Polymer-Supported Pd Nanoparticles for Solvent-Free Hydrogenation.

Breaking the trade-off between activity and stability of supported metal catalysts has been a long-standing challenge in catalysis, especially for metal nanoparticles (NPs) with high hydrogenation activity but poor stability. Herein, we report a porous poly(divinylbenzene) polymer-supported Pd NP catalyst (Pd/PDVB) with both high activity and excellent stability for the solvent-free hydrogenation of nitrobenzene, even at ambient temperature (25 °C) and H2 pressure (0.1 MPa). Pd/PDVB gave a turnover frequency as high as 22,632 h-1 at 70 °C and 0.4 MPa, exceeding 5556 h-1 of the classical Pd/C catalyst under equivalent conditions. Mechanistic studies reveal that the polymer support benefits the desorption of the aniline product from the Pd surface, which is crucial for rapid hydrogenation under solvent-free conditions. In addition, the polymer support in Pd/PDVB efficiently hindered Pd leaching, resulting in good stability.

Atom-Economic Synthesis of Zeolites.

Zeolites are typically synthesized in the presence of strong alkaline or fluoride species, which is not atom-economic for zeolite synthesis due to the high solubility of strong alkaline and fluoride species to silica. One of the solutions for this issue is to reduce solubility of silica in the zeolite synthesis, but it is challenging. Herein, we show that nucleation and growth of zeolites can occur under near neutral conditions, giving an atom-economical synthesis of zeolites with almost full silica utilization due to very low silica solubility. Compared to conventional hydrothermal synthesis, this work both enhances the zeolite yield and reduces waste emissions, even water zero emission. Particularly, structural defects (terminal silanols) in zeolites are obviously lowered, thus giving high thermal and hydrothermal stabilities and good performance in the Beckmann rearrangement.

Highly efficient and selective synthesis of renewable isoprene over Mo-Fe-O and MgO/Mg(OH)2 composite catalysts.

Synthesis of renewable isoprene continues to attract significant interest, yet catalysts still need improvement for industrial applications. We report herein an efficient and novel Prins tandem approach for highly selective production of isoprene from bio-based methanol and isobutene over Mo-Fe-O and MgO/Mg(OH)2 acid-base bifunctional catalysts. Hydration decreases the number of strong basic sites O2- ions and increases OH groups over MgO, thus improving the isoprene selectivity. Basic OH on Mg(OH)2 promotes the Prins condensation of formaldehyde and isobutene, while acidic OH promotes dehydration of isoprenol to isoprene. Suitable contents and proportions of basic and acidic OH groups over Mg(OH)2 increase isoprene selectivity and methanol conversion to 90 and 92% on the Mo-Fe-O+Mg(OH)2 composite catalysts, respectively. It exhibits good recycling stability, with isoprene selectivity remaining 90% after five successive regenerations. DFT calculations reveal OH groups formed after hydration reduce the energy barrier of the H transfer step, thereby promoting the overall reaction.

A Six-Membered Ring Molecular Sieve Achieved by a Reconstruction Route.

Zeolite molecular sieves with at least eight-membered rings are widely applied in industrial applications, while zeolite crystals with six-membered rings are normally regarded as useless products due to the occupancy of the organic templates and/or inorganic cation in the micropores that could not be removed. Herein, we showed that a novel six-membered ring molecular sieve (ZJM-9) with fully open micropores could be achieved by a reconstruction route. The mixed gas breakthrough experiments such as CH3OH/H2O, CH4/H2O, CO2/H2O, and CO/H2O at 25 °C showed that this molecular sieve was efficient for selective dehydration. Particularly, a lower desorption temperature (95 °C) of ZJM-9 than that (250 °C) of the commercial 3A molecular sieve might offer an opportunity for saving more energy in dehydration processes.

Design of an Organic Template for Synthesizing ITR Zeolites under Ge-Free Conditions.

