From Zeolites to Porous MOF Materials - The 40th Anniversary of International Zeolite Conference, Proceedings of the 15 International Zeolite Conference

753 Pages·2007·44.87 MB·English

by  Ruren Xu

v
PREFACE

It has been exactly 40 years since the first International Zeolite Conference (IZC) was
held in London in 1967, and 14 IZCs have been convened so far. The past 40 years has seen
the rapid expansion of topics covered by the IZCs. From molecular sieves which mainly
consist of zeolites to those with over 30 compositional framework elements and 170 structure
types, from microporous crystals to mesoporous materials, from porous inorganic frameworks
to metal-organic-framework (MOF) compounds, the areas of zeolite science and technology
have continued to grow, as reflected by the IZC scientific program in the past. Moreover, with
the exploration of new applications and the emergence of new interdisciplinary areas, the
basic and applied research on zeolites and related porous materials has been thriving rapidly,
and consequently an increasing number of researchers have been engaged in the field of
zeolites and related porous materials, leading to the distinct expansion of the international
zeolite community. With such a background, the 15th IZC seeks to reflect and to further
promote the development of research in zeolite science and technology. To achieve this goal,
the Organizing Committee of the 15th IZC has arranged 5 plenary lectures, 12 keynote
lectures, and a symposium in memory of R. M. Barrer with four invited lectures for the
conference program.
Noticeably, with the strong support from the international zeolite community and positive
responses from colleagues working in related areas, the Organizing Committee received 850
abstracts from 54 countries and regions, which laid a solid foundation for the successful
convening of the conference and the production of the current proceedings. Due to limitation
of space, the editors of the proceedings had to deal with the challenge of selecting the most
representative and original papers for publication among a huge number of contributions. In
this regard, the Organizing Committee, the Scientific Program Committee of the conference
and the editors of the proceedings would like to express their sincere gratitude to the chairmen
of the 12 scientific sub-committees of the 15th IZC, whose efforts in the review and selection
of contributions greatly aided during the production of these proceedings. We are equally
indebted to members of the scientific sub-committees and reviewers invited by the
sub-committees. The 12 scientific sub-committees were formed on the basis of 12 topics
including synthesis (chaired by S. Wilson), modifications (chaired by T. Tatsumi), structures
(chaired by L. McCusker), characterization (chaired by J. Fraissard), adsorption, separation
and diffusion (chaired by M. Bulow), catalysis (chaired by J. Weitkamp), host-guest chemistry
and advanced materials (chaired by T. Bein), industrial applications (chaired by W. Mortier),
theory and modeling (chaired by M. Treacy), mesostructured materials (chaired by S.
Kaliaguine), MOF materials (chaired by G. Férey), and natural zeolites (chaired by C.
Colella).
All the abstracts and full manuscripts submitted to the conference were thoroughly
reviewed, and on the basis of the review results and by taking into account balance for topics,
countries or regions, about 16 percent of the contributions were selected for oral presentations,
and about 18 percent were selected for full paper poster presentations. Given the limitation of
space, the editors regret that only the papers of plenary, keynote, Barrer symposium lectures,
oral, and full paper poster presentations can be included in the proceedings. It should be
mentioned that the close collaboration of the Elsevier Publisher made it possible for the
proceedings to be published and to be available to the participants prior to the convening of
the conference.
The large number of high quality contributions, the active involvement and strong
support of the international zeolite community, the thorough review process, and the wide
vi
representation of research areas, research frontiers, and countries and regions by the
contributions lead us to believe that the papers in the proceedings have faithfully reflected the
achievements and progress in the field of zeolites and related porous materials. We would like
to entitle the proceedings “From Zeolites to Porous MOF Materials – the 40th Anniversary of
International Zeolite Conference” to celebrate the development of this important field and the
growth of the international zeolite community.
Finally, the editors would like to express special gratitude to the staffs (especially J. H. Yu,
Y. L. Liu, J. Y. Li, Y. Li and F. J. Zhang) of the “State Key Laboratory of Inorganic Synthesis
and Preparative Chemistry” at Jilin University and L. J. Song at Liaoning University of
Petroleum and Chemical Technology for their involvement in the preparation of these
proceedings.

