Crystallization of Mordenite Platelets using Cooperative Organic Structure-Directing Agents

Article abstract of DOI:10.1021/jacs.9b09697

Organic structure-directing agents (OSDAs) are exploited in the crystallization of microporous materials to tailor the physicochemical properties of the resulting zeolite for applications ranging from separations to catalysis. The rational design of these OSDAs often entails the identification of molecules with a geometry that is commensurate with the channels and cages of the target zeolite structure. Syntheses tend to employ only a single OSDA, but there are a few examples where two or more organics operate synergistically to yield a desired product. Using a combination of state-of-the-art characterization techniques and molecular modeling, we show that the coupling of N,N,N-trimethyl-1,1-adamantammonium and 1,2-hexanediol, each yielding distinct zeolites when used alone, results in the cooperative direction of a third structure, HOU-4, with the mordenite framework type (MOR). Rietveld refinement using synchrotron X-ray diffraction data reveals the spatial arrangement of the organics in the HOU-4 crystals, with amines located in the large channels and alcohols oriented in the side pockets lining the one-dimensional pores. These results are in excellent agreement with molecular dynamics calculations, which predict similar spatial distributions of organics with an energetically favorable packing density that agrees with experimental measurements of OSDA loading, as well as with solid-state two-dimensional ²⁷Al{²⁹Si}, ²⁷Al{¹H}, and ¹³C{¹H} NMR correlation spectra, which establish the proximities and interactions of occluded OSDAs. A combination of high-resolution transmission electron microscopy and atomic force microscopy is used to quantify the size of the HOU-4 crystals, which exhibit a platelike morphology, and to index the crystal facets. Our findings reveal that the combined OSDAs work in tandem to produce ultrathin, nonfaulted HOU-4 crystals that exhibit improved catalytic activity for cumene cracking in comparison to mordenite crystals prepared via conventional syntheses. This novel demonstration of cooperativity highlights the potential possibilities for expanding the use of dual structure-directing agents in zeolite synthesis.

Full text of DOI:10.1021/jacs.9b09697

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Article
Crystallization of Mordenite Platelets using
Cooperative Organic Structure-directing Agents
Manjesh Kumar, Zachariah J. Berkson, R. John Clark, Yufeng Shen, Nathan A. Prisco, Zhiyuan Zeng,
Haimei Zheng, Lynne B. McCusker, Jeremy C. Palmer, Bradley F. Chmelka, and Jeffrey D Rimer
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b09697 • Publication Date (Web): 21 Nov 2019
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Crystallization of Mordenite Platelets using Cooperative Organic
Structure-directing Agents
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Manjesh Kumar1, Zachariah J. Berkson2, R. John Clark1, Yufeng Shen1, Nathan A. Prisco2, Zhiyuan
Zeng3,4, Haimei Zheng3,4, Lynne B. McCusker2,5, Jeremy C. Palmer1, Bradley F. Chmelka2,*, and Jeffrey
D. Rimer1,*
1 Department of Chemical and Biomolecular Engineering, University of Houston, 4726 Calhoun Road, Houston, TX, 77204,
USA
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2 Department of Chemical Engineering, University of California Santa Barbara, 3327 Engineering II, Santa Barbara, CA,
93106, USA
3 Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, 1 Cyclotron Road, CA, 94720, USA
4 Department of Materials Science and Engineering, University of California, Berkeley, CA, 94720, USA
5 Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, CH-8093 Zurich, Switzerland
ABSTRACT: Organic structure-directing agents (OSDAs) are exploited in the crystallization of microporous materials to tailor the
physicochemical properties of the resulting zeolite for applications ranging from separations to catalysis. The rational design of these OSDAs
often entails the identification of molecules with a geometry that is commensurate with the channels and cages of the target zeolite structure.
Syntheses tend to employ only a single OSDA, but there are a few examples where two or more organics operate synergistically to yield a
desired product. Using a combination of state-of-the-art characterization techniques and molecular modeling, we show that the coupling of
N,N,N-trimethyl-1-1-adamantammonium and 1,2-hexanediol, each yielding distinct zeolites when used alone, results in the cooperative
direction of a third structure, HOU-4 with the mordenite framework type (MOR). Rietveld refinement using synchrotron X-ray diffraction
data reveals the spatial arrangement of the organics in the HOU-4 crystals, with amines located in the large channels and alcohols oriented
in the side pockets lining the 1-dimensional pores. These results are in excellent agreement with molecular dynamic calculations, which
predict similar spatial distributions of organics with an energetically favorable packing density that agrees with experimental measurements
of OSDA loading, as well as with solid-state two-dimensional 27Al{29Si}, 27Al{1H}, and 13C{1H} NMR correlation spectra, which establish
the proximities and interactions of occluded OSDAs. A combination of high-resolution transmission electron microscopy and atomic force
microscopy are used to quantify the size of the HOU-4 crystals, which exhibit a plate-like morphology, and to index the crystal facets. Our
findings reveal that the combined OSDAs work in tandem to produce ultrathin, non-faulted HOU-4 crystals that exhibit improved catalytic
activity for cumene cracking compared to mordenite crystals prepared via conventional syntheses. This unique demonstration of cooperativity
highlights the potential possibilities for expanding the use of dual structure-directing agents in zeolite synthesis.
is used as a commercial catalyst in reactions such as
dehydration of alcohols to olefins,17 oxidation of methane to
methanol,18 (hydro)isomerization,19 cracking,20 alkylation,21
and carbonylation.22 Prior studies have attributed the catalytic
activity of mordenite to the intersection of 12-ring channels
with 8-ring side-pockets (Figure S1) that facilitate shape-
selective reactions; however, mordenite is highly susceptible
to deactivation owing to mass transport limitations imposed
by its 1-dimensional pores and large channels that facilitate
the formation of polyaromatics (i.e., coke precursors).
