Fractal MTW Zeolite Crystals: Hidden Dimensions in Nanoporous Materials

Article abstract of DOI:10.1002/anie.201704499

Screw dislocation structures in crystals are an origin of symmetry breaking in a wide range of dense-phase crystals. Preparation of such analogous structures in framework-phase crystals is of great importance in zeolites but is still a challenge. On the basis of crystal-structure solving and model building, it was found that the two specific intergrowths in MTW zeolite produce this complex fractal and spiral structure. With the structurally determined parameters (spiral pitch h, screw angle θ, and spatial angle ψ) of Burgers circuit, the screw dislocation structure can be constructed by two different dimensional intergrowth sections. Thus the reported complexity of various dimensions in diverse crystals can be unified.

Full text of DOI:10.1002/anie.201704499

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Accepted Article
Title: Fractal Crystals: Hunting the Hidden Dimension in Nanoporous
Materials
Authors: Lei Wang, Shengcai Zhu, Meikun Shen, Haiwen Tian,
Songhai Xie, Hongbin Zhang, Yahong Zhang, and Yi Tang
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Fractal Crystals: Hunting the Hidden Dimension in Nanoporous
Materials
Lei Wang, [a] Sheng-cai Zhu, [b] Mei-kun Shen, [a] Hai-wen Tian, [a] Song-hai Xie, [a] Hong-bin Zhang, [a]
[
a]
[a]
Ya-hong Zhang and Yi Tang*
Abstract: Screw dislocation structure in crystal are origin of symmetry
breaking in a wide range of dense phase crystals. Preparation of such
analogous structure in framework phase crystals is of great
importance in zeolites but still a challenge. On the basis of crystal
structure-solving and model building, we found that the two specific
intergrowths in MTW zeolite produce this complex fractal and spiral
structure. With the structure determined parameters (spiral pitch h,
screw angle θ and spatial angle ψ) of Burgers circuit, the screw
dislocation structure can be constructed by two different dimensional
intergrowth sections. Thus the reported complexity of various
dimensions in diverse crystals can be unified.
4
ZnPO -Faujasite. In fact, although the screw dislocation core
structure was predicted in atomic scale of LTA zeolite by Walker
and coworkers [ , the real ones of these frameworks remain
elusive. Importantly, the high symmetry of these framework
materials make the screw structure easy to be fused, leading
screw dislocation structure to be embedded in the bulky crystal.
MTW zeolite is known for its catalytic properties as a useful solid-
acid catalyst [8]. MTW zeolite composes of “butterfly building units
7]
4
1
(5 6 )” layers, and the butterfly building layers stack into a 3D
framework along a-axis by sharing four member ring structure. It
often exists as intergrown polymorphs of two end-members of
monoclinic (stacking sequence: ABCABC, C2/c, a=24.86 Å,
b=5.01 Å, c=24.33 Å, β=107.7°) and orthorhombic phase
In the prosperous field of nanoscience, a major challenge is to
fabricate intricate mesostructured crystalline materials with
desired architecture, morphology and dimensions. Among
fascinated phenomena in nature, fractal and spiral structures
have been the evergreen topics in the fields from crystallography
to material science for their intriguing contributions on both
fundamental researches and practical applications. The natural
world we live in teems with a plenty of branching structures (e.g.,
snowflake, tree and galaxy). The recursive division of branches in
the networks is treated as a self-similarity in fractal geometry.
Additionally, the branching patterns are assembled by these
fractal structures following self-similar law. On the other hand, the
pivot to form spiral structure of crystal lies in the generation of
screw dislocation to break the symmetry of crystal growth and
promote the anisotropic nanostructures. Such dislocation
structure has been widely captured in dense phase materials,
such as metal oxides and alloy compounds [1], ceramics [2], carbon
(
stacking sequence: ABABAB, Pmcn, a=24.30 Å, b=23.70 Å,
c=5.01 Å). Remarkably, some other twining behaviors, e. g.,
hexagonal star shape [9], are also found apart from this polymorph
twinning, but the origin still remains elusive. Herein, we
successfully solve crystal boundary in the branching hexagonal
star of MTW zeolite with full connectivity, which is crucial in
directing the evolution of regular morphology of hexagonal star.
By the combination of two intergrowth along <310> and <100>
directions, the unique screw dislocation core structure can be
achieved by above collaborative growth behaviors in two different
dimensions. Thanks to the one dimensional channel system of
zeolite MTW, the unique pore direction can be adopted as
dimensional indicator. Due to the lower symmetry of MTW
framework, the segments around the screw dislocation cannot
fuse into a bulky crystal for structure mismatching, which is
different from that in the higher symmetry system (LTA, CHA/AEI,
etc.). In addition, the phenomena in the framework materials with
different symmetries can be unified and interpreted by the
following conceptual structure.
nanotubes [ , and even ice
3]
[4]
.
