Microporous and Mesoporous Materials 353 (2023) 112511

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Synthesis of PHI-type zeolite harmotome using barium as an inorganic

structure-directing agent inspired from natural mineral compositions
Yu Liang a, Allan J. Jacobson a, b, **, Jeffrey D. Rimer a, c, *
a
Department of Chemistry, University of Houston, Houston, TX, 77204, USA
b
Texas Center for Superconductivity, University of Houston, Houston, TX, 77204, USA
c
Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX, 77204, USA

A B S T R A C T

Zeolites are nanoporous aluminosilicates widely used as commercial adsorbents, heterogeneous catalysts, and ion-exchange materials due to their unique porosity,
acidity, and thermal stability. The vast majority of synthetically-realized zeolite structures are prepared under hydrothermal conditions in alkaline media, and often
in the presence of an organic structure-directing agent that facilitates the crystallization of diverse porous networks. Due to economic and environmental disad­
vantages of organic-based syntheses, it is often desirable to produce zeolites in organic-free media using alkali metal ions as the most commonly employed inorganic
structure-directing agents (ISDAs). In this study, we were inspired by the elemental compositions of natural zeolite minerals to examine the use of an alkaline earth
metal ion as the ISDA to prepare zeolites with the PHI framework type. Two natural minerals exhibiting this crystal structure are phillipsite and harmotome. Both
structures contain sodium and potassium as extra-framework cations, but only harmotome contains barium cations. Here we examined how the combination of alkali
and alkaline earth ISDAs promote the formation of PHI-type zeolites. Our findings reveal that each isostructure is prepared under different synthesis conditions where
simply adding barium to a growth mixture does not always lead to harmotome formation. Harmotome is formed in more dilute and alkaline growth media; however,
time-resolved analyses of zeolite crystallization reveal that harmotome can be synthesized at low temperatures (ca. 65 ◦ C) with rates that are 5-times faster than
syntheses of phillipsite. This seemingly indicates that barium reduces the energetic barrier for PHI-type zeolite nucleation in ways that are not fully understood.
Moreover, harmotome crystals exhibit an average particle size of ca. 60 nm, which is nearly 40-fold smaller than phillipsite crystals prepared under similar con­
ditions. Collectively, these findings identify routes to control crystallization of PHI-type zeolites and may provide a broader strategy for using the composition of
natural zeolite minerals to optimize the preparation of synthetic analogues.

1. Introduction [13–18]. To avoid the negative environmental impacts of calcining or­

For decades, a wide range of zeolite structures have been intensely
investigated on the basis of their diverse porosity, acidity, and (hydro)
thermal stability [1–5]. From the mid-18th century, zeolites were
recognized as a category of naturally occurring minerals [6]. In the
1940’s, Barrer pioneered the study of zeolite synthesis, which led to the
first preparation of zeolite framework types without natural analogues
[7–9]. Since these pioneering studies there have been significant efforts
to optimize zeolite crystallization through diverse methods, often
guided by the elemental composition and geothermal conditions for
natural zeolite mineralization [10–12]. State-of-the-art syntheses of
zeolites for commercial applications often require the use of costly
organic molecules that function as organic structure-directing agents
(OSDAs); however, a majority of commercial zeolites (e.g., faujasite,
mordenite, and chabazite) can be crystallized in the absence of organics
using alkali metals as inorganic structure-directing agents (ISDAs)
ganics in zeolites post-synthesis, and to minimize the costs associated
with producing/using OSDAs, it is desirable to develop organic-free
methods for zeolite synthesis. This active research area has numerous
challenges for developing low-cost routes to prepare zeolites with
desired physicochemical properties without the aid of OSDAs [19,20].
This study focuses on zeolites with the PHI framework type. In the
1960’s, crystallographic investigations of naturally occurring zeolite
minerals uncovered two structures with a PHI-type framework: har­
motome and phillipsite [21,22]. Kuhl successfully synthesized phil­
lipsite using growth mixtures with ratios Si/Al = 2–8 and Na2O/(Na2O
+ K2O) = 0.3–0.85, which closely resemble the composition of natural
phillipsite [23]. Synthetic harmotome was first prepared by Perrotta in a
growth mixture with molar composition 5.25 SiO2: 1 Al2O3: 9.5 Na2O:
0.24 BaO: 1528 H2O after 96 h of heating at 95 ◦ C [24]. Both phillipsite
and harmotome share the same topology, while the elemental compo­
sitions of extra-framework species characterize their structural

* Corresponding author. Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX, 77204, USA.
** Corresponding author. Department of Chemistry, University of Houston, Houston, TX, 77204, USA.
E-mail addresses: ajjacob@central.uh.edu (A.J. Jacobson), jrimer@central.uh.edu (J.D. Rimer).

