Chemistry Journals

Adsorption isotherm of dibenzyltoluene and its partially hydrogenated forms over

phenylhexyl silica
--Manuscript Draft--

Manuscript Number: Chemistry Journals-17-221

Full Title: Adsorption isotherm of dibenzyltoluene and its partially hydrogenated forms over
phenylhexyl silica

Short Title:

Article Type: Research Article

Section/Category: Modern Chemistry & Applications

Keywords: adsorption isotherms; LOHC; RP-HPL

Corresponding Author: Rabya Aslam, Ph.D

University of the Punjab, Lahore
Lahore, PAKISTAN

Corresponding Author Secondary

Information:

Corresponding Author's Institution: University of the Punjab, Lahore

Corresponding Author's Secondary

Institution:

First Author: Rabya Aslam, Ph.D

First Author Secondary Information:

Order of Authors: Rabya Aslam, Ph.D

Karsten Mller, PhD

Order of Authors Secondary Information:

Manuscript Region of Origin: GERMANY

Abstract: Liquid organic hydrogen carriers (LOHC) are an interesting option for chemical energy
storage and hydrogen transportation. Dibenzyltoluene (H0-DBT), heat transfer oil, is
capable of reversibly storing hydrogen emerged as a feasible LOHC system. However,
it is not available as a pure compound but consists of an isomeric mixture of 6 to 8
compounds. During the hydrogen storage process a high number of stable
intermediate species is formed. These compounds can be categorized into four main
classes according to their degree of hydrogenation. To implement H0-DBT as a LOHC
system, thermophysical data of these intermediate compounds are required. In our
previous work, a reversed phase HPLC method was developed using phenylhexyl
silica stationary phase and acetone/water as eluent to separate these partially
hydrogenated fractions with a purity > 98%. For further designing a batch or continuous
HPLC process, adsorption isotherm data are required. In this work, adsorption
isotherms for dibenzyltoluene and its partial and fully hydrogenated forms namely
hexahydro-dibenzyltoluene, dodecahydro-dibenzyltoluene, and octadecahydro-
dibenzyltoluene are measured over phenylhexyl silica in acetone/water solvent using
the static method. Sip's equation (Combined Langmuir-Freundlich isotherm) fits the
data better as compared to simple Freundlich, Langmuir or competitive Langmuir
adsorption isotherms.

Suggested Reviewers: Sofia Chaudry, PhD

Murdoch University
sofichem.au@gmail.com
Experienced in the field

Chung Sung-Tan
National Tsing Hua University
cstan@che.nthy.edu.tw

Powered by Editorial Manager and ProduXion Manager from Aries Systems Corporation
 Experienced in the field.

Mirjana Mincheva
Technische Universitat Munchen
mirjana.mincheva@tum.de
Expert in the field

Opposed Reviewers:

Powered by Editorial Manager and ProduXion Manager from Aries Systems Corporation
Manuscript Click here to download Manuscript manuscript-OMIC.docx

Adsorption isotherm of dibenzyltoluene and its

partially hydrogenated forms over phenylhexyl silica

Rabya Aslam1,2, Karsten Mller,*1

1
Institute of Separation Science and Technology, Friedrich-Alexander-Universitt Erlangen-Nrnberg.
2
Institute of Chemical Engineering & Technology, University of the Punjab, Lahore, Pakistan.
* (Tel.: +92 42 9230462; Fax. +92 42 9231159; e-mail: rabya.icet@pu.edu.pk )
Abstract

Liquid organic hydrogen carriers (LOHC) are an interesting option for chemical energy storage
and hydrogen transportation. Dibenzyltoluene (H0-DBT), heat transfer oil, is capable of reversibly
storing hydrogen emerged as a feasible LOHC system. However, it is not available as a pure
compound but consists of an isomeric mixture of 6 to 8 compounds. During the hydrogen storage
process a high number of stable intermediate species is formed. These compounds can be
categorized into four main classes according to their degree of hydrogenation. To implement H0-
DBT as a LOHC system, thermophysical data of these intermediate compounds are required. In
our previous work, a reversed phase HPLC method was developed using phenylhexyl silica
stationary phase and acetone/water as eluent to separate these partially hydrogenated fractions with
a purity > 98%. For further designing a batch or continuous HPLC process, adsorption isotherm
data are required. In this work, adsorption isotherms for dibenzyltoluene and its partial and fully
hydrogenated forms namely hexahydro-dibenzyltoluene, dodecahydro-dibenzyltoluene, and
octadecahydro-dibenzyltoluene are measured over phenylhexyl silica in acetone/water solvent
using the static method. Sips equation (Combined Langmuir-Freundlich isotherm) fits the data
better as compared to simple Freundlich, Langmuir or competitive Langmuir adsorption isotherms.