In
a typical synthesis, the reaction was performed by
Comparatively, in framework materials, the complex
dimension can be captured individually: i) hierarchal architecture
hydrothermal method with a diquaternary ammonium type organic
structure-directing
N (CH )C H (abbreviated as 1,5-MPP, hereafter, Figure S1, S2)
+
[
5]
agent
(OSDA)
C H (CH )N -C H -
formed by self-repeating pillared MFI or rational intergrowth of
4
8
3
5
10
+
[
6]
FAU nanosheets , and ii) spiral structure in which spiral contour
can be observed on the flat surface of various crystals, for
3
4
8
containing siliceous gel. And then different type and concentration
of aluminum or boron sources was selectively added into the
above gel to control the supersaturation level of the system. Once
homogenous gel formed, it was transferred into a Teflon-lined
autoclave and hydrothermally treated at 433 K for 3 days under
autogenous pressure statically. As exhibited in Figure 1, the
crystallization of MTW zeolite can be divided into three regimes in
its phase diagram referring to evolution of crystal structure and
morphology (Figure S3-S6 and Table S1): hexagonal shape plate
4
instances, LTA, STA-7 (SAV), CHA/AEI, ZnPO -Sodalite and
[
a]
L. Wang, M. Shen, H. Tian, S. Xie, H. Zhang, Prof. Y. Zhang, Prof.
Y. Tang
Department of Chemistry, Shanghai Key Laboratory of Molecular
Catalysis and Innovative Materials, Laboratory of Advanced
Materials, and Collaborative Innovation Centre of Chemistry for
Energy Materials
Fudan University
Handan Rd. 220, Shanghai 200433 (P. R. China)
E-mail: yitang@fudan.edu.cn
(
Phase I, Si-Al system), numerous nanorods with layer by layer
and branching mode (Phase II, Si-B system), and dendritic growth
with frequently branching and stacking faults to form a spiral plate
[
b]
S. Zhu
Center for High Pressure Science and Technology Advanced
Research (HPSTAR)
(Phase III, Si-B system).
Shanghai 201203 (P. R. China)
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overlap along [310], i.e., the two adjacent branches intergrow
along the specific plane. With respect to the newly formed
boundary along the [310], the ED pattern of Region II exists a 180°
rotation around (310) plane normal (Figure 2c-II). Interestingly,
the ED pattern acquired at Region III displays the diffraction dots
of all of three individual trunk/branches from [001] (Figure 2c-III).
Different from the second branch, the third one intergrow to the
main trunk along [3-10]. Based on anisotropic growth of MTW
crystal (Figure S17), a plausible model can be constructed for
pseudo-hexagonal plate with one main trunk and two minor
twinning branches sharing a common c-axis (Figure 2d, Figure
S18, S19), whose simulated ED patterns (fig S18 and S20) are in
line with experimental results (Figure 2I, 2II, 2III). Its local
structure of interface (Figure 2e, 2f and Figure S21) shows full
atomic connectivity with the 67.9° in (the same as Figure 2b) and
20.3° out of ab plane. If in the concentrated system, more complex
dendritic morphology with snowflake-like fractal structure of at
least two generations can be clearly identified (Figure S22), where
each branch was interconnected via {310} facets with a common
intersection angle of ca.~65°.
Figure 1. Evolution diagram of zeolite MTW under different supersaturation. Up:
Phase I: branching growth (Si-Al system, SAR: 30-120, scale bar: 5, 2 and 5
μm), Phase II: layer by layer and branching growth (Si-B system, SBR: 20-15,
medium supersaturation, scale bar: 1, 1 and 1 μm), and Phase III: dendritic
growth (Si-B system, SBR:10-2, high supersaturation, scale bar: 1, 2 and 2 μm).
Down: Enlarged view of MTW particles in corresponding phase diagram (scale
bar: 2, 0.5 and 1 μm).
Phase I: For the zeolites synthesized in aluminosliceous
system (Figure 1), the MTW zeolite is collected when Si/Al ratio
in starting gel is higher than 30. The obtained samples mainly
present the pseudo-hexagonal morphology composed of
monoclinic phase of MTW zeolite via Rietveld refinement and
related physicochemical analysis (Figure 2a, Figure S7-S9, Table
S2, S3). From the TEM image (Figure 2b), one can see all
particles follow a relative fixed geometry composed of one major
and two minor spindle-like prisms with the angular relations of ca.