Reported syntheses of mordenite typically yield large
crystallites with sizes that range from 5 to 20 µm and with
stacking faults that alter the placement of 8-ring pockets
within the channels.23-24 Post-synthesis modification to
introduce mesoporosity is one way of mitigating internal
diffusion limitations.25 Alternatively, the synthesis of
crystallites with sub-micron dimensions of the [001] facet can
extend catalyst lifetime. Suib and coworkers have reported
sizes as small as 40 - 60 nm using complicated synthesis
protocols that include the use of crystalline seeds,26 alcohol
additives, and/or microwave heating.27 Mordenite nanorods
(ca. 10 × 100 nm) have been synthesized using seeds or
cationic gemini surfactants by Xiao28 and Ryoo29 and their
coworkers, respectively. These syntheses have resulted in
INTRODUCTION
The demand for more efficient zeolite catalysts creates a need
to develop new synthesis approaches capable of tailoring
crystal properties for optimal performance. Among many
physicochemical properties of zeolites, crystal size plays a
significant role in mediating internal mass transport1-2 wherein
diffusion path lengths of less than 100 nm can markedly
improve catalyst lifetime and alter product selectivity.3
Various approaches have been explored to tune the
anisotropic growth of zeolite crystals precisely, including the
modification of synthesis conditions, introduction of growth
modifiers,4 design of new organic structure-directing agents
(OSDAs),5-9 and the use of crystalline seeds.10 Achieving
materials with well-controlled properties is often challenging,
because the mechanisms of zeolite crystallization11-14 are
complex and poorly understood. Here, we combine state-of-
the-art X-ray powder diffraction (XPD) and solid-state NMR
characterization techniques with computer modeling to
examine the role of OSDAs in the formation of the mordenite
framework type (MOR),15 which is difficult to prepare with
sub-micron dimensions.16
Mordenite is a large-pore zeolite (pore diameter ca. 0.7
nm) with unidirectional channels aligned along the c-axis that
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nanometer-sized domains within larger aggregates, which
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similarly involve limitations in internal mass transport.
A combination of inorganic and organic structure-
directing agents are often used in zeolite syntheses to regulate
the kinetics of crystallization.30 The synthesis of most zeolites
requires the use of OSDA molecules with sizes and shapes
that are commensurate with the cages/channels of the target
zeolite, thereby facilitating the generation of the desired
porous structure.7 OSDAs are occluded within the framework
and are typically removed by post-synthesis calcination. It is
common practice to use a single OSDA. In select cases,
OSDAs can form clusters (e.g., dimers or aggregates) to
stabilize the framework.31-32 Few syntheses employ two or
more different OSDAs. Examples often involve scenarios
where only one organic functions as the OSDA and the other
alters properties such as crystal size or habit, but is a bystander
for structure direction.33 Combinations of OSDAs have also
been used to prevent polymorphism in order to improve
product purity.34 Wright and coworkers have demonstrated for
zeotypes, such as STA-20, that two organics may be necessary
to achieve a desired crystalline phase.35 In such cases, the
OSDAs act cooperatively to produce a product that could not
be achieved with either one alone.
Herein, we demonstrate how two OSDAs (one bearing a
quaternary amine group and the other an alcohol)
cooperatively direct the formation of mordenite crystals with
an ultrathin platelet morphology unlike that obtained with
conventional methods. The synthesis condition selected for
this study produces two different framework types (MFI- or
CHA-type zeolites) when each OSDA is used separately;
however, the combination of organics yields mordenite. In
order to elucidate the spatial distribution of organics within
the channels and side pockets of the mordenite crystals, we
used a combination of high-resolution electron microscopy,
spectroscopy, and diffraction techniques coupled with
molecular modeling to show how the distinct combination of
OSDAs work synergistically to direct the mordenite
framework structure. Parametric evaluation of synthesis
conditions reveals that the judicious selection of OSDAs and
growth media are critical to the formation of mordenite.
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Figure 1. The OSDA(s), corresponding zeolite structure, and
representative scanning electron micrograph for (A) SSZ-13 (CHA)
prepared with TMAda+; (B) ZSM-5 (MFI) prepared with D61,2 or Na+
ions; and (C) HOU-4 (MOR) prepared with TMAda+ and D61,2. Scale
bars equal 1 m. (D) X-ray powder diffraction patterns of the solid
precipitates obtained after 6 days of hydrothermal treatment at 180°C
(table S1) confirms the formation of SSZ-13 (blue), ZSM-5 (green), and
HOU-4 (red). The structure of HOU-4 was confirmed using a reference
pattern for mordenite (black). Reflections corresponding to a quartz
impurity in the HOU-4 sample (Figure S6) are labelled with diamonds.
The presence of quartz is attributed to excess silica in the reaction
mixture. Parametric studies reduced the quantity of quartz, but were
unable to eliminate the impurity entirely (see the Supporting Information
for more details).
RESULTS AND DISCUSSION
Our findings have shown that two OSDAs, N,N,N-trimethyl-
1-1-adamantammonium (TMAda+) and 1,2-hexanediol
(D61,2), work cooperatively to yield a MOR-type zeolite,
referred to hereafter as HOU-4. TMAda+ is a well-
documented OSDA for commercial SSZ-13 (CHA) (Figure
1A). The same synthesis using only D61,2 results in ZSM-5
(MFI) (Figure 1B), whereas an organic-free synthesis with
Na+ as an inorganic structure-directing agent also yields ZSM-
5 (Figures S2 and S3). Interestingly, the combination of D61,2
and TMAda+ in solutions containing Na+ produces HOU-4
(Figures 1C and S4). We observe that individual OSDAs and
their binary combination generate three different zeolites
(Figure 1D): ZSM-5 is a 3-dimensional medium-pore zeolite;
SSZ-13 is a 3-dimensional small-pore zeolite; and mordenite
is a 1-dimensional large-pore zeolite. The composite building
units (CBUs)15 of these three structures are vastly different,
with the exception of mor being shared by both MFI and
MOR framework types (Figure S5). The three zeolites have
similar elemental compositions (Table S2), but differ with
respect to crystal habit and quantity of occluded OSDA
(Figure S7 and Table S3).
SSZ-13 crystals have a spheroidal morphology with sizes
of 1 – 2 m and 10 wt% organic (ca. 1.3 TMAda+ per unit
cell). ZSM-5 crystals exhibit an indistinct morphology with
sub-micron dimensions, and contain 5 wt% organic (ca. 2.7
D61,2 per unit cell). HOU-4 crystallizes as thin plate-like
particles that retain ca. 2 D61,2 and 2 TMAda+ molecules per
unit cell, as determined from synchrotron XPD data (Figure
S8). All of the D61,2 molecules are removed by post-synthetic
washing with water (Figures S9 and S10), which establishes
that D61,2 molecules are able to diffuse out of the mordenite
nanochannels without appreciable restrictions. The mobility
of D61,2 within the large pore channels of mordenite was
corroborated by molecular dynamics (MD) simulations
(Movie S1). Facile extraction of the diol molecules from
zeolite frameworks without the need for post-synthesis
calcination is uncommon; therefore, the synthesis of HOU-4
offers a unique route to recover and potentially recycle the
OSDAs.
