Nanomaterials

Pore-confined Liquids

Petra de Jongh
Inorganic Chemistry and Catalysis
Debye Institute for Nanomaterials Science
Utrecht University
P.E.deJongh@uu.nl

Drive: beat “Abbe’s criterion” (Ernest Abbe 1873):

It is impossible to resolve two elements of a structure which are closer
to each other than about half of the wavelength ….

(diffraction limit)

Wavelength electrons 0.01 nm

But unsuitable for biological (let

alone living) samples

1
 2014 Nobel Prize in Chemistry:

for the development of super-resolved fluorescence

microscopy

Eric Betzig Stefan W. William E.

HH Med Inst Hell Moerner
Ashburn, MPI Stanford
USA Göttingen University

“Nanomicroscopy”
First papers in the late 1980’s, first prototypes 2000, now rapidly
spreading as a “standard” approach

Allows to look at biological and other (electron) beam sensitive

samples with single molecule resolution

Two criteria have to be met simultaneously to make it possible:

• Only one entity “optically active” in the field of view at a time
• Signal/noise ratio high enough to detect single molecules

Several techniques can be used to achieve that goal:

• Confocal microscopy
• Near field scanning optical microscopy
• Epifluorescence
• Total internal reflection

It allows to locate and study single molecules, but also follow their
behaviour as a function of time…

2
 /

Stefan Hell

e.g. single defects in diamond

Unlike conventional microscopy (left) which renders a featureless image, the super-
resoling STED microscope reveals individual luminescent atomic defects inside the
diamond crystal (center). The position of each defect (right) can subsequently be
determined with atomic scale precision (0.15 nanometer). Before breaking the diffraction
barrier by STED microscopy such recordings were considered to be practical impossible

3
Moerner: found how to switch molecule’s fluorescence off (1997)
Betzig (IBM) developed principle into working microscope (2005)

4
Overview of todays lecture

Nanopore-confined liquids

• Capillary condensation (liquid-vapour equilibrium)

• Wetting

• Melting-point depression (solid-liquid equilibrium)

Questions

Phase diagram

Equilibrium vapour ↔ liquid ↔ solid - normal situation

solid liquid

vapour

triple point
critical point

5
Phase diagram

Mind the difference between water and other compounds:

Nanopore-confined phases

What changes if you confine the phases in nanopores?

solid liquid

vapour

triple point
critical point

6
Nanopore-confined phases

What changes if you confine the phases in nanopores?

solid liquid

vapour

triple point
critical point

Nanopore-confined phases

Liquid-vapour equilibrium: capillary condensation

solid liquid

vapour

triple point
critical point

7
Confined liquids

Solid - liquid equilibrium: melting point depression

solid liquid

vapour

triple point
critical point

Overview of todays lecture

Nanopore-confined liquids

• Capillary condensation (liquid-vapour equilibrium)

• Wetting

• Melting-point depression (solid-liquid equilibrium)

Questions

8
Capillary condensation
If an object contains small pores, the water level is much higher inside
than outside the object. Why?

-> Capillary forces

Capillary condensation p  pliquid  pgas

Laplace equation:
liquid H2O

outward force: inward force:

2
4πr pgas = 4πr 2 pliquid  8πr
gasphase
2 H2O
pliquid  p
pgas  
r air cavity

surface tension 
tries to collaps the cavity
pgas>pliquid
p=balancing force

9
Capillary condensation
droplets with radius r

gasphase H2O gasphase H2O

liquid H2O
liquid H2O
flat surface

 liquid   gas  liquid    gas

gas
pliquid  pgas  p0 vliquiddp  vgas dp
vliquiddp  RT ln p  RT ln p0
2
2vl p p 
Kelvin equation:  RT ln r
r p0

H2O, T=293 K
Capillary condensation  = 0.072 J/m2
p0 = 0.023 atm
pores are filled at p<condensation pressure p0 vl = 18 cm3/mol
due to capillary forces:
2 vl
p 2v  
ln  l p fill  p0 e rRT
p0 rRT
r = 1 mm r = 1 m r = 1 nm
1.00 p0 0.999 p0 0.345 p0
r=
pfill = p0
gasphase H2O

liquid H2O

flat surface

10
Nanoporous materials

Nanoporous=containing pores with a diameter of less than 100 nm

IUPAC divides nanopores into:

micropores
(0.5-2 nm)

mesopores
(2-50 nm)

macropores
(>50 nm pores)

Ordered versus disordered porosity

Gasses interact with surfaces - thin adsorbed layer

gas phase

layer 2
layer 1

solid phase

11
Gasses interact with surfaces - thin adsorbed layer
K1
c gives the interaction strength between gas and surface
K2
6

4
/M

3
total

c=1
N

c=1000
2
c=100
c=10
1

0
0.0 0.2 0.4 0.6 0.8 1.0
relative pressure (p/p0)

Capillary action in micropores

Generally strong interaction (0.4 nm molecule in pores of different sizes)

plaatje

12
 N2, T=77 K
Capillary condensation p 2v 
ln  l  = 0.0085 J/m2
p0 rRT vl = 30 cm3/mol

Kelvin equation for N2 at 77 K:

1000
1.0
(nm)p/p0

0.8
100
pressure
diameter

0.6
10
relative

0.4
pore

1
0.2

0.1
0.0
0.0
0.1 0.21 0.4 10 0.6 1000.8 1.0
1000
relative pressure
pore diameter p/p0
(nm)

From 0.01<p/p0<0.99 : corresponds to 0.4 nm<pore diameter< 160 nm

Capillary action in micropores

micropores are filled at very low pressures
-> gas adsoprtion isotherms shift upwards

desorption
800 adsorption
Vads (cm /g STP)