https://doi.org/10.1016/j.micromeso.2023.112511
Received 15 January 2023; Received in revised form 13 February 2023; Accepted 23 February 2023
Available online 25 February 2023
1387-1811/© 2023 Elsevier Inc. All rights reserved.
Y. Liang et al.
differences. Rinaldi and coworkers [25] investigated the structures of
phillipsite and harmotome from refinement of X-ray data from single
crystals of natural minerals. Their findings revealed the same cationic
sites and water molecule distributions with slight distortions; however,
syntheses of PHI-type zeolites have been rarely studied to elucidate the
role of growth medium composition, particularly those mimicking the
chemical compositions of their respective natural minerals.
Herein, we investigate the formation of PHI-type zeolite frameworks
and explore the synthetic conditions that promote the crystallization of
either harmotome or phillipsite zeolites. We systematically examined
the impact of multiple ISDAs on zeolite structure and its physicochem­
ical properties. Our methodology of zeolite synthesis was guided by the
composition of natural zeolites wherein we use a combination of alkali
and alkaline earth metals to tailor the final zeolite structure while
simultaneously reducing crystallization time compared to conventional
methods of preparation. Our findings reveal that the exploration of
OSDA-free zeolite syntheses could benefit from careful consideration of
natural zeolites in order to provide new opportunities for zeolite crys­
tallization via green routes.
2. Experimental methods
Materials. The following reagents were purchased from Sigma-
Aldrich: sodium aluminate (technical grade), sodium hydroxide
(NaOH, 98%), potassium hydroxide solution (KOH, 40%), LUDOX AS-40
colloidal silica (SiO2, 40%), and barium hydroxide octahydrate (Ba
(OH)2⋅8H2O, 98%). All reagents were used as received without further
purification. Deionized (DI) water was produced with an Aqua Solutions
RODI-C-12A purification system (18.2 MΩ).
Zeolite synthesis. Phillipsite zeolite was prepared by modifying a
reported protocol [26] using a growth mixture with molar composition 1
SiO2: 0.24 Al2O3: 0.10 K2O: 0.31 Na2O: 16.48 H2O. In a typical syn­
thesis, potassium hydroxide solution and sodium hydroxide were mixed
in DI water until the sodium hydroxide was fully dissolved. To this so­
lution was added sodium aluminate, followed by continuous stirring
until the mixture was homogenous. LUDOX AS-40 colloidal silica was
then added as the silica source.
Harmotome zeolite containing barium ions was synthesized using a
growth mixture with molar composition 1 SiO2: 0.50 Al2O3: 2.75 Na2O:
0.25 BaO: 95 H2O. First, sodium hydroxide pellets and barium hydrox­
ide octahydrate crystals were dissolved in DI water. To this solution was
added sodium aluminate, which was then mixed until homogenous,
followed by the addition of LUDOX AS-40 colloidal silica.
Growth mixtures were aged for 24 h at room temperature prior to
being transferred to a 60 mL polypropylene (PP) laboratory bottle
(VWR) for syntheses at 65 ◦ C. For higher temperatures, the growth
mixture was placed in a 23-mL Teflon-lined metal autoclave (Parr In­
struments). The synthesis temperature (65 or 100 ◦ C) was maintained
using a ThermoFisher Precision oven and reaction vessels were heated
under static conditions (i.e. without rotation). Containers were removed
after heating times ranging from 1 h to 7 d. Upon removal from the oven,
the container was quenched to room temperature in a water bath. Solids
were recovered by three cycles of centrifugation, each at 5 ◦ C and
13,000 rpm for 5 min using a Beckman Coulter Avanti J-E centrifuge and
intermediate washings with DI water. The recovered products were
dried in air at 50 ◦ C overnight prior to characterization.
Characterization. The crystalline phase purity of each zeolite sam­
ple was determined by powder X-ray diffraction (XRD) using a Rigaku
diffractometer with Cu Kα radiation (40 kV, 44 mA). Scanning electron
microscopy (SEM) was conducted on a FEI-235 Dual-Beam Focused Ion
Beam instrument operated at 15 kV and a 5 mm working distance.
Samples for SEM analysis were prepared by affixing dried crystals to a
SEM sample holder with carbon tape. Elemental analysis was performed
by energy dispersive X-ray spectroscopy (EDX) using a JEOL JSM 6330F
Field Emission scanning electron microscope at a working distance of 15
mm and voltage of 15 kV. Fourier-transform infrared spectroscopy
2
Microporous and Mesoporous Materials 353 (2023) 112511
(FTIR) was measured with a Thermo Scientific Nicolet iS20 FTIR
Spectrometer.
