Control of Zeolite Local Polarity toward Efficient Xenon/Krypton Separation.

The inherent inertness and striking physicochemical similarities of krypton and xenon pose significant challenges to their separation. Reported herein is the efficient xenon capture and xenon/krypton adsorptive separation by transition metal-free zeolites under ambient conditions. The polarized environment of zeolite, denoted as local polarity, can be tuned by changing the topology, framework composition, and counter-cations, which in turn correlates with the guest-host interaction and separation performance. Chabazite zeolite with a framework Si/Al ratio of 2.5 and Ca2+ as the counter-cations, namely, Ca-CHA-2.5, is developed as a state-of-the-art zeolite adsorbent, showing remarkable performance, i.e., high dynamic xenon uptake, high xenon/krypton separation selectivity, and good recyclability, in the adsorptive separation of the xenon/krypton mixture. Grand Canonical Monte Carlo simulation reveals that extraframework Ca2+ cations act as the primary binding sites for xenon and can stabilize xenon molecules together with the chabazite framework, whereas krypton molecules are stabilized by weak guest-host interaction with the zeolite framework.

Direct Propylene Epoxidation with Molecular Oxygen over Cobalt-Containing Zeolites.

Direct propylene epoxidation with molecular oxygen is a dream reaction with 100% atom economy, but aerobic epoxidation is challenging because of the undesired over-oxidation and isomerization of epoxide products. Herein, we report the construction of uniform cobalt ions confined in faujasite zeolite, namely, Co@Y, which exhibits unprecedented catalytic performance in the aerobic epoxidation of propylene. Propylene conversion of 24.6% is achieved at propylene oxide selectivity of 57% at 773 K, giving a state-of-the-art propylene oxide production rate of 4.7 mmol/gcat/h. The catalytic performance of Co@Y is very stable, and no activity loss can be observed for over 200 h. Spectroscopic analyses reveal the details of molecular oxygen activation on isolated cobalt ions, followed by interaction with propylene to produce epoxide, in which the Co2+-Coδ+-Co2+ (2 < δ < 3) redox cycle is involved. The reaction pathway of propylene oxide and byproduct acrolein formation from propylene epoxidation is investigated by density functional theory calculations, and the unique catalytic performance of Co@Y is interpreted. This work presents an explicit example of constructing specific transition-metal ions within the zeolite matrix toward selective catalytic oxidations.

Directional Construction of Active Naphthalenic Species within SAPO-34 Crystals toward More Efficient Methanol-to-Olefin Conversion.

Olefin selectivity and catalyst lifetime are two key metrics for industrial methanol-to-olefin catalysts. Currently, it is very difficult to obtain high olefin selectivity and long catalyst lifetime at the same time. Herein, a feasible strategy combining precoking and steaming to directionally construct the active naphthalenic species within the crystal center of the SAPO-34 catalyst has been developed, which can not only promote the lower olefin selectivity to ∼89% (ethylene and propylene) but also prolong the catalyst lifetime by ∼3.7-fold in the methanol-to-olefin conversion. Structured illumination microscopy, in situ ultraviolet-visible spectroscopy, and online mass spectrometry elucidate the spatiotemporal distribution and evolution of the naphthalenic species during the precoking and steaming processes. This one-stone-two-birds strategy is applicable to a commercial SAPO-34 catalyst containing a binder, demonstrating its bright prospect in the methanol-to-olefin industry.

Confinement in a Zeolite and Zeolite Catalysis.