600
3

400

200

0
0.0 0.2 0.4 0.6 0.8 1.0
p/p0

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 p 2v 
Capillary action in mesopores? ln  l
p0 rRT
Following the Kelvin equation, the gas becomes a liquid (at a given T)
at pressures much lower than the condensation pressure

adsorption isotherms are precise fingerprints of the porosity of materials

Capillary condensation in open cylindrical mesopores

Isotherm shows a sudden jump, and hysteresis

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Capillary condensation in open cylindrical mesopores

when filling a cylindrical adsorbate layer is present:

2 1 1
r t r  
reff r1 r2
r1 2 1 1
 
h reff  (r  t ) 

reff  2(r1  t )
r2=

vl 

in the adsorption isotherm a sudden jump ( r t ) RT
is expected for a critical pressure at:
p  p0 e

filling: reff  2(r  t )

Capillary condensation in open cylindrical mesopores

however when emptying the situation is different: hemispherical meniscus:

t reff 2 1 1
 
reff r1 r2
r1
2 2

reff (r  t )

reff  (r1  t )
r2
2v l

in the desorption isotherm a sudden jump
is expected for a critical pressure at:
p  p0 e ( r t )RT

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Capillary condensation in open cylindrical mesopores

Hence in the isotherm both adsorption and desorption show a sudden

jump, but at different p/p0!

v l 2v l
 
pads, jump  p0 e ( r t )RT
pdes, jump  p0 e ( r t )RT

Capillary condensation in open cylindrical mesopores

Mind, the effective radius is smaller if an adsorbed surface layer is

already present...

cylinder
height h
radius r

16
Can we see these effects?
Water in a carbon nanotube closed at one end

Environmental SEM

increasing pressure.

• constant shape of meniscus

• non uniformity

Open nanotube

emptying

filling Marangoni effect

17
Overview of todays lecture

Nanopore-confined liquids

• Capillary condensation (liquid-gas equilibrium)

• Wetting

• Melting-point depression (solid-liquid equilibrium)

Questions

Wetting

Kelvin equation:

p 2vl
ln 
p0 rR T
However, this is assuming “complete wetting”

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Wetting

Contact angle 

water on water on
hydrophilic surface hydrophobic surface
 is close to 0o  > 90o

Surface energy  J/m2

Surface tension  N/m

Wetting

Young Equation:  sv   sl   lv cos 

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Combining with Kelvin equation:

p 2v  cos 
ln  l
p0 rRT

• gas has weak interaction

• solid rather chemical bonds

This is only relevant to liquids

-> liquid <-> vapour equilibrium
-> solid <-> liquid equilibrium

Overview of todays lecture

Nanopore-confined liquids

• Capillary condensation (liquid-gas equilibrium)

• Wetting

• Melting-point depression (solid-liquid equilibrium)

Questions

20
Confined liquids

Vapour - liquid equilibrium: Capillary condensation:

solid liquid

vapour

triple point
critical point

Confined liquids

Solid - liquid equilibrium: melting point depression

solid liquid

vapour

triple point
critical point

21
Melting and Freezing

Gibbs-Thomson equation: T 2vl sl


influence particle size Tm reff H m
(surface energy)
on melting point

experimental melting temperatures for small gold

particles: experiments and theory (solid line)

J.P. Borel, Surf. Sci. 106 (1981) 1-9

Melting and Freezing:

The Gibbs-Thomson equation is generally nicely obeyed,

if a non-freezing (wetting) layer is taking into account…

T  T0  Tm (reff )

2T0 ( ws   wl ) l cos 

H f reff

C GT
T 
rp  t

to = 0.20-1.08 nm

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Melting and Freezing:  ws   wl   sl cos
The curvature is now determined by the
T 2v  cos 
  l lv
interaction of the liquid with the pore wall:
Tm reff H m

θ = 0o, wetting, lower Tm

θ = 180o, dewetting, higher Tm

θ = 90o, no change in Tm

T 2v  cos
Melting and Freezing   l lv
Tm reff H m

no wetting-> higher melting point

wetting-> lower melting point

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Melting and Freezing:

The freezing/melting temperature and enthalpy of a liquid

are conveniently measured calorimetrically (DSC)

water in ordered mesoporous silica with different pore sizes

(almost perfect wetting)

Melting and Freezing:

If more water is added than is needed to fill the pores…

increasing
the amount
of liquid

… another method to determine the porosity of nanoporous materials

Eggenhuisen, Talsma, de Jong(h), JPCC 113 (2009) 16785

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What you should understand:
• wetting and capillary pressure
• the impact of pore confinement on melting point
• the impact of pore confinement on the condensation pressure

What you should be able to do:

• calculate expected change in phase behaviour due to nanoconfinement
• explain observed behaviour of liquids in nanopores

For the next lecture: please read Chapter 5 (Supported Nanoparticles)

which is provided in the reader

Overview of todays lecture

Nanopore-confined liquids

• Capillary condensation (liquid-gas equilibrium)

• Wetting

• Melting-point depression (solid-liquid equilibrium)

Exercises:
• Question 3 from chapter 4 (reader)
• Question2 on page 22-23 (course manual)

25
 Phase diagram Ni(NO3)2-H2O

115

Molten phases
95

75

55
Homogeneous
solution
T (°C)

35

15
Solid phases
-5 0 10 20 30 40 50 60 70 80 90 100

Ice Eutectic 6H2O

-25

-45

Pure H2O Ni(NO3)2 in weight% 9H2O 4H2O Pure Ni(NO3)2

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Confined liquids

RbBr solution in porous carbon:

• Preferential adsorption of ions to the wall (Rb+)

• Variation in coordination number (Br-)

-> differences in solubility product, heat of dissolution,

density of solvent, dielectric properties, …

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