Nanoscience and Nanotechnology

Dr. M. Midhun Kumar

Assistant Professor
School of Chemical Engineering (SCHEME)
Vellore Institute of Technology, Vellore
Email ID: midhunkumar.m@[Link]
Module-3
Precipitation Method
• A wet chemical technique to synthesize nanoparticles by inducing a reaction in solution
that forms an insoluble solid (precipitate).
• One of the simplest and most scalable methods for metal, metal oxide, ceramic, and
polymer nanoparticles.
• Produces fine and controlled particles.
• It works with a wide range of materials under mild temperatures

Definition: In precipitation synthesis, nanoparticles are formed by chemical reaction of

dissolved precursors that exceed solubility limits, causing them to nucleate and grow into
solid nanoparticles.
Supersaturation: Mixing reactants creates a solution where solute concentration exceeds
solubility.
Nucleation: At high supersaturation, small clusters form.
Growth: Controlled growth of nuclei to form nanoparticles.
Separation: Collection of precipitated nanoparticles by filtration/centrifugation.
Drying/Calcination: Removal of solvents and possible heat treatment to improve crystallinity.

Applications:
• Catalysis
• Sensors and Electronics
• Biomedical Applications
• Ceramics and Composites
• Environmental Adsorbents for Pollutants
• Photocatalysts for degradation
Advantages Disadvantages
• Simple and scalable • Particle agglomeration is common
• Low cost & low temperature operation • Difficult to achieve narrow size distribution
• Good for large-scale production without stabilisers
• Size tuning by adjusting reactant • Requires careful control of reaction
concentration, pH, and temperature parameters
• Works for diverse materials (oxides, • Impurities from precursors may remain
metals, sulfides) • Post-processing (washing, drying) may
affect particle properties
Co-Precipitation Method
• Co-precipitation is a wet-chemical synthesis method where two or more soluble metal
precursors precipitate simultaneously from a solution to form multi-component
nanoparticles.
• Widely used for mixed oxides, ferrites, doped nanoparticles, and composites.
• It works with a wide range of materials under mild temperatures

Unlike simple precipitation (single precursor), co-precipitation ensures atomic-level mixing of

multiple components during nucleation and growth.

Difference: Precipitation forms nanoparticles from a single precursor, whereas co-

precipitation involves the simultaneous precipitation of multiple precursors to produce
compositionally homogeneous multi-component nanoparticles.
Principle: When multiple metal ions are present in
solution, the Controlled addition of a precipitating
agent (e.g., NaOH, NH₄OH, Na₂CO₃) causes
simultaneous supersaturation, co-nucleation, and
co-growth, ensuring a uniform composition in the
final nanoparticles.

• Excellent composition control

• Homogeneous distribution of elements
• Almost the same applications as the
precipitation method
Aspect Precipitation Co-precipitation
Number of precursors Single Two or more
Single-component Multi-component / mixed
Type of product
nanoparticles nanoparticles

Nucleation Individual nucleation Simultaneous co-nucleation

Composition control Limited Excellent

Homogeneity Moderate High (atomic-level mixing)
Ferrites, doped & composite
Typical use Simple oxides, metals
materials
Sol-Gel Method
• Sol-gel is a wet-chemical method in which nanoparticles are synthesized through the
hydrolysis and condensation of metal alkoxides or inorganic salts, forming a colloidal
Sol that evolves into a Gel network.
• Nanoparticles are formed through a chemical polymerisation process, not direct
precipitation.
• Common precursors: Metal alkoxides (e.g., TEOS, titanium isopropoxide), Metal
chlorides or nitrates (in some cases)
• Materials Synthesized: Metal oxides (SiO₂, TiO₂, ZrO₂, Al₂O₃) Thin films, coatings,
aerogels, nanocomposites
Fundamental Reactions
[Link]
M–OR + H₂O → M–OH + ROH
[Link]
M–OH + M–OH → M–O–M + H₂O

• Formation of a Sol (colloidal particles in liquid)

• Sol transforms into a 3D Gel network
• Drying and heat treatment produce nanostructured solids

