Institute for Materials Research

University of Salford

Hydrogen adsorption on carbon

surfaces

Keith Ross, Ian Morrison, Peter Georgiev, Jian Liu, Xiangyuan

Cui, Dan Bull, Juan Fernandez-Garcia;
Institute for Materials Research
University of Salford, Manchester, UK.

Timmy Ramirez-Cuesta, Mark Adams, Daniel Cologneisi, Ken

Anderson,
ISIS, Rutherford Appleton Laboratory, Didcot, Oxon
Institute for Materials Research
University of Salford
† Hydrogen adsorption on carbon
surfaces
† Measured using IGA
† N2 BET Measurements
† H2 at pressures up top 20 Bars
† On a Chemical Potential plot, a fixed
adsorption energy gives a straight
line
 0.030

a
0.025

0.020

mg H2/m adsorbent
Storage density,
0.015

2
0.010

AP
0.005 SE
Darco
0.000

0 2000 4000 6000 8000 10000 12000

Pressure, mBar

0.030
AP

b
SE
0.025
Darco

0.020
mg H2/m adsorbent
Storage capacity,

0.015
2

0.010

0.005

0.000

-90 -80 -70 -60 -50 -40 -30

Chemical potential, meV

Hydrogen storage densities of the three materials as

functions of the equilibrium pressure in a, and the
chemical potential in b.
 1.0 o
Data: H 2 on SE @ 77 K
Model: Fermi-Dirac Double
0.8 Chi^2 = 0.00002
E 1 -83.88681 ±0.4791meV
C 1 0.20903 ±0
Fractional coverage,Θ

0.6 E 2 -41.53018 ±0.05515meV

C 2 0.8 ±0
T 9.43231 ±0.09288meV
0.4

0.2

0.0

-0.2
-90 -80 -70 -60 -50 -40 -30
Chemical potential, meV

Fig. 8.6 Hydrogen adsorption isotherm of the SE grade nanotube material fitted with a two-site Fermi-Dirac
model. The site frequency was kept fixed during the fiiting.
Analysis of adsorption data
† The isotherms can be fitted with Fermi Dirac statistics
(Langmuir) with two different adsorption energies

Material Surface Storage Isosteric heat Effective adsorbate

area, capacity, of adsorption, temperature, oK
m2/g wt% at meV/H2 molecule
N2 10Bar and
sorption 77oK
at 77oK

Carbolex
AP 247 0.70 Fitted 110 K

Carbolex 374 1.05 -74.5, -32.1

SE fixed to 77 K with two
adsorption energies
HSA Darco 1325 2.43 -52.6, -34.9
IINS Spectra from H2 on SWNT for different H2 coverages
Sample is Carbolex (Selected grade) - Instrument is TOSCA at ISIS
Spectra for range of surface coverages
Sharp peak at 14.7 meV, no recoil – broad peaks at higher energy
include recoil

3 a c o v e ra g e
0%
22%
38%
Neutrons/meV

2
77%
110%

50 100 150 200 250 300 350

E n e r g y lo s s , m e V
Detail in the 14.7 meV peak showing the development of the
different peak components with increasing surface coverage.
Note that the double peak structure dominates at lower
coverages

3 coverage
a 0%
22%
38%
77%
Neutrons/meV

2
110%

9 10 11 12 13 14 15 16 17 18 19 20
Energy loss, meV
Variation of peak intensities as a function of surface
coverage

2:1 peak intensity ratio suggests asymmetric site, i.e. vdW potential normal to
planar surface. The m =+/- 1 states are at a lower average potential energy than
the m=0 level where the molecule precesses with the defined axis of spin parallel
to the surface.

2.2
2.0 E=13.5meV Rotationally
E=14.2meV free H 2
1.8 E=14.6meV
1.6 E=15.1meV

1.4
Peak integral intensity

1.2 J=0,m=0 to J=1,m=+-1

transition of the perturbed
1.0 Perpendicular
adsorbate
0.8 vibration ?

0.6
J=0,m=0 to J=1,m=0
0.4
transition
0.2
0.0
-0.2
-20 0 20 40 60 80 100 120 140 160
Surface coverage, %
Comparison of the rotational levels for SWNT and a high
surface area activated carbon. The activated carbon
appears to have a more strongly distorted adsorption site

SWNT
Activated carbon

10 12 14 16 18 20

Neutron energy loss, meV

Young and Koppel Expression
† SJ-J’ (Q,ω) =

ΣJm,J’m FJm,J’m (Q) δ(ω-ωmJ,m’J’) * SCM (Q,ω)

FJm,J’m (Q) is the Form Factor for the transition

SCM (Q,ω) is the Scattering Function for the Centre of Mass

motion in the potential energy surface seen by the molecule

For a bound atom, this consists of a delta function modified by

the Debye-Waller factor for the molecule and an inelastic
part – which for large Q becomes like the Perfect Gas Law
but with a higher temperature
Molecular form factors for different angular momentum
transitions (Y & K). NB We are measuring the 0-1
transition.

