RSC Advances View Article Online PAPER View Journal | View Issue Kinetically-controlled laser-synthesis of colloidal high-entropy alloy nanoparticles† Cite this: RSC Adv.,2019,9, 18547 Friedrich Waag,a Yao Li,a Anna Rosa Ziefuß,a Erwan Bertin,‡a Marius Kamp,b Viola Duppel,c Galina Marzun,a Lorenz Kienle,b Stephan Barcikowski a a and Bilal Gokce¨ * The single-step incorporation of multiple immiscible elements into colloidal high-entropy alloy (HEA) nanoparticles has manifold technological potential, but it continues to be a challenge for state-of-the- art synthesis methods. Hence, the development of a synthesis approach by which the chemical composition and phase of colloidal HEA nanoparticles can be controlled could lead to a new pool of nanoalloys with unparalleled functionalities. Herein, this study reports the single-step synthesis of colloidal CoCrFeMnNi HEA nanoparticles with targeted equimolar stoichiometry and diameters less than 5 nm by liquid-phase, ultrashort-pulsed laser ablation of the consolidated and heat-treated micropowders of the five constituent metals. Further, the scalability of the process with an Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Received 1st May 2019 unprecedented productivity of 3 grams of colloidal HEA nanoparticles per hour is demonstrated. Accepted 29th May 2019 Electrochemical analysis reveals a unique redox behavior of the particles' surfaces in an alkaline DOI: 10.1039/c9ra03254a environment and a potential for future application as a heterogeneous catalyst for the oxygen evolution rsc.li/rsc-advances reaction. Introduction industrial application. In another recent approach, CoCrCuFeNi-HEA NPs with 9 nm diameter immobilized on High-entropy alloys (HEAs) have evolved to one of the most graphene were synthesized by mechanical ball milling of single This article is licensed under a popular material classes in the last decades in both funda- metal powders mixed with graphene.14 This solid-state mental and applied material science.1–3 Unique mechanical,4–6 synthesis is more convenient than the carbothermal shock electromagnetic,7–9 and electrochemical10–12 properties originate synthesis but cannot achieve the targeted chemical distribution Open Access Article. Published on 12 June 2019. Downloaded 10/1/2021 7:45:34 PM. from their multi-elemental, solid-solution character. However, of the NPs. A production route for CoCrCuNiAl-HEA NPs with an research has been focused primarily on bulk HEA, ignoring HEA average diameter of 14 nm is based on the popular sol–gel nanoparticles (NPs), due to the absence of a reliable, scalable, autocombustion process.15 However, no colloidal NPs have been and straightforward synthesis method for HEA NPs. Very produced by the method so far, and the chemical compositions recently, HEA NPs with up to eight elements, i.e., Pt, Pd, Co, Ni, of the NPs that were synthesized were not studied in detail. By Fe, Cu, Au, and Sn, were produced by the carbothermal shock plasma arc discharge synthesis, CoCrCuFeNi-HEA NPs of synthesis.13 The remarkable method allows uniform elemental average diameters larger than 80 nm were produced in a reac- distributions in single NPs that thereaer are kinetically tive gas atmosphere.16 This method is advantageous in terms of controllable in size by the shock duration with a minimum simplicity and scalability but is bound to the gas phase and diameter of 3 nm. However, carbothermal shock synthesis only yields only large HEA NPs. produces NPs immobilized on conductive, surface-oxidized In brief, none of the above-mentioned studies describes the carbon support materials, and that limits the possibilities for synthesis of colloidal HEA NPs. There are only two known synthesis approaches for isolated, colloidal HEA NPs. The rst approach was published in 2015.17 A common wet chemical aTechnical Chemistry I, Center for Nanointegration Duisburg-Essen (CENIDE), approach was used and the obtained NPs had large diameters University of Duisburg-Essen, 45141 Essen, Germany. E-mail: [email protected] (26.7 nm) with strong deviations in the chemical composition bSynthesis and Real Structure, Institute for Materials Science, Kiel University, 24143 from the targeted equimolar CoCrCuFeNi. The second Kiel, Germany cNanochemistry, Max Planck Institute for Solid State Research, 70569 Stuttgart, approach yielded in ultrasmall CoCrFeMnNi NPs with diame- Germany ters ranging from 2 to 4 nm with either amorphous or crystal- 18 † Electronic supplementary information (ESI) available. See DOI: line structure depending on the experimental parameters. By 10.1039/c9ra03254a sputtering material from a nearly equimolar HEA target into an ‡ Present address: Department of Chemistry, University of Calgary, Calgary, AB, ionic liquid, NPs can be synthesized instead of lms usually T2N 1N4, Canada. This journal is © The Royal Society of Chemistry 2019 RSC Adv.,2019,9,18547–18558 | 18547 View Article Online RSC Advances Paper obtained by the method. However, the required ionic liquid and bulk targets immersed in liquids.26 In the zoom into the the complexity of the method