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Comparison of transmission electron micrographs from
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multiple batches (Figure 2A, C, D) show that the width of the
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Figure 2. Indexing the habit of HOU-4 crystals. (A) HAADF STEM image of representative HOU-4 crystals taken in low magnification. (B) AFM amplitude
mode image of a crystal in air. Inset: height profile measured along the dashed line. Scale bar equals 500 nm. (C) TEM image of a HOU-4 crystal with the
[001] growth direction highlighted (arrow). (D) Indexed HOU-4 crystal with a (100) basal surface. (E) The selected area electron diffraction (SAED) pattern
of the region in (C) marked by the dashed white circle. The zone axis is [100]. (F) Simulated SAED pattern from [100] based on the mordenite crystal structure
(see Figure S12 for patterns of the [010] and [001] zone axes). (G) High-resolution TEM image of a HOU-4 crystal along the [100] zone axis. The black strips
could be regarded as pore channels, with ca. 0.32 nm average width. (H) The HRTEM image in (G) after applying a Fourier filter, overlaid with the crystal
structure model of mordenite along the [100] direction. Atoms are color coded as red (oxygen) and yellow (silicon or aluminum).
shape anisotropy or stacking faults was apparent in the peak-
shape profiles or in the structure refinement. HOU-4 appears
to be free of the stacking disorder along the c-direction that is
present in
HOU-4 crystallites in the [010] direction can reach 1 m with
an average length-to-width (or [001]/[010]) aspect ratio of 4.0
± 0.7. Atomic force microscopy (AFM) topographical images
of HOU-4 crystals (Figure 2B) reveal an ultrathin habit
wherein the analysis of numerous crystals shows a distribution
of thicknesses in the [100] direction around 80 nm (see Figure
S11). Selected-area electron diffraction patterns (Figure 2E)
were compared against simulated patterns for mordenite along
the three principal crystallographic directions (Figures 2F and
S12). These comparisons confirm that the basal surface of
HOU-4 is the (100) face. High resolution TEM (HRTEM,
Figure 2G) and the corresponding Fourier filtered image
(Figure 2H) show that the 1D channels are oriented parallel to
the longest dimension of the HOU-4 crystals. The indexing
was further corroborated by overlaying the framework
structure of mordenite along the [100] direction on the filtered
HRTEM image (Figure 2G), revealing an excellent match.
Prior crystallographic analyses of synthetic mordenite
commonly assign the 6-edged surface as the (001) face. 24, 36-
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Indeed, this general morphology is characteristic of most
mordenite crystals prepared in the absence of organics (for
example, see Figure 6). Assuming that the indexing of the
facets of conventional mordenite crystals is correct, it appears
that the cooperativity of OSDAs dramatically alters the HOU-
4 crystal habit in ways that are neither predictable nor fully
understood.
In order to ascertain the spatial arrangement of OSDAs
within the zeolite channels, we analyzed an unwashed HOU-
4 sample using synchrotron XPD data (Figure 3A) and
confirmed that TMAda+ resides within the 12-ring channels
(Figure 3B and D), Na+ in the oval 8-ring channels, and D61,2
in the 8-ring side pockets (Figure 3C). Rietveld refinement of
the framework structure with occluded structure-directing
agents indicates that there are 2 Na+, 2 TMAda+, 2 D61,2 and
2 water molecules per unit cell. No evidence of crystallite
Figure 3. Rietveld refinement of HOU-4 using synchrotron powder
diffraction data. (A) Measured (black), calculated (red) and difference
profiles (blue) (table S4). Reflections from a quartz impurity are marked
with a green asterisk. (B – D) An arrangement of the non-framework
species within the channels of the MOR framework compatible with the
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refined structure of HOU-4 (see also Figure S13): (B) viewed down the
Figure 4. Molecular simulations of organic occlusion in HOU-4
c-axis; (C) close-up of the 8-ring side pocket (highlighted in blue in (B))
showing the octahedral coordination of a Na+ ion to 4 framework oxygen
atoms, one water molecule and one D61,2 molecule; and (D) orthogonal
view of the 12-ring channel (highlighted in pink in (B)) showing the
arrangement of TMAda+ ions along the channel. Atoms are color coded
as grey (carbon), red (oxygen), blue (nitrogen), white (hydrogen), green
(sodium), and yellow (T-sites occupied by silicon or aluminum).
channels. (A) MD calculation of the stabilization energy for organics
occluded in mordenite as a function of D61,2 loading using a fixed 1.5
TMAda+ per unit cell. Solid line is a guide for the eye. (B – D) MD
simulation of OSDA molecules aligned within the 12-ring channel: (B)
view along the c-direction; (C) D61,2 aligned within the 8-ring pocket; and
(D) TMAda+ molecules arranged in the 12-ring channel. Images C and D
contain 2 Na+, 2 TMAda+, and 2 D61,2 per unit cell. Atoms are color coded
as grey (carbon), red (oxygen), blue (nitrogen), white (hydrogen), green
(sodium), and yellow (T-sites occupied by silicon/aluminum).
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many mordenite syntheses. Quantitative solid-state one-
dimensional (1D) single-pulse 13C and 1H magic-angle-
spinning (MAS) NMR analyses (Figure S14) yield a larger
estimated quantity of D61,2 (6 – 13 D61,2/TMAda+). This
suggests that unwashed samples probably retain significant
quantities of diol molecules on the particle surfaces, and this
is in agreement with thermogravimetric analysis of unwashed
HOU-4 showing 37 wt% mass loss, consistent with the
desorption of surface-adsorbed diol molecules (Figure S7C).
To further understand the role of occluded organics in
HOU-4, we performed MD simulations of both OSDAs and
Na+ ions in mordenite. Models placing an increasing amount
of alcohol within a single mordenite unit cell at fixed TMAda+
loading (Figure 4A) show that alcohols stabilize the structure,
leading to a minimum in the energy profile around 1.5 – 2.0
D61,2 molecule per unit cell. This indicates that the alcohol is
not merely acting as a space filler,38 but has a significant
impact on the energetics of crystallization. As the quantity of
TMAda+ per unit cell is increased, less alcohol is required to
minimize the energy (Figure S15). In agreement with XPD
data revealing the presence of TMAda+ within the large pores
of HOU-4, MD simulations show that TMAda+ is
energetically favored to be within the 12-ring channels
(Figure
4B and D) with the amine groups oriented in close proximity
to the 8-ring pockets. At high TMAda+ loading (2 per unit cell),
D61,2 molecules are oriented within the 8-ring pockets (Figure
4C), consistent with the XPD refinement. At lower TMAda+
loadings, D61,2 molecules are also observed to reside within
the 12-ring channels between adjacent TMAda+ molecules
(Figure S16). Hence, both experiment and simulation suggest
that the two OSDAs direct formation of mordenite in a
synergistic fashion by stabilizing different features of the
framework: TMAda+ directs growth of the 12-ring channels,
whereas D61,2 predominately functions by stabilizing the 8-
ring pockets.
