HETEROGENEOUS CATALYSTS

Sergio Rojas
ICP-CSIC
January 2013

1.

WHAT IS A CATALYST? RELEVANCE IN TODAYS SOCIETY

2.

RELEVANT PARAMETERS DURING THE SYNTHESIS OF

HETEROGENEOUS CATALYTS

3.

1.

PREPARATION METHODS

2.

SIZE AND STRUCTURE CONTROL

CONCLUSIONS

Catalysts is a substance that

accelerates the rate of a chemical
reaction by lowering the

activation energy of the reaction

It is not consumed during the course
of the reaction

Solids (NaOH, Pt/C, V2O5)

Liquids (H2SO4)

Conversion can not be higher than thermodynamic value

Chemical reactions results from

Maxwell Boltzman distribution

collisions with a certain minimum

90
80

energy (Activation Energy)

A catalyst provides an alternative
route for the reaction with a lower
activation energy."

It does not strictly "lower the

activation energy of the reaction

Number of particles

70
60
50

Molecules
that wont
react
because
they lack of
energy

40
30
20
10

Activation Energy

0
0

Energy

Conversion can not be higher than thermodynamic value

10

Chemical reactions results from

Maxwell Boltzman distribution

collisions with a certain minimum

90
80

energy (Activation Energy)

A catalyst provides an alternative
route for the reaction with a lower
activation energy."

It does not strictly "lower the

activation energy of the reaction

Number of particles

70
60
50

Molecules
that wont
react
because
they lack of
energy

40
30
20
10

Activation Energy with catalyst

Activation Energy

0
0

Energy
Extra molecules to react

Conversion can not be higher than thermodynamic value

10

Catalysts are present in key industrial/society sectors

such as production of chemicals, energy transformation
and environmental processes
Most industrial process rely on the use of solid catalysts
(heterogeneous catalysis)
Petrochemistry
Fine chemicals

85% of all chemical processes have use catalysts

during, at least, one step during their preparation.

Catalysis in industry is dominated by heterogeneous processes

World catalysts sales in 2004 amounted to 15 billion US$/a (growth rate
about 5% year)
The ratio of product margin divided by catalyst cost is around 100-300

Catalysis in Industry

Heterogeneous
80%

Homogeneous
17%

Biocatalysis
3%

Synthesis of solid catalysts, Ed. K.P. de Jong, 2009, Wiley

Two phase process

on to the surface of the

Solid phase (catalyst)

catalyst (active site)

Gas/Liquid phase
(reactants)

Heterogeneous catalysis is a
surface process

1. Adsorption of reactants

2. Reaction

3. Desorption of products

Simplified mechanism
heterogeneous catalysis

Heterogeneous catalysis is a surface phenomenon

The performance of heterogeneous catalysts is determined
by the exposed surface area
Solid support

Adapted from: G. Mul and J.A. Moulijn. Preparation of supported metal catalysts

Exposed (specific) area increases by

decreasing particle size

Stabilization of particles by
deposition onto supports

What are the components of a heterogeneous

catalysts?

Solid support

Support; stabilize the catalytic particles

Catalytic particles; (oxide, metal or sulphide) hold the active
sites
Promoters; enhance the catalytic performance or structural
effects

Irregular
granule

Ring

Pellet

Sphere

Minilith

Wagon wheel

Extruded
cylindrical

Monolith
ceramic

metallic

Spheres

Low manufacturing costs

Relatively high pressure drop
Large diffusion length HDS, Methanation

Granules

Not common Low-surface-area catalysts

Ammonia Synthesis, Fromaldehyde

Pellets

Regular shape; Most common

Good strength. CO shift Hydrogenation

Extrudates

Low pressure drop; Poor strength HDS

Rings

High strength; Low pressure drop

Small diffusion length. Steam Reforming

Monoliths

Low pressure drop; Insensitive to dust; Small

diffusion length Exhaust gas cleaning

Gauzes

Low-surface-area catalysts Ammonia oxidation

High Temperature reactions

Micros(nanos)copic scale
< 2 nm
1-2 mm
10 nm

Porous support body

Metal particles
1-10 nm

Macroscopic scale
Support particles
20-50 nm

Adapted from: Synthesis of solid catalysts, Ed. K.P. de Jong, 2009, Wiley

Microscopic scale involves the structure of the active sites. It determines

the intrinsic activity of the catalyst

The mesoscopic scale the pore system and the sizes of the support
particles as well as catalyst particles of the active phase. It affects
intraparticle mass transfer of the catalyst

