Synthesis of New Microporous Zincosilicates with CHA Zeolite Topology as Efficient Platforms for Ion-Exchange of Divalent Cations

Article abstract of DOI:10.1002/chem.201705277

There is growing interest to develop zeolite materials capable of stabilizing divalent cations such as Cu²⁺, Fe²⁺, and Ni²⁺ for catalytic applications. Herein the synthesis of a new microporous zincosilicate with CHA zeolite topology is reported for the first time, by particularly focusing on the mixing procedures of the raw materials to prevent the precipitation of zinc oxides/hydroxides and the formation of impurity phases. The obtained zincosilicate CHA products possess remarkably higher ion-exchange ability for catalytically useful, divalent cations, demonstrated here using Ni²⁺ as an example, compared to that of aluminosilicate and zincoaluminosilicate analogs. It is anticipated that these zincosilicate CHA materials can be an efficient platform for several important catalytic reactions. In addition, the present finding would provide a general guideline for effective substitution of other heteroatoms into the zeolite frameworks.

Full text of DOI:10.1002/chem.201705277

A Journal of
Accepted Article
Title: Synthesis of a New Microporous Zincosilicate with CHA Zeolite
Topology as Efficient Platforms for Ion-Exchange of Divalent
Cations
Authors: Natsume Koike, Kenta Iyoki, Sye Hoe Keoh, Watcharop
Chaikittisilp, and Tatsuya Okubo
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To be cited as: Chem. Eur. J. 10.1002/chem.201705277
Link to VoR: http://dx.doi.org/10.1002/chem.201705277
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COMMUNICATION
Synthesis of a New Microporous Zincosilicate with CHA Zeolite
Topology as Efficient Platforms for Ion-Exchange of Divalent
Cations
Natsume Koike, Kenta Iyoki, Sye Hoe Keoh, Watcharop Chaikittisilp,* and Tatsuya Okubo*[a]
Abstract: There is growing interest to develop zeolite materials
Divalent cation-exchanged zeolites have recently shown great
promise in several new applications relevant to energy and
environment. For example, Cu - and Fe -exchanged zeolites
have proven to be efficient catalysts for selective catalytic
reduction (SCR) of NO
x
and methane conversions.[6–9] For such
2+
2+
2+
capable of stabilizing divalent cations such as Cu , Fe , and Ni for
catalytic applications. Herein, we describe for the first time the
synthesis of a new microporous zincosilicate with CHA zeolite
topology by particularly focusing on the mixing procedures of the raw
materials to prevent the precipitation of zinc oxides/hydroxides and
the formation of impure phases. The obtained zincosilicate CHA
products possess remarkably higher ion-exchange ability for
2
+
2+
reactions, the local environments of divalent cations remarkably
affect the catalytic activity.[8–11] For example, monocopper sites in
small-pore zeolites were reported to be active sites for SCR of
2+
NO
x
.[7,10] Note that in larger pore zeolites di- and trinuclear metal
catalytically useful, divalent cations, demonstrated here using Ni as
an example, compared to that of aluminosilicate and
zincoaluminosilicate analogs. We anticipate that these zincosilicate
CHA materials can be an efficient platform for several important
catalytic reactions. In addition, the present finding would provide a
general guideline for effective substitution of other heteroatoms into
the zeolite frameworks.
oxo-clusters can also catalyze such reactions through different
catalytic mechanisms.[9,11,12] For aluminosilicate zeolites to
stabilize the active monomeric sites of divalent metals, two Al with
n
close proximity (e.g., Al paired configuration Al–O–(Si–O) –Al (n
= 1, 2) in 6r), are required because isomorphous substitution of
Al(III) for Si(IV) in the zeolite framework generates only one
anionic charge per Al atom.[ On the other hand, isolated Al is
suitable for stabilization of oxo-species of divalent cations, which
are sometimes undesired.[7,14] In addition, isolated Al sites can
13]
Diversification of the framework elements of inorganic framework
materials by heteroatom substitution is of great scientific and
technological significance because the physicochemical
properties of the materials can be substantially altered by such
heteroatoms, thereby providing specific functionality for particular
applications. As one of the representative classes of the inorganic
remain as Brønsted acid sites when counterbalanced by protons
[15]
and hence cause side reactions and catalyst deactivation.
