4th year undergraduate course

Lectures
2 and 3

Solid State Chemistry: Synthetic

techniques
Leigh F. Jones
School of Chemistry
NUI Galway
Rm. 133

Lecture 2: Outcomes
Conventional Solid State Reaction (SSR) Routes

Solid state Reaction rates (SSRs)

Shake and bake methods
Equipment used in SSRs
Problems encountered + ways around them
Advantages and Disadvantages of SSR routes

Synthetic techniques towards Inorganic Materials

Inorganic materials are characterised by extended lattices, not
discrete molecules

Inorganic materials are mainly prepared in the form of powders and

single crystals

SYNTHESIS ROUTES

Conventional Routes

Non-conventional Routes

NOTE: It is important to prepare single phase compounds (no secondary

compounds), as the products cannot be purified.

Synthesis & Reactions of 3D Inorganics

Rules of thumb
Making, breaking, modifying multiple bonds (3D) = generally need lots of E
= high Temps
Very different to making molecules!
Major problems:
1) Purity
2) Control of stoichiometry
3) High Temp = expensive!

Factors to consider when choosing reactants:

1) availability & cost
2) purity
3) Avoidance of problems!

Conventional Synthetic Routes

Solid State Reactions (SSR)
Solid state reaction: the direct reaction of a mixture of starting reagents (usually
powders) at high temperature (700 - 1600C)
High temperature provides the necessary energy for the reaction to occur
Products from solid state reactions are always
thermodynamically stable compounds

Oldest, simplest and most widely used method is to mix

together powdered reactants (sometimes they are pressed into
pellets) and heat for prolonged periods of time.
Some call it shake and bake
It is very effective.almost all the new superconductors were
first prepared via SSR methods

Conventional synthetic routes

General route = mix components together and heat for extended periods
Shake and Bake
Solid-solid
Solid-liquid
Solid-gas
Liquid-gas
Gas-gas
2 general reaction types:
addition e.g.
exchange e.g.

BaO(s) + TiO2(s)

900 C

ZnS(s) + CdO(s)

BaTiO3(s)

900 C

ZnO(s) + CdS(s)

In general, they are all EXOTHERMIC.

The driving force being the difference between the free energies of
formation (Gfor) of the products and reactants.

Example: solid-solid addition synthesis of SrTiO3

a) SrO & TiO2 ground together in 1:1 stoich.
b) Pelletised (pressure-pump) forces grains together
c) Heated in furnace @ 900C, 24 hrs
SrO + TiO2

900 C
24 hrs

SrTiO3

What actually happens?

Pellet = mix microcrystalline particles & voids
Reaction = migration of most mobile ions (cations) across interface.
Mn+ ions with low charge:radius ratio = weakest lattice interaction
= react at lower T (e.g. Cs+ vs Mg2+)

Requires breaking/forming many bonds (complete disruption of structure)

Al2O3

MgO

Contact between grains

of the reagents

High temperature

MgAl2O4

MgO

Al2O3

Diffusion, starts at the

interface

Product layer / interface

Product layer / interface

Product = MgAl2O4 (spinel)

As the interface thickens =

reaction rate slows down

MgAl2O4 spinel

The Spinels are any class of compound of general formula XY2O4

Crystallise in the cubic crystal system
Oxide anions exhibit CCP arrangement in the lattice
X and Y occupy some or all of the tetrahedral and octahedral holes
X and Y can be divalent, trivalent or quadrivalent:
Zn, Mg, Fe, Mn, Al, Cr, Ti, Si
MFe2O4 (M = Fe, Ni, Zn) are used as materials for magnetic recording
(Fe 3+)(Fe2+,Fe 3+)O4 = Magnetite !

O2- anions form CCP (FCC) lattice (similar to NaCl).

The metals (A and B) occupy 1/8th of the tetrahedral sites and (which
alternate) the octahedral sites.
Large cubic cells (~8 for MgAl2O4).

COMPOUND WITH CCP LATTICES

Cl

Na+

Balls and sticks representation

Polyhedral representation

NaCl (Rock-Salt)

For the ions to migrate = ENERGY to overcome lattice E = high T

T = 400C-2000C.

e.g.

MgO + Al2O3

T=

1400C
2 days

diffusion rate

MgAl2O4 (AB O = spinel)

2 4

NB: only true below MPt = SINTERING

reaction rate
Making materials from powders
by heating at below their melting
points until the particles adhere to
each other. Common in making
ceramics.

Exchange reactions much more complicated and not understood!

