Studies in Surface Science and Catalysis 162 SCIENTIFIC BASES FOR THE PREPARATION OF HETEROGENEOUS CATALYSTS
4HISPAGEINTENTIONALLYLEFTBLANK
Studies in Surface Science and Catalysis Advisory Editors: B. Delmon and J.T. Yates Series Editor: G. Centi Vol. 162
SCIENTIFIC BASES FOR THE PREPARATION OF HETEROGENEOUS CATALYSTS Proceedings of the 9th International Symposium, Louvain-la-Neuve, Belgium, September 10-14, 2006
Edited by E.M. Gaigneaux*, M. Devillers*, D.E. De Vos**, S. Hermans*, P.A. Jacobs**, J.A. Martens**, P. Ruiz* * Université Catholique de Louvain, Louvain-la-Neuve, Belgium ** Katholieke Universiteit Leuven, Heverlee (Leuven), Belgium
Amsterdam – Boston – Heidelberg – London – New York – Oxford – Paris San Diego – San Francisco – Singapore – Sydney – Tokyo
Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK First edition 2006 Copyright © 2006 Elsevier B.V. All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email:
[email protected]. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN-13: 978-0-444-52827-8 ISBN-10: 0-444-52827-X ISSN: 0167-2991 For information on all Elsevier publications visit our website at books.elsevier.com
Printed and bound in The Netherlands 06 07 08 09 10
10 9 8 7 6 5 4 3 2 1
v
vi
Foreword
Foreword
vii
viii
Foreword
ix
4HISPAGEINTENTIONALLYLEFTBLANK
xi
xii
Contents
Contents
xiii
xiv
Contents
Contents
xv
xvi
Contents
Contents
xvii
xviii
Contents
Contents
xix
xx
Contents
Contents
xxi
xxii
Contents
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
1
2
U. Dingerdissen and D. Linke
Scopes and limitations of high throughput preparation and screening tools
3
4
U. Dingerdissen and D. Linke
Evaluation Screening: >1000 /week Main Screening: 100 /week
standard lab
chemical engineering domain
Classic Screening: 10 /week Pilot Plant Plant
Precision of Data
HTS domain
Number of Experiments/Formulations
Exploration Screening: >1000 /day
Scopes and limitations of high throughput preparation and screening tools
5
6
U. Dingerdissen and D. Linke
Scopes and limitations of high throughput preparation and screening tools
7
8
U. Dingerdissen and D. Linke
Scopes and limitations of high throughput preparation and screening tools
9
10
U. Dingerdissen and D. Linke
Scopes and limitations of high throughput preparation and screening tools
11
12
U. Dingerdissen and D. Linke
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
13
14
E. de la Rochefoucauld et al.
Mesoporous alumina obtained by surface alumination of pure silica SBA-15
15
16
E. de la Rochefoucauld et al.
Mesoporous alumina obtained by surface alumination of pure silica SBA-15
Figure 2
Figure 1
800
d) c) b) a) 2
3 2θ (°)
4
5
Surface area (m2 . g- 1)
e)
600
70
a) c)
65
500 400
60
300 200
b) 55
100 0 50 SBA Blank Iso1 Iso2 Iso3 Iso4 -15
Sample type
Pore diameter (Å)
Intensity (a.u.)
700
1
17
18
E. de la Rochefoucauld et al.
Intensity (a.u.)
30
6
54 Number of graftings
100
50 0 -50 -100 δ (ppm)
19
10
2,5 2
8
1,5
6
1
4
0,5
2
0
0 0 15.1 24.1 30.0 35.0 100 (SiO2 ) (Iso1) (Iso2)(Iso3)(Iso4)(Al2 O 3 )
% Al2 O3
MoO3 dispersion capacity (μm o l . m- 2)
Cumene cracking activity *104 (mmol.h- 1. m- 2)
