Florian Waltz

Bio: Florian Waltz is an academic researcher from Leibniz University of Hanover. The author has contributed to research in topics: Crystallite & Dynamic light scattering. The author has an hindex of 5, co-authored 7 publications receiving 1102 citations.

Modulated Synthesis of Zr‐Based Metal–Organic Frameworks: From Nano to Single Crystals

Abstract: We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH(2) (UiO-66-NH(2)), Zr-bpdc (UiO-67), and Zr-tpdc-NH(2) (UiO-68-NH(2)) (H(2) bdc: terephthalic acid, H(2) bpdc: biphenyl-4,4'-dicarboxylic acid, H(2) tpdc: terphenyl-4,4''-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH(2) . Zr-tpdc-NH(2), a material with a structure analogous to that of Zr-bdc and Zr-bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1''-terphenyl-4,4''-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.

Evolution of the Morphologies of Zinc Oxide Mesocrystals Under the Influence of Natural Polysaccharides

Abstract: In the present investigation, we have analyzed the influence of naturally occurring negatively charged polysaccharides on the morphology of zinc oxide obtained in low-temperature precipitation experiments. Performing detailed analyses of scanning electron microscopy (SEM) micrographs, we inferred the morphology of individual nanocrystals as well as the construction of their aggregates. X-ray and electron diffraction were used to identify directions of preferred growth. Whereas addition of hyaluronic acid (HYA) to the synthesis batch resulted in a rod-like morphology of the primary crystallites, addition of chondroitin-6-sulfate (C6S) leads to platelet-like crystallites. Despite their different shapes, the respective subunits aggregated in similar ways, with perfect orientation with regard to their a–b planes, thus leading to symmetrical superstructures. Further growth proceeded, via different mechanisms, that is, subunit growth or further aggregation of subunits, dependent on whether the precipitation was...

Synthesis of highly stable magnesium fluoride suspensions and their application in the corrosion protection of a Magnesium alloy

Abstract: This study presents a new approach to enhance the corrosion resistance of tungsten inert gas (TIG) welded AZ31 magnesium alloys by using nanocrystalline magnesium fluoride suspensions in a suspension plasma spray (SPS) process. We have developed a synthesis for the preparation of nanocrystalline magnesium fluoride suspensions, which delivers nearly monodisperse nanoparticles in a gram scale yield. The particles were analyzed with transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). Stable suspensions of magnesium fluoride nanoparticles in water were characterized by dynamic light scattering (DLS), zeta-potential, and viscosity measurements. Such suspensions were deposited with an SPS torch onto TIG welded seams of the magnesium alloy AZ31, thus producing a protective magnesium fluoride layer. Magnesium fluoride covered welded seams were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive X-ray spectroscopy (EDXS). In order to introduce a simple method for sensoring the deposited magnesium fluoride coatings, the magnesium fluoride nanoparticles can also be fluorescence-labeled by co-doping with cerium(III) and terbium(III), the respective optical properties were characterized by reflection and luminescence spectroscopy. The deposited layers can, thus, be inspected by illumination with an UV lamp, because of their bright green emission. The corrosion properties of the magnesium fluoride layer on the welded seams were studied by means of potentiodynamic potential measurements.

Highly biocompatible behaviour and slow degradation of a LDH (layered double hydroxide)-coating on implants in the middle ear of rabbits

Abstract: Chronic inflammation can irreversibly damage components of the ossicular chain which may lead to sound conduction deafness. The replacement of impaired ossicles with prostheses does not reduce the risk of bacterial infections which may lead to loss of function of the implant and consequently to additional damage of the connected structures such as inner ear, meninges and brain. Therefore, implants that could do both, reconstruct the sound conduction and in addition provide antibacterial protection are of high interest for ear surgery. Layered double hydroxides (LDHs) are promising novel biomaterials that have previously been used as an antibiotic-releasing implant coating to curb bacterial infections in the middle ear. However, animal studies of LDHs are scarce and there exist only few additional data on the biocompatibility and hardly any on the biodegradation of these compounds. In this study, middle ear prostheses were coated with an LDH compound, using suspensions of nanoparticles of an LDH containing Mg and Al as well as carbonate ions. These coatings were characterized and implanted into the middle ear of healthy rabbits for 10 days. Analysis of the explanted prostheses showed only little signs of degradation. A stable health constitution was observed throughout the whole experiment in every animal. The results show that LDH-based implant coatings are biocompatible and dissolve only slowly in the middle ear. They, therefore, appear as promising materials for the construction of controlled drug delivery vehicles.