Improving reactions rates

a)

particle size =

b) pelletising =

no. of interfaces

inter-particle void space

c) thorough pre-grinding (0.1 m) = homogenous mixture

d) continual re-grinding = as vol. of product , harder for remaining
particles to react
Disadvantages of simple mixing / sintering:
a) some metal oxides pick up H2O (hygroscopic) / CO2
not air-stable e.g. commercial BaO = BaO + Ba(OH)2 + BaCO3
b) stoich. difficult to control
c) prod. often impure
d) requires v. high T
e) slow
f) difficult to separate products (impurities)
g) Product particles can often coat unreacted starting materials
= stops reaction = impure final product.
Possible solutions.?

MgAl2O4 has also been synthesised in a microwave

School of Chemistry, NUI Galway

Decomposing precursors
Use precursors that decompose at low T to gen. metal oxide reactants:
I.E: metal carbonates, CO32-; metal hydroxides, OH; metal nitrates, NO3
e.g.

heat
-CO2

BaCO3

BaO

heat
+TiO2

BaTiO3

Advantage: precursors air-stable

very fine (<<0.1 m) particles
Volatile products
Allows simple separation from contaminants.
Complex purity and incomplete reactions less problematic.

e.g. Al2O3(s) + 3C(s) + 3Cl2(g)

2AlCl3(s) + 3CO(g)
Volatile gas
Separate with Temp control

Make one of the solids a liquid!

Liquid-solid reactions

A(l) + B(s)

D(s)

Advantage:
Liquid A gives greater contact & mobility and
dissolves some D (product) = prevents reaction blockage.
Make both liquid!
Liquidliquid - extremely homogeneous initial mixture
i) Dissolve mix of reactants in H2O (solvent) - mixing at atomic level
ii) Precipitate precursor by: pH or addition of organic molecule
iii) Heat ppt to remove H2O and/or CO2, leaving MxOy (desired product)
e.g. Zn2+(aq) + 2Fe2+(aq) + 3C2O42-(aq)

ZnFe2(C2O4)3(s)

This is a precipitation method

Solid state reaction - Reaction rates

Solid state reactions are usually slow (from 8 hours to several days)

Why???

large amount of structural reorganization

bonds break and ions migrate through a solid

Unlike gas phase and solution reactions, the limiting factor in solid-solid
reactions is usually diffusion.
The rate controlling step in a solid state reaction is the diffusion of the
cations through the product layer

dx
kx 1
dt

or

x k 't

1
2

thickness of product layer

time

k, k '

Rate law governing diffusion through

a planar layer

rate constants

Solid state reaction - Temperature dependance

15

1400C
10

MgAl2O4

1500C

1300C

MgO + Al2O3

x2 106 (cm2)

20

.again the synthesis of MgAl2O4 spinel

100
x = thickness of the product layer

200

time (hours)

The reaction occurs much more quickly with increasing temperature

A solid-state reaction will not occur until the temperature reaches at least 2/3
of the melting point of one of the reactants.

Problems encountered using SSRs

Some starting reagents are chemically reactive and / or contain ions that
diffuse easily.

Other problems may then arise such as:

1) Evaporation of a reactant due to high T (e.g. Alkali oxides, Tl2O, PbO, Bi2O3,
HgO).
2) Reaction of a reagent with the container (i.e. Transition metal containing
vessels).

However, SSRs can be (and has been) used to synthesis thousands of solids.
With due care and attention to detail the above problems can be avoided.

Reagents and Equipment

Another example of solid-solid addition: Reagents (synthesis of BaTiO3)

BaO + TiO2

BaTiO3
BaCO3 + TiO2

BaTiO3
BaO + CO2(g)

(1200C)
Volatile by
product

Alkaline earth oxides are moisture sensitive and therefore not used as starting reactants
Hydroxides, nitrates, oxalates and carbonates are often used as starting reactants
instead of oxides.
Pestle and mortar
Starting reagents are mixed in
desired stoichiometric
amounts.
a newer version is the ball mill:

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Reaction vessels (crucibles)

Refractory material: retains strength

at high temperatures (> 540 C)
Crucibles are made of refractory materials
(Al2O3, ZrO2, Pt) for 2 reasons:
1.

Chemically inert to the reactants

2. High melting point

Furnaces (Ovens)
Starting materials (reagents) are
placed inside crucible and put into high
temperature furnace.
Furnaces provide the temperature
to initiate and carry on the reaction.

