{"title":"低温下丙烷氧化脱氢的热稳定掺铬UiO-66负载Zn-Cr催化剂:催化活性和动力学建模","authors":"Hossein Samadi, Majid Taghizadeh, Hanieh Habibpoor","doi":"10.1016/j.micromeso.2025.113815","DOIUrl":null,"url":null,"abstract":"<div><div>This research focused on the low-temperature oxidative dehydrogenation of propane by CO<sub>2</sub> (ODHP-CO<sub>2</sub>) using zinc-promoted chromium nanoparticles supported on Cr-doped UiO-66. A Cr-doped UiO-66 metal-organic framework was synthesized by a hydrothermal reaction, and Cr/UiO-66(Cr) composites with different mass percentages of Cr were developed by the co-precipitation method. In addition, zinc was applied as a promoter by the impregnation method. The characteristics of the synthesized catalysts were determined by XRD, BET, FE-SEM, EDS-dot mapping, FT-IR, NH<sub>3</sub>-TPD, and TGA. Catalytic performance tests for ODHP-CO<sub>2</sub> were conducted in a fixed-bed reactor at temperatures of 350, 400 and 450 °C, under atmospheric pressure, a C<sub>3</sub>H<sub>8</sub>/CO<sub>2</sub> molar ratio of 1, and a WHSV ranging from 0.27 to 1.62 h<sup>−1</sup>. As a result, the 2 %Zn–5 %Cr/UiO-66(Cr) catalyst achieved a propylene selectivity of 75.5 % and a propane conversion of 18.7 % at a temperature of 450 °C, C<sub>3</sub>H<sub>8</sub>/CO<sub>2</sub> molar ratio of 1, and WHSV of 0.27 h<sup>−1</sup> after 8 h of reaction time. Furthermore, kinetic modeling of ODHP-CO<sub>2</sub> was also performed, using the Langmuir-Hinshelwood mechanism to calculate the kinetic parameters. According to this mechanism, the apparent activation energy was calculated to be 12.34 kJ mol<sup>−1</sup>.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"398 ","pages":"Article 113815"},"PeriodicalIF":4.7000,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A thermally stable Cr-doped UiO-66 supported Zn-Cr catalyst for the oxidative dehydrogenation of propane with CO2 at low temperature: Catalytic activity and kinetic modeling\",\"authors\":\"Hossein Samadi, Majid Taghizadeh, Hanieh Habibpoor\",\"doi\":\"10.1016/j.micromeso.2025.113815\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>This research focused on the low-temperature oxidative dehydrogenation of propane by CO<sub>2</sub> (ODHP-CO<sub>2</sub>) using zinc-promoted chromium nanoparticles supported on Cr-doped UiO-66. A Cr-doped UiO-66 metal-organic framework was synthesized by a hydrothermal reaction, and Cr/UiO-66(Cr) composites with different mass percentages of Cr were developed by the co-precipitation method. In addition, zinc was applied as a promoter by the impregnation method. The characteristics of the synthesized catalysts were determined by XRD, BET, FE-SEM, EDS-dot mapping, FT-IR, NH<sub>3</sub>-TPD, and TGA. Catalytic performance tests for ODHP-CO<sub>2</sub> were conducted in a fixed-bed reactor at temperatures of 350, 400 and 450 °C, under atmospheric pressure, a C<sub>3</sub>H<sub>8</sub>/CO<sub>2</sub> molar ratio of 1, and a WHSV ranging from 0.27 to 1.62 h<sup>−1</sup>. As a result, the 2 %Zn–5 %Cr/UiO-66(Cr) catalyst achieved a propylene selectivity of 75.5 % and a propane conversion of 18.7 % at a temperature of 450 °C, C<sub>3</sub>H<sub>8</sub>/CO<sub>2</sub> molar ratio of 1, and WHSV of 0.27 h<sup>−1</sup> after 8 h of reaction time. Furthermore, kinetic modeling of ODHP-CO<sub>2</sub> was also performed, using the Langmuir-Hinshelwood mechanism to calculate the kinetic parameters. According to this mechanism, the apparent activation energy was calculated to be 12.34 kJ mol<sup>−1</sup>.</div></div>\",\"PeriodicalId\":392,\"journal\":{\"name\":\"Microporous and Mesoporous Materials\",\"volume\":\"398 \",\"pages\":\"Article 113815\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-08-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Microporous and Mesoporous Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1387181125003300\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Microporous and Mesoporous Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1387181125003300","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
A thermally stable Cr-doped UiO-66 supported Zn-Cr catalyst for the oxidative dehydrogenation of propane with CO2 at low temperature: Catalytic activity and kinetic modeling
This research focused on the low-temperature oxidative dehydrogenation of propane by CO2 (ODHP-CO2) using zinc-promoted chromium nanoparticles supported on Cr-doped UiO-66. A Cr-doped UiO-66 metal-organic framework was synthesized by a hydrothermal reaction, and Cr/UiO-66(Cr) composites with different mass percentages of Cr were developed by the co-precipitation method. In addition, zinc was applied as a promoter by the impregnation method. The characteristics of the synthesized catalysts were determined by XRD, BET, FE-SEM, EDS-dot mapping, FT-IR, NH3-TPD, and TGA. Catalytic performance tests for ODHP-CO2 were conducted in a fixed-bed reactor at temperatures of 350, 400 and 450 °C, under atmospheric pressure, a C3H8/CO2 molar ratio of 1, and a WHSV ranging from 0.27 to 1.62 h−1. As a result, the 2 %Zn–5 %Cr/UiO-66(Cr) catalyst achieved a propylene selectivity of 75.5 % and a propane conversion of 18.7 % at a temperature of 450 °C, C3H8/CO2 molar ratio of 1, and WHSV of 0.27 h−1 after 8 h of reaction time. Furthermore, kinetic modeling of ODHP-CO2 was also performed, using the Langmuir-Hinshelwood mechanism to calculate the kinetic parameters. According to this mechanism, the apparent activation energy was calculated to be 12.34 kJ mol−1.
期刊介绍:
Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal.
Topics which are particularly of interest include:
All aspects of natural microporous and mesoporous solids
The synthesis of crystalline or amorphous porous materials
The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic
The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions
All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials
Adsorption (and other separation techniques) using microporous or mesoporous adsorbents
Catalysis by microporous and mesoporous materials
Host/guest interactions
Theoretical chemistry and modelling of host/guest interactions
All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.