Zeotype Materials Research Articles

Tuning the atomic ordering of AFI framework with templates charge

In this work, AlPO4-5 (AFI) zeotype materials were synthesized using the microwave approach in the presence of two organic templates i.e. tripropylamine (R) and tetrapropylammonium (R+). The long- and short-range crystalline order of the samples were investigated by considering the effect of the template's charge on the atomic-level ordering of the AFI framework. Using advanced NMR spectroscopy, we shed the light on the importance of templates' role on the organization of the inorganic framework of aluminophosphates. The spectroscopic data clearly show a wider distribution of Al and P environments in the materials synthesized with the charged template (R+) due to the need of hydroxyl groups charge compensators that induce some bridges distortions. When a charged molecule (R+) was used, aluminum appears to be responsible for the charge compensation mechanism via the association of OH groups, impacting the environment of phosphorus as well. The hydroxyl groups needed for charge compensation in samples synthesized with R+ persist after calcination. Consequently, the hydrophilicity of the sample synthesized with R+ features approximatively two times higher values compared to the one synthesized with R.

Advances in Aluminophosphates for Catalytic Upgrading of Lignocellulose and Derived Compounds

AbstractUtilization of lignocellulosic biomass as a renewable resource to produce liquid fuels/fuel additives and commodity chemicals offer solutions to minimize the exhaustion of nonrenewable carbon‐based fossil resources and mitigate environmental problems. Cellulose and hemicellulose derived from lignocellulose can be converted into several important platform molecules like glucose, fructose, xylose, 5‐hydroxymethylfurfural, furfural, levulinic acid, etc., which subsequently can be transformed into fuels/fuel additives and value‐added chemicals using heterogeneous catalytic processes. Aluminophosphates (AlPO‐n) are zeotype materials with tunable physicochemical properties like acidity and porosity, and this have promoted their wide use as versatile catalysts for several acid‐catalyzed reactions, including hydrolysis, dehydration, isomerization, transfer hydrogenation, reductive etherification, acetalization and aldol condensation. This review summarizes the design and synthetic advances of AlPO‐n catalysts as well as their application in the valorization of lignocellulose and derivatives to platform chemicals and fuel compounds. Perspectives for future design strategies are finally outlined.

Adsorption isotherms of enantiomers on a chiral open-framework copper borophosphate LiCu2[BP2O8(OH)2

The chiral recognition during adsorption in pores with only supramolecular (not molecular) chirality was shown for the first time on zeotype material copper borophosphate LiCu2[BP2O8(OH)2].

Synthesis and Catalytic Applications of Advanced Sn- and Zr-Zeolites Materials.

The incorporation of isolated Sn (IV) and Zr (IV) ions into silica frameworks is attracting widespread attention, which exhibits remarkable catalytic performance (conversion, selectivity, and stability) in a broad range of reactions, especially in the field of biomass catalytic conversion. As a representative example, the conversion route of carbohydrates into valuable platform and commodity chemicals such as lactic acid and alkyl lactates, has already been established. The zeotype materials also possess water-tolerant ability and are capable to be served as promising heterogeneous catalysts for aqueous reactions. Therefore, dozens of Sn- and Zr-containing silica materials with various channel systems have been prepared successfully in the past decades, containing 8 membered rings (MR) small pore CHA zeolite, 10-MR medium pore zeolites (FER, MCM-56, MEL, MFI, MWW), 12-MR large pore zeolites (Beta, BEC, FAU, MOR, MSE, MTW), and 14-MR extra-large pore UTL zeolite. This review about Sn- and Zr-containing metallosilicate materials focuses on their synthesis strategy, catalytic applications for diverse reactions, and the effect of zeolite characteristics on their catalytic performances.

