Coupling Different Periodic Building Units for Intergrowth Zeolites.

Multiple-phase disordered zeolites, i.e., intergrowth zeolites, are important industrial catalysts, like single-phase ordered zeolites, but little is known about their rational synthesis and phase competition, mainly due to current poor understanding of the zeolite crystallization mechanism. Here, we theoretically demonstrated that sodalite and cancrinite cage layers, the periodic building units (PerBUs) of FAU/EMT and SBT/SBS structures, respectively, could be nondefectively connected to each other across double rings of 6 tetrahedral atoms when inverted and mirrored. We then synthesized an unprecedented family of FAU/SBT/SBS intergrowths with controllable FAU portions (named as the PST-34 family of intergrowth zeolites) using a multiple inorganic cation approach, providing clear experimental evidence for the layer-by-layer crystal growth mechanism of zeolites. This study shows that control of interactive cooperation extent between different inorganic structure-directing agents in the presence of an unselective organic structure-directing agent may enable repeated stacking of different but structurally related PerBUs in intergrowth zeolite synthesis.

Hydrothermal Aging Enhances Nitrogen Oxide Reduction over Iron-Exchanged Zeolites at 150 °C.

Ammonia selective catalytic reduction (NH3-SCR) over copper- and iron-exchanged zeolites is a state-of-the-art technology for removal of nitrogen oxides (NOx, NO, and NO2) from exhaust emissions but suffers from poor low-temperature (i.e., 150 °C) activity. Here we show that hydrothermal aging of Fe-beta, Fe-ZSM-5, and Fe-ferrierite at 650 °C or higher leads to a remarkable increase in NOx conversion from ∼30 to ∼80% under fast NH3-SCR conditions at 150 °C. The practical relevance of this finding becomes more evident as an aged Fe-beta/fresh Cu-SSZ-13 composite catalyst exhibits ∼90% conversion. We propose that a neutral heteronuclear bis-µ-oxo ironaluminum dimer might be created within iron zeolites during hydrothermal aging and catalyze ammonium nitrate reduction by NO at 150 °C. Density functional theory calculations reveal that the activation free energy (125 versus 147 kJ mol-1) for the reaction of NO with adsorbed NO3- species, the rate-determining step of ammonium nitrate reduction, is considerably lower on the bis-µ-oxo ironaluminum site than on the well-known mononuclear iron-oxo cation site, thus greatly enhancing the overall SCR activity.

Unveiling the Structural Characteristics of Intergrowth Zeolites Synthesized in the Presence of Isopropylimidazolium-Based Cations and Fluoride Anions.

Here, we present the synthesis of RTH/ITE and MEL/MFI intergrowth zeolites using 2-isopropylimidazolium-based cations as organic structure-directing agents (OSDAs) in concentrated fluoride media and their local structural properties. Phase selectivity in the synthesis of zeolite intergrowths was found to differ according to the concentration of OSDA cations and fluoride anions in the synthesis mixture as well as to the type of OSDA employed. Molecular modeling results suggest that the crystallization of intergrowth zeolites in fluoride media may be kinetically rather than thermodynamically controlled, as in ordered zeolites. Cs-corrected STEM analysis of MEL/MFI crystals synthesized at HF/OSDA = 2.0 in the presence of 2-isopropyl-1,3-dipropylimidazolium ions as an OSDA indicates the existence of previously unobserved MEL-MFI intergrowth along the [100] direction, leading to a partial blockage of MEL 10-ring channels.

Highly Cooperative CO2 Adsorption via a Cation Crowding Mechanism on a Cesium-Exchanged Phillipsite Zeolite.

An understanding of the CO2 adsorption mechanisms on small-pore zeolites is of practical importance in the development of more efficient adsorbents for the separation of CO2 from N2 or CH4 . Here we report that the CO2 isotherms at 25-75 °C on cesium-exchanged phillipsite zeolite with a Si/Al ratio of 2.5 (Cs-PHI-2.5) are characterized by a rectilinear step shape: limited uptake at low CO2 pressure (PCO2 ) is followed by highly cooperative uptake at a critical pressure, above which adsorption rapidly approaches capacity (2.0 mmol g-1 ). Structural analysis reveals that this isotherm behavior is attributed to the high concentration and large size of Cs+ ions in dehydrated Cs-PHI-2.5. This results in Cs+ cation crowding and subsequent dispersal at a critical loading of CO2 , which allows the PHI framework to relax to its wide pore form and enables its pores to fill with CO2 over a very narrow range of PCO2 . Such a highly cooperative phenomenon has not been observed for other zeolites.

