Osamu Terasaki School of Physical Science and Technology (SPST), ShanghaiTech University, China.

ℏCentre for High-resolution Electron Microscopy (C EM)
Mesoporous crystals:
Looking through scattering, diffraction & imaging
Osamu TERASAKI
School of Physical Science & Technology, ShanghaiTech Univ, China
Madrid, April 2018
We are setting up
Centre for High-resolution Electron Microscopy (ChEM)
will have an Inauguration on May 27-29. 2018

Outline
What kind of structure solution or characterisation we want to
know for pharmaceutical & Biological Applications ?
Key Factors:
Pore arrangement : 2d- (channel type) or 3d- (pore or bi-/tri- continuous type
Crystal morphology and size
Wall: crystalline or amorphous
Uniformity of functional-group (low Z-number atoms) distribution in a pore
Pore opening to external surface
Fine structures within pore surfaces
Electrons as a probe for structural study of mesoporous:
TEM and SEM
In-situ SAXS, Gas adsorption crystallography

Electrons as a probe for structural studies
1. Strong interaction with matter: Large scattering amplitude
at K=4π sinθ / λ for Si atom, f electron(K=0) : 5.8 x 10-8 (cm)
f X-ray(K=0) : 3.9 x 10-12 (cm)
f neutron(K=0) : 4.1 x 10-13(cm)
2. Charged particle:
Electromagnetic Lens ED pattern & EM image
Wave length de Broglie λ = 0.0197 Å at 300kV
3. Structural Information:
Image: Local, ED pattern: Average
4. Elemental and electron state information as function of positions
Problems in fine structural studies of porous crystals
Small crystal size: ca 1 μm or smaller
Smaller is better for kinematical approximation!
Crystals are electron beam sensitive, especially zeolites
HREM images are projection along the beam direction
Cf: At present, X-ray diffraction intensity can be obtained much more precisely
than ED intensity with large dynamic range !

Electrons can provide various information
Incident
electronsBack scattered
electrons
Secondary
electrons
Transmitted
electrons
Scattered
electrons
Surface
structure
by TEMX-ray
S/TEM
Diffraction pattern
(HREM) Image
SEM
SE: surface topological info.
BSE: carry volume and elemental info.
X-ray: elemental & electronic info.
To be studied

How to improve resolution of SEs image
toward incident e-probe size
~ R/2
X-ray linear absorption coefficient of amorphous Silica (ρ~2.2 gcm-3) for 1.0 keV X-ray (~Na
K edge) is ~ 6.7 10-3 cm-1. 1.0 keV X-ray intensity will be diminished only by a factor of e-1
through amorphous silica with thickness of 1.5 μm, and therefore it is very easy to be detected.
SE escape-depth is ca 5 times of
mean free-path of SE.
Mean average escape-depth is a
few nm for metals and 10 ~20 nm
for insulators.
Characteristic
X-ray
K. Kanaya & S. Okayama, J. Phys. D5, 1972, 43-58.
R(nm) = 27.6
A(g×mole-1
)E(impact e- energy:kV)5 3
r(g×cm-3
)Z(atomic- number)8 9
where A and r:atomic weight and density,

ℏCentre for High-resolution Electron Microscopy (C EM)Ion-Slicer + TEMCross-section Polisher + SEM
Internal structure of mesoporous silica sphere:
Comparison Cross-section Polisher + SEM & Ion-Slicer + TEM
e-beam e-beam
Projection
through
Thin slice
Surface of
Semisphere

IRMOF-74-VII
Powder X-ray diff pattern, TEM & SEM images
H. Deng et. al, “Large-Pore Apertures in a Series of Metal-Organic
Frameworks”, Science, 336 (2012) 1018-1023.
Landing energy 300 eV
Bias: - 5kV
7
SEM image
TEM image
Pore dia：3.5 nm

Lung alveolar structure: Natural mesoporous material
100 kV
Marcus Larsson, Kare Larsson & Osamu Terasaki: Solid State Sciences 5(2003), 109-114
(stained)

X-ray diffraction profiles from different silicas
Powder XRD
pattern of AMS-9
Intensity
2d sin θ = λ
sin θ / λ = 1/(2d)
q = 4π sin θ / λ

Powder XRD pattern and HRTEM image: AMS-9
Powder XRD
pattern
Intensity

Fourier
Transformation
410
330
AMS-9
SG: P42/mnm,
a=19.7 nm,
c=38.1 nm.
Fourier diffractogra (FD) of HRTEM image
HRTEM image
1d- diffraction
intensity profile
from 2-d FD
Image & FD: AMS-9: [001]
Powder XRD
pattern
Intensity
Powder XRD doesn’t have
enough resolution for 1/d
compared with ED !

ℏCentre for High-resolution Electron Microscopy (C EM)12
Mesoporous crystals: Cooperative self-assembly of
silica/surfactant molecules in water
MCM-48/ Gyroid
＋＋
Water
Hydrophobic
tail (B)
Hydrophilic
part (A)
Silica network
is formed on the
BOUNDARY
Silica network is formed at the boundary between water-surfactants !
Diameter of rod (~pore diameter of silica meso) is 20-100 Å and can be controlled.
Powder XRD

50 nm
HREM image of MCM-48, [111]
Silica mesoporous material is crystalline !
SEM image of MCM-48
Silica & Channel structures determined by EC

Various silica mesoporous crystals:
Beautiful morphology tells point group symmetries
p6mm (6mm) P63/mmc (6/mmm) Ia-3d (m-3m) Pm-3n (m-3m)
Samples: Prof Shunai Che

C r( )= B r( )*L r( ){ }×Z r( )= B r( )* L r( )×Z r( ){ }
Crystal structure C(r) is described by
Lattice L(r), Basis B(r) and Shape/Size Z(r )
Crystal structure factor F(qhkl) is Fourier transform of C(r)
and complex number.
This part is crystal structure factor normally defined in text book.
F qhkl( ) µ I qhkl( )
Crystal structure factor F(qhkl) is obtained from diffraction intensity.
Crystal structure C(r )
α(hkl)
Asuume
F qhkl( )= F qhkl( ) eia (hkl)
= F C r( )éë ùû
= F B r( )éë ùû×F L r( )éë ùûéë ùû*F Z r( )éë ùû

Organic/Inorganic Interfacial Curvature Decrease
Cage-Type Cylindrical Hyperbolic Surfaces
Quasicrystal, Cmmm, Modulated
structures, etc.
c2mm, p2gg, etc Im-3m (DP), etc
PolyhedralSpherical
Mesoporous silica crystal structures solved by EC
we have developed through HRTEM image analysis

Two-dimensional case:
Plane groups: p6mm, c2mm, p2gg
p6mm c2mm p2gg
a
b b
a
b
a
(a = b, 120º) (a = b/√3, 90º) (a = b/√3, 90º)
H Qiu, Y Sakamoto, O Terasaki & S Che, Adv. Mater. 2008, 20, 425–429

KSW-2 from Kanemite (Layered Silicate)
T. Kimura, T. Kamata, M. Fuziwara, Y. Takano, M.
Kaneda, Y. Sakamoto, O. Terasaki, Y. Sugahara & K.
Kuroda, Angew. Chem. Int. Ed. 39(2000), 3855-3859.
20 nm
DecreasepH+calcination

From kanemite to FSM-16
Synthesis time increases, kept at pH 8.5
3 hours at RT then heated to 70 C for 3h Additional 45 h at 70 C
Structure Analysis of Mesoporous Material”FSM-16”: Studies by Electron Microscopy
and X-ray Diffraction, Y.Sakamoto, S.Inagaki, T.Ohsuna, N.Ohnishi, Y.Fukushima,
Y.Nozue & O.Terasaki, Microporous Mesoporous Materials, 21(1998), 589-596.

