What catalysis needs from the electron microscopist

1988 ◽  
Vol 46 ◽  
pp. 694-695
Author(s):  
Alexis T. Bell
Keyword(s):  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Catalyst Deactivation ◽  
Surface Composition ◽  
Internal Surface ◽  
Active Phase ◽  
Atomic Scale ◽  
Metal Catalyst ◽  
Internal Surface Area ◽  
Porous Support

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.

scholarly journals Designing Heterogeneous Catalysts for Renewable Catalysis Applications Using Metal Oxide Deposition

2019 ◽  
Vol 73 (9) ◽  
pp. 698-706
Author(s):  
Yuan-Peng Du ◽  
Jeremy S. Luterbacher
Keyword(s):  
Heterogeneous Catalysis ◽  
Metal Oxide ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Catalyst Deactivation ◽  
High Surface ◽  
Catalyst Stability ◽  
Synthetic Control ◽  
High Oxygen Content ◽  
Oxide Deposition

Heterogeneous catalysis has long been a workhorse for the chemical industry and will likely play a key role in the emerging area of renewable chemistry. However, renewable molecule streams pose unique challenges for heterogeneous catalysis due to their high oxygen content, frequent low volatility and the near constant presence of water. These constraints can often lead to the need for catalyst operation in harsh liquid phase conditions, which has compounded traditional catalyst deactivation issues. Oxygenated molecules are also frequently more reactive than petroleum-derived molecules, which creates a need for highly selective catalysts. Synthetic control over the nanostructured environment of catalytic active sites could facilitate the creation of both more stable and selective catalysts. In this review, we discuss the use of metal oxide deposition as an emerging strategy that can be used to synthesize and/or modify heterogeneous catalysts to introduce tailored nanostructures. Several important applications are reviewed, including the synthesis of high surface area mesoporous metal oxides, the enhancement of catalyst stability, and the improvement of catalyst selectivity.

scholarly journals Pd-Functionalized SnO2 Nanofibers Prepared by Shaddock Peels as Bio-Templates for High Gas Sensing Performance toward Butane

Nanomaterials ◽  
2018 ◽  
Vol 9 (1) ◽  
pp. 13 ◽  
Author(s):  
Rongjun Zhao ◽  
Zhezhe Wang ◽  
Yue Yang ◽  
Xinxin Xing ◽  
Tong Zou ◽  
...  
Keyword(s):  
Active Sites ◽  
Gas Sensing ◽  
Spillover Effect ◽  
Internal Surface ◽  
Pd Nanoparticles ◽  
Sno2 Nanostructures ◽  
Pure Sno2 ◽  
Internal Surface Area ◽  
One Dimensional ◽  
Practical Applications

Pd-functionalized one-dimensional (1D) SnO2 nanostructures were synthesized via a facile hydrothermal method and shaddock peels were used as bio-templates to induce a 1D-fiber-like morphology into the gas sensing materials. The gas-sensing performances of sensors based on different ratios of Pd-functionalized SnO2 composites were measured. All results indicate that the sensor based on 5 mol % Pd-functionalized SnO2 composites exhibited significantly enhanced gas-sensing performances toward butane. With regard to pure SnO2, enhanced levels of gas response and selectivity were observed. With 5 mol % Pd-functionalized SnO2 composites, detection limits as low as 10 ppm with responses of 1.38 ± 0.26 were attained. Additionally, the sensor exhibited rapid response/recovery times (3.20/6.28 s) at 3000 ppm butane, good repeatability and long-term stability, demonstrating their potential in practical applications. The excellent gas-sensing performances are attributed to the unique one-dimensional morphology and the large internal surface area of sensing materials afforded using bio-templates, which provide more active sites for the reaction between butane molecules and adsorbed oxygen ions. The catalysis and “spillover effect” of Pd nanoparticles also play an important role in the sensing of butane gas as further discussed in the paper.

scholarly journals Directing reaction pathways via in situ control of active site geometries in PdAu single-atom alloy catalysts

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Mengyao Ouyang ◽  
Konstantinos G. Papanikolaou ◽  
Alexey Boubnov ◽  
Adam S. Hoffman ◽  
Georgios Giannakakis ◽  
...  
Keyword(s):  
Active Site ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Bimetallic Catalyst ◽  
Theoretical Calculations ◽  
Atomic Scale ◽  
Single Atom ◽  
In Situ Control ◽  
Single Atom Alloy

AbstractThe atomic scale structure of the active sites in heterogeneous catalysts is central to their reactivity and selectivity. Therefore, understanding active site stability and evolution under different reaction conditions is key to the design of efficient and robust catalysts. Herein we describe theoretical calculations which predict that carbon monoxide can be used to stabilize different active site geometries in bimetallic alloys and then demonstrate experimentally that the same PdAu bimetallic catalyst can be transitioned between a single-atom alloy and a Pd cluster phase. Each state of the catalyst exhibits distinct selectivity for the dehydrogenation of ethanol reaction with the single-atom alloy phase exhibiting high selectivity to acetaldehyde and hydrogen versus a range of products from Pd clusters. First-principles based Monte Carlo calculations explain the origin of this active site ensemble size tuning effect, and this work serves as a demonstration of what should be a general phenomenon that enables in situ control over catalyst selectivity.