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The site-specific interactions of different framework 27Al
species with OSDA molecules are established by solid-state
two-dimensional
(2D)
HETeronuclear
CORrelation
(HETCOR) NMR spectra of HOU-4 (Figure 5). The 2D NMR
correlation spectra exploit internuclear dipole-dipole
(through-space) or J (through-covalent-bond) couplings and
are plotted as 2D contour plots where correlated signal
intensities manifest the mutual proximities or covalent
1
connectivities of the corresponding H, 13C, 27Al, or 29Si
species.39-40 For example, covalent 27Al-O-29Si bonds within
the HOU-4 frameworks are unambiguously established by the
2D 27Al{29Si} J-mediated NMR correlation spectrum (Figure
5A), which shows a distribution of correlated signal intensity
at 54 ppm in the 27Al dimension and -109 to -99 ppm in the
29Si dimension arising from framework aluminum atoms
bonded to fully- or partially-crosslinked 29Si atoms.
Previously, such 2D 27Al{29Si} through-bond-mediated
correlation spectra of aluminosilicate zeolites have been
limited due in part to the low natural isotopic abundance of
29Si (4.7%) and weak 27Al-O-29Si J couplings (<20 Hz), but
are enabled here by the improved sensitivity of low-
temperature measurement conditions. The 27Al signals exhibit
Czjzek lineshapes41 that reflect an unbiased distribution of
27Al heteroatom environments within the mordenite
framework and among the four distinct tetrahedral (T) sites,
corroborated by complementary 27Al triple-quantum MAS
NMR analyses (Figure S17). The relatively small percentage
of partially-crosslinked 29Si species (ca. 2%, Figure S18) are
probably associated with defect sites at the exterior of the
particle surfaces. The Si/Al ratio of HOU-4 estimated by
quantitative 29Si MAS NMR is ca. 10 (Figure S18), which is
consistent with values of ca. 10 and 13 measured by energy-
dispersive X-ray spectroscopy (table S2) and estimated from
synchrotron XPD refinement, respectively.
Different types of framework aluminum sites in HOU-4
are distinguished on the basis of their site-specific interactions
with different OSDA molecules, which are established by the
2D 27Al{1H} (Figure 5B) and 13C{1H} HETCOR (Figure 5C)
NMR spectra. The HETCOR spectra yield correlated 13C- or
27Al-1H signal intensities from 13C-1H or 27Al-1H nuclear spin
pairs that are dipole-dipole-coupled through space over sub-
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nanometer distances. The different H and 13C signals are
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assigned to H and 13C moieties on D61,2 (green shaded
regions) or TMAda+ (red shaded regions) molecules by
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analyses of complementary solid-state 1D and 2D 13C{1H}
two 27Al signals: one at 55 ppm, which is correlated to H
signals at 2.2 to 3.6 ppm from TMAda+ and D61,2 1H moieties,
and one at 53 ppm, which is correlated
1
NMR spectra (Figures S10 and S14) and solution state 1D 13C
NMR spectra of the zeolite synthesis effluent (Figure S19).
The 2D 27Al{1H} HETCOR spectrum (Figure 5B) resolves
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Figure 5. (A) Solid-state 2D 27Al{29Si} J-mediated NMR correlation spectrum acquired at 95 K, 9.4 T, and 10 kHz MAS. (B) Solid-state 2D 27Al{1H}
HETCOR spectrum acquired at 263 K, 18.8 T, 12.5 kHz MAS, and a 27Al{1H} contact time of 0.5 ms. The ‡ symbol indicates a center-frequency artifact (for
more details refer to the Supporting Information). (C) Solid-state 2D 13C{1H} HETCOR spectrum acquired at 263 K, 11.7 T, 12.5 kHz MAS and with a
13C{1H} contact time of 5 ms. All of the 13C signals are assigned to 13C moieties on the TMAda+ and D61,2 molecules, as indicated in the inset molecular
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structures. 1D 27Al, 13C{1H}, or H MAS NMR spectra acquired under the same conditions are shown along the corresponding 27Al, 13C, or H axes for
comparison with the 1D projections of the 2D spectra. (D) Idealized depiction of framework-OSDA and intermolecular interactions established by 2D NMR
analyses. Green and red arrows indicate framework 27Al interactions with D61,2 and TMAda+ molecules, respectively; purple arrows indicate intermolecular
interactions of commingled OSDA molecules.
only to the 1H signal at 3.6 ppm from D61,2 alcohol headgroups
coordinated to Na+ cations.42 These correlated signals
evidence two different types of framework 27Al species with
either TMAda+ or Na+ cations charge-balancing the associated
framework negative charges. As the TMAda+ molecules are
sterically hindered from entering the 8-ring mordenite
channels, the framework 27Al species proximate to TMAda+
cations must be within the 12-ring channels. Those framework
27Al species associated with charge-balancing Na+ cations are
likely located within the 8-ring pockets where the Na+ species
are positioned as determined by the synchrotron XPD analysis
(Figure 3) and as corroborated by 2D 23Na{1H} HETCOR
analyses (Figure S20). Furthermore, the different OSDA
molecules are in close mutual proximities within the
mordenite channels, as established by the 2D 13C{1H}
HETCOR spectrum of HOU-4 (Figure 5C). This spectrum
and at 13C shifts of 15, 24, 26, 34, 67, and 73 ppm (purple
shaded regions) that arise from intermolecular interactions of
1H environments in TMAda+ molecules and the different 13
C
environments in proximate (<1 nm) D61,2 molecules. Based
on complementary 2D 29Si{1H} HETCOR spectra (Figure
S21) and the synchrotron XPD analyses, we conclude that the
different OSDA molecules are intimately commingled within
the zeolite pores and act cooperatively (as idealized in Figure
5D) during the hydrothermal syntheses of HOU-4 to direct the
formation of the mordenite framework and the distribution of
Al heteroatoms within both the linear 12-ring channels and the
8-ring pockets.
Parametric studies of HOU-4 synthesis reveal a
sensitivity to growth mixture composition (Figure S22 – S25).