Germanosilicate zeolites with various structures have been extensively synthesized, but the syntheses of corresponding zeolite structures in the absence of germanium species remain a challenge. One such example is an ITR zeolite structure, which is a twin of the ITH zeolite structure. Through the modification of a classic organic template for synthesizing ITH zeolites and thus designing a new organic template with high compatibility to ITR zeolite assisted by theoretical simulation, we, for the first time, show the Ge-free synthesis of an ITR structure including pure silica, aluminosilicate, and borosilicate ITR zeolites. These materials have high crystallinity, corresponding to an ITR content of more than 95%. In the methanol-to-propylene (MTP) reaction, the obtained aluminosilicate ITR zeolite exhibits excellent propylene selectivity and a long lifetime compared with conventional aluminosilicate ZSM-5 zeolite. The strategy for the design of organic templates might offer a new opportunity for rational syntheses of novel zeolites and, thus, the development of highly efficient zeolite catalysts in the future.

Porous Supramolecular Assemblies for Efficient Suzuki Coupling of Aryl Chlorides.

The development of catalytic systems that can activate aryl chlorides for palladium-catalyzed cross-coupling reactions is at the forefront of ongoing efforts to synthesize fine chemicals. In this study, a facile ligand-template approach is adopted to achieve active-site encapsulation by forming supramolecular assemblies; this bestowed the pristine inert counterparts with reactivity, which is further increased upon the construction of a porous framework. Experimental results indicated that the isolation of ligands by the surrounding template units is key to the formation of catalytically active monoligated palladium complexes. Additionally, the construction of porous frameworks using the resulting supramolecular assemblies prevented the decomposition of the Pd complexes into nanoparticles, which drastically increased the catalyst lifetime. These findings, along with the simplicity and generality of the synthesis scheme, suggest that the strategy can be leveraged to achieve unique reactivity and potentially enable fine-chemical synthesis.

Zeolite nanosheets for catalysis.

Zeolites with well-defined micropores have been widely used as heterogeneous catalysts in the fields of petroleum refining, fine chemicals, and environment protection. However, the sole micropores in the zeolite structures usually impose diffusion constraints, which would greatly influence their catalytic performances. Therefore, it is highly desirable to shorten the diffusion pathway of zeolites and thus eliminate the diffusion constraints. One of the efficient methods is to synthesize zeolite nanosheets, which has become a hot topic in the past decades. In this tutorial review, the recent progresses in the synthesis of zeolite nanosheets and their relevant catalysis are briefly discussed. Various strategies for the synthesis of zeolite nanosheets are summarized including delamination, templated crystallization, additive-assisted synthesis, seed-directed synthesis, and gaseous expansion synthesis. In addition, the catalytic reactions of zeolite nanosheets with acidic and metal sites are also outlined. This tutorial review should be significant for the design and preparation of highly efficient zeolite catalysts.

Advances in emission control of diesel vehicles in China.

Diesel vehicles have caused serious environmental problems in China. Hence, the Chinese government has launched serious actions against air pollution and imposed more stringent regulations on diesel vehicle emissions in the latest China VI standard. To fulfill this stringent legislation, two major technical routes, including the exhaust gas recirculation (EGR) and high-efficiency selective catalytic reduction (SCR) routes, have been developed for diesel engines. Moreover, complicated aftertreatment technologies have also been developed, including use of a diesel oxidation catalyst (DOC) for controlling carbon monoxide (CO) and hydrocarbon (HC) emissions, diesel particulate filter (DPF) for particle mass (PM) emission control, SCR for the control of NOx emission, and an ammonia slip catalyst (ASC) for the control of unreacted NH3. Due to the stringent requirements of the China VI standard, the aftertreatment system needs to be more deeply integrated with the engine system. In the future, aftertreatment technologies will need further upgrades to fulfill the requirements of the near-zero emission target for diesel vehicles.

Efficient Catalytic Production of Hydrogen Peroxide Using Tin-containing Zeolite Fixed Palladium Nanoparticles with Oxidation Resistance.

