Light and anoxia fading of Prussian blue dyed textiles.

Although Prussian blue is a popular pigment, its stability has been questioned since its discovery in 1704. Its stability upon exposure to light and anoxia remains difficult to apprehend. The present paper focuses on the relative influences of light, anoxia and type of substrate on the discoloration of Prussian blue dyed textiles. Spectrophotometry and X-ray absorption spectroscopy measurements of samples artificially aged by light in air or anoxia show that both the extent of the reduction process at the origin of Prussian blue discoloration and the aging of the textile substrate are linked and strongly differ with the environment. The complex inter-relationship existing between Prussian blue discoloration and textile degradation and the final impact it may have on the conservation of the entire system is discussed

"Live” Prussian blue fading by time-resolved X-ray absorption spectroscopy

Prussian blue (PB) is an artists' pigment that has been frequently used in many artworks but poses several problems of conservation because of its fading under light and anoxia treatment. PB fading is due to the reduction of iron(III) into iron(II) and depends a lot on the object investigated. Due to the complexity of the structure, the precise physico-chemical mechanisms behind the redox process remain obscure. In this paper, we present a procedure to investigate light- and anoxia-induced fading of PB-paper samples by means of time resolved X-ray absorption spectroscopy performed at the Fe K-edge. A system composed of a visible light source and a flux-controlled environmental cell allowed light, gas and humidity to be modified in situ. The synchrotron X-ray beam was evidenced to induce a reduction of PB and to play a major role in the kinetics. The analysis of the PB fading kinetics of a sample submitted to various gas and light environments showed that both synchrotron beam and anoxia were influencing PB reduction in a correlated way. In comparison, light was found to play a minor role. Finally, we have demonstrated that the type of paper substrate could influence significantly the kinetics of reduction. Several hypotheses to explain the correlation between PB reduction mechanism and substrate are presente

Chemical tuning of Coulomb blockade at room-temperature in ultra-small platinum nanoparticle self-assemblies

This work describes self-assemblies of ultra-small platinum nanoparticles, the electrical properties of which can be adjusted through slight modifications of the assemblies' constituents. Elaborating such systems, stable in air for months, is a first step towards nanoelectronic systems, where the charging energy of the nanoparticles is tuned by the nature of the ligands

Bidimensional lamellar assembly by coordination of peptidic homopolymers to platinum nanoparticles

A key challenge for designing hybrid materials is the development of chemical tools to control the organization of inorganic nanoobjects at low scales, from mesoscopic (~µm) to nanometric (~nm). So far, the most efficient strategy to align assemblies of nanoparticles consists in a bottom-up approach by decorating block copolymer lamellae with nanoobjects. This well accomplished procedure is nonetheless limited by the thermodynamic constraints that govern copolymer assembly, the entropy of mixing as described by the Flory–Huggins solution theory supplemented by the critical influence of the volume fraction of the block components. Here we show that a completely different approach can lead to tunable 2D lamellar organization of nanoparticles with homopolymers only, on condition that few elementary rules are respected: 1) the polymer spontaneously allows a structural preorganization, 2) the polymer owns functional groups that interact with the nanoparticle surface, 3) the nanoparticles show a surface accessible for coordination

Spin crossover in Fe(triazole)–Pt nanoparticle self-assembly structured at the sub-5 nm scale

A main goal of molecular electronics is to relate the performance of devices to the structure and electronic state of molecules. Among the variety of possibilities that organic, organometallic and coordination chemistries offer to tune the energy levels of molecular components, spin crossover phenomenon is a perfect candidate for elaboration of molecular switches. The reorganization of the electronic state population of the molecules associated to the spin crossover can indeed lead to a significant change in conductivity. However, molecular spin crossover is very sensitive to the environment and can disappear once the molecules are integrated into devices. Here, we show that the association of ultra-small 1.2 nm platinum nanoparticles with FeII triazole-based spin crossover coordination polymers leads to self-assemblies, extremely well organized at the sub-3 nm scale. The quasi-perfect alignment of nanoparticles observed by transmission electron microscopy, in addition to specific signature in infrared spectroscopy, demonstrates the coordination of the long-chain molecules with the nanoparticles. Spin crossover is confirmed in such assemblies by X-ray absorption spectroscopic measurements and shows unambiguous characteristics both in magnetic and charge transport measurements. Coordinating polymers are therefore ideal candidates for the elaboration of robust, well-organized, hybrid self-assemblies with metallic nanoparticles, while maintaining sensitive functional properties, such as spin crossover

Facile one-pot synthesis of rhenium nanoparticles

cited By 0; Conference of 2014 MRS Spring Meeting ; Conference Date: 21 April 2014 Through 25 April 2014; Conference Code:110472International audienceThis paper describes the organometallic synthesis of pure rhenium nanoparticles (Re NPs) and their characterization by a combination of state-of-the art techniques (TEM, HAADF-STEM, EDX, WAXS, EA, FT-1R). The Re NPs synthesis is achieved by reducing the [Re2(C3H5)4] complex in solution under a dihydrogen atmosphere and in the presence of hexadecylamine or polyvinylpyrrolidone as stabilizing agents. The so-obtained Re NPs are monodisperse with a mean size of 1.1 nm (0.3) nm and display a spherical shape with a disordered hcp structure

Facile synthesis of ultra-small rhenium nanoparticles

cited By 15International audienceUltra-small monodisperse rhenium nanoparticles (Re NPs; ca. 1.0-1.2 nm) were easily prepared by reducing the organometallic complex [Re 2(C3H5)4] under a dihydrogen atmosphere under mild reaction conditions (3 bar H2; 120 °C). The particles can be stabilized by a ligand, hexadecylamine, or a polymer, polyvinylpyrrolidone and accommodate surface hydrides

“Live” Prussian blue fading by time-resolved X-ray absorption spectroscopy

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Why does Prussian blue fade? Understanding the role(s) of the substrate

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