Ruren Xu
Zi Gao
Jiesheng Chen
Wenfu Yan
(Editors)

Changchun, March, 2007
vii
EXECUTIVE COMMITTEE

Chair:
Ruren Xu Jilin Univ., Changchun, China
Co-Chairs:
Enze Min RIPP - SINOPEC, Beijing, China
Mingyuan He RIPP - SINOPEC, Beijing, China

Secretary-General:
Shilun Qiu Jilin Univ., Changchun, China

Vice Secretary-General:
Wenfang Tan SINOPEC Catalyst Co., Beijing, China

Scientific Program:
Shilun Qiu Jilin Univ., Changchun, China
Dongyuan Zhao Fudan Univ., Shanghai, China

Finance:
Xianping Meng NSFC, Beijing, China
Baoning Zong RIPP - SINOPEC, Beijing, China

Treasurer:
Fengshou Xiao Jilin Univ., Changchun, China

Publications:
Zi Gao Fudan Univ., Shanghai, China
Jiesheng Chen Jilin Univ., Changchun, China

Field Trip:
Naijia Guan Nankai Univ., Tianjin, China
Jun Fu RIPP - SINOPEC, Beijing, China

Pre-Conference School:
Xinhe Bao Dalian Inst. of Chem. Phys., Dalian, China

Local Arrangements:
Feng Mi Jilin Univ., Changchun, China
Dong Wu Shanxi Inst. of Coal Chemistry, Taiyuan, China

Post-Conference Forum:
Jihong Yu Jilin Univ., Changchun, China
viii
SCIENTIFIC PROGRAM COMMITTEE

Chair:
Shilun Qiu Jilin Univ., Changchun, China

Members:
Dongyuan Zhao Fudan Univ., Shanghai, China
Jiesheng Chen Jilin Univ., Changchun, China
Wenfu Yan Jilin Univ., Changchun, China
Peng Wu East China Normal Univ., Shanghai, China
Yuhan Sun Shanxi Inst. of Coal Chemistry, Taiyuan, China

PRE-CONFERENCE SCHOOL

Chair:
Ruren Xu Jilin Univ., Changchun, China

Co-Chairs:
J. Weitkamp Universitat Stuttgart, Stuttgart, Germany
Xinhe Bao Dalian Inst. of Chem. Phys., Dalian, China

CONFERENCE PROCEEDINGS EDITORS

Ruren Xu Jilin Univ., Changchun, China
Zi Gao Fudan Univ., Shanghai, China
Jieshegn Chen Jilin Univ., Changchun, China
Wenfu Yan Jilin Univ., Changchun, China

POST-CONFERENCE FORUM “The Future Perspective of Zeolite Synthesis”

Chairs:
Avelino Corma Instituto de Tecnología Química (CSIC-UPV), Spain
Shilun Qiu Jilin Univ., Changchun, China
Jihong Yu Jilin Univ., Changchun, China
ix
15th IZC INTERNATIONAL ADVISORY BOARD

