Çelik Gökhan
Department of Chemical Engineering, Faculty of Engineering, Middle East Technical University, Ankara, Turkiye.
Turk J Chem. 2023 Dec 4;48(1):166-175. doi: 10.55730/1300-0527.3648. eCollection 2024.
Nonoxidative dehydrogenation of propane to propylene using Pt-based supported catalysts is an active research area in catalysis because catalyst attributes of Pt sites can be controlled by careful design of active sites. One way to achieve this is by the addition of a second metal that may impart a change in the electron density of active sites, which in turn affects catalytic performance. In this study, bimetallic Pt and B sites were deposited on powder SiO using atomic layer deposition (ALD). Boron was first deposited on SiO via half-cycle ALD using triisoproplyborate as the B source. Following calcination, Pt deposition was performed via half-cycle ALD using trimethyl(methylcyclopentadienyl)platinum(IV) as the Pt source. The synthesized catalysts were reduced under H at 550 °C and characterized using inductively coupled plasma optical emission spectroscopy for elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy of adsorbed CO to examine the properties of Pt, and time-resolved X-ray absorption near edge structure spectroscopy to examine the changes in the reducibility of Pt sites. The samples were then tested for nonoxidative dehydrogenation of propane at 550 °C using a fixed-bed plug-flow reactor to examine the role of B on the catalytic performance. Characterization