Steering the Metal Precursor Location in Pd/Zeotype Catalysts and Its Implications for Catalysis

Bifunctional catalysts containing a dehydrogenation–hydrogenation function and an acidic function are widely applied for the hydroconversion of hydrocarbon feedstocks obtained from both fossil and renewable resources. It is well known that the distance between the two functionalities is important for the performance of the catalyst. In this study, we show that the heat treatment of the catalyst precursor can be used to steer the location of the Pd precursor with respect to the acid sites in SAPO-11 and ZSM-22 zeotype materials when ions are exchanged with Pd(NH3)4(NO3)2. Two sets of catalysts were prepared based on composite materials of alumina with either SAPO-11 or ZSM-22. Pd was placed on/in the zeotype, followed by a calcination-reduction (CR) or direct reduction (DR) treatment. Furthermore, catalysts with Pd on the alumina binder were prepared. CR results in having more Pd nanoparticles inside the zeotype crystals, whereas DR yields more particles on the outer surface of the zeotype crystals as is confirmed using HAADF-STEM and XPS measurements. The catalytic performance in both n-heptane and n-hexadecane hydroconversion of the catalysts shows that having the Pd nanoparticles on the alumina binder is most beneficial for maximizing the isomer yields. Pd-on-zeotype catalysts prepared using the DR approach show intermediate performances, outperforming their Pd-in-zeotype counterparts that were prepared with the CR approach.

Amine Functionalization Within Hierarchically‐Porous Zeotype Framework for Plasmonic Catalysis over PdAu Nanoparticles

AbstractPlasmonic catalysis has revealed improved product yield and selectivity in various chemical transformation reactions over the past decade. In this report, the effect of tertiary amine (‐NR3) functionalization on the surface of hierarchically‐porous zeotype (HP‐AlPO‐5) materials to enhance the plasmon‐mediated catalysis, utilizing a combination of the plasmonic antenna (Au) and catalytic reactor (Pd) nanoparticles (NPs) was investigated. The catalysts have been characterized using enhanced techniques such as HAADF‐STEM, FT‐EXAFS, and probe‐based FT‐IR to reveal the proximity and interaction between bimetallic NPs, and thermal stability of amines in the presence of Au or PdAu NPs. Interestingly, a four‐fold enhancement in the Suzuki‐Miyaura coupling reaction product yield was obtained over PdAu/HP‐AlPO‐5‐NR3 when compared with the analogous plasmonic catalyst with no amine functionalization under visible light irradiation. A range of amines were functionalized and their influence in the nucleation, uniform growth and stabilization of catalytic active site (Pd) and formation of electron‐rich species under visible light irradiation has also been investigated. The presence of tertiary amine in the nanostructured catalyst enhanced the turnover number (TON) significantly under light irradiation conditions in comparison to dark conditions. This study provides an enriched understanding of plasmon‐driven chemistry, where the maximized reaction rate enhancement requires the existence of active metal species and the formation of electron‐enriched species under light irradiation conditions.

Aluminophosphate - Based adsorbents for atmospheric water generation

Freshwater resources are being heavily depleted and not replenished at the same high rate, thus, atmospheric water vapor harvesting has earned growing interest. Development of high-performing desiccant or adsorbent materials offering high sorption capacity and selectivity as well as regeneration capability in atmospheric conditions is crucial to tackle water scarcity. The required properties to generate potent water sorbents include pore accessibility, high specific surface area and porosity to enable high capture capacity and kinetics, and hydrothermal resilience to resist cyclic sorption and desorption. Further, polarity, hydrogen bonding, adhesion ability of water molecules to adsorbent surface, and hydrophilic functional groups can boost water adsorption. A highly promising class of water vapor adsorbents is the aluminophosphate molecular sieves (AlPOs), which are microporous zeotype materials. In this review, AlPO-based adsorbents are discussed for water sorption applications and a link is established between performance of materials and their chemical and morphological properties. Synthesis-properties-performance relationships are elucidated in light of synthesis techniques and adsorption behavior, and prospects to enhance AlPOs' water vapor sorption performance toward large-scale water harvesting applications are highlighted.