A. Alberti Univ. di Ferrara
M. W. Anderson UMIST – Manchester
K. Balkus Jr. Univ. of Texas - Dallas
T. Bein Univ. of Munich
G. Bellussi EniTecnologie S.P.A.
H. Beyer R&D for Silicates & Ceram. Ltd.- Budapest
M. Bülow BOC Tech. Center
X. H. Cao SINOPEC - Beijing
C. R. A. Catlow Royal Inst. of Great Britain
J. Cejka J. Heyrovsky Inst. of Phys. Chem.
K. J. Chao National Tsinghua Univ. - Hsingchu
A. K. Cheetham Univ. of California - Santa Barbara
P. Ciambelli Univ. di Salerno
C. Colella Univ. Federico II - Napoli
A. Corma Univ. Politecnica de Valencia
M. E. Davis California Inst. of Technol.
M. Derewinski Polish Academy of Sciences
F. Di Renzo ENSCM – Montpellier
F. Fajula ENSCM - Montpellier
G. Férey Inst. Lavoisier –Versailles
E. Flanigen UOP
J. Fraissard Univ. Pierre et Marie Curie
W. Hölderich Univ. of Technol. RWTH - Aachen
T. Inui King Fahd Univ. of Petroleum & Minerals
I. I. Ivanova Moscow State Univ.
M. Iwamoto Tokyo Inst. of Technol.
P. Jacobs Katholieke Univ. Leuven
S. Kaliaguine Laval Univ.
D. Kallo Hungarian Academy of Sciences
F. Kapteijn Delft Univ. of Technol.
H. G. Karge Fritz-Haber Inst. der MPG - Berlin
J. Kärger Univ. of Leipzig
I. Kiricsi Univ. of Szeged
C.T. Kresge Dow Chemical Company
K. Kuroda Waseda Univ.
L. Kustov Russian Academy of Sciences
J. A. Lercher Technische Univ. München
D. D. Li Res. Inst. Petrol. Process. - Beijing
L. W. Lin Dalian Inst. of Chem. Phys.
M. Lu Univ. of Queensland
J. Martens Katholieke Univ. Leuven
L. McCusker ETH - Zurich
A. Mélthivier Inst. Fancais du Péltrole
N. Milestone Univ. of Sheffield
C. Minchev Bulgarian Academy of Sciences
C. Y. Mou National Taiwan Univ. – Taipei
A. Navrotsky Univ. of California - Davis
C. O'Connor Univ. of Cape Town
M. O'Keeffe Arizona State Univ.
W. Q. Pang Jilin Univ.
S. E. Park Inha Univ.
J. Patarin Univ. de Haute-Alsace
J. Perez-Pariente Inst. de Catal. Petrol. – Madrid
x
T. Pinnavaia Michigan State Univ.
C. N. R. Rao Jawaharlal Nehru Center for ASR
P. Ratnasamy National Chem. Lab. - Pune
L. V. C. Rees Univ. of Edinburgh
G. Rodriguez-Fuentes Univ. of Havana
E. R. Russu Univ. Petrol Gaze Ploiesti
R. Ryoo Korea Adv. Inst. of Sci. Technol.
A. Sayari Univ. of Ottawa
B. J. Schoeman Dow Chemical Company
F. Schüth MPI für Kohlenforshung
M. Stöcker SINTEF - Oslo
G. D. Stucky Univ. of California - Santa Barbara
B. L. Su Univ. of Namur
B. Subotic Rudjer Boskovic Inst. - Zagreb
R. Szostak Clark Atlanta Univ.
T. Tatsumi Tokyo Inst. of Technol.
O. Terasaki Stockholm Univ.
J. M. Thomas Royal Inst. of Great Britain
N. Y. Topsøe Haldor Topsøe Co. - Lyngby
M. M. J. Treacy Arizona State Univ.
G. Tsitsishvili Georgian Academy of Sciences
H. van Bekkum Delft Univ. of Technol.
R. van Santen Eindhoven Univ. of Technol.
D. Vaughan Pennsylvania State Univ.
J. Védrine Ecole Natl. Supér. de Paris
J. Weitkamp Univ. of Stuttgart
B. Wichterlova J. Heyrovsky Inst. of Phys. Chem.
S. Wilson UOP
C. Wu Chinese Univ. of Hong Kong
T. Yashima Nihon Univ.
K. B. Yoon Sogang Univ.
M. Ziolek Mickiewicz Univ.
S. I. Zones Chevron Res. Technol. Company
From Zeolites to Porous MOF Materials – the 40th Anniversary 3
ofInternationalZeol ite Conference
R. Xu, Z. Gao, J. Chen and W. Yan (Editors)
© 2007 Elsevier B.V. All rights reserved.

Overview of zeolite synthesis strategies

Stephen T. Wilson

UOP LLC 25 E. Algonquin Rd., Des Plaines, IL 60017

1. INTRODUCTION

The period since the 14th International Zeolite Conference (Apr. 2004) has seen the report of a
significant number of new framework types and new compositions. The 22 new framework
types approved by the IZA Structure Commission during this period include 4 minerals and 4
AlPO-based structures, but the bulk of the remaining 14 framework types are synthetic silicate-
based structures.