Reactions in controlled atmospheres

Compounds containing metals in unstable oxidation state cannot be prepared in
air. A reducing or oxidising atmosphere is required.
Experimentally: a gas (H2/N2,O2) is passed over
the reaction mixture in a tubular furnace

Reaction in a reducing atmosphere (V5+

V2+)

H2 / N2
V2O5 s
VOs

Reaction in an oxidising atmosphere (Ni2+

H2 extracts O2
via formation of
H2O

Ni3+)

LaNiO2.5 s LaNiO3 s
O2

0.5/2 O2 is added to the

chemical formula

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Solid State Reactions

Advantages:
Starting materials readily available
Compounds can be prepared in large amounts
Easy to carry out the synthetic procedure

Disadvantages:
Long duration (can take ages!!)
Poor chemical homogeneity (sometimes secondary phases are present, as
BaTi2O5 in the preparation of BaTiO3)
Large grain size (often not mono-disperse)
Use of high temperature (always dangerous and tricky to handle safely)
Lack of control of products formed

Lecture 3: Outcomes
Non conventional synthetic
routes
Soft chemistry methods
Precipitation method
PRECURSOR ROUTES

Sol-gel processes
Inter- and de-intercalation (topotactic process)
Hydrothermal synthesis
Zeolites

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Non-conventional synthetic routes

Products from solid state reactions are always thermodynamically stable
compounds
Non-conventional synthetic routes can be complementary or an alternative to SSR

Complementary to SSR:
Aims to improve
homogeneity and particle
size in thermodynamically
stable compounds

Alternative to SSR:
The synthesis
of metastable compounds
which cannot be prepared
by SSR

Co-precipitation

Soft chemistry routes

Sol-gel methods

Co-precipitation
Sol-gel

Precursor routes

Soft Chemistry Routes (chimie douche)

Soft chemistry routes are used to prepare non-thermodynamically stable
compounds (called metastable)
Range of reactions: intercalation, de-intercalation, anion substitution,
dehydration, cation exchange etc

Sr2CuO2F2+ is a
metastable
compound: cannot be
prepared via solid
state reactions (SSR)

Soft Chemistry reactions are carried out under moderate conditions

(typically T <500 C).

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Soft chemistry reactions are topotactic, i.e. only specific parts of the
starting materials (parent compounds) are targeted.
The use of low temperature does not provide enough energy to build
new structures (conventional SSR), but useful for modification or tuning
of existing structures.
therefore:
Products retains the main structural features of the parent compounds
Advantages
Design of new compounds with targeted structural (physical) properties

Synthesis of metastable compounds

Disadvantages

Difficulty in finding appropriate precursors

Metastable compounds decompose at high temperatures

Intercalation and deintercalation

DEFINTIONS:
Intercalation: The insertion of ions into a 3-D structure.
Deintercalation: The removal of ions from 3-D structure.
(commonly involve H+, Li+, Na+ and O2-)
AIMS:
These are carried out to improve on the materials physical properties
(i.e. to increase conductivity (ion mobility).
These are effectively solid-state redox processes
These processes are topotactic reactions (thus a form of soft chemistry /
chimie douche)
An elegant way to synthesise new materials with extremely similar
structures as their precursors with improved physical properties.

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Intercalation and deintercalation

Insertion of ions = intercalation
removal of ions = deintercalation

(usually in layered structures)

Reduction = cations insertion of the host

Oxidation (anion insertion) of the host

TiS2 + nBuLi

LixTiS2

+ Li+

Intercalation

LixVS2

VS2
- Li+

deintercalation

Example of a remarkable physical property transformation via intercalation

TiO2

xn-BuLi in
hexane

(Anatase polymorph)
Insulating solid

LixTiO2
Lithium Titanate superconductor
Tc = 13 K

LixTiO2

+ x/2 octane

Lithiated anatase
(no structural change occurred, still an
insulating white solid)

500 C

Causes structural reorganization.

Now has a spinel structure (like
MgAl2O4 earlier)
Now a superconductor!!

The Li+ and electrons intercalate inside the

anatase structure
The anatase structure has open 1-D channels
similar to rutile (right).