The macroscopic length scale involves the size and shape of the catalyst
body. Relevant for properties such as pressure drop, mechanical
strength and attrition resistance

Criteria for a good catalyst

Activity
Selectivity
Thermal and Mechanical Properties
Stability
Morphology
Cost

A catalytic process is the combination of a catalyst a

reactor and reaction conditions (P, T, space velocity)

The shape of the catalyst body (macroscopic scale) is

paramount to determine its performance at the
industrial level

Precursor
Support
Organic or
inorganic

Metal salt or
coordination
complex

Modified

T, P, pH,
templates,
size control
agents

CATALYST
Catalysts preparation

Relevant aspects and strategies for

the synthesis of solid catalysts for
heterogeneous applications

The preparation of supported catalysts aims to attach the

active phase onto the support

Impregnation, co-precipitation (controlled pH or not),

homogeneous deposition, deposition of surfactant (organic
agent) stabilized metal particles

The support is either a powder or a pre-shaped solid the

most common ones being -Al2O3, -Al2O3, SiO2, TiO2 or
carbons

Mixing
solutions/solids

Drying

Equilibration or
aging

Calcination

Solid liquid
separation

activation

Impregnation is related to
ion-exchange / adsorption
processes and the
interaction with the
support is dominant

Precipitation is in principle
a crystallization process
and can occur in the bulk
of the liquid or on a
relatively inert surface. The
support particles act as
crystallization nuclei for the
active site precursor

Coprecipitation One or more metals are precipitated

together with the support or precursor

Chemical phases dispersion surface areas, porous structure

and particle size and shape are created in a single steep

It can reach very high metal loading of up to 80%

Low solubility of hydroxides alkaline media

Careful with counter ions

Zn2+
Cu2+

CuOx

ZnOx

CuO//ZnO

OH-

Liquid mixing
Nucleation rate

nucleation

crystallization
growth rate

High supersaturation promotes nucleation

Very concentrated solutions of highly soluble precursors

Carbonates or hydroxides are intended due to their

low solubility
[Ni][OH]2=5.4710-6 moll-1; [Ni][CO3]=5.4710-7 moll-1

Based upon solubility constants the precipitation

order of the hydroxides is as follows Fe3+, Cr3+, Cu2+,
Zn2+ and Ni2+

Forward precipitation
Adding the base solution to
the acid (metal containing)
solution (pH increases)

pH=8.0

Reverse precipitation

Ce

Adding the metal solution to

the base (pH decreases)

Fe

343 K

Simultaneous precipitation
Base and acid are added
simultaneously to a base
solution and pH is carefully
controlled

NH4OH

pH, temperature, stirring, precursors and recovery

and thermal treatments are key features in the final
material morphology, structure and performance.

Mixed Cu/Zn/Al2O3 (methanol synthesis) are usually

prepared by coprecipitation from nitrate precursors
If pH = 7.0 very active catalyst is obtained as compared to
the solid obtained at pH < 6

Impregnation is the simplest method to preparing

supported catalysts.
(Water) solution containing the metal precursors is
contacted with a porous support
Dry impregnation (pore volume impregnation) the exact
amount of liquid to fill the pore volume of the support is
used vs Wet impregnation the amount of liquid is only
controlled by the solubility of the metal precursor

Electrostatic forces control the adsorption mechanism

Depending of the process conditions different profiles
of the active phase are obtained