Interplay between copper redox and transfer and support acidity and topology in low temperature NH3-SCR.

Low-temperature standard NH3-SCR over copper-exchanged zeolite catalysts occurs on NH3-solvated Cu-ion active sites in a quasi-homogeneous manner. As key kinetically relevant reaction steps, the reaction intermediate CuII(NH3)4 ion hydrolyzes to CuII(OH)(NH3)3 ion to gain redox activity. The CuII(OH)(NH3)3 ion also transfers between neighboring zeolite cages to form highly reactive reaction intermediates. Via operando electron paramagnetic resonance spectroscopy and SCR kinetic measurements and density functional theory calculations, we demonstrate here that such kinetically relevant steps become energetically more difficult with lower support Brønsted acid strength and density. Consequently, Cu/LTA displays lower Cu atomic efficiency than Cu/CHA and Cu/AEI, which can also be rationalized by considering differences in their support topology. By carrying out hydrothermal aging to eliminate support Brønsted acid sites, both CuII(NH3)4 ion hydrolysis and CuII(OH)(NH3)3 ion migration are hindered, leading to a marked decrease in Cu atomic efficiency for all catalysts.

Synthesis and structure of the medium-pore zeolite PST-35 with two interconnected cages of unusual orthorhombic shape.

The search for new zeolite structures and compositions remains important in synthetic materials science due to the high impact on developing new chemical technologies, as well as on improving existing ones. Herein we present the synthesis and structure of PST-35, a novel medium-pore germanosilicate (Si/Ge = 2.1-6.6) zeolite, achieved by combining the excess fluoride approach and the unique structure directing ability of Ge in the presence of 1,2,3-triethylimidazolium ions as an organic structure-directing agent. PST-35 contains a zig-zag 10-ring (4.6 × 6.7 Å) channel system constructed of strictly alternating large 28-hedral ([48·58·68·82·102]) and smaller 18-hedral ([46·54·64·82·102]) cages of anomalous orthorhombic shape. The PST-35 structure is built from the connection of pst-35 layers consisting of small 8-hedral ([43·54·6]) cages, previously unobserved zeolite building layers, through single 4-rings.

Hydrogen-Bonded Water-Aminium Assemblies for Synthesis of Zeotypes with Ordered Heteroatoms.

Water plays a central role in the crystallization of a variety of organic, inorganic, biological, and hybrid materials. This is also true for zeolites and zeolite-like materials, an important class of industrial catalysts and adsorbents. Water is always present during their hydrothermal synthesis, either with or without organic species as structure-directing agents. Apart from its role as a solvent or a catalyst, structure direction by water in zeolite synthesis has never been clearly elucidated. Here, we report the crystallization of phosphate-based molecular sieves using rationally designed, hydrogen-bonded water-aminium assemblies, resulting in molecular sieves exhibiting the crystallographic ordering of heteroatoms. We demonstrate that a 1:1 assembly of water and diprotonated N,N-dimethyl-1,2-ethanediamine acts as a structure-directing agent in the synthesis of a silicoaluminophosphate material with phillipsite (PHI) topology, using SMARTER crystallography, which combines single-crystal X-ray diffraction and nuclear magnetic resonance spectroscopy, as well as ab initio molecular dynamics simulations. The molecular arrangement of the hydrogen-bonded assembly matches well with the shape and size of subunits in the PHI structure, and their charge distributions result in the strict ordering of framework tetrahedral atoms. This concept of structure direction by water-containing supramolecular assemblies should be applicable to the synthesis of many classes of porous materials.

Synthesis and Crystal Growth Mechanism of PST-2: An Aluminosilicate SBS/SBT Zeolite Intergrowth.

The synthesis of PST-2, an aluminosilicate zeolite intergrowth of cage-based, large-pore SBS and SBT topologies, and its intergrowth characteristics are presented. With the Si/Al ratio and crystallization inorganic structure-directing agent in zeolite synthesis mixtures fixed to 8.0 and Cs+ ions, respectively, pure PST-2 is obtained at 120 °C using tetraalkylammonium ions with C/N+ ratios of 5-9 as a charge density mismatch (CDM) organic structure-directing agent (OSDA). More interestingly, the intergrowth ratio between SBS and SBT in PST-2 was found to vary notably not only with the type of CDM OSDA employed but also with the crystallization time, unlike the case of other well-known zeolite intergrowths such as ß and MFI/MEL. When tetraethylammonium ions are used as a CDM OSDA at 100 °C in the presence of Cs+, the SBS portion in PST-2 decreases from over 60% to less than 45% with increasing crystallization time from 2.5 to 14 days, suggesting that SBS formation is kinetically more favorable than SBT formation. A thorough characterization of changes in the crystallite dimension of PST-2 with crystallization time, together with those in the chemical composition, allowed us to propose a plausible crystal growth mechanism of this large-pore zeolite intergrowth.