Water adsorption behavior of Mg and Fe substituted microporous AlPO4-5

Isomorphic substitution of zeolite and zeotype materials plays a dominant role in tuning the performance of the materials in adsorption and catalysis. Here, aluminophosphate AlPO4-5 crystals (AFI-type) with variable content of incorporated iron or magnesium were hydrothermally synthesized, characterized, and tested for water adsorption. The metal incorporation altered the growth direction and thus morphology of the resulting crystals, while the Al/P ratio decreased below unity with increasing Fe/Al2O3 or Mg/Al2O3, confirming selective substitution of aluminum. Moreover, the unit cell experienced shrinkage when Fe substituted Al, whereas the MgAPO-5 lattice refinement results revealed minor variation in the lattice parameters. Water vapor adsorption studies revealed that the materials exhibit non-typical, type-V adsorption behavior with initial low uptake, indicating hydrophobicity, followed by a steep capacity increase indicating capillary-like adsorption at higher relative pressures. Metal substitution could tune the behavior, i.e. by increasing hydrophilicity at the lower range of relative pressures, with the onset of the inflection point being shifted to lower P/P0 values with increasing metal content. An Fe-based AlPO4-5 yielded the highest absorption capacity among all adsorbents tested (13 mmol/g at 43 °C). Fowler-Guggenheim calculations showed that the interaction energy (ω) between the adsorbed water molecules was positive for both MgAPO-5 and FeAPO-5 indicating attractive intermolecular interactions, yet a decrease of ω with increasing Me/Al2O3 ratio in the synthesis mixture revealed suppression of intermolecular interactions with metal loading. The reported results and the tailoring of water adsorption behavior by metal substitution can be promising for water sorption/separation applications such as atmospheric water harvesting.

Relativistic topological and spectral characteristics of zeolite SAS structures

Zeolite SAS is a novel microporous zeotype material known as magnesioaluminophosphate with small pores and large cavities. The framework morphology of SAS is an excellent choice for isomorphic substitution to incorporate various types of metal ions into its pores, offering it distinct acidic and redox characteristics. Zeolite SAS type materials are receiving significant attention due to diverse applications in catalysis, iron exchange, environmental remediation and gas separation. A recent study shows that the SAS type materials remove, reduce or retard the adsorption of toxins, especially in water. In order to explore the structural characteristics of zeolite SAS and enhance its possible applications in QSPR and QSAR investigations, we employ graph theoretical techniques to derive the exact analytical formula of Wiener, Szeged, Mostar and degree type topological indices, which contain various information on molecules that can be useful in describing the physicochemical and biological properties of the materials. Furthermore we obtain the vertex partitions and spectral characteristics which in turn can aid in the interpretation of ESR and NMR spectral features as well as in relative comparisons of structures and their stabilities.

Generating nanocrystalline SAPO-34 through bead-milling and porogen-assisted recrystallization: Structural evolution and catalytic consequence in dimethyl ether-to-olefin conversion

Mechanochemical bead-milling is a promising post-synthetic way to generate nanocrystalline zeotype materials with promoted catalytic performance. Post-milling recrystallization is often entailed to remedy the damaged framework but leads to crystal growth. Herein, using SAPO-34 (ca. 20 µm) derived from inexpensive morpholine as an example, we showcase that secondary growth can be suppressed by porogen-assisted recrystallization, resulting in formation of tiny crystals (100–200 nm) with better mass transport property. The presence of porogen (polydiallyldimethylammonium chloride) also induced a reduction of acid site density owing to a re-distribution of Si across the crystal, which alleviated zoning of Si at the external surface. The catalytic advantages, with respect to a control sample recrystallized in the absence of porogen, have been experimentally verified in dimethyl ether-to-olefin conversion, exhibiting an exaggerated light olefin selectivity and prolonged catalyst lifetime. This advancement of mechanochemical synthesis opens an avenue to better tailor crystal size for zeotype materials.

Carbon dioxide capture with zeotype materials.

The accumulation of carbon dioxide (CO2) in the atmosphere has been recognized as one of the primary factors attributed to global warming. Various strategies have been proposed to mitigate the amount of atmospheric CO2 such as its separation from emission streams with storage or utilization in fuels and chemicals. Zeolite-based materials (zeotype materials), a class of microporous solids with: (i) structural features of high surface area, chemical tunability and high stability, and (ii) a long history of global scale industrial use, have been extensively investigated for CO2 capture. In this review, a comprehensive summary and discussion of the progress in the design and use of zeotype materials, e.g., cation and amine modifications, composites and templated carbons, for the capture of CO2 is presented. The CO2 adsorption mechanisms in these materials are described, and the factors that determine their performance are discussed. The application of zeotype materials for CO2 capture under conditions such as post-combustion, indoor air cleaning and direct air capture are presented. Further, the mechanisms of water-zeolites interaction as well as their impacts on CO2 adsorption performance are discussed. The review closes with a brief presentation on the challenges and opportunities for future research in the field.