The composition selected for this study (solution C1) falls
within the range typically reported for organic-free ZSM-5.43
Attempts to prepare HOU-4 in growth mixtures more
1
shows correlated signals at 2.2-3.1 ppm in the H dimension
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commonly reported for mordenite (i.e. solution C5 with both channels (c-direction) while hindering growth in the a-
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8
OSDAs) at higher aluminum content resulted in much larger
crystals. Mordenite is typically synthesized using Na+ ions as
the sole structure-directing agent, which leads to crystals with
a large variance in size and shape (Figure 6). Introduction of
D61,2 and/or TMAda+ to conventional synthesis mixtures does
not markedly reduce crystal size. Indeed, the growth mixture
direction. The role of cooperative OSDAs in HOU-4
crystallization is seemingly unrelated to that of a growth
modifier that alters the crystal morphology in conventional
mordenite synthesis, as neither organic produces solely thin
crystals. In fact, the presence of D61,2 has the opposite effect
in conventional mordenite syntheses, where it increases
crystal thickness in the absence of TMAda+ (Figure S26)
relative to the control (Figure 6). The ability to prepare
nanosized crystals has significant implications for catalytic
applications. Zeolite catalysts with restricted mass transport,
such as mordenite and other
44
that generates HOU-4 is adopted from a SSZ-13 synthesis
where we have reported D61,2 to be an effective modifier of
SSZ-13
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Figure 6. Scanning electron micrograph of a conventional mordenite
prepared by an organic-free synthesis using Na+ as an inorganic structure-
directing agent. The arrow highlights a 6-edged surface that is
characteristic of many MOR-type crystals reported in literature. This
surface is commonly indexed as the (001) face.
crystallization at low concentration (i.e., molar ratios less than
1.0 D61,2: 1.0 SiO2). Under such conditions, the diol reduces
the size of SSZ-13 crystals by an order of magnitude;
however, increased diol content (i.e., molar ratios in excess of
1.6 D61,2: 1.0 SiO2) shifts its role from that of crystal growth
modifier to an OSDA that operates synergistically with
TMAda+ to direct the formation of ultrathin mordenite
crystals. This reveals that HOU-4 requires a threshold amount
of diol and growth mixtures with much higher silicon content
than is typically required for conventional mordenite
synthesis.
The formation of HOU-4 and its purity are sensitive to
the carbon length of the diol. For example, combinations of
TMAda+ with either 1,2-pentanediol (Figure 7A) or 1,2-
butanediol (Figure S25) lead to a SSZ-13 impurity, whereas
1,2-propanediol (Figure 7B) results in pure SSZ-13.
Experiments with carbon lengths in excess of six were not
tested owing to their immiscibility in water. The results of diol
substitution are consistent with MD simulations of mordenite
with TMAda+ and diols of varying carbon length. At fixed
TMAda+ content and varying diol quantity, the minimum in
the stabilization energy (Figure 7C) for D61,2 indicates the
combination of this diol with TMAda+ is an energetically
favorable pairing for HOU-4 synthesis, consistent with
experimental observations. Thus, both experiment and
simulation suggest that D61,2 is optimal in size to span the 8-
ring pockets and direct their growth.
Figure 7. Scanning electron micrographs of the HOU-4 synthesis using a
combination of TMAda+ with (A) 1,2-pentanediol and (B) 1,2-
propanediol. Crystals in (A) contain mixed phases of mordenite and SSZ-
13 (isometric crystals) while those in (B) are pure SSZ-13 by XPD. (C)
Stabilization energy from MD calculations as a function of x alcohols per
unit cell (x = 0.5, 1.0, and 2.0) for a fixed loading of 1.5 TMAda+ per unit
cell. We find that D61,2 at a loading of 1.0 - 2.0 molecules per unit cell
provides the greatest stabilization.
It is not fully understood how the plate-like morphology
of HOU-4 crystals is derived from the combined structure-
directing influences of TMAda+ and D61,2 molecules. The dual
action of organics enhances growth along the direction of
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CONCLUSION
1
2
The generation of HOU-4 crystallites using a combination of
two organics is one of only a few reported cases where
multiple OSDAs work cooperatively to direct zeolite
crystallization and structure. Using a collection of high
resolution characterization and modeling, we are able to
resolve the location of both OSDAs in the pores of HOU-4.
Combined synchrotron XPD, 2D solid-state NMR, HRTEM,
and molecular modeling analyses reveal the framework
structure and local compositions, types of framework-organic
interactions, and spatial distribution of organics within 12-
ring channels and 8-ring pockets of mordenite. The
combination of these complementary techniques offers
unparalleled insight into the roles of different OSDAs in
directing zeolite crystallization to achieve distinct properties.
We expect that the methods and analyses reported here can be
more broadly extended to ascertain how SDAs tailor zeolite
crystal size, shape, and composition. Indeed, one challenge in
zeolite synthesis is determining how multiple organic and
inorganic structure-directing species function in a concerted
manner to influence the physicochemical properties of
zeolites, and control crystal polymorphism a priori. A unique
aspect of HOU-4 crystallization is the role of non-ionic
alcohols, which interact relatively weakly with crystallizing
zeolite frameworks, and are rarely employed as OSDAs in
zeolite syntheses. Here, diol molecules work in tandem with
cationic Na+ and TMAda+ species to stabilize the different
linear nanopore networks in mordenite.
The synthesis of non-faulted sub-micron mordenite
crystals has been a significant challenge. The ability to
generate materials with greater accessibility to acid sites and
reduced internal mass transportations has implications for
improving the design of commercial catalysts. Here, we show
that the ability to prepare mordenite crystals with reduced
stacking faults and high surface area improves catalyst
lifetime fourfold relative to materials prepared by
conventional methods. Collectively, the findings in this study
suggest that further exploration into the use of cooperative
organics in zeolite syntheses holds considerable promise for
the engineering and optimization of microporous materials.
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Figure 8. Comparative catalytic performance of H-mordenite crystals
(Si/Al = 8 by EDX) from a conventional synthesis and H-HOU-4 crystals
(Si/Al = 9.5 by EDX). Cumene cracking was performed in a packed bed
reactor at 450°C using a weight hourly space velocity (WHSV) of 2 h-1.
