Elemental (im-)miscibility determines phase formation of multinary nanoparticles co-sputtered in ionic liquids.

Non-equilibrium synthesis methods allow the alloying of bulk-immiscible elements into multinary nanoparticles, which broadens the design space for new materials. Whereas sputtering onto solid substrates can combine immiscible elements into thin film solid solutions, this is not clear for sputtering of nanoparticles in ionic liquids. Thus, the suitability of sputtering in ionic liquids for producing nanoparticles of immiscible elements is investigated by co-sputtering the systems Au-Cu (miscible), Au-Ru and Cu-Ru (both immiscible), and Au-Cu-Ru on the surface of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][(Tf)2N]. The sputtered nanoparticles were analyzed to obtain (i) knowledge concerning the general formation process of nanoparticles when sputtering onto ionic liquid surfaces and (ii) information, if alloy nanoparticles of immiscible elements can be synthesized as well as (iii) evidence if the Hume-Rothery rules for solid solubility are valid for sputtered nanoparticles. Nanoparticle characteristics were found to depend on elemental miscibility: (1) nanoparticles from immiscible elemental combinations showed bigger mean diameters ranging from (3.3 ± 1.4) nm to (5.0 ± 1.7) nm in contrast to mean diameters of nanoparticles from elemental combinations with at least one miscible element pair ((1.7 ± 0.7) nm to (1.8 ± 0.6) nm). (2) Nanoparticles from immiscible combinations showed compositions with one element strongly dominating the ratio and very narrow differences between the highest and lowest fraction of the dominating element (Cu94Ru6 to Cu100Ru0; Au96Ru4 to Au99Ru1) in contrast to the other compositions (Au64Cu36 to Au81Cu19; Au83Cu13Ru4/Au75Cu22Ru3 to Au87Cu11Ru2). Accompanying atomistic simulations using density-functional theory for clusters of different size and ordering confirm that the miscibility of Au-Cu and the immiscibility of Au-Ru and Cu-Ru govern the thermodynamic stability of the nanoparticles. Based on the matching experimental and theoretical results for the NP/IL-systems concerning NP stability, a formation model of multinary NPs in ILs was developed.

Sputter deposition of highly active complex solid solution electrocatalysts into an ionic liquid library: effect of structure and composition on oxygen reduction activity.

Complex solid solution electrocatalysts (often called high-entropy alloys) present a new catalyst class with highly promising features due to the interplay of multi-element active sites. One hurdle is the limited knowledge about structure-activity correlations needed for targeted catalyst design. We prepared Cr-Mn-Fe-Co-Ni nanoparticles by magnetron sputtering a high entropy Cantor alloy target simultaneously into an ionic liquid library. The synthesized nanoparticles have a narrow size distribution but different sizes (from 1.3 ± 0.1 nm up to 2.6 ± 0.3 nm), different crystallinity (amorphous, face-centered cubic or body-centered cubic) and composition (i.e. high Mn versus low Mn content). The Cr-Mn-Fe-Co-Ni complex solid solution nanoparticles possess an unprecedented intrinsic electrocatalytic activity for the oxygen reduction reaction in alkaline media, some of them even surpassing that of Pt. The highest intrinsic activity was obtained for body-centered cubic nanoparticles with a low Mn and Fe content which were synthesized using the ionic liquid 1-etyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Emimi][(Tf)2N].

On the Effects of Diluted and Mixed Ionic Liquids as Liquid Substrates for the Sputter Synthesis of Nanoparticles.

The synthesis of nanoparticles by combinatorial sputtering in ionic liquids is a versatile approach for discovering new materials. Whereas the influence on nanoparticle formation of different pure ionic liquids has been addressed, the influence of (I) dilution of ionic liquid with solvents and (II) different mixtures of ionic liquids is less known. Therefore, mixtures of the ionic liquid [Bmim][(Tf)2N] with the organic solvent anisole and other ionic liquids ([Bmim][(Pf)2N], [BmPyr][(Tf)2N]) were used as liquid substrates for the sputter synthesis of nanoparticles, in order to investigate the influence of these mixtures on the size of the nanoparticles. First, mixtures of anisole with a suspension of sputtered Ag nanoparticles in [Bmim][(Tf)2N] were prepared in different volumetric steps to investigate if the stabilization of the NPs by the ionic liquid could be reduced by the solvent. However, a continuous reduction in nanoparticle size and amount with increasing anisole volume was observed. Second, Ag, Au and Cu were sputtered on ionic liquid mixtures. Ag nanoparticles in [Bmim][(Tf)2N]/[Bmim][(Pf)2N] mixtures showed a decrease in size with the increasing volumetric fraction of [Bmim][(Tf)2N], whereas all nanoparticles obtained from [Bmim][(Tf)2N]/[BmPyr][(Tf)2N] mixtures showed increasing size and broadening of the size distribution. Maximum sizes of sputtered Ag and Au NPs were reached in mixtures of [Bmim][(Tf)2N] with 20 vol.% and 40 vol.% [BmPyr][(Tf)2N]. The results indicate that ionic liquid mixtures with different portions of cations and anions have the capability of influencing the ionic liquid stabilization characteristics with respect to, e.g., nanoparticle size and size distribution.