Mixture of
n=1 : ATMABr
&
n=2 : ATEABr
for C14-, only n = 1.
Surfactant
C
CC
CC
C
H2
H2
H2
H2
H2
H2
C
C
CC
CC H2
H2
H2
H2
H2
H3
...
Br-
CnH2n+1
N+ CnH2n+1
CnH2n+1
Hydrophobic: Alkyl Chain Hydrophilic Head
M. Kruk, M. Jaroniec, Y. Sakamoto, R. Ryong & CH Ko, J. Phys. Chem. B104 (2000), 292.
Plane Group: p6mm
Pore Shape : hexagon
Pore-Wall Thickness : 10 Å
Lattice const : 42 Å
Pore Diameter : 32 Å
Results for C14/MCM-41
Two dimensional hexagonal MCM- 41
d10
d11
d10
Electrons
20 nm
Electrons
(a)
Electrons
(b)
(a) (b)
(a)

Chiral Mesoporous Crystals

Structural Model of Chiral (twisted) Tube
Chiral channels
in the tube
At the positions indicated by the arrowheads in (a) and (c),
{10} planes of 2d-hex are parallel to <10>.
123
Projection
Pt
Ä 10
tube
direction
Side view
along <10>
(a)
(c)
Cross section
(b)
d10=a// 3
t
D
tube diameter
d11= a/2
123
a

To study whether straight channels are
connected each other through holes or not

Low magnification TEM image (a) and
HREM image (b) of Pt nanowires extracted
from the Pt/MCM-41 samples.
Pt is single crystaline nanowire with a
diameter of 3.5 nm, which was pore-
diameter of MCM-41.
Single crystal Pt nanowire formed in MCM-41

ℏCentre for High-resolution Electron Microscopy (C EM)Z. Liu, O. Terasaki, T. Ohsuna, K. Hiraga, H. J. Shin & R. Ryoo, ChemPhysChem 2001, 229-231.
Pt rods do not destroy the channels of SBA-15. Pt rods are connected each other by bridges.
They are forming almost single crystals.
A bundle of Pt-nanowires formed within SBA-15

SEM Image of SBA-15:
Manner of channel openings & Crystal growth process
Direct observation of three dimensional mesoporous structure by Scanning
Electron Microscopy (SEM): SBA-15 silica and CMK-5 carbon,
S. Che, K. Lund, T. Tatsumi, S. Iijima, S.H. Joo, R. Ryoo and O. Terasaki,
Angew. Chem. Int. Ed.42( 2003), 2182.
HITACH S-5200, 2keV

Mesoporous Silica: SBA-15
Landing energy: 300 eV
Probe current: 5 pA
Sample bias: -5 kV
27
Micro pores
Plugs

“Two-dimensional” case
Amorphous wall
Crystalline wall
Three-dimensional case in strict sense !

Detection of atomic- and meso- scale density modulations
along c-axis and perpendicular to the axis, respectively,
in ED pattern, [100] incidence
S. Inagaki, S. Guan, T. Ohsuna & O. Terasaki,
Nature 416 (2002), 304-307.
C*
(000)
(7.5 Å ) -1
(45.5 Å ) -1
Question was thrown to us:
Is the crystal a pure phase or
physical mixture of two
with different length scales ?

An orderedmesoporous organosilica hybrid material with a crystal-like wall structure
S. Inagaki, S. Guan, T. Ohsuna & O. Terasaki, Nature 416, 2002, 304.
1st Ordered mesoporous organosilica hybrid material
with hierarchecal order, meso- and atomic-scales

ℏCentre for High-resolution Electron Microscopy (C EM)An orderedmesoporous organosilica hybrid material with a crystal-like wall structure
S. Inagaki, S. Guan, T. Ohsuna & O. Terasaki, Nature 416, 2002, 304.
1st Ordered mesoporous organosilica hybrid material
with hierarchecal order, meso- and atomic-scales

Three-dimensional case

Mesoporous crystals: Cooperative self-assembly of
silica/surfactant molecules in water
MCM-48/ Gyroid
＋＋
Water
Hydrophobic
tail (B)
Hydrophilic
part (A)
Silica network
is formed on the
BOUNDARY
Silica network is formed at the boundary between water-surfactants !
Diameter of rod (~pore diameter of silica meso) is 20-100 Å and can be controlled.
Powder XRD

Minimal surfaces defined by H=0,
so that k1=-k2
...the surface is equally concave and convex….
…. K (:= k1.k2) is negative (hyperbolic geometry)
Minimal surface

Monkey saddle
From Sten Andersson (Lund)

P-surface

P-surface and LTA
Close to Periodic 0
Potential Surface for
CsCl

D-surface and Faujasite (FAU)

An Example: Ia3d case
[100] [110] [111]
hkl: h+k+l =2n, 0kl: k and l =2n, hhl: 2h+l = 4n, h00: h=4n leads to Ia-3d uniquely

Electron crystallography for 3d-mesoporous
crystals
h
k
l
3D-reciprocal space
3d data set of F(hkl)
Amplitude + Phase
Inverse FT
Extinction Conditions
+ Point Group
Space Group
A. Carlsson, M. Kaneda, Y. Sakamoto, O. Terasaki, R. Ryoo & H. Joo, J. Electron Microsc. 48 (1999), 795-798.