3. Results and discussion
Syntheses of zeolites in the absence of organic-structure-directing
agents (OSDAs) typically use alkali metals as inorganic structure-
directing agents (ISDAs) [27–31]. Relatively few studies have explored
the use of multivalent ions as ISDAs, either as replacements of alkali
metals or in combination with monovalent ions as mixtures. A survey of
the database of natural zeolites and their elemental compositions reveal
that divalent ions are common in zeolite minerals [32]. Table 1 lists
several naturally occurring zeolites that have been synthesized using
organic-free reactions. Many of these zeolites (e.g., faujasite, chabazite
and phillipsite) contain more than one extra-framework metal ion,
owing to variations in natural synthesis conditions (i.e. abundance of
natural minerals in various regions of the world) and presumably the
similarity of atomic radii of alkali and alkaline earth metals. We observe
only a marginal difference in the silicon-to-aluminum ratio (Si/Al)
among natural minerals with different monovalent/divalent cation
compositions. Considering the high abundance of alkaline earth metals
in the earth’s crust, it is reasonable to anticipate the elemental compo­
sition of natural zeolites reflects the local environment of mineraliza­
tion. This calls into question whether the cations are merely spectators
that function as charge-balancing extra-framework species, or if their
role is that of an ISDA that impacts either polymorph selection or the
rate of zeolite crystallization. This question has not been thoroughly
examined in the literature for laboratory syntheses employing mixtures
of alkali and alkaline earth metals, which is the subject of this study.
Taking inspiration from the compositions of natural zeolites listed in
Table 1, we examine herein the impact of substituting alkali metals with
barium in conventional Na,K-zeolite syntheses.
Combinations of Na, K, and Ba for the molar compositions and
conditions selected for this study (see Table 2) resulted in four different
zeolite structures: LTA, FAU, GIS, and PHI. Herein, we focus on the role
of cation mixtures to promote PHI-type zeolite, which has a 3-dimen­
sional pore network with 8-member ring (8 MR) pore apertures
(Fig. 1A). We report the synthesis of two materials exhibiting the same
PHI topology: phillipsite and harmotome. The framework atoms (i.e., Si,
Table 1
Examples of natural zeolites that have been synthetically realized in organic-free
syntheses [32].
Natural Framework Composition
Zeolite Typea
Chabazite CHA K |(K,Na,Ca0.5)x(H2O)12| [Alx Si12-x O24] x =
3.0–4.5
Na |(Na,K,Ca0.5)x(H2O)12| [Alx Si12-x O24] x =
2.5–4.8
Sr |(Sr0.5,Ca0.5,K)4(H2O)12| [Al4 Si8 O24]
Faujasite FAU Na |(Na,Ca0.5,Mg0.5,K)x(H2O)16|[AlxSi12-xO24]
x = 3.2–4.3
Ca |(Ca0.5,Na,Mg0.5,K)x(H2O)16|[AlxSi12-xO24]
x = 3.3–3.9
Mg |(Mg0.5,Ca0.5,Na,K)3.5(H2O)16|[Al3.5Si8.5
O24]
Merlinoite MER |(K,Ca0.5,Ba0.5,Na)10 (H2O)22| [Al10Si22O64]
Mordenite MOR |Na2,Ca,K2)4(H2O)28| [Al8Si40O96]
Offretite OFF |Ca,K,Mg)(H2O)16|[Al5Si13O36]
Gismondine GIS |Ca4 (H2O)18| [Al8Si8O32]
Harmotome PHI |(Ba0.5,Ca0.5,K,Na)5(H2O)12| [Al5Si11O32]
Phillipsite PHI |(Na,K,Ca0.5)x(H2O)12| [AlxSi16-xO32] x =
3.7–6.7
|(K,Na,Ca0.5)x(H2O)12| [AlxSi16-xO32] x =
3.8–6.4
|(Ca0.5,Na,K)x(H2O)12| [AlxSi16-xO32] x =
4.1–6.8
a
Three-letter codes for each zeolite framework are assigned by the Interna­
tional Zeolite Association (IZA) Structure Commission.
Y. Liang et al. Microporous and Mesoporous Materials 353 (2023) 112511

Table 2 MR) and 8 MR of (Si, Al)O4 tetrahedra. The 8 MR channel has an opening
Parametric study of zeolite crystal phase(s) with varying molar ratios of inor­ of 5.4 Å that is nearly parallel to the a-axis. The framework tetrahedral
ganic cations. (T) sites (T = Si or Al) in 8 MR units are highlighted by the yellow
SiO2 Al2O3 H2O ISDA(s) Zeolite Product(s) tetrahedra in Fig. 1B and C. The oxygen atoms bonded to the T atoms are
Na2O K2O BaO
shown as red spheres in these schemes. Extra-framework Ca cations
(grey) are located in the 8 MR cavity, coordinated by four water mole­
1 0.2 16 0.3 0.1 Phillipsite
–
cules (cyan). Calcium sites can be partially or completely occupied by
– 0.1 Phillipsite
0.02 0.08 Phillipsite Na, considering that Ca and Na have comparable ionic radii of 116 and
0.05 0.05 Phillipsite 114 p.m., respectively. In phillipsite, extra-framework K cations (green)
0.08 0.02 Phillipsite sit in cradle-shaped cavities within the elongated 8 MR cavity, coordi­
2 1 190 5.5 – 0.5 Harmotome nated by five framework O atoms and three water molecules (Fig. 1B).
