In this work, supported Pt monometallic catalysts were prepared using oxide and carbon supports by conventional impregnation methods. Similar Pt metallic nanoparticle sizes (mean sizes about 1.8-2 nm) have been obtained using different Pt precursor loadings (0.3 to 5 wt%). For comparison, catalysts with larger nanoparticle sizes were prepared using the liquid phase reduction method. Characterization results indicate different electronic and structural characteristics for the Pt nanoparticles, comparing nanoparticles with similar and different sizes, implying that both the Pt loading and the preparation method affect the formation of different metallic phases. We used the direct dehydrogenation of -butane to -butenes reaction as a test reaction to study the catalytic behavior of the Pt nanoparticles obtained at different Pt atomic concentrations. Surprisingly, Pt catalysts with the lowest metallic loading show the highest selectivities to olefins. Besides, Pt catalysts supported on carbon materials showed higher selectivity to butenes than those supported on oxide materials, this was attributed to a higher electron density in the Pt active sites. Likewise, at low Pt loadings, the CNP-supported Pt nanoparticles could be confined at the defect in the nanotube structure as crystalline agglomerates of atoms with few layers or monolayers with very few surface adatom or stepped adatom nanostructures or simply as a group of atoms, thus creating active Pt sites that favor the dehydrogenation reaction over secondary reactions.
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http://dx.doi.org/10.1039/d4cp00922c | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, Birla Institute of Technology and Science Pilani, Pilani Campus, Rajasthan 333031, India.
A convenient and efficient transition-metal-free method has been developed for the C(sp)-H alkoxylation/aryloxylation of 1,4-quinones by direct cross-dehydrogenative coupling with readily available alcohols and phenols in the presence of TEMPO under simple and mild conditions. The method allowed the installation of a wide range of alkoxy/aryloxy groups, exhibited high functional group tolerance, showed a broad substrate scope, afforded good to excellent yields of products in a simple one-pot operation, and could be performed on a gram scale. Mechanistic investigation indicated the involvement of the radical pathway.
View Article and Find Full Text PDFPrecis Chem
December 2024
State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
The interfacial proton transfer (PT) reaction on the metal oxide surface is an important step in many chemical processes including photoelectrocatalytic water splitting, dehydrogenation, and hydrogen storage. The investigation of the PT process, in terms of thermodynamics and kinetics, has received considerable attention, but the individual free energy barriers and solvent effects for different PT pathways on rutile oxide are still lacking. Here, by applying a combination of ab initio and deep potential molecular dynamics methods, we have studied interfacial PT mechanisms by selecting the rutile SnO(110)/HO interface as an example of an oxide with the characteristic of frequently interfacial PT processes.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, Lomonosov Moscow State University, Moscow 119991 Russia.
The recent detection of benzonitrile (CHCN) in the interstellar medium is one of the most fascinating discoveries in astrochemistry and molecular astrophysics. However, the mechanism of its formation in interstellar ices remains unclear. Here, we report the first evidence for the direct synthesis of benzonitrile through the radiation-induced transformations of an isolated CH···HCN complex in inert rigid media at cryogenic temperature (4.
View Article and Find Full Text PDFSmall
December 2024
Center for Energy and Environmental Sciences, Paul Scherrer Institute, Villigen, 5232, Switzerland.
Ethylene oxide (EO) is a crucial building block in the chemical industry, and its production via ethylene epoxidation (EPO) is a pivotal process. Silver-based catalysts are known for their high selectivity and are currently largely used in the industrial process. Extensive research over the past 20 years has assumed the oxametallacycle (OMC) as a reaction intermediate, implying that ethylene reacts with adsorbed oxygen on the surface of silver.
View Article and Find Full Text PDFACS Sustain Chem Eng
December 2024
United States Department of Energy, National Energy Technology Laboratory, Pittsburgh, Pennsylvania 15236, United States.
Direct conversion of point-source CO into fine chemicals over cooperative and bifunctional materials (BFMs) - composed of adsorbents and catalysts - has emerged as a promising approach to improve the energy efficiency of the carbon capture and conversion processes. In this study, a bifunctional material consisting of CrO/ZSM-5 catalyst and CaO adsorbent was developed and tested in the CO-oxidative dehydrogenation of propane (CO-ODHP) for reactive capture of CO in a fixed bed reactor. First, CaO was prepared using two distinct methods: solid-state and citrate sol-gel.
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