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Stone deterioration is the result of a complex interaction of external physical, chemical and biological forces with the mineralogical-petrophysical properties of the stone. With a better understanding of how these properties are linked to material behavior and durability, more effective measures for stone conservation can be developed. Studying these interactions in tuff is particularly complex due to the naturally high heterogeneity of tuff rocks.
The first aim of a current research project is to combine the results of recent and older studies on tuff deterioration. Furthermore, the literature overview is complemented by our own investigation of Weibern and Ettringen tuff, with a focus on pore structure characteristics.
Zeolitic imidazolate framework (ZIF) hybrid fluorescent nanoparticles and ZIF antibody conjugates have been synthesized, characterized, and employed in lateral-flow immunoassay (LFIA). The bright fluorescence of the conjugates and the possibility to tailor their mobility gives a huge potential for diagnostic assays. An enzyme-linked immunosorbent assay (ELISA) with horseradish peroxidase (HRP) as label, proved the integrity, stability, and dispersibility of the antibody conjugates, LC-MS/MS provided evidence that a covalent link was established between these metal-organic frameworks and lysine residues in IgG antibodies.
Lanthanide-based, spectrally shifting, and multi-color luminescent upconverting nanoparticles (UCNPs) have received much attention in the last decades because of their applicability as reporter for bioimaging, super-resolution microscopy, and sensing as well as barcoding and anti-counterfeiting tags. A prerequisite for the broad application of UCNPs in areas such as sensing and encoding are simple, robust, and easily upscalable synthesis protocols that yield large quantities of UCNPs with sizes of 20 nm or more with precisely controlled and tunable physicochemical properties from lowcost reagents with a high reproducibility. In this context, we studied the reproducibility, robustness, and upscalability of the synthesis of β-NaYF4:Yb, Er UCNPs via thermal decomposition. Reaction parameters included solvent, precursor chemical compositions, ratio, and concentration. The resulting UCNPs were then examined regarding their application-relevant physicochemical properties such as size, size distribution, morphology, crystal phase, chemical composition, and photoluminescence.
Based on these screening studies, we propose a small volume and high-concentration synthesis approach that can provide UCNPs with different, yet controlled size, an excellent phase purity and tunable morphology in batch sizes of up to at least 5 g which are well suited for the fabrication of sensors, printable barcodes or authentication and recycling tags.
This paper reports the results of an international interlaboratory study sponsored by the Versailles Project on Advanced Materials and Standards (VAMAS) and led by the National Institute of Standards and Technology (NIST) on the measurement of water vapor sorption isotherms at 25 °C on a pelletized nanoporous carbon (BAM-P109, a certified reference material). Thirteen laboratories participated in the study and contributed nine pure water vapor isotherms and four relative humidity isotherms, using nitrogen as the carrier gas. From these data, reference isotherms, along with the 95% uncertainty interval (Uk=2), were determined and are reported in a tabular format.
Relaxation phenomena observed in the electrical low-frequency range (approximately 1 mHz-10 kHz) of natural porous media like sandstones is often assumed to be directly related to the dominant (modal) pore throat sizes measured, for instance, with mercury intrusion porosimetry. Attempts to establish a universally valid relationship between pore size and peak Spectral Induced Polarization (SIP) relaxation time have failed, considering sandstones from very different origins and featuring great variations in textural and chemical compositions as well as in geometrical pore space properties. In addition working with characteristic relaxation times determined in Cole-Cole or Debye decomposition fits to build the relationship have not been successful. In particular, samples with narrow pore throats are often characterized by long SIP relaxation times corresponding to long “characteristic length scales” in these media, assuming that the diffusion coefficients along the electrical double layer were constant. Based on these observations, three different types of SIP relaxation can be distinguished. We present a new way of assessing complex pore spaces of very different sandstones in a multi-methodical approach to combine the benefits of mercury intrusion porosimetry, micro-computed tomography, and nuclear magnetic resonance. In this way, we achieve much deeper insight into the pore space due to the different resolutions and sensitivities of the applied methods to both pore constrictions (throats) and wide pores (pore bodies). We experimentally quantify pore aspect ratios and volume distributions within the two pore regions. We clearly observe systematic differences between three SIP relaxation types identified previously and can attribute the SIP peak relaxation times to measured characteristic length scales within our materials. We highlight selected results for a total of nine sandstones. It seems that SIP relaxation behavior depends on the size difference of the narrow pore throats to the wide pore bodies, which increases from SIP Type 1 to Type 3.
