Scientific insights of electrochemical replacement approach to describe the origin of Pre-Columbian Peruvian gilded copper-based objects

Pre-Columbian Peruvian goldsmiths developed gilded copper-based objects by ancient techniques that require identification to propose conservation strategies. Lechtman H, conducted experiments to suggest that the electrochemical replacement was the gilding technique used by the Moche and Vicus cultural groups. Despite her remarkable achievement, the quantitative data provided by her is still open to discussion. This work focused on obtaining experimental data to recreate her protocol by introducing less gold precursor. Polished copper pieces were plated with an adherent gold film of up to 7.5 µm after immersing them into an electrolytic solution for 3 min and 6 min at 80 °C. Our results demonstrated that the electrochemical replacement technique gives rise to anodic regions in the plated objects. Further studies around the corrosion process that undergoes these heritage objects in burial and environmental conditions are suggested to determine their deterioration rate. Moreover, electroless and galvanic techniques should be explored in order to improve current approaches.

Additive Manufacturing of Gold Nanostructures Using Nonlinear Photoreduction under Controlled Ionic Diffusion

Multiphoton photoreduction of photosensitive metallic precursors via direct laser writing (DLW) is a promising technique for the synthesis of metallic structures onto solid substrates at the sub-micron scale. DLW triggered by a two photon absorption process is done using a femtosecond NIR laser (λ = 780 nm), tetrachloroauric acid (HAuCl4) as a gold precursor, and isinglass as a natural hydrogel matrix. The presence of a polymeric, transparent matrix avoids unwanted diffusive processes acting as a network for the metallic nanoparticles. After the writing process, a bath in deionized water removes the gold precursor ions and eliminates the polymer matrix. Different aspects underlying the growth of the gold nanostructures (AuNSs) are here investigated to achieve full control on the size and density of the AuNSs. Writing parameters (laser power, exposure time, and scanning speed) are optimized to control the patterns and the AuNSs size. The influence of a second bath containing Au3+ to further control the size and density of the AuNSs is also investigated, observing that these AuNSs are composed of individual gold nanoparticles (AuNPs) that grow individually. A fine-tuning of these parameters leads to an important improvement of the created structures’ quality, with a fine control on size and density of AuNSs.

Structural and Optical Sensing Properties of Nonthermal Atmospheric Plasma-Synthesized Polyethylene Glycol-Functionalized Gold Nanoparticles

Polyethylene glycol-functionalized gold nanoparticles (Au@PEG NPs) were prepared by a simple plasma-assisted method without additional reducing chemicals. After irradiating tetrachloroauric acid (HAuCl4) and polyethylene glycol (PEG) in aqueous medium with an argon plasma jet, the gold precursor transformed into an Au@PEG NP colloid that exhibited surface plasma resonance at 530 nm. When the plasma jet entered the water, additional reactive species were induced through interactions between plasma-generated reactive species and aqueous media. Interaction of the gold precursor with the plasma-activated medium allowed the synthesis of gold nanoparticles (AuNPs) without reductants. The plasma-synthesized Au@PEG NPs had a quasi-spherical shape with an average particle diameter of 32.5 nm. The addition of PEG not only helped to stabilize the AuNPs but also increased the number of AuNPs. Au@PEG NP-loaded paper (AuNP-paper) was able to detect the degradation of rhodamine B, therefore, indicating that AuNP-paper can act as a surface-enhanced Raman scattering platform. Dye degradation by plasma treatment was investigated by optical absorption and Raman spectroscopy. The method proposed for the fabrication of Au@PEG NPs is rapid, low-cost, and environment-friendly and will facilitate the application of plasma-synthesized nanomaterials in sensors.

Gold(I) N-heterocyclic carbene precursors for focused electron beam-induced deposition

Seven gold(I) N-heterocyclic carbene (NHC) complexes were synthesized, characterized, and identified as suitable precursors for focused electron beam-induced deposition (FEBID). Several variations on the core Au(NHC)X moiety were introduced, that is, variations of the NHC ring (imidazole or triazole), of the alkyl N-substituents (Me, Et, or iPr), and of the ancillary ligand X (Cl, Br, I, or CF3). The seven complexes were tested as FEBID precursors in an on-substrate custom setup. The effect of the substitutions on deposit composition and growth rate indicates that the most suitable organic ligand for the gold precursor is triazole-based, with the best deposit composition of 15 atom % gold, while the most suitable anionic ligand is the trifluoromethyl group, leading to a growth rate of 1 × 10−2 nm3/e−.