The shaded regions were used to calculate catalyst turnover number using
the density of acid sites as determined by NH3-TPD to account for the
different number of active (Brønsted acid) sites for each catalyst.
one-dimensional framework types, are the most susceptible to
rapid deactivation by coking. Comparisons between HOU-4
and conventional mordenite crystals reveal that the crystal
dimension along the c-direction (parallel to the large-pore
channels) is comparable, on the order of a micron; however,
the generation of ultrathin platelets leads to higher specific
surface area, which can influence catalytic performance. To
illustrate this point, we prepared acid forms of the platelets
(H-HOU-4) and conventional crystals (H-mordenite). For
catalytic testing we selected a reaction where shape selectivity
was not critical in order to assess differences in catalyst
activity. To this end, we used cumene cracking as a model
reaction to evaluate time-on-stream lifetime. The total number
of acid sites on each sample was quantified by NH3
temperature programmed desorption (TPD). Tests in a packed
bed reactor at 450°C reveal that the turnover number
(evaluated in the shaded regions of Figure 8) is much larger
for H-HOU-4 (38.7 mol cumene/mol H+) compared to
conventional mordenite (10.3 mol cumene/mol H+) owing to
the faster rate of H-mordenite deactivation. These results are
qualitatively consistent with studies of nanosized zeolite
catalysts in literature2, 45 that generally report much longer
lifetime owing to reduced mass transport limitations. For the
study reported here, external acid sites probably play a role in
the observed differences; however, it remains to be
determined if the lack of stacking faults in HOU-4 improves
internal mass transport and contributes to its improved
lifetime. The different synthesis conditions may also yield
distinct distributions of framework Al heteroatoms and
associated Brønsted acid sites in H-mordenite and H-HOU-4,
which would influence the catalytic activity and stability.
Rationalizing the differences in catalyst performance is
outside the scope of this work, but is a topic of ongoing
investigation.
EXPERIMENTAL SECTION
Materials. The following chemicals were used as
reagents: Cab-O-Sil (M-5, Spectrum Chemical), silica gel
(91%, Sigma-Aldrich), sodium hydroxide (98% pellets,
MACRON
Fine
Chemicals),
N,N,N-trimethyl-1-1-
adamantammonium hydroxide (TMAda-OH, 25 wt % in
water, SACHEM Inc.), 1,2-hexanediol (D61,2, 98%), 1,2-
pentanediol (D51,2, 96% Aldrich), 1,2-butanediol (D41,2,
≥98%,Sigma-Aldrich),
1,2-propanediol
(D31,2,
≥99.5%,Sigma-Aldrich), and aluminum hydroxide (80.3 wt %
Al(OH)3, SPI0250 hydrogel). It should be noted that the
IUPAC names for the two OSDAs used in this study are
hexane-1,2-diol and 1-adamantyl(trimethyl)azanium. Ion
exchange was performed using ammonium nitrate (ACS
reagent ≥98%, Sigma-Aldrich. Deionized (DI) water used in
all experiments was purified with an Aqua Solutions RODI-
C-12A purification system (18.2 MΩ). All reagents were used
as received without further purification.
Synthesis of mordenite. Mordenite (HOU-4) was
synthesized with the OSDA N,N,N-trimethyl-1-1-
adamantammonium hydroxide (TMAda-OH) and 1,2-
hexanediol (D61,2) using solutions with a molar composition
of 0.052 Al(OH)3:1.0 SiO2:0.2 NaOH:44 H2O:0.1 TMAda-
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OH:1.6 1,2-hexanediol. Sodium hydroxide (0.09 g, 0.0022
total acquisition time of 7 h. The 2D 29Si{1H} and 13C{1H}
1
2
3
4
5
6
7
8
mol) was first dissolved in water (8.21 g, 0.4959 mol),
followed by the addition of TMAda-OH (0.95 g, 0.0011 mol)
and 1,2-hexanediol (2.17 g, 0.018 mol). This solution was
stirred until clear (ca. 15 min). Aluminum hydroxide (0.06 g,
0.0005 mol) was added to the solution and left to stir for
another 15 min at room temperature. To this clear solution
was added the silica source (0.67 g, 0.0112 mol), and the
resulting mixture was first manually stirred with a plastic rod
for ca. 15 min, followed by continuous stirring using a stir bar
(400 rpm) for 4 h at 80°C in a mineral oil bath. Approximately
10 g of growth solution after 4 h of heated stirring was placed
in a Teflon-lined stainless steel acid digestion bomb (Parr
Instruments) and was heated under rotation (∼30 rpm) and
autogenous pressure in a Thermo-Fisher Precision Premium
3050 Series gravity oven. The nominal time and temperature
for HOU-4 synthesis was 6 days at 180 °C. The products of
all syntheses were isolated as white powder (ca. 600 mg) by
centrifuging the mother liquor (13,000 rpm for 45 min) for
three cycles with DI water washes. Samples for microscopy
were prepared by first redispersing a small amount of powder
(ca. 5 mg) in DI water. An aliquot of this solution was placed
on a glass slide and dried overnight. Crystals were transferred
to metal sample disks for microscopy studies by contacting
the glass slide with carbon tape for SEM.
Conventional mordenite was synthesized using a growth
solution with a molar composition of 1 Al2O3: 30 SiO2:5
Na2O:780 H2O.26, 46 Sodium hydroxide (0.25 g, 0.0061 mol)
was first dissolved in water (8.437 g, 0.468 mol), followed by
the addition of sodium aluminate (0.1003 g, 0.00061 mol).
The solution was stirred until clear (ca. 15 min) followed by
the addition of silica gel (1.212 g, 0.0183 mol), and the
resulting mixture was stirred at 400 rpm for 4 h.
Approximately 10 g of the growth mixture was placed in a
Teflon-lined stainless steel acid digestion bomb and was
heated under static and autogenous pressure. The nominal
time and temperature for synthesis was 4 days and 170°C,
respectively. The products of all syntheses were isolated from
mother liquor using vacuum filtration and 0.45 m membrane
filter with copious amount of DI water washes. Samples for
microscopy were prepared as described above.