The catalyst precursor in the

The Point of Zero Charge is the

solution becomes fixed to the

pH at which the surface is

support by different means;

electrically neutral

reaction, exchange with surface

OH groups or by adsorption

OH

The support has -OH groups

Si O Si O Si

OH

OH

depending on the thermal and

chemical history

The surface has OH groups

PZC is the pH where the surface

overall is electrically neutral

The charge of the surface hydroxyl groups varies with the pH

Electrostatic forces will lead to the preferential adsorption of

anions or cations onto the charged surface
+

OH2

OH2

OH2

Si O Si O Si

pH<pzc

Protonated surface pH< PZC

Si O Si O Si

pH>pzc

Deprotonated surface pH > PZC

pH<ZPC

OH2+

[PtCl6]2-

OH
pH>ZPC

O-

[(NH3)4Pt]2+

The maximum loading obtained is a monolayer

In reality it is much lower than a monolayer 1

complex/nm2 vs 8 OH/nm2 for alumina

CAREFUL: Solutions that are mild acid or basic do not

contain sufficient proton cations/hydroxyl anions to
protonate/deprotonate the surface so the pH of the
solution reaches the ZPC of the support

Support

PZC

Complex

MoO3

<1

Cations

Nb2O5

2-2.5

Cations

SiO2

Cations

Oxidized carbon

2-4

Cations

TiO2

4-6

Cations or anions

CeO2

Cations or anions

ZrO2

Cations or anions

Co3O4

7-9

Cations or anions

Al2O3

8.5

Anions or cations

Carbon black

8-10

Anions

Adapted from: Synthesis of solid catalysts, Ed. K.P. de Jong, 2009, Wiley

The distribution of the solute is

governed by the balance
between diffusion of solute
into the pores and adsorption
onto the support.
Concentration, viscosity and
contact time

Drying. Elimination of solvent.

Precipitation of ions. Fast
drying lead better dispersions
by creating higher
supersaturation
Adapted from: Synthesis of solid catalysts, Ed. K.P. de Jong, 2009, Wiley

Uniform distribution. Weakly interacting

precursors + mild drying
Egg-shell: Strong adsorption during
impregnation. Viscous solution. Slow
drying regime.
Egg-yolk. Fast drying regime. Preferential
adsorption of other species (citric acid)

Deposition-precipitation (DP).
DP is possible by the presence of the support which
provides nucleation sites for the metal precursor after
addition of a nucleation agent (base)
It is important to control base addition to avoid
concentration gradients during precipitation
Urea is an optimum precipitating agent since it gently
varies the pH leading to marginal concentration
gradients

Controlling atomic arrangement, size and shape

Size control (metal dispersion) by thermal treatments

Incipient wetness
impregnation

Ru(NO)(NO3)3

H2
-Al2O3

Dry at room
temperature for 12 h

1.5 wt.%
Ru

523 K / 1 h

4Ru

773 K / 1 h

5Ru

873 K / 1 h

7Ru

923 K / 1 h

8Ru

973 K / 1 h

12Ru

973 K / 2 h

16Ru

973 K / 3 h

23Ru

Size determines catalytic performances

200

TOF for CO dissociation vs size

4Ru

0.2

2.00.3 nm

0
150

0.1

8Ru

100

TOFCO(s )

Frequency

100

6.01.9 nm

50
0
30

12Ru

20

12.04.0 nm

10
0

10

15

Rusize(nm)

20

25

10

15

Rusize(nm)

20

25

microemulsion

1.00

H 2O
0.25

0.75

Or
ico
gn

Ag
ua

0.00

0.50

0.50

0.75

0.25

1.00
0.00

0.00
0.25

0.50

Surfactante
Orgnico

0.75

1.00

Metal
precursor

Ratio
0

oil
Particle
size
Surfactant/
Oil

Temperature

Surfactant

Metallic particles

H2 O

Bimetallic particles

H2 O

RhCl3

RhCl3

H2 O

HAuCl4
H2PtCl6

AuHCl4

H 2N2

Rh0

xides

H2PtCl6

Fe(NO3)3

Fe(NO3)3

H2N2 /NaBH4

PtAu

NaOH/NH4
OH
Fe[Oy(OH)x]

Size control of Rh particles by using MEM

Careful control of water/surfacant ratio determines the size of the
micelles
Catal
.

H2O
%

Org.
%

Surf.
%

oa

s/ob

nm

RhA

9,6

71,4

19,0

9,18

0,27

n.d.