Identifying Crystallographically Different Si-OH-Al Brønsted Acid Sites in LTA Zeolites.

A clear understanding of the acidic properties of bridging Si-OH-Al groups containing crystallographically different oxygen atoms in zeolites is a prerequisite for optimizing their performance as industrial solid catalysts and developing new acid-catalyzed reactions, but presents many challenges. Here, we report the direct observation of yet unrecognized bridging Si-OH-Al groups in the LTA zeolite whose oxygen atoms are crystallographically different from those of already known Brønsted acid sites. We also report that the creation of a crystallographically particular type of bridging OH groups in zeolites and its concentration and acid strength can vary strongly with the content and spatial distribution of framework Al atoms, thus being synthetic in nature, which has been rationalized in terms of the secondary building unit concept.

An intrinsic synthesis parameter governing the crystallization of silico(zinco)aluminophosphate molecular sieves.

One of the most fundamental but yet unanswered questions in the synthesis of zeolites and zeolite-like materials is whether or not any parameter controlling the microporosity of the crystallized product from synthesis mixtures with feasible chemical compositions exists. Here we report that an experimentally optimized parameter (ca. 3.3 ≤ MOH/P2O5 ≤ 5.3, where M is alkali metal ions) is the criterion bringing about the successful formation of various high-charge-density silicoaluminophosphate (SAPO) and zincoaluminophosphate (ZnAPO) molecular sieves, without the aid of organic structure-directing agents. The materials obtained using this empirical concept include SAPO molecular sieves with CHA and LTA topologies, as well as a SAPO FAU/EMT intergrowth, and ZnAPO ones with CZP and SOD topologies. This study demonstrates the existence of an essential factor determining not only phase selectivity but also microporosity (0.3-2 nm) in the synthesis of zeotypes with charged frameworks which may offer interesting opportunities for more efficiently producing novel zeolite structures and/or compositions.

Synthesis of thermally stable SBT and SBS/SBT intergrowth zeolites.

UCSB-6 (framework type SBS) and UCSB-10 (SBT), two three-dimensional phosphate-based molecular sieves with supercages accessible through 12-ring (circumscribed by 12 tetrahedral atoms) windows, are structurally similar to the hexagonal and cubic polytypes of faujasite or zeolite Y, an industrially relevant catalyst, but the cage structures are substantially different. Nonetheless, their inherent thermal instability has precluded any catalytic application so far. By using multiple inorganic cation and charge density mismatch approaches, we synthesized PST-32 and PST-2, a thermally stable aluminosilicate version of UCSB-10 and the hypothetical SBS/SBT intergrowth family member, respectively. This study suggests that many hypothetical cage-based zeolite structures with multidimensional channel systems can be synthesized as compositionally robust forms by systematically exploring the synergy effect of inorganic and organic structure-directing agents.

The Origin of Selective Adsorption of CO2 on Merlinoite Zeolites.

The CO2 adsorption behavior at 25-75 °C and 0-1.0 bar of various alkali cation-exchanged forms of merlinoite (framework type MER) zeolites with Si/Al=2.3 and 3.8 is described. The adsorption isotherms at 25 °C on the Na+ , K+ , Rb+ , and Cs+ forms of MER zeolite with Si/Al=2.3 are characterized by a clear step, the CO2 pressure of which differs notably according to the type of their extraframework cations. Structural analysis shows that CO2 adsorption on the former three zeolites includes the relocation of gating cations with high site occupancy and the remarkable concomitant structural breathing. We define this unusual adsorption phenomenon as a cooperative cation gating-breathing mechanism. The overall results suggest that the actual mechanism of selective CO2 adsorption on intermediate-silica small-pore zeolites can change from cation gating to cooperative cation gating-breathing to breathing, depending on a combination of their topological and compositional flexibilities.

An Aluminosilicate Zeolite Containing Rings of Tetrahedral Atoms with All Odd Numbers from Five to Eleven.