0.1 0.4 Harmotome The anisotropic positioning of the K cation in the cavity is presumably
0.2 0.3 Harmotome due to the electrostatic force from the presence of the Ca cation(s) at
0.3 0.2 GIS
neighboring site(s). In harmotome, the Ba cation (purple) sits at the
0.4 0.1 GIS
0.5 – LTA + FAU same site as the K cation in phillipsite and has similar coordination to
neighboring Ca ions, Na ions, and water molecules (Fig. 1C). The
refinement data from previously reported crystallography measure­
ments of natural PHI-type zeolites (Table S1) shows a significant
decrease of all Ba–O bond lengths between the Ba cation and water
molecules or framework O atoms. We speculate that Ba2+ cations exhibit
stronger electrostatic interactions with O sites compared to alkali
metals, which putatively stabilizes the structure of harmotome.
To our knowledge, few studies have reported the synthetic prepa­
ration of harmotome [24,34]; therefore, we investigated methods to
synthesize harmotome in environments that deviate from harsh
geothermal conditions (i.e., elevated temperature and prolonged treat­
ment time) required to form its natural counterpart. We observed that
the composition of natural harmotome is similar to that of natural fau­
jasite (FAU); thus, we attempted to synthesize harmotome by selecting a
laboratory FAU synthesis protocol and replacing a portion of sodium
with barium (i.e. a putative ISDA for the natural PHI-type mineral). The
growth mixture had a molar composition of 1 SiO2: 0.50 Al2O3: 2.75
Na2O: 0.25 BaO: 95 H2O. The temperature of FAU syntheses in literature
varies from 30 to 100 ◦ C. In our previous study of Na-zeolite poly­
morphism [35] we used 65 ◦ C as an average condition, which we
emulated in this study of Na,Ba-zeolite synthesis. Time-resolved bulk
crystallization was performed wherein the solid-phase was extracted
from the growth mixture after various heating times, and the product
was characterized by powder X-ray diffraction (XRD). Analysis of solids
after 24 h of heating revealed a powder XRD pattern (Fig. 2A) that is
Fig. 1. (A) Crystal structure of the zeolite PHI framework oriented along the identical to the harmotome reference pattern. The sharp peaks at 2θ =
[001] direction, composed of composite building units dcc and phi. Color 10–15◦ indicate a high crystallinity of as-synthesized harmotome.
coding is based on the concept of natural tiling proposed by Blatov and co­
Scanning electron micrographs (Fig. 2B) showed that this synthesis
workers as a new type of zeolite taxonomy wherein natural tiles of zeolites are
protocol resulted in nanocrystalline spheroidal harmotome particles
defined as natural building units (NBUs) [33]. The natural tiling method offers
a categorization system to compare the organizational characteristics of zeolite
with an average size of 56 ± 8 nm. This is both the smallest particle size
structures. For PHI-type zeolites there are two NBUs: t-oto (blue) and t-phi and shortest crystallization time reported for synthetic harmotome.
(green). (B and C) Location of atoms in two PHI-type materials, (B) phillipsite Synthetic phillipsite was reported by Cichocki et al. [26] using a
and (C) harmotome, are shown in crystal structures viewed along the [001] growth mixture containing both sodium and potassium ions as binary
direction. Images were created with the software DIAMOND using structural ISDAs. Here we used a similar molar composition, 1 SiO2: 0.24 Al2O3:
data for the natural minerals provided by the International Zeolite Association. 0.10 K2O: 0.31 Na2O: 16.48 H2O, but decreased the nominal tempera­
Note that while calcium is present in natural minerals, this element was omitted ture from 100 to 65 ◦ C for direct comparison with the harmotome syn­
from growth mixtures used to synthesize PHI-type zeolites in this study in order thesis. To our knowledge, this is the lowest temperature used for
to focus on the effect(s) of barium. phillipsite synthesis where a fully-crystalline product was achieved after
ca. 5 days of heating. The powder XRD pattern of as-synthesized phil­
Al, and O) in both materials are arranged similarly, but positioning of lipsite (Fig. 2C) agrees well with the reference pattern for its natural
extra-framework cations is distinct in each PHI-type material. Fig. 1 il­ counterpart. Although phillipsite and harmotome share the same PHI
lustrates the similarities and differences in the crystal structures of framework topology, the different distributions of extra-framework
phillipsite (Fig. 1B) and harmotome (Fig. 1C) determined by single cations (Fig. 1B and C, respectively) leads to distinct powder XRD pat­
crystal X-ray diffraction (SCXRD) of natural minerals [25]. The com­ terns. The majority of peaks overlap for both structures, but there are
positions of natural zeolites used to extract this crystallographic data differences in the range 2θ = 15–20◦ where phillipsite has four peaks in
were K~2Cã1.5Nã0.4Al~5Si~10O32.12H2O for phillipsite and contrast to the single peak at 17.5◦ for harmotome. A critical difference
Bã2Cã0.5Al~5Si~11O32.12H2O for harmotome. Given the small size of in powder XRD patterns, however, is the relative peak intensities. In the
synthetic PHI-type zeolites (<10 μm), SCXRD data is not available; range 2θ = 10–15◦ the three peaks of harmotome have similar intensity
therefore, we use the natural forms as guides for structural interpreta­ whereas the peak at 12.5◦ for phillipsite is significantly stronger than its
tion of the data presented in this study. two neighboring peaks. There is also a clear difference in the particle
The PHI framework is comprised of layers of four-membered rings (4 size of both PHI-type zeolites. Scanning electron micrographs of

