In this paper we study and compare the anodic and cathodic electrodeposition of Metal–Organic Frameworks (MOFs) and suggest guidelines for the electrodeposition of new MOFs with this technique. KHUST-1 was electrodeposited both anodically and cathodically and a four step mechanism is proposed to explain the anodic synthesis.
The growth of gold nanoparticles (NPs) synthesized by sputter deposition on an ionic liquid surface is studied in situ in the bulk phase of the ionic liquids (ILs) 1-butyl-3-methylimidazolium dicyanamide [C(1)C(4)Im][N(CN)(2)], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [C(1)C(4)Im][Tf(2)N], 1-butyl-3-methylimidazolium tetrafluoroborate [C(1)C(4)Im][BF(4)], 1-butyl-3-methylimidazolium hexafluorophosphate [C(1)C(4)Im][PF(6)] and 1-butyl-3-methylimidazolium triflate [C(1)C(4)Im][TfO]. It is found that primary nanoparticles with a diameter smaller than 2.5 nm are present in the sample immediately after sputtering. Growth of these primary particles proceeds after the end of the sputtering process and stops when the nanoparticles reach a certain size. Depending on the viscosity of the ionic liquid this growth process can proceed several hours to several days. The growth speed is fastest for the least viscous ionic liquid and follows the trend [C(1)C(4)Im][N(CN)(2)] > [C(1)C(4)Im][Tf(2)N] > [C(1)C(4)Im][TfO] > [C(1)C(4)Im][BF(4)] > [C(1)C(4)Im][PF(6)]. It is also found that a higher concentration of sputtered gold results in faster growth of the gold nanoparticles. A discussion on the growth mechanism of sputtered gold NPs is included.
The stability of gold nanoparticles synthesised by sputter deposition has been studied in situ in 1-butyl-3-methylimidazolium ionic liquids with bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate and dicyanamide anions with UV-VIS absorption spectroscopy and transmission electron microscopy. Besides the growth of the gold nanoparticles, two other processes were observed after sputtering, namely aggregation and sedimentation of these nanoparticles. To model the absorption spectra of the sputtered gold nanoparticles, generalized multiparticle Mie calculations were performed. These theoretical calculations confirm the increase in absorbance at longer wavelength for larger aggregates and are in agreement with the experimental observations. It was found that the kinetics of aggregation and sedimentation scale with the viscosity of the ionic liquid. Small amounts of water were found to have a large detrimental influence on the stability of the colloidal suspensions of the gold nanoparticles in ionic liquids. From the large discrepancy between the theoretical and the experimentally observed stability of the NPs, it was concluded that structural forces stabilize the gold nanoparticles. This was also borne out by AFM measurements.
Composite supercapacitor electrodes based on carbon nanotubes, carbon black, and a metal–organic framework with iron(III) coordination centers [MIL‐100(Fe), MIL‐88B(Fe), or MIL‐53(Fe)] were prepared and tested with several aqueous electrolytes. A correlation between hydrated ion size and the electric response of the electrodes was found, which sheds light on how these materials work as energy‐storage devices. MIL‐100(Fe) shows the most promising results, and the capacitance obtained with the samples in the solutions used is higher than that of a mixture of carbon and nanotubes in the same solution. Unfortunately, shortcomings due to reductive dissolution still hamper the long‐term cyclability of the electrodes.
Liquid metal salts are electrolytes with the highest possible metal concentration for electrodeposition, because the metal ion is an integral part of the solvent. This paper introduces the new ionic silver complexes [Ag(MeCN)(4)](2)[Ag(Tf(2)N)(3)], [Ag(MeCN)][Tf(2)N] and [Ag(EtIm)(2)][Tf(2)N], where MeCN stands for acetonitrile, EtIm for 1-ethylimidazole and Tf(2)N is bis(trifluoromethylsulfonyl)imide. These complexes have been characterized by differential scanning calorimetry, single crystal X-ray crystallography, thermogravimetrical analysis, Raman spectroscopy and cyclic voltammetry. [Ag(MeCN)(4)](2)[Ag(Tf(2)N)(3)] is a room temperature ionic liquid. Smooth silver layers of good quality could be deposited from it, at current densities of up to 25 A dm(-2) in unstirred solutions. [Ag(EtIm)(2)][Tf(2)N] melts at 65 °C and can be used as an electrolyte for silver deposition above this temperature. [Ag(MeCN)][Tf(2)N] has a melting point that is too high to be useful in electrodeposition. Addition of thiourea or 1H-benzotriazole to the electrolyte decreased the surface roughness of the silver coatings. The morphology of the metal layers was investigated by atomic force microscopy (AFM). Adsorption of 1H-benzotriazole on the silver metal surface has been proven by Raman spectroscopy. This work shows the usefulness of additives in improving the quality of metal films electrodeposited from ionic liquids.
The deposition profile of metal around particles during electrodeposition was studied by atomic force microscopy measurements. In addition to these measurements, the local metal deposition rate around particles was determined from electrodeposited nickel–iron multilayers using “process archeology.” A strong correlation was found between the metal deposition profile and the surface properties of the particles. Hydrophilic particles are pushed ahead by metal that deposits underneath the particles before they become incorporated. Metal deposition does not take place underneath hydrophobic particles, hence incorporating from the start of the metal deposition. For electrically conductive particles, metal deposits on the particles which causes such particles to incorporate almost immediately.
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