scholarly journals Desalination Performance of Modified Multiwall Carbon Nanotubes

2017 ◽  
Vol 1 (1) ◽  
Author(s):  
Dengsong Zhang ◽  
Liyi Shil ◽  
Jianhui Fang ◽  
Kai Dai
Keyword(s):  
Carbon Nanotubes ◽  
Surface Area ◽  
Sea Water ◽  
Multiwall Carbon Nanotubes ◽  
Internal Surface ◽  
Water Desalination ◽  
Metal Catalyst ◽  
Internal Surface Area ◽  
Hno3 Solution ◽  
Multiwall Carbon

Modified multiwall carbon nanotubes (MWCNTs) were used as the electrodes of flow–through capacitor for the desalination, which were cost–cutting, energy–saving, and enviromnent–friendly and could be expected to be an altemative technology for reverse osmosis membrane for sea water desalination. Investigated by transmission electron microscope (TEM) and nitrogen adsorption/desorption for modified MWCNTs, it was confirmed that after modification treatment by immersion in diluted HNO3 solution with ultrasonic and then milling by ball at a high velocity, the metal catalyst particles at the tip of MWCNTs disappeared, the MWCNT length became short, the cap at the tip of nanotube was opened, the internal surface area could be effectively used, leading to the increase of the specific surface area and pore volume, and thus MWCNTs modified by that method had the best desalination performance. This modification technique is simple and the efficiency is high.

Novel Xerogel Catalyst Materials for Hydrogenation Reactions and the Role of Atomic Scale Interfaces

1999 ◽  
Vol 5 (S2) ◽  
pp. 704-705
Author(s):  
P.L. Gai ◽  
K. Kourtakis ◽  
H. Dindi ◽  
S. Ziemecki
Keyword(s):  
High Resolution ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Low Voltage ◽  
High Surface ◽  
Sol Gel ◽  
High Surface Area ◽  
High Resolution Electron Microscopy ◽  
Atomic Scale ◽  
Hydrogenation Reactions

We are developing a new family of heterogeneous catalysts for hydrogenation catalysis. Catalyst synthesis is accomplished using colloidal polymerization chemistry which produce high surface area xerogel catalysts. These xerogels have been synthesized by one-step sol gel chemistry. These catalysts contain ruthenium and modifiers such as gold occluded or incorporated in a titanium oxide matrix. The materials, especially the modified systems exhibit favorable performance in microreactor evaluations for hydrogenation reactions and exhibit high activities. Nanostructural studies have revealed that the materials contain dispersed catalyst clusters which are desirable microstructures for the catalysis since the majority of the atoms are exposed to catalysis and are potentially active sites.The composition and atomic structure of the xerogel catalysts containing ruthenium and other metals have been examined using our in-house developments of environmental high resolution electron microscopy (EHREM) the atomic scale [1-3] and low voltage high resolution SEM (LVSEM)[4] methods.

Electron holography of catalysts

1995 ◽  
Vol 53 ◽  
pp. 416-417
Author(s):  
A. K. Datye ◽  
D. S. Kalakkad ◽  
L. F. Allard ◽  
E. Völkl
Keyword(s):  
Heterogeneous Catalysts ◽  
High Surface ◽  
High Surface Area ◽  
Atomic Scale ◽  
Nano Particles ◽  
Phase Image ◽  
Electron Holography ◽  
Specimen Thickness ◽  
Phase Information ◽  
Particle Structure

The active phase in heterogeneous catalysts consists of nanometer-sized metal or oxide particles dispersed within the tortuous pore structure of a high surface area matrix. Such catalysts are extensively used for controlling emissions from automobile exhausts or in industrial processes such as the refining of crude oil to produce gasoline. The morphology of these nano-particles is of great interest to catalytic chemists since it affects the activity and selectivity for a class of reactions known as structure-sensitive reactions. In this paper, we describe some of the challenges in the study of heterogeneous catalysts, and provide examples of how electron holography can help in extracting details of particle structure and morphology on an atomic scale.Conventional high-resolution TEM imaging methods permit the image intensity to be recorded, but the phase information in the complex image wave is lost. However, it is the phase information which is sensitive at the atomic scale to changes in specimen thickness and composition, and thus analysis of the phase image can yield important information on morphological details at the nanometer level.

scholarly journals Synergistic Effect of Alkali Na and K Promoter on Fe-Co-Cu-Al Catalysts for CO2 Hydrogenation to Light Hydrocarbons

