A molecular understanding of citrate adsorption on calcium oxalate polyhydrates.

Calcium oxalate precipitation is a common pathological calcification in the human body, whereby crystallite morphology is influenced by the chelating properties of biological ions such as citrate. It has been suggested that citrate could steer oxalate formation towards its dihydrated form and away from the monohydrated form, which was identified as a major cause for disease. To assess the influence of the citrate ion on the resulting calcium oxalate, surface energies were calculated at the dispersion-corrected density functional level of theory for both monohydrated and dihydrated calcium oxalate. Different adsorption geometries were considered by varying the attacking angle of citrate as well as by considering the citrate ion on top of an adsorbed water layer or penetrating the water layer. The obtained results were compared to ab initio molecular dynamics simulations and experimental scanning electron microscope images. A strong preference for citrate adsorption on calcium oxalate dihydrate was observed, suggesting medical applications for the treatment of such pathological calcifications.

Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks.

Metal-organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices.

Vapor-Phase Loading of an Ionic Liquid into a Zeolitic Imidazolate Framework.

Composites formed by a metal-organic framework (MOF) and an ionic liquid (IL) are potentially interesting materials for applications ranging from gas separation to electrochemical devices. Consequently, there is a need for robust and low-cost preparation procedures that are compatible with the desired applications. We herein report a solvent-free, one-step, and vapor-based ship-in-bottle synthesis of the IL@MOF composite 1-butyl-3-methylimidazolium bromide@ZIF-8 in powder and thin film forms. In this approach, volatile IL precursors evaporate and subsequently adsorb and react within the MOF cages to form the IL.

Chemical Vapor Deposition of Ionic Liquids for the Fabrication of Ionogel Films and Patterns.

Film deposition and high-resolution patterning of ionic liquids (ILs) remain a challenge, despite a broad range of applications that would benefit from this type of processing. Here, we demonstrate for the first time the chemical vapor deposition (CVD) of ILs. The IL-CVD method is based on the formation of a non-volatile IL through the reaction of two vaporized precursors. Ionogel micropatterns can be easily obtained via the combination of IL-CVD and standard photolithography, and the resulting microdrop arrays can be used as microreactors. The IL-CVD approach will facilitate leveraging the properties of ILs in a range of applications and microfabricated devices.

TEM and AES investigations of the natural surface nano-oxide layer of an AISI 316L stainless steel microfibre.

The chemical composition, nanostructure and electronic structure of nanosized oxide scales naturally formed on the surface of AISI 316L stainless steel microfibres used for strengthening of composite materials have been characterised using a combination of scanning and transmission electron microscopy with energy-dispersive X-ray, electron energy loss and Auger spectroscopy. The analysis reveals the presence of three sublayers within the total surface oxide scale of 5.0-6.7 nm thick: an outer oxide layer rich in a mixture of FeO.Fe2 O3 , an intermediate layer rich in Cr2 O3 with a mixture of FeO.Fe2 O3 and an inner oxide layer rich in nickel.

Comprehensive study of the macropore and mesopore size distributions in polymer monoliths using complementary physical characterization techniques and liquid chromatography.

Poly(styrene-co-divinylbenzene) monolithic stationary phases with two different domain sizes were synthesized by a thermally initiated free-radical copolymerization in capillary columns. The morphology was investigated at the meso- and macroscopic level using complementary physical characterization techniques aiming at better understanding the effect of column structure on separation performance. Varying the porogenic solvent ratio yielded materials with a mode pore size of 200 nm and 1.5 µm, respectively. Subsequently, nano-liquid chromatography experiments were performed on 200 µm id × 200 mm columns using unretained markers, linking structure inhomogeneity to eddy dispersion. Although small-domain-size monoliths feature a relatively narrow macropore-size distribution, their homogeneity is compromised by the presence of a small number of large macropores, which induces a significant eddy-dispersion contribution to band broadening. The small-domain size monolith also has a relatively steep mass-transfer term, compared to a monolith containing larger globules and macropores. Structural inhomogeneity was also studied at the mesoscopic level using gas-adsorption techniques combined with the non-local-density-function-theory. This model allows to accurately determine the mesopore properties in the dry state. The styrene-based monolith with small domain size has a distinctive trimodal mesopore distribution with pores of 5, 15, and 25 nm, whereas the monolith with larger feature sizes only contains mesopores around 5 nm in size.