Herein we report the synthesis, structure solution, and catalytic properties of PST-31, which has an unprecedented framework topology. This high-silica (Si/Al=16) zeolite was synthesized using a pyrazolium-based dication with a tetramethylene linker as an organic structure-directing agent (OSDA) in hydroxide media. The PST-31 structure is built from new building layers containing four-, five-, six-, and seven-membered rings, which are connected by single four-membered rings in the interlayer region to form a two-dimensional pore system. Its channels consist of [4.56 .6.9.11] and [5.6.7.9.10.11] cavities and are thus delimited by nine-, ten-, and eleven-membered rings. The OSDA cations in as-synthesized PST-31 were determined to reside without disorder in the large [42 .514 .64 .72 .94 ] cavities composed of smaller [4.56 .6.9.11] and [5.6.7.9.10.11] ones, leading to a symmetry coincidence between the OSDA and the surrounding zeolite cavity. The proton form of PST-31 was found to be selective for the cracking of n-hexane to light olefins.

3D-3D topotactic transformation in aluminophosphate molecular sieves and its implication in new zeolite structure generation.

Zeolites have unique pore structures of molecular dimensions and tunable compositions, making them ideal for shape selective catalysis and separation. However, targeted synthesis of zeolites with new pore structures and compositions remains a key challenge. Here, we propose an approach based on a unique 3D-3D topotactic transformation, which takes advantage of weak bonding in zeolites. This is inspired by the structure transformation of PST-5, a new aluminophosphate molecular sieve, to PST-6 by calcination. The structure of nano-sized PST-5 crystals is determined by 3D electron diffraction. We find that the 3D-3D topotactic transformation involves two types of building units where penta- or hexa-coordinated Al is present. We apply this approach to several other zeolite systems and predict a series of new zeolite structures that would be synthetically feasible. This method provides a concept for the synthesis of targeted zeolites, especially those which may not be feasible by conventional methods.

PST-24: A Zeolite with Varying Intracrystalline Channel Dimensionality.

Herein we report the synthesis, structure solution, and catalytic properties of PST-24, a novel channel-based medium-pore zeolite. This zeolite was synthesized via the excess fluoride approach. Electron diffraction shows that its structure is built by composite cas-zigzag (cas-zz) building chains, which are connected by double 5-ring (d5r) columns. While the cas-zz building chains are ordered in the PST-24 framework, the d5r columns adopt one of two possible arrangements; the two adjacent d5r columns are either at the same height or at different heights, denoted arrangements S and D, which can be regarded as open and closed valves that connect the channels, respectively. A framework with arrangement D only has a 2D 10-ring channel system, whereas that with arrangement S only contains 3D channels. In actual PST-24 crystals, the open and closed valves are almost randomly dispersed to yield a zeolite framework where the channel dimensionality varies locally from 2D to 3D.

Colloidal Porous AuAg Alloyed Nanoparticles for Enhanced Photoacoustic Imaging.

Colloidal porous AuAg alloyed nanoparticles (pAuAgNPs) were synthesized by galvanic replacement reaction from Ag nanocubes. pAuAgNPs have a 50 nm exterior diameter and half of their inner space consists of voids that have a bimodal size distribution with peaks at 21 and 8.3 nm. pAuAgNPs showed a plasmonic peak at 750 nm, which was exploited for photoacoustic (PA) imaging. Gold nanorods (AuNRs) were prepared and used as the control; they have a strong plasmonic peak at 720 nm. In in vitro experiments at respective plasmonic peak excitations, pAuAgNPs gave stronger PA signals than AuNRs by 8.9 times per particle and 11.7 times per dosage by exogenous atom. The high surface area per volume as a result of the inner voids amplified the PA signals by efficient thermoacoustic conversion. In experiments of chicken-tissue phantoms, pAuAgNPs showed PA signals through 4.5 cm thick tissue, whereas AuNRs gave no detectable signal. In whole-body in vivo experiments, pAuAgNPs injected into the body showed 2.7 times stronger PA signals than AuNRs. Coating the pAuAgNPs with a silica layer additionally increased their PA signal by 1.8 times when compared to the uncoated ones.

Targeted Synthesis of a Zeolite with Pre-established Framework Topology.