Biomineralization at the Molecular Level: Amino Acid-Assisted Crystallization of Zeotype AlPO4·1.5H2O–H3

Three aminoacids: proline, histidine, and lysine are used as organic additives in the hydrothermal synthesis of the zeotype material AlPO 4 •1.5H 2 O-H3 (framework topology code APC). A detailed analysis of the factors controlling the formation of AlPO 4 •1.5H 2 O-H3 is performed. The role of aminoacids in the formation process of the frameworks is addressed based on comparisons of the crystal phase selection of different synthetic recipes and the insights provided by the FTIR analysis of the synthetic gels and the crystalline products. The phase transition of AlPO 4 •1.5H 2 O-H3 to AlPO 4-C (APC), and subsequently to AlPO 4-D (APD) upon heating to 1000 o C was followed by in situ XRD analysis. The present work has been the first progress to understanding the role of the bioactive molecules in the crystallization of inorganic open-framework microporous materials. An active, non-classical structuredirecting role that aminoacids play during the zeotype crystallization is proposed, i.e., positively charged aminoacids cap the growing surface of microporous AlPO 4 , and attract aluminate and phosphate anions from the solution phase for further growth.

How Many Molecules Can Fit in a Zeolite Pore? Implications for the Hydrocarbon Pool Mechanism of the Methanol-to-Hydrocarbons Process

The methanol-to-hydrocarbons (MTH) process is a very advantageous way to upgrade methanol to more valuable commodity chemicals such as light alkenes and gasoline. There is general agreement that, at steady state, the process operates via a dual cycle “hydrocarbon pool” mechanism. This mechanism defines a minimum number of reactants, intermediates, and products that must be present for the reaction to occur. In this paper, we calculate (by three independent methods) the volume required for a range of compounds that must be present in a working catalyst. These are compared to the available volume in a range of zeolites that have been used, or tested, for MTH. We show that this straightforward comparison provides a means to rationalize the product slate and the deactivation pathways in zeotype materials used for the MTH reaction.

Induced Active Sites by Adsorbate in Zeotype Materials.

There has been a long debate on how and where active sites are created for molecular adsorption and catalysis in zeolites, which underpin many important industrial applications. It is well accepted that Lewis acidic sites (LASs) and basic sites (LBSs) as active sites in pristine zeolites are generally believed to be the extra-framework Al species and residue anion (OH-) species formed at fixed crystallographic positions after their synthesis. However, the dynamic interactions of adsorbates/reactants with pristine zeotype materials to "create" sites during real conditions remain largely unexplored. Herein, direct experimental observation of the establishment of induced active sites in silicoaluminophosphate (SAPO) by an adsorbate is for the first time made, which contradicts the traditional view of the fixed active sites in zeotype materials. Evidence shows that an induced frustrated Lewis pair (FLP, three-coordinated framework Al as LAS and SiO (H) as LBS) can be transiently favored for heterolytic molecular binding/reactions of competitive polar adsorbates due to their ineffective orbital overlap in the rigid framework. High-resolution magic-angle-spinning solid-state NMR, synchrotron X-ray diffraction, neutron powder diffraction, in situ diffuse reflectance infrared Fourier transform spectroscopy, and ab initio molecular dynamics demonstrate the transformation of a typical Brønsted acid site (Al(OH)Si) in SAPO zeolites to new induced FLP structure for hetereolytic binding upon adsorption of a strong polar adsorbate. Our unprecedented finding opens up a new avenue to understanding the dynamic establishment of active sites for adsorption or chemical reactions under molecular bombardment of zeolitic structures.

Observing a Zeolite Nucleus (Subcrystal) with a Uniform Framework Structure and Its Oriented Attachment without Single-Molecule Addition.

Multiple and complex crystallization process of zeolite including complementary single-molecule condensation and particle assembly, and alternately dominant nucleation and growth behavior, plays the critical role in zeolite crystallization but meanwhile makes us hard to study the respective effects. Herein, we strip nuclei from the synthetic solution and find that high-ordered nucleus (subcrystal) is the premise to ignite high-speed growth of zeolite crystal. The high-ordered subcrystals with the size of only 6-10 nm possess regular aperture structure and microporous area similar to zeolite nanocrystal. Interestingly, a unitary oriented aggregation process of the subcrystals towards nanosheets is well observed and characterized where single-molecule addition process is greatly repressed. If a wider range of zeotype nuclei can be expanded, a new synthetic strategy of zeotype materials with heterogeneous framework and active sites may be expected, which may novelize zeolite catalytic properties.

