Catalytic oxidation of formaldehyde over silver supported on ZSM-5: The role of Ag and mesopores

Silver nanoparticles (AgNPs) are increasingly drawing a great deal of attention because of their exclusive properties and a huge variety of applications. In recent years, using AgNPs supported on various carriers as heterogeneous catalysts has become promising for treating some toxic gases in the environment, such as HCHO. This study has successfully synthesized AgNPs onto ZSM-5 microporous zeolite and ZSM-5 mesopore-modified zeolite (Meso-ZSM-5) by ion-exchange method using sodium borohydride as a reducing agent. The resulting catalysts were then characterized by N2 adsorption-desorption method. In order to evaluate HCHO adsorption, desorption, and the surface reaction of these catalysts, temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) were employed. The TPD and TPSR experiments were conducted with different relative humidity. The results showed that Ag/Meso-ZSM-5 exhibited higher catalyst activity in HCHO complete oxidation than Ag/ZSM-5 at high temperatures because of a new larger pore system within the zeolite. Furthermore, TPD and TPSR experiments provided an explanation for the poor performance of the catalysts at low temperatures, which was associated with the high adsorption capacity of the zeolite.

Novel aluminophosphate Na6[Al3P5O20] with the original microporous crystal structure established in the study of a pseudomerohedric microtwin

The synthesis and characterization of a new aluminophosphate, Na6[Al3P5O20], obtained as single crystals in the same experiment together with Cl-sodalite, Na8[Al6Si6O24]Cl2, is reported. Na6[Al3P5O20], with a strongly pseudo-orthorhombic lattice, is described by the monoclinic crystal structure established in the study of a pseudomerohedric microtwin. The design of Na6[Al3P5O20] can be interpreted as an alternative to sodalite, with a monoclinic (pseudo-orthorhombic) 2×4×1 super-structure and unit-cell parameters multiples of those of sodalite: a ≃ 2a s, b ≃ 4b s and c ≃ c s. The triperiodic framework is built by AlO6, AlO4 and PO4 polyhedra having vertex-bridging contacts. While all the oxygen vertices of the Al-centred octahedra and tetrahedra are shared with phosphate groups, some of the PO4 tetrahedra remain `pendant', e.g. containing vertices not shared with other polyhedra of the aluminophosphate construction. Na atoms occupy framework channels and cavities surrounded by eight-, six- and four-membered windows with maximal effective pore widths of 4.86 × 3.24 and 4.31 × 3.18 Å. The generalized framework density is equal to 19.8, which means that the compound may be classified as a microporous zeolite. The Na6[Al3P5O20] crystal structure is discussed as being formed from octahedral rods arranged in two perpendicular directions, similar to the rods elongated in one direction in the NASICON-type compounds, which have been intensively investigated as promising materials for batteries. Analogous properties can be expected for phases with a modified composition of the Na6Al3P5O20 topology, where the Al atoms at the centres of octahedra are replaced by Fe, V or Cr.

Conversion of Glycerol to Value Added Products in a Semi-Continuous Batch Reactor Using Noble Metals Supported on ZSM-11 Zeolite

Au, Pt, and Pd supported on ZSM-11 microporous zeolite were investigated as catalysts for glycerol (GLY) oxidation towards higher value added products. ZSM-11 was synthesized by hydrothermal treatment. Subsequently, ion exchange with NH4Cl was performed to recover acidic sites and then, Au, Pt, and Pd were incorporated onto this material by wet impregnation procedure. After thermal treatment of desorption and calcination, the corresponding Au, Pt, and Pd-ZSM-11 catalysts were obtained. These materials were characterized by different techniques, such as XRD, ICP, TEM- XEDS, and XPS, and were evaluated in the glycerol oxidation reaction by using alkaline medium and molecular oxygen as oxidizing agent. The higher conversion of GLY (66.5 mol.%) was reached for the Pt–ZSM-11 catalyst with moderate selectivity towards lactic acid (LA), while the bimetallic Au-Pt-ZSM-11 catalyst offered high selectivity to LA at moderate GLY conversion. Optimization of the main reaction parameters (i.e., temperature, reaction time and NaOH/GLY ratio) was carried out to maximize the selectivity towards the LA desired product. Thus, LA selectivity values close to 55% at GLY conversion >65% can be reached by using Pt-ZSM-11 as a catalyst under mild reaction conditions.