The metal surfaces tend to be oxidized in air through dissociation of the O-O bond of oxygen to reduce the performances in various fields. Although several ligand modification routes have alleviated the oxidation of bulky metal surfaces, it is still a challenge for the oxidation resistance of small-size metal nanoparticles. Herein, we fixed the small-size Pd nanoparticles in tin-contained MFI zeolite crystals, where the tin acts as an electron donor to efficiently hinder the oxidation of Pd by weakening the adsorption of molecular oxygen and suppressing the O-O cleavage. This oxidation-resistant Pd catalyst exhibited superior performance in directly synthesizing hydrogen peroxide from hydrogen and oxygen, with the productivity of hydrogen peroxide at ≈10,170 mmol gPd -1 h-1 , steadily outperforming the catalysts tested previously. This work leads to the hypothesis that tin is an electron donor to realize oxidation-resistant Pd within zeolite crystals for efficient catalysis to overcome the limitation of generally supported Pd catalysts and further motivates the use of oxidation-resistant metal nanoparticles in various fields.

Design of a Small Organic Template for the Synthesis of Self-Pillared Pentasil Zeolite Nanosheets.

Zeolite nanosheets with excellent mass transfer are attractive, but their successful syntheses are normally resulted from a huge number of experiments. Here, we show the design of a small organic template for the synthesis of self-pillared pentasil (SPP) zeolite nanosheets from theoretical calculations in interaction energies between organic templates and pentasil zeolite skeletons. As expected, the SPP zeolite nanosheets with the thickness at 10-20 nm have been synthesized successfully. Characterizations show that the SPP zeolite nanosheets with about 90% MFI and 10% MEL structures have good crystallinity, the house-of-card morphology, large surface area, and fully four-coordinated aluminum species. More importantly, methanol-to-propylene tests show that the SPP zeolite nanosheets exhibit much higher propylene selectivity and longer reaction lifetime than conventional ZSM-5 zeolite. These results offer a good opportunity to develop highly efficient zeolite catalysts in the future.

Coking-Resistant Polyethylene Upcycling Modulated by Zeolite Micropore Diffusion.

Although the mass production of synthetic plastics has transformed human lives, it has resulted in waste accumulation on the earth. Here, we report a low-temperature conversion of polyethylene into olefins. By mixing the polyethylene feed with rationally designed ZSM-5 zeolite nanosheets at 280 °C in flowing hydrogen as a carrier gas, light hydrocarbons (C1-C7) were produced with a yield of up to 74.6%, where 83.9% of these products were C3-C6 olefins with almost undetectable coke formation. The reaction proceeds in multiple steps, including polyethylene melting, flowing to access the zeolite surface, cracking on the zeolite surface, formation of intermediates to diffuse into the zeolite micropores, and cracking into small molecules in the zeolite micropores. The ZSM-5 zeolite nanosheets kinetically matched the cascade cracking steps on the zeolite external surface and within micropores by boosting the intermediate diffusion. This feature efficiently suppressed the intermediate accumulation on the zeolite surface to minimize coke formation. In addition, we found that hydrogen participation in the cracking process could hinder the formation of polycyclic species within zeolite micropores, which also contributes to the rapid molecule diffusion. The coking-resistant polyethylene upcycling process at a low temperature not only overturns the general viewpoint for facile coke formation in the catalytic cracking over the zeolites but also demonstrates how the polyethylene-based plastics can be upcycled to valuable chemicals. In addition to the model polyethylene, the reaction system worked efficiently for the depolymerization of multiple practically used polyethylene-rich plastics, enabling an industrially and economically viable path for dealing with plastic wastes.

Zeolite Fixed Metal Nanoparticles: New Perspective in Catalysis.

