Structure-Property Relationships of Microphase-Separated Metallosupramolecular Polymers

The structural, thermomechanical, and viscoelastic properties of metallosupramolecular polymers (MSPs) can be controlled through the choice of the multiligand monomer and the nature of the metal salt from which these materials are assembled. This versatility and the dynamic nature of certain metal-ligand (ML) complexes make MSPs very interesting for the design of stimuli-responsive materials. We here report on the investigation of the structure-property relationships of MSPs based on a macromonomer formed by terminating telechelic poly(ethylene-co-butylene) (PEB) with 2,6-bis(1'-methyl-benzimidazolyl)pyridine (Mebip) ligands and transition metal or lanthanoid salts. The nature of the metal ion (Zn2+, Fe2+, Tb3+, La3+, or Gd3+), the counterion (trifluoromethanesulfonate (OTf-), perchlorate (ClO4-), or bis(trifluoromethylsulfonyl)imide (NTf2-)), and the number-average molecular weight (M-n) of the PEB core (2100 or 3100 g mol(-1)) were systematically varied with the aim to provide an improved understanding of how these parameters influence the properties. In all MSPs, the polar ML complexes and the nonpolar PEB were found to microphase separate into lamellar or hexagonal morphologies with a soft PEB phase and a ML hard phase. The microstructure formation and the mechanical properties were significantly influenced by the coordination geometry of the metal-ligand complexes as well as the volume fraction of the ML phase. The nature of the metal and counterions further affected the glass or melting transitions of the hard phase. In general, lower softening temperatures were observed for the MSPs made with lanthanoid salts. Measurements of the frequency-dependent oscillatory shear moduli were used to study the relaxation processes in the different MSPs and allowed determining the activation energy of the ML complexes in lanthanoid-based MSPs.

Shear Thickening Fluid Impregnated Foam Composites for Vibration Control and Impact Protection

Mathieu Soutrenon

Highly concentrated suspensions of silica particles present shear thickening properties, shifting from a low to a high viscosity state, instantly and reversibly at a critical shear rate. Their viscosity increases by up to 3 orders of magnitude, changing from a honey-like liquid to a brittle solid material. This sharp rise in viscosity is associated with a large absorption of energy that can be used in damping applications. These shear thickening fluids (STF) are among the few passive materials that can simultaneously bring both an increase in damping and in stiffness properties. In mechanical design, this leads potentially to a weight reduction of the overall system. This thesis work is aimed to develop and test a composite material solution for vibration control and impact protection, using STF as the damping element. A main challenge was to overcome the fact that STF are liquid at rest, and very sensitive to their environment. The proposed damping material was therefore constituted of foam impregnated with STF and encapsulated with silicone (STF/foam). A comparison of properties with other damping materials such as Smactane®was emphasized along the thesis. Storage and processing conditions of STF constituted of highly concentrated suspensions were shown to affect their rheological properties similarly to other sensitive parameters such as particle concentration. Rigorous processing methods were thus required to produce STF with defined and stable rheological properties. The use of sonication was preferred to disperse the aggregates of particles in concentrated colloidal suspensions due to the packing of the dry powder. Contact with air or humidity deteriorates the shear thickening properties of STF. Storage of STF in a freezer at −24 ◦C or under nitrogen prevents this. The use of a physical barrier to air and humidity such as silicone to protect STF is also shown to greatly reduce the ageing problem. The energy dissipated during a cyclic strain cycle was used as a measure of the damping property of the STF, and compared to that of other materials. It was measured with dynamic rheological measurements performed on suspensions with variations of particle concentration, size and test frequency. STF were shown to dissipate a large amount of energy during their transition, which increases with the increase of frequency and particle concentration and decrease with the increase of particle size. In specific cases of large strain amplitude, they potentially dissipate more energy than viscoelastic materials such as rubber. An open cell melamine resin foam was used as a lightweight scaffold to provide a three dimensional structure to the STF. The foam distributes the load and locally shears the STF. The shape of the foam is easily adjustable. To impregnate the foam with the STF, a system similar to vacuum infusion was used. The foam was placed under vacuum in a mold and the STF heated at 70 ◦C to reduce its viscosity and shear thickening properties was sucked in the foam with the depressurization. The STF/foam systems were then encapsulated in silicone to protect the STF/foam damping pads from contamination and avoid outgassing. During compression tests at low frequencies and large deformations, we demonstrated that STF could be activated in this type of structure, with mechanical properties comparable to those of a viscous honey-like fluid at rest and silicone when the STF is in the solid state. The same behavior was observed during impact solicitations. STF/foam presents a very low coefficient of restitution and absorbs the shock wave associated with impacts. Shock tests done separately confirm the shock absorption properties of STF/foam even if the STF is not activated. The combination of mechanical and damping properties of the foam/STF systems remain lower than for very high performance damping materials like Smactane®. The reasons are their low mechanical compression and shear properties at rest and the need to overcome a threshold strain or stress to activate the STF. However, the large dissimilarity between the states before and after the transition makes these materials interesting for impact or large strain amplitude applications such as sole for running shoes or several space structures.