Silica wall structure from electrostatic potential map:
Self-consistent approach
0. A. Carlsson, M. Kaneda, Y. Sakamoto, O. Terasaki, R. Ryoo & H. Joo, J. Electron Microsc. 48
(1999), 795-798.
1. Y. Sakamoto, M. Kaneda, O. Terasaki, D.Y. Zhao, J.M. Kim, G. Stucky, H.J. Shin & R. Ryoo;
Nature 408 (2000), 449.
2. K. Miyasaka & O. Terasaki, Angew Chem Int Ed, 49, 2010 , 8867-8871.
3D-structural solution
Electrostatic potential map:  (x,y,z)
Pore:
Wall:
Two approaches
1. Pore volume
from gas adsorption
2. Curvature assessment

Phase information of Crystal Structure Factor
is essential for structural solution!
Thousands different structures can
give the same diffraction patterns!
Carbon: CMK-1Silica: MCM-48
Bavinet’s Principle

The Phase Problem in crystal structure factor:
From Jianwei (John)
Miao (UCLA), 23rd
IUCr, 2014

We have solved mesoporous structures by EC
44
By other
groups

Structure defects

Structure transformations

New hierarchical porous crystals
based on zeolites

Top surface imaging at extreme low voltage:
Mesoporous LTA Zeolite
1μm
Taken at 80 eV as landing energy, Gun voltage at 5.08 kV
Specimen bias as -5.0 kV, Sample : Sample: Ryong Ryoo
K. Cho, et al., Solid State Sciences. Vol. 13. (4). 750–756, April 2011 48

Pillared-MFI nano-sheets
K. Na, M. Choi, W. Park, Y. Sakamoto, O. Terasaki and R. Ryoo, J. Am. Chem. Soc.
132, 2010, 4169-4177.

Ion chamber
X-ray
Shutter
Collimator
Sample
Slit
Imaging plate
Glass
capillary
Goniometer
head
Gas import tube
L.T. N2 gas blower
He leak
detector
Cold
head
VV
Gas
V
Gas import tube
V
Pressure gauge
Experimental system for in-situ powder XRD
at SPring-8, BL02B2
Debye- Scherrer Camera, Cooling by boilling N2 gas; Gas adsorption is separately measured
Meso-, macro-pores: we
need longer wave length
& data of smaller
scattering angele

Imaging plate
Powder sample
(capillary, 0.3mm in diameter)
Collimator
X-ray
Liquid N2 gas blower
Adsorption gas at 90K
Sample
(~2mm)
Gas inlet
glass rod
Transmission mode: Sample is mounted in a capillary
for in-situ experiment at SPring-8

Single type of pore

Analysis on the reconstructed SBA-16 (Im-3m)
calcined sample
A unit cell of bcc lattice
Potential contour map
Pore size = 12.3 nm
Curvature distributions
Dimensionless surface area = 4.12
(cf. Fm-3m: 5.2, Pn-3m: 6.5, Fd-3m: 9.2)
Specific surface area = 277 m2/g
cf. BET surface = 743 m2/g

The wall structure
by electron
crystallography
Gas adsorption ability of SBA-16 mesostructure by
different techniques
Synchrotron In-situ
powder XRD
Quenched solid
density functional
theory
Structural model for SBA-16
Mesopores in bcc lattice mesopore Silica
wall
Micropores’ corona

ℏCentre for High-resolution Electron Microscopy (C EM)A Stand-Alone Mesoporous Crystal Structure Model from in situ X-ray Diffraction: Nitrogen Adsorption
on 3D Cagelike Mesoporous Silica SBA-16, K. Miyasaka et al.,Chem. Eur. J., 18, 2012, 10300-10311.
Structure solution
from in-situ SAXS
and comparison with
Quenched DFT iso-
therm calculation

Multiple pores with different size

Sample holder
Kratky Block
Detector
X-ray
generator
(Rotating
Anode)
λ:1.54178 Å
Gas adsorption
Instrument
Be-window
X-rayX-ray
CoolingGas inlet
vacuum
Sampl
e
Cryostat
Confocal
mirror
In-situ gas adsorption SAXS instrument
Cho, H. S. et al. Nature 2015, 527, 503.
2D Debye-Scherrer type:
Pilatus
1)Transmission mode
2)Specimen temperature:
At any points between
liq N2 and 350 K with
temp stability better
than 0.1K
Precise measurement of diffraction
intensity profile, from which we can
obtain followings as a function of
gas pressure;
1)Integrated intensity
2)Unit cell change
3)Line widths

Ar gas adsorption isotherm of a MOF &
Unit cell parameter change
We can identify three cavities with
different sizes, and numbers and
positions of Ar adsorbates in each cavitiy,
“how many and where”, from Fourier
analysis of diffraction intensities !

1) To solve mesoporous crystal structure solely from ED
intensities
2) To find positions of functional molecules composed of
light elements
3) To describe dynamic behavior of functional molecules
under a certain condition
4) To find mechanism of “drug release” through electron
state change
Thanks for your attention !

2D mesoporous silica thin film (2MPSF_as)3D mesoporous silica thin film (3MPSF_as).
M. Kobayashi.K. Kuroda. et. al., Langmuir, 2017, 33 (9), pp 2148–2156
SEM images of mesoporous silica films vs
various landing voltages
※ Etched with aqueous ammonium fluoride solution (0.1 M)

ℏCentre for High-resolution Electron Microscopy (C EM)M. Kobayashi. K. Kuroda. et. al., Langmuir, 2017, 33 (9), pp 2148–2156
80 V 200 V 2 kV
3D mesoporous silica thin film
(3MPSF_as) Before etching

MCM-48 CMK-4
z = 0
z = 1/8
Black contrast: silica wall in MCM-48, carbon rods in CMK-4
Comparison: 3d-structure solutions of MCM-48 and CMK-4
hkl d/nm Amp. Phase Amp. Phase
211 3.52 100. π 100 0
220 3.04 43.6 π 41.7 0
321 2.30 4.1 0 5.3 π
400 2.15 14.5 0 9.7 π
420 1.92 10.7 0 4.6 π
332 1.83 13.5 π 6.5 0
422 1.75 5.3 π 2.2 0
431 1.69 3.4 π 0.6 0
MCM-48CMK-1
Observed crystal structure-
factors of CMK-1 & MCM-48

Mesoporous zeolite LTA
LTA1
LTA01
LTA05
LTA8

R
V
R/2
Interaction volume V and Penetration depth R increases as impact electron
energy E increases or atomic number (atomic weight) Z decreases.
Interaction volume & Penetration depth:
Dependence on Atomic number (Z) and electron energy (E)
Penetration depth R is a function of impact electron energy E,
atomic weight and number A and Z, density r (empirical formula)
R = 0.0276 A×E1.67
Z0.889
× r
Penetration
Depth R
Increasing impact electron energy E
Increasing atomic number Z
Interaction
Volume

Outline
Definition of Crystal
Pores/channels play as pseudo atoms
Mathematical formalism of Crystal Structure Factor for crystal
with finite size
Crystal Structure Factor is complex number, and importance of
its Phase
Structure characterisation and Structure solution
Amphiphilic molecules minimamise surface energy of boundary
between hydrophilic & hydrophobic  Curvature
Crystals with order in two different length scales

Wave length
of X-ray
Wave length
of electron
Resolution of EM
Atomic Coordinates
Atomic coordinates are
refined by statistical
treatment from many
reflections up to large
scattering vectors.
Framework
Structure of
Zeolites
Bond distances,
T-O = 1.6 Å
T- (O) -T= 3 Å
Structures of
Mosoporous
Wave length of
visible light
d (Å)
100 Å 2 Å 1Å 0.1Å10 Å
Pore / Cage diameter
20-500 Å
Length scale for different structures