65° between major and minor branches and ca. 50° for two
adjacent minor branches. During the crystallization (Figure S10,
S11), the major prism forms prior to the minor ones, which can be
proven in a dilute system (Figure S12). As suggested by electron
diffraction (ED) patterns (Figure S13, Table S4), each prism in the
crystal plate extends along its microchannel ([010] direction) and
intersects to the adjacent one by sharing (hk0) twinning plane.
Focused ion beam (FIB) dual beam experiment (Figure S14, S15)
is employed to acquire the interested central thin slice in the
hexagonal plate with twinning intersection. The spatial analysis in
TEM-EDS experiment on the twinning slice indicates that there is
no remarkable elemental difference between the domains and
twinning boundaries (Figure S16, Table S5). In the low
magnification TEM image, the twinning boundary of major and
minor branches can be easily discerned by different textures
Figure 2. Morphology and twinning texture of hexagonal MTW plate. a) Rietveld
refinement analysis of MTW twinning structure, Rwp: 7.54%, Rwp(w/o bck):
2
9
.06%, R
p
: 5.44%, χ : 1.92, (inset: representative morphology of twinning MTW
plate, scale bar: 50 μm). b) Typical TEM image of hexagonal star composed of
three branches with geometry 4×65°+2×50°. c) Cross-section slice of hexagonal
plate, three individual branches are highlighted by different colours (inset:
original hexagonal plate). Electron diffraction patterns of twinning boundaries
locate at I, II and III. d) Atomistic projection model of hexagonal star with
highlighted twinning boundary (arrows indicate the 1D-12MR channel system,
view along c-axis). e-f) Atomic connectivity profiles of twinning boundary (top
and aspect view), respectively.
Phase II: By screening the synthesis conditions, MTW fine
structure can be deliberately control via partial substitution of T
atom with boron (Figure 1, Figure S23, S24). It should be noted
that, the as-synthesized zeolite displays the same hexagonal
habitus (Figure S25). When SBR > 10 in which the system would
locate in the medium supersaturation, MTW crystals exhibit the
hexagonal plate morphology with layer-by-layer stacking
crystalline branches at higher temperature for longer time (Figure
S26). These rod-like branches become thinner and their stacking
mode become denser with the increasement of boron content
(Figure 2c). The ED patterns of different areas exhibit increasing
complexity: from Region I (the area of single main trunk) to II (that
upon the intersection of the main trunk and a minor intergrown
branch) and III (that upon two intersections of the main trunk and
two minor intergrown branches). Firstly, in the ED pattern of the
main branch locate at Region I, only a sharp dots from the [001]
can be obtained (Figure 2c-I). While in ED pattern at Region II,
apart from the original set of sharp dots of main trunk, another set
of diffraction dots is imposed from the same [001] zone axis but
with a rotation angle about 65°, implying that two sets of ED spots
(
Figure S27). The phenomena could be anticipated by Burton-
Cabrera-Frank (BCF) theorem [10], in which the crystal growth is
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governed by mechanisms of dislocation growth, layer-by-layer
growth and fractal growth as increasing supersaturation (Figure
S28).
(Figure S39-S41), the hyper-branching and racemic features can
be easily captured. From the further inspection on the HRTEM
images along channel direction, the sample exhibits a severely
stacking disorder of numerous domains (Figure S42). Figures 3e
and 3f show the rendered screw dislocation structure of two
crystalline layers with different stacking sequences, which derives
from the HRTEM results (Figure S42). Interestingly, one can see
the layer by layer structures of the zeolite domains along channel
direction and their related dim areas (Figure 3d, Figure S43).
Figure 3. Stacking faults in MTW and related screw dislocation core structure.
a) HRTEM image of the thin slice, arrows indicate the SFs position and the trace
line presents the crystal growth direction (scale bar: 20 nm, inset: the intact
cutting slice, thickness: ~ 40 nm). b) Rotated ED pattern of intact thin slice in
inset of Figure 3a. c) Reconstructed ED pattern, and the dash lines mark
principal direction for monoclinic phase along the [010] zone axis. d) HRTEM
image of screw dislocation structures, arrows marks the fuzzy area resulted
from superimposition of bilayer with different SFs, scale bar: 10 nm. e-f)
0
Rendered 3D atomistic model of screw dislocation core (C : unit parameters
along c-axis, h: spiral pitch, detailed atomistic framework scheme is deposited
in Figure S42).
