One-Pot Synthesis of Ce-SSZ-39 Zeolite with Performance in the NH3-SCR Reaction.

Cu-SSZ-39 zeolite with 8-membered rings is regarded as a very promising catalyst in the NH3-SCR reaction, but its hydrothermal stability still remains to be improved. One of the solutions to promote hydrothermal stability is the insertion of rare earth elements in the product. Nevertheless, normal ion exchange of rare earth elements limits their contents in the zeolite product due to their large hydrated ionic radius and alkaline environment under hydrothermal conditions. Herein, we for the first time present a new method for the one-pot synthesis of Ce-SSZ-39 zeolite under solvent-free conditions. The key to success is the use of Ce-FAU zeolite as a precursor. The obtained product shows good crystallinity, sheet-like morphology, large BET surface area, and 4-coordinated Al species. Detailed investigations illustrate that Ce species in the Cu/Ce-SSZ-39 zeolite micropore can prevent the dealumination and thus formation of CuAlOx species during hydrothermal aging at 850 °C for 16 h, giving the excellent hydrothermal stability and thus showing the excellent catalytic performance in the NH3-SCR reaction. One-pot synthesis of Ce-SSZ-39 zeolite with excellent catalytic performance might open a new door for developing very efficient selective catalytic reduction (SCR) catalysts in near future.

Insights into the Synthesis of Spiral Beta Zeolite with Enhanced Catalytic Performance in VOC Abatement.

The rational synthesis of zeolites with designed morphology is a highly challenging task. In this study, we propose 1,5-bis(methylpiperidine)pentylammonium hydroxide (BMPPAOH) as an organic structure-directing agent (OSDA) based on theoretical calculations. The morphology of zeolite samples is characterized by XRD, SEM, TEM, N2 sorption isotherms, and UV Raman spectroscopy. This simple bis-quaternary ammonium salt favored the formation of spiral morphology in Beta zeolite spheres (S-Beta). The crystallization of zeolite in the presence of BMMPAOH is a two-stage process, where nanoparticles agglomerate into spheres in the early stages followed by the emergence of S-Beta crystals with spiral morphology. The synthesized Pt-S-Beta catalysts show higher catalytic activity in VOC abatement compared with other Pt-Beta samples.

Enhanced Ammonia Decomposition by Tuning the Support Properties of Ni/GdxCe1-xO2-δ at 600 °C.

Ammonia decomposition is a promising method to produce high-purity hydrogen. However, this process typically requires precious metals (such as Ru, Pt, etc.) as catalysts to ensure high efficiency at relatively low temperatures. In this study, we propose using several Ni/GdxCe1-xO2-δ catalysts to improve ammonia decomposition performance by adjusting the support properties. We also investigate the underlying mechanism for this enhanced performance. Our results show that Ni/Ce0.8Gd0.2O2-δ at 600 °C can achieve nearly complete ammonia decomposition, resulting in a hydrogen production rate of 2008.9 mmol.g-1.h-1 with minimal decrease over 150 h. Density functional theory calculations reveal that the recombinative desorption of nitrogen is the rate-limiting step of ammonia decomposition over Ni. Our characterizations indicate that Ni/Ce0.8Gd0.2O2-δ exhibits a high concentration of oxygen vacancies, highly dispersed Ni on the surface, and abundant strong basic sites. These properties significantly enhance the associative desorption of N and strengthen the metal support interactions, resulting in high catalytic activity and stability. We anticipate that the mechanism could be applied to designing additional catalysts with high ammonia decomposition performance at relatively low temperatures.

Exploration of the Corrosion Behavior of Electroless Plated Ni-P Amorphous Alloys via X-ray Photoelectron Spectroscopy.

A Ni-P amorphous alloy was deposited on a low carbon steel substrate via electroless plating. Further, the prepared samples were crystallized under the high temperature with a range from 200 °C to 500 °C in air for 1 h. The crystallization process was studied via XRD, AFM, and XPS, and anodic electrochemical behavior was investigated by potentiostatic methods in a 3.5 wt% NaCl solution. The experimental results indicate that the diffusion, dissolution, and enrichment of the component elements in the Ni-P alloy are essential during crystallization because the various corrosion behaviors corresponding to Ni and P are directly affected. More importantly, under the 400 °C treatment, H2PO2- was enriched in the alloy, which effectively hinders the anodic dissolution of nickel and forms a complete adsorption layer on the surface of the alloy. Our results demonstrate that P can effectively block the anodic dissolution of Ni during the corrosion process, and the crystallization process can effectively promote the surface enrichment of P to improve the corrosion resistance of the coating.

Advances in the Synthesis of Crystalline Metallosilicate Zeolites via Interlayer Expansion.

Given the numerous industrial applications of zeolites as adsorbents, catalysts, and ion-exchangers, the development of new zeolite structures is highly desired to expand their practical applications. Currently, a general route to develop new zeolite structures is to use interlayer expansion agents to connect layered silicates. In this review, we briefly summarize the novel zeolite structures constructed from the lamellar precursor zeolites MWW, RUB-36, PREFER, Nu-6(1), COK-5, and PLS-1 via interlayer expansion. The contents of the summary contain detailed experiments, physicochemical characterizations, possible expansion mechanisms, and catalytic properties. In addition, the insertion of metal heteroatoms (such as Ti, Fe, Sn) into the layered zeolite precursor through interlayer expansion, which could be helpful to modify the catalytic function, is discussed.

Facile Synthesis of Uniform Mesoporous Nb2O5 Micro-Flowers for Enhancing Photodegradation of Methyl Orange.

The removal of organic pollutants using green environmental photocatalytic degradation techniques urgently need high-performance catalysts. In this work, a facile one-step hydrothermal technique has been successfully applied to synthesize a Nb2O5 photocatalyst with uniform micro-flower structure for the degradation of methyl orange (MO) under UV irradiation. These nanocatalysts are characterized by transmission and scanning electron microscopies (TEM and SEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, and UV-Vis diffuse reflectance spectroscopy (DRS). It is found that the prepared Nb2O5 micro-flowers presents a good crystal phases and consist of 3D hierarchical nanosheets with 400-500 nm in diameter. The surface area is as large as 48.6 m2 g-1. Importantly, the Nb2O5 micro-flowers exhibit superior catalytic activity up to 99.9% for the photodegradation of MO within 20 mins, which is about 60-fold and 4-fold larger than that of without catalysts (W/O) and commercial TiO2 (P25) sample, respectively. This excellent performance may be attributed to 3D porous structure with abundant catalytic active sites.

Preparation of Aluminosilicate Ferrierite Zeolite Nanosheets with Controllable Thickness in the Presence of a Sole Organic Structure Directing Agent.

Preparation of aluminosilicate ferrierite (FER) zeolite nanosheets with controllable thickness in the presence of a sole organic ammonium is attractive, but still challenging. In this report, with the employment of N,N-diethyl-cis-2,6-dimethylpiperidinium (DMP) as both a structure directing agent and crystal growth inhibitor, aluminosilicate FER zeolite nanosheets, with a variety of crystal thicknesses, ranging from 6 to 200 nm, are successfully synthesized under hydrothermal conditions. Very interestingly, the amount of DMP in the starting gel is the key factor for crystal thickness control of aluminosilicate FER zeolite nanosheets. The obtained FER products, with different thicknesses, are well characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), N2 sorption, thermogravimetric analysis (TG), inductively coupled plasma (ICP), and magic angle spinning nuclear magnetic resonance (MAS NMR) techniques. This simple strategy might provide a novel avenue for the synthesis of other zeolite nanosheets with controllable thickness.

Controllable cyanation of carbon-hydrogen bonds by zeolite crystals over manganese oxide catalyst.

The synthesis of organic nitriles without using toxic cyanides is in great demand but challenging to make. Here we report an environmentally benign and cost-efficient synthesis of nitriles from the direct oxidative cyanation of primary carbon-hydrogen bonds with easily available molecular oxygen and urea. The key to this success is to design and synthesize manganese oxide catalysts fixed inside zeolite crystals, forming a manganese oxide catalyst with zeolite sheath (MnOx@S-1), which exhibits high selectivity for producing nitriles by efficiently facilitating the oxidative cyanation reaction and hindering the side hydration reaction. The work delineates a sustainable strategy for synthesizing nitriles while avoiding conventional toxic cyanide, which might open a new avenue for selective transformation of carbon-hydrogen bonds.

Design and preparation of efficient hydroisomerization catalysts by the formation of stable SAPO-11 molecular sieve nanosheets with 10-20 nm thickness and partially blocked acidic sites.

SAPO-11 nanosheets with partially filled micropores (N-SAPO-11) and a thickness of 10-20 nm were synthesized using polyhexamethylene biguanide hydrochloride (PHMB) as a mesoporogen and di-n-propylamine (DPA) as a microporous template. After Pt loading (0.5 wt%), the Pt/N-SAPO-11 catalyst exhibits higher selectivity for the isomers and lower selectivity for cracking products than conventional Pt/SAPO-11 catalysts in the hydroisomerization of n-dodecane.

Selective hydrogenolysis of carbon-oxygen bonds with formic acid over a Au-Pt alloy catalyst.

We reported selective hydrogenolysis of carbon-oxygen species over a CeO2-supported Au-Pt alloy catalyst (Au-Pt/CeO2) using biomass-derived formic acid as the hydrogen source. The success of this reaction is reasonably attributed to the high efficiency of Au-Pt/CeO2 in the tandem steps of formic acid dehydrogenation and carbon-oxygen species hydrodeoxygenation.

A Hierarchical Bipyridine-Constructed Framework for Highly Efficient Carbon Dioxide Capture and Catalytic Conversion.

As a C1 feedstock, CO2 has the potential to be uniquely highly economical in both a chemical and a financial sense. Porous materials bearing particular binding and active sites that can capture and convert CO2 simultaneously are promising candidates for CO2 utilization. In this work, a bipyridine-constructed polymer featuring a high surface area, a hierarchical porous structure, and excellent stability was synthesized through free-radical polymerization. After metalation, the resultant catalysts exhibited superior activities in comparison with those of their homogeneous counterparts in the cycloaddition of CO2 to epoxides. The high performance of the heterogeneous catalysts originates from cooperative effects between the CO2 -philic polymer and the embedded metal species. In addition, the catalysts showed excellent stabilities and are readily recyclable; thus, they are promising for practical utilization for the conversion of CO2 into value-added chemicals.

Importance of platinum particle size for complete oxidation of toluene over Pt/ZSM-5 catalysts.

Size-controllable Pt nanoparticles ranging from 1.3 to 2.3 nm were successfully loaded onto ZSM-5 (Pt-x/ZSM-5, where x is the mean diameter of the Pt nanoparticles). Catalytic tests in complete oxidation of toluene as a model for VOC removal show that Pt-1.9/ZSM-5 has the highest activity, due to a balance of Pt dispersion and Pt(0) proportion.

Solvent-free synthesis of zeolites from anhydrous starting raw solids.

Development of sustainable routes for synthesis of zeolites is very important because of wide applications of zeolites at large scale in the fields of catalysis, adsorption, and separation. Here we report a novel and generalized route for synthesis of zeolites in the presence of NH4F from grinding the anhydrous starting solid materials and heating at 140-240 °C. Accordingly, zeolites of MFI, BEA*, EUO, and TON structures have been successfully synthesized. The presence of F(-) drives the crystallization of these zeolites from amorphous phase. Compared with conventional hydrothermal synthesis, the synthesis in this work not only simplifies the synthesis process but also significantly enhances the zeolite yields. These features should be potentially of great importance for industrial production of zeolites at large scale in the future.

Solvent-free syntheses of hierarchically porous aluminophosphate-based zeolites with AEL and AFI structures.

Development of sustainable routes for synthesizing aluminophosphate-based zeolites are very important because of their wide applications. As a typical sustainable route, solvent-free synthesis of zeolites not only decreases polluted wastes but also increases product yields. Systematic solvent-free syntheses of hierarchically porous aluminophosphate-based zeolites with AEL and AFI structures is presented. XRD patterns and SEM images show that these samples have high crystallinity. N2 sorption isotherm tests show that these samples are hierarchically porous, and their surface areas are comparable with those of corresponding zeolites from hydrothermal route. Chosen as an example, catalytic oxidation of ethylbenzene with O2 shows that cobalt substituted APO-11 from the solvent-free route (S-CoAPO-11) is more active than conventional CoAPO-11 from hydrothermal route owing to the sample hierarchical porosity.