SEM images of SBA-16 (Im3m)
Along 3-fold axis. Surface steps,
channel openings and their
arrangements are clearly observed.
HITACH S-5200, 2keV
O. Terasaki & R.Ryoo, Review Article ℏCentre for High-resolution Electron Microscopy (C EM)
SEM images of SBA-16 (Im3m)
Along 3-fold axis. Surface steps,
channel openings and their
arrangements are clearly observed.
HITACH S-5200, 2keV
O. Terasaki & R.Ryoo, Review Article

Powder XRD profile
AMS-9 (P42/mnm)
Fourier Diffractogram
Rotationally integrated
intensity profile obtained
from FD of HRTEM image
Rotational integration

Mesoporous Silica: SBA-15
Landing energy: 300 eV
Probe current: 5 pA
Sample bias: -5 kV
71

Gaussian curvature is
positive zero
negative
elliptic parabolic hyperbolic
closed micelles
(sphere) rod micelles, lamellae
(planes, cylinder)
bicontinuous phases
(saddles)
Curvatures of a (2d) surface are characterised by principal curvatures;
k1 and k2 := 1/(extremal radii of curvature)
More commonly, we use:
•Mean curvature, H :=< k1 , k2 > (dimensions of L^(-1))
•Gaussian curvature, K :=k1 . k2 (dimensions of L^(-2))
Curvatures of a surface

Crystallographic surfaces
Equi-electron density map
Fourier sum of crystal structure factors
Crystal structure factor graphs and periodic nodal surface
Equi-potential surface in real space
Periodic 0 Potential Surface for CsCl gives almost “P-surface”
Equi-energy surface in a reciprocal (momentum) space
Fermi surface
Morphology
Boundaries, Voronoi polyhedra

Two-dimensional case
Amorphous wall
Crystalline wall

R
cR
L
Scattering amplitude : F
for Cylinder ( outer radius = R, inner radius = cR, L >> R )
where
J0 , J1 : Cylindrical Bessel Function
k= 4 π sin θ / λ
=
2J1(kR)
kR
for c = 0 (rod)
= J0(kR) for c = 1 (thin pipe)
for 0 < c < 1F = 2
kR J1(kR) - ckRJ1(ckR)
(kR)2 (1-c2)
Scattering amplitude for cylinder
Z
x
y

Coral from Gotland island (Sweden)

Crystallographic surfaces
Equi-electron density map/equi-potential density map
Fourier sum of crystal structure factors Atomic arrangement
Crystal structure factor graphs and periodic nodal surface
Equi-potential surface in real space
Periodic 0 Potential Surface for CsCl gives almost “P-surface”
Equi-energy surface in reciprocal (momentum) space
Fermi surface
Boundaries, Voronoi polyhedra

Wave lengths:
Electromagnetic wave (X-ray) & Matter wave (electron & neutron)
l µ 1
E
l µ 1
E
Electromagnetic wave (EMW): E=h /(2)=h,  =c/=ch/Ε
X-ray: EMW,  (Å) = 12.4 / E (keV)
CuK ( =1.54 Å) = 8.27 (keV)
Matter wave (MW): p = mv, E = p2 /(2m), λ= h / p =h / (2mE)1/2
Electron: MW,  (Å) = 0.3873 / E 1/2 (keV)
(without relativistic correction)
Electrons with  =1.54
Å = 66.7 eV
Neutron: MW,  (Å) = 0.2860 / E 1/2 (eV)

Partition of space (Space Filling)
Soft Materials

Lung alveolar structure (unstained)
100 kV
Marcus Larsson, Kare Larsson & Osamu Terasaki: Solid State Sciences 5(2003), 109-114

Schematic phase diagram of a water-surfactant
20 nm
20 nmMCM-48/ Gyroid Surfactant rod

Corresponding TEM images
amount of NaOH
(a) (b) (c)
C18MIMBr/TEOS/H2O/NaOH = 0.9 : 6.8 : 10000 : x x = 2.2 (a), = 2.9 (b), = 3.6 (c)

Three different domains with p2gg: x=3.6 highest pH
C18MIMBr/TEOS/H2O/NaOH = 0.9 : 6.8 : 10000 : x x = 3.6
Fourier filtered three domains obtained from different coloured spots in FD (left top)

Structural Change with synthesis time
Pm-3np6mm
It is confirmed that structure of T2-T5 is
p6mm and that of T10 is Pm-3n.

Structural change:
From 2d-p6mm to 3d-Pm-3n epitaxially
The most important waves: {10} for p6mm, {211} for Pm-3n, and {210} {211} for Ia-3d
structures, respectively. F(h,k,l) has the following phase relations for Pm 3n and Ia-3d,
For Pm-3n: F(h,k,l) = F(-h,-k,-l) = F(-h,k,l) = F(h,-k,l) = F(h,k,-l),
For {211} in Ia-3d: F(h,k,l) = F(-h,-k,-l) = -F(-h,k,l) =- F(h,-k,l) = F(h,k,-l).

HREM images of SBA-6: [100] & [111] incidences
[100] [111]
[120]
[110]

Extinction condition obtained from Fourier
diffractograms of HREM images for SBA-6
[00l]
[h0h]
[010] [120] [110]
[111]
Reflection condition
hkl no condition
0kl no condition
hhl l=2n
00l l=2n
Pm3n or P43n
Crystal morphology indicates PG : m3m

HREM imageFourier diffractogram
from marked area
Crystal structure factors
Crystal structure factors from Fourier analysis of
HREM image

255
Threshhold
Wall(amorphous)Cavity
0
197
Electrostatic Potential
Map(z = 0)
N2 gas adsorption exp.
pore volume = 0.84 cm3/g
wall density = 2.2 g/cm3
Vpore/Vtotal=0.65
Structures of MCM-48 and Surfactants from EC

Silica-wall structure of MCM-48
A B
Black 0
White 255
Wall
Pore
197
From images
Wall
Pore
165
From ED patterns
z = 0
z = 1/8
From HREM images:
we can choose thin area,
effect of CTF function.
From ED patterns:
effect of multiple scattering ,
free from CTF effect.
Both cases give the same wall
thickness of ca. 11 Å.