It
was reported that, in the case of high-silica CHA zeolites, the
isolated Al exists dominantly.[16] Although the fraction of paired Al
in the CHA zeolites can be increased by carefully tuning the
synthesis conditions, the density of paired Al cannot be increased
more than that found in zeolites with random Al distribution.[16]
framework
materials,
zeolites,
crystalline
microporous
aluminosilicates, have been indispensable for several
applications as adsorbents, ion-exchangers, separation
membranes and catalysts.[1,2] Recently, small-pore zeolites
defined as the zeolites having the pore openings limited by 8
tetrahedral atoms (8-ring, 8r) have received particular attention
because they have exhibited excellent performance in several
important applications, for example, as catalysts for methanol-to-
olefin (MTO) and ethene-to-propene (ETP) reactions, and as
adsorbents and membranes for gas separations.[3–5] Among
several small pore zeolites, CHA-type zeolite possessing a large
cha cage cavities with 8r openings has been intensively studied.
Both aluminosilicate and silicoaluminophosphate versions of the
CHA materials (i.e., SSZ-13 and SAPO-34, respectively) are
efficient catalysts for MTO and ETP reactions, for which they have
been commercialized or close to be commercialized.[4]
On the contrary, isomorphous substitution of Zn(II) for Si(IV)
in the zeolite framework can generate two anionic charges per Zn
atom, making zincosilicate zeolite-like materials a promising
platform for stabilization of divalent cations.[15] However, a number
of available zincosilicates are quite limited to only few zeolite
frameworks.[17–19] In addition, Zn is easily precipitated as oxides
[20]
or hydroxides in basic media during hydrothermal synthesis,
akin to other metal-substituted zeolite-like materials. Recently,
synthesis of zincoaluminosilicate CHA having both Al and Zn in
their frameworks was reported.[21] In this case, a large amount of
Al is necessary for directing the crystallization of CHA. Still,
synthesis of zincosilicate CHA without any Al in the framework is
desired because framework Al can sometime lead to undesired
side reactions.[15]
Aluminosilicate CHA zeolites naturally occur as a mineral and
can be synthesized without using any organic structure-directing
agent (OSDA) in Al-rich aluminosilicate compositions. The Si-rich
CHA zeolite, known as SSZ-13, was successfully synthesized
[
a]
N. Koike, Dr. K. Iyoki, Dr. S. H. Keoh, Dr. W. Chaikittisilp, Prof. Dr.
T. Okubo
Department of Chemical System Engineering
The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
using
N,N,N-trimethyl-1-adamantylammonium
hydroxide
E-mail: watcha@chemsys.t.u-tokyo.ac.jp
okubo@chemsys.t.u-tokyo.ac.jp
(
TMAdaOH) as an OSDA.[22] Recently, the synthesis of silicate-
based CHA materials has advanced beyond the aluminosilicate
composition to, for example, titanosilicate[23] and stannosilicate,[24]
Supporting information for this article is given via a link at the end of
the document.
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which have been achieved in fluoride media. In their syntheses,
balanced reaction (hydrolysis/dissolution and condensation) rates
of Si source and metal precursors were reported to be of
significance.[23,24]
For the synthesis of zeolite-like materials with Zn in the
frameworks, the formation of the homogeneous mixture of Zn and
Si species is crucial to form the zincosilicate structures while
preventing the precipitation of zinc oxides/hydroxides during
hydrothermal treatment.[25] In the procedure (i), Zn species are
We report herein for the first time the synthesis of a new
microporous zincosilicate with CHA zeolite topology. To prevent
the precipitation of extraframework zinc oxides/hydroxides, we
pay particular attention to the mixing procedures of the raw
materials prior to hydrothermal treatment. For the successful
synthesis of zincosilicate CHA, the initial state of Zn species in a
basic solution is very crucial. In a typical procedure (see
procedure (i) in Figure 1a), lithium hydroxide monohydrate was
dissolved in distilled water and fumed silica was then added to the
solution. After stirring for 2 h, a semitransparent suspension is
obtained. In another vessel, anhydrous zinc acetate was added to
an aqueous solution of TMAdaOH and stirred for 5 min to obtain
a clear solution. The amounts of water in the silica suspension
and the Zn solution are identical. The Zn solution was then added
to the silica suspension and further stirred for 5 min. The molar
−
totally dissolved as [Zn(OH)
4
]2− or [Zn(OH)
3
] in the clear solution
[
26]
because of the high alkalinity of TMAdaOH solution (pH > 14).