ConspectusZeolites, accompanied by their initial discovery as natural mines and the subsequent large-scale commercial production, have played indispensable roles in various fields such as petroleum refining and the chemical industry. Understanding the characteristics of zeolites, in contrast to their counterparts with similar chemical compositions and the origin thereof, is always a hot and challenging topic. Zeolites are known as intrinsic confined systems with ordered channels on the molecular scale, and structural confinement has been proposed to explain the unique chemical behaviors of zeolites. Generally, the channels of zeolites can regulate the diffusion of molecules, leading to a visible difference in molecular transportation and the ultimate shape-selective catalysis. On the other hand, the local electric field within the zeolite channels or cages can act on the guest molecules and change their energy levels. Confinement can be simply interpreted from both spatial and electronic issues; however, the nature of zeolite confinement is ambiguous and needs to be clarified.In this Account, we make a concise summary and analysis of the topics of confinement in a zeolite and zeolite catalysis from two specific views of spatial constraint and a local electric field to answer two basic questions of why zeolites and what else can we do with zeolites. First, it is shown how to construct functional sites including Brønsted acid sites, Lewis acid sites, extraframework cation sites, and entrapped metal or oxide aggregates in zeolites via confinement and how to understand the specific role of confinement in their reactivity. Second, the multiple impacts of confinement in zeolite-catalyzed reactions are discussed, which rationally lead to several unique processes, namely, Brønsted acid catalysis confined in zeolites, Lewis acid catalysis confined in zeolites, catalysis by zeolite-confined coordinatively unsaturated cation sites, and a cascade reaction within the confined space of zeolites. Overall, confinement effects do exist in zeolite systems and have already played extremely important roles in adsorption and catalysis. Although confinement might exist in many systems, the confinement by zeolites is more straightforward thanks to their well-ordered and rigid structure, deriving unique chemical behaviors within the confined space of zeolites. A zeolite is a fantastic scaffold for constructing isolated sites spatially and electrostatically confined in its matrix. Furthermore, zeolites containing well-defined transition-metal sites can be treated as inorganometallic complexes (i.e., a zeolite framework as the ligand of transition-metal ions) and can catalyze reactions resembling organometallic complexes or even metalloenzymes. The local electric field within the confined space of zeolites is strong enough to induce or assist the activation of small molecules, following the working fashion of frustrated Lewis pairs. The tactful utilization of structural confinement, both spatially and electronically, becomes the key to robust zeolites for adsorption and catalysis.

Regulating Extra-Framework Cations in Faujasite Zeolites for Capture of Trace Carbon Dioxide.

The development of cost-effective sorbents for direct capture of trace CO2 (<1 %) from the atmosphere is an important and challenging task. Natural or commercial zeolites are promising sorbents, but their performance in adsorption of trace CO2 has been poorly explored to date. A systematic study on capture of trace CO2 by commercial faujasite zeolites reveals that the extra-framework cations play a key role on their performance. Under dry conditions, Ba-X displays high dynamic uptake of 1.79 and 0.69 mmol g-1 at CO2 concentrations of 10000 and 1000 ppm, respectively, and shows excellent recyclability in the temperature-swing adsorption processes. K-X exhibits perfect moisture resistance, and >95 % dry CO2 uptake can be preserved under relative humidity of 74 %. In situ solid-state NMR spectroscopy, synchrotron X-ray diffraction and neutron diffraction reveal two binding sites for CO2 in these zeolites, namely the basic framework oxygen atoms and the divalent alkaline earth metal ions. This study unlocks the potential of low-cost natural zeolites for applications in direct air capture.

Platelike MFI Crystals with Controlled Crystal Faces Aspect Ratio.

Zeolite crystals offering a short diffusion pathway through the pore network are highly desired for a number of catalytic and molecule separation applications. Herein, we develop a simple synthetic strategy toward reducing the thickness along the b-axis of MFI-type crystals, thus providing a short diffusion path along the straight channel. Our approach combines preliminary aging and a fluoride-assisted low-temperature crystallization. The synthesized MFI crystals are in the micrometer-size range along the a- and c-axis, while the thickness along the b-axis is a few tens of nanometers. The synthesis parameters controlling the formation of platelike zeolite are studied, and the factors controlling the zeolite growth are identified. The synthesis strategy works equally well with all-silica MFI (silicalite-1) and its Al- and Ga-containing derivatives. The catalytic activity of platelike ZSM-5 in the methanol-to-hydrocarbons (MTH) reaction is compared with a commercial nanosized ZSM-5 sample, as the platelike ZSM-5 exhibits a substantially extended lifetime. The synthesis of platelike MFI crystals is successfully scaled up to a kilogram scale.

Zeolite-Encaged Isolated Platinum Ions Enable Heterolytic Dihydrogen Activation and Selective Hydrogenations.

Understanding the unique behaviors of atomically dispersed catalysts and the origin thereof is a challenging topic. Herein, we demonstrate a facile strategy to encapsulate Ptδ+ species within Y zeolite and reveal the nature of selective hydrogenation over a Pt@Y model catalyst. The unique configuration of Pt@Y, namely atomically dispersed Ptδ+ stabilized by the surrounding oxygen atoms of six-membered rings shared by sodalite cages and supercages, enables the exclusive heterolytic activation of dihydrogen over Ptδ+···O2- units, resembling the well-known classical Lewis pairs. The charged hydrogen species, i.e., H+ and Hδ-, are active reagents for selective hydrogenations, and therefore, the Pt@Y catalyst exhibits remarkable performance in the selective hydrogenation of α,ß-unsaturated aldehydes to unsaturated alcohols and of nitroarenes to arylamines.

