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

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-08-12 DOI:10.1016/j.micromeso.2025.113815

Hossein Samadi, Majid Taghizadeh, Hanieh Habibpoor

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Abstract

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.

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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

本文主要研究了在掺杂铬的UiO-66上负载锌促进铬纳米颗粒进行丙烷低温氧化脱氢（ODHP-CO2）。通过水热反应合成了Cr掺杂的UiO-66金属有机骨架，并通过共沉淀法制备了Cr质量分数不同的Cr/UiO-66（Cr）复合材料。此外，还采用浸渍法将锌作为促进剂。采用XRD、BET、FE-SEM、eds点阵图、FT-IR、NH3-TPD和TGA对合成的催化剂进行了表征。在固定床反应器中进行了ODHP-CO2的催化性能测试，温度分别为350、400和450℃，常压，C3H8/CO2摩尔比为1，WHSV为0.27 ~ 1.62 h−1。结果表明，在反应温度450℃、C3H8/CO2摩尔比为1、WHSV为0.27 h−1的条件下，2% zn - 5% Cr/ uiu -66（Cr）催化剂的丙烯选择性为75.5%，丙烷转化率为18.7%。此外，还对ODHP-CO2进行了动力学建模，采用Langmuir-Hinshelwood机理计算了动力学参数。根据这一机理，计算出表观活化能为12.34 kJ mol−1。

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

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.