3
Y. Liang et al.
Fig. 2. Powder X-ray diffraction patterns of (A) harmotome and (C) phillipsite compared to reference patterns of corresponding natural PHI-type zeolites obtained
from the International Zeolite Association (IZA) Structure Database. Two overlapping peaks denoted by the asterisks (*) are assigned to crystalline BaCO3 impurity.
Scanning electron micrographs of (B) harmotome and (D) phillipsite prepared by the partial substitution of Na+ ions with Ba2+ and K+ ions, respectively.
as-synthesized phillipsite (Fig. 2D) show a spheroidal morphology with
a much larger average crystal size (2.4 ± 0.3 μm) compared to
harmotome.
Comparison of phillipsite and harmotome syntheses at the same
temperature reveal that the latter is nearly 5-times faster. Both syntheses
used identical sources of silicon and aluminum, but a key difference
between the two synthesis compositions is a much higher water content
in the growth mixture of harmotome (Table 2), which seems to indicate
the more dilute system exhibits a faster rate of crystallization. The role of
ISDAs in both syntheses is difficult to rationalize. For instance, we
4
Microporous and Mesoporous Materials 353 (2023) 112511
performed a parametric study wherein the alkalinity, temperature
(65 ◦ C), and time (1 and 5 days for harmotome and phillipsite, respec­
tively) for each synthesis was fixed while the ratios of Na, K, and Ba ions
were varied. As shown in Table 2, introduction of Ba2+ to phillipsite
syntheses had no impact on the final product, and was unable to pro­
mote the formation of harmotome. It appears that phillipsite crystalli­
zation is more robust to changes in the ISDA composition with full
crystallinity obtained when (K2O + BaO)/Na2O ≥ 3. Elemental analysis
of all phillipsite products did not detect the presence of barium, indi­
cating this divalent cation is a bystander that functions neither as an
Fig. 3. (A) Powder X-ray diffraction patterns of as-
synthesized harmotome (bottom pattern) and the
same sample after post-synthesis treatment with 0.1
M HCl for 24 h (top pattern). The dashed lines are
peaks associated with BaCO3 as a minor impurity. (B)
FTIR patterns of four different samples: reference
BaCO3, solids extracted from a harmotome growth
mixture after 24-h aging at room temperature (pre­
cursor), as-synthesized harmotome (7-day synthesis),
and the acid-treated form of the latter. The dashed
lines at 693, 855, and 1417 cm− 1 confirm the pres­
ence of BaCO3 impurity. The two lowest wave­
numbers correspond to O–C–O bending vibrations in
CO2−
3 while the highest wavenumber corresponds to
an asymmetric C–O stretching vibration.
Y. Liang et al.
ISDA nor as a charge-compensating extra-framework species under
synthesis conditions favoring phillipsite formation. In contrast, harmo­
tome can only form in the presence of Ba2+ at the condition BaO/Na2O
= 0.05–0.09 (Table 2). When this ratio exceeds 0.09, we obtain an
amorphous product (Table S2); when the ratio falls below 0.05, we
obtain GIS; and when no barium was added to the system we produce a
mixture of LTA and FAU. Collectively, these studies indicate that har­
motome synthesis is sensitive to the molar composition of the growth
mixture as well as the presence of Ba2+ in ways that are not fully
understood.