+
The negatively charged Zn species can interact with TMAda ,
thereby preventing the precipitation of Zn even in such a highly
alkaline solution. Separately, fumed silica particles are dispersed
in the LiOH solution, yielding a semitransparent suspension (pH
12.5). When the Zn solution is mixed with the silica suspension,
pH of the mixture drops to ca. 13, in which the solubility of Zn
decreases.[26] Similar to aluminosilicates,[27] we surmise that the
dissolved Zn species react with dissolved silicate, forming
zincosilicate, and/or precipitate on the surface of dispersed silica
particles. As a result, Zn and Si species are well mixed before
hydrothermal treatment. In the procedure (ii), fumed silica is not
dispersed beforehand; therefore, when it is added to the Zn
solution, the reactions between dissolved Zn species and silica
are restricted only at the external surface of agglomerated silica
particles. The large amount of the unreacted silica would hence
lead to the formation of layered silicate after hydrothermal
treatment.
ratio of the final mixture was SiO
2
: 0.03 ZnO: 0.42 TMAdaOH:
0
.08 LiOH: 30 H O. After hydrothermal treatment at 150 °C under
2
a static condition for a week, a highly crystalline CHA product was
obtained, hereafter referred to as Zn-CHA1 (Figure 1b).
To further explain the difference between the procedures (i)
and (ii), the intermediate products during hydrothermal treatment
were recovered and characterized by UV-vis spectroscopy. As
shown in Figure 2, only the product prepared via the procedure
(
ii) collected after 2 days exhibited a marked absorption band at
2
−
2+
around 360 nm, assigned to the O →Zn ligand-to-metal charge
transfer transition in ZnO. The ZnO observed in the initial stage is
probably due to the formation of Zn-rich species precipitated apart
from the silicate species in the procedure (ii).
Figure 1. (a) Schemes of mixing procedures of synthetic mixtures prior to
hydrothermal treatment (see experimental details in the Supporting Information).
(b) Powder XRD patterns of products obtained via different mixing procedures
(i)–(iv) after hydrothermal treatment at 150 °C for 7 days under a static condition.
Interestingly, when the synthetic mixtures were prepared in
different ways (procedures (ii)–(iv) in Figure 1a), the products
were either amorphous solid or the mixture of layered silicate and
CHA (see Figure 1b). Figure S2 in the Supporting Information
shows SEM images of the product obtained from the different
procedures (i)–(iv). The CHA product obtained from the
procedure (i) was uniform, cubic particles with a size of ca. 6 μm.
On the other hand, the layered material-like particles were
observed in the product prepared by the procedure (ii) with only a
small portion of cubic particles. For the procedure (iii), irregularly
shaped particles, likely amorphous solid, were observed without
any cubic particles. The product obtained from the procedure (iv)
was the mixture of layered materials and cubic zeolite-like
particles.
Figure 2. DR UV-Vis spectra of products collected after hydrothermal treatment
at 150 °C for (a) 2 and (b) 7 days following procedures (i) and (ii).
In the procedure (iii), ZnO is formed immediately after addition
of zinc acetate into the LiOH solution (pH 13), confirmed by XRD
measurement (data not shown), because the solubility of Zn is
[26,28]
somewhat low at this pH.