Synthesis, characterization, and evaluation of lubrication properties of composites of ordered mesoporous carbons and luminescent CePO4:Tb nanocrystals

Abstract: Having new potential applications in forging processes in mind, composites of an ordered mesoporous carbon and luminescent metal phosphate nanocrystals were synthesized for the first time. Three kinds of CMK-3/CePO4:Tb nanocomposites were prepared by treating a mesoporous CMK-3 host with different lanthanide phosphate precursor solutions. Characterization of the obtained nanocomposites by small-angle X-ray scattering, wide-angle X-ray diffraction, transmission electron microscopy, thermogravimetry, and nitrogen physisorption analysis showed that in two cases, the nanocrystals (ca. 2–3 nm in size) were located inside the mesopores, whereas in the third case the nanocystals (ca. 6 nm in size) merely adhered to the outer surfaces of the carbon particles. The CMK-3 and the two nanocomposites had ordered hexagonal structures (space group p6mm); all the materials possessed amorphous carbon walls. After combustion of the nanocomposites, the residues upon excitation with UV light exhibited the typical green luminescence of Tb3+. A preliminary evaluation of the lubrication properties of the CMK-3 and one nanocomposite material was performed. The friction factors determined by means of ring upsetting tests revealed that the carbon materials were able to lower frictional forces although they were 3–4 times less efficient than a commercial graphite-based reference lubricant.

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications.

Abstract: Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Bronsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

Zr-based metal-organic frameworks: design, synthesis, structure, and applications.

Abstract: Among the large family of metal–organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.

Tuning the structure and function of metal–organic frameworks via linker design

Abstract: Metal–organic frameworks (MOFs) are constructed from metal ions/clusters coordinated by organic linkers (or bridging-ligands). The hallmark of MOFs is their permanent porosity, which is frequently found in MOFs constructed from metal-clusters. These clusters are often formed in situ, whereas the linkers are generally pre-formed. The geometry and connectivity of a linker dictate the structure of the resulting MOF. Adjustments of linker geometry, length, ratio, and functional-group can tune the size, shape, and internal surface property of a MOF for a targeted application. In this critical review, we highlight advances in MOF synthesis focusing on linker design. Examples of building MOFs to reach unique properties, such as unprecedented surface area, pore aperture, molecular recognition, stability, and catalysis, through linker design are described. Further search for application-oriented MOFs through judicious selection of metal clusters and organic linkers is desirable. In this review, linkers are categorized as ditopic (Section 1), tritopic (Section 2), tetratopic (Section 3), hexatopic (Section 4), octatopic (Section 5), mixed (Section 6), desymmetrized (Section 7), metallo (Section 8), and N-heterocyclic linkers (Section 9).

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal–Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts†

Abstract: In nature, metalloporphyrins are well known for performing many biological functions in aqueous media, such as light harvesting, oxygen transportation, and catalysis. Heme, the iron–porphyrin derivative, is the cofactor for many enzyme/ protein families, including peroxidases, cytochromes, hemoglobins, and myoglobins. Using synthetic systems to mimic natural enzymes with high catalytic activity and substrate selectivity has been a sought-after goal in the last decade. Direct application of a heme as an oxidation catalyst in aqueous solution is usually challenging due to the formation of catalytically inactive dimers and catalyst self-destruction in the oxidizing reaction media. One promising approach is to load heme on supports, such as zeolites, clays, nanoparticles, hydrogels, or carbon materials, a practice which inevitably dilutes the density of active sites. An alternative approach is to protect the heme center by modifying the porphyrin to produce dendrimers or molecular crystals, which is a synthetically demanding method. Herein, we propose a unique strategy employing heme-like active centers as structural motifs for the assembly of highly stable porous materials, which should possess well-defined mesochannels and ultrahigh stability in aqueous solution. Metal-organic frameworks (MOFs) are a new class of crystalline porous materials with fascinating structures and intriguing properties, such as permanent porosity, high surface area, and uniform open cavities. The availability of various building blocks consisting of metals and organic linkers makes it possible to construct MOFs with unique properties for diverse applications. However, these desirable features of MOFs have rarely been applied to an enzymatic mimic, especially for catalysis in an aqueous medium, despite the fact that the assembly of ligands bearing high-density active sites into 3D frameworks may provide an ideal system to both enhance the catalytic activity and protect the cofactors. One of the main reasons is the lack of water-stable MOFs containing redox-active metal centers. Furthermore, most MOFs are microporous (pore size< 2 nm). Although they are suitable for gas storage, the small pore size slows down diffusion and limits the access of large substrate molecules to the active sites inside a MOF. Therefore, MOFs with mesopores, accessible redox sites, and ultrahigh stability, especially in aqueous media, are indispensible for any successful biomimetic attempt. Herein we have employed Fe-TCPP (TCPP= tetrakis(4carboxyphenyl)porphyrin) as a heme-like ligand and chosen highly stable Zr6 clusters as nodes for the assembly of stable Zr-MOFs. With carefully selected starting materials, we have successfully constructed a 3D heme-like MOF, designated as PCN-222(Fe) (Figure 1; PCN= porous coordination net-