Atomic-level engineering and in-situ spectroscopy studies of metal-organic frameworks in heterogeneous catalysis

Metal-organic frameworks (MOFs) have shown promise as an efficient platform in various applications especially in the field of heterogeneous catalysis. The inherent properties of MOFs such as high surface area and porosity, thermal and chemical stability while remaining as a highly crystalline solid with molecular precision tunability allow us to perform many fundamental studies to resolve structural-property relationship in the application in heterogeneous catalysis. In this thesis, we discussed the atomic-level engineering approach to design MOFs to be an active catalyst for application in visible light photocatalysis and using MOFs as a host to stabilize monodisperse ultrafine nanoclusters. The high crystallinity of the MOF further provides a uniform local chemical environment that allows us to resolve the structure to various advance spectroscopy techniques such as in-situ X-ray Absorption Spectroscopy (XAS), diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS), and solid-state nuclear magnetic resonance (ssNMR) spectroscop

Enhanced 1H-X D-HMQC performance through improved 1H homonuclear decoupling

The sensitivity of solid-state NMR experiments that utilize 1H zero-quantum heteronuclear dipolar recoupling, such as D-HMQC, is compromised by poor homonuclear decoupling. This leads to a rapid decay of recoupled magnetization and an inefficient recoupling of long-range dipolar interactions, especially for nuclides with low gyromagnetic ratios. We investigated the use, in symmetry-based 1H heteronuclear recoupling sequences, of a basic R element that was principally designed for efficient homonuclear decoupling. By shortening the time required to suppress the effects of homonuclear dipolar interactions to the duration of a single inversion pulse, spin diffusion was effectively quenched and long-lived recoupled coherence lifetimes could be obtained. We show, both theoretically and experimentally, that these modified sequences can yield considerable sensitivity improvements over the current state-of-the-art methods and applied them to the indirect detection of 89Y in a metal-organic framework

In Situ X-ray Absorption Spectroscopy Studies of Kinetic Interaction between Platinum(II) Ions and UiO-66 Series Metal–Organic Frameworks

The interaction of guest Pt(II) ions with UiO-66–X (X = NH2, H, NO2, OMe, F) series metal–organic frameworks (MOFs) in aqueous solution was investigated using in situ X-ray absorption spectroscopy. All of these MOFs were found to be able to coordinate with Pt(II) ions. The Pt(II) ions in UiO-66–X MOFs generally coordinate with 1.6–2.4 Cl and 1.4–2.4 N or O atoms. We also studied the time evolution of the coordination structure and found that Pt(II) maintained a coordination number of 4 throughout the whole process. Furthermore, the kinetic parameters of the interaction of Pt(II) ions with UiO-66–X series MOFs (X = NH2, H, NO2, OMe, F) were determined by combinational linear fitting of extended X-ray absorption fine structure (EXAFS) spectra of the samples. The Pt(II) adsorption rate constants were found to be 0.063 h–1 for UiO-66–NH2 and 0.011–0.017 h–1 for other UiO-66–X (X = H, NO2, OMe, F) MOFs, which means that Pt(II) adsorption in UiO-66–NH2 is 4–6 times faster than that in other UiO-66 series MOFs. FTIR studies suggested that the carboxyl groups could be the major host ligands binding with Pt(II) ions in UiO-66 series MOFs, except for UiO-66–NH2, in which amino groups coordinate with Pt(II) ions

Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks

A bifunctional Zr-MOF catalyst containing palladium nanoclusters (NCs) has been developed. The formation of Pd NCs was confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS). Combining the oxidation activity of Pd NCs and the acetalization activity of the Lewis acid sites in UiO-66-NH2, this catalyst (Pd@UiO-66-NH2) exhibits excellent catalytic activity and selectivity in a one-pot tandem oxidation-acetalization reaction. This catalyst shows 99.9% selectivity to benzaldehyde ethylene acetal in the tandem reaction of benzyl alcohol and ethylene glycol at 99.9% conversion of benzyl alcohol. We also examined various substituted benzyl alcohols and found that alcohols with electron-donating groups showed better conversion and selectivity compared to those with electron-withdrawing groups. We further proved that there was no leaching of active catalytic species during the reaction and the catalyst can be recycled at least five times without significant deactivation

DNP-Enhanced Ultrawideline Solid-State NMR Spectroscopy: Studies of Platinum in Metal–Organic Frameworks