Experimental and Theoretical Evidence for the Promotional Effect of Acid Sites on the Diffusion of Alkenes through Small-Pore Zeolites.

The diffusion of saturated and unsaturated hydrocarbons is of fundamental importance for many zeolite-catalyzed processes. Transport of small alkenes in the confined zeolite pores can become hindered, resulting in a significant impact on the ultimate product selectivity and separation. Herein, intracrystalline light olefin/paraffin diffusion through the 8-ring windows of zeolite SAPO-34 is characterized by a complementary set of first-principle molecular dynamics simulations, PFG-NMR experiments, and pulse-response temporal analysis of products measurements, yielding information at different length and time scales. Our results clearly show a promotional effect of the presence of Brønsted acid sites on the diffusion rate of ethene and propene, whereas transport of alkanes is found to be insensitive to the presence of acid sites. The enhanced diffusivity of unsaturated hydrocarbons is ascribed to the formation of favorable π-H interactions with acid protons, as confirmed by IR spectroscopy measurements. The acid site distribution is proven to be an important design parameter for optimizing product distributions and separations.

Efficient Separation of Acetylene and Carbon Dioxide in a Decorated Zeolite.

The almost identical molecular sizes and volatilities of acetylene and carbon dioxide make their separation extremely challenging in industry. Reported here is the efficient separation of acetylene and carbon dioxide (v/v=2/1, which is relevant to that in the industrial cracking stream) in faujasite zeolites decorated with atomically-dispersed copper(II) sites under ambient conditions. In situ neutron powder diffraction and inelastic neutron scattering confirm that the confined copper(II) site displays chemoselective yet reversible binding to acetylene, whereas adsorbed carbon dioxide molecules are stabilized by weak host-guest supramolecular interactions with the framework oxygen centers, thus resulting in the efficient separation of these two gases under flow conditions. A designed adsorption-purging-desorption system based upon Cu@FAU is established for the recovery of high purity acetylene (98-99 %) from the mixture of acetylene and carbon dioxide, offering an unprecedented separation factor of 22.2 with an effective dynamic uptake of acetylene of 1.51 mmol g-1 at 298 K.

Acetylene-Selective Hydrogenation Catalyzed by Cationic Nickel Confined in Zeolite.

The selective hydrogenation of alkynes to alkenes is an important type of organic transformation with large-scale industrial applications. This transformation requires efficient catalysts with precise selectivity control, and palladium-based metallic catalysts are currently employed. Here we show that four-coordinated cationic nickel(II) confined in zeolite can efficiently catalyze the selective hydrogenation of acetylene to ethylene, a key process for trace acetylene removal prior to the polymerization process. Under optimized conditions, 100% acetylene conversion and an ethylene selectivity up to 97% are simultaneously achieved. This catalyst system also exhibits good stability and recyclability for potential applications. Spectroscopy investigations and density functional theory calculations reveal the heterolytic dissociation of hydrogen molecules and the importance of hydride and protons in the selective hydrogenation of acetylene to ethylene. This work provides an efficient strategy toward active and selective zeolite catalysts by utilizing the local electrostatic field within the zeolite confined space for small-molecule activation and by linking heterogeneous and homogeneous catalysis.

Polyoxometalate-Based Metal-Organic Frameworks as Visible-Light-Induced Photocatalysts.

Two stable 3D polyoxometalate-based metal-organic frameworks (PMOFs), [CuI12(trz)8(H2O)2][α-SiW12O40]·2H2O (1) and [CuI12(trz)8Cl][α-PW12O40] (2) (Htrz = 1- H-1,2,4-triazole) based on Keggin-type POMs were successfully obtained and fully characterized. The basic building units of the two PMOFs are [CuI12(trz)8], but polyoxoanion (POA) template effect leads to different structures and properties: 1 represents an interesting example that [α-SiW12O40]4- locate in the nine-membered Cu-trz rings through Cu···O weak interactions to form a 3D framework, whereas 2 shows a 3D structure constructed from 2D bilayer cationic network [CuI12(trz)8Cl]3+ and [α-PW12O40]3- lying in the adjacent layers via Cu···O weak interactions. PMOF 1 as unusual visible-light photocatalyst exhibit significantly enhanced photocatalytic activity under visible-light and excellent stability during the photocatalysis process for recovering and recycling, as well as photocatalytic hydrogen evolution activity.

Identification of tert-Butyl Cations in Zeolite H-ZSM-5: Evidence from NMR Spectroscopy and DFT Calculations.