As a result, the reactions between
Zn and Si species are limited. The procedure (iv) provides a
weakly acidic, clear aqueous solution of Zn, in which Zn is present
in the cationic Zn2+ form. When the acidic Zn solution is added to
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COMMUNICATION
the highly basic silica suspension (pH > 14), Zn is precipitated
readily because of the rapid change in pH, yielding the
inhomogeneous mixture of Zn and Si species. As a result, layered
silicate and CHA are formed after hydrothermal treatment.
The incorporation of Zn into the zeolite framework was
confirmed by the peak shifting toward lower angles in XRD
patterns, compared to pure silica CHA (Figure 3). By assuming all
As shown in Figure S3 in the Supporting Information, by
applying the successful procedure (i), effect of the types of alkali
metal cation was investigated. When LiOH was replaced by
NaOH or KOH, the CHA product was not obtained, even with the
̅
products possess the same space group of R 3 m, the cell
parameters were calculated to be a = b = 13.49 Å and c = 14.82
Å for pure silica CHA (Rwp = 0.109, R
p
= 0.0854), and a = b =
= 0.0857).
13.55 Å and c = 14.97 Å for Zn-CHA1 (Rwp = 0.116, R
p
2
addition of seed crystals (pure silica CHA, 5 wt% based on SiO ).
As the Zn–O bond length (ca. 2 Å) is longer than the Si–O (ca. 1.6
Å), the lattice expansion clearly suggests the successful formation
of CHA products with Zn in the framework.
In the absence of alkali metal cation, the CHA product was formed
together with layered silicate when the seed crystals were added,
while no crystalline product was observed without seed addition.
+
These results suggest the important role of Li on the formation of
zincosilicate CHA, akin to the previous reports of zincosilicate
*
BEA and VET zeolite-like materials.[20,29]
Several synthetic parameters were examined to obtain
zincosilicate CHA with varied Zn contents. As shown in Figure S4
in the Supporting Information, when the amount of Zn in the
synthetic mixture was decreased to Si/Zn = 40, distinct XRD peak
from layered silicate was observed, while peaks from CHA
structure were hardly seen. However, when pure silica CHA was
added as seed crystals, the formation of CHA product was
confirmed at Si/Zn = 40. When the amount of Zn was further
decreased to Si/Zn = 50, however, highly crystalline CHA product
was not formed. Given the targeted use of zincosilicates for
stabilization of multivalent cations, the Zn content in the synthetic
mixture was also increased. The formation of CHA product was
observed together with the unknown phase both with and without
seed crystals when Si/Zn = 25. The formation of such impurity can
be suppressed by carrying out the hydrothermal treatment under
a tumbling condition (see Figure S5 in the Supporting Information).
Figure 3. Comparison of powder XRD patterns of CHA products with various
Zn contents.
As reported recently, zincosilicate zeolite-like materials show
strong Lewis acidity.[25,30,31] FT-IR analysis of Zn-CHA2 after
adsorption of deuterated acetonitrile (CD CN) at 80 °C and then
3
Chemical compositions of the selected products are
summarized in Table 1. The molar Si/Zn ratios of the CHA
products were lower than those of the initial synthetic mixture,
especially in the case of Zn-CHA1, which is likely because the
solid product had low yield due to the absence of seed crystals.
Nitrogen physisorption analysis confirms that all of the obtained
zincosilicates had high micropore volumes. Thermogravimetric
desorbed at 80–250 °C was performed to characterize its Lewis
acid sites in comparison with zincoaluminosilicate CHA[21] (Zn,Al-
CHA; Si/Al = 10.5, Si/Zn = 15.3) (see Figures S8 and S9, and
Table S1 in the Supporting Information). As shown in Figure S7a
in the Supporting Information, the absorption band due to
+
analysis shows that about 2.8 TMAda cations were occluded in
−
1
+
3
physisorbed CD CN was observed at 2267 cm , while the band
a unit cell of CHA structure, equivalent to 0.93 TMAda per cha
−
1
at ca. 2284 cm is probably associated with Li-bearing Zn
sites.[ The bands present at 2308 and 2319 cm−1 are associated
cage (Figure S6 in the Supporting Information). Note that the
30]
+
sharp weight loss due to TMAda cation was not observed in the
with CD
3
CN coordinated to Lewis acid sites.[25,30] The existence of
product synthesized by the procedure (ii).
these two absorption bands suggests that there were two different
Lewis acid sites in the zincosilicate CHA product, as the metal-
substituted zeolite-like materials are known to have different
metal sites, so-called “closed” and “open” sites (see Scheme
Table 1. Chemical compositions, solid yields and micropore volumes of the
obtained zincosilicate CHA products.