One Step Photochemical Synthesis of Surface-Supported Naked Gold Nanoparticles and Its Application as a SERS Substrate

<p>A direct and straightforward method is proposed to synthetize a surface-supported gold nanoparticles mediated by pulsed laser irradiation of quartz surfaces in contact with a gold precursor solutions. The substrates´ performance as SERS sensors is tested by the Rhodamine 6G (R6G) Raman signal enhancement.</p>

One Step Photochemical Synthesis of Surface-Supported Naked Gold Nanoparticles and Its Application as a SERS Substrate

<p>A direct and straightforward method is proposed to synthetize a surface-supported gold nanoparticles mediated by pulsed laser irradiation of quartz surfaces in contact with a gold precursor solutions. The substrates´ performance as SERS sensors is tested by the Rhodamine 6G (R6G) Raman signal enhancement.</p>

Removal of Nonylphenol Polyethylene Glycol (NPEG) with Au-TiO2 Catalysts: Kinetic and Initial Transformation Path

The purpose of this study was to evaluate the efficiency of the Au-TiO2 catalyst in the degradation of nonylphenol polyethylene glycol (NPEG). In the first part of the study, the catalyst was synthesized and characterized. Initially, the catalyst (TiO2 Degussa P-25) was doped with gold precursor salts (HAuCl4) at different concentrations (5, 10, and 15%) and the photodeposition method with UV light. It was determined by diffuse reflectance (DF) and scanning electron microscopy (SEM) that the photodeposition method was effective for the inclusion of gold particles on the surface. The catalyst band gap showed a reduction to 2.9 e.v (compared to TiO2 Degussa P-25), and it was observed that the gold-doped catalyst showed absorption in the visible light range 500 to 600 nm. The percentage of deposited gold was determined by energy dispersive spectroscopy (EDS). In the second part of the study, various NPEG degradation experiments were performed; with the catalyst that showed the best conversion percentages of NPEG, the experimental data were analyzed using UV-Vis spectrophotometry and TOC (total organic carbon). With these results, a carbon-based mass balance and reaction kinetics were generated using the Langmuir–Hinshelwood (L–H) heterogeneous catalysis model. For the estimation of the kinetic constants, the non-linear regression of the Levenger–Marquardt algorithm was used. With these results, kinetic models of the degradation of the molecule and the generation and consumption of organic intermediate products (OIPs) were generated.

Micro-Reactor System for Complete Oxidation of Volatile Organic Compounds

Based on previous Computational Fluid Dynamics (CFD) design results, an 11 channel microreactor of dimensions (0.5 mm × 0.5 mm × 100 mm) (width × depth × length) and optimal manifold geometry was fabricated, coated with a newly-developed Au/SBA-15 catalyst and then integrated in an experimental rig specifically built for this research. Propane (as model volatile organic compound) oxidation experiments were conducted at three different flow velocities, 12.5, 15.4 and 17.5 m/min, respectively, at six temperatures, 150, 200, 225, 250, 275, and 300 °C, respectively. The catalyst was prepared by one-pot sol-gel synthesis of SBA-15 with MPTMS (3-mercaptopropyl-trimethoxy-silane) before loading with HAuCl4 gold precursor and then characterized by SEM/EDX, TEM and wide angle XRD. A novel catalyst coating technique was developed, using airbrush (0.3 nozzle) to spray a catalyst slurry into the microchannels that produced a thin, firm and uniform layer of Au/SBA-15 catalyst coating inside the microreactor. The experimental measurements revealed that propane conversion increased as the flow feed rates decreased and increased with increasing temperatures in the reactor. For the built microreactor and for the flows and temperatures set, the combustion of propane was possible with measurable conversions and reasonable reactor stability, the performance of the catalyst appeared to be central to the satisfactory operation of the reactor.

Crystal Growth and Kinetic Behaviour of Pseudoalteromonas espejiana Assisted Biosynthesized Gold Nanoparticles

Pseudoalteromonas espejiana (P. espejiana) is a marine bacterium known for its high resistance to alkalinity. The ability of P. espejiana to reduce Au (III) and biosynthesize gold nanoparticles (AuNPs) is found positive and was confirmed using UV-VIS, EDS, SEM, and TEM studies. Previously, many studies have been reported regarding the crystalline nature of AuNPs; therefore, this research aims at studying the crystal growth behaviour of AuNPs through DLS and TEM studies. Spherically shaped and monodispersed, AuNPs ranging between 5 to 160 nm were obtained with an average particle size of 62 nm. Also, to achieve maximum production of AuNPs, the reaction kinetic study was performed using an ICP-OES method and the effect of various parameters including pH, temperature, rpm, and concentration of substrate was analyzed. During the biosynthesis process, an appropriate phase of nucleation, crystal growth, and saturation was observed and this helped to determine the rate constants and order of reaction. The parameters such as pH profile (pH 9), temperature (30°C), agitation speed (150 rpm), and enzyme substrate ratio (2 : 3) were found to be the best fits for maximum production of low size AuNPs. This demonstrates that in initial few hours, a quick conversion of the ionic gold precursor takes place into metallic gold nuclei, trailed by crystal growth via coalescence of small nuclei. Subsequently, it can be concluded that coalescence processes drive the crystal growth process of AuNPs over a time interval and finally leads to saturation and no newer particle formation in the solution.