Observed crystal structure factors of CMK-4 fit well to potential with step by convolution of
a Gaussian function (σ = 0.08, same as σ -parameter for MCM-48).
A trial to solve 3d-structure without pore volume

SEM & TEM image
500nm
100nm
10nm
10nm
MFI
MFI
straight
channel
direction
b
a
a
b
b
a
D.D. Xu et al., Nature Commun. 2014, 5, 4262

Double ice

Crystal structure factors: MCM-48 (after CTF correction)
h k l h2+k2+l2 d(Å) Amp Phase
2 1 1 6 35.9 100.00 180°
2 2 0 8 31.1 39.84 180°
3 2 1 14 23.5 4.13 0°
4 0 0 16 22.0 5.29 0°
4 2 0 20 19.7 4.14 0°
3 3 2 22 18.8 2.89 180°
4 2 2 24 18.0 0.97 180°
4 3 1 26 17.3 0.80 180°
4 4 0 32 15.6 0.56 0°
5 3 2 38 14.3 0.06 0°
6 1 1 38 14.3 0.16 0°
6 2 0 40 13.9 0.11 180°
5 4 1 42 13.6 0.14 0°
h k l h2+k2+l2 d(Å) Amp Phase
4 4 4 48 12.7
6 4 0 52 12.2 0.09 180°
5 5 2 54 12.0
6 3 3 54 12.0
6 4 2 56 11.8 0.08 0°
6 5 1 62 11.2 0.04 180°
8 0 0 64 11.0 0.08 0°
8 2 0 68 10.7 0.04 0°
6 6 0 72 10.4 0.07 180°
7 4 3 74 10.2
8 4 0 80 9.8
The reflections of 521, 631, 543, 721, 732, 741, 653, and 831 cannot be obtained from [100],
[110], and [111] incidences. The 822 and 752 reflections are too small to be determined.
34 unique reflections were obtained within resolution limit of h2+k2+l2 < 80 .
However, it was confirmed through ED observations by tilting the
crystal that the intensities of all of these reflections were very weak.

What space filling arrangement of cells of equal
volume has minimum surface energy (area)?
The rules observed by Plateau (1873).
(1) The surface which bound the cells must meet 120 degrees.
(2) The lines which are formed by the intersections of the surfaces must meet at cos-1(-1/3),
the tetrahedral angle.
Experimental observations in biological cells:
(1) The average number of faces is close to 14 per body.
(2) The average number of sides per face is 5.413.
(3) The vertices are generally tetrahedral.
Kelvin proposed the body-centred-cubic (bcc) structure as a likely candidate for the
optimal arrangement. Wigner-Seitz cell of the bcc structure is a tetrakaidecahedron,
sodalite-cage, constructed from six square surfaces and eight hexagons.
Polyhedra of interest in relation to foam structures.
(1) Rhombic dodecahedron (Wigner-Seitz cell of the fcc structure)
(2) Pentagonal dodecahedron
(3) Tetrakaidecahedron (Wigner-Seitz cell of the bcc structure)

Regular packings of equal discs (2-d)
Regular Tessellation
r = p /SQRT(12)
= 0.906
(a) Triangles (b) Squares
r = p / 4
(c) Hexagons
r = p / SQRT(27)
= 0.604
Packing density ρ =
Area covered
Total area

There is a strong tendency, in general, towards disorder when differently sized
discs are packed tightly together.
This is especially true when there is a marked difference in the disc sizes ( at
least 25 %) and the effect is stronger when a few large discs are mixed with
small ones.
See: Nelson DR, Rubinstein M & Spaepen F, Phil. Mag. A46(1982), 105
When discs with special size ratios are chosen, beautiful arrangements can be
created. For instance, equal quantities of discs with two diameters in the ratio
SQRT(3-τ) / τ, where τ is golden ratio.
See: Lancon F & Billard L, Lectures on Quasicrystals, 1995.
Disordered packing

ℏCentre for High-resolution Electron Microscopy (C EM) 9
Plane and Spherical Waves
Spherical wave (from a point source):
A exp {i(k r -  t)}
r
Plane wave (from a point source at infinity):
A exp {i(k r -  t)}
Amplitude Phase
Wave: Periodic modulation [ u(x,t) ] in a medium,
Time dependence: (i) traveling (progressive) and (ii) stationary,
Direction of modulation: (i) transverse and (ii) longitudinal.
Concentric ripples (spherical waves)
formed by throwing a stone
Wave front
(locus or surface with constant phase at time t)
k
k = k = 2
Ex. Electromagnetic wave
r
Sign assignment for waves is chosen
to mach time dependent QM.
Wave equation:
¶2
u(x,t)
¶t2
-w2 ¶2
u(x,t)
¶x2
= 0

Plane wave, exp{ik0 r}, is scattered into
spherical wave, exp{ik r’}/r’ , by a point
scatterer (a) and two point scatters, which
are separated by r12(b).
Scattering of plane wave and interference

Interaction parameter
χAB = Z [εAB - ( εAA + εBB ) / 2] / kBT
Z: Cordination number
εAB : Interaction energy between A and B
per monomer
χAB > 0 : repulsive between A and B,
separation-type
Helfrich Hamiltonian
(Elastic energy of membrane) :Macroscopic
F = ∫ dS [ 2Kb(H-c)2 + KsG ]
H: mean curvature = (1/R1 +1/R2)/2,
G: Gaussian curvature = 1/R1R2,
c: Spontaneous-curvature of surfactant
Kb: elastic bending modulus,
Ks: saddle-splay modulus
Boundary formed by surfactant
"surfactant parameter"
s = v/(aol)
Volume
v Area
a0
l
Hydrophobic interaction
Attraction
Repulsive
heads

v: hydrocarbon chain volume
a: head group area
l: optimal chain length
s = v/al Organisation
s = 1/3 micells
1/3 < s < 1/2 rod shaped micelles
1/2< s < 1 lamellar or vesicles
s > 1 reverse
Surfactant Parameters (geometrical)

0
0.2
0.4
0.6
0.8
1
2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4
c(=r/R)
c(r/R)
kR
J1(kR) = 0 at kR = 3.85
( C=0: Rod )
J0(kR) = 0 at kR = 2.45
( C=1: Thin cylinder )
Accidental extinction might happen not only systematic !!
for 2.45 < kR < 3.85
=
2J1(kR)
kR
( for rod, c=0)
F = J0(kR) ( for thin pipe, c=1 )
for 0 < c < 1
F = 2
kR J1(kR) - ckRJ1(ckR)
(kR)2(1-c2)
r = cR
R
r
Long cylinder
Z
x
y

N-acyl-L-Glutamic acid (C12- or C14- or C16-), co-structure directing agents
(APS or TMAPS) and TEOS were used.
APS: 3-aminopropyltrimethoxysilane
TMAPS: [N-trimethoxylpropyl-N,N,N-trimethylammonium] chloride
New Silica Mesoporous Crystals: ASM-n
S. Che, AE Garcia-Bennett, T. Yokoi, K. Sakamoto, H. Kunieda,
O. Terasaki & T. Tatsumi, Nature Materials 2(2003), 801.

Chiral Mesoporous Materials
Twisted tube
Spiral tube
model
model

Case 3
2Pt = Ps
L-L
Case 2
Pt = Ps
L-R
Case 1
Pt = Ps
L-L
Structural Model of Spiral Tube (with clear facets)
offset
spiral axis
Ps 123
Projection of the channel along the axis
shows clear difference between the two cases,
handedness of channel and twist are same or different

Observed cross sectional TEM image
A honeycomb arrangement of
bright dots(channels) is
observed at the central part.
Lattice fringes corresponding
to {10} are also observed at the
bands indicated by arrows.
123

Observed TEM image : Perpendicular to the spiral
tube direction, {10} and {11} fringes are observed

Observed tilting effect on the {10} fringes
All intermitted {10} fringes curve to
the same direction toward the right.
The chiral direction (handedness)
can be determined by tilting.

