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Nanoparticles synthesis by Laser Ablation in Liquid

Nanoparticles synthesis by Laser Ablation in Liquid

Antonio Santagata  - antonio.santagata@ism.cnr.it

LIBS-FTIR/FemtoLAB

Tito Scalo (Pz)
 
The laser ablation process performed in liquid, referred to Laser Ablation or Pulsed Laser Ablation in Liquid, LAL  Pulsed Laser Ablation in Liquid or PLAL, Laser Ablation Synthesis in Solution - LASIS) allows to generate colloidal solutions of nanoparticles without using neither chemical reagents nor stabilizers. The great success of the technique is due to its ability in obtaining, with relative simplicity, solutions of nanoparticles of any material (metals, oxides, carbides, alloys etc.). As a consequence to the absence of any contamination deriving from chemical synthesis, LAL can open new scenarios for the use of the synthesised species in both new devices and as catalysts or reagents.
By "ablation" one refers to the "vaporization" induced, in the form of plasma, of a solid material. The process is characterized by the complex interaction mechanism that is generated by focusing a high power laser beam onto the surface of a target material. The generation and expansion of the plasma in liquid involves firstly the formation of a shock wave and then of a cavitation bubble. This bubble, whose expansion is limited by the surrounding liquid, is confined and compressed until collapsing and oscillating with the formation of new damped cavitation bubbles. During the cavitation bubbles collapse repeated coalescence phenomena of the "vaporized" species is involved which give rise to colloidal solutions of nanoparticles (NPs) of the ablated material. The NPs, which are negatively charged, have high stability even in the absence of surfactants and can often have surface layers (e.g. core shell) of oxides or other components coming from the solvent or other components on purpose added to the solution. The parameters that control the process are connected both to the pulsed laser used (e.g. pulse duration) and to the type of liquid, or type of solution, which, the species produced after the collapse process of the cavitation bubble, can continue to react.
The LAL activities are also carried out in collaboration with the Physical-Chemistry Laser Laboratory of the University of Basilicata which expands the offer by the availability of other experimental equipments and techniques for characterizing the obtained NPs (e.g. HR-TEM).
 

TECHNICAL SPECIFICATIONS

  • Spectra Physics Ti:Sa “fs” Laser
    Spitfire Pro - Regenerative Amplifier (120 fs; 1kHz; 4 mJ @ 800 nm; SH: 1.5 mJ @ 400 nm)
  • Quanta System Nd:YAG “ns” Laser
    Prototype (7 ns; 10 Hz; 100 mJ @ 532 nm)
  • Time resolved shadowgraphy
    • Andor iStar “Inductively Charge Couple Device – ICCD” camera (t ≥ 2 ns; Spectral range = 250-900 nm, Pixeldim = 13 μm x 13 μm)

AVAILABLE TECHNIQUES

  • Production of colloidal solutions of nanoparticles  

  • Expansion dynamics of the cavitation bubbles and shock waves by shadowgraphy  

 

SAMPLES

  • Flat samples with lateral dimension 10  mm x 10 mm (minimum) and 15 mm x 25 mm (maximun); thickness 15 mm (maximun).
 

USED FOR

  • Catalysts

  • Biosensors

  • Colorimetric sensors

  • Biomedical applications

  • Optoelectronics

  • Nanocomposites

 
 

CASE STUDIES

Generation of Nanodiamonds

During the collapse of the cavitation bubbles of the LAL process both high temperatures (thousands of K) and high pressures (GPa) can be reached. These parameters play a relevant role within the condensation process of the ablated species which can lead to the formation of metastable phases. For instance, nanodiamonds can be formed through simple ablation of graphite submerged in water by employing fs laser pulses. However, in order to obtain nanodiamonds, a proper laser repetition rate should be employed. As a matter of fact, the nanoparticles produced by LAL can change their properties as a function of the fs pulsed laser repetition rate used, which, as shown with Raman spectroscopy, switch, from diamond-like carbon (DLC),  nanoparticles (10-100 Hz) to nanodiamonds (1 kHz)

See: Antonio, Santagata et al. J. Phys. Chem. C 115, 5160 (2011)
DOI: 10:1021/jp1094239

 
 
 