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Precursor Routes (co-precipitation and sol-gel processes)

Co-precipitation - synthesis of BaTiO3
(BaTiO3 is an important ferroelectric material used in capacitors)
Precursor:
A solution of BaCl2 is added to an aqueous solution of TiO(CO2)2

Ba 2 (aq) TiO (COO) 2 (aq) Ba[TiO ((COO) 2 ) 2 ]( s )

Barium titanyl oxalate precursor containing Ba2+ and Ti4+
in the correct ratio to form BaTiO3
K
Ba[TiO ((COO ) 2 ) 2 ]( s ) 920

BaTiO3 ( s ) 2CO2 ( g ) 2CO ( g )

Decomposes on heating

Sol-Gel synthesis
-a wet technique forming the fabrication of a material: (i.e. a metal oxide)
Relatively cheap technique requiring reasonably low T
Dried
(heated)
gradually)
Homogenous
Solution(s) or
colloid
Reagent(s)

Viscous sol
turning to
gel

Fired at
high T

Homogenous amorphous
solid
3-D integrated network

Sol-gel process

Product

The last stage comprises high T heating of the gel (firing) to:
Remove volatile components
Remove any side bonded organics (explained later)

Colloid: a material consisting of solid particles (size range:

1nm to 1 m) dispersed in a solution

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Typical precursors (starting materials / reagents):

Metal alkoxides and Metal Chlorides

1) TEOS:
Tetraethylorthosilicate

Si(OCH2CH3)4

Starting reagent for the sol-gel synthesis of SiO2 (quartz)

(described in Lecture 1)

2) Ti(OiPr)4:

Precursor to the sol-gel

synthesis of TiO2
Uses:
Paint / pigment
Sunscreen
Food colouring

Titanium isopropoxide

Extremely high refractive index

Sol-gel synthesis: Mechanisms / processes

Note:

Si(OCH2CH3)4
Ti(OCH(CH3)2)4
Al(OCH2CH2CH2CH3)3

All covalent liquids

Covalent liquids used in appropriate ratios / stoichiometries

Alcohol often added Promotes miscibility of H2O with Alkoxide
Water is vital!!.............H2O hydrolyses alkoxides

M(OR)

M(OH)

This process can be acid and base catalysed (described later)

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 Hydrolysis occurs in 2 STEPS:

1) Replacement of OR with OH
i.e.
Si(OCH2CH3)4

Si(OCH2CH3)3(OH) + Si(OCH2CH3)2(OH)2

etc

2) Condensation polymerisation to eliminate H2O

i.e.
(RO)3-Si-OH

HO-Si(OR)3

-H2O

(RO)3-Si-O-Si(OR)3
ETC

Composite + structure + viscosity depends GREATLY on:

DEGREE OF HYDROLYSIS + CONDENSATION = need synthetic control

Cross condensation:
Consider synthesising a material comprising
two (or more cations) M and M'

-M-OH + HO-M-

H2O
-M-O-M-

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Sol-gel hydrolysis step:

May be acid or base catalysed.
ACID CATALYSED: Electrophillic attack (H+ i.e using HCl)

Si(OR)4 + H+ + Cl

Si(OR)3(OH) + RCl

BASE CATALYSED: Nucleophillic substitution (OH)

Si-(OR)4 + OH

Si(OR)3(OH) + OR

Calcination (firing as described earlier in notes):

Heating (calcine) the gel at relatively high temperatures (200-450C)

BURNS OFF VOLATILE ORGANICS TO GIVE METAL OXIDE PRODUCT after

condensation of Si(OH)x species (i.e. to eventually give SiO2 in this instance)

Sol-Gel: Alternative synthesis of MgAl2O4 (spinel)

Mg(OCH3)2 +

Al(OCH2CH2CH2CH3)3
(i) Mixing
(ii) Hydrolysis
(iii) Condensation
(iv) Drying

Amorphous GEL
FINAL FIRING at 250C (calcination)
leads to thermal decomposition to very
fine particles of SPINEL

MgAl2O4

Advantages: Energetically favourable compared to other preparation SSR route

(250 vs. heating at 1400 C for days).
Disadvantages: Starting materials are very expensive.

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Sol-Gel: Synthesis of ScMnO3

Sc2O3 and MnCO3 separately dissolved in heated aqueous solutions of formic acid
to form the formate salts:

Sc2O3 ( s ) 6 HCOOH ( l ) 2 Sc( HCOO )3 3H 2O

MnCO3 ( s ) 2 HCOOH ( l ) 2 H 2O Mn( COOH )2 2 H 2O( s ) H 2CO3 ( l )
Sc(HCOO)3 and Mn(COOH)22H2O are added to melted citric acid monohydrate
and this results in the formation of a (Sc,Mn) citrate polymer.
Heat to 180C = Removal of excess water and organics
Heat to 450C = Formation of an amorphous oxide product
Heat to 690C = Formation of crystalline ScMnO3