Key words: adsorption isotherms, LOHC, RP-HPLC

1 Introduction

Liquid organic hydrogen carriers (LOHC) are a promising approach for hydrogen storage and

transportation. This concept is based on the reversible cycle of hydrogenation and dehydrogenation

for uptake and release of hydrogen[1-5]. The LOHC system consists of a pair of dehydrogenated

and hydrogenated compounds representing the hydrogen lean and rich forms, respectively. Due to

the chemical bonding of the hydrogen in the hydrogenated LOHC compound, the latter can store

H2 at ambient conditions over longer periods. Recent studies shows the potential of dibenzyltoluene

(H0-DBT) as a competitive LOHC system due to its reasonable hydrogen storage capacity and

thermal stability [5, 6]. Each H0-DBT molecule can store 9 molecules of hydrogen in the form of

octadecahydro-dibenzyltoluene (H18-DBT). However, to implement it as LOHC system, its

thermophysical data are required. Since it is not available as pure compound and partial

hydrogenation further produces a number of stable intermediate species. More than 24 compounds

are observed in a partially hydrogenated reaction mixture which can be classified into four main

fractions on the basis of their degree of hydrogenation namely dibenzyltoluene (H0-DBT),

hexahydro-dibenzyltoluene (H6-DBT), dodecahydro-dibenzyltoluene (H12-DBT), and

octadecahydro-dibenzyltoluene (H18-DBT). In our previous work, a reversed phase high pressure

liquid chromatography method was developed and successfully scaled up to semi preparative scale

for the separation of these partially hydrogenated derivatives of dibenzyltoluene with phenylhexyl

silica as stationary phase and a acetone water mixture as mobile phase (96/4, v/v %)[7].

In order to simulate and design a linear or non-linear chromatographic processes, adsorption

isotherm data over mobile and stationary phase are required which describe the distribution

behavior of the DBT fractions in the chromatographic system[8-10]. Adsorption isotherms can

experimentally be determined using static (shake-flask and adsorption-desorption methods) or

dynamic methods (frontal analysis method, elution curve methods and minor perturbation
methods)[8, 11, 12]. Moreover, for a mixture, competitive isotherms can be predicted using single

solute adsorption isotherm but it often comes with limited applicability range and accuracy[8].

In this work, adsorption isotherm data of single isomers of dibenzyltoluene derivatives such as

dibenzyltoluene, hexahydro-dibenzyltoluene, dodecahydro-dibenzyltoluene, and octadecahydro-

dibenzyltoluene are determined using static method over phenylhexyl silica from a acetone/water

solution (96/4, v/v%) within a concentration range of 0-25 mg/ml at 22 1 C.

2 Materials and methods

2.1 Materials

The stationary phase phenylhexyl silica (Luna 15 m, 100 A) was purchased from Phenomenex,

Germany. The specifications of the adsorbent provided by the supplier are summarized in Table 1.

The single isomers of dibenzyltoluene, hexahydro-dibenzyltoluene, dodecahydro-dibenzyltoluene

and octadecahydro-dibenzyltoluene were separated and purified via vacuum distillation and

reversed phase high pressure liquid chromatography with > 99 % purity. The details of the

separation process are described in section 2.2.1. The HPLC grade acetone was purchased from

VWR Germany and 18 M water produced by a Milli Q integral-3 system (Merck Millipore) was

used in the experimental work. The details of the chemicals used are given in Table 2.