Microtubes formation by selfassembling of NPs

The ablation by fs pulses of metallic Ti submerged in water, leads to the formation of Ti species having different oxidation states, that means the co-presence of Ti2O3, TiO2 and TiOH NPs in which rutile (TiO2)represents the crystalline phase. Although the NPs dimensions are in the range of 5-100 nm, the most probable ones have diameters between 5-10 nm. The main feature of the ablation process induced by fs laser pulses performed in these conditions is, however, characterized by the presence of nanoscopic lamellae which, together with the NPs, give rise, after a few days of permanence in solution, to the formation of nanofilaments of length and thickness of tens and a few nanometers, respectively. The permanence of these nanostructures in solution (e.g. > 7 days) induces the spontaneous formation of microtubes having length and diameter of the internal wall of some mm and 2 µm, respectively. The mechanism of microtube formation, onto which the NP aggregate by coalescence, it is related the presence of TiOH species and the whole chemistry induced in solution by the LAL process itself.μm.

See: Angela, De Bonis et al. Surf. Coat. Tech. 207, 279 (2012)   
DOI: 10.1016/j.surfcoat.2012.06.084

 
 

Silver-silica core-shells nanocomposites prepared from nanoporous silica and silver target by ultra-short pulsed laser ablation in liquid

Hexagonally ordered mesoporous silica materials, MCM-41 and SBA-15, have been synthesized and loaded with Ag nanoparticles (Ag/SBA-15 and Ag/MCM-41), utilizing both chemical synthesis and ultra-short pulsed laser ablation in liquid. All preparations have significant amount of 5–50 nm size silver agglomerates on the outer surface of the silica particles. The laser ablation process did not cause significant destruction of the SBA-15 structure and metallic silver (Ag0) nanoparticles were mainly generated. Moreover, it has been also evidenced by us also the formation of stable silver-silica core-shell (Ag@SBA-15 and Ag@MCM-41) nanoparticles by direct laser ablation of a Ag target submerged in a static colloidal solution of MCM-41 or SBA-15 silica nanoporous materials. The outcomes show that the choice of the mesoporous silica material can affect the silica shell thickness in addition to the Ag NPs size distribution.

See:

  • Ágnes, Szegedi, et al., Appl. Phys. A 117, 55 (2014) DOI: 10.1007/s00339-014-8499-8
  • Antonio, Santagata, et al., J. Phys. D: Appl. Phys. 48, 205304 (2015)  
  • DOI: 10.1088/0022-3727/48/20/205304

Contact: Ambra Guarnaccio - ambra.guarnaccio@ism.cnr.it

 
 
 
 

Magnetic Nano-Architecture Laboratory

Magnetic Nano-Architecture Laboratory

Davide Peddis (associato ISM)  - davide.peddis@ism.cnr.it

Magnetic Nano-Architecture Laboratory (nM2-Lab)

Rome - Monterotondo
 
Magnetic Nano-Architecture Laboratory has the expertise on design and synthesis by chemical methods of nano-hetero-structure (e.g. controlled morphology nanoparticles, core-shell and multi-shell bi-magnetic structures, superstructures of nanoparticles) with a magnetic nano-core (e.g. Fe2O3, CoFe2O4, NiO, LaCaMnO4; BaFeO3) suitably functionalized with specific molecules ( e.g. amorphous silica also mesostructured, zirconia, organic molecules). In addition, such magnetic nanoarchitectures magnetic nanoparticles can used as building blocks to prepare 2-D and 3-D magnetic super-structures, opening the possibility to prepare a new generation of tailored multifunctional materials with new and tunable physical properties (e.g. magnetic, transport, electronic).
 

TECHNICAL SPECIFICATIONS

  • Stirring / heating plates also with PID regulation system (Tmax 350°C.)
  • ines with rotary vacuum (P = 2x10-3 mmHg)

AVAILABLE TECHNIQUES

  • Chemical synthesis

 

SAMPLES

  • The prepared samples are usually powders or crystals in quantities of the order of 10-1000 mg.