Mesoporous alumina obtained by surface alumination of pure silica SBA-15
20
E. de la Rochefoucauld et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
21
22
F. Klasovsky and P. Claus
Biomimetic catalyst preparation with carbohydrates: The CHSG process
23
24
F. Klasovsky and P. Claus
Biomimetic catalyst preparation with carbohydrates: The CHSG process
25
26
F. Klasovsky and P. Claus
Biomimetic catalyst preparation with carbohydrates: The CHSG process
27
28
F. Klasovsky and P. Claus
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
29
30
S. van Dommele et al.
Synthesis of heterogeneous base catalysts: nitrogen containing carbon nanotubes
31
32
S. van Dommele et al.
Synthesis of heterogeneous base catalysts: nitrogen containing carbon nanotubes
sample
T (K)
N/C source
Tube diameter rangea (nm)
Amount N (mmol/g NCNT) XPS
Titration
33
NPb
NQc
(%)
(%)
Co823ACN
823
ACN
5 – 38 (16)
7.4
0.03
50
23
Co923ACN
923
ACN
4 – 52 (17)
4.0
0.03
36
36
Co1023ACN
1023
ACN
5 – 50 (18)
4.3
0.02
28
44
Co923PYR
923
PYR
5 – 43 (18)
7.5
0.05
50
24
Co1023PYR
1023
PYR
40 – 86 (62)
7.4
0.02
40
27
Co1123PYR
1123
PYR
-
5.8
0.02
25
28
34
S. van Dommele et al.
Synthesis of heterogeneous base catalysts: nitrogen containing carbon nanotubes
35
36
S. van Dommele et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
37
38
I. Melián-Cabrera et al.
Tooling up heterogeneous catalysis through Fenton’s chemistry...
39
40
I. Melián-Cabrera et al.
Tooling up heterogeneous catalysis through Fenton’s chemistry...
(A)
(B)
80 80
N2O conversion / %
N2O conversion / %
100
41
60 40 20 0 550
+ 3% - 3% 60
Stability test at 700 K
40
Fe-FER (citrate, 353 K, 1 h) 20
600
650 700 750 Temperature /K
800
0
5
10
15
20
25
30
Time on stream / h
35
40
45
42
I. Melián-Cabrera et al.
Tooling up heterogeneous catalysis through Fenton’s chemistry...
43
Intensity / a.u.
Fe
Fe3+ / H2 O2
2θ (Cu Kα) / degree
H2O/CO2 Fe
333 K / [H2O2]=10% Fe
1 μm
44
I. Melián-Cabrera et al.
100
0.10 12 6.6 x 6.7** ↔ [001] 12 5.6 x 5.6*
80
/ %
One-pot Fe-BEA
0.06
N2O conversion
dV/dD
3
/ cm /( g∗Å)
0.08
0.04 0.02
2.0Fe-BEA TOSOH
60
2.3Fe-BEA ZE OLYST
40
20
0.00 4
6
8
10
12
14
pore diameter (D)
16 /Å
18
20
0 658
683
708
Temperature / K
733
Tooling up heterogeneous catalysis through Fenton’s chemistry...
45
46
I. Melián-Cabrera et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
47
48
A.I. Reyes de la Torre et al.
Molybdenum and tungsten carbides supported on mesostructured MCM-41
49
50
A.I. Reyes de la Torre et al.
Molybdenum and tungsten carbides supported on mesostructured MCM-41
a
b
Amorphous
MCM41-PAN-P
Graphite
Diamond
51
52
A.I. Reyes de la Torre et al.
Molybdenum and tungsten carbides supported on mesostructured MCM-41
53
54
A.I. Reyes de la Torre et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
55
56
S.-C. Han et al.
Microwave and hydrothermal synthesis
57
58
S.-C. Han et al.
Microwave and hydrothermal synthesis
59
(a)
(b)
(c)
(d)
60
S.-C. Han et al.
Microwave and hydrothermal synthesis
61
62
S.-C. Han et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
63
64
S. Naito et al.
Preparation of hollow silica-Rh, -Ir, and -Rh-Ir-bimetallic nanocomposites...
65
50
100
40
80
30
SiO2
60
20
40
hollow 10
20
0 437 573 673 773 873
0 973 1073 1173
Calcination Temperature / K
B E T s u r f a c e a r e a / m 2 g -1
S. Naito et al.
D ia m e t e r / n m
66
Preparation of hollow silica-Rh, -Ir, and -Rh-Ir-bimetallic nanocomposites...
67
14
(B)
Amount of adsorption / cm3g-1
(A) 12 10
CO 8 6
H2
H2 4 2 0 473
CO 673
873
1073
473
673
873
Calcination Temperature / K
1073
68
S. Naito et al.
Conversion / %
Preparation of hollow silica-Rh, -Ir, and -Rh-Ir-bimetallic nanocomposites...
Reaction Time / min
Reaction Time / min
69
70
S. Naito et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
71
72
G.M. Veith et al.