Simulation:
Projected potential
density and images
 = 15º = 0º
A
B
e-
A
B
z
y

Acc. V: 300kV
Df~200nm
V0~10V
The rod is tilted as shown in the figure (area A is higher than area B in z-cords, chiral with the left hand
gives the curved fringes toward the right, and the rod is tilted opposite way the fringes shows left curvature.

Observed TEM image of Spiral tube
A
B
q
e-
A
B

Simulation for the Spiral tube
 =0º
A
B
 =15º  =-15º
q
e-
A
B
curved toward the
left
curved toward the right
Feature of {10} fringes
almost straight

 =15ºA
B
 =15º
{10} fringes curvature
in the projection tell us
the relation.
Tube has same
Left hand
Effect of chiral directions of tube on image
Case: Channels are left hand
Tube has opposite
Right hand

TEM image & FD pattern: highest pH
10
01
Three sets of streaky spots (colored circles), as well as the ordinary
diffraction spots indexed by 2D-hexagonal (p6mm).
HRTEM image (x=3.6).
C18MIMBr/TEOS/H2O/NaOH = 0.9 : 6.8 : 10000 : x x = 3.6

ℏCentre for High-resolution Electron Microscopy (C EM)S. Inagaki, S. Guan, T. Ohsuna & O. Terasaki, Nature 416
(2002), 304-307.
Experimental evidence for periodic structure of wall

2d-hexagonal
(p6mm)
Water / Surfactant / Silica
System
SBA-1
(Pm3n)
Structural Change in silica-mesoporous crystals, from p6mm to
Pm3n, with synthesis time

Structural evolution in silica-mesoporous crystals,
from p6mm to Pm-3n, with synthesis time
2d-hexagonal
(p6mm)
SBA-1
(Pm3n)

Structural change in Pm-3n with synthesis time

(10)
(211)
(200)
Epitaxial structural evolution from p6mm to
Pm-3n with synthesis time
HREM image
Fourier Diffractograms

5.5 hours 7.5 hours
10.5 hours
3d-structural analysis of evolution by
electron crystallography

p6mm Pm-3n
00 10
01
000 211
112
121
Real space
Reciprocal space
Structural evolution from p6mm to Pm-3n
Modulation with 65 Å
along [111] Three fold
screw (L)
Three fold
screw (R)
Wave vector of density modulation,
six {10}type
Wave vector of density modulation, twenty four
{211} type
Uniform
rods

SBA-6
Pore volume：0.86 cm3/g
(gas adsorption exp.)

N2 gas adsorption
Pore volume = 0.86 cm3/g
Pore Silica wall
Vtotal/Vpore = 0.65
a = 146Å
Cage diameter
A: 85 Å
B: 73 Å
Pore aperture
A-A: 32Å x 41 Å
A-B: 20 Å
3d-structure solution of SBA-6
by Electron Crystallography

Structural description for SBA-6
J.Charvolin et al., J. Phys. France 49 (1988) 521-526.
a = 146Å
Structure of SBA-16
MEP-type or clathrateA3B-type
Nodal surface
(SG: Pm-3n)

SEM images & Powder XRD profiles; SBA-1 & SBA-6
λ: CuKα λ: CuKα

Lattice & Basis
A Bravais lattice L(r) is an infinite array of points in space, in
which each points has identical surrounding. The lattice point rn is
given by a linear combination of the primitive translation vectors,
a, b and c, as rn =n1 a + n2 b + n3 c (n1,2,3 are any integers).
Crystal is the periodic arrangement, which is defined by a lattice,
of atoms/molecules. Therefore crystal can be described by
associating with each lattice point a group of atoms which is called
the basis of the structure.
The basis can be reduced by crystallographic point symmetry at
the lattice point to an asymmetric unit which is the smallest part of
the basis. The whole basis will be generated when all symmetry
operations are applied.
L r( )= d r - rn( )
rn
å rn = niai
i=1
n
å

Two dimensional model: B(r) has infinite size perpendicular to the
screen
B r( ) ( )rL
= *
C r( )
Crystal Basis Lattice
= *
·
( )rS
Size
·
( ) ( )[ ] ( ) ( ) ( ){ }[ ]
( )[ ] ( ) ( )
( ) ( )kk
rrr
rrrrk
FLSFB
SLB
SLBCF
×=
××=
×*==
][FF
FF
Convolution
F is Fourier transform Peaks are at reciprocal lattice points. Line-width(w) is inversely
proportional to size b.
Laue function
w
0
1
r
S(r)
b

Two dimensional model: B(r) has finite length Z perpendicular to the screen (z-axis)

Mesoporous Crystals
Water-Surfactant System - Self-assembly of the surfactant
- Meso-scale ordering of the pore
- Amorphous silica wall
λ =1.542 Å

TEM images taken with the incident beam parallel to the channels of calcined MCM-41
(a), SBA-15 (c), [111] direction of MCM-48 (e), and Pt nanowires synthesized in the spaces
of MCM-42 (b), SBA-15 (d), and MCM-48 (f).
Examples: Nano-structured Pt wires

SBA-15 and Carbon ( CMK-3 )
Synthesis of New Nanoporous Carbon with Hexagonally Ordered Mesostructure, S. Jun, S. H. Joo, R. Ryoo, M. Kruk,
M. Jaroniec, Z. Liu, T. Ohsuna & O. Terasaki, J. Am. Chem. Soc. 122 (2000) 10712-10713.

Powder X-ray diffraction pattern of MCM-48
Cu k

Y. Sakamoto, TW Kim, R. Ryoo & O. Terasaki. Angew. Chem. Int. Ed.
In the press.
We can produce complementary pore in Ia3d silica

New approach for making
nano-structured materials
MCM-48 CMK-4
HREM
Image
Fourier
Pattern
FourierTrans.
M. Kaneda, T. Tsubakiyama, A. Carlsson, Y. Sakamoto, T. Ohsuna,O. Terasaki,
S.H. Joo and R. Ryoo, J. Phys. Chem. B106 (2002), 1256-1266.
211 211

Red lines (gyroid surface) : cos(2πx)sin(2πy) +
cos(2πz)sin(2πx) + cos(2πy)sin(2πz) = 0
Reconstructed electrostatic potential map of MCM-48
z = 0 1 / 8
Plastic model, [111]
by Sten Andersson
Gyroid
The principal curvature : c1, c2
Mean curvature : H = (c1+c2)/2
Gaussian curvature : K = c1×c2
Minimal surface : H = 0, K <0 Gyroid surface (one of the periodic minimal surface of Space Group Ia-3d)
cos(2πx)sin(2πy) + cos(2πz)sin(2πx) + cos(2πy)sin(2πz) = 0
3d-structure solution
of MCM-48 by
electron crystallography
3d-structure of MCM-48 and Gyroid minimal surface

{110} reflections{110} , {211}, {220} reflections {211}, {220} reflections
022
202
112
011
Fourier Trans
Filtered images of CMK-1, [11-1] incidence
Images show “domain” character and three fold symmetry was lost by removing silica MCM-48 !!