spectra were acquired on a Bruker AVANCE 500 MHz (11.7
T) wide-bore spectrometer operating at Larmor frequencies of
1
500.222, 125.789, and 99.369 MHz for H, 13C, and 29Si,
respectively. Recycle delay times of 0.75 s were used with t1
increment step sizes of 128 μs. The 2D 29Si{1H} HETCOR
spectrum acquired at a short contact time (0.5 ms, Figure 3B)
was acquired with 196 t1 increments and 256 transients for a
total acquisition time of 10.5 h. The 2D 29Si{1H} HETCOR
spectrum acquired at a longer contact time (5 ms, Figure S19)
was acquired with 256 t1 increments and 64 transients for a
total acquisition time of 3.5 h. The 2D 13C{1H} HETCOR
spectra acquired with contact times of 0.5 and 5 ms (Figure
S10) were acquired respectively with 250 and 430 t1
increments and 512 and 128 transients for total acquisition
times of 27 h and 11.5 h. The 2D 27Al{1H} (Figure 3C) and
23Na{1H} (Fig. S20) HETCOR spectra were acquired on a
Bruker AVANCE-III Ultrashield Plus 800 MHz (18.8 T)
narrow-bore spectrometer operating at Larmor frequencies of
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1
208.527, 211.681, and 800.242 MHz for 27Al, 23Na, and H,
respectively, and a Bruker 3.2 mm broadband double-
resonance HX probehead was used. The 2D 27Al{1H}
HETCOR spectrum was acquired with a repetition time of 1
s, 50 t1 increments and 512 transients for a total acquisition
time of 7 h. The 2D 23Na{1H} HETCOR spectrum was
acquired with a repetition time of 1 s, 32 t1 increments and
1024 transients for a total acquisition time of 9 h. All of the
1
2D HETCOR spectra were acquired using homonuclear H-
50
1H eDUMBO-122 decoupling
during the 1H evolution
1
periods to improve resolution in the H dimensions. For the
2D 29Si{1H}, 13C{1H}, 23Na{1H}, and 27Al{1H} HECTOR
experiments, a variable-temperature chiller unit was to cool
the sample temperature to approximately 263 K to reduce the
mobility of the OSDA species and improve cross-polarization
signal sensitivity. All of the 1D and 2D spectra were acquired
51
with 100 kHz heteronuclear SPINAL-64
during the acquisition period.
1H decoupling
Atomic force microscopy (AFM). AFM measurements
were performed in air using an Asylum Research MFP-3D-
SA instrument (Santa Barbara, CA). An aliquot of HOU-4
dispersed in water was placed on silicon wafer and was
allowed to dry at room temperature. The silicon wafer was
calcined at 500°C for 5 h, followed by cleaning under inert Ar
gas flow to remove loosely-bound crystals. AFM images were
collected using a Cr/Au-coated silicon nitride cantilever
(Olympus RC800PB with a spring constant of 0.82 N/m) in
contact mode at a scan rate of 1.2 Hz and 256 lines/scan.
Electron microscopy. Scanning electron microscopy
(SEM) was performed with a FEI 235 dual-beam (focused
ion-beam) system operated at 15 kV and a 5 mm working
distance. All SEM samples were coated with a thin carbon
layer (ca. 20 nm) prior to imaging. Transmission electron
microscopy (TEM) was carried out for structural and
Solid-state nuclear magnetic resonance (NMR). Solid-
state 1D and 2D 1H, 13C, 27Al, and 29Si MAS NMR
1
spectroscopy was used to analyze the H, 13C, 27Al, and 29Si
environments in as-made ultrathin HOU-4 crystallites. The
2D 27Al{29Si} J-mediated NMR correlation spectrum (Figure
3A) was acquired on a Bruker ASCEND 400 MHz (9.4 T)
DNP NMR spectrometer operating at Larmor frequencies of
1
400.203, 104.283, and 79.501 MHz for H, 27Al, and 29Si
nuclei, respectively. This instrument is equipped with a 3.2
mm triple-resonance HXY low-temperature MAS probehead.
Low-temperature measurement conditions of 95 K were used
for improved signal sensitivity. The spectrum was acquired
using a 2D Heteronuclear Multiple Quantum Correlation
(HMQC) pulse sequence47-48 with an experimentally-
optimized half-echo tau delay of 20 ms used to refocus the
weak (ca. 1/(4τ) = 12.5 Hz) through-bond 27Al-O-29Si J-
couplings. The signal sensitivity was enhanced by applying a
morphology characterization using
a Thermo Fischer
(formerly FEI) 200 kV TitanX transmission electron
microscope equipped with the windowless SDD Bruker EDS
detector with fast processor.
X-ray analysis. Energy-dispersive X-ray spectroscopy
(EDX) was performed using a JEOL JSM 6330F field
emission SEM at working distance of 15 mm and voltage of
15 kV and 12 mA. X-ray powder diffraction (XPD) patterns
of as-made zeolite samples were collected on a Siemens
D5000 X-ray diffractometer using a Cu Kα1 source (40 kV,
30 mA). For reference intensity ratio (RIR) analysis using
1 ms 27Al adiabatic double-frequency sweep pulse during the
49
preparation period to invert the 27Al satellite transitions
.
During the rotor-synchronized tau delay periods, 100 kHz of
continuous wave 1H decoupling was applied. A recycle delay
time of 1 s was used with a rotor-synchronized t1 increment
step size of 100 μs, 96 t1 increments, and 256 transients for a
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Rigaku SmartLab Catalyst preparation and testing. Samples for catalysis
mordenite-quartz
mixtures,
a
1
diffractometer (40 kV, 44 mA) was used. The MOR-type
framework was confirmed using a reference pattern from the
Database of Zeolite Structures.15 Synchrotron powder
diffraction data were collected on an unwashed sample of
HOU-4 in a 0.5 mm glass capillary on the Materials Science
Beamline at the Swiss Light Source (SLS) in Villigen,
Switzerland.52 The wavelength was determined from a Si
standard to be 0.7087Å. Additional details of XPD analysis
are provided in the Supporting Information.
were calcined in a Thermo Fisher Lindberg Blue furnace
under constant flow of 100 sccm dried air (Matheson Tri-Gas)
at 550°C for 5 h with a temperature ramping/cooling rate of
1°C/min. These samples were converted to an acid form
(Brønsted acids) by ion exchange wherein calcined zeolite
was mixed with 1.0 M ammonium nitrate solution to obtain a
2 wt% suspension. This mixture was heated to 80°C for 2 h to
2
3
4
5
6
7
8
9
+
allow the exchange of Na+ with NH4 . This process was
performed three times with centrifugation/washing between
each ion exchange cycle. The final NH4-zeolite samples were
washed three times with DI water before they were calcined
once again with the same conditions stated above, thus
becoming H-form zeolite.
Molecular dynamics (MD) simulations. MD
simulations were performed with GROMACS 4.6.7.53 The
MOR zeolite framework was modeled as an all silica structure
using the ClayFF potential,54 whereas the OSDAs (TMAda+,
1,2-pentanediol, 1,2-butanediol, 1-2-hexanediol, and 1-2-
heptanediol) were described using the generalized AMBER
force field 55. Atomic positions and lattice parameters for the
mordenite framework were taken from the Database of Zeolite
Structures. Na+ ions were inserted into the 8-ring pockets, in
the positions suggested by XRPD analysis (Figure S13).