strongly limit its applicability. atomic scale, we considered the likely ablation process and Accordingly, since the rst observation of spherical nano- NP formation for the laser ablation of a HEA ablation target. precipitations in bulk HEA,19 no successful, scalable synthesis In brief, a laser beam of sufficient energy uence irradiates of colloidal HEA NPs with targeted elemental composition has the surface of a bulk HEA (Fig. 1a), leading to the formation been reported. of a plume. Later a cavitation bubble is formed (Fig. 1b) by In this work, we demonstrate the simple, reproducible, and the ablation of hot atoms, ions and clusters from the bulk scalable synthesis of isolated, colloidal NPs of the equimolar HEA and their mixing with the liquid's vapor (Fig. 1b, le CoCrFeNiMn HEA, rst investigated by Cantor et al.,20 by zoom). Then, the plume cools and the ablated species picosecond-pulsed laser ablation of a solid CoCrFeNiMn HEA condense (Fig. 1b, right zoom). Ultimately, the growth of the target immersed in a ow cell. Since the rst report on laser condensates is quenched and they are released as NPs to the synthesis of colloids was published,21 the method ultimately liquid during the collapse of the cavitation bubble (Fig. 1c). became a competitive method for the synthesis of NP The HEA ablation targets were produced by mixing, pressing, colloids.22–25 With this synthesis approach, we were able to and heat-treating of micropowders of the single metals. obtain highly stable colloids of isolated HEA NPs without the Fig. S1 (ESI†)showsasimplied sketch of the different steps use of any ligands for stabilization. To demonstrate the indus- in the entire procedure, starting at single metal micro- trial applicability, we also investigated the reproducibility and powders and resulting in NPs. scalability of the laser-based method. The investigation of the Analytic disc centrifugation (ADC) analysis of the liquids reproducibility of the approach included the evaluation of the synthesized by laser-ablation of HEA targets revealed the performance of the as-synthesized NPs of the CoCrFeNiMn HEA presence of NPs with a bimodal volume-weighted size loaded on carbon black (CB) for the oxygen evolution reaction distribution with peak maxima at hydrodynamic diameters of (OER) in alkaline environment. 7.7 and 87.7 nm (Fig. 2a). It remained unclear from the ADC Creative Commons Attribution-NonCommercial 3.0 Unported Licence. measurement, if particles larger 300 nm existed in the colloid. By transmission electron microscopy, no particles Results and discussion with Feret diameters larger than 100 nm were found (Fig. S2 Colloidal state of the laser ablation product and S13, ESI†). Furthermore, a size fraction smaller than the Picosecond-pulsed laser ablation of CoCrFeMnNi HEA limit for reliable detection of NPs with moderate gravi- targets in ethanol yielded brownish-colored, transparent metrical density by ADC showed up during TEM analysis. ff liquids, indicating the formation of a NP colloid. Fig. 1 shows Analytical ultracentrifugation (AUC) was applied at di erent a qualitative representation of the general formation mech- rotation speeds for a statistically reliable determination of anism of NPs during picosecond-pulsed laser ablation of the size distribution at small diameters. This article is licensed under a Open Access Article. Published on 12 June 2019. Downloaded 10/1/2021 7:45:34 PM. Fig. 1 Qualitative representation of the laser-based synthesis of high-entropy alloy nanoparticles. The synthesis method consisted of the following stages: ultrashort-pulsed laser irradiation of the bulk high-entropy alloy (HEA) (a), the atomization/ionization of the bulk causing the formation of a plume, and subsequent nucleation and condensation of the ablated matter in the vapor phase of the liquid (b) and the colloidal high-entropy alloy nanoparticles electrostatically stabilized in ethanol (c). 18548 | RSC Adv.,2019,9,18547–18558 This journal is © The Royal Society of Chemistry 2019 View Article Online Paper RSC Advances mechanisms in the picosecond-pulsed laser synthesis of colloids.28 Whereas ultrasmall NPs originate from nucleation and condensation in a low-density mixing region of the ablated metal species and the liquid environment in a supercritical state, larger NPs emerge from a highly dynamic molten layer on the surface of the ablation target due to Rayleigh–Taylor insta- bility. However, the main product of the picosecond-pulsed laser ablation consisted of ultrasmall NPs, predicted to be formed in the low-density region.26 The small hydrodynamic diameters of laser-generated NPs result from fast kinetics. À Cooling rates of the condensates in the order of 1012 Ks 1 can be expected,26 and passivation of the surface of the NPs that occurs by the interaction with solvent species suppresses further growth.29,79 Crystal structure of the laser-generated nanoparticles Next, we investigated the crystal structure of NPs by X-ray diffraction (XRD), selected area electron diffraction (SAED), and high-resolution transmission electron microscopy (HRTEM).