ConspectusLoading metal nanoparticles on the surface of solid supports has emerged as an efficient route for the preparation of heterogeneous catalysts. Notably, most of these supported metal nanoparticles still have shortcomings such as dissatisfactory activity and low product selectivity in catalysis. In addition, these metal nanoparticles also suffer from deactivation because of nanoparticle sintering, leaching, and coke formation under harsh conditions. The fixation of metal nanoparticles within zeolite crystals should have advantages of high activities for metal nanoparticles and excellent shape selectivity for zeolite micropores as well as extraordinary stability of metal nanoparticles immobilized with a stable zeolite framework, which is a good solution for the shortcomings of supported metal nanoparticles.Materials with metal nanostructures within the zeolite crystals are normally denoted as metal@zeolite, where the metal nanoparticles with diameters similar to those of industrial catalysts are usually larger than the micropore size. These metal nanoparticles are enveloped with the zeolite rigid framework to prevent migration under harsh reaction conditions, which is described as a fixed structure. The zeolite micropores allow the diffusion of reactants to the metal nanoparticles. As a result, metal@zeolite catalysts combine the features of both metal nanoparticles (high activity) and zeolites (shape selectivity and thermal stability), compared with the supported metal nanoparticles.In this Account, we describe how the zeolite micropore and metal nanoparticle synergistically work to improve the catalytic performance by the preparation of a variety of metal@zeolite catalysts. Multiple functions of zeolites with respect to the metal nanoparticles are highlighted, including control of the reactant/product diffusion in the micropores, the adjustment of reactant adsorption on the metal nanoparticles, and sieving the reactants and products with zeolite micropores. Furthermore, by optimizing the wettability of the zeolite external surface, the zeolite crystals could form a nanoreactor to efficiently enrich the crucial intermediates, thus boosting the performance in low-temperature methane oxidation. Also, the microporous confinement weakens the adsorption of C1 intermediates on the metal sites, accelerating the C-C coupling to improve C2 oxygenate productivity in syngas conversion. In particular, the zeolite framework efficiently stabilizes the metal nanoparticles against sintering and leaching to give durable catalysts. Clearly, this strategy not only guides the rational design of efficient heterogeneous catalysts for potential applications in a variety of industrial chemical reactions but also accelerates the fundamental understanding of the catalytic mechanisms by providing new model catalysts.

Porous Organic Phenanthroline-Based Polymer as an Efficient Transition-Metal-Free Heterogeneous Catalyst for Direct Aromatic C-H Activation.

Direct C-H bond transformation has been regarded as one of the most important areas in organic synthesis in both academia and industry. However, the heterogeneous transition-metal-free catalysis of direct C-H bond transformation has remained a contemporary challenge. To tackle this challenge, we designed and constructed a porous phenanthroline-based polymer (namely POP-Phen) via free radical polymerization of vinyl-functionalized phenanthroline monomers. POP-Phen shows excellent catalytic performances in transition-metal-free catalyzed C-H arylation, even better than those of the corresponding homogeneous catalyst, which is mainly attributed to the high density of catalytically active sites in the heterogeneous catalyst. Kinetic isotope experiments and spectral characterizations demonstrate the electron-transfer between the heterogeneous catalyst and the base (t-BuOK), a key step for C-H activation. We believe that this porous organic phenanthroline polymer could open a new door for the design of novel heterogeneous transition-metal-free catalysts for direct C-H activation.

Coking-Resistant Iron Catalyst in Ethane Dehydrogenation Achieved through Siliceous Zeolite Modulation.

Nonoxidative dehydrogenation is promising for production of light olefins from shale gas, but current technology relies on precious Pt or toxic Cr catalysts and suffers from thermodynamically oriented coke formation. To solve these issues, the earth-abundant iron catalyst is employed, where Fe species are effectively modulated by siliceous zeolite, which is realized by the synthesis of Fe-containing MFI siliceous zeolite in the presence of ethylenediaminetetraacetic sodium (FeS-1-EDTA). Catalytic tests in ethane dehydrogenation show that this catalyst has a superior coke resistance in a 200 h run without any deactivation with extremely high activity and selectivity (e.g., 26.3% conversion and over 97.5% selectivity to ethene in at 873 K, close to the thermodynamic equilibrium limitation). Multiple characterizations demonstrate that the catalyst has uniformly and stably isolated Fe sites, which improves ethane dehydrogenation to facilitate the fast desorption of hydrogen and olefin products in the zeolite micropores and hinders the coke formation, as also identified by density functional calculations.