------------------------Table 1-------------------------

---------------------Table 2-----------------------------

2.2 Methods

2.2.1 Separation of dibenzyltoluene derivatives

Single isomers of dibenzyltoluene derivatives representing each fraction of dibenzyltoluene were

separated in two steps. Firstly, vacuum distillation was used to separate a partially hydrogenated

reaction mixture. The distillation was performed in packed distillation column (Normag GmbH,

Germany) equipped with Sulzer structured packing (L = 2m, DXP, SS 1.4404). Due to the

overlapping range of boiling points, pure compounds were not obtained via distillation but fractions

consisting of compounds with similar boiling points were obtained. The batch plot for vacuum

distillation experiment and boiling point range of DBT-fractions is provided in the supporting

information. Then in the second step, using those fractions as feed, single isomers representing

each fraction of dibenzyltoluene were separated on semi-preparative scale column (250 mm (L) x

50 mm (I.D.)) using reversed phase liquid chromatography. The detailed procedure can be found

somewhere else[7]. The GC analysis and NMR analysis of each isomer used in this work is given

in the supporting information.

2.2.1 Measurement of adsorption isotherm

The adsorption isotherms were measured using a static method (shake-flask method)[13]. Solutions

in acetone/water (96/4 %, v/v) containing equal concentration of dibenzyltoluene (H0-DBT),

hexahydro-dibenzyltoluene (H6-DBT), dodecahydro-dibenzyltoluene (H12-DBT), and

octadecahydro-dibenzyltoluene (H18-DBT) were prepared in 10 ml bottles for the concentration

range of 0.1-25 mg/ml . The upper threshold of concentration was determined on the basis of the

least soluble compound, i.e., H18-DBT in acetone/water solvent. The uncertainty of the initial

concentration was 0.01 mg/ml. Then a fixed amount (0.5 0.003 g) of phenylhexyl silica was

added to each bottle and the tightly closed bottles were kept for 24 hours under stirring. Preliminary

experimental studies indicate that the adsorption equilibrium was reached after 18 hours for all

components. The same procedure was repeated for the determination of the isotherms of
dibenzyltoluene and octadecahydro-dibenzyltoluene fractions. It should be noted that fraction

represents the isomeric mixture of components with same degree of hydrogenation. The initial and

final concentrations were measured using Gas Chromatography (Agilent technology 7890 A

system). The amount of solutes adsorbed on phenylhexyl silica were determined with initial and

equilibrium concentrations using eq. (1).

( )
= (1)

where Ci and Ce are initial and equilibrium concentrations of solutes, respectively; m is the mass

of the phenylhexyl silica phase in gram and v is the volume of solution. Each measurement was

repeated three times and the standard deviation was found to be less than 5 %.

3 Results

The experimental data for the adsorption isotherm for fraction of dibenzyltoluene and

octadecahydro-dibenzyltoluene and single components of dibenzyltoluene, hexahydro-

dibenzyltoluene, dodecahydro-dibenzyltoluene, and octadecahydro-dibenzyltoluene over

phenylhexyl silica in acetone/water solvent (96/4, v/v %) at 22 1 C are presented in Table 3 and

4. It was observed that adsorption to stationary phase increased with degree of hydrogenation of

compounds i.e. phenylhexyl silica has three times more adsorption capacity for fully hydrogenated

octadecahydro-dibenzyltoluene in comparison to fully dehydrogenated dibenzyltoluene at the same

concentration.

-----------------Table 3-----------------

------------------Table 4-------------------
Moreover, the results show that within the studied concentration range (0 to 25 mg/ml), the

adsorption isotherm for H0-DBT and H18-DBT were not influenced by other species as single

component data were comparable with the competitive adsorption isotherms within deviation of

only 1 % as shown in Figure 1.

------------------------------------Figure 1-----------------------

3.1 Correlation of experimental data

Due to the negligible difference between the single and competitive adsorption isotherms (Figure

1), it was assumed that components do not influence each other during adsorption within

concentration range studied. Several equations for correlating single component adsorption data

such as Freundlich, Langmuir and combined Langmuir-Freundlich (also known as Sips equation)

were evaluated for the correlation of the experimental data. The Freundlich isotherm with two

parameters is given by eq (2).[14, 15]

= (2)
Where qe is the amount of solute adsorbed on the stationary phase, k and n are Freundlich

parameters. The Langmuir adsorption isotherm with two parameters is described by eq (3) [14, 15].

= qsat (3)
1 +

Where qsat is the saturation capacity of monolayer and b is second Langmuir parameter which

quantifies the adsorption energy Hads using eq (4)[14].

= (4)
qsat
The parameters for the Freundlich equation, Langmuir equation, and Sips equation are presented

in Table 4. The Freundlich correlation did not fit the experimental data satisfactorily (with 13 data
points for each compound), especially at low concentrations. The average relative error for the

Freundlich model was 11.6 % with a maximum deviation of 18.4 % observed at low concentrations.

For the Langmuir model, the fitting results were better in comparison to the Freundlich correlations.

However, the Langmuir model fits the H0-DBT and H6-DBT data satisfactorily but gives poor

fitting for H12-DBT and H18-DBT data. The average relative error for the Langmuir isotherm was

6.2 % with a maximum error of 13 %. The relative error was high at low concentrations while the

fit was observed to be better at high concentrations. A comparison of the Langmuir and Freundlich

isotherms with experimental data is presented in Figure 2.

------------------Figure 2-------------

The Sips equation with three parameters (eq (5)) correlates the experimental data within the

working concentration range better compared to the other correlations.

(. )
= (5)
1 + (. )
Although the number of parameters (three instead of two) increases, higher values of adj. R2

(adjusted determination coefficient) and Q2 (cross validated determination coefficient) show the

better fit quality (compare Table 5). Additionally, the calculated average relative deviation was

only 0.5 % with a maximum value of 0.6 %. The comparison of the Sips equation data with the

experimental data is presented in Figure 3.

-----------------------Figure 3: --------------------

Additionally, the bi-Langmuir adsorption isotherm (eq (6)) was used to correlate the experimental

data by assuming the maximum loadability equal for all components in the system [14, 15]..

, = , 6
1 + =1

As expected, the model based on this assumption did not fit the data well because the loadability

for various hydrogenated fractions is fairly different for the different compounds. If maximum

loadability is considered to be different for all compounds, 8 parameters would be needed to fit eq

(6) to 13 experimental data points. Such a high number of parameters do not seem to be reasonable.

Thus, within the studied concentration range, Sips equation was found to be the best suited

correlation for the adsorption isotherms of all partially hydrogenated derivatives of

dibenzyltoluene.

4 Conclusions

In this work, adsorption isotherm data for single isomers of dibenzyltoluene, hexahydro-

dibenzyltoluene, dodecahydro-dibenzyltoluene and octadecahydro-dibenzyltoluene are presented.

The distribution of these components has been investigated between a acetone/water (96/4, v/v)

liquid phase and a phenylhexyl silica (stationary phase) at 22 1C within the concentration range

from 0 to 25 mg/ml. Langmuir and Freundlich isotherms with 2 parameters and Sips equation

(combined Langmuir-Freundlich equation) with 3 parameters and multicomponent isotherm based

on the Langmuir model (with 8 parameters) were used to correlate the experimental data. Good

agreement with experimental data was found for Sips equation as compared to the other models.

Moreover, adsorption isotherms data for single components of dibenzyltoluene and octadecahydro-

dibenzyltoluene were comparable with their competitive adsorption isotherms. Thus, influence of

the individual components on each other were found to be negligible within the studied

concentration range.
Acknowledgments

This work has been done within the framework of the Bavarian Hydrogen Center and has been

funded by the state of Bavaria. The authors wish to thank Prof. Peter Wasserscheid, Dr. Andreas

Bsmann, and Michael Mller for the provision of partially hydrogenated dibenzyltoluene mixture

and Prof. Wolfgang Arlt as well as Prof. Malte Kaspereit for valuable discussion.

List of Tables

Table 1: Specifications of phenylhexyl Silica provided by manufacturer

Table 2: Purity information of chemicals used

Table 3: Experimental competitive adsorption isotherm data for dibenzyltoluene derivatives from
acetone/water (96/4, v/v) solution over phenylhexyl silica

Table 4: Single component adsorption isotherm data for dibenzyltoluene and octadecahydro-
dibenzyltoluene from acetone/water (96/4, v/v) solution over phenylhexyl silica

Table 5: Model parameters for adsorption isotherms with statistical parameters

List of Figures

Figure 1: Comparison of single component isotherm with competitive isotherm for H0-DBT and
H18-DBT
Figure 2: Comparison of experimental and modelled data using Langmuir and Freundlich
isotherms.
Figure 3: Comparison of experimental and modelled data using Sips equation.
References:

1. Mller, K. and W. Arlt, Status and Development in Hydrogen Transport and Storage for
Energy Applications. Energy Technology, 2013. 1(9): p. 501-511.
2. Mller, K., et al., Amine Borane Based Hydrogen Carriers: An Evaluation. Energy &
Fuels, 2012. 26(6): p. 3691-3696.
3. Usman, M.R., The Catalytic Dehydrogenation of Methylcyclohexane over Monometallic
Catalysts for On-board Hydrogen Storage, Production, and Utilization. Energy Sources,
Part A: Recovery, Utilization, and Environmental Effects, 2011. 33(24): p. 2231-2238.
4. Teichmann, D., W. Arlt, and P. Wasserscheid, Liquid Organic Hydrogen Carriers as an
efficient vector for the transport and storage of renewable energy. International Journal of
Hydrogen Energy, 2012. 37(23): p. 18118-18132.
5. Markiewicz, M., et al., Environmental and health impact assessment of Liquid Organic
Hydrogen Carrier (LOHC) systems - challenges and preliminary results. Energy &
Environmental Science, 2015. 8(3): p. 1035-1045.
6. Brckner, N., et al., Evaluation of Industrially Applied Heat-Transfer Fluids as Liquid
Organic Hydrogen Carrier Systems. ChemSusChem, 2014. 7(1): p. 229-235.
7. Aslam, R., et al., Development of a liquid chromatographic method for the separation of a
liquid organic hydrogen carrier mixture Separation and Purification Technology, 2016.
8. Lisec, O., P. Hugo, and A. Seidel-Morgenstern, Frontal analysis method to determine
competitive adsorption isotherms. Journal of Chromatography A, 2001. 908(12): p. 19-
34.
9. Schmidt-Traub, H., Preparative Chromatography: Of Fine Chemicals and
Pharmaceutical Agents. 2005: Wiley.
10. Ching, C.B., K.H. Chu, and D.M. Ruthven, A study of multicomponent adsorption
equilibria by liquid chromatography. AIChE Journal, 1990. 36(2): p. 275-281.
11. Knoerzer, K., et al., Innovative Food Processing Technologies: Advances in Multiphysics
Simulation. 2011: Wiley.
12. Myers, A.L. and J.M. Prausnitz, Thermodynamics of mixed-gas adsorption. AIChE
Journal, 1965. 11(1): p. 121-127.
13. Bonomo, R., Multicomponent adsorption of whey proteins by ion exchanger.
14. Hindarso, H., et al., Adsorption of Benzene and Toluene from Aqueous Solution onto
Granular Activated Carbon. Journal of Chemical & Engineering Data, 2001. 46(4): p.
788-791.
15. Wan, X., J. Lee, and K. Row, Nonlinear isotherm of benzene and its derivatives by frontal
analysis. Korean Journal of Chemical Engineering, 2009. 26(1): p. 182-188.
Cover Letter

Dear Editor,

Please find enclosed the manuscript Adsorption isotherm of dibenzyltoluene and its
partially hydrogenated forms over phenylhexyl silica by the authors Rabya Aslam and
Karsten Mller to be submitted for publication in OMICS Group - Chemistry Journals.

The manuscript has not been submitted simultaneously for publication elsewhere and has
not been published before.

Looking forward to hearing from you.

Sincerely yours,
Dr. Rabya Aslam

Researcher
Chair of Separation Science & Technology
Friedrich-Alexander University Erlangen-Nuremberg
Egerlandstrasse 3
Erlangen, D-91058
Tel +49 9131 85 27449
Fax +49 9131 85 27441
rabya.icet@pu.edu.pk
Figure 1 Click here to download Figure Figure 1.JPG
Figure 2 Click here to download Figure Figure 2.JPG
Figure 3 Click here to download Figure Fig 3.JPG
Table 1 Click here to download Table Tables 1.docx

Table 1: Specifications of phenylhexyl Silica provided by manufacturer

Parameter Value
Particle size 11-15 m
Particle size distribution 1.8 (dp 90/10)
Pore diameter 100 A
Surface diameter 390 m2/g
Bulk density 0.58 g/cm3
Total carbon 16 %
Metal contents 11 ppm
Table 2 Click here to download Table table 2.docx

Table 2: Purity information of chemicals used

Degree of
Purity Analysis
Chemicals hydrogenation
(mass %) method
(%)
Dibenzyltoulene
> 99 0 GC-MSa
(H0-DBT)+
Hexahydro-dibenzyltoluene
> 99 33 GC-MSa
(H6-DBT)+
dodecahydro-dibenzyltoluene
> 99 67 GC-MSa
(H12-DBT)+
octadecahydro-dibenzyltoluene
> 99 100 GC-MSa
(H18-DBT)+
Acetone > 99 - -
Table 3 Click here to download Table table 3.docx

Table 3: Experimental competitive adsorption isotherm data for dibenzyltoluene derivatives from
acetone/water (96/4, v/v) solution over phenylhexyl silica

H0-DBT H6-DBT H12-DBT H18-DBT

Ce qe Ce qe Ce qe Ce qe
mgml-1 mg.g-1 mgml-1 mgg-1 mgml-1 mgg-1 mgml-1 mgg-1
0.25 17.9 0.25 36.5 0.24 41.8 0.24 47.9
0.38 27.2 0.39 59.7 0.37 69.7 0.38 84.9
0.56 39.7 0.57 92.2 0.54 109.1 0.57 143.1
1.00 70.5 0.98 169.6 0.93 206.9 0.98 283.2
1.92 133.3 1.92 357.9 1.84 450.3 1.92 656.0
2.87 195.8 2.89 553.6 2.77 704.8 2.86 1055.4
3.64 244.2 4.61 928.0 4.86 1264.8 4.52 1760.9
4.98 325.1 5.27 1025.8 6.88 1754.4 4.92 1927.4
8.81 533.4 7.52 1435.4 9.24 2260.5 7.04 2749.7
10.61 620.5 10.08 1856.8 11.73 2721.7 9.55 3602.3
14.58 793.2 14.45 2470.3 14.40 2960.0 14.06 4814.8
26.55 1190.4 25.38 3564.0 23.42 4160.4 23.98 6484.8
Table 4 Click here to download Table table 4.docx

Table 4: Single component adsorption isotherm data for dibenzyltoluene and octadecahydro-
dibenzyltoluene from acetone/water (96/4, v/v) solution over phenylhexyl silica

H0-DBT H18-DBT
Ce qe Ce qe
mgml-1 mg.g-1 mgml-1 mg.g-1
0.24 17.7 0.24 48.0
0.36 27.1 0.37 84.7
0.54 39.5 0.58 143.0
0.95 70.5 0.99 283.0
1.88 133.0 1.95 656.3
2.85 195.8 2.80 1054.0
3.6 244.2 4.50 1760.2
4.92 325.3 4.88 1925.4
8.9 533.4 7.10 2749.7
10.58 620.5 9.56 3602.3
14.55 793.3 14.10 4814.8
25.98 1190.2 24.05 6487.8
Table 5 Click here to download Table table 5.docx

Table 5: Model parameters for adsorption isotherms with statistical parameters

Parameters H18-DBT H12-DBT H6-DBT H0-DBT

Langmuir equation
qsat 14.215 10.207 9.883 3.068
b 0.034 0.029 0.023 0.024
Adj. R2 0.996 0.998 0.999 0.999
Q2 0.995 0.977 0.995 0.999
ARD / % 13.5 6.21 3.89 1.01
Freundlich equation
k 0.55 0.37 0.293 0.099
n 0.79 0.78 0.779 0.752
Adj. R2 0.979 0.988 0.961 0.996
Q2 0.945 0.920 0.942 0.991
ARD / % 14.5 16.4 9.8 5.8
Sips equation
qsat 9.92 7.042 6.915 2.991
b 0.068 0.058 0.042 0.025
n 1.32 1.2 1.15 1.01
Adj. R2 0.999 0.999 0.999 0.999
Q2 0.999 0.999 0.999 0.999
ARD / % 0.0023 0.0078 0.0003 0.0001
Supplementary files

SUPPORTING INFORMATION

Adsorption isotherm of dibenzyltoluene and its

partially hydrogenated forms over phenylhexyl silica

Rabya Aslam1,2, Karsten Mller,*1

1
Institute of Separation Science and Technology, Friedrich-Alexander-Universitt Erlangen-Nrnberg.
2
Institute of Chemical Engineering & Technology, University of the Punjab, Lahore, Pakistan.
* (Tel.: +49 9131 8527455; Fax. +49 9131 8527441; e-mail: rabya.icet@pu.edu.pk )
S1: Batch plot of vacuum distillation experiment
The batch plot representing the main DBT-fractions as a function of time is presented in Figure
S1. All the isomers of the same degree of hydrogenation were collected as one fraction and the
overall purity of a fraction was determined using GC-MS. Fully hydrogenated and
dehydrogenated fractions were separated with a high purity but intermediate fractions were
separated with an overall purities of up to 50 % due to the overlapping boiling point range of
various fractions. Boiling point range of dibenzyltoluene fractions is given in Table S1.

Figure Error! No text of specified style in document..1: Batch plot for the DBT-reaction mixture

Table S1: Boiling point range of DBT-Fractions at 1.0 1 mbar

Boiling
Degree of
DBT-Fraction Chemical Formula point
hydrogenation/ %
range/ C
dibenzyltoulene
C21H20 0 208-227
(H0-DBT)
Hexahydro-dibenzyltoluene
C21H26 33 198-213
(H6-DBT)
Dodecahydro-dibenzyltoluene
C21H32 67 184 - 205
(H12-DBT)
octadecahydro-dibenzyltoluene
C21H38 100 180 - 193
(H18-DBT)
S2 Analysis of dibenzyltoluene derivatives

GC-analysis dibenzyltoluene derivatives was performed using an Agilent technology 7890 A

system. The system was equipped with a flame ionization detector, an auto sampler (7683 D and
a Restek Rxil7Sil column (30 m x 250 m x 0.25 m). For the analysis, the injection sample was
prepared in n-hexane (injection conc. 10 mg/ml). The injection temperature was 300 C and the
program for oven was as follows: 70 C for 2 min, then 40C/min to 160 C, and then 3 C/min
to 300 C with the final holding time of 1 min. The gas chromatograms for both H0-DBT and
H18-DBT are shown in Figure S2 to S5, respectively. The retention times for dibenzyltoluene
derivatives used in this work are given in Table S2.

Figure S2: Gas chromatogram of dibenzyltoluene (isomeric mixture)

 Figure S2: Gas chromatogram of perhydro-dibenzyltoluene (isomeric mixture)

Table S3: Composition of dibenzyltoluene

Isomer Retention time/ min % age in the mixture
H0-DBT-1 30.92 17.1
H6-DBT-2 31.47 11.4
H12-DBT-3 32.45 29.7
H18-DBT-4 33.91 8.6

S3 GC Analysis of single isomers

The GC analysis of purified isomers using semi-preparative HPLC are given in Figure S3-S6.
The purity information is provided in table S4.

Figure S3: GC analysis of H0-DBT-single isomer

Figure S4: GC analysis of H6-DBT-single isomer
 Figure S5: GC analysis of H12-DBT-single isomer

Figure S6: GC analysis of H18-DBT-single isomer

Table S4: purity information of single isomers of Dibenzyltoluene and its derivatives separated using
HPLC
DBT-Fraction Chemical Formula Purity/ mass-%
dibenzyltoulene
C21H20 99.9
(H0-DBT)
Hexahydro-dibenzyltoluene
C21H26 99.0
(H6-DBT)
Dodecahydro-dibenzyltoluene
C21H32 99.6
(H12-DBT)
octadecahydro-dibenzyltoluene
C21H38 98.6
(H18-DBT)

S4 NMR-Analysis
Nuclear magnetic Resonance (NMR) analysis was ECX 400 from JEOL. 0. 1 mL of liquid
sample was diluted in 1 mL of Dichloromethane-d2. The NMR analysis of full fractions of
dibenzyltoluene and octadecahydro-dibenzyltoluene is shown in Figure S7 and S8. The NMR of
single isomers of dibenzyltoluene derivatives are shown in Figure S9 to S12.

Figure S7: 1H NMR spectrum for dibenzyltoluene

Figure S8: 1H NMR spectrum for octadecahydro-dibenzyltoluene

Figure S9: 1H NMR spectrum for dibenzyltoluene (H0-DBT)

Figure S10: 1H NMR spectrum for dibenzyltoluene (H6-DBT)

Figure S11: 1H NMR spectrum for dibenzyltoluene (H12-DBT)

Figure S12: 1H NMR spectrum for dibenzyltoluene (H18-DBT)

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