110
004
220
HREM image of CMK-1, [1-10] incidence
00l: l = 4n
(002: extinct, 004: observed)
Image was taken with [1-10]
41 along [001]
Fourier
Trans

AB
C
(1)(2)
Domain structure of CMK-1, [001] incidence
The image has domain character as observed by out of phase in lattice fringes of {110} ( lines).
Fringes in domains A, B and C(right hand) are explained by shift along [010], [100] and [0-10].
A
B
Cx
y
Ia-3d

0.00
0.02
0.04
0.06
0.08
0.10
0.00 0.05 0.10 0.15
|Fhkl|
110
101 011
112
211 121
220
202022
110
101
011
220
202
022
211
112
121
Relative displacement
along [100]
Origin of {110} reflexion in powder XRD of CMK-1
Ia3d I41/a

The simplest model for CMK-1:
(i) Carbon rods are equally formed in two non-interconnecting channels of MCM-48.
(ii) During dissolution of the silica wall, two carbon rods are displaced each other
without rotation along the [001] axis by keeping each rod rigidly, and the resultant
space group is I41 /a (No. 88).
(iii) Unique tetragonal axis can be either [100] or [010] or [001] of cubic, and therefore
it shows domain structure and appears as cubic.
Observations of CMK-1:
1. The symmetry is lower than cubic keeping 41 along the [001], that is tetragonal.
2. The crystal consists of small domains, and on average, over these domains it
appears as cubic.
3. Strong 110 reflection was observed in powder XRD.
Structure model for CMK-1

Crystal structure factors & Extinction rule:
From Fourier transforms of thin areas of HRTEM images(SBA-6)

N2 gas adsorption
Pore volume = 0.86 cm3/g
Pore Silica wall
Vtotal/Vpore = 0.65
a = 146Å
Cage diameter
A: 85 Å
B: 73 Å
Pore aperture
A-A: 32Å x 41 Å
A-B: 20 Å
3d-structure of SBA-6 by Electron Crystallography
SG: Pm3n

HREM images of SBA-16:
[100], [110] & [111] incidences,
JEM-3010,
300 kV
[100] [110] [111]
Electrostatic potential map, z = 0(L) & z = 1/2(R) Cage arrangement
(SG: Im3m )
Blockcopolymer, F127
Cage diameter: 95 Å
Pore aperture: 23 Å
IWP-
Surface

Intergrowth in SBA-12
Closed packed plane, (111)c or (001)h
An example of stacking disorder
111c000
112c
Schematic diffraction pattern of [110]
Y. Sakamoto, I. Díaz, O. Terasaki, D. Zhao, J. Pérez-Pariente, J.
M. Kim & G. D. Stucky,
J. Phys. Chem. B106(2002), 3118-3123.

Peak positions in powder XRD patterns for
F-type and 3d-hex. type
0 0.5 1 1.5 2 2.5 3 3.5 4
2 Theta [degree]
100
002
101
102
110
103
200
112
201
004
111
200
220
311
222
Cubic
Hex_c/a=1.633
Hex_c/a=1.6
CuKa cubic(a=82.0Å), hexagonal(a=58.0Å, c=94.7Å)
Y. Sakamoto, I. Díaz, O. Terasaki, D. Zhao, J. Pérez-Pariente, J. M. Kim & G. D. Stucky,
J. Phys. Chem. B106(2002), 3118-3123.

HREM image and ED pattern, [110]cubic
Fourier Diffractogram
of left image.
HREM image, ED & FD patterns of SBA-12
J. Phys. Chem. B106(2002), 3118-3123.

Electrostatic potential map of functionalized SBA-12
J. Phys. Chem. B106(2002), 3118-3123.
Observed crystal Structure Factors

f[x,y,z) = -25
3d- structure of SBA-12
J. Phys. Chem. B106(2002), 3118-3123.

SBA-1 AMS-2
Pm-3n Modulated
Pm-3n
The cage connectivity of AMS-2 is different to that of conventional
SBA-1. Representations of the structure based on the clathrate MEP
(above) suggest the presence of a zig-zag arrangement of cages along the
[100] orientation
Modulated structure in AMS-2
Structural Investigations of AMS-n Mesoporous Materials by TEM,
A E Garcia-Bennett, O. Terasaki, S. Che & T. Tatsumi, Chem. Mater. ,
16(2004), 813.

a
b
A B C
B C AB
B
A
C
A
B
C
a
A B C A B C
B
A
C
b
70°
70°
Various stacking faults are observed(highlighted by
arrows). Higher magnifications of regions a and b
(Insets). FD generated from the image shows streaking.
400
c
AMS-8 SG:Fd-3m , a = 183.4 Å
HRTEM image[110].
FD
Large cages are connected to 12 individual smaller cages through small openings
and to 4 additional larger cages through larger openings. Smaller cages are
connected to each other through a single small pore opening.

AMS-2 Stacking faults
AMS-8
AMS-8
AMS-9SBA-1 type
Various AMS-n structures, which are controllable !
AE Garcia-Bennett et al., in preparation

Some essential Mathematics:
(i) Fourier Transformation
(ii) Primitive lattice& reciprocal lattice
(iii)Symmetry
Definition of a group
Crystallographic Point Group
Crystal morphology
Space groups (Line, Plane & Space)

F f r( )éë ùû = F q( )º
1
2p( )n
f r( )e-iq×r
dn
rò
F g r( )éë ùû = G q( )
F h r( )éë ùû = H q( )
F -1
F q( )éë ùû =
1
2p( )n
F q( )eiq×r
dn
q =ò f r( )
F -1
G q( )éë ùû = g r( )
F -1
H q( )éë ùû = h r( )
h r( )= f r( )*g r( )º f r'( )g r - r'( )ò dn
r'
F h r( )éë ùû = F f r( )*g r( )éë ùû = F f r( )éë ùû×F g r( )éë ùû = F q( )×G q( )= H q( )
f r( )Äg r( )º f r'( )g r + r'( )ò dn
r'
F f r( )Ä f -r( )éë ùû = F f r( )éë ùû×F f -r( )éë ùû = F q( )×F q( )*
= F q( )
2
Fourier transforms (FTs) are defined for gentle functions
Convolution h(r) of functions f(r) and g(r) is defined:
Correlation function of f(r) and g(r) is defined:
Autocorrelation function of f(r) is defined:
Fourier Transformation and Related Functions

Electron Crystallography for structure solution
This part will be discussed the last day.
L. Han, K. Miyasaka & O. Terasaki, Wiley text book “Inorganic Materials Series, Structure from Diffraction Methods”
Extinction condition
Crystal morphology

Systematic and accidental extinction
F qhkl( )= F qhkl( ) eia (hkl)
= F C r( )éë ùû
= F B r( )éë ùû×F L r( )éë ùûéë ùû*F Z r( )éë ùû
F qhkl( ) µ I qhkl( )
Extinction rule can be observed from diffraction intensity,
however we are facing new problems which will be discussed
separately !