Synthesis of Aluminophosphate Molecular Sieves in Alkaline Media.

Unlike conventional aluminosilicate zeolites synthesized in alkaline media, aluminophosphate molecular sieves (AlPOs) have always been prepared under acidic conditions in the past three decades; this has been regarded as one of essential factors for synthesis, except for the case of silica-substituted analogues (SAPOs). For the first time, we demonstrate herein a simple and generalized route for synthesizing various types of aluminophosphate molecular sieves in alkaline media. A series of aluminophosphate sieves and their analogues have been prepared with different quaternary ammonium cations as structure-directing agents in this manner. The above successes have extended the systematic media from acidic or neutral to alkaline for the preparation of a series of aluminophosphate molecular sieves, which possibly open an alternative route for the synthesis of aluminophosphate molecular sieves.

A Cationic Oligomer as an Organic Template for Direct Synthesis of Aluminosilicate ITH Zeolite.

There are a large number of zeolites, such as ITH, that cannot be prepared in the aluminosilicate form. Now, the successful synthesis of aluminosilicate ITH zeolite using a simple cationic oligomer as an organic template is presented. Key to the success is that the cationic oligomer has a strong complexation ability with aluminum species combined with a structural directing ability for the ITH structure similar to that of the conventional organic template. The aluminosilicate ITH zeolite has very high crystallinity, nanosheet-like crystal morphology, large surface area, fully four-coordinated Al species, and abundant acidic sites. Methanol-to-propylene (MTP) tests reveal that the Al-ITH zeolite shows much higher selectivity for propylene and longer lifetime than commercial ZSM-5. FCC tests show that Al-ITH zeolite is a good candidate as a shape-selective FCC additive for enhancing propylene and butylene selectivity.

Wet-Chemistry Strong Metal-Support Interactions in Titania-Supported Au Catalysts.

Classical strong metal-support interactions (SMSI), which play a crucial role in the preparation of supported metal nanoparticle catalysts, is one of the most important concepts in heterogeneous catalysis. The conventional wisdom for construction of classical SMSI involves in redox treatments at high-temperatures by molecular oxygen or hydrogen, sometimes causing sintered metal nanoparticles before SMSI formation. Herein, we report that the aforementioned issue can be effectively avoided by a wet-chemistry methodology. As a typical example, we demonstrate a new concept of wet-chemistry SMSI (wcSMSI) that can be constructed on titania-supported Au nanoparticles (Au/TiO2-wcSMSI), where the key is to employ a redox interaction between Auδ+ and Ti3+ precursors in aqueous solution. The wcSMSI is evidenced by covering Au nanoparticles with the TiO x overlayer, electronic interaction between Au and TiO2, and suppression of CO adsorption on Au nanoparticles. Owing to the wcSMSI, the Au-TiO x interface with an improved redox property is favorable for oxygen activation, accelerating CO oxidation. In addition, the oxide overlayer efficiently stabilizes the Au nanoparticles, achieving sinter-resistant Au/TiO2-wcSMSI catalyst in CO oxidation.

Product Selectivity Controlled by Nanoporous Environments in Zeolite Crystals Enveloping Rhodium Nanoparticle Catalysts for CO2 Hydrogenation.

Supported rhodium nanoparticles (NPs) are well-known for catalyzing methanation in CO2 hydrogenation. Now we demonstrate that the selectivity in this process can be optimized for CO production by choice of molecular sieve crystals as supports. The NPs are enveloped within the crystals with controlled nanopore environments that allow tuning of the catalytic selectivity to minimize methanation and favor the reverse water-gas shift reaction. Pure silica MFI (S-1)-fixed rhodium NPs exhibited maximized CO selectivity at high CO2 conversions, whereas aluminosilicate MFI zeolite-supported rhodium NPs displayed high methane selectivity under the equivalent conditions. Strong correlations were observed between the nanoporous environment and catalytic selectivity, indicating that S-1 minimizes hydrogen spillover and favors fast desorption of CO to limit deep hydrogenation. Materials in this class appear to offer appealing opportunities for tailoring selective supported catalysts for a variety of reactions.