An undesirable outcome of harmotome synthesis is the presence of
an impurity, which is evident by the appearance of two prominent
overlapping peaks at 2θ ≈ 24◦ in the powder XRD pattern (asterisks in
Fig. 3A). The impurity has a distinct crystal size and habit (vide infra),
thus the inability to detect this phase in electron micrographs of fully
crystalline zeolite indicates its weight percentage of the total product is
low. The impurity forms prior to zeolite nucleation, even after aging the
growth mixture at room temperature for 24 h where the powder XRD
pattern of extracted solids shows intense peaks relative to the amor­
phous background (see Fig. 4A). We identified the impurity as BaCO3,
5
Microporous and Mesoporous Materials 353 (2023) 112511
which is generated by a carbonation reaction of CO2 from air in contact
with the highly alkaline (pH > 14) harmotome growth mixture. The
BaCO3 peaks in powder XRD patterns are labelled in Fig. 3A, which was
confirmed with a reference pattern (Fig. S1) where peaks at 2θ ≈ 24◦
correspond to the (111) and (021) reflections of BaCO3. Removal of the
impurity post-synthesis is possible by treating the sample with a mild
acid (0.1 M HCl) solution. Analysis of the acid-treated sample by powder
XRD (Fig. 3A) shows complete removal of the impurity. To further
confirm the formation and removal of BaCO3 impurity, we performed
FTIR measurements (Fig. 3B). Comparison of FTIR spectra for a BaCO3
reference with the amorphous precursor extracted from a harmotome
growth mixture after 24-h room temperature aging reveals nearly
identical signatures. Notably, there is a strong absorption peak at 1417
cm− 1, which is assigned to the stretching of CO2−
3 [36]. This peak is also
present in as-synthesized harmotome, but is expectedly absent from the
sample after acid treatment (Fig. 3B). Based on these analyses, we
confirmed that the impurity in harmotome syntheses is BaCO3 and that
its presence can be removed through a facile post-synthesis treatment to
produce a pure zeolite product.
Time-resolved syntheses were performed to determine the duration
Fig. 4. (A) Powder X-ray diffraction patterns of as-
synthesized harmotome samples prepared at 65 ◦ C
and extracted after various time periods of heating.
Two overlapping peaks denoted by the asterisks (*)
are assigned to crystalline BaCO3. (B - E) Scanning
electron micrographs of solids extracted from syn­
thesis mixtures used to prepare harmotome. (B)
Sample after aging the growth mixture for 24 h at
room temperature (RT) where both crystalline BaCO3
(arrow) and partially crystalline harmotome are pre­
sent. Additional images of extracted solids after
heating times of (C) 1 h, (D) 4 h, and (E) 24 h are
provided. All scale bars equal 500 nm.
Y. Liang et al.
of heating that is required to achieve fully-crystalline harmotome and
phillipsite. The initial appearance of BaCO3 impurity observed in pow­
der XRD patterns of harmotome precursors after room temperature (RT)
aging (Fig. 4A, bottom pattern) results in needle-shaped crystals
(Fig. 4B, arrow) within a solid phase that is predominantly comprised of
amorphous aluminosilicates. The habit of BaCO3 crystals agrees with
those reported in studies of witherite nanorods [37]. The presence of the
amorphous phase is not detected in the powder XRD pattern owing to
the strong scattering of Ba, which is a much heavier element than Si and
Al. The fact that amorphous precursors exhibit a spheroidal morphology
that matches that of the final harmotome product also makes it difficult
to determine when crystallization is complete. After 1 h of heating at
65 ◦ C, all Bragg peaks of the harmotome crystal were present in the
powder XRD pattern (Fig. 4A). Heating for 4 h resulted in very little
change to the peak intensities, whereas the high intensities after 24-h of
heating signify a crystalline product. Comparison of scanning electron
microscopy (SEM) images throughout the duration of heating shows
Fig. 5. (A) Powder X-ray diffraction patterns of as-synthesized phillipsite samples prepared at 65 ◦ C and extracted after various time periods of heating: 7, 24, 72,
and 120 h. (B–E) Scanning electron micrographs of solids extracted from growth mixtures used to prepare phillipsite after heating for (B) 7 h, (C) 24 h, (D) 72 h, and
(E) 120 h. Scale bars in all insets are equal to 500 nm.
6
Microporous and Mesoporous Materials 353 (2023) 112511
very little difference in particle size and shape (Fig. 4C–E), and also
reveals the absence of rod-like BaCO3 particles that are clearly evident in
the powder XRD patterns. This suggests that the initial precursors may
undergo a solid-state transformation to harmotome, although direct
evidence of this mechanism is lacking from our ex situ analysis. Such a
process was recently proposed for zeolite FAU using in situ atomic force
microscopy to show that the supernatant solution had no observable role
in crystal growth [38].