 

USED FOR

  • Biomedical Application (MRI, Magnetic Hyperthermia)

  • Permanent magnet

  • Cultural Heritage

  • Catalysis

  • Thermoelectric applications

 

CASE STUDIES

magnetic nanoparticles and complex magnetic nano architecture

MNAL design and synthetize high-quality magnetic nanoparticles with different size and morphology in order to tune the magnetic properties (i.e. magnetic anisotropy and saturation magnetization) by shape and surface effects. In figure example of spinel iron oxide nanoparticles, even with complex stoichiometry, with cubic and star shape and hollow morphology are reported. Also bi-magnetic and multi-magnetic system can be synthetized in order to exploit interface effect to tune magnetic properties (e.g. Ferro/Ferri/Antiferro interface) or to design new multifunctional materials (e.g. Ferro(Ferri)/Ferroeletric/multiferroic interface). Nanoparticles can be also used as building block to design complex magnetic supracrustal: last panel in figure shows NiFe2O4 Suprastructures synthetized under magnetic field.

See:

  • F. Sayed, [..] and D. Peddis*, Journal of Physical Chemistry C 112F, 7516-7524, (2018)
  • G. Muscas, [..] and D. Peddis*, Nanoscale 8, 2081 (2016)
  • G. Muscas, N. [..…] and D. Peddis*, Nanoscale 7, 13576 (2015)
 
 
 

Organic Inorganic Hybrid Magnetic Nanoarchitecture

Organic Inorganic Hybrid Magnetic Nanoarchitecture As an examples Magnetic nano-architectures Magnetic mesoporous silica nanocomposites give the possibility of generating multi-functional objects for application in several technological areas (e.g. MRI, Magnetic Hyperthermia, catalysis, cultural heritage). Also organic molecular coating can strongly change magnetic properties of nanoparticles. As an example we recently study the effect of two representative organic ligands: diethylene glycol (DEG) and oleic acid (OA) bonded at the surface of small (∼5 nm in size)CoFe2O4 particles. The combined results of the bulk dc susceptibility, local-probe Mössbauer spectroscopy and physical modelling, which is based on electronic structure calculations and Monte Carlo simulations, reveal the effect of different ionic distributions of the particles due to the different surfactant layers on their magnetic behavior. They result in an unexpected increase of the saturation magnetization and the blocking temperature, and a decrease of the coercive field of DEG coated CoFe2O4 nanoparticles. Our work pro- vides a pathway for the production of colloidal assemblies of nanocrystals for the engineering of functional nanomaterials.

(Photo: Picture of magnetic nanoparticles of spinel iron oxide embedded in mesoporous silica matrix)

See:

  • M. Vasilakaki, [..] D. Peddis and KN Trohidou,, Nanotechnology 31, 025707 (2020)
  • N. Ntallis, [..], D. Peddis and K. Trohidou, Nanoscale 10, 21244 (2018)
  • N. Z. Knezevic, [..…] and D. Peddis , MRS Advanced 1, 1 (2017)
 
 

Nanocomposites and nanohybrid synthesis

Nanocomposites and nanohybrid synthesis

Elvira Maria Bauer  - elvira.bauer@ism.cnr.it

Laboratory BC5-BC6

Roma - Monterotondo
 
The research activities are focused on the synthesis, analysis and characterization of organic/inorganic hybrid materials and nanomaterials for applications in the fields of sustainable energy and health protection. Hydrothermal synthesis, sol-gel methods, sonochemical synthesis, solid state synthesis, soft chemistry or preparations in high boiling solvents are the most important techniques used in this field for the production of nanoparticles and hybrid materials. Many materials obtained in this way are sensitive the air and therefore their preparation requires specific techniques to ensure the purity and reproducibility of synthetic processes. Preparation methods that exclude the presence of air (Schlenck techniques) and heat treatments in controlled conditions allow to control the preparation processes of these materials.
 

SPECIFIC TECHNIQUES

  • Chemical laboratory equipped with N.5 vacuum-gas inert lines (N2 o Ar) with workstations connected to special filters for oxygen and vacuum pumps
  • Instrumentation for synthesis with Schlenck techniques
  • Hydrothermal bombs (70-200 ml) and programmable stoves (230 ° C)
  • Sublimation/vacuum heat treatment (10-5mbar)
  • Centrifuge, mechanical and orbital shaker
  • Ultrasound probe (Sonics VC 130)
  • pH-meters and automatic titration station
  • ice machine
  • Muffle furnace Nabertherm HT 04/17
  • Tubular oven Lenton LTF 16/75/350
  • Glove-box MBraunLabStar