1 [
).
30–33]
The closed Zn site (observed at 2308 cm ) creating two
−1
[
a]
[c]
[d]
Sample
Seed
wt%]
Condition
Reactant
Si/Zn
Product
Yield
[%]
V
micro
3
negative charges is suitable for stabilization of bare divalent metal
[
b]
−1
[
Si/Zn
[cm
g
]
[15,25]
−1
cations,
while the open Zn site (observed at 2319 cm ), a
Zn-CHA1
Zn-CHA2
Zn-CHA3
0
5
5
Static
33
25
20
12.8
18.2
14.5
47
63
70
0.24
0.25
0.25
monocation ion-exchangeable site, has been considered as an
active Lewis acid.[30,31] The Zn,Al-CHA sample also showed
similar spectra; however, the band assigned to the Li-bearing
20 rpm
20 rpm
−
1
−1
sites at 2284 cm observed in Zn-CHA2 was shifted to 2277 cm ,
[a] Pure silica CHA. [b] Determined by ICP-AES. [c] Calculated based on
+
oxides. [d] Micropore volumes calculated by a t-plot method.
which is likely associated with Na present in the Zn,Al-CHA
sample (see Figure S7b in the Supporting Information).[ While
30]
in the case of relating stannosilicates (well known as a Lewis acid
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10.1002/chem.201705277
COMMUNICATION
+
catalyst), most of adsorbed CD
3
CN is desorbed upon evacuation
zeolite due to the high charge density of TMAda employed for its
at room temperature,[32] in both Zn-containing CHA samples
synthesis.[16] As a result, the SSZ-13 sample used here is not
suitable for ion-exchange of divalent cations. On the contrary, the
zincosilicate CHA products exhibited higher ion-exchange
efficiency (80% and 62% after 96 h for Zn-CHA1 and Zn-CHA2,
respectively) despite the fact that the zincosilicate CHA products
have comparable substitution contents to that of aluminosilicate
SSZ-13 (i.e., similar Si/Zn and Si/Al ratios). The
zincoaluminosilicate CHA[21] has intermediate ion-exchange
efficiency (39% after 96 h), suggesting that Zn in the
3
CD CN remains on samples even after evacuation at 250 °C,
suggesting the stronger Lewis acidity of zincosilicate materials.
2
+
zincoaluminosilicate framework can stabilize Ni , while the
content of the paired Al sites is insufficient for the divalent cation-
exchange.
Scheme 1. Local structures of two different Zn sites: (a) closed site and (b) open
site (M+ is a monovalent cation).