Experimental evidence for the presence of tert-butyl cations, which are important intermediates in acid-catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with (1)H/(13)C magic-angle-spinning NMR spectroscopy, the tert-butyl cation was successfully identified on zeolite H-ZSM-5 upon conversion of isobutene by capturing this intermediate with ammonia.

Conductive catalysis by subsurface transition metals.

The nature of catalysis has been hotly pursued for over a century, and current research is focused on understanding active centers and their electronic structures. Herein, the concept of conductive catalysis is proposed and verified by theoretical simulations and experimental observations. Metallic systems containing buried catalytically active transitional metals and exposed catalytically inert main group metals are constructed, and the electronic interaction between them via metallic bonding is disclosed. Through the electronic interaction, the catalytic properties of subsurface transitional metals (Pd or Rh) can be transferred to outermost main group metals (Al or Mg) for several important transformations like semi-hydrogenation, Suzuki-coupling and hydroformylation. The catalytic force is conductive, in analogy with the magnetic force and electrostatic force. The traditional definition of active centers is challenged by the concept of conductive catalysis and the electronic nature of catalysis is more easily understood. It might provide new opportunities for shielding traditional active centers against poisoning or leaching and allow for precise regulation of their catalytic properties by the conductive layer.

Understanding the effect of surface/bulk defects on the photocatalytic activity of TiO2: anatase versus rutile.

The sole effect of surface/bulk defects of TiO2 samples on their photocatalytic activity was investigated. Nano-sized anatase and rutile TiO2 were prepared by hydrothermal method and their surface/bulk defects were adjusted simply by calcination at different temperatures, i.e. 400-700 °C. High temperature calcinations induced the growth of crystalline sizes and a decrease in the surface areas, while the crystalline phase and the exposed facets were kept unchanged during calcination, as indicated by the characterization results from XRD, Raman, nitrogen adsorption-desorption, TEM and UV-Vis spectra. The existence of surface/bulk defects in calcined TiO2 samples was confirmed by photoluminescence and XPS spectra, and the surface/bulk defect ratio was quantitatively analyzed according to positron annihilation results. The photocatalytic activity of calcined TiO2 samples was evaluated in the photocatalytic reforming of methanol and the photocatalytic oxidation of α-phenethyl alcohol. Based on the characterization and catalytic results, a direct correlation between the surface specific photocatalytic activity and the surface/bulk defect density ratio could be drawn for both anatase TiO2 and rutile TiO2. The surface defects of TiO2, i.e. oxygen vacancy clusters, could promote the separation of electron-hole pairs under irradiation, and therefore, enhance the activity during photocatalytic reaction.

Facile synthesis of aluminosilicate zeolites with STT, CHA and MWW topology structures.

Efficient synthesis of zeolites with different topologies is of great significance for both fundamental research and industrial application. Herein, the SSZ-23 zeolite, an odd zeolite containing 7-membered ring (7-MR) and 9-MR channels, has been synthesized under fluorine-free conditions via the route of pre-aging and pH regulation. By this novel synthesis route, the crystallization time can be significantly shortened to 3 days, nearly half as that by the conventional route in fluoride media. The pH value of the aging gel, i.e., the basicity, is found to play a key role in the synthesis, as SSZ-13 and SSZ-25 zeolites can be synthesized simply by changing the basicity of the same aging gel. Characterization results indicate that decreasing the basicity can promote the condensation between Si and Si/Al species and thus increase the framework density of the resulting zeolites. Finally, the dimethyl ether (DME) carbonylation reaction is employed to evaluate the catalytic properties of the above three zeolites with an identical chemical composition, and to reveal the unique confinement effect in various zeolite topologies.

Zeolite-encaged mononuclear copper centers catalyze CO2 selective hydrogenation to methanol.

The selective hydrogenation of CO2 to methanol by renewable hydrogen source represents an attractive route for CO2 recycling and is carbon neutral. Stable catalysts with high activity and methanol selectivity are being vigorously pursued, and current debates on the active site and reaction pathway need to be clarified. Here, we report a design of faujasite-encaged mononuclear Cu centers, namely Cu@FAU, for this challenging reaction. Stable methanol space-time-yield (STY) of 12.8 mmol gcat-1 h-1 and methanol selectivity of 89.5% are simultaneously achieved at a relatively low reaction temperature of 513 K, making Cu@FAU a potential methanol synthesis catalyst from CO2 hydrogenation. With zeolite-encaged mononuclear Cu centers as the destined active sites, the unique reaction pathway of stepwise CO2 hydrogenation over Cu@FAU is illustrated. This work provides a clear example of catalytic reaction with explicit structure-activity relationship and highlights the power of zeolite catalysis in complex chemical transformations.