Furthermore, more detailed structure in each branch could be
discerned in the HRTEM image of a microtombed slice cut from
hexagonal MTW zeolite plate (SBR=17, Figure 3a). The branch
has the regular hexagonal shape (Figure 3a, inset), and the
stacking faults (SFs) can frequently appear along the c* direction
Figure 4. Collaborative growth behaviors along two different directions in MTW
zeolite. a-c) Representative structure in MTW under increasing supersaturation
(a: SAR=60, b: SBR=17, c: SBR=2), scale bar: 5, 1 and 2 μm, respectively. d-
e) General structure of the fractal spiral structure of MTW. f-g) Rendered atomic
model of the two independent growing dimensions in MTW structure observed
from different directions (Detailed atomistic framework scheme is deposited in
Figure S48).
(Figure S29). And the ED pattern (Figure 3b) indicates that the
structure is viewed along [010]. According to the MTW framework,
the SFs in the crystals can be attributed to the intergrowth of
monoclinic structure with mirror or two-fold operation
perpendicular to c-axis via an intrinsic twining plane with
orthorhombic symmetry and re-aligning to (100) plane (Figure
S30, Table S6, S7). Such structure can be proved by consistence
of the experimental ED pattern (Figure 3b，taken from the well-
ordered microtomed thin slice in Figure 3a) and the reconstructed
one (Figure 3c) from [010] zone axis of MTW zeolite. The frequent
occurrence of SFs along the a-axis results in the diffuse streaks
when h≠3n, while the sharp spots can be observed along the
The spiral, hyper-branched structure of Phase III can be
recognized as the overlay of above twinning status of MTW zeolite
in two different dimensions, i.e., (1) the stacking disorder in ac
planes (Figure 3) and (2) the deformation twinning in ab plane
(
Figure 2), which construct the screw dislocation core region as
the driving force to form this spiral structure in the hexagonal plate
Figure 4). On one hand, as shown in Figure 3E and 4H as
(
example, the unique stacking disordered structure is born to break
[010]mono when h=3n (n, integer number). The phenomena indicate
the crystal symmetry in ac plane (which can also be captured in
that the intrinsic stacking disorder derives from original monoclinic
framework and presents the layer shears of ±1/3a [11]. As indicated
dense crystal [
1c, 1d, 2]
): (i) first domain (top layer) with even
numbered (2n; n, integer number) SFs (Figure S44, S45) and (ii)
the other one (bottom layer) without SFs. The top domain with
even numbered faults aligns in parallel to the bottom defect-free
one in starting and ending parts due to the same stacking vector
by structure simulation and electron diffraction, the frequent
stacking disorders lead to the appearance of thin layers with
orthorhombic symmetry between the monoclinic MTW domains
(Figure S31, S32). For the complex crystallization process of
(
Figure S46, S47). An intact Burgers circuits is thus formed [13] for
exertion of the screw dislocation structure (Figure 3e, 3f) with a
regular spiral pitch h=nC (n, integer number; C , 1/2 unit
zeolites, the layer by layer stacking structures may derive from
multiple pathways of crystal growth involving the oriented
aggregation between different crystal domains of MTW [12]
0
0
.
parameters along c-axis). On the other hand, the deformation
Phase III: When the crystallization system is turned into a
high supersaturation status (SBR<10), different from those in
Phase I (Figure 2 and 4a) and II (Figure 3 and 4b) with lower
supersaturation, the final plates become a spiral, dendritic
structure with main phase of boron-substituted monoclinic MTW
twinning at (310) plane leads the generation of the branches with
o
o
screw angle (θ) of 67.9 in ab plane and spatial angle (ψ) of 20.3
out of ab plane (Figure 4f-4h) referred to results in Figure 2. These
two factors are the structural foundation of the spiral, hyper-
branched structure of Phase III, and the collaborative growth
behavior in two dimensions generates fractal spiral structure. With
(Figure 4c, S33-S39). Combining the SEM and TEM patterns
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increasement of boron content, the prisms in the hexagonal plate
particles appear more frequently with smaller size to form a
dendritic pine tree-like branches in ab plane. Furthermore, the
frequently 2-D nucleation events on the plates bring about the
frequent appearance of SFs along a-axis (looking down ac plane)
to form the screw dislocation core region with numerous
fragments (Figure S48), which further promotes fractal growth in
ab plane by fast extension along the channel direction and
facilitates the continuous self-iteration process.
novel strategy toward hierarchical materials with interconnected
abundant pore structures (Figure S53-S55). This strategy might
be applied to other zeolite structures that can (i) derive a novel
zeolite phase by regular extension of deformation twinning
boundary (Figure S56) and (ii) offer a potential opportunity to
distinguish the end-polymorph from hybrid phases (Table S6, S7).
Furthermore, such zeolite with confirmed complex twinning and
stacking faults were proven with an enhanced catalytic
performance due to its textural and framework properties
(
Supplementary Text, Figure S57, S58).