Time-resolved analysis of the phillipsite synthesis reveals additional
details of its crystallization. Solids extracted after 7 h of heating appear
to be completely amorphous by XRD analysis (Fig. 5A). The amorphous
peaks are more clearly observed in comparison to those of harmotome
precursors due to the absence of barium. The first Bragg peaks appear
after ca. 24 h of heating; however, these peaks do not match PHI-type
zeolite, but are in excellent agreement with zeolite LTA (Fig. S2). It is
well known that Na+ ions promote LTA-type zeolite at these synthesis
conditions (65 ◦ C, Si/Al = 2.5) [35]. Complete substitution of Na with K
Y. Liang et al.
would result in an entirely different zeolite product [39]. The phillipsite
growth mixture has a ratio of Na/K = 3, which does not suppress LTA
nucleation. As the heating time increases, however, we observe a
LTA-to-PHI interzeolite transformation with Bragg peaks for phillipsite
observed after ca. 72 h of heating (Fig. 5A). We do not observe a fully
crystalline phillipsite product until around 120 h of heating. Comparison
of SEM images at periodic stages of synthesis (Fig. 5B–E) shows pro­
gressive changes in particle size of each phase: amorphous precursors
(Fig. 5B), LTA crystals (Fig. 5C), and phillipsite crystals (Fig. 5E). The
morphology of each phase is much less defined with all products
appearing to be spheroidal.
We examined the sensitivity of harmotome synthesis with respect to
changes in growth mixture composition, using the three principle
components (Si, Al, OH molar fractions) as variables and holding all
other conditions fixed with molar ratios y SiO2: z Al2O3: 2.75 Na2O: 0.25
BaO: 95 H2O. The shaded areas within the ternary reaction diagram
(Fig. 6A) depict regions of a single crystalline phase: yellow corresponds
to harmotome (PHI type) and green corresponds to gismondine (GIS
type). Pure harmotome products are limited to a region spanning 1 < Si/
Al < 4 with bordering regions leading to higher fractions of amorphous
product. Interestingly, zeolite GIS is shown to crystallize at 65 ◦ C
compared to higher temperatures (e.g. 100 ◦ C) reported in literature
[40]. Energy dispersive spectroscopy (EDS) elemental analysis of the GIS
products show evidence of extra-framework Ba2+. The latter could not
be ion exchanged post-synthesis with NH+ 4 at 80 C, which was
◦
confirmed by the identical compositions and powder XRD patterns of
samples before and after three cycles of ion exchange. We posit that Ba2+
functions as an ISDA for the GIS framework and lowers its barrier for
nucleation compared to when Na+ is the sole inorganic cation. The latter
is a conventional ISDA for GIS syntheses but requires a higher temper­
ature (i.e., >80 ◦ C). Zeolite GIS is a similar zeolite framework comprised
of 3-dimensional pores with 8 MR apertures and two composite building
units: gis cages and dcc chains (Fig. S3).
EDS analysis of harmotome also reveals that Na+ and Ba2+ ions are
incorporated in the crystalline product as extra-framework cations (with
Na/Ba = 1.7). All previous experiments of harmotome in this study used
a fixed barium concentration; however, we also investigated the impact
of Ba2+ content on harmotome crystallization by selecting growth
mixtures with molar compositions of 1 SiO2: 0.50 Al2O3: 2.75 Na2O: x
BaO: 95 H2O (with x = 0.1–2.0). Fig. 6B reveals a non-monotonic
relationship between percent crystallinity and the Al/Ba molar ratio of
the synthesis mixture. Under the conditions tested, harmotome exhibits
the highest percent crystallinity when Al/Ba = 4 with reduced harmo­
tome yields achieved at lower and higher Al/Ba ratios. This indicates
that the concentration of barium is critical for harmotome
crystallization.
We assessed whether harmotome is a metastable zeolite that is
7
Microporous and Mesoporous Materials 353 (2023) 112511
subject to interzeolite transformation when increasing the synthesis
temperature to 100 ◦ C and extending the synthesis time to 7 days. This is
commonly observed for other zeolites, such as FAU, which transforms to
GIS when the temperature is increased from 65 to 100 ◦ C and the syn­
thesis time is extended [41]. The ternary reaction diagram in Fig. 7A,
however, shows that higher temperature reduces many (partially-)
amorphous products and preserves the harmotome structure. We begin
to see a reduction in the harmotome region once the water content is
increased (Fig. 7A, top diagram). Surprisingly, a more dilute synthesis
mixture results in the formation of zeolite LTL (or zeolite L) in a region of
the ternary reaction diagram that is highly unusual for this zeolite
structure [42]. To our knowledge, organic-free syntheses of zeolite L
have only been reported in media where K+ ions are the sole ISDA. Here,
we observe zeolite L crystallization in a binary Na+ and Ba2+ growth
mixture. Moreover, zeolite L syntheses are typically reported at much
higher temperatures, suggesting this ISDA combination lowers the bar­
rier for LTL nucleation.