Stable and Uniform Extraframework Cations in Faujasite Zeolites.

Extraframework transition metal ions (TMIs) in zeolites can serve as active sites for adsorption and catalysis. However, due to the complexity and mobility of extraframework cation sites, their applications are significantly limited and the structure-performance relationship is poorly understood. In this Perspective, stable and uniform TMIs in zeolites are exemplified and their characteristics are discussed. A series of TMIs can be introduced to specific cation sites of faujasite via a ligand-protected in situ synthesis route to construct uniform TMIs in the zeolite matrix, namely, TMI@FAU (TMI= Co, Ni, Cu, Rh, and Pt). Coordinatively unsaturated TMIs within faujasite are active for small-molecule adsorption and activation, and therefore, TMI@FAU zeolites show unique properties in adsorption and catalysis. TMI@FAU zeolites appear to be ideal model systems, and the well-defined structure of TMI@FAU greatly facilitates the mechanism studies by spectroscopic investigations and theoretical simulations.

Plate-Like ZSM-5 Zeolites as Robust Catalysts for the Cracking of Hydrocarbons.

Zeolites with good acid site accessibility and high diffusion rates are highly desirable catalysts, especially when dealing with bulk molecules. In this work, ZSM-5 zeolites with similar Si/Al ratios but different thicknesses along the b-axis (from ∼30 nm to ∼5 µm), namely, two plate-like ZSM-5 zeolites and two reference zeolites have been prepared and the impacts of b-axis thickness on the surface properties and catalytic cracking performances are explored. Comprehensive physiochemical studies demonstrate that reducing the b-axis thickness of the zeolite crystals endows the samples with better acid site accessibility and more external surface acid sites. Two model compounds with different molecule sizes, namely, 1,3,5-triisopropylbenzene (TIPB) and cumene, are selected to explore the catalytic cracking performances of the as-synthesized samples. The results reveal that decreasing the b-axis thickness of zeolite crystals can effectually promote the catalytic activity and stability in catalytic cracking reactions. For TIPB cracking, the greatly enhanced catalytic activity is ascribed to the enhanced acid site accessibility in plate-like ZSM-5 zeolites, and for cumene cracking, the improved catalytic stability is ascribed to the shortened diffusion length of plate-like zeolites.

Progressive steps and catalytic cycles in methanol-to-hydrocarbons reaction over acidic zeolites.

Understanding the complete reaction network and mechanism of methanol-to-hydrocarbons remains a key challenge in the field of zeolite catalysis and C1 chemistry. Inspired by the identification of the reactive surface methoxy species on solid acids, several direct mechanisms associated with the formation of the first C-C bond in methanol conversion have been recently disclosed. Identifying the stepwise involvement of the initial intermediates containing the first C-C bond in the whole reaction process of methanol-to-hydrocarbons conversion becomes possible and attractive for the further development of this important reaction. Herein, several initial unsaturated aldehydes/ketones containing the C-C bond are identified via complementary spectroscopic techniques. With the combination of kinetic and spectroscopic analyses, a complete roadmap of the zeolite-catalyzed methanol-to-hydrocarbons conversion from the initial C-C bonds to the hydrocarbon pool species via the oxygen-containing unsaturated intermediates is clearly illustrated. With the participation of both Brønsted and Lewis acid sites in H-ZSM-5 zeolite, an initial aldol-cycle is proposed, which can be closely connected to the well-known dual-cycle mechanism in the methanol-to-hydrocarbons conversion.

Stabilizing the framework of SAPO-34 zeolite toward long-term methanol-to-olefins conversion.

As a commercial MTO catalyst, SAPO-34 zeolite exhibits excellent recyclability probably due to its intrinsic good hydrothermal stability. However, the structural dynamic changes of SAPO-34 catalyst induced by hydrocarbon pool (HP) species and the water formed during the MTO conversion as well as its long-term stability after continuous regenerations are rarely investigated and poorly understood. Herein, the dynamic changes of SAPO-34 framework during the MTO conversion were identified by 1D 27Al, 31P MAS NMR, and 2D 31P-27Al HETCOR NMR spectroscopy. The breakage of T-O-T bonds in SAPO-34 catalyst during long-term continuous regenerations in the MTO conversion could be efficiently suppressed by pre-coking. The combination of catalyst pre-coking and water co-feeding is established to be an efficient strategy to promote the catalytic efficiency and long-term stability of SAPO-34 catalysts in the commercial MTO processes, also sheds light on the development of other high stable zeolite catalyst in the commercial catalysis.