Ultrawideline dynamic nuclear polarization (DNP)-enhanced 195Pt solid-state NMR (SSNMR) spectroscopy and theoretical calculations are used to determine the coordination of atomic Pt species supported within the pores of metal–organic frameworks (MOFs). The 195Pt SSNMR spectra, with breadths reaching 10 000 ppm, were obtained by combining DNP with broadbanded cross-polarization and CPMG acquisition. Although the DNP enhancements in static samples are lower than those typically observed under magic-angle spinning conditions, the presented measurements would be very challenging using the conventional SSNMR methods. The DNP-enhanced ultrawideline NMR spectra served to separate signals from cis- and trans-coordinated atomic Pt2+ species supported on the UiO-66-NH2 MOF. Additionally, the data revealed a dominance of kinetic effects in the formation of Pt2+ complexes and the thermodynamic effects in their reduction to nanoparticles. A single cis-coordinated Pt2+ complex was confirmed in MOF-253

Sustainability analysis of reused industrial buildings in China: an assessment method

The sustainable development of old industrial buildings is in line with the national construction strategy and has an important impact on current urban renewal. Only by achieving a unified balance among economic, social, and environmental factors can reused industrial buildings be considered sustainable. However, there are no relevant sustainability assessment indicators and methods for reused industrial buildings in China. The purpose of this study was to provide a reasonable and effective method for assessing the sustainability of reused industrial buildings. First, this study analysed the factors influencing reused industrial building sustainability through a project investigation. Second, based on the assessment indicator setting procedure, the sustainability assessment indicator system for reused industrial buildings was optimised. Moreover, a multi-level sustainability assessment model based on extenics was established to identify the correlation functions of indicators with different attributes. Finally, a case was considered to verify this assessment method. The results showed that this assessment method in good agreement with the actual state of the case was validated to be more effective and practical. The assessment method could provide a basis for decision-making to improve sustainability and could be adopted by relevant rating agencies to determine the sustainability level of reused industrial buildings

Controlling Catalytic Properties of Pd Nanoclusters through Their Chemical Environment at the Atomic Level Using Isoreticular Metal–Organic Frameworks

Control of heterogeneous catalytic sites through their surrounding chemical environment at an atomic level is crucial to catalyst design. We synthesize Pd nanoclusters (NCs) in an atomically tunable chemical environment using isoreticular metal–organic framework (MOF) supports (Pd@UiO-66-X, X = H, NH2, OMe). In an aerobic reaction between benzaldehyde and ethylene glycol, these catalysts show product distributions that are completely altered from the acetal to the ester when we change the functional groups on the MOF linkers from −NH2 to −H/–OMe. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies, along with density functional theory (DFT) calculations, show that the coordination of the −NH2 groups to the Pd NCs could weaken their oxidation capability to a greater extent in comparison to that of the −OMe group. Moreover, the limited number of −NH2 groups per cavity in the MOF change the electronic properties of the Pd NCs while still leaving open sites for catalysis

Conversion of Levulinic Acid to γ-Valerolactone over Few-Layer Graphene-Supported Ruthenium Catalysts

Few-layer graphene (FLG) supported ruthenium nanoparticle catalysts were synthesized and used for the hydrogenation of levulinic acid (LA), one of the “top 10” biomass platform molecules derived from carbohydrates. FLG-supported ruthenium catalyst showed 99.7% conversion and 100% selectivity toward γ-valerolactone (GVL) at room temperature in a batch reactor under high-pressure hydrogen. This catalyst showed 4 times higher activity and exceptional stability in comparison with traditional activated carbon supported ruthenium catalysts (Ru/C). X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) studies suggest that the superior catalytic properties of Ru nanoparticles supported on FLG in LA hydrogenation could be attributed to the greater metallic Ru content present in the Ru/FLG in comparison to that in Ru/C

An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic properties and thermal stabilities compared with those prepared with organic capping agents. This inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties

Morphology inherence from hollow MOFs to hollow carbon polyhedrons in preparing carbon-based electrocatalysts

Hollow carbon nanostructures are emerging as advanced electrocatalysts for the oxygen reduction reaction (ORR) due to the effective usage of active sites and the reduced dependence on expensive noble metals. Conventional preparation of these hollow structures is achieved through templates (e.g. SiO2, CdS, and Ni3C), which serve to retain the void interiors during carbonization, leading to an essential template-removal procedure using hazardous chemical etchants. Herein, we demonstrate the direct carbonization of unique hollow zeolitic imidazolate frameworks (ZIFs) for the synthesis of hollow carbon polyhedrons (HCPs) with well-defined morphologies. The hollow ZIF particles behave bi-functionally as a carbon source and a morphology directing agent. This method evidences the strong morphology inherence from the hollow ZIFs during the carbonization, advancing the significant simplicity and environmental friendliness of this synthesis strategy. The as-prepared HCPs show a uniform polyhedral morphology and large void interiors, which enable their superior ORR activity. Iron can be doped into the HCPs (Fe/HCPs), providing the Fe/HCPs with enhanced ORR properties (E1/2 = 0.850 V) in comparison with those of HCPs. We highlight the efficient structural engineering to transform ZIFs into advanced carbon nanostructures accomplishing morphological control and high electrocatalytic activity