The potential applications for harmotome and any performance ad­
vantages that it may have over phillipsite have yet to be realized. Here
we assess differences in their relative hydrophilicity using thermogra­
vimetric analysis (TGA) to compare the water loss from as-synthesized
samples. Fig. 7B shows that harmotome more strongly binds water
based on a delayed weight reduction (e.g. +46 ◦ C difference). On the
contrary, the presence of extra-framework Ba2+ ions in harmotome re­
duces its water capacity with phillipsite adsorbing 1.1% more water by
weight. Extension of these analyses to gas adsorption using CO2 as a
probe molecule (Fig. S4) showed no differences between the two PHI-
type zeolites; however, future studies may uncover other differences
in physicochemical properties that impact their performance in diverse
applications.
4. Conclusion
In summary, we have used a combination of both alkali and alkaline
earth metals as inorganic structure-directing agents to synthesize PHI-
type zeolites. The selection of Ba2+ was inspired by the natural min­
eral harmotome, which contains this alkaline earth metal as one of
several extra-framework cations. The isostructural counterpart, phil­
lipsite, is prepared with K+ and Na+ as ISDAs. Our findings uncovered a
low-temperature route to prepare harmotome (at 65 ◦ C) wherein the
presence of Ba2+ leads to crystallization 5-times faster than the synthesis
of phillipsite. Our study indicates that harmotome is not formed by
simply replacing a fraction of K+ with Ba2+ cations. On the contrary, the
growth mixture required to synthesize harmotome is more dilute and
alkaline than those used to prepare phillipsite. Moreover, there is a
relatively narrow Al-to-Ba molar ratio of the starting gel that is required
to achieve a purely crystalline harmotome product, whereas purely
Fig. 6. (A) Ternary reaction diagram plotting the
zeolite phase(s) obtained from syntheses at 65 ◦ C
using different molar fractions of Si, Al, and OH− .
Growth mixtures were prepared with an initial molar
composition of x Si: y Al: 11 MOH: 173 H2O (where
M = Na+ and Ba2+ with Na+/Ba2+ = 22). Symbols
correspond to the solid phase(s) detected by powder
XRD after extraction from 168 h of heating at 65 ◦ C.
The circles represent areas of single phases: harmo­
tome (yellow) and GIS (green). Amorphous products
are represented as filled black symbols whereas
partially-amorphous samples are represented by
symbols with varying degrees of black shading
depending on its relative percentage in powder XRD
patterns. (B) Analysis of the nominal harmotome
synthesis mixture prepared with different Al-to-Ba
ratios with the percent crystallinity from powder
XRD patterns showing an optimum Ba concentration
around Al/Ba = 4.
Y. Liang et al.
crystalline phillipsite can be prepared using a broader range of synthesis
conditions.
The physicochemical properties of the two PHI-type zeolites pre­
pared in this study are distinct, despite having similar crystal structures.
Harmotome forms nanosized crystals (56 ± 8 nm) that are nearly 40-
times smaller than the size of phillipsite (2.4 ± 0.3 μm). Both zeolites
have similar Si/Al ratios, but harmotome is slightly more hydrophilic.
From the collective findings in this study, we posit that the composition
(s) of natural zeolite minerals may serve as a guideline for the design of
synthetic analogues; however, the conditions required to successfully
prepare each zeolite may be narrow, as was observed here for harmo­
tome. Given that natural zeolites exhibit a variety of elemental com­
positions that frequently include alkaline earth metals, it is reasonable to
8
Microporous and Mesoporous Materials 353 (2023) 112511
Fig. 7. (A) Ternary reaction diagrams plotting the
zeolite phase(s) obtained from syntheses using
different molar fractions of Si, Al, and OH− . Growth
mixtures were prepared with two different initial
molar ratios: (top) x Si: y Al: 11 MOH: 590 H2O and
(bottom) x Si: y Al: 11 MOH: 173 H2O (where M =
Na+ and Ba2+ with Na+/Ba2+ = 22). Symbols corre­
spond to the solid phase(s) detected in powder XRD
patterns after extraction from their growth mixtures
after 7 days heating at 100 ◦ C. (B) Thermogravimetric
analysis of as-synthesized harmotome (orange) and
phillipsite (black) percent weight loss with increasing
temperature at a heating rate of 5 ◦ C min− 1.
suggest that combinations of ISDAs mimicking natural zeolites could
provide new opportunities to modify the crystal structure and/or
physicochemical properties of synthetic zeolites.
CRediT authorship contribution statement
Yu Liang: Writing – review & editing, Writing – original draft,
Investigation, Formal analysis, Data curation, Conceptualization. Allan
J. Jacobson: Writing – review & editing, Supervision, Funding acqui­
sition, Formal analysis, Conceptualization. Jeffrey D. Rimer: Writing –
review & editing, Writing – original draft, Supervision, Project admin­
istration, Funding acquisition, Conceptualization.
Y. Liang et al.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
JDR acknowledges support primarily from the U.S. Department of
Energy Office of Basic Energy Sciences (Award DE-SC0021384). JDR
and AJJ acknowledge financial support from The Welch Foundation
(Awards E-1794 and E-0024, respectively).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2023.112511.
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