Laser ablation synthesis of metal-doped gold clusters from composites of gold nanoparticles with metal organic frameworks

Abstract

Metal-doped gold clusters, mainly cages, are receiving rapidly increasing attention due to their tunable catalytic properties. Their synthesis is mostly based on complex procedures, including several steps. In this work, via adsorption of gold nanoparticles (AuNPs) from aqueous solution to MOF (metal organic frameworks) of M = Co, Cu, Ni, and Zn with various linkers the {AuNPs, MOF} composites were prepared. These composites were used for laser ablation synthesis (LAS) using a common mass spectrometer. Several series of positively and negatively charged AumMn+/− clusters were observed in mass spectra and their stoichiometry (m = 1–35, n = 1–5) was determined. For each dopant (Co, Cu, Ni, and Zn) ~ 50 different clusters were identified in positive, as well as in negative ion modes. About 100 of these clusters were proposed to be endohedral metal-doped gold cages (for m > 12). The developed approach represents a simple procedure for generating metal-doped gold clusters or endohedral metal-doped gold cages materials with potential applications in medicine and/or electronics.

Laser-Assisted Design of MOF-Derivative Platforms from Nano- to Centimeter Scales for Photonic and Catalytic Applications

“…However, the laser conversion, metallurgy, manufacturing, annealing, scribing, or even ablation of hierarchical metal–organic materials like MOFs was started less than 4 years ago. , Nevertheless, these results are highly promising for photonics, electronics, and catalysis. Indeed, the laser conversion of MOFs makes it possible to obtain complex and even unique forms of nanomaterials such as metal oxides, , carbides and sulfides, multicomponent alloys, ,,− carbon, and metal–carbon and organometallic nanostructures, ,, as well as to initiate the structural defects and laser writing. ,, Most of these works have been carried out in the nanosecond laser regime, paying special attention to the effect of the initial structure and composition of the MOF precursors − ,− , and the laser power ,,,,, on the decomposition yield.…”

“…Indeed, the laser conversion of MOFs makes it possible to obtain complex and even unique forms of nanomaterials such as metal oxides, 24,26 carbides 40 and sulfides, 41 multicomponent alloys, 28,31,42−44 carbon, 29 and metal−carbon and organometallic nanostructures, 30,32,45 as well as to initiate the structural defects 46 and laser writing. 25,27,47 Most of these works have been carried out in the nanosecond laser regime, paying special attention to the effect of the initial structure and composition of the MOF precursors [24][25][26][27][28][29][30][31][32][40][41][42][43][44][45]48 and the laser power 24,25,27,30,40,43 on the decomposition yield.…”

DFT investigation of pyramidal Au\(_{9}\)M\(^{2+}\) and Au\(_{19}\)M (M = Sc-Ni): Similarities and Differences of Structural Evolution, Electronic and Magnetic Properties

“…It is worth to mention that the study of potential superatoms is not limited to the monoatomic species. A considerable amount of experimental and theoretical investigations has been carried out on gold clusters doped with transition metal (M) atoms in order to obtain novel species with the desired structural, magnetic, and chemical properties [23][24][25][26]. For instance, Li and coworkers used the laser evaporation technique to produce M@Au 6 clusters (M=Ti, V, Cr) in the gas phase and measure their photoelectron spectra using the high-energy laser excimer [27].…”

Reversible and Irreversible Laser Interference Patterning of MOF Thin Films

“…In this sense, regardless of its photosensitivity, MOF can be considered as an ideal model crystal for creating micrometer-scale patterns inside or on the surface of a crystal for sensing, light control, and image development. Indeed, the porosity and the high degree of optical transparency of some MOFs [17] facilitate the step-by-step, three-dimensional laser drawing of QR codes through multiphoton absorption [17][18][19]; alternatively, the complex chemical composition of MOFs provides a step-by-step laser drawing of metal contacts for electrical circuits [13], capacitors [20] or for producing new types of functional nanoclusters [21][22][23][24]. Nevertheless, the concept of single-step interference laser patterning has not yet been implemented for MOFs.…”