A MAS NMR and DRIFT study of the Ga species in Ga/H-ZSM5 catalysts and their effect on propane ammoxidation

2005 ◽  
Vol 83 (6-7) ◽  
pp. 574-580 ◽  
Author(s):  
Prem Pal ◽  
Juliette Quartararo ◽  
Sharifah B Abd Hamid ◽  
Eric G Derouane ◽  
Jacques C Védrine ◽  
...  
Keyword(s):  
Main Product ◽  
External Surface ◽  
Catalytic Performance ◽  
Mas Nmr ◽  
Propane Ammoxidation ◽  
Bifunctional Mechanism ◽  
Propane Activation ◽  
Cationic Exchange ◽  
Zeolite Crystals

71Ga, 27Al, and 29Si MAS NMR and DRIFT spectroscopies were used to characterize the state of gallium in Ga/H-ZSM5 catalysts tested for their ability to catalyse the ammoxidation of propane. Ga species were observed in two different possible environments: octahedrally coordinated gallium in small Ga2O3 particles at the external surface of the zeolite crystals, octahedrally coordinated gallium in GaO(OH) or related species, and tetrahedrally coordinated gallium in cationic-exchange positions inside the zeolite. Redox (H2–O2) cycles promote the migration of gallium from the GaO(OH) or Ga2O3 species at the external surface of the zeolite crystals to cationic-exchange sites within the zeolite channels. The redox treatment definitely had a beneficial effect on its catalytic performance for the ammoxidation of propane, which is known to occur via a bifunctional mechanism. The main product was acetonitrile at high Ga and Al contents while acrylonitrile was also observed as a side product at high Ga and low Al contents.Key words: ZSM5, MFI, in situ studies, MAS NMR, DRIFT, propane activation, ammoxidation.

The Nature of Chemisorbed CO2 in Zeolite A

2019 ◽  
Author(s):  
Przemyslaw Rzepka ◽  
Zoltán Bacsik ◽  
Andrew J. Pell ◽  
Niklas Hedin ◽  
Aleksander Jaworski
Keyword(s):  
Solid State ◽  
Ir Spectroscopy ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Surface Coverage ◽  
Gas Mixtures ◽  
Mas Nmr ◽  
Significant Fraction ◽  
Zeolite A

Formation of CO<sub>3</sub><sup>2-</sup> and HCO<sub>3</sub><sup>-</sup> species without participation of the framework oxygen atoms upon chemisorption of CO<sub>2</sub> in zeolite |Na<sub>12</sub>|-A is revealed. The transfer of O and H atoms is very likely to have proceeded via the involvement of residual H<sub>2</sub>O or acid groups. A combined study by solid-state <sup>13</sup>C MAS NMR, quantum chemical calculations, and <i>in situ</i> IR spectroscopy showed that the chemisorption mainly occurred by the formation of HCO<sub>3</sub><sup>-</sup>. However, at a low surface coverage of physisorbed and acidic CO<sub>2</sub>, a significant fraction of the HCO<sub>3</sub><sup>-</sup> was deprotonated and transformed into CO<sub>3</sub><sup>2-</sup>. We expect that similar chemisorption of CO<sub>2</sub> would occur for low-silica zeolites and other basic silicates of interest for the capture of CO<sub>2</sub> from gas mixtures.

scholarly journals Ambient base-free glycerol oxidation over bimetallic PdFe/SiO2 by in situ generated active oxygen species

2021 ◽  
Author(s):  
Ricci Underhill ◽  
Mark Douthwaite ◽  
Richard J. Lewis ◽  
Peter J. Miedziak ◽  
Robert D. Armstrong ◽  
...  
Keyword(s):  
Heterogeneous Catalysts ◽  
Bimetallic Catalyst ◽  
Electron Paramagnetic Resonance Spectroscopy ◽  
Active Oxygen Species ◽  
Catalytic Performance ◽  
Resonance Spectroscopy ◽  
Oxygen Species ◽  
Paramagnetic Resonance ◽  
Temperature Oxidation

AbstractLow temperature oxidation of alcohols over heterogeneous catalysts is exceptionally challenging, particularly under neutral conditions. Herein, we report on an efficient, base-free method to oxidise glycerol over a 0.5%Pd-0.5%Fe/SiO2 catalyst at ambient temperature in the presence of gaseous H2 and O2. The exceptional catalytic performance was attributed to the in situ formation of highly reactive surface-bound oxygenated species, which promote the dehydrogenation on the alcohol. The PdFe bimetallic catalyst was determined to be significantly more active than corresponding monometallic analogues, highlighting the important role both metals have in this oxidative transformation. Fe leaching was confirmed to occur over the course of the reaction but sequestering experiments, involving the addition of bare carbon to the reactions, confirmed that the reaction was predominantly heterogeneous in nature. Investigations with electron paramagnetic resonance spectroscopy suggested that the reactivity in the early stages was mediated by surface-bound reactive oxygen species; no homogeneous radical species were observed in solution. This theory was further evidenced by a direct H2O2 synthesis study, which confirmed that the presence of Fe in the bimetallic catalyst neither improved the synthesis of H2O2 nor promoted its decomposition over the PdFe/SiO2 catalyst.

