scholarly journals An air-stable, reusable Ni@Ni(OH)2 nanocatalyst for CO2/bicarbonates hydrogenation to formate

Nanoscale ◽  
2021 ◽  
Author(s):  
Xinpu Fu ◽  
Laurent Peres ◽  
Jerome Esvan ◽  
Catherine AMIENS ◽  
Karine Philippot ◽  
...  

Production of formate via CO2/bicarbonate hydrogenation using cheap metal-based heterogeneous catalysts is attractive. Herein, we report the organometallic synthesis of a foam-like Ni@Ni(OH)2 composite nanomaterial which exhibited remarkable air stability...

2017 ◽  
Vol 46 (41) ◽  
pp. 14318-14324
Author(s):  
Natália J. S. Costa ◽  
Lucas L. R. Vono ◽  
Robert Wojcieszak ◽  
Érico Teixiera-Neto ◽  
Karine Philippot ◽  
...  

The decomposition of Pd2(dba)3 by H2 in the presence of Al(iPrO)3 generated a stable Pd colloid, which was easily converted into a composite nanomaterial, namely Al2O3-embedded Pd NPs.


Author(s):  
Alexis T. Bell

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.


Author(s):  
A. K. Datye ◽  
D. S. Kalakkad ◽  
L. F. Allard ◽  
E. Völkl

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.


Author(s):  
P.A. Crozier ◽  
M. Pan

Heterogeneous catalysts can be of varying complexity ranging from single or double phase systems to complicated mixtures of metals and oxides with additives to help promote chemical reactions, extend the life of the catalysts, prevent poisoning etc. Although catalysis occurs on the surface of most systems, detailed descriptions of the microstructure and chemistry of catalysts can be helpful for developing an understanding of the mechanism by which a catalyst facilitates a reaction. Recent years have seen continued development and improvement of various TEM, STEM and AEM techniques for yielding information on the structure and chemistry of catalysts on the nanometer scale. Here we review some quantitative approaches to catalyst characterization that have resulted from new developments in instrumentation.HREM has been used to examine structural features of catalysts often by employing profile imaging techniques to study atomic details on the surface. Digital recording techniques employing slow-scan CCD cameras have facilitated the use of low-dose imaging in zeolite structure analysis and electron crystallography. Fig. la shows a low-dose image from SSZ-33 zeolite revealing the presence of a stacking fault.


2020 ◽  
pp. 1-18
Author(s):  
Yu.V. Bilokopytov ◽  
◽  
S.L. Melnykova ◽  
N.Yu. Khimach ◽  
◽  
...  

CO2 is a harmful greenhouse gas, a product of chemical emissions, the combustion of fossil fuels and car exhausts, and it is a widely available source of carbon. The review considers various ways of hydrogenation of carbon dioxide into components of motor fuels - methanol, dimethyl ether, ethanol, hydrocarbons - in the presence of heterogeneous catalysts. At each route of conversion of CO2 (into oxygenates or hydrocarbons) the first stage is the formation of CO by the reverse water gas shift (rWGS) reaction, which must be taken into account when catalysts of process are choosing. The influence of chemical nature, specific surface area, particle size and interaction between catalyst components, as well as the method of its production on the CO2 conversion processes is analyzed. It is noted that the main active components of CO2 conversion into methanol are copper atoms and ions which interact with the oxide components of the catalyst. There is a positive effect of other metals oxides additives with strong basic centers on the surface on the activity of the traditional copper-zinc-aluminum oxide catalyst for the synthesis of methanol from the synthesis gas. The most active catalysts for the synthesis of DME from CO2 and H2 are bifunctional. These catalysts contain both a methanol synthesis catalyst and a dehydrating component, such as mesoporous zeolites with acid centers of weak and medium strength, evenly distributed on the surface. The synthesis of gasoline hydrocarbons (≥ C5) is carried out through the formation of CO or CH3OH and DME as intermediates on multifunctional catalysts, which also contain zeolites. Hydrogenation of CO2 into ethanol can be considered as an alternative to the synthesis of ethanol through the hydration of ethylene. High activation energy of carbon dioxide, harsh synthesis conditions as well as high selectivity for hydrocarbons, in particular methane remains the main problems. Further increase of selectivity and efficiency of carbon dioxide hydrogenation processes involves the use of nanocatalysts taking into account the mechanism of CO2 conversion reactions, development of methods for removing excess water as a by-product from the reaction zone and increasing catalyst stability over time.


2018 ◽  
Author(s):  
Chaofeng Huang ◽  
Jing Wen ◽  
Yanfei Shen ◽  
Fei He ◽  
Li Mi ◽  
...  

<a></a><a>As a metal-free conjugated polymer, carbon nitride (CN) has attracted tremendous attention as heterogeneous (photo)catalysts. </a><a></a><a>By following prototype of enzymes, making all catalytic sites of accessible via homogeneous reactions is a promising approach toward maximizing CN activity, but hindered due to </a><a></a><a>the poor insolubility of CN</a>. Herein, we report the dissolution of CN in environment-friendly methane sulfonic acid and the homogeneous photocatalysis driven by CN for the first time with the activity boosted up to 10-times, comparing to the heterogeneous counterparts. Moreover, facile recycling and reusability, the <a>hallmark</a> of heterogeneous catalysts, were kept for the homogeneous CN photocatalyst via reversible precipitation using poor solvents. It opens new vista of CN in homogeneous catalysis and offers a successful example of polymeric catalysts in bridging gaps of homo/heterogeneous catalysis.


2019 ◽  
Author(s):  
Nan An ◽  
Diana Ainembabazi ◽  
Kavya Samudrala ◽  
Christopher Reid ◽  
Kare Wilson ◽  
...  

<p>Here we report the synthesis, characterization and activity of tunable Pd-doped hydrotalcites (Pd-HTs) for the decarbonylation of furfural, hydroxymethylfurfural (HMF), aromatic and aliphatic aldehydes under microwave conditions. The decarbonylation activity reported is a notable improvement over prior heterogeneous catalysts for this process. Furfural decarbonylation is optimized in a benign solvent compatible with biomass processing - ethanol, under relatively mild conditions and short reaction times. HMF selectively affords excellent yields of furfuryl alcohol with no humin formation, but longer reaction can also afford furan via tandem alcohol dehydrogenation and decarbonylation. Yields of substituted benzaldehydes are related to calculated Mulliken charge of the carbonyl carbon. The activity and selectivity differences can be traced to loading-dependent differences in Pd speciation on the catalysts. Poisoning studies show inverse correlation between Pd loading and metal leaching: Pd-HTs with lowest Pd loading, which consist of highly dispersed and oxidized Pd species, operate heterogeneously with negligible metal leaching. Recycling experiments are consistent with this trend, offering potential for further optimization to improve robustness.</p>


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