RhB

1,8

85,4

12,8

2,46

0,15

RhC

2,6

84,7

12,7

3,69

0,15

10

RhD

0,7

78,4

20,9

0,53

0,27

22

RhE

2,6

76,9

20,5

2,26

0,27

30

3wt% Rh/Al2O3

PtRu/C from MEM

Positive effect on methanol
electrooxidation

111 fcc

200 fcc

220 fcc

331 fcc

222 fcc

Pt1

PR1
PR2
PR4
100 hcp
002 hcp 101 hcp

10

20

30

40

50

102 hcp

60

PR6
110 hcp

70

80

90

2 ()

Alloyed Pt-Ru (DRX)

H2PtCl6 + Ru(NO)(NO3)3
Berol O50; isooctano

Preferential growht directions

<111> (HRTEM)

100

Polyol method.

Easy method to prepare reduced

particles by taking advantage of the reducing power

of the polyol which acts both as solvent and reducing
agent.
CH2OH-CH2OH(l) + 14 OH- 2 CO32- + 10 H2O + 10 e- 0 = 1,65 V

0.9212 RT
E E
log OH
F

Pt particles in the range 15 nm can be obtained

The presence of protecting
agents or the support in
the reaction medium
impedes agglomeration of
primary particles
pH of 11 and higher are
needed to reduce Ru, Mo
or other metals
Narrow distribution of
nanosized Pt particles

SnCl2H2O
H2PtCl6
EG/NaOH
Carbon

Does it work with PtSn?

The polyol method does not work for all metallic

combinations
aPt3Sn=4,01

Pt/Sn=3

Temperature

Cell constant

TXRF
Pt/Sn

190C

a = 3,937

14

140C

a = 3,916

42

140C /5%
H2O

a = 3,916

42

Sn is loss during the synthesis !

H2PtCl6
SnCl2H2O
H2O/HCl
Carbon

EDS

Pt

Sn

Intensidad / u.a.

Cl

2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0

Energa / keV

45

Intensidad / u.a.

Pt

Cl

Sn

Thermal treatments
3

EDS

Sn??

2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0

Energa / keV

46

SnClx species are volatile

at ca. 160-200 C
They can be hydrolized in
water to Sn(OH)Cl

SnClx

H2O
HCl Cl2

Cl2

PtImp

SnCl3- + H2O Sn(OH)Cl+ HCl + ClSnClx is volatile during

thermal treatments

Sn(OH)Cl remains in the solid

47

Repeated wasing in water until pH = 7

Pt/Sn=3

fcc111

Tratamiento con agua

DRX

30

40

50

60

Pt3Sn

PtSnx

fcc311

fcc220

C002
20

fcc220

fcc200

EDS
u.a.

Fresch 1

70

2 Grados

80

90

S. Garca-Rodrguez y col. J.
Power Sources 195 (2010) 5564
48

Encapsulating metal

precursors with in
dendrimers renders
precursors for the
formation of very small
particles (few atoms)
It is possible to produce
alloys and core@shell
structures

Simultaneous
reduction of Pt&Ru
precursors
9
8
7
6
5
4
3
2
1
0
EDX counts (Ru L 1) / a.u.

EDX counts (Pt M 1) / a.u.

1.-Reduction of Pt
2.-Addition and Ru of Ru

8
7
6
5
4
3
2
1
0

0.0

0 .5

1 .0

1 .5

2 .0

2 .5

P o sitio n / n m

0.0 0 .5 1 .0 1 .5 2 .0 2.5 3 .0 3.5

3 .0

3 .5

It is possible to control the structure, shape and metal

content when preparing heterogeneous catalysts

Reaction conditions strongly affect the final catalyst

and as a consequence its final performance

There are many aspect yet to be rationalized

Nucleation by addition of
adequate agents
Above critical
supersaturation nucleation
commences
Below critical
supersaturation aggregation
of particles occurs
The larger the area the more
nuclei, the smaller the
particle
In microemulsion growing is
constrained within the
micelles

Interaccin
Metal-ion

Nucleacin

Interaccin
tomos
metlicos

Ncleo estable irreversible

H. B nemman et al and electrocatalysis at

M. Lade
et al, Colloids
and Surf.
A 163 (2000)
nanoparticles
surfaces;
A.Wieckowski
(Ed)3
Dekker, 2003