Synthesis of plasmonic Fe/Al nanoparticles in ionic liquids.

Bottom-up and top-down approaches are described for the challenging synthesis of Fe/Al nanoparticles (NPs) in ionic liquids (ILs) under mild conditions. The crystalline phase and morphology of the metal nanoparticles synthesized in three different ionic liquids were identified by powder X-ray diffractometry (PXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), selected-area electron diffraction (SAED) and fast Fourier transform (FFT) of high-resolution TEM images. Characterization was completed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) for the analysis of the element composition of the whole sample consisting of the NPs and the amorphous background. The bottom-up approaches resulted in crystalline FeAl NPs on an amorphous background. The top-down approach revealed small NPs and could be identified as Fe4Al13 NPs which in the IL [OPy][NTf2] yield two absorption bands in the green-blue to green spectral region at 475 and 520 nm which give rise to a complementary red color, akin to appropriate Au NPs.

Design of Complex Solid-Solution Electrocatalysts by Correlating Configuration, Adsorption Energy Distribution Patterns, and Activity Curves.

Complex solid-solution electrocatalysts (also referred to as high-entropy alloy) are gaining increasing interest owing to their promising properties which were only recently discovered. With the capability of forming complex single-phase solid solutions from five or more constituents, they offer unique capabilities of fine-tuning adsorption energies. However, the elemental complexity within the crystal structure and its effect on electrocatalytic properties is poorly understood. We discuss how addition or replacement of elements affect the adsorption energy distribution pattern and how this impacts the shape and activity of catalytic response curves. We highlight the implications of these conceptual findings on improved screening of new catalyst configurations and illustrate this strategy based on the discovery and experimental evaluation of several highly active complex solid solution nanoparticle catalysts for the oxygen reduction reaction in alkaline media.

Enhanced antibacterial performance of ultrathin silver/platinum nanopatches by a sacrificial anode mechanism.

The development of antibacterial implant surfaces is a challenging task in biomaterial research. We fabricated a highly antibacterial bimetallic platinum (Pt)/silver(Ag) nanopatch surface by short time sputtering of Pt and Ag on titanium. The sputter process led to a patch-like distribution with crystalline areas in the nanometer-size range (1.3-3.9 nm thickness, 3-60 nm extension). Structural analyses of Pt/Ag samples showed Ag- and Pt-rich areas containing nanoparticle-like Pt deposits of 1-2 nm. The adhesion and proliferation properties of S. aureus on the nanopatch samples were analyzed. Consecutively sputtered Ag/Pt nanopatches (Pt followed by Ag) induced enhanced antimicrobial activity compared to co-sputtered Pt/Ag samples or pure Ag patches of similar Ag amounts. The underlying sacrificial anode mechanism was proved by linear sweep voltammetry. The advantages of this nanopatch coating are the enhanced antimicrobial activity despite a reduced total amount of Ag/Pt and a self-limited effect due the rapid Ag dissolution.

Combinatorial Synthesis of Binary Nanoparticles in Ionic Liquids by Cosputtering and Mixing of Elemental Nanoparticles.

Binary alloy nanoparticles were fabricated by two combinatorial methods: (I) cosputtering from elemental targets into the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][(Tf)2N] and (II) by mixing elemental nanoparticles after sputtering them separately into [Bmim][(Tf)2N]. Both methods lead to the formation of Au-Cu nanoparticles (2.3 nm for cosputtered, 3.6 nm for mixed), however with different resulting compositions: cosputtered nanoparticles show a composition range of Au80-90Cu20-10; mixing of Au- and Cu-loaded ionic liquids leads to the formation of Au75Cu25 nanoparticles. Annealing the binary nanoparticles at 100 °C shows that the mixed nanoparticles grow to sizes of 4.1 nm, whereas the cosputtered nanoparticles grow only to 3 nm.

Rapid Assessment of Sputtered Nanoparticle Ionic Liquid Combinations.

A high-throughput method is presented for the efficient assessment of the formation and stability of nanoparticle suspensions in ionic liquids which differ in their cations and anions. As a proof of principle, Ag was sputtered on a cavity array filled with 9 different ionic liquids. Not all nanoparticle ionic liquid combinations form a stable suspension with separated nanoparticles. Directly after synthesis, the formation of nonagglomerated nanoparticle suspensions with sizes from 4 to 9 nm is observed by transmission electron microscopy as well as different time dependencies of the suspension stabilities. Only 3 out of the tested 9 nanoparticle ionic liquid suspensions show long-term stability: Stable suspension of spherical nanoparticles are formed in the ionic liquids 1-butyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide [Bmim][(Pf)2N], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][(Tf)2N], and 1-butyl-1-methylpyrrolidinum bis(trifluoromethylsulfonyl)imide [BmPyr][(Tf)2N].