C r( )= B r( )*L r( ){ }×Z r( )= B r( )* L r( )×Z r( ){ }
Crystal structure C(r) is described by Lattice L (r),
Basis B(r) and Shape/Size Z(r )
Crystal system
Lattice
Bravais Lattice
Symmetry
Point Symmetry
Crystallographic
Point Symmetry
We obtain structure solution through scattering/diffraction.
 Reciprocal unit cell and reflection intensities at reciprocal points

MCM−48, KIT−6, FDU−5,
AMS−6, etc.
Ia-3d
AMS-10Pn-3m
G- and D-surfaces

160
Garcia-Bennett, A. E.; Xiao, C.; Zhou, C.; Castle, T.; Miyasaka, K.; Terasaki, O. Chem-Eur J 2011, 17, 13510.
Intergrowth of D-surface and G-surface

Gao, C.; Sakamoto, Y.; Sakamoto, K.; Terasaki, O.; Che, S. Angew Chem Int Ed 2006, 45, 4295.
Gao, C.; Qiu, H.; Sakamoto, Y.; Terasaki, O.; Sakamoto, K.; Che, S. et. al. Chem Mater 2006, 18, 3904.
Gao, C.; Sakamoto, Y.; Terasaki, O.; Che, S. Chem-Eur J 2008, 14, 11423.
？
Synthesis-field diagrams of AMS

MFI zeolite unit-cell layer thickness
Zeolites have strong acid sites and uniform micropores (aperture dia < 1nm) are widely
used in petrochemical synthesis as size- & shape-selective catalysis. But the micropores
affect catalytic activity through diffusion limitations. Thin layers and pillared ones, were
studied.
Thin layer of MFI zeolite
M Choi, K Na, J Kim, Y Sakamoto, O Terasaki & R Ryoo, Nature 461, 2009, 246

Micro-, meso and macro-porous crystals,
and nano-composite materials
FAU & Hydrocarbon molecules
Wall thickness
11 ~ 12 Å
Micro-
Meso-
Macro-
Silica Mesoporous crystal MCM-48
3-D Ordered Macroporous (3DOM)Carbon
Nano-composite
GaN on Si
Peidong Yang,
UC Berkeley
Sample from Andreas Stein, Univ Minnesota

MFI zeolite unit-cell layer thickness
Zeolites have strong acid sites and uniform micropores (aperture dia < 1nm) are widely
used in petrochemical synthesis as size- & shape-selective catalysis. But the micropores
affect catalytic activity through diffusion limitations. Thin layers and pillared ones, were
studied.
Thin layer of MFI zeolite
M Choi, K Na, J Kim, Y Sakamoto, O Terasaki & R Ryoo, Nature 461, 2009, 246

Ryoo’s work
165
Michael Tsapatsis

Pillared-MFI nano-sheets
K. Na, M. Choi, W. Park, Y. Sakamoto, O. Terasaki and R. Ryoo, J. Am. Chem. Soc. 132, 2010, 4169-
4177.

Mesopore in zeolite single crystal
LTA1-13
LTA1-02
Samples: Ryong Ryoo

SEM images of mesoporous LTA acquired at low landing energy, thereby reducing the effect
of beam damage. Conditions: Specimen bias = −5 kV.
Electron beam damage can be reduced by reducing landing energy
Why TiO2 ?

X. Zhang, D. Liu, D. Xu, S. Asahina, K. A. Cychosz, K. V. Agrawal, Y. A. Wahedi, A. Bhan, S. Al.
Hashimi, O. Terasaki, M. Thommes, and M.Tsapatsis, “Synthesis of Self-Pillared Zeolite Nanosheets by
Repetitive Branching”, Science, 336 (2012) 1684-1687.
Landing energy： 500eV
Sample bias：-5 kV
169
SEM image
Zeolite (Self pillared MFI Nano sheet)
Schematic drawing
10nm
Sample: M. Tsapatsis

HRSEM images (Low energy)
(A)and (B): the unaltered SBA-15 crystals clearly displaying surface channels and terminations.
(C) and (D): the cross-sectioned, boundaries and change of channel direction are clearly visible.

Cubic mesoporous silica crystal strucutres obtained by
EC
Bi-continuous type
MCM-48 (Ia-3d)
AMS-10 (Pn-3m)
Cage type
AMS-8 (Fd-3m) SBA-6 (Pm-3n)
SBA-12 (Fm-3m) SBA-16 (Im-3m)
a
b
c

3d-silica wall structures for MCM-48 (Ia-3d),
SBA-6 (Pm-3n) and AMS-10 (Pn-3m)
(a) (b) (c)
B
A

Fm-3m
Fd-3m
Ia-3d
Pm-3n
Pn-3m
Cage-type Bicontinuous-type
P63/mmc
Other modulated structures based on Pm-
3n including Cmmm, P42/mnm
Rod-type
Solved structure types by TEM(Electron
Crystallography)
p6mm
123
Chiral
Multiply twinned
Sphere packing Polyhedra packing
Trcontinuous-type
has been also
reported by Han Yu
et al

Meso-porous crystal MCM-48 and nano-Pt networks
MCM-48 & Nano-network of Pt
Pt nano-network
Wall thickness
11 ~ 12 Å
R
L
L
R
Silica MCM-48

All of the polyhedra, which
Matzke observed in the random
foam structure, have been
observed in silica mesoporous
crystals.
Intergrowth of Fm-3m and Fd-3m
Y. Sakamoto, L. Han, S. Che, and
O. Terasaki, Chem. Mater., 21,
2009, 223-229.

Normalised atomic scattering factors of
Fe for different probes
For electron
f (qhkl ) = (1+ E E0 )[1 sin(qhkl 2)]2
(Z - fx ) (8p2
a0 )
Diffraction intensity
I(hkl) µ f (hkl)
2
f (qhkl ) º f (qhkl ), qhkl º sin(qhkl ) 4pl
Scattering factor
7.3 x 10 -4 Å
7.4 Å

jk (r) ®
r®¥
2p( )-3
2
[exp(ikz)+
f (2q)
r
exp(ikr)]
Scattering problem
Plane wave
Spherical wave
outward
z
r
2θ
The spherical wave from a point
scatterer can be in phase (top) or 180
out of phase (bottom) with the incident
plane wave.
The refractive index is greater than
unity in the first case and smaller in
the second case.

2D-hexagonal to lamellar transformation
via 2D-rectangular p2gg

Osamu Terasaki School of Physical Science and Technology (SPST), ShanghaiTech University, China.

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Osamu Terasaki School of Physical Science and Technology (SPST), ShanghaiTech University, China.