Propane dehydrogenation (PDH) is a crucial approach for propylene production. However, commonly used CrO-based catalysts have issues including easy sintering at elevated reaction temperatures and relying on high acidity supports. In this work, we develop a strategy, to strongly anchor and isolate active sites against their commonly observed aggregation during reactions, by taking advantage of the net trap effect in chromate intercalated Zn-Cr layered hydroxides as precursors. Furthermore, the intercalated chromate overcomes the collapse of traditional layered hydroxides during their transformation to metal oxide, thus exposing more available active sites. A joint fine modulation including crystal structure, surface acidity, specific surface area, and active sites dispersion is performed on the final mixed metal oxides for propane dehydrogenation. As a result, ZnCr-CrO-MMO delivers attractive propane conversion (~27%) and propylene selectivity (>90%) as compared to other non-noble-metal-based catalysts.
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http://dx.doi.org/10.3390/molecules29133063 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Purdue University, Davidson School of Chemical Engineering, 480 Stadium Mall, 47907, West Lafayette, UNITED STATES OF AMERICA.
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
December 2024
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
December 2024
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.
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.
View Article and Find Full Text PDFACS Nano
December 2024
School of Environment and Energy, State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, South China University of Technology, Guangzhou 510006, China.
Bimetallic Pt-based catalysts, for example, PtZn and PtSn catalysts, have gained significant attention for addressing the poor stability and low selectivity of pristine Pt catalysts over propane dehydrogenation (PDH). However, the structures of the active sites and the corresponding catalytic mechanism of PDH are still elusive. Here, we demonstrate a spatially confined Pt-ZnO@RUB-15 catalyst (where "" is the mole ratio of Zn/Pt and RUB-15 is a layered silica), which exhibited high catalytic activity, ultrahigh selectivity (>99%), and resistance to coking at 550 °C for PDH.
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