Observing a Zeolite Nucleus (Subcrystal) with a Uniform Framework Structure and Its Oriented Attachment without Single‐Molecule Addition

AbstractMultiple and complex crystallization process of zeolite including complementary single‐molecule condensation and particle assembly, and alternately dominant nucleation and growth behavior, plays the critical role in zeolite crystallization but meanwhile makes us hard to study the respective effects. Herein, we strip nuclei from the synthetic solution and find that high‐ordered nucleus (subcrystal) is the premise to ignite high‐speed growth of zeolite crystal. The high‐ordered subcrystals with the size of only 6–10 nm possess regular aperture structure and microporous area similar to zeolite nanocrystal. Interestingly, a unitary oriented aggregation process of the subcrystals towards nanosheets is well observed and characterized where single‐molecule addition process is greatly repressed. If a wider range of zeotype nuclei can be expanded, a new synthetic strategy of zeotype materials with heterogeneous framework and active sites may be expected, which may novelize zeolite catalytic properties.

Chromium Environment within Cr-Doped Silico-Aluminophosphate Molecular Sieves from Spin Density Studies.

X-/Q-band electron paramagnetic resonance (EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopies have been employed, in conjunction with density functional theory (DFT) modeling, to determine the location of Cr5+ions in SAPO-5 zeotype materials. The interaction of the unpaired electron of the paramagnetic Cr5+ species with 27Al could be resolved, allowing for the first detailed structural analysis of Cr5+ paramagnetic ions in SAPO materials. The interpretation of the experimental results is corroborated by DFT modeling, which affords a microscopic description of the system investigated. The EPR-active species is found to be consistent with isolated Cr5+ species isomorphously substituted in the framework at P5+ sites.

Bimetallic PdAu Catalysts within Hierarchically Porous Architectures for Aerobic Oxidation of Benzyl Alcohol.

Hierarchically porous (HP) zeotype materials (possessing both micropores and mesopores) offer improved diffusional access to intra-framework active sites, analogous to mesoporous materials, yet retain the high selectivity of the microporous (MP) bulk. We have recently designed crystalline hierarchically porous silicoaluminophosphates (SAPOs) with enhanced mass-transport characteristics, which can lead to significant improvement in catalytic activity and catalyst lifetime. In this study, we have prepared PdAu bimetallic nanostructures supported on HP-SAPO frameworks by an incipient impregnation of metal precursors followed by H2 reduction at 300 °C, for the aerobic oxidation of benzyl alcohol to benzaldehyde. PdAu NPs supported on HP framework displayed significantly enhanced catalytic activities, when compared with their MP analogues, clearly highlighting the benefits of introducing hierarchical porosity in the SAPO support matrix.

Control of location and distribution of heteroatoms substituted isomorphously in framework of zeolites and zeotype materials

Well-controlled incorporation of heteroatoms in frameworks of zeolites and zeotype materials has been achieved by a variety of new synthetic approaches, generating outstanding catalysts compared to uncontrolled materials.

Atomically Dispersed Metals on Well-Defined Supports including Zeolites and Metal–Organic Frameworks: Structure, Bonding, Reactivity, and Catalysis

When metals in supported catalysts are atomically dispersed, they are usually cationic and bonded chemically to supports. Investigations of noble metals in this class are growing rapidly, leading to discoveries of catalysts with new properties. Characterization of these materials is challenging because the metal atoms reside on surfaces that are typically nonuniform in composition and structure. We posit that understanding of structures and catalytic properties of these materials is emerging most strongly from investigations of structurally uniform catalysts (metal atoms dispersed on crystalline supports) which can be characterized incisively with atomic-resolution electron microscopy, X-ray absorption spectroscopy, and infrared spectroscopy, bolstered by density functional theory. We assess the literature of such catalysts supported on zeotype materials, metal-organic frameworks, and covalent organic frameworks. Assessing characterization, reactivity, and catalytic performance of catalysts for oxidation, hydrogenation, the water-gas shift reaction, and others, we consider metal-support interactions and ligand effects for various metal-support combinations, evaluating the degree of structural uniformity of exemplary catalysts and summarizing structure-reactivity and structure-catalytic property relationships.