Molecul
ar
form- 15
factor,
F 0 -1
Barn
F 1 -1
F 1 -2
10

0 1 2 3 4 5
Q, Å
 (a) Fits to the recoil spectra for 100% and 144% surface
coverage using Y and K between 85 and 500meV
(b) Plot of fitted temperature versus surface coverage

140

135
1
130

125

120
<EK
115
>,
S(Q K 110
,ω
105

100

95

90

85

0 80
200 400 600 20 40 60 80 100 120 140 160
Neutron energy loss, Surface coverage, %of
meV monolayer
Comparison of the Debye Waller factor derived from the
Q dependence of the rotational peak with the mean
thermal energy of the recoil peaks

6.5

6.0

5.5

5.0

4.5
1/<U >

4.0
2

3.5

3.0

2.5

2.0

1.5

1.0
80 90 100 110 120 130 140

<EK>, K
 Parameters from fitting c-m elastic term and recoil together
H2, content Peak FWHH (meV) Peak Area Mixing , <Ek> , K
% of a position, (forward, (forward factor U2 Å2
monolayer meV backward) de, Å
Backward)
80, 30K 13.9±0.1 2.2±1.0 1.2±0.2 0 0.20±0.07 129±1
2.2±0.7 1.0±0.1 0
14.1±0.4 1.5±0.8 0.33±0.2 1 0.26±0.3
1.2±0.9 0.35±0.2 1 0.774
14.55±0.03 0.7±0.3 0.7±0.2 1 0.40±0.17
0.7±0.2 1.25±0.4 1
15.0±0.1 1.9±0.3 0.6±0.1 0 0.23±0.07
2.1±0.3 0.6±0.2 0
85, 25K 13.8±0.5 2.0±0.7 1.6±0.7 0 0.15±0.3 121±1
2.3±0.6 1.1±0.9 0
14.4±0.1 0.7±0.2 0.6±0.2 1 0.35±0.2
1.1±0.2 0.9±0.4 1 0.775
14.6±0.05 0.5±0.3 0.4±0.3 1 0.49±0.15
0.6±0.2 1.0±0.3 1
15.3±0.3 1.8±0.4 0.7±0.2 0 0.08±0.2
1.4±0.5 0.4±0.3 0
100, 20K 13.6±0.5 1.6±0.3 1.1±0.1 0 0.13±0.1 116±1
1.6±0.5 0.7±0.3 0
14.3±0.1 0.6±0.1 0.7±0.1 1 0.37±0.15
0.7±0.2 1.1±0.5 1 0.775
14.63±0.04 0.6±0.06 1.2±0.3 1 0.32±0.14
0.5±0.1 1.6±0.4 1
15.3±0.3 1.7±0.4 0.6±0.2 0 0.18±0.2
1.6±0.6 0.5±0.3 0
Graph showing the rate of conversion of ortho to para hydrogen
when adsorbed on SWNT and DARCO carbon.
Transition half live SWNTs 3 mins DARCO 16 mins
Magnetic SWNTs? Iron catalyst is covered with amorphous
carbon.

EISF,
arb.
units

0 10 20 30 40 50

n-H 2 on SW N T , 20K
n-H 2 on D A R C O ,20K

0 100 200 300 400

Time, min
New MARI data on SWNT sample from Heben
Monolayer coverage 140m ccs H2 at NTP

Q=2.4-2.9, T=17K
140cc pH2
40cc
17cc
S(Q,ω)

0 12 14 16 18 20

X Neutron energy loss, meV

Axis Title
Heben Sample MARI 20% coverage
Average over full Q range

27cc p-H2
S(Q,ω) Q=1.7-3.8A

8 10 12 14 16 18 20

X Axis Title
Q dependence of the peak intensity
for 27 ccs (20% coverage)
Inset compares 17ccs
values are <u2> for different coverages

16

14 27cc p-H2
0.27±0.01Å2
T=17 K
12

10
Y Axis Title

S(Q,ω)

8
10

6 8 0.24±0.02Å2
6
Y Axis Title

4
4

2 2 0.29±0.01Å2
0 0

0 1 2 3 4 5

-2 X Axis Title

0 1 2 3 4 5
Q, Å-1
X Axis Title