Propane dehydrogenation (PDH) is a promising chemical process that can satisfy the increasing global demand for propylene. However, the Pt-based catalysts that have been reported thus far are typically deactivated at ≥600 °C by side reactions and coke formation. Thus, such catalysts possess an insufficient life. Herein, we report a novel catalyst design concept, namely, the double decoration of PtGa intermetallics by Pb and Ca, which synergize the geometric and electronic promotion effects on the catalyst stability, respectively. Pb is deposited on the three-fold Pt sites of the PtGa nanoparticles to block them, whereas Ca, which affords an electron-enriched single-atom-like Pt site, is placed around the nanoparticles. Thus, PtGa-Ca-Pb/SiO exhibits an outstandingly high catalytic stability, even at 600 °C (k =0.00033 h , τ=3067 h), and almost no deactivation of the catalyst was observed for up to 1 month for the first time.
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http://dx.doi.org/10.1002/anie.202107210 | DOI Listing |
ChemSusChem
January 2025
Key Laboratory of Luminescence and Optical Information Technology, School of Physical Science and Engineering, Beijing Jiaotong University, Beijing, 100044, P. R. China.
The eco-friendly features and desirable catalytic activities of Fe-based catalysts make them highly promising for propane dehydrogenation (PDH). However, simultaneously improving their stability and activity remains a challenge. Here, we present a strategy to address these issues synergistically by anchoring single-atom Fe-Cl sites in Al vacancies of AlO.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States.
Iron sites dispersed on nonacidic siliceous supports have been reported to be catalytically active for propane dehydrogenation (PDH), yet the precise relationship between site structure and catalytic activity remains elusive. This study provides a comprehensive understanding of the catalytic performance of iron supported on dealuminated BEA (DeAlBEA) zeolites for PDH. Using XAS, UV-vis, and IR spectroscopy of adsorbed pyridine and deuterated acetonitrile, it was found that, at an Fe/Al of 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Davidson School of Chemical Engineering, Purdue University, Forney Hall of Chemical Engineering, 480 Stadium Mall Drive, West Lafayette, IN 47907-2100, USA.
C-H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon-intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low-temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds and Applications, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou, Hunan 423000, P. R. China.
Adsorbate free energies are important parameters in surface chemistry and catalysis. Because of its simplicity, the harmonic oscillator (HO) model remains the most widely used method for calculating adsorbate free energy in many fields, including microkinetic modeling. However, it is well-known that the HO method is ineffective for weak adsorption.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemical and Biomolecular Engineering, 250 Nieuwland Hall, University of Notre Dame, Notre Dame, Indiana 46556, United States.
Nonthermal plasma-surface interactions enable transformative advancements in green chemistry, healthcare, materials processing, pollution abatement, and the ever-growing area of plasma catalysis. In the context of plasma catalysis, the fate of the active sites during plasma treatment has remained enigmatic, and observation of low-temperature plasma-catalyst events has been challenging. The induction of strong metal-support interactions (SMSI) through high-temperature hydrogen treatment is a well-documented and established, yet limited, method to impact selectivity and stability of noble metal catalysts on reducible supports.
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