Adsorption

MF Suárez
Surface potential energy
Ideal surface
 Constant-height AFM images of
pentacene on NaCl(2ML)/Cu(111) using
different tips

"The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy," Science, 325, 1110 (2009)
Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine
coordinating to single iron and manganese atoms on Au(111)
a) STM image (12 × 12 nm2) of TMA−Fe network on Au(111). (b) High-resolution (3.75 ×
3.75 nm2) STM image of TMA−Fe with the model superposed. (c) STM image (8 × 8 nm2)
of PBP−Fe network on Au(111). (d) High-resolution (3.5 × 3.5 nm2),

Átomos en movimiento
Dynamic Surface

Imagen PEEM de los

patrones en espiral en la
escala de los micrómetros
durante la oxidación de CO
sobre Pt(110) en la
interface gas – sólido
(lapso de tiempo entre
cada imagen 30s). El
contraste se debe a la
variación en la función de
trabajo. Las áreas
brillantes corresponden a
zonas donde el CO esta
adsorbido y las oscuras al
oxigeno adsorbido.
FIM and time-of-flight mass
spectrometer

Topics in Catalysis Vol. 14, No. 1-4, 2001

A particle surface can undergo deep adsorption-
induced reconstruction. Field ion image of an Rh tip
conditioned as a nanoparticle either clean (a) or after exposure to O2
(b) at elevated temperatures (500 K). Adapted from Visart de Bocarme
´, T.; Kruse, N. Top. Catal. 2000, 14(1), 35–42.
SEM images of (a) an anatase particle
after UV irradiation in aqueous solution
containing 1 mM H2PtCl6 and 0.52M 2-
propanol and (b) an anatase particle after
sequential UV irradiation in the same
solution as in (a) and then in an aqueous
solution of 0.1 M Pb(NO3)2
 The highest surface areas

Carbon Nanotubes Grown Directly

on an Fe-Doped Carbon Aerogel

The British researchers will be developing Metal Organic

Frameworks (MOF) which can store gases like CO2 and
use catalysts to convert them into fuel or plastics.
Hierarchically porous metastable β-
Ag2WO4 hollow nanospheres

The material exhibits a large specific surface

area and hierarchically porous structure.
Nanotechnology, 24, 165602
Mesoporous single crystals of titanium
dioxide, Nature 495, 180–181 (14 March
2013) doi:10.1038/nature11961
SEM image of TiO2 nanowires as grown upon
Ti foil using the controlled oxidation method.
FESEM images of the nanostructured TiO2
obtained at different temperature from
100°C to 190°C. Scientific Reports 3,
Article number: 3004 (2013)
doi:10.1038/srep03004
Isotherm

BET capillary condensation

 Langmuir isotherm

Langmuir isotherm plot for the adsorption of

Cr(VI) into the micelle-clay complex. Contact
time = 3 h, temperature = 25.0 ± 0.2°C, and
adsorbent dosage = 5.0 g L−1. Data represent
averages of Cr(VI) triplicate measurements
(UV-vis) ± SE.
The Scientific World Journal 2013(1–
3):942703

kC
Γ(mol / g )=
(1+ kC )
BET isotherm
 Assumptions used to derive the BET
● No adsorbate - adsorbate interactions
● Gaseous molecules behave ideally
● Multiple molecules can be adsorbed to each site
● Each adsorbed molecule provides a site for the
adsorption of the molecule
In the layer above it
● All sites on the surface are equivalent
● An adsorbed molecule is immobile
● molecules in the second and higher layers are assumed
to be part of a liquid
 Nn kn - rate of condensation to form the nth layer
θn= k-n - rate of evaporation to form the nth layer
N
P - pressure above the surface
N - total number of sites

d θ0 k 1 θ0
=0=N (k −1 θ1 −k 1 P θ0) θ 1= P
dt k −1

d θ1
=0= N (k 1 P θ0 + k −2 θ2 −k 2 P θ1−k −1 θ1 )
dt

k2 2 k 2 k1
k −2 θ2=k 2 P θ1 θ2= P θ1=P θ0
k −2 k −2 k −1
 k2 2 k 2 k1
θ2= P θ1=P θ0
k −2 k −2 k −1
i−1
k k1 k2
i
θi =P ( 2
k −2
)
k −1
θ0 x=P
( )
k −2

i−1 k1 i 1 k1 P k1
θi =P x θ0=P x θ0 c=
k −1 x k −1 x k −1

θi =c x i θ0 Para i distinto de cero

 ∞ ∞
na =∑ i N θi n=∑ N θi θi =c x i θ0
i=0 i=0
∞ ∞ ∞
i
∑ i N θi ∑ θ0
i c x c θ0 ∑ i x i
na i=0
θ= = ∞ = i=0 ∞ = i=0
∞
n
∑ N θi θ0+ c θ0 ∑ x θ0+ c θ0 ∑ x
i i

i=0 i=1 i=1

∞
i x ∞
x
∑ x = 1− x i
∑ ix = (1− x)2
i=1 i=1

cx
θ=
(1− x)(1+ (c−1) x)
 Making Physical Sense of the Constants

k2 k2 P
x= P
k −2( ) 1
=
( )
P 0 k −2
x=
P0

P k1 k1 k −2 k 1
c=
x k −1 c= P 0
k −1
c=
( )
k 2 k −1

−Δ G vap −Δ G ad

c=e
( RT ) e( RT )
 Frumkin isotherm
−(Δ G+ g θ)
θ k 1
(
RT
)
= =e
P (θ−1) k −1

Simulated voltammetric profiles for the

Frumkin isotherm as afunction of the g value.

Phys.Chem.Chem.Phys.,2008,10, 1359–1373
The Gibbs approach to defining the surface excess
concentration Γ

σ
n
Γi = i
σ
A
U σ =TS σ −P σ V σ + γ A+ ∑ μ σi nσi
i
dU =TdS + γ dA+ ∑ μ d n
σ σ σ
i
σ
i
i

S dT + A d γ+ ∑ n d μ =0
σ σ
i
σ
i
i
σ
dγ n 1 dγ
= i =Γ i Γi =
d μi A RT d ln x 1
Interface structure
Surface relaxation

Atomic structure of MoS2 triangular

nanoclusters on the golden substrate
Au(111) surface. Author: Mr. Jakob
Kibsgaard (University of Aarhus,
Denmark).
Solid modifications
Competitive adsorption

k A PA
θ A=
(1+ k A P A+ k B P B )
Gas Chromatography
 Catalysis

Nature Communications 6, Article number: 6731 doi:10.1038/ncomms7731