Table 1
New framework types approved by the IZA Structure Commission
Date approved IZA Species Elements Source Ring sizea FDb Synthesis Features
9/15/04 MAR Marinellite Si,Al Natural 6 17.6 None
OBW OSB-2 Be,Si Synthetic 10,10,8 13.1 Be,Si
RRO RUB-41 Si Synthetic 10,8 18.0 Organic, solid state transform
RWR RUB-24 Si Synthetic 8 20.1 Organic, solid state transform
UTL IM-12 Si,Ge Synthetic 14,12 15.6 Ge, organic
11/8/04 CDO CDS-1 Si Synthetic 8,8 18.1 Organic, solid state transform
GIU Giusseppettite Si,Al Natural 6 15.9 None
SFO SSZ-51 Al,P Synthetic 12,8 15.1 Organic, F
SOS SU-16 B,Ge Synthetic 12,8,8 16.1 B,Ge, organic
5/20/05 EON ECR-1 Si,Al Synthetic 12,8 16.9 Organic, not occluded
-LIT Lithosite Si,Al Natural 10,8 18.3 Alkali
NSI Nu-6(2) Si Synthetic 8,8 21.0 Organic, solid state transform
OWE UiO-28 Mg,Al,P Synthetic 8,8 16.0 Organic
1/28/06 IHW ITQ-32 Si,Al Synthetic 8,8 18.7 Organic, F
MOZ ZSM-10 Si,Al Synthetic 12,8,8 16.6 Organic (not occluded), K
11/13/06 EZT EMM-3 Al,P Synthetic 12 16.8 Organic
FAR Farneseite Si,Al Natural 6 15.8 None
IWV ITQ-27 Si,Al Synthetic 12,12 15.7 Organic, F
MSE MCM-68 Si,Al Synthetic 12,10,10 16.6 Organic, K
SIV SIZ-7 Co,Al,P Synthetic 8,8,8 15.1 Organic, solvent
SZR SUZ-4 Si,Al Synthetic 10,8,8 18.0 Organic, K
TUN TNU-9 Si,Al Synthetic 10,10,10 17.5 Organic
a number of T-atoms in rings controlling diffusion. b framework density, TO2/1000 Å3

Each of the synthetic framework types illustrates one or more of the synthesis strategies
currently being used successfully in the quest for new zeolitic materials:
1. novel organic templates
4
2. F-media
3. alternative framework elements, e.g. Ge or Be
4. combinatorial synthesis with multiple structure directing agents (SDA)
5. solid state (topotactic) transformation of layered structures

Although the use of organic templates as structure-directing agents has been the main driver
in the synthesis of new framework types, framework elements like Ge or Be can dramatically
influence the formation of particular building units. It is well known that the presence of fluoride
in the synthesis media can lead to new structures, even with previously studied organic templates.
This is particularly true in media with low HO/Si. Following the initial synthesis of a new
2
framework, it is becoming more commonplace to map out the accessible compositional range,
particularly with an eye toward possible cost reduction, framework element substitution, and
manufacturability.

2. NOVEL ORGANIC TEMPLATES

The use of large, increasingly elaborate quaternary ammonium cations as templating or structure-
directing agents (SDA) has been a very fruitful source of novel framework types in zeolite
synthesis. In this approach, it is hoped that the shear size and shape of the organic cation will
produce unique, large pore structures with three-dimensional channel systems. The size of the
SDA can place some limitations on the framework charge density, leading to upper limits on the
incorporation of framework Al or B. Increased branching and stereochemical rigidity of the SDA
can increase the chances of making a large pore structure with intersecting channels.

