Host-Guest Interactions in a Metal-Organic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction.

A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3 (4,4'-dcbpy)] and a photosensitizer [Ru(bpy)2 (5,5'-dcbpy)]Cl2 using the isoreticular series of metal-organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location-either at the outer MOF particle surface or inside the MOF cavities-affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.

Looking at Silver-Based Nanoparticles in Environmental Water Samples: Repetitive Cloud Point Extraction Bridges Gaps in Electron Microscopy for Naturally Occurring Nanoparticles.

The growing use of silver-based nanoparticles (Ag-b-NPs) in everyday products goes hand in hand with their release into the environment, resulting in ng L-1 traces in natural water bodies. In order to assess their fate, possible transformations and ecotoxicology-essential information to proper risk assessment-particle size, shape, and chemical composition have to be determined. Transmission electron microscopy coupled with energy dispersive X-ray spectroscopy (TEM-EDX) is a powerful tool for determining these particle characteristics, but it requires high particle concentrations in order to produce statistically reliable results. In this study, we will present the extraction of Ag-b-NPs at environmentally relevant concentrations down to 5 ng L-1 from artificial as well as environmental water samples via cloud point extraction on a repetitive basis. The combination with an on-grid centrifugation technique ensures an efficient concentration and deposition of the extracted particles onto the TEM grid for subsequent TEM-EDX measurements. Furthermore, electron microscopy investigations were supplemented by single particle inductively coupled plasma mass spectrometry (sp-ICP-MS) measurements. Ag-b-NPs were successfully visualized and characterized at environmentally relevant concentrations of 5 ng L-1 with TEM-EDX and sp-ICP-MS measurements. Their size, shape, and chemical composition were not affected by the sample preparation.

Separating dissolved silver from nanoparticulate silver is the key: Improved cloud-point-extraction hyphenated to single particle ICP-MS for comprehensive analysis of silver-based nanoparticles in real environmental samples down to single-digit nm particle sizes.

Investigating silver-based nanoparticles (Ag-b-NPs) in environmental samples is challenging with current analytical techniques, owing to their low concentrations (ng L-1) in the presence of high quantities of dissolved Ag(I) species. sp-ICP-MS is a promising technique able to simultaneously determine the concentration and particle sizes of Ag-b-NPs even at concentrations of several ng L-1. However, sp-ICP-MS suffers from the coexistence of dissolved analyte species causing high background signals. These background signals cover particle signals and therefore limit the size detection limit (SDL) in sp-ICP-MS. Ag-b-NPs in environmental samples exhibit diameters of < 20 nm, whereas the current sp-ICP-MS approaches barely reach an SDL as low as 20 nm. Using a surfactant-mediated sample pre-treatment (improved cloud point extraction, iCPE), we were able to separate Ag-b-NPs in aqueous samples from dissolved Ag(I) species and enrich the NPs in the extract. By hyphenating iCPE to sp-ICP-MS, we were able to reach SDL values as low as 4.5 nm, thus paving the way for the successful monitoring of Ag-b-NPs in the environment.

Magnetic solid phase extraction of silver-based nanoparticles in aqueous samples: Influence of particle composition and matrix effects on its application to environmental samples and species-selective elution and determination of silver sulphide nanoparticles with sp-ICP-MS.

Silver-based nanoparticles (Ag-b-NPs) are currently a cause for concern because they are being produced in increasing quantities for use in industrial goods and consumer products. This goes hand in hand with their release to the environment and the resultant risks for the entire ecosystem. Therefore, it is essential that these materials are monitored. A promising technique that overcomes a number of shortcomings in handling environmental samples is magnetic solid phase extraction (MSPE) of Ag-b-NPs, which is applied in this study. It has been possible to extract different kinds of Ag-b-NPs at environmentally relevant concentrations in the low ng L-1 range using iron oxide magnetic particles (IOMPs) of different size and shape with efficiencies in the range from 80 to 100%. Furthermore, environmentally relevant inorganic ions and TiO2 particles exhibited no major effect on the extraction efficiency. However, natural organic matter (NOM) exhibited a significant influence from 1 mg L-1 resulting in a 50% drop in extraction efficiency. This effect could be overcome by adding 10 mM Ca2+ or increasing the iron oxide magnetic particle (IOMP) concentration to 500 mg L-1. Applying the presented procedure, Ag-b-NPs added to a river water sample at ßAg = 50 ng L-1 were successfully extracted. We also investigated the coextraction of Ag+, demonstrating that NOM could eliminate coextraction. The subsequent species-selective elution of Ag2S-NPs after MSPE, was carried out based on ethylene diamine tetraacetate (EDTA) as eluent in different matrices. A desorption efficiency of 76 ± 6% could be achieved while preserving the Ag2S-NPs' size. By contrast, core Ag-NPs and AgCl-NPs are dissolved if the presented method is followed.