Surface Species Formed during Aniline Methylation on Zeolite H–Y Investigated by in Situ MAS NMR Spectroscopy

2001 ◽  
Vol 203 (2) ◽  
pp. 375-381 ◽  
Author(s):  
Irina I Ivanova ◽  
Elena B Pomakhina ◽  
Alexander I Rebrov ◽  
Michael Hunger ◽  
Yuryi G Kolyagin ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Mas Nmr ◽  
Surface Species

In situ growth of ultrathin Ni–Fe LDH nanosheets for high performance oxygen evolution reaction

2017 ◽  
Vol 4 (7) ◽  
pp. 1173-1181 ◽  
Author(s):  
Haidong Yang ◽  
Sha Luo ◽  
Yun Bao ◽  
Yutong Luo ◽  
Jun Jin ◽  
...  
Keyword(s):  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
High Performance ◽  
Copper Foil ◽  
Catalytic Performance ◽  
In Situ Growth ◽  
Ultrathin Nanosheet

The ultrathin Ni70Fe30LDH nanosheets were successfullyin situgrown on anodic polarized copper foil, denoted as u-Ni70Fe30LDHs/a-CF. Benefiting from the ultrathin nanosheet structure, the catalyst exhibits remarkable catalytic performance for OER in 1 M KOH solution.

scholarly journals Sealed rotors for in situ high temperature high pressure MAS NMR

2015 ◽  
Vol 51 (70) ◽  
pp. 13458-13461 ◽  
Author(s):  
Jian Zhi Hu ◽  
Mary Y. Hu ◽  
Zhenchao Zhao ◽  
Suochang Xu ◽  
Aleksei Vjunov ◽  
...  
Keyword(s):  
High Pressure ◽  
High Temperature ◽  
Mas Nmr ◽  
Material Synthesis ◽  
Widespread Application ◽  
High Temperature High Pressure

Perfectly sealed rotors were designed for the widespread application of in situ MAS NMR in catalysis, material synthesis, metabolomics, and more.

Spinalin, a new glycine- and histidine-rich protein in spines of Hydra nematocysts

1998 ◽  
Vol 111 (11) ◽  
pp. 1545-1554 ◽  
Author(s):  
A.W. Koch ◽  
T.W. Holstein ◽  
C. Mala ◽  
E. Kurz ◽  
J. Engel ◽  
...  
Keyword(s):  
External Surface ◽  
Insoluble Fraction ◽  
Cdna Clones ◽  
Mature Protein ◽  
Capsule Wall ◽  
The Matrix ◽  
Acidic Region ◽  
Basic Region ◽  
Full Length Clone

Here we present the cloning, expression and immunocytochemical localization of a novel 24 kDa protein, designated spinalin, which is present in the spines and operculum of Hydra nematocysts. Spinalin cDNA clones were identified by in situ hybridization to differentiating nematocytes. Sequencing of a full-length clone revealed the presence of an N-terminal signal peptide, suggesting that the mature protein is sorted via the endoplasmic reticulum to the post-Golgi vacuole in which the nematocyst is formed. The N-terminal region of spinalin (154 residues) is very rich in glycines (48 residues) and histidines (33 residues). A central region of 35 residues contains 19 glycines, occurring mainly as pairs. For both regions a polyglycine-like structure is likely and this may be stabilized by hydrogen bond-mediated chain association. Similar sequences found in loricrins, cytokeratins and avian keratins are postulated to participate in formation of supramolecular structures. Spinalin is terminated by a basic region (6 lysines out of 15 residues) and an acidic region (9 glutamates and 9 aspartates out of 32 residues). Western blot analysis with a polyclonal antibody generated against a recombinant 19 kDa fragment of spinalin showed that spinalin is localized in nematocysts. Following dissociation of the nematocyst's capsule wall with DTT, spinalin was found in the insoluble fraction containing spines and the operculum. Immunocytochemical analysis of developing nematocysts revealed that spinalin first appears in the matrix but then is transferred through the capsule wall at the end of morphogenesis to form spines on the external surface of the inverted tubule and the operculum.

scholarly journals Ultra-Small Pd(0) Nanoparticles into a Designed Semisynthetic Lipase: An Efficient and Recyclable Heterogeneous Biohybrid Catalyst for the Heck Reaction under Mild Conditions

Molecules ◽  
2018 ◽  
Vol 23 (9) ◽  
pp. 2358 ◽  
Author(s):  
David Lopez-Tejedor ◽  
Blanca de las Rivas ◽  
Jose M. Palomo
Keyword(s):  
Catalytic Activity ◽  
Protein Structure ◽  
Heck Reaction ◽  
Catalytic Performance ◽  
Reducing Agent ◽  
Chemically Modified ◽  
Mild Conditions ◽  
In Situ Formation ◽  
Geobacillus Thermocatenulatus

A novel heterogeneous enzyme-palladium (Pd) (0) nanoparticles (PdNPs) bionanohybrid has been synthesized by an efficient, green, and straightforward methodology. A designed Geobacillus thermocatenulatus lipase (GTL) variant genetically and then chemically modified by the introduction of a tailor-made cysteine-containing complementary peptide- was used as the stabilizing and reducing agent for the in situ formation of ultra-small PdNPs nanoparticles embedded on the protein structure. This bionanohybrid was an excellent catalyst in the synthesis of trans-ethyl cinnamate by Heck reaction at 65 °C. It showed the best catalytic performance in dimethylformamide (DMF) containing 10–25% of water as a solvent but was also able to catalyze the reaction in pure DMF or with a higher amount of water as co-solvent. The recyclability and stability were excellent, maintaining more than 90% of catalytic activity after five cycles of use.

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