Table 2
New zeolites enabled primarily by novel organic templates
Species IZA Framework Ring Size Template Ref
Elements
MCM-68 MSE Si/Al = 9 12,10,10 TBOD + K+ [1,2]
SUZ-4 SZR Si/Al = 6-8 10 EtN+ or EtN-(CH)-NEt2+ + K+ [3]
4 3 25 3
COK-5 Si/Al = 24 10 and/or 12 EtN-(CH)-NEt2+ [4]
3 25 3
SSZ-32X MTT Si/Al = 15 10 N,N’-diisopropylimidizolium + isobutylamine [5]
SSZ-47B EUO/NES Si/Al = ca. 32-64 10 TMDP + N-cyclopentylDABCO [6]
SSZ-56 Si/B na DEMD [7]
SSZ-63 BEA/BEC Si/B > 39 12,12,12 1-cyclodecyl-1-methylpyrrolidinium [8, 9]
SSZ-65 Si/B = 7-140 (cid:149) 12? EPCP [10]
ECR-1 EON Si/Al = 3-6 12 (HOCHCH)(CH)N+ [11]
2 22 32
TNU-7 EON Si/Ga = 4 None [12]
TNU-9 TUN Si/Al = 20 10,10,10 1,4-bis(N-methylpyrrolidinium)butane [13]
TBOD = N,N,N’,N’-tetraethyl-bicyclo[2.2.2]-oct-7-ene-2R,3S:5R,6S-dipyrrolidinium diiodide
TMDP = 4,4’-trimethylenedipiperidine; DEMD = N,N-diethyl-2-methyldecahydroquinolinium
EPCP = 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium

In all but one of the examples in Table 2 the product is primarily the result of the structure-
directing effect of an organic template. Unlike the Ge discussed below, the framework elements
B, Al, or Ga are not normally seen as structure-directing agents, but they do influence synthesis.
Boron seems to be more easily incorporated than Al when the very large cations are employed.
5

2.1. MCM-68, SUZ-4, and COK-5
MCM-68 is a multi-dimensional zeolite with intersecting large and medium pore channels
[1]. Surprisingly it seems to crystallize in a very narrow range of Si/Al = 9-10. Lower values of
Si/Al tend to introduce BEA impurity, higher values produce MTW impurity, similar to the
behavior of TEAOH. Thus, despite the size and shape of the organic cation TBOD (Fig. 1a),
there are still conditions where it can template MTW. Potassium cation also appears to be
necessary for synthesis of MCM-68, since substitution of Na+ for K+ yields zeolite beta instead.
Although SUZ-4 was first reported by Barri in 1992 [14] and a framework proposed soon
thereafter by Lawton et al. [15], a definitive structure solution was only recently achieved by
Strohmaier et al. [3]. The SZR framework type has a three-dimensional channel system, with a
10-ring channel intersected by elliptical 8-ring channels. The organic SDA’s for this structure
are Et N+ or Et N-(CH)-NEt 2+ (which can be viewed as conjoined EtN+) [16]. The alkali K+
4 3 25 3 4
also appears to be required in both cases. The framework Si/Al ratio of this structure falls in a
narrow range.
Kirschhock et al. recently reported the COK-5 structure which is related to ZSM-57 (MFS).
Both of these structures are also prepared with the SDA, Et N-(CH) -NEt 2+ but in combination
3 2 5 3
with the alkali Na+[4] and at higher framework Si/Al than the SUZ-4. The COK-5 seems to be a
layered structure containing modified structural elements found in the MFS type zeolite. The
building layers can be stacked in various ways, leading to three new structures. COK-5 is an
intergrowth of these new structures and MFS, producing a channel system comprising four types
of pores with 10- or 12-membered rings.