Given their great potential as new industrial catalysts and adsorbents, the search for new zeolite structures is of major importance in nanoporous materials chemistry. However, although innumerable theoretical frameworks have been proposed, none of them have been synthesized by a priori design yet. We generated a library of diazolium-based cations inspired from the organic structure-directing agents (OSDAs) recently reported to give two structurally related zeolites (PST-21 and PST-22) under highly concentrated, excess-fluoride conditions and compared the stabilization energies of each OSDA cation in ten pre-established hypothetical structures. A combination of the ability of the OSDA selected in this way with the excess-fluoride approach has allowed us to crystallize PST-30, the targeted aluminosilicate zeolite structure. We anticipate that our approach, which aims to rationally couple computational predictions of OSDAs with an experimental setup, will advance further development in the synthesis of zeolites with desired properties.

Phase Transformation Behavior of a Two-Dimensional Zeolite.

Understanding the molecular-level mechanisms of phase transformation in solids is of fundamental interest for functional materials such as zeolites. Two-dimensional (2D) zeolites, when used as shape-selective catalysts, can offer improved access to the catalytically active sites and a shortened diffusion length in comparison with their 3D analogues. However, few materials are known to maintain both their intralayer microporosity and structure during calcination for organic structure-directing agent (SDA) removal. Herein we report that PST-9, a new 2D zeolite which has been synthesized via the multiple inorganic cation approach and fulfills the requirements for true layered zeolites, can be transformed into the small-pore zeolite EU-12 under its crystallization conditions through the single-layer folding process, but not through the traditional dissolution/recrystallization route. We also show that zeolite crystal growth pathway can differ according to the type of organic SDAs employed.

Combined Alkali-Organoammonium Structure Direction of High-Charge-Density Heteroatom-Containing Aluminophosphate Molecular Sieves.

The charge density mismatch concept was applied to the synthesis of high-charge-density silicoaluminophosphate SAPO-69 (OFF) and SAPO-79 (ERI) and zincoaluminophosphate PST-16 (CGS), PST-17 (BPH), PST-19 (SBS), and ZnAPO-88 (MER) molecular sieves. Combined alkali-organoammonium structure direction in these systems is thus enabled. Structure direction is treated from the perspective of stabilizing an ionic framework, the relationships between reaction charge density (OH- /H3 PO4 ), alkali and organoammonium content, and ionicity of tetrahedral framework atoms in successful structure direction are presented.

Rediscovery of the Importance of Inorganic Synthesis Parameters in the Search for New Zeolites.

Zeolites and related crystalline microporous materials with cavities and channels of molecular dimensions are of major importance for applications ranging from ion-exchange to adsorption and to catalysis. Because their unique shape-selective properties are closely related to the size, shape, and dimensionality of the intracrystalline channels and cavities, much interest has been devoted to the discovery of novel zeolitic materials over the last several decades. As a result, a dramatic expansion in the structural domain of crystalline microporous materials, as well as in their compositional range, has been achieved. This is largely due to the development of innovative synthetic strategies, for example, organic structure-directing agent (OSDA) design, introduction of heteroatoms like Ge in OSDA-mediated zeolite synthesis, topotactic transformation of two-dimensional layered zeolite precursors, assembly-disassembly-organization-reassembly method, etc. However, although many of these methodologies are quite successful in finding unprecedented zeolite structures, the resulting materials tend to be (hydro)thermally unstable and are often commercially impractical from a manufacturing perspective because of the high cost of the OSDA and/or heteroatom employed. Therefore, we focused on inorganic synthesis parameters as the key phase selectivity factor that has received relatively little attention in the search for new industrially relevant zeolites. This Account describes our recent efforts to find previously undiscovered aluminosilicate zeolites by boosting the roles of inorganic structure-directing agents (ISDAs) in the presence of OSDAs. They include the multiple inorganic cation and excess fluoride approaches, which aim to promote a synergistic cooperation between ISDAs and/or OSDAs and thus to hold a rational design concept, although the latter is not friendly to the practical zeolite manufacturing process due to the toxicity of fluoride. Using these two approaches, we were able to synthesize not only the second generation (PST-29) and four higher generations (PST-20 (RHO-G5), PST-25 (RHO-G6), PST-26 (RHO-G7), and PST-28 (RHO-G8)) of the RHO family of embedded isoreticular zeolites but also three other novel zeolite structures (EU-12, PST-21, and PST-22). We also explored the synthesis of a number of heteroatom-containing aluminophosphate (AlPO4) molecular sieves with different framework structures and unusually high framework charge density through the cooperative structure direction of alkali metal and small OSDA cations or under wholly inorganic conditions. Although we need to clarify the nature and extent of interactions between the inorganic cations and framework components in synthesis mixtures, we believe that our synthetic concepts, shedding new light on the importance of inorganic synthesis parameters, will open a door for achieving many other novel zeolite structures and compositions.