Important Control Parameters

• pH
• Water-to-alkoxide ratio
• Temperature
• Aging time
Key difference

Aspect Precipitation Co-precipitation Sol-Gel

Hydrolysis +
Driving mechanism Supersaturation Co-supersaturation
condensation
Alkoxides / molecular
Precursors Single salt Multiple salts
precursors
Mixing level Particle-level Atomic-level Molecular-level
Gel → dense/porous
Product form Powder Mixed powder
solid
Size control Moderate Good Excellent
Thin films, coatings,
Typical products Simple oxides Ferrites, doped oxides
aerogels
Chemical Reduction method
• Chemical reduction is a solution-based synthesis method where metal ions are reduced
to zero-valent atoms using a chemical reducing agent, leading to nucleation and growth
of nanoparticles.
• Metal salts → reduced chemically → metal atoms → nanoparticles
• Commonly Synthesised Nanoparticles are Noble metals: Ag, Au, Pt, Pd and Base metals:
Cu, Ni, and Bimetallic nanoparticles
• One of the most widely used methods for metallic nanoparticles due to simplicity and
size control.

Chemical reduction synthesizes nanoparticles by reducing metal ions into atoms using
chemical reducing agents, enabling precise control over metallic nanoparticle formation.
 Basic Principle
•A reducing agent donates electrons to metal ions in solution:
M𝑛+ + 𝑛𝑒 − → M 0

Key Steps in the Process

Role of Stabilizers (Very Important)
• Dissolution of metal precursor (salt)
• Prevent agglomeration
• Addition of reducing agent
• Control particle size and shape
• Rapid nucleation of metal atoms
Examples: PVP Citrate ions, Surfactants
• Controlled growth into nanoparticles
• Stabilization to prevent aggregation

Common Reducing Agents

Sodium borohydride (NaBH₄)
Hydrazine (N₂H₄)
Ascorbic acid
Citrate (also acts as a stabiliser)
Hydrothermal method
• Hydrothermal synthesis is a solution-based method where nanoparticles are synthesized
in a sealed autoclave using aqueous solutions at elevated temperature and pressure.
• Reactions occur above the boiling point of water under autogenous pressure.
• High temperature and pressure enhance solubility, diffusion, and crystallization, leading
to highly crystalline nanoparticles.
• Materials Commonly Synthesized Metal oxides (TiO₂, ZnO, Fe₃O₄), Hydroxides, Zeolites,
Perovskites, Nanorods, nanowires, nanosheets

Hydrothermal synthesis produces highly crystalline nanoparticles by carrying out

reactions in aqueous media at high temperature and pressure inside a sealed autoclave.
Basic Principle
• Under high temperature and pressure, water acts as: Solvent and Reactant
• Increased solubility of precursors
• Controlled nucleation and crystal growth
• Shape- and size-controlled nanostructures

Important Process Parameters

Why the Hydrothermal Method is Preferred
• Temperature (100-300 °C)
Excellent crystallinity
• Pressure (autogenous)
Shape-controlled nanostructures
• Reaction time
• pH / mineralizers (NaOH, KOH)
Microemulsion (reverse micelle)
• A microemulsion is a thermodynamically stable, isotropic mixture of: Oil, Water,
Surfactant (Often) co-surfactant
• In reverse (water-in-oil) microemulsions: Nano-sized water droplets are dispersed in a
continuous oil phase where each droplet acts as a nanoreactor
• Nanoparticle size is controlled by the size of the reverse micelle, leading to uniform and
ultra-fine nanoparticles.
• Surfactant molecules arrange such that:
• Hydrophilic tails face inward (towards water),
and Hydrophobic head face oil phase
• Metal precursors are dissolved inside the water
core
• Chemical reaction occurs inside confined
nanoscale droplets
Key Mechanism
• Formation of reverse micelles
• Encapsulation of metal ions
• Micelle collision and exchange
• Nucleation inside droplets
• Growth limited by micelle size
Why Microemulsion is Special Advantages
Excellent size uniformity • Precise size control (2–20 nm)
Narrow particle size distribution • Monodispersed nanoparticles
Low-temperature synthesis • Mild synthesis conditions
Major Applications • Excellent reproducibility
• Metal nanoparticles Au, Ag, Pt, Pd • Suitable for metal and metal oxide NPs
• Magnetic nanoparticles Fe₃O₄, CoFe₂O₄
• Catalysis: Supported metal catalysts Disadvantages
• Biomedical • Large amount of surfactant required
• Sensors : Electrochemical and biosensors • Difficult surfactant removal
• Limited large-scale production
• Organic solvents may be toxic
• Lower yield compared to bulk methods
Polyol Method
• Polyol method is a chemical reduction technique in which metal precursors are dissolved
in a polyol solvent (e.g., ethylene glycol, diethylene glycol), which acts as both Solvent
Reducing agent
• The polyol reduces metal ions to zero-valent atoms while simultaneously stabilizing
nanoparticles, allowing precise size and shape control.
• Materials Commonly Synthesised Noble metals: Ag, Au, Pt, Pd, Alloy and bimetallic
nanoparticles, Magnetic nanoparticles (Fe, Co, Ni)
Why Polyol Method?
• Operates at moderate temperatures (100-200 °C)
• Produces monodisperse, high-purity nanoparticles
• Mild reaction, scalable, and environmentally friendly