Catalysts ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 735
Author(s):  
Yuhao Zheng ◽  
Chenghua Xu ◽  
Xia Zhang ◽  
Qiong Wu ◽  
Jie Liu
Keyword(s):  
Synergistic Effect ◽  
Active Sites ◽  
Intermediate Formation ◽  
Active Phase ◽  
Dissociative Adsorption ◽  
Co2 Hydrogenation ◽  
Chain Growth ◽  
Co2 Conversion ◽  
Light Hydrocarbons ◽  
Active Centers

Alkali metal K- and/or Na-promoted FeCoCuAl catalysts were synthesized by precipitation and impregnation, and their physicochemical and catalytic performance for CO2 hydrogenation to light hydrocarbons was also investigated in the present work. The results indicate that Na and/or K introduction leads to the formation of active phase metallic Fe and Fe-Co crystals in the order Na < K < K-Na. The simultaneous introduction of Na and K causes a synergistic effect on increasing the basicity and electron-rich property, promoting the formation of active sites Fe@Cu and Fe-Co@Cu with Cu0 as a crystal core. These effects are advantageous to H2 dissociative adsorption and CO2 activation, giving a high CO2 conversion with hydrogenation. Moreover, electron-rich Fe@Cu (110) and Fe-Co@Cu (200) provide active centers for further H2 dissociative adsorption and O-C-Fe intermediate formation after adsorption of CO produced by RWGS. It is beneficial for carbon chain growth in C2+ hydrocarbons, including olefins and alkanes. FeCoCuAl simultaneously modified by K-Na exhibits the highest CO2 conversion and C2+ selectivity of 52.87 mol% and 89.70 mol%, respectively.

scholarly journals Heat-Up Performance of Catalyst Carriers—A Parameter Study and Thermodynamic Analysis

Energies ◽  
2021 ◽  
Vol 14 (4) ◽  
pp. 964
Author(s):  
Thomas Steiner ◽  
Daniel Neurauter ◽  
Peer Moewius ◽  
Christoph Pfeifer ◽  
Verena Schallhart ◽  
...  
Keyword(s):  
Heat Transfer ◽  
Heat Transfer Coefficient ◽  
Transfer Coefficient ◽  
Surface Area ◽  
Internal Surface ◽  
Installation Space ◽  
Parameter Study ◽  
Thin Wall ◽  
Primary Role ◽  
Internal Surface Area

This study investigates geometric parameters of commercially available or recently published models of catalyst substrates for passenger vehicles and provides a numerical evaluation of their influence on heat-up behavior. Parameters considered to have a significant impact on the thermal economy of a monolith are: internal surface area, heat transfer coefficient, and mass of the converter, as well as its heat capacity. During simulation experiments, it could be determined that the primary role is played by the mass of the monolith and its internal surface area, while the heat transfer coefficient only has a secondary role. Furthermore, an optimization loop was implemented, whereby the internal surface area of a commonly used substrate was chosen as a reference. The lengths of the thin wall and high cell density monoliths investigated were adapted consecutively to obtain the reference internal surface area. The results obtained by this optimization process contribute to improving the heat-up performance while simultaneously reducing the valuable installation space required.

scholarly journals Exploiting the Potential of Biosilica from Rice Husk as Porous Support for Catalytically Active Iron Oxide Nanoparticles

Nanomaterials ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 1259
Author(s):  
Ana Franco ◽  
Rafael Luque ◽  
Carolina Carrillo-Carrión
Keyword(s):  
Iron Oxide ◽  
Iron Oxide Nanoparticles ◽  
Rice Husk ◽  
Heterogeneous Catalysts ◽  
Catalytic Performance ◽  
Added Value ◽  
Oxide Nanoparticles ◽  
Porous Support ◽  
Green Materials ◽  
Catalytically Active

Biomass-derived materials are put forward as eco-friendly alternatives to design heterogeneous catalysts. To contribute in this field, we explored the potential of mesoporous biogenic silica (RH-Silica) obtained from lignocellulosic waste, in particular from rice husk, as an inorganic support to prepare heterogenized iron oxide-based catalysts. Mechanochemistry, considered as a green and sustainable technique, was employed to synthetize iron oxide nanoparticles in pure hematite phase onto the biosilica (α-Fe2O3/RH-Silica), making this material a good candidate to perform catalyzed organic reactions. The obtained material was characterized by different techniques, and its catalytic activity was tested in the selective oxidation of styrene under microwave irradiation. α-Fe2O3/RH-Silica displayed a good catalytic performance, achieving a conversion of 45% under optimized conditions, and more importantly, with a total selectivity to benzaldehyde. Furthermore, a good reusability was achieved without decreasing its activity after multiple catalytic cycles. This work represents a good example of using sustainable approaches and green materials as alternatives to conventional methods in the production of high-added value products.

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