AVAILABLE TECHNIQUES

  • Chemical synthesis of hybrids and nanoparticles from -20 °C - 1750 °C
    • Schlenck techniques
    • Hydrothermal and sol-gel synthesis
    • Ultrasonic dispersion and synthesis
    • Methods of solvent-deposition and liquid-phase synthesis (self-assembling, surfactant assisted)
    • Tablet production
  • Muffle and tubular furnaces
    • Availability of different working tubes in quartz  
    • Line for working gas (N2, Ar, Ar/H2, H2, NH3)
    • Alumina boats and crucibles
  • Glove-box for handling air-sensitive or dangerous samples   
    • Vapor absorption system for handling liquids
    • Open accessibility after training

 

SAMPLES

  • Hybrid organic-inorganic and nanomaterials

    • Metals and metal oxides
    • Perovskites and spinels
    • Layered and carbon-based hybrids
    • Metallorganic materials

  • Muffle furnace:

    • Finely mixed solid reagents (up to 250 g)
    • Sol-gel samples

  • Tubular oven

    • Finely mixed solid reagents up to 5 g
    • Tmax850 ° C with quartz working tube

  • Glove-box

    • Water-free solids and liquids in vacuum resistant containers (10-2mbar)
    • Glassware, small instruments and non-pointed and non-sharp metal tools
 

USED FOR

  • Synthesis of metal nanoparticles and metal oxides
  • Investigation of commercial products based on organic-inorganic hybrids (tattoo inks)
  • Production of electrode materials for lithium ion batteries
  • Synthesis of ceramics and alloys through chemical solid state synthesis
  • Preparation and handling of inorganic materials, hybrids and air-sensitive nanoparticles
  • Calcinations, Sintering
  • Nitrogen-doping of carbonaceous materials (graphene, CNTs)
  • Reduction/Oxidation of solid materials
  • Organic photovoltaics
 

CASE STUDIES

Magnetic Order through Super-Super Exchange in Cr[(D3N-(CH2)2-PO3)(Cl)(D2O)], a Magnoelettric and Polar Organic-Inorganic Hybrid.

A hybrid layered material consisting of partially deuterated chromium(II) aminoethylphosphonate was prepared by dissolving metallic chromium in DCl under inert atmosphere and mild heating inside a Schlenck tube. The blue solution thus obtained is filtered and transferred under nitrogen into another Schlenck tube containing 2-aminoethylphosphonic acid. After a few days of reaction at 85-90 ° C in an inert environment, an extremely air-sensitive blue microcrystalline precipitate is formed which is sealed in quartz ampoules. The observed strong magnetoelectric coupling was investigated by neutron diffraction on powders and magnetization measurements down to 2 K.
 
See: G. Nénert, H.-J. Koo, C. V. Colins, E. M. Bauer, C. Bellitto, C. Ritter, G. Righini, M.H. Whangbo, Inorg. Chem., 2013, 52, 753-760, doi: 10.1021/ic301874v

 
 
 

Synthesis of LiFePO4 doped with manganese starting from organic-inorganic hybrid precursors  
 
Organic-inorganic hybrids based on phenyl phosphonates containing Fe(II) and Mn(II) were prepared from aqueous solutions by means of Schlenck's techniques. The obtained air-stable solids were mixed with Li2CO3 and used as precursors for the preparation of manganese doped LiFePO4, which is an interesting cathodic material for application in lithium ion batteries. Calcination of the precursor mixtures under inert environment results in the formation of a black powder. The electrochemical behavior of lithium iron manganese phosphate were compared with LiFePO4 and pure LiMnPO4 to evaluate the influence of doping on the material.
 
See: A. Dell'Era, M. Pasquali, E.M. Bauer, S. Vecchio Ciprioti, F.A. Scaramuzzo, C. Lupi, Materials, 2018, 11, 56; doi: 10.3390/ma11010056

 
 

Nanochemistry for the synthesis of nanoparticles and nanocomposites

Nanochemistry for the synthesis of nanoparticles and nanocomposites

Aldo Capobianchi  - aldo.capobianchi@ism.cnr.it

Laboratory BC12 (nM2-Lab)