The use of magnetron sputtering for the production of heterogeneous catalysts
73
74
G.M. Veith et al.
The use of magnetron sputtering for the production of heterogeneous catalysts
75
30 1.37 wt% Au on γ-Al O
25
2 3
Avg. Dia. = 2.29 nm Dispersion = 49% σ = 0.75 nm
Count
20 15 10 5
2 nm
4 nm
0
1
2
3
4
5
nm
6
7
8
9
76
G.M. Veith et al.
200 0.69 wt% Au on X40S via sputtering Dispersion = 72.5% 242 data points
150
Avg. Dia. = 1.72 nm
*
*
Does not include single atom s σ = 0.61 nm
100
50
0
0
2
4
6
8
10 12 14 16 18 20 22
nm
1.5 nm
The use of magnetron sputtering for the production of heterogeneous catalysts
77
28 E-TEK 20 wt% Pt on Vulcan XC72 11.1 wt% Pt on Vulcan XC72 Avg. Pt size = 1.62 nm σ = 0.49 nm Dispersion = 72%
80
60
Avg. Pt size = 2.57 nm
24 σ = 0.79 nm Dispersion = 53%
20 16
40
12 8
20
4 0
0 0.5
1
1.5
2
2.5
3
nm
3.5
4
4.5
5
0.5
1
1.5
2
2.5
nm
3
3.5
4
4.5
5
78
G.M. Veith et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
79
80
A. Deffernez et al.
Preparation of carbon-supported Pd and Au-Pd catalysts
81
A. Deffernez et al.
Amount of Pd adsorbed on C (% )
82
100 80 60 40 20 0 0
2
4
6
8 pH
10
12
14
Au/C determined by XPS (*100)
Preparation of carbon-supported Pd and Au-Pd catalysts
83
2 1.6 1.2 0.8 0.4 0 0
2
4
6
8 pH
10
12
14
A. Deffernez et al.
84
100 90 80 [Pd(H2O)4]2+
Fraction (% )
70
[Pd(OH)(H2O)3]+
60
[Pd(OH)2(H2O)2]
50
[Pd(OH)3(H2O)]-
40
[Pd(OH)4]2-
30 20 10 0 0
2
4
6
8
10
12
14
pH
100 90
F r ac tio n ( % )
80
[AuCl4]-
70
[AuCl3(OH)]-
60
[AuCl2(OH)2]-
50
[AuCl(OH)3]-
40
[Au(OH)4]-
30 20 10 0 0
2
4
6
8 pH
10
12
14
Preparation of carbon-supported Pd and Au-Pd catalysts
85
86
A. Deffernez et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
87
88
P. Mäki-Arvela et al.
O H 2
Citral
O
Citronellal
H2
O
3,7-dimethyloctanal
Supported ionic liquid catalyst (SILCA) in the hydrogenation of citral
89
90
P. Mäki-Arvela et al.
Supported ionic liquid catalyst (SILCA) in the hydrogenation of citral
91
92
P. Mäki-Arvela et al.
Conversion (%)/mgPd
10
8
6
4
2
0 0
50
100
150
200 3
ρbulk *time (g/dm *min)
250
300
Supported ionic liquid catalyst (SILCA) in the hydrogenation of citral
93
50
a)
Conversion (%)
40
30
20
10
0 0
50
100
150
200
250
300
3
ρbulk*time (g/dm *min)
b)
Selectivity to citronellal (%)
50
40
30
20
10
0 0
10
20
30
Conversion (%)
40
50
94
P. Mäki-Arvela et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
95
96
J.R.A. Sietsma et al.
Ordered mesoporous model supports as a tool to study catalyst preparation
97
98
J.R.A. Sietsma et al.
(a)
(b)
Ordered mesoporous model supports as a tool to study catalyst preparation
99
100
J.R.A. Sietsma et al.
Ordered mesoporous model supports as a tool to study catalyst preparation
101
102
J.R.A. Sietsma et al.
Scientific Bases for the Preparation of Heterogeneous Catalysts E.M. Gaigneaux et al. (Editors) © 2006 Elsevier B.V. All rights reserved.
103
104
S.L. Soled et al.
Supported metal catalysts: some interesting new leads in an old field
105
106
S.L. Soled et al.
Supported metal catalysts: some interesting new leads in an old field
107
0 DTA