FT-IR spectra of Zn-CHA2 before and after ion-exchange with
Ni2+ are depicted in Figure S10 in the Supporting Information. The
−
1
disappearance of the broad band centered at 3630 cm ,
presumably assigned to the bridging SiOHZn groups, after ion-
The ion-exchange ability of the zincosilicate CHA products
was investigated for both monovalent and divalent cations in
comparison with aluminosilicate (SSZ-13; Si/Al = 13.2) and
zincoaluminosilicate[21] (Zn,Al-CHA) CHA materials (see Figures
2
+
exchange confirmed the ion-exchange from protons to Ni . In
addition, no marked absorption band due to the Ni–OH vibration,
−
1 [35]
typically appearing at around 3640 cm ,
was observed,
+
suggesting that no significant amount of Ni(OH) species was
formed after ion-exchange. Effect of thermal treatment on the
environment of Ni2 species was investigated. After ion-exchange
for 96 h, DR UV-vis spectra of the Ni -exchanged Zn-CHA2
Ni/Zn = 0.62) and Zn,Al-CHA (Ni/(Zn+0.5Al) = 0.39) samples
+
S8 and S9, and Table S1 in the Supporting Information). K and
Ni2+ cations were used as model monovalent and divalent cations,
respectively. As shown in Figure 4a, the aluminosilicate SSZ-13
zeolite reached 86% ion-exchange efficiency after 48 h. In
contrast, the zincosilicate CHA products exhibited slower ion-
exchange rate and the ion-exchange efficiency became 31% for
Zn-CHA1 (Si/Zn = 12.8) and 52% for Zn-CHA2 (Si/Zn = 18.2) after
+
2
+
(
2
+
showed characteristic absorption bands correlated to Ni cations
in octahedral symmetry,[
36]
suggesting the presence of
2 6
O)
]2+ complexes in the samples (Figure S11a in the
[
Ni(H
Supporting Information). After thermal treatment under dried air at
00 °C for 6 h, both Zn-CHA2 and Zn,Al-CHA samples exhibited
48 h. Note that the ion-exchange efficiency was calculated by
assuming that all Zn in the framework generate two negative
charges per Zn atom (i.e., closed Zn sites). This slower rate may
be due to the larger particle sizes of the zincosilicate CHA
products and the structure constrain arising from the high density
of the negative charges in the structures
6
additional bands at around 260 nm (Figure S11b in the Supporting
Information), attributed to an electronic transition with charge
transfer (CT) in NiO.[37] The position of this O →Ni CT band is
related to the degree of agglomeration of NiO species (note that
the CT band for bulk NiO is observed at 320 nm).[ The blue shift
of this band observed in both samples suggests the formation of
small NiO clusters.[37] The band observed in Zn,Al-CHA was
stronger than that in Zn-CHA2 and had a broad shoulder between
2−
2+
37]
260 and 350 nm, suggesting the higher degree of NiO
agglomeration (i.e., larger clusters). Collectively, these results
suggest that the zincosilicate CHA products were superior to the
aluminosilicate and zincoaluminosilicate counterparts for ion-
2
+
exchange and stabilization of divalent cations such as Ni .
In summary, microporous zincosilicate CHA materials were
synthesized for the first time with a particular focus on the mixing
procedures of the raw materials, yielding CHA products with
varied Zn contents (Si/Zn = 12.8–18.2). Control of the initial state
of Zn species was found to be very crucial to prevent the
precipitation of zinc oxides/hydroxides, the formation of
extraframework Zn species, and the formation of impure phases.
The obtained zincosilicate CHA products possessed remarkably
higher ion-exchange ability for divalent cations, demonstrated
Figure 4. Contents of ion-exchange versus time of (a) K+ and (b) Ni2+ cations
for zincosilicate, aluminosilicate (SSZ-13) and zincoaluminosilicate CHA
samples.
The benefit of Zn in the zeolite framework for ion-exchange of
divalent cations was demonstrated using Ni2+ because Ni2+-
exchanged zeolites and zeolite-like materials are promising
catalysts for dimerization and oligomerization of olefins.[15,34] As
shown in Figure 4b, the SSZ-13 sample showed very low ion-
exchange efficiency (only 6% after 96 h). The formation of the
2
+
using Ni , compared to that of aluminosilicate and
zincoaluminosilicate counterparts.
paired Al sites is known to be unfavorable in the case of SSZ-13 Acknowledgements
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Chemistry - A European Journal
10.1002/chem.201705277
COMMUNICATION
Entry for the Table of Contents
Layout 1:
COMMUNICATION
Catching Two Charges. Microporous
zincosilicates with CHA topology are
synthesized for the first time with a
particular focus on the mixing
N. Koike, K. Iyoki, S. H. Keoh, W.
Chaikittisilp,* T Okubo*
Page No. – Page No.
procedures of the raw materials. The
resulting zincosilicate materials show
remarkably high ion-exchange ability
for divalent cations, compared to their
aluminosilicate and
Synthesis of a New Microporous
Zincosilicate with CHA Zeolite
Topology as Efficient Platforms for
Ion-Exchange of Divalent Cations
zincoaluminosilicate analogs.
This article is protected by copyright. All rights reserved.