The solid state reaction at 700 C gives a a mixture of binary

oxides:
2Sc(HCOO)3 + 2Mn(COOH)22H2O

Sc2O3 + Mn2O3 + 5CO2 + 2H2O + H2

Hydrothermal Synthesis (used in 2nd step of zeolite production)

Extended to heating the water soln: HYDROTHERMAL
steel
pot

Reaction
Mixture in
H 2O

Teflon
pot

Sealed reaction vessel

Advantages:
Controlled heating / cooling rates / pressure
Heat above BPt (super-heating)
Excellent method for obtaining crystalline material (cool slowly)
Con. Oven / microwave (rel.cheap)

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Excellent technique for crystal growth due to

very slow cooling rates:

Hydrothermal Synthesis
(NOTE: Solvothermal = carried
out in another solvent (not H2O)

SiO2
(solid)

NaOH in H2O

SiO2

Hydrothermal
bomb

(single crystals)

NaOH acts as a mineraliser

SiO2 only sparingly soluble in H2O
Solubility increases with presence of NaOH
Solubility also increases with higher Temperature
NaOH/H2O soln. increases crystal growth rate cf. pure H2O

Solvothermal Oven @ School of Chemistry

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ZEOLITES

Zein Greek for to boil

Lithos Greek for a stone

A stone that boils

Discovered in 1756 by Alex Cronstedt

A large class of extremely porous Aluminosilicate 3-D extended framework
Crystalline compounds made both naturally and may be synthesised in the laboratory
175 Zeolites known (to date), 80 are naturally occurring.
Comprise of SiO4 and AlO4 tetrahedral building blocks (think of molecular lego)

=
AlO4

SiO4

ZEOLITES: structure

SiO4 and AlO4 building blocks:

General formula: My+(SiO2)x(AlO2)y.nH2O

Some AlO4 tetahedra have substituted SiO4 units (neutrally charged).
Negative charge of AlO4 is accounted for by the presence of M+ cations.
These are located within the channels and cavities.

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Synthetic routes to ZEOLITES

1.) Sol-gel technique

NaAl(OH)4 (aq) + Na2SiO3 (aq) + NaOH

A typical reaction is:

1st step: 25C

25-175C in H2O (hydrothermal

conditions: heat in high pressure
H2O)

GEL

NawAlxSiyOz zeolite
Particular zeolite formed depends on starting
compostion, temperature and pressure conditions.
The specific zeolite made also depends on the
template used: usually an Alkylammonium cation.
The templates are then calcined or burned off by
heating between 300-400C.

(the 3-D framework

crystallises around the
template)

Leaving desired inorganic framework (zeolite)

ZEOLITES: their uses (1)

Microporous solids possess large
interconnected VOIDS and CHANNELS

Large VOIDS and CHANNELS permit:

Industrial Catalytic Applications

Ion exchange (water softening and purifying)
Gas separation and removal
Very regular pore (channel / void) size of molecular dimensions
means that they ideal for separating (or sorting) molecules depending on their size

MOLECULAR SIEVES

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ZEOLITES: their uses (2)

1) HETEROGENOUS CATALYSTS
(shape selective)
ZSM-5 is a high Si / low Al (conc.) zeolite made
by Mobil Oil.
ZSM-5 is highly acidic (H+ rife in channels) and
therefore used by hydrocarbon interconversion by
petrochemical Industry.
i.e. Xylene isomerisation (carbocation isomerisation)

ZSM-5
para

meta

ZEOLITES: their uses (3)

Ion exchange for H2O

separation and purification

Sodium Zeolite A
Water hardness stems from presence of Ca2+ and Mg2+ ions in water
which do not decompose on boiling the water.
The loosely bound Na+ in the cavities / channels are readily replaced by
Ca2+ and Mg2+ ions in aqueous conditions. This process is water softening.
This is why you will find zeolites in commercial washing powders

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ZEOLITES: their uses (4)

Gas separation and removal

In terms of gas separation: the gaseous molecules may be differentiated (thus

separated) by their differing electrostatic interactions with the loosely bound Mx+
cations within the framework channels and voids.

H2, NH3

H2

H2

H2

H2

NH3

Cation rich Zeolitic materials are also used as dessicators due to their high affinity
for water
Hydrophobic zeolites (not cation rich) are used in the absorption of organic materials.

Zeolites can therefore separate molecules on the basis of their:

SIZE, SHAPE and POLARITY

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