The polyol method synthesizes metal nanoparticles by reducing metal salts in a polyol
solvent, which acts as both solvent and reducing agent, providing excellent size and shape
control.
Steps in Polyol Method Advantages of Polyol
• Dissolve metal precursor in polyol • Dual role: solvent + reducing agent
• Heat solution (100-200 °C) • Mild reaction, no extra reducing agent often
• Polyol reduces metal ions → metal atoms needed
• Nucleation and controlled growth • Excellent size, shape, and dispersity control
• Stabilization by polyol molecules prevents
aggregation
• Collection of nanoparticles
Major Applications Advantages
•Catalysis •Monodisperse nanoparticles
• Fuel cells (Pt, Pd nanoparticles) •Mild temperature and simple setup
• Hydrogenation/dehydrogenation •Dual role of solvent/reducing agent
reactions •High purity and reproducibility
•Biomedical •Scalable
• Gold nanoparticles for imaging and
drug delivery Disadvantages
•Electronics •Polyol can be viscous, limiting mixing
• Conductive inks (Ag nanoparticles) •Not ideal for very large-scale production
•Sensors •Post-processing may be needed to remove
• Electrochemical sensors, gas sensors excess polyol
•Optical Materials •Limited to metals soluble in polyols
• Surface plasmon resonance
applications
Chemical oxidation
• Chemical oxidation method is a solution-based synthesis technique where a metal or metal
precursor is oxidized to form metal oxide nanoparticles.
• Often used for metal oxides with controlled stoichiometry and crystallinity.
• Metal ions or metallic species are oxidised by chemical oxidizing agents in solution, forming
nanoparticles in a controlled manner.
• Commonly Synthesized Nanoparticles Iron oxides: Fe₃O₄, γ-Fe₂O₃ Copper oxides: CuO, Cu₂O
Titanium dioxide: TiO₂ Manganese oxides: MnO₂

Why Chemical Oxidation?

• Simple, low-temperature synthesis
• Controlled particle size and morphology
• Suitable for both aqueous and non-aqueous systems

Chemical oxidation synthesizes metal oxide nanoparticles by oxidizing metal precursors in

solution, allowing controlled size, morphology, and composition.
 Basic Principle
Metal species (M⁰ or Mⁿ⁺) are oxidised using an oxidising agent in solution:
0
Oxidant
M M𝑛+ (Nanoparticle)
M𝑛+ + Oxidant → Metal oxide nanoparticle

Common Oxidizing Agents H₂O₂ (hydrogen peroxide) KMnO₄ (potassium permanganate)

NaOCl (sodium hypochlorite) O₂ (dissolved oxygen)

Steps
[Link] precursor in solvent (water/alcohol) Key Control Parameters
[Link] oxidizing agent under stirring •pH of solution
[Link] of nuclei and controlled growth •Temperature
[Link] using surfactants or polymers •Oxidant concentration
[Link] and washing of nanoparticles •Reaction time
Why Chemical Oxidation is Important
Produces metal oxide nanoparticles with controlled size and morphology
Can synthesize magnetic, catalytic, and semiconductor nanomaterials
Major Applications
Advantages
•Catalysis
• Oxidation reactions •Low temperature and simple setup
• Environmental catalysts (degradation of dyes, •Tunable size and morphology
pollutants) •Compatible with aqueous systems
•Magnetic nanoparticles •Can produce high-purity oxides
• Fe₃O₄ for MRI, ferrofluids
•Scalable for lab-scale production
•Energy materials
• Metal oxide electrodes for batteries and Disadvantages
supercapacitors •Requires careful control of oxidant to
•Sensors avoid over-oxidation
• Gas sensors (ZnO, CuO)
•Biomedical
•Particle aggregation possible
• Antimicrobial nanoparticles (CuO, ZnO) •Post-treatment may be needed for
•Ceramics crystallinity
• Functional ceramics, coatings •Limited for some metal oxides
requiring extreme conditions
C. N. R. Rao et al., Chemical Methods for Nanomaterials
Synthesis, Wiley-VCH, 2007