Melamine-Formaldehyde Microcapsules: Micro- and Nanostructural Characterization with Electron Microscopy.

A systematic study has been carried out to compare the surface morphology, shell thickness, mechanical properties, and binding behavior of melamine-formaldehyde microcapsules of 5-30 µm diameter size with various amounts of core content by using scanning and transmission electron microscopy including electron tomography, in situ nanomechanical tensile testing, and electron energy-loss spectroscopy. It is found that porosities are present on the outside surface of the capsule shell, but not on the inner surface of the shell. Nanomechanical tensile tests on the capsule shells reveal that Young's modulus of the shell material is higher than that of bulk melamine-formaldehyde and that the shells exhibit a larger fracture strain compared with the bulk. Core-loss elemental analysis of microcapsules embedded in epoxy indicates that during the curing process, the microcapsule-matrix interface remains uniform and the epoxy matrix penetrates into the surface micro-porosities of the capsule shells.

Nano-TiO2/TiN Systems for Electrocatalysis: Mapping the Changes in Energy Band Diagram across the Semiconductor|Current Collector Interface and the Study of Effects of TiO2 Electrochemical Reduction Using UV Photoelectron Spectroscopy.

TiO2 is the most widely used material in photoelectrocatalytic systems. A key parameter to understand its efficacy in such systems is the band bending in the semiconductor layer. In this regard, knowledge on the band energetics at the semiconductor/current collector interface, especially for a nanosemiconductor electrode, is extremely vital as it will directly impact any charge transfer processes at its interface with the electrolyte. Since direct investigation of interfacial electronic features without compromising its structure is difficult, only seldom are attempts made to study the semiconductor/current collector interface specifically. This work utilizes ultraviolet photoelectron spectroscopy (UPS) to determine the valence band maximum (EVBM) and Fermi level (EF) at different depths in a nano-TiO2/TiN thin-film system reached using an Ar gas-clustered ion beam (GCIB). By combining UPS with GCIB depth profiling, we report an innovative approach for truly mapping the energy band structure across a nanosemiconductor/current collector interface. By coupling it with X-ray photoelectron spectroscopy (XPS), correlations among chemistry, chemical bonding, and electronic properties for the nano-TiO2/TiN interface could also be studied. The effects of TiO2 in situ electrochemical reduction in aqueous electrolytes are also investigated where UPS confirmed a decrease in the semiconductor work function (WF) and an associated increase in n-type Ti3+ centers of nano-TiO2 electrodes post use in a 0.2 M potassium chloride solution. We report the use of UPS to precisely determine the energy band diagrams for a nano-TiO2/TiN thin-film interface and confirm the increase in TiO2 n-type dopant concentrations during electrocatalysis, promoting a much more comprehensive and intuitive understanding of the TiO2 activation mechanism by proton intercalation and therefore further optimizing the design process of efficient photocatalytic materials for solar conversion.

Systematic design and functionalisation of amorphous zirconium metal-organic frameworks.

Controlling the structure and functionality of crystalline metal-organic frameworks (MOFs) using molecular building units and post-synthetic functionalisation presents challenges when extending this approach to their amorphous counterparts (aMOFs). Here, we present a new bottom-up approach for synthesising a series of Zr-based aMOFs, which involves linking metal-organic clusters with specific ligands to regulate local connectivity. In addition, we overcome the limitations of post-synthetic modifications in amorphous systems, demonstrating that homogeneous functionalisation is achievable even without regular internal voids. By altering the acidity of the side group, length, and degree of connectivity of the linker, we could control the porosity, proton conductivity, and mechanical properties of the resulting aMOFs.

Facile Fabrication of Flexible and High-Performing Thermoelectrics by Direct Laser Printing on Plastic Foil.