Although Na+ ions stabilize Al in the framework, the positions
of the Al sites are not precisely known. Consequently, Al was
implicitly modeled by smearing a negative charge over the
oxygens in the 8-ring pockets to counterbalance the Na+ ions
and ensure electroneutrality. Potential parameters for
describing van der Waals interactions between the OSDAs
and zeolite framework atoms were evaluated using standard
Lorentz-Berthelot combining rules.56 Van der Waals and real-
space Coulombic interactions were truncated using a cutoff of
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Cumene cracking over H-form catalysts was carried out
in a ¼ inch stainless steel tube installed in a Thermo Scientific
Lindberg Blue M furnace. The catalyst bed was supported
between two plugs of quartz wool, and a K-type thermocouple
(Omega Engineering) was inserted into the stainless tube to
measure the temperature of the catalyst bed. Prior to the
reaction, the catalyst bed was pretreated in situ at 550°C for 3
h under flow of dried air (6 cm3/min of O2, 24 cm3/min of N2).
After this pretreatment, the catalyst bed was cooled down to
the reaction temperature, i.e. 450°C. Cumene (98%, Sigma
Aldrich) was fed by a syringe pump (Harvard Apparatus) at 2
μl/min into a heated inert gas stream of Ar (50 cm3/min),
which resulted in a reactant flow with a weight hourly space
velocity (WHSV) of 2 h-1. The cumene conversion is defined
as the percentage of cumene reacted at the effluent of catalyst
bed. To compare the deactivation rate between different
catalyst samples, the turnover number (TON) is calculated for
a selected span of time-on-stream (TOS) using a modified
form of the equation reported by Bhan and coworkers,63
56
0.9 nm, and the particle mesh Ewald method was used to
treat long-range electrostatics, with parameters chosen to
ensure a relative error of less than 10-4 in the calculated
energy. The equations of motion were propagated using a
leapfrog integration scheme with a 2 fs time step.56 The
temperature and pressure of the system were maintained using
a Bussi-Parrinello velocity-rescaling thermostat57 and a
Parrinello-Rahman barostat58, respectively. The relaxation
time constants for both the thermostat and barostat were set to
2 ps.
Following our recent study of surfactant occlusion in
MFI structured zeolites,59 energetically favorable
conformations for the OSDAs in mordenite were sampled
using a three-step procedure. First, the OSDAs were gradually
inserted into the zeolite framework using the alchemical
transformation procedure described by Kim et al.,60 whereby
the OSDAs were converted from an ideal gas to fully
interacting molecules over the course of a short MD
simulation (500 ps) at ambient temperature. This gradual
insertion step ensured that the system did not become trapped
in unphysical, high-energy conformations. Next, the
conjugate gradient algorithm was used to minimize the
configurational energy of the system. Finally, the
configuration from the energy minimization step was use to
initialize a ns-long MD simulation at 300 K and 0 bar. Data
from the last half of the MD trajectory were to evaluate the
ퟏ
퐇 +
퐓퐎퐍(풕) = [
∫풕풕ퟐ푭(흉)풅흉
(1)
]
ퟏ
ퟎ
where [H+]0 is the total number of Brønsted acid sites
(obtained from the NH3-TPD data in Table S3), F() is the
molar flow rate of converted carbon (reacted cumene), and t
is TOS selected between times t1 and t2 corresponding to 85
and 70% cumene conversion (i.e., regions of nearly linear
deactivation in Figure 4E).
Temperature-programed desorption of ammonia
(NH3-TPD). Temperature-programmed desorption of
ammonia was performed by the Bhan Group (University of
Minnesota) on a Micromeritics Autochem II 2920 equipped
with a TCD detector. Prior to TPD, ca. 100 mg of catalyst was
first out gassed in He for 1 h at 600°C with a heating ramp of
10°C min-1. Ammonia was adsorbed at 100°C until saturated,
followed by flushing with He for 120 min at 100°C. The
ammonia desorption was monitored using a TCD detector
until an upper temperature of 600°C with a ramp of 10°C min-
1, using a flow of 25 mL min-1.
ASSOCIATED CONTENT
stabilization energy61-62
∑
〈
〉
〈
〉
〈 〉
푛푖 푈푆퐷퐴,푖
,
퐸푠 ≡ 푈푠푦푠 ― 푈푧푒표
―
푖
SUPPORTING INFORMATION
〈
〉
〈
〉
푛푖
푈푆퐷퐴,푖
푈푠푦푠
푈푧푒표
where
the average energy of the system,
average energy of the empty zeolite framework,
number of inserted OSDA molecules of type i, and
is the
is the
Additional details of materials characterization are provided,
including XRD patterns, SEM and TEM images, TGA
profiles, elemental analysis, solid state NMR, AFM images
and height profiles, details of molecular modeling, and
examples of alternative synthesis conditions employing
variants of OSDAs and the addition of modifiers (PDF). This
material is available free of charge via the Internet at
http://pubs.acs.org.
〈
〉
is
the average energy computed for a single OSDA molecule in
퐸푠
vacuum. The steps above were repeated to evaluate
for
~103 different conformations at each OSDA loading
퐸
considered in the study. Conformations with low
(lowest 10%) were saved for subsequent analysis.
values
푠
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AUTHOR INFORMATION
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Corresponding Author
*E-mail: bradc@engineering.ucsb.edu
*E-mail: jrimer@central.uh.edu
Notes
The authors declare no competing financial interests.
Author Contributions
All authors have given approval to the final version of the
manuscript.
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ACKNOWLEDGMENTS
J.D.R. acknowledges support primarily from the U.S.
Department of Energy Office of Basic Energy Sciences
(Award DE-SC0014468). J.D.R. and J.C.P. acknowledge
funding from the Welch Foundation (Award Nos. E-1794 and
E-1882, respectively). Z.J.B. was supported by a grant from
the BASF Corporation. The solid-state MAS NMR
measurements at the University of California, Santa Barbara
(UCSB) made use of the MRL Shared Experimental
Facilities, which are supported by the MRSEC program of the
NSF under Award No. DMR 1720256; a member of the
Materials Research Facilities Network (www.mrfn.org).
L.B.M. thanks Nicola Casati for his assistance with the
synchrotron powder diffraction measurements on the
Materials Science Beamline at the SLS in Villigen,
Switzerland and UCSB for hosting her as a visiting scholar.
H.Z. acknowledges funding from DOE Office of Basic
Energy Sciences, Materials Sciences and Engineering
Division under Contract No. DE-AC02-05-CH11231 within
the KC22ZH program. We are grateful to M.F. Hsieh for help
with catalyst testing and M.D. Susman for help with quartz
calibration analysis. We thank A. Bhan and Z. Shi at the
University of Minnesota for help with NH3-TPD
measurements.
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