃. Our finding emphasizes that the description of molecular occupation in MOFs at equilibrium cannot simply be established by comparing molecules’ binding energies at their strongest binding sites derived by single-component measurements; rather, intermolecular interactions can greatly affect molecular distribution at equilibrium. Furthermore, we show that vibrational modes of adsorbed NH₃ are markedly perturbed upon contact with water molecules, accompanied by a large frequency shift (>30 cm^–1) and considerable intensity decrease, which arises from the freezing of NH₃ vibrations by coadsorbed H₂O. As a result, the mechanistic insight obtained through our study sheds light on molecular coadsorption processes in MOFs and helps to assess NH₃ removal efficiency of MOFs containing open-metal sites under realistic conditions, particularly in the presence of humidity.« less

Photoinduced phase transitions in metal-organic frameworks are provoked by structural changes of photoresponsive linkers within the framework under light irradiation. These transitions are rare but fundamentally important as they can bring about light-switchability on a variety of properties of the materials. In this work, phenothiazine as a photoresponsive unit with distinctive photochemical properties is incorporated into a Zn-based metal-organic framework, PCN-401. The structural characterization of PCN-401 revealed a reversible structural transition upon light irradiation. The mechanisms behind the photoinduced phase transition are studied systematically by spectrometric methods and structural stability characterization. Our mechanistic studies successfully showcased how the phenothiazine unitmore » in the framework undergoes structural transformation under light irradiation and how the reversible phase transition leads to the property changes. The findings have emphasized the significance of phenothiazine in photoresponsive materials and can serve as inspiration for the design and understandings of next-generation photoresponsive metal-organic materials.« less

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Carbon capture and sequestration reduces carbon dioxide emissions and is critical in accomplishing carbon neutrality targets. Here, we demonstrate new sustainable, solid-state, polyamine-appended, cyanuric acid–stabilized melamine nanoporous networks (MNNs) via dynamic combinatorial chemistry (DCC) at the kilogram scale toward effective and high-capacity carbon dioxide capture. Polyamine-appended MNNs reaction mechanisms with carbon dioxide were elucidated with double-level DCC where two-dimensional heteronuclear chemical shift correlation nuclear magnetic resonance spectroscopy was performed to demonstrate the interatomic interactions. We distinguished ammonium carbamate pairs and a mix of ammonium carbamate and carbamic acid during carbon dioxide chemisorption. The coordination of polyamine and cyanuric acid modificationmore » endows MNNs with high adsorption capacity (1.82 millimoles per gram at 1 bar), fast adsorption time (less than 1 minute), low price, and extraordinary stability to cycling by flue gas. This work creates a general industrialization method toward carbon dioxide capture via DCC atomic-level design strategies.« less

Porous coordination cages (PCCs) constructed from a zirconocene-based cluster have drawn great attention for their high stability and structural tunability. These features have enabled these cages to be utilized for a wide array of applications. Here this work demonstrates the structural flexibility and stimulus-responsive features of two interconvertible zirconocene-based PCCs. The subjects, PCC-20c (capsular) and PCC-20t (tetrahedral), are constructed from the same cluster and ligand but exhibit different shapes and properties. In the synthetic study of the cages, it is found that higher temperatures of synthesis yield PCC-20c in several different crystalline phases while lower temperatures of synthesis yield puremore » phase PCC-20t. Thermodynamic studies on the interconversion of the two cages show that the conversion from PCC-20t into PCC-20c is an entropically driven process and can be largely affected by the solvent environment. Additionally, the process of PCC-20t/c conversion can be mediated by the counter anions and light irradiation as evidenced by the change in equilibrium constants under these influences. The current studies are conducted to decipher how the PCC-20t/c phase can be controllably synthesized, interconverted, and their properties can be modified under the use of external stimuli: heat, light, and guest molecules.« less

Energy-efficient capture and release of small gas molecules, particularly carbon dioxide (CO₂) and methane (CH₄), are of significant interest in academia and industry. Porous materials such as metal–organic frameworks (MOFs) have been extensively studied, as their ultrahigh porosities and tunability enable significant amounts of gas to be adsorbed while also allowing specific applications to be targeted. However, because of the microporous nature of MOFs, the gas adsorption performance is dominated by high uptake capacity at low pressures, limiting their application. Hence, methods involving stimuli-responsive materials, particularly light-induced switchable adsorption (LISA), offer a unique alternative to thermal methods. Here, we reportmore » the mechanism of a well-known LISA system, the azobenzene-based material PCN-250, for CO₂ and CH₄ adsorption. There is a noticeable difference in the LISA effect dependent on the metal cluster involved, with the most significant being PCN-250-Al, where the adsorption can change by 83.1% CH₄ and 56.1% CO₂ at 298 K and 1 bar and inducing volumetric storage changes of 36.2 and 33.9 cm³/cm³ at 298 K between 5 and 85 bar (CH₄) and 2 and 9 bar (CO₂), respectively. Using UV light in both single-crystal X-ray diffraction and gas adsorption testing, we show that upon photoirradiation, the framework undergoes a “localized heating” phenomenon comparable to an increase of 130 K for PCN-250-Fe and improves the working capacity. Furthermore, this process functions because of the constrained nature of the ligand, preventing the typical trans-to-cis isomerization observed in free azobenzene. In addition, we observed that the degree of localized heating is highly dependent on the metal cluster involved, with the series of isostructural PCN-250 systems showing variable performance based upon the degree of interaction between the ligand and the metal center.« less