The emerging fields of wearables and the Internet of Things introduce the need for electronics and power sources with unconventional form factors: large area, customizable shape, and flexibility. Thermoelectric (TE) generators can power those systems by converting abundant waste heat into electricity, whereas the versatility of additive manufacturing suits heterogeneous form factors. Here, additive manufacturing of high-performing flexible TEs is proposed. Maskless and large-area patterning of Bi2Te3-based films is performed by laser powder bed fusion directly on plastic foil. Mechanical interlocking allows simultaneous patterning, sintering, and attachment of the films to the substrate without using organic binders that jeopardize the final performance. Material waste could be minimized by recycling the unexposed powder. The particular microstructure of the laser-printed material renders the-otherwise brittle-Bi2Te3 films highly flexible despite their high thickness. The films survive 500 extreme-bending cycles to a 0.76 mm radius. Power factors above 1500 µW m-1K-2 and a record-low sheet resistance for flexible TEs of 0.4 Ω sq-1 are achieved, leading to unprecedented potential for power generation. This versatile fabrication route enables innovative implementations, such as cuttable arrays adapting to specific applications in self-powered sensing, and energy harvesting from unusual scenarios like human skin and curved hot surfaces.

Self-Induced and Progressive Photo-Oxidation of Organophosphonic Acid Grafted Titanium Dioxide.

While synthesis-properties-performance correlations are being studied for organophosphonic acid grafted TiO2 , their stability and the impact of the exposure conditions on possible changes in the interfacial surface chemistry remain unexplored. Here, the impact of different ageing conditions on the evolution of the surface properties of propyl- and 3-aminopropylphosphonic acid grafted mesoporous TiO2 over a period of 2 years is reported, using solid-state 31 P and 13 C NMR, ToF-SIMS and EPR as main techniques. In humid conditions under ambient light exposure, PA grafted TiO2 surfaces initiate and facilitate photo-induced oxidative reactions, resulting in the formation of phosphate species and degradation of the grafted organic group with a loss of carbon content ranging from 40 to 60 wt %. By revealing its mechanism, solutions were provided to prevent degradation. This work provides valuable insights for the broad community in choosing optimal exposure/storage conditions that extend the lifetime and improve the materials' performance, positively impacting sustainability.

In situ study of the deposition of (ultra)thin organic phosphonic acid layers on the oxide of aluminum.

The interest in self-assembling monolayer deposition on various oxide substrate surfaces is steeply increasing in the last decades. Although many studies are being performed, literature does not come with a general insight in the adsorption of these layers on oxide surfaces. Also for the deposition of phosphonic acids on aluminum oxides, there is no global consensus. In this paper, we present an original in situ analysis in order to eludicate the real layer formation mechanism. First of all, the state of the phosphonic acid molecules was determined using DOSY NMR, making sure that no structures other than free molecules were present at the concentration used. With in situ atomic force microscopy and in situ visual ellipsometry, multilayers of phosphonic acids, showing 3D island growth, were determined. It was shown that using the variation of the in situ obtained roughness and bearing ratio, together with the equivalent thickness modeled by ellipsometry, the growth of the layers occurs in situ in three different stages. They consist of increasing number of islands growth, followed by filling up the gaps between islands. At last, within the adsorption time frame measured, the islands grow further in dimensions but not in numbers. This closely corresponds with the behavior of the octylphosphonic acid films analyzed by ex situ techniques.

Simple and Scalable Chemical Surface Patterning via Direct Deposition from Immobilized Plasma Filaments in a Dielectric Barrier Discharge.

In this work, immobilization of the often unwanted filaments in dielectric barrier discharges (DBD) is achieved and used for one-step deposition of patterned coatings. By texturing one of the dielectric surfaces, a discharge containing stationary plasma filaments is ignited in a mix of argon and propargyl methacrylate (PMA) in a reactor operating at atmospheric pressure. From PMA, hydrophobic and hydrophilic chemical and topographical contrasts at sub-millimeter scale are obtained on silicon and glass substrates. Chemical and physical characterizations of the samples are performed by micrometer-scale X-ray photoelectron spectroscopy and infrared imaging and by water contact angle and profilometry, respectively. From the latter and additional information from high-speed imaging of the plasma phase and electrical measurements, it is suggested that filaments, denser in energetic species, lead to higher deposition rate with higher fragmentation of the precursor, while surface discharges igniting outwards the filaments are leading to smoother and slower deposition. This work opens a new route for a one-step large-area chemical and morphological patterning of surfaces at sub-millimeter scales. Moreover, the possibility to separately deposit coatings from filaments and the surrounding plasma phase can be helpful to better understand the processes occurring during plasma polymerization in filamentary DBD.

Amino-Alkylphosphonate-Grafted TiO2: How the Alkyl Chain Length Impacts the Surface Properties and the Adsorption Efficiency for Pd.