Direct Synthesis of Aluminosilicate IWR Zeolite from a Strong Interaction between Zeolite Framework and Organic Template.

A large amount of zeolite structures are still not synthetically available or not available in the form of aluminosilicate currently. Despite significant progress in the development of predictive concepts for zeolite synthesis, accessing some of these new materials is still challenging. One example is the IWR structure as well. Despite successful synthesis of Ge-based IWR zeolites, direct synthesis of aluminosilicate IWR zeolite is still not successful. In this report we show how a suitable organic structure directing agent (OSDA), through modeling of an OSDA/zeolite cage interaction, could access directly the aluminum-containing IWR structure (denoted as COE-6), which might allow access to new classes of materials and thus open opportunities in valuable chemical applications. The experimental results reveal that the COE-6 zeolites with a SiO2/Al2O3 ratio as low as 30 could be obtained. Very interestingly, the COE-6 zeolite has much higher hydrothermal and thermal stabilities than those of the conventional Ge-Al-IWR zeolite. In methanol-to-propylene (MTP) reaction, the COE-6 zeolite exhibits excellent selectivity for propylene, offering a potential catalyst for MTP reaction in the future.

Solvent-Free Synthesis of Zeolites: Mechanism and Utility.

Zeolites have been extensively studied for years in different areas of chemical industry, such as shape selective catalysis, ion-exchange, and gas adsorption and separation. Generally, zeolites are prepared from solvothermal synthesis in the presence of a large amounts of solvents such as water and alcohols in sealed autoclaves under autogenous pressure. Water has been regarded as essential to synthesize zeolites for fast mass transfer of reactants, but it occupies a large space in autoclaves, which greatly reduces the yield of zeolite products. Furthermore, polluted wastes and relatively high pressure due to the presence of water solvent in the synthesis also leads to environmental and safety issues. Recently, inspired by great benefits of solvent-free synthesis, including the environmental concerns, energy consumption, safety, and economic cost, researchers continually challenge the rationale of the solvent and reconsider the age-old question "Do we actually need solvents at all in zeolite synthesis?" In this Account, we briefly summarize our efforts to rationally synthesize zeolites via a solvent-free route. Our research demonstrates that a series of silica, aluminosilicate, and aluminophosphate-based zeolites can be successfully prepared by mixing, grinding, and heating starting solid materials under solvent-free conditions. Combining an organotemplate-free synthesis with a solvent-free approach maximizes the advantages resulting in a more sustainable synthetic route, which avoids using toxic and costly organic templates and the formation of harmful gases by calcination of organic templates at high temperature. Furthermore, new insights into the solvent-free crystallization process of zeolites have been provided by modern techniques such as NMR and UV-Raman spectroscopy, which should be helpful in designing new zeolite structures and developing novel routes for synthesis of zeolites. The role of water and the vital intermediates during the crystallization of zeolites have been proposed and verified. In addition to a significant reduction in liquid wastes and a remarkable increase in zeolite yields, the solvent-free synthesis of zeolites exhibits more unprecedented benefits, including (i) the formation of hierarchical micro-, meso-, and macrostructures, which benefit the mass transfer in the reactions, (ii) rapid synthesis at higher temperatures, which greatly improve the space-time yields of zeolites, and (iii) construction of a novel catalytic system for encapsulation of metal nanoparticles and metal oxide particles within zeolite crystals synergistically combining the advantages of catalytic metal nanoparticles and metal oxide particles (high activity) and zeolites (shape selectivity). We believe that the concept of "solvent-free synthesis of zeolites" would open a door for deep understanding of zeolite crystallization and the design of efficient zeolitic catalysts.