EPFL2013

Synthesis, Characterization, and Applications of Visible Light Active Metal-Organic Frameworks

Samantha Lynn Anderson

Understanding how crystalline materials are assembled is important for the rational design of metal-organic frameworks (MOFs). Controlling their formation can allow researchers to streamline the synthesis of new materials as well as control their properties for targeted applications. In the first chapter of this thesis we report the construction of two 3-dimensional TbIII based MOFs (SION-1 and SION-2). Here, SION-2 acts as a metastable MOF and intermediate phase that partially dissolves and transforms into the thermodynamically stable MOF, SION-1. This chemical transformation occurs in a DMF/water solvent mixture, and is triggered when additional energy is provided to the reaction. In situ studies reveal the partial dissolution of the metastable phase after which the MOF components are reassembled into the thermodynamically stable phase. The marked difference in thermal and chemical stability between the kinetically and thermodynamically controlled phases is contrasted by their identical chemical building unit composition. Following the understanding of this transformation, an isostructural family of SION-1 and SION-2 had been constructed using lanthanide metal salts, where LnIII-SION-1 is comprised of Ce, Nd, Eu, Gd, Tb, Dy, Ho, Er, Yb and Lu and LnIII-SION-2 is formed using Ce, Nd, Eu, Gd, Tb and Yb. The electronic properties of lanthanide based MOFs have not been extensively studied due to the general cognizance that LnIII ions behave as isolated free ions as their 4f orbitals do not contribute to bonding. Here, we systematically studied the electronic properties (UV-vis) of LnIII-SION-1 and LnIII-SION-2 and show that the higher the intensity of this absorption band in LnIII-SION-1 is due to the better overlap between Ln(5d) and ligand(pi*) orbitals and reveals that the lowest unoccupied crystalline orbitals are dispersed over an energy range and can be considered as a conduction band. We validated this observation by the non-linear I-V curves collected on CeIII- and YbIII-SION-1, both of which display dielectric properties. In the second chapter of this thesis, we rationally design a novel biologically derived MOF featuring unobstructed Watson-Crick faces of Ade pointing towards the MOF cavities. We show, through a combined experimental and computational approach, that Thy molecules diffuse through the pores of the MOF and become base-paired with Ade. The Ade-Thy pair binding at 40-45% loading reveals that Thy molecules are packed within the channels in a way that fulfill both the Woodward-Hoffmann and Schmidt rules, and upon UV irradiation, Thy molecules dimerize into ThyThy. This study highlights the utility of MOFs as nanoreactors for the synthesis of molecules that are otherwise difficult. Concluding this thesis, a biologically derived multimodal sensor MOF is synthesized and a formed into a device. The MOF, SION-9, is comprised of Ade and a porphyrin based ligand, and has tuneable conductive properties ranged from 2.69-4.20 x 10-8 - 7.43-7.34 x 10-6 S/cm. SION-9 is sensitive to both pressure and temperature simultaneously, and demonstrated both fast response times (< 60 ms) and a long shelf life (> 6 months).

EPFL2019

Engineering the ZrO2–Pd Interface for Selective CO2 Hydrogenation by Overcoating an Atomically Dispersed Pd Precatalyst

Alimohammad Bahmanpour, Yuan-Peng Du, Florent Emmanuel Héroguel, Oliver Kröcher, Jeremy Luterbacher, Mounir Driss Mensi, Luka Milosevic

Tailoring the interfacial sites between metals and metal oxides can be an essential tool in designing heterogeneous catalysts. These interfacial sites play a vital role in many renewable applications, for instance, catalytic CO2 reduction. Postsynthesis deposition of metal oxide on supported metal catalysts can not only create such interfacial sites but also prevent particle sintering at high temperature. Here, we report a sol–gel-based strategy to synthesize an atomically dispersed “precatalyst”. In contrast to the deposition on catalysts containing preformed nanoparticles, overcoating this material before reductive treatment can inhibit particle growth during thermal activation steps, yielding highly accessible, sintering-resistant Pd clusters that are less than 2 nm in diameter. This synthetic approach allows us to engineer interfacial sites while maintaining high metal accessibility, which was difficult to achieve in previous overcoated materials. Notably, engineering the Pd–ZrO2 interface into an inverted interface with an amorphous ZrO2 overcoat might facilitate a C–O cleavage route instead of a mechanism containing a bicarbonate intermediate during CO2 hydrogenation. We also observed that carbon deposition occurring on methanation sites could be a key factor for improving CO selectivity. Alteration of the reaction pathway, along with the deactivation of certain sites, led to 100% CO selectivity on the ZrO2@Pd/ZrO2 catalyst. This work demonstrated that overcoated materials could represent a promising class of heterogeneous catalysts for selective CO2 conversion over noble metals, which have higher rates and thermal stability compared to state-of-the-art Cu-based catalysts.