Roma - Monterotondo
 
The laboratory of nanochemistry for the synthesis of nanoparticles and nanocomposites is focused on the synthesis of magnetic and non-magnetic materials at the nanometer scale. The typical synthesized magnetic materials are nanoparticles of metal alloys with L10 structure (eg FePt, CoPt, MnPt, etc.), with peculiar magnetic properties that depend on the metals making up the alloy beside being of interest for various applications including biomedicine, magnetic recording and catalysis. Different methods of synthesis are also applied to the production of metallic nanoparticles such as Ag or Ru and semiconductors such as CdS. The laboratory is also characterized by the activity of synthesis of nanocomposites based on carbon nanotubes, graphene and graphene oxide linked to magnetic and non-magnetic nanoparticles. The synergistic effect gives particular properties to the nanocomposite compared to the individual components. Green synthesis methods are used for the synthesis of nanoparticles and nanocomposites. In particular, the mill grinding technique allows to obtain excellent results in terms of quantity of material produced and dimensional control at the nanometric level. The laboratory allows refined processing under controlled and reductive atmosphere for low oxidation states. The typical equipment of the chemical laboratory is enriched with vacuum lines and nitrogen lines mounted under fume hoods. The laboratory uses ovens and muffles for air treatments and a horizontal tubular oven for heat treatments in a controlled atmosphere.
 

TECHNICAL SPECIFICATIONS

  • Stirring/heating plates: various models, Tmax 300°C.
  • Lines with rotary vacuum (P = 2x10-3mmHg).
  • LB deposition apparatus: (Nordtest, KSV 5000)

AVAILABLE TECHNIQUES

  • Chemical synthesis and deposition of organic thin films and nanoparticles using the Lagmuir-Blodgett (LB) technique. 

 

SAMPLES

  • Powders or crystals in typical quantities of the order of 100 mg. The easy scalability of the methods allows the preparation of larger quantities.

  • Organic thin films and nanoparticles with a maximum surface area of ​​10x10 cm2 (by LB).

 

USED ​​FOR

  • Permanent magnets •
  • Catalysis •
  • Sensors •
  • Semiconductor / microelectronics •
  • Cleaning and purification of water •
  • Chemical industry
 
 

CASE STUDIES

Nanoarchitectures of FePt@MWCNTs/Ru with double functionalization.

The example shows the synthesis of nanocomposites with a complex three-component nanoarchitecture: carbon nanotubes (CNTs) that give a large surface, Ru nanoparticles (NPs) that decorate the CNTs and act as a catalyst and FePt NPs inside the CNTs that have the purpose of giving the nanocomposite a magnetic behavior. This last one has a dual function: the first and simpler is to move or remove the catalyst nanocomposite how it prefers in the reaction environment. The second and more complex is to provide local heating to the catalyst without heating the whole solution. Local heating is obtainable through an alternating magnetic field applied from the outside as occurs in the case of hyperthermia of magnetic NPs for therapeutic purposes. In the catalysis phase this can lead to a strong saving of energy and to a greater specificity of the reaction.   The uniqueness of this work lies in the great control over the structure of the nanocomposites and the highly specific positioning (internal or external to the CNTs) of its components.
 
See: B. Astinchap,R. Moradian, A. Ardu, C. Cannas, G. Varvaro, A. Capobianchi. Chem. Mater. 24, 3393(2012)

 
 
 

Effective synthesis of L10 alloy nanoparticles from stratified precursor salts.  
 
An intelligent and easily scalable synthesis strategy, called Preordered-Precursors Reduction, has been successfully applied to synthesize highly ordered L10 MPt (M = Fe, Co Ni, Mn) alloy nanoparticles under milder conditions than ordinary processes. The natural order of the crystalline M(H2O)6PtCl6 precursor salts, consisting of M and Pt atoms on alternating planes that imitate the atomic disposition of the L10 structure, plays a fundamental role in providing all systems with a certain initial quantity of chemical order that facilitates the formation of the ordered phase L10, which is therefore obtained in milder conditions, in terms of process temperature and reaction times, compared to what is required by ordinary strategies.


See:

  • X.C. Hu, E. Agostinelli, C. Ni, G.C. Hadjipanayis, A. Capobianchi. Green Chem. 16, 2292 (2014) 
  • G. Varvaro, P. Imperatori, S. Laureti, C. Cannas, A. Ardu, P. Plescia, A. Capobianchi, JALCOM, In press (2020)
 
 
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