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采用溶剂热法对铁基金属有机框架衍生催化剂的铁纳米颗粒尺寸进行控制:对费托合成活性和烯烃生成的影响

Fe Nanoparticle Size Control of the Fe-MOF-Derived Catalyst Using a Solvothermal Method: Effect on FTS Activity and Olefin Production.

作者信息

Rashed Ahmed E, Nasser Alhassan, Elkady Marwa F, Matsushita Yoshihisa, El-Moneim Ahmed Abd

机构信息

Basic and Applied Science Institute, Egypt-Japan University of Science and Technology, New Borg El-Arab 21934, Egypt.

Environmental Sciences Department, Faculty of Science, Alexandria University, Alexandria 21511, Egypt.

出版信息

ACS Omega. 2022 Feb 28;7(10):8403-8419. doi: 10.1021/acsomega.1c05927. eCollection 2022 Mar 15.

Abstract

The design of a highly active Fe-supported catalyst with the optimum particle and pore size, dispersion, loading, and stability is essential for obtaining the desired product selectivity. This study employed a solvothermal method to prepare two Fe-MIL-88B metal-organic framework (MOF)-derived catalysts using triethylamine (TEA) or NaOH as deprotonation catalysts. The catalysts were analyzed using X-ray diffraction, N-physisorption, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, H temperature-programed reduction, and thermogravimetric analysis and were evaluated for the Fischer-Tropsch synthesis performance. It was evident that the catalyst preparation in the presence of TEA produces a higher MOF yield and smaller crystal size than those produced using NaOH. The pyrolysis of MOFs yielded catalysts with different Fe particle sizes of 6 and 35 nm for the preparation in the presence of TEA and NaOH, respectively. Also, both types of catalysts exhibited a high Fe loading (50%) and good stability after 100 h reaction time. The smaller particle size TEA catalyst showed higher activity and higher olefin yield, with 94% CO conversion and a higher olefin yield of 24% at a lower reaction temperature of 280 °C and 20 bar at H/CO = 1. Moreover, the smaller particle size TEA catalyst exhibited higher Fe time yield and CH selectivity but with lower chain growth probability (α) and C selectivity.

摘要

设计具有最佳颗粒和孔径、分散度、负载量及稳定性的高活性铁负载型催化剂对于获得所需的产物选择性至关重要。本研究采用溶剂热法,以三乙胺(TEA)或氢氧化钠作为去质子化催化剂,制备了两种铁基金属有机骨架(MOF)衍生的催化剂。使用X射线衍射、N物理吸附、傅里叶变换红外光谱、扫描电子显微镜、透射电子显微镜、H程序升温还原和热重分析对催化剂进行了分析,并对其费托合成性能进行了评估。显然,与使用氢氧化钠制备的催化剂相比,在TEA存在下制备的催化剂具有更高的MOF产率和更小的晶体尺寸。MOF的热解分别在TEA和氢氧化钠存在下制备出具有6和35 nm不同铁颗粒尺寸的催化剂。此外,两种类型的催化剂在100 h反应时间后均表现出高铁负载量(50%)和良好的稳定性。较小颗粒尺寸的TEA催化剂表现出更高的活性和更高的烯烃产率,在H/CO = 1、280 °C较低反应温度和20 bar条件下,CO转化率为94%,烯烃产率更高,为24%。此外,较小颗粒尺寸的TEA催化剂表现出更高的铁时空产率和CH选择性,但链增长概率(α)和C选择性较低。

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