Nanometallurgy in solution: organometallic synthesis of intermetallic Pd-Ga colloids and their activity in semi-hydrogenation catalysis.

Nanoparticles (NPs) of Pd1--xGax (x = 0.67, 0.5, 0.33), stabilized in non-aqueous colloidal solution, were obtained via an organometallic approach under mild conditions using [Pd2(dvds)3] and GaCp* as all-hydrocarbon ligated metal-precursor compounds (dvds = 1,1,3,3-tetramethyl-1,3-divinyl-disiloxane; Cp* = η5-C5Me5; Me = CH3). The reaction of the two precursors involves the formation of a library of molecular clusters [PdnGamCp*y(dvds)z], as shown by liquid injection field desorption ionization mass spectrometry (LIFDI-MS). Full characterization of the catalytic system (HR-TEM, EDX, DLS, PXRD, XPS, NMR, IR, Raman) confirmed the formation of ultra-small, spherical NPs with narrow size distributions ranging from 1.2 ± 0.2 nm to 2.1 ± 0.4 nm (depending on the Pd : Ga ratio). The catalytic performance of the Pd1--xGax NPs in the semi-hydrogenation of terminal and internal alkynes and the influence of the gallium content on product selectivity were investigated. The highest activities (65%) and selectivities (81%) are achieved using colloids with a "stoichiometric" Pd/Ga ratio of 1 : 1 at 0 °C and 2.0 bar H2 pressure. While lower Ga ratios lead to an increase in activity, higher Ga contents increase the olefin selectivity but are detrimental to the activity.

What happens to silver-based nanoparticles if they meet seawater?

Silver based nanoparticles (Ag-b-NPs) in the environment are of current concern as they may pose risks to human and environmental health, even at low concentration levels. It is widely known that Ag-b-NPs, once released from products containing these particles for antimicrobial reasons, can pass through wastewater treatment plants to some extent. These particles are transported via running waterways and eventually reach the sea. However, the fate of environmentally relevant ng L-1 traces of Ag-b-NPs in seawater has not yet been sufficiently studied. Analytical techniques capable of determining these ultratraces of Ag-b-NPs in seawater are scarce and struggle furthermore with the high chloride content in highly saline matrices, such as seawater. In this study, we extracted Ag-b-NPs from matrices with varying salinity via cloud point extraction (CPE) and determined concentration and size of Ag-b-NPs in extracts with single particle inductively coupled plasma mass spectrometry (sp-ICP-MS). Applying this extraction and measurement technique, we were able to investigate the fate of Ag-b-NPs with different coatings (citrate and the predominant coatings in nature, silver sulfide and silver chloride) in matrices with increasing salinity and real seawater. All types of Ag-b-NPs were dissolved in all matrices almost independently of the chemical composition of the nanoparticles (NPs), whereas dissolution rates increased with increasing salinity due to the formation of soluble Ag(I) species and - in the presence of chloride - AgClx1-x (x > 1) complexes. After an incubation time of not more than 72 h, Ag-b-NPs were dissolved almost completely. During the dissolution process, NP shrinkage could be clearly observed by sp-ICP-MS. Supplementary electron microscopy measurements revealed that the sulfur content in silver sulfide nanoparticles (Ag2S-NPs) increased during the dissolution process. Finally, we were able to investigate the dissolution process of real Ag-b-NPs in wastewater after increasing the salinity to seawater levels.