Such screw dislocation structure creates inner strain (Estrain) in
the periodic crystalline lattice. According to the elastic theory, the
stress field exerts a torque throughout the whole plate at the
central area, and the strain energy depends on the magnitude
Additionally, the model for polymorph intergrowth in this work
is totally different from the known models that developed for
MFI/MEL and FAU/EMT systems. For MFI/MEL, the central MEL
node with higher symmetry plays as direct connector with lower
symmetrical MFI nanosheets to form self-pillared pentasil [ . For
FAU/EMT, the random EMT nuclei intergrowth with FAU
nanosheets to break the cubic symmetry to form hierarchical
structure [6]. The orthorhombic polymorph in the screw dislocation
of MTW zeolite only acts as a bridge to change the relative
position along the screw dislocation circuit, and can be
manipulated by surpersaturation. The unique phenomena also
provide a novel vision to understand the polymorph intergrowth
and its role in the architectural evolution of zeolite. Vary from the
exact fractal patterns by mathematical expressions, the fractal
pattern in practice is self-similarity in statistics and evolves under
certain circumstance with time. Essentially, the fractal system
depends on the two crucial factors: element with self-similarity
and dynamic iteration procedure. The present fractal pattern is
self-organized by branching and intrinsic twinning to construct a
hierarchal dissipative structure under the domination of energy.
E
strain ∝ b2 (b, Burgers vector). The phenomena were often
observed in dislocation-driven dense phase materials, such as
5]
[
1c,
1d]. An energy balance
ZnO nanotubes or Bi
between surface energy 2πrγ (γ, surface energy) and inner strain
strain can be spoiled, and the solid plate becomes a hollow one as
2
Se
3
plates
E
be confirmed in this work (Figure S49-S51).
The above conceptual evolution model of spiral structure of
MTW also can be adopt to interpret those in the nanoporous
materials with different topology. For a known screw dislocation,
there must be a birth in plane and a spread along vertical direction
in crystal, which involves the two collaborative growth behaviors
along the two different dimensions. As previously reported spirals
[
7, 14]
in nanoporous systems, like LTA
(Figure S52, Table S8),
4
-Sodalite and ZnPO -
CHA/AEI [ , STA-7 (SAV) [16], ZnPO
15]
4
Faujasite [17], 3D spiral terraces are considered here to be defined
by three crucial parameters: spiral pitch h, screw angle θ and
spatial angle ψ. For LTA zeolite, the above two angles are 90° and
0°, respectively. In the each corner of the LTA square spiral
terrace, the adjacent segments rotate about 90° and fuse into the
bulky crystal owing to the identical atomic arrangement in the (010)
and (001) planes. It worth noting that other nanoporous materials
with high symmetric level always fuse into their bulky crystal and
leave a spiral terrace on the surface due to the overlap of two
dimensions, which may explain that why we seldom capture the
screw dislocation structure in nanoporous system [7, 18]. In MTW
zeolite with lower symmetry (C2/c), the three parameters are
determined as spiral pitch: 1.2 nm, screw angle: 67.9° with spatial
angle: 20.3°, and the layer by layer stacked branches aggregate
Acknowledgements
This work was supported by National Key Basic Research
Program of China (2013CB934101), and NSFC (21433002,
21573046, 21473037 and U1463206). We thank Dr. J. L. Sun
(Peking University) for helpful suggestions on disordered
structures and Dr. P. Guo (DICP) for thoughtful discussions. We
thank G. R. Zhou for cutting thin slice of the samples for HRTEM
observation. Special thanks are due to reviewers for many helpful
into a pine tree-like, spiral contour on the original hexagonal plane. comments.
[
13-
Different from regular spiral terrace on the flat zeolite surface,
16]
it is hard to obtain the regular spiral step height on the highly
Keywords: zeolite structure • coincidence boundary •
intergrowth • structure evolution • fractal pattern
dendritic surface structure of MTW (equal to the Burgers vector
along the vertical direction) by atomic force microscopy, but the
spiral patterns and hillocks can still be clearly recognized.
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screw dislocation core and hollow core structure. Different from
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Angewandte Chemie International Edition
10.1002/anie.201704499
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L. Wang, S. Zhu, M. Shen, H. Tian, S.
Xie, H. Zhang, Y. Zhang and Y. Tang*
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Fractal Crystals: Hunting the Hidden
Dimension in Nanoporous Materials
Hunting the hidden dimension in nanoporous materials! Revealing that
experimental screw dislocation structure in MTW zeolite is constructed by two
specific rational intergrowth along different dimensions.
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