Amino-alkylphosphonic acid-grafted TiO2 materials are of increasing interest in a variety of applications such as metal sorption, heterogeneous catalysis, CO2 capture, and enzyme immobilization. To date, systematic insights into the synthesis-properties-performance correlation are missing for such materials, albeit giving important know-how towards their applicability and limitations. In this work, the impact of the chain length and modification conditions (concentration and temperature) of amino-alkylphosphonic acid-grafted TiO2 on the surface properties and adsorption performance of palladium is studied. Via grafting with aminomethyl-, 3-aminopropyl-, and 6-aminohexylphosphonic acid, combined with the spectroscopic techniques (DRIFT, 31P NMR, XPS) and zeta potential measurements, differences in surface properties between the C1, C3, and C6 chains are revealed. The modification degree decreases with increasing chain length under the same synthesis conditions, indicative of folded grafted groups that sterically shield an increasing area of binding sites with increasing chain length. Next, all techniques confirm the different surface interactions of a C1 chain compared to a C3 or C6 chain. This is in line with palladium adsorption experiments, where only for a C1 chain, the adsorption efficiency is affected by the precursor concentration used for modification. The absence of a straightforward correlation between the number of free NH2 groups and the adsorption capacity for the different chain lengths indicates that other chain-length-specific surface interactions are controlling the adsorption performance. The increasing pH stability in the order of C1 < C3 < C6 can possibly be associated to a higher fraction of inaccessible hydrophilic sites due to the presence of folded structures. Lastly, the comparison of adsorption performance and pH stability with 3-aminopropyl(triethoxysilane)-grafted TiO2 reveals the applicability of both grafting methods depending on the envisaged pH during sorption.

Selective Pd recovery from acidic leachates by 3-mercaptopropylphosphonic acid grafted TiO2: does surface coverage correlate to performance?

Modification of metal oxides with organophosphonic acids (PAs) provides the ability to control and tailor the surface properties. The metal oxide phosphonic acid bond (M-O-P) is known to be stable under harsh conditions, making PAs a promising candidate for the recovery of metals from complex acidic leachates. The thiol functional group is an excellent regenerable scavenging group for these applications. However, the research on organophosphonic acid grafting with thiol groups is very limited. In this study, four different metal sorbent materials were designed with different thiol surface coverages. An aqueous-based grafting of 3-mercaptopropylphosphonic acid (3MPPA) on mesoporous TiO2 was employed. Surface grafted thiol groups could be obtained in the range from 0.9 to 1.9 groups per nm2. The different obtained surface properties were studied and correlated to the Pd adsorption performance. High Pd/S adsorption efficiencies were achieved, indicating the presence of readily available sorption sites. A large difference in their selectivity towards Pd removal from a spend automotive catalyst leachate was observed due to the co-adsorption of Fe on the titania support. The highest surface coverage showed the highest selectivity (K d: 530 mL g-1) and adsorption capacity (Q max: 0.32 mmol g-1) towards Pd, while strongly reducing the co-adsorption of Fe on remaining TiO2 sites.

The Type and Concentration of Inoculum and Substrate as Well as the Presence of Oxygen Impact the Water Kefir Fermentation Process.

Eleven series of water kefir fermentation processes differing in the presence of oxygen and the type and concentration of inoculum and substrate, were followed as a function of time to quantify the impact of these parameters on the kinetics of this process via a modeling approach. Increasing concentrations of the water kefir grain inoculum increased the water kefir fermentation rate, so that the metabolic activity during water kefir fermentation was mainly associated with the grains. Water kefir liquor could also be used as an alternative means of inoculation, but the resulting fermentation process progressed slower than the one inoculated with water kefir grains, and the production of water kefir grain mass was absent. Substitution of sucrose with glucose and/or fructose reduced the water kefir grain growth, whereby glucose was fermented faster than fructose. Lacticaseibacillus paracasei (formerly known as Lactobacillus paracasei), Lentilactobacillus hilgardii (formerly known as Lactobacillus hilgardii), Liquorilactobacillus nagelii (formerly known as Lactobacillus nagelii), Saccharomyces cerevisiae, and Dekkera bruxellensis were the main microorganisms present. Acetic acid bacteria were present in low abundances under anaerobic conditions and only proliferated under aerobic conditions. Visualization of the water kefir grains through scanning electron microscopy revealed that the majority of the microorganisms was attached onto their surface. Lactic acid bacteria and yeasts were predominantly associated with the grains, whereas acetic acid bacteria were predominantly associated with the liquor.

