Abstract:Silver catalysis has a rich and versatile chemistry now expanding from processes mediated by silver complexes and silver nanoparticles to transformations catalyzed by silver metal organic alloys and single-atom catalysts. Focusing on selected recent advances, we identify the key advantages offered by these highly selective heterogeneous catalysts. We conclude by offering seven research and educational guidelines aimed at further progressing the field of new generation silver-based catalytic materials.
“…This narrow size distribution of small Ag NPs achieved within the solid matrix is remarkable. Small Ag NPs are not only interesting due to their plasmonic properties but have been increasingly employed in design of remarkable catalytic systems [ 23 ], indicating that our strategy has a potential beyond the use in optoelectronic devices. Fig.…”
DNA-templated metallization is broadly investigated in the fabrication of metallic structures by virtue of the unique DNA-metal ion interaction. However, current DNA-templated synthesis is primarily carried out based on pure DNA in an aqueous solution. In this study, we present in situ synthesis of metallic structures in a natural DNA complex bulk film by UV light irradiation, where the growth of silver particles is resolved by in situ time-resolved small-angle X-ray scattering and dielectric spectroscopy. Our studies provide physical insights into the kinetics and mechanisms of natural DNA metallization, in correlation with the multi-stage switching operations in the bulk phase, paving the way towards the development of versatile biomaterial composites with tunable physical properties for optical storage, plasmonics, and catalytic applications.
“…This narrow size distribution of small Ag NPs achieved within the solid matrix is remarkable. Small Ag NPs are not only interesting due to their plasmonic properties but have been increasingly employed in design of remarkable catalytic systems [ 23 ], indicating that our strategy has a potential beyond the use in optoelectronic devices. Fig.…”
DNA-templated metallization is broadly investigated in the fabrication of metallic structures by virtue of the unique DNA-metal ion interaction. However, current DNA-templated synthesis is primarily carried out based on pure DNA in an aqueous solution. In this study, we present in situ synthesis of metallic structures in a natural DNA complex bulk film by UV light irradiation, where the growth of silver particles is resolved by in situ time-resolved small-angle X-ray scattering and dielectric spectroscopy. Our studies provide physical insights into the kinetics and mechanisms of natural DNA metallization, in correlation with the multi-stage switching operations in the bulk phase, paving the way towards the development of versatile biomaterial composites with tunable physical properties for optical storage, plasmonics, and catalytic applications.
“…LDPE disks loaded with sub-microgram amounts of Ag NPs were chosen as model NP-loaded substrates for this study. Silver NPs were selected owing to their very wide application in the construction of supported functional materials, e.g., antibacterial and antifungal systems [49,50], sensing devices [51,52] and catalysts [53,54]. Ag nanoparticles are additionally the metallic NPs industrially produced in the largest amount [55].…”
Section: Characterization Of Ag-loaded Disksmentioning
A laser ablationâinductively coupled plasmaâmass spectrometry (LAâICPâMS) based method is proposed for the quantitative determination of the spatial distribution of metal nanoparticles (NPs) supported on planar substrates. The surface is sampled using tailored ablation patterns and the data are used to define three-dimensional functions describing the spatial distribution of NPs. The volume integrals of such interpolated surfaces are calibrated to obtain the mass distribution of Ag NPs by correlation with the total mass of metal as determined by metal extraction and ICPâMS analysis. Once this mass calibration is carried out on a sacrificial sample, quantifications can be performed over multiple samples by a simple micro-destructive LAâICPâMS analysis without requiring the extraction/dissolution of metal NPs. The proposed approach is here tested using a model sample consisting of a low-density polyethylene (LDPE) disk decorated with silver NPs, achieving high spatial resolution over cm2-sized samples and very high sensitivity. The developed method is accordingly a useful analytical tool for applications requiring both the total mass and the spatial distribution of metal NPs to be determined without damaging the sample surface (e.g., composite functional materials and NPs, decorated catalysts or electrodic materials).
“…Silver is currently considered as a âlow risk supplyâ material [ 19 ], nevertheless, its demand is increasing for several applications, such as nanomaterial synthesis [ 20 ], optical [ 21 ], catalytic [ 22 ], energy storage [ 23 ], adsorptive and medical technologies [ 24 , 25 , 26 ]. The synergic effect of increasing demand and supply shortages [ 27 , 28 ] stimulated the development of technologies aimed also at recovering silver from secondary sources, such as e-waste [ 29 ].…”
Access to the enthalpy and entropy of the formation of metal complexes in solution is essential for understanding the factors determining their thermodynamic stability and speciation. As a case study, in this report we systematically examine the complexation of silver(I) in acetonitrile (AN) with the following monoamines: n-propylamine (n-pr), n-butylamine (n-but), hexylamine (hexyl), diethylamine (di-et), dipropylamine (di-pr), dibutylamine (di-but), triethylamine (tri-et) and tripropylamine (tri-pr). The study shows that the complex stabilities are quite independent of the length of the substitution chain on the N atom and demonstrates that, in general, the overall enthalpy terms associated with the complex formation are strongly exothermic, whereas the entropy values oppose the complex formations. In addition, we examined the similarity of the formation constants of AgL complexes of the primary monoamines in AN, dimethylsulfoxide (DMSO) and water, which were unexpected on the basis of the difference between the donor properties of solvents.
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