2.2. Alternate SDA’s and cost reduction: SSZ-25, SSZ-32X, SSZ-47B
Zones and Hwang reported a zeolite synthesis system to address the significant cost of using
expensive structure-directing agents. In their approach a minor amount of structure-directing
agent was used to specify the nucleation product and a larger amount of an amine was used to
provide both pore filling and basicity capacities in the synthesis [17]. This synthesis route
offered cost-saving benefits by reducing structure-directing agent cost, waste stream cleanup
costs, and time in reactor and increasing the reagent flexibility. In one example the amount of
quaternized aminoadamantane needed to synthesize SSZ-25, a MWW framework type, was
significantly reduced by substitution with isobutylamine.
In a second example SSZ-47 was discovered using this approach. It is a complex
intergrowth of three framework types, EUO, NES, and NON [18]. The presence of NON (a
clathrasil) in this intergrowth severely reduces sorption capacity and ease of diffusion. The
measured N micropore volume of this material is 0.06 cc/g. In a recent variation of this
2
approach, SSZ-47B [6], a related intergrowth with a significantly lower level of NON, was
prepared using a combination of two structure-directing agents, N-cyclopentylDABCO and
TMDP (Table 2). Both templates are occluded and the size of the TMPD is thought to prevent
NON formation. The N micropore volume of SSZ-47B is significantly increased to 0.15 cc/g.
2
A similar synthetic approach was used with N,N’-diisopropylimidizolium hydroxide and
isobutylamine to make SSZ-32X (MTT) [5]. Compared to the method for making standard SSZ-
32 using the imidozolium template alone, this method had the added benefits of reducing the
product Si/Al (from 18 to 15), reducing the crystal size (170nm to 40-60nm), and making a better
dewaxing catalyst.
6

CH
H C 3
3 N+ N+ H3C
N+ CH CH3 N+
3
CH3 CH3 CH3
a. MCM-68 template b. SSZ-56 template c. SSZ-65 template
Fig. 1. SDA’s for selected structures

2.3. Large Pore Borosilicates: SSZ-56, SSZ-63, and SSZ-65
SSZ-56 is the latest example of a zeolite prepared by Elomari using a template derived from
the decahydroquinolinium cation (Fig. 1b). Previous examples using other substituted forms of
this core cation include SSZ-31, SSZ-48 (framework type SFE) and SSZ-43 [19, 20, 21]. The
SDA’s for SSZ-56 and SSZ-48 differ only in the presence or absence of a methyl group at the 2-
position.
SSZ-63 is a novel borosilicate related to zeolite beta that is synthesized using the 1-
cyclodecyl-1-methylpyrrolidinium cation as a structure-directing agent [8, 9]. Whereas
conventional zeolite beta may be described as a random intergrowth of polytypes A and B, SSZ-
63 is more accurately described as a random intergrowth of polytypes B and C (the hypothetical
H
polytype C proposed by Higgins). Polytype C itself is essentially an ordered intergrowth of
H
polytypes A and B. Substitution of Al for the B in synthesis with this template produces
conventional beta. One noteworthy feature of this structure is a high density of double four-ring
units, usually not observed in highly siliceous structures unless there is significant Ge or F
incorporated. Ironically, this SDA when used in all-silica synthesis in F-media yields
conventional beta [22].
SSZ-65 is another structure prepared with a complex pyrrolidinium-based SDA (Fig. 1c). It
most readily crystallizes as a borosilicate [10], but an aluminosilicate composition can be made
using an Al source pre-reacted with silica, such as a silica-alumina sol. This structure has a
micropore volume of 0.16 cc/g, and its constraint index suggests that it is large pore with perhaps
large cavities.

2.4. Nucleation without occlusion: ECR-1, TNU-7, and ZSM-10
The large pore structure ECR-1 (Table 3) was first synthesized by Vaughan and Strohmaier
using the bis-(2-hydroxyethyl) dimethylammonium cation as SDA (R1), but the product
contained very low levels of the R1. Subsequent preparations with other organic SDA, such as
trioxane (R2) and TMAOH (R3), also failed to occlude significant organic [25, 26]. For this
framework type, structure-direction by the organic is more indirect, perhaps influencing
nucleation only. Recent synthesis in the Ga/Si system yields the EON framework type, TNU-7,
without the necessity of an organic. Further study may also reveal organic-free conditions for
making EON with a Si/Al composition.
All these products with the EON framework type, regardless of whether organic is used, fall
within a fairly narrow range of oxide ratio (Table 3). In the synthesis phase space studied with
trioxane, the competing phases are the MAZ, MOR, and SOD framework types [25], which is