Effect of different oxide and hybrid precursors on MOF-CVD of ZIF-8 films.

Chemical vapor deposition of metal-organic frameworks (MOF-CVD) will facilitate the integration of porous and crystalline coatings in electronic devices. In the two-step MOF-CVD process, a precursor layer is first deposited and subsequently converted to a MOF through exposure to linker vapor. We herein report the impact of different metal oxide and metalcone layers as precursors for zeolitic imidazolate framework ZIF-8 films.

Mapping Composition-Selectivity Relationships of Supported Sub-10 nm Cu-Ag Nanocrystals for High-Rate CO2 Electroreduction.

Colloidal Cu-Ag nanocrystals measuring less than 10 nm across are promising candidates for integration in hybrid CO2 reduction reaction (CO2RR) interfaces, especially in the context of tandem catalysis and selective multicarbon (C2-C3) product formation. In this work, we vary the synthetic-ligand/copper molar ratio from 0.1 to 1.0 and the silver/copper atomic ratio from 0 to 0.7 and study the variations in the nanocrystals' size distribution, morphology and reactivity at rates of ≥100 mA cm-2 in a gas-fed recycle electrolyzer operating under neutral to mildly basic conditions (0.1-1.0 M KHCO3). High-resolution electron microscopy and spectroscopy are used in order to characterize the morphology of sub-10 nm Cu-Ag nanodimers and core-shells and to elucidate trends in Ag coverage and surface composition. It is shown that Cu-Ag nanocrystals can be densely dispersed onto a carbon black support without the need for immediate ligand removal or binder addition, which considerably facilitates their application. Although CO2RR product distribution remains an intricate function of time, (kinetic) overpotential and processing conditions, we nevertheless conclude that the ratio of oxygenates to hydrocarbons (which depends primarily on the initial dispersion of the nanocrystals and their composition) rises 3-fold at moderate Ag atom % relative to Cu NCs-based electrodes. Finally, the merits of this particular Cu-Ag/C system and the recycling reactor employed are utilized to obtain maximum C2-C3 partial current densities of 92-140 mA cm-2 at -1.15 VRHE and liquid product concentrations in excess of 0.05 wt % in 1 M KHCO3 after short electrolysis periods.

Efficient long-range conduction in cable bacteria through nickel protein wires.

Filamentous cable bacteria display long-range electron transport, generating electrical currents over centimeter distances through a highly ordered network of fibers embedded in their cell envelope. The conductivity of these periplasmic wires is exceptionally high for a biological material, but their chemical structure and underlying electron transport mechanism remain unresolved. Here, we combine high-resolution microscopy, spectroscopy, and chemical imaging on individual cable bacterium filaments to demonstrate that the periplasmic wires consist of a conductive protein core surrounded by an insulating protein shell layer. The core proteins contain a sulfur-ligated nickel cofactor, and conductivity decreases when nickel is oxidized or selectively removed. The involvement of nickel as the active metal in biological conduction is remarkable, and suggests a hitherto unknown form of electron transport that enables efficient conduction in centimeter-long protein structures.

Molecular Characterization of Multiple Bonding Interactions at the Steel Oxide-Aminopropyl triethoxysilane Interface by ToF-SIMS.

Organofunctional silanes are applied as coupling agents between organic coatings and low carbon steel substrates to promote adhesion. Although the metal oxide-silane interface plays an important role in the performance of the entire overlying coating system, it remains challenging to obtain a clear understanding of the interfacial molecular bonding mechanism and its influence on adhesion. In this work, time-of-flight secondary ion mass spectrometry is used to study interfacial interactions between aminopropyl triethoxysilane (APS) and low carbon steel. APS is shown to bond to the steel substrate through silanol steel and amine-steel interactions, and coatings are cured at varying temperatures to evaluate the influence of curing on these different types of bonding interactions. Unambiguous evidence for hydrogen bond interactions between APS silanol groups and steel surface hydroxyl groups is provided for the first time in this work through deuteration of the steel substrate and allows to tackle long-lasting doubts about the most wide-spread bonding theory that has been postulated for silane adsorption on metals.