Developing high-efficiency, high-stability, and low-cost deoxygenation and hydrocracking catalysts could be considered one of the most significant breakthroughs in catalytic hydroprocessing. The present study utilized aluminophosphate (AlPO4-18), a zeolite-like molecular sieve, as catalyst support for producing carbon-coated β-Mo2C, Ni3C, and WC nanoparticles. The synthesis used an incipient wetness impregnation followed by a temperature-programmed reduction-carburization approach which involved cracking a hydrocarbon gas, propane, in a hydrogen environment. The synthesis parameters were a 1:7 propane/hydrogen reductive-carburizing gas stream, 15 wt.% metal loading, an 800 °C carburization temperature ramped-up at a heating rate of 10 °C min−1, a 2-h holding time, and a 1-h holding time in hydrogen. The synthesized catalysts were characterized using thermogravimetry mass spectroscopy/temperature-programmed oxidation (TPO TG-MS), nitrogen physisorption at 77 K, X-ray diffraction (XRD), and transmission electron microscopy/energy-dispersive X-ray spectroscopy (TEM EDS). TPO TG-MS, nitrogen physisorption, TEM, and XRD characterization results proved that atomic carbon was successfully incorporated into the lattice interstitials, resulting in thermally stable, well-dispersed, crystalline and mesoporous β-Mo2C/AlPO4-18, Ni3C/AlPO4-18, and WC/AlPO4-18 nanoparticles. XRD analysis showed structural evolution during reduction-carburization, with average crystallite sizes of metal-containing particles of 8.2–9.22, 6.64–8.50, and 6.03–7.56 nm for β-Mo2C/AlPO4-18, Ni3C/AlPO4-18, and WC/AlPO4-18, respectively. These values did not significantly deviate from high-resolution TEM analysis. The surface areas of the nanoparticles were categorized in decreasing order as WC/AlPO4-18 > Ni3C/AlPO4-18 > β-Mo2C/AlPO4-18, with values of 193.79, 169.05, and 66.57 m2 g−1, respectively. In conclusion, these carbon-coated metal carbide nanoparticles with excellent thermal, structural, microscopic, and textural properties can be viable alternatives to noble metal catalysts for producing bio-jet fuel using the hydroprocessing pathway.
AbstractSorbents are promising materials for applications in atmospheric water harvesting, thermal energy storage, and passive cooling, thereby addressing central challenges related to water scarcity and the global energy transition. Recently, hygroscopic hydrogel composites have emerged as high‐performance sorbents. However, many of these systems are fabricated with unsustainable and costly sorbent materials, which hinders their wide deployment. Here, the synthesis of high‐performance, cost‐efficient polyacrylamide hydrogels loaded with unprecedented amounts of calcium chloride is demonstrated. To this end, the swelling procedure of polyacrylamide hydrogels in aqueous calcium chloride solutions is optimized. The achievable salt loading in the hydrogel is characterized as a function of temperature, calcium chloride concentration in the swelling solution, and the hydrogel preparation conditions. The obtained hydrogel‐salt composites are shown to be stable under repeated sorption‐desorption cycling and enable water uptakes of 0.92 and 2.38 grams of water per gram of dry materials at 30% and 70% relative humidity, respectively. The resulting cost‐performance ratio substantially exceeds lithium chloride‐based systems. Further, the mechanistic insights on hydrogel salt interactions can guide the design of sustainable and low‐cost sorbent materials for future applications in water and energy.
Emission reference materials (ERMs) are sought after to further control and improve indoor air quality. The impregnation of porous materials with volatile organic compounds (VOCs) is a promising approach to produce ERMs. Different VOCs were used to impregnate various porous materials (mainly zeolites, activated carbons and a metal organic framework). The influence of different methodological parameters and material properties were studied to optimize the impregnation procedure and to find the best material/VOC combination. The impregnation procedure remains quite irreproducible, nevertheless, very good ERM candidates were identified. Two materials (zeolite 4 and AC 1 impregnated with n-hexadecane) showed a very stable emission over 14 days (<10 % change). Another material (AC 1 impregnated with toluene) showed a declining emission profile but with a very good in-batch reproducibility and a storage stability of up to 12 months.
The adsorptive performance of divalent manganese onto single-walled carbon nanotubes (SWCNTs) is investigated by X-ray absorption spectroscopy (XAS). The study is focused on the one hand, on the use of SWCNT as adsorbent to remove divalent manganese II) pollutant controlling batch parameters such as pH, adsorbent dose and contact time; and on the other hand, on the characterization of manganese adsorbed by SWCNT (Mn-SWCNT) adsorbent to probe the chemical composition, oxidation state, and local structural environment of Mn absorber. Freundlich adsorption isotherm well fitted the experimental data and suggested the maximum adsorption capacity at pH 2. Ion exchange was proposed as the main adsorption mechanism for removing manganese using SWCNT. XAS results revealed the change in the oxidation state of manganese. The effect of pH, adsorbent dose, and contact time is shown. XAS also showed that Mn-SWCNT material is principally composed of MnCl2, Mn2O3, MnO2, Mn3O4, and MnO in decreasing order with MnCl2 and Mn2O3 as major compounds.
We demonstrate the potential of time-resolved luminescence spectroscopy for the straightforward assessment and in situ monitoring of the stability of upconversion nanocrystals (UCNPs). Therefore, we prepared hexagonal NaYF4:Yb3+,Er3+ UCNPs with various coatings with a focus on phosphonate ligands of different valency, using different ligand exchange procedures, and studied their dissolution behaviour in phosphate-buffered saline (PBS) dispersions at 20 °C and 37 °C with various analytical methods. The amount of the released UCNPs constituting fluoride ions was quantified by potentiometry using a Fluoride ion-sensitive electrode and particle disintegration was confirmed by transmission electron microscopy studies of the differently aged UCNPs. In parallel, the luminescence features of the UCNPs were measured with special emphasis on the lifetime of the sensitizer emission to demonstrate its suitability as Screening parameter for UCNP stability and changes in particle composition. The excellent correlation between the changes in luminescence lifetime and fluoride concentration highlights the potential of our luminescence lifetime method for UCNP stability screening and thereby indirect monitoring of the release of potentially hazardous fluoride ions during uptake and dissolution in biological systems. Additionally, the developed in situ optical method was used to distinguish the dissolution dynamics of differently sized and differently coated UCNPs.