Activation and conversion of alkanes in the confined space of zeolite-type materials

Microporous zeolite-type materials are able to activate and efficiently convert stable C1+ alkanes. This review analyzes, at the molecular level, the role of active sites and the contribution of diffusion, shape-selectivity and confinement effects.

Krasnoshteinite, Al8[B2O4(OH)2](OH)16Cl4⋅7H2O, a New Microporous Mineral with a Novel Type of Borate Polyanion

A new mineral, krasnoshteinite (Al8[B2O4(OH)2](OH)16Cl4⋅7H2O), was found in the Verkhnekamskoe potassium salt deposit, Perm Krai, Western Urals, Russia. It occurs as transparent colourless tabular to lamellar crystals embedded up to 0.06 x 0.25 x 0.3 mm in halite-carnallite rock and is associated with dritsite, dolomite, magnesite, quartz, baryte, kaolinite, potassic feldspar, congolite, members of the goyazite–woodhouseite series, fluorite, hematite, and anatase. Dmeas = 2.11 (1) and Dcalc = 2.115 g/cm3. Krasnoshteinite is optically biaxial (+), α = 1.563 (2), β = 1.565 (2), γ = 1.574 (2), and 2Vmeas = 50 (10)°. The chemical composition (wt.%; by combination of electron microprobe and ICP-MS; H2O calculated from structure data) is: B2O3 8.15, Al2O3 46.27, SiO2 0.06, Cl 15.48, H2Ocalc. 33.74, –O=Cl –3.50, totalling 100.20. The empirical formula calculated based on O + Cl = 33 apfu is (Al7.87Si0.01)Σ7.88[B2.03O4(OH)2][(OH)15.74(H2O)0.26]Σ16[(Cl3.79(OH)0.21]Σ4⋅7H2O. The mineral is monoclinic, P21, a = 8.73980 (19), b = 14.4129 (3), c = 11.3060 (3) Å, β = 106.665 (2)°, V = 1364.35 (5) Å3, and Z = 2. The crystal structure of krasnoshteinite (solved using single-crystal data, R1 = 0.0557) is unique. It is based upon corrugated layers of Al-centered octahedra connected via common vertices. BO3 triangles and BO2(OH)2 tetrahedra share a common vertex, forming insular [B2O4(OH)2]4− groups (this is a novel borate polyanion) which are connected with Al-centered octahedra via common vertices to form the aluminoborate pseudo-framework. The structure is microporous, zeolite-like, with a three-dimensional system of wide channels containing Cl- anions and weakly bonded H2O molecules. The mineral is named in honour of the Russian mining engineer and scientist Arkadiy Evgenievich Krasnoshtein (1937–2009). The differences in crystal chemistry and properties between high-temperature and low-temperature natural Al borates are discussed.

Catalytic Performance of Toluene Combustion over Pt Nanoparticles Supported on Pore-Modified Macro-Meso-Microporous Zeolite Foam

Herein, to investigate the pore effect on toluene catalytic oxidation activity, novel supports for Pt nanoparticles—ZSM-5 foam (ZF) fabricated using polyurethane foam (PUF) templates and pore-modified ZSM-5 foam (ZF-D) treated by acid etching, comparing with conventional ZSM-5 and pore-modified ZSM-5 (ZSM-5-D), were successfully synthesized. Pt nanoparticles were loaded on series ZSM-5 supports by the impregnation method. The Pt loaded on ZF-D (Pt/ZF-D) showed the highest activity of toluene catalytic combustion (i.e., T90 = 158 °C), with extraordinary stability and an anti-coking ability. Based on various catalysts characterizations, the unique macropores of ZF facilitated the process of acid etching as compared to conventional ZSM-5. The mesopores volume of ZF-D significantly increased due to acid etching, which enlarged toluene adsorption capacity and led to a better Pt distribution since some Pt nanoparticles were immobilized into some mesopores. Specifically, the microporous distribution was centered in the range of 0.7–0.8 nm close to the molecular diameter of toluene (ca. 0.67 nm), which was key to the increasing toluene diffusion rate due to pore levitation effect of catalysts and accessibility of metal. Furthermore, the reducibility of Pt nanoparticles was improved on Pt/ZF-D, which enhanced the activity of toluene catalytic oxidation.