Supporting Information
For
Ruthenium catalysts based on mesoporous aromatic frameworks for
the hydrogenation of arenes
Anton Maximov, Anna Zolotukhina, Leonid Kulikov, Yulia Kardasheva and Eduard Karakhanov
Department of Petroleum Chemistry and Organic Catalysis, Moscow State University,
Leninskiye Gory 1-3, GSP-1, Moscow 119991, Russian Federation
Fax:(+7)495-9391951; E-mail: kar@petrol.chem.msu.ru
Content
Figure S1. Solid-state 1H MAS NMR spectra of frameworks PAF-20 and PAF-30
Figure S2. N2 adsorption isotherms of PAF-20 measured at 77K
Figure S3. N2 adsorption isotherms of PAF-30 measured at 77K
Figure S4. TEM images of PAF-20 (top) and PAF-30 (bottom).
Table S5. Temperature programs used in GLC-analysis
Table S6. Element concentrations and ruthenium forms on materials surface by XPS-analysis
Table S7. Hydrogenation of arenes in present of Ru-PAF-30
Table S8. List of equations
PAF-30
.
PAF-20
25
20
15
10
5
0
-5
-10
-15
Chemical shift, ppm
Figure S1. Solid-state 1H MAS NMR spectra of frameworks PAF-20 and PAF-30
Figure S2. N2 adsorption isotherms of PAF-20 measured at 77K
Figure S3. N2 adsorption isotherms of PAF-30 measured at 77K
Figure S4. TEM images of PAF-20 (top) and PAF-30 (bottom).
Table S5. Temperature programs used in GLC-analysis
Parameters
Program 1
Program 2
Program 3
250
250
250
250
250
250
250
150
250
Oven’s initial temperature, С
60
35
50
Oven’s final temperature, оС
220
35
220
Temperature rise, С/min
10
0
5
Initial time (time before rising oven’s
temperature), min
5
20
10
Final time (time after reaching oven’s
final temperature), min
10
1
5
Substances that analyzed
Toluene,
ethylbenzene,
p-xylene,
tetralin, styrene,
phenylacetylene
and products of
their
hydrogenation
Benzene and
products of its
hydrogenation
Phenol and
products of its
hydrogenation
о
Column limit, С
о
Detector temperature, С
Injector temperature, оС
о
о
Table S6. Element concentrations and ruthenium forms on materials surface by XPS-analysis
Catalyst
Ru-PAF-20
Ru-PAF-30
Element concentrations, atomic %
C
O
Br
Ru
Pd
73,3
22,7
4,0
―
―
82,6
15,9
1,5
―
―
Ruthenium forms, %
Ru
RuO2 RuO2*xH2O
79
21
―
39
61
―
0
Table S7. Hydrogenation of arenes in present of Ru-PAF-30
Substrate
Substrate/Ru
Conv., %
Reaction rate,
mole(Sub)*
-1*
h mole(Ru)-1
2000
97%
1940
2273
100%
2273
2013
63%
1274
96%
2038
36%
729
95%
Products distribution
100%
OH
OH
2025
34%
100%
4%
5%
66%
29%
3%
1%
693
H
H
85%
2352
27%
635
H
9%
H
6%
Reaction conditions: 80 оС, 3MPa. Н2, 1 h., 3 mg. Ru-PAF-30., V(H2O) = V(substrate).
Table S8. List of equations
Parameters
Equation
Initial reaction rate in
recalculation on
ruthenium content
Ruthenium content
Dispersion of ruthenium
nanoparticles
𝑛(𝑅𝑢) =
𝐷=
𝑚(𝑐𝑎𝑡) ∗ 𝑊(𝑅𝑢)
𝑀(𝑅𝑢)
6𝑉A
6𝑉M(𝑅𝑢) ∗ 𝑘
=
𝑆A ∗ 𝑑pt 𝑁A ∗ 𝑆A ∗ 𝑑pt
Constants and variables
Conv – conversion;
n(Sub) – arene quantity, mol
n(Ru) – ruthenium quantity, mol
D – NPs dispersion
𝛥t – reaction time; 5 minutes
m(cat) – catalyst mass, g.
W(Ru) – ruthenium content in catalyst
M(Ru) – ruthenium molar mass; 101,07 g/mol
dpt – mean diameter of the particle, Å
VA – effective volume per metal atom in the
bulk; 10,02 Å 3 for Ru
SA – the effective average surface area per
atom ; 6,13 Å 2 for Ru
VM(Ru) – Ru molar volume; 8,14 cm3/mol
k – packing density of hexagonal-close
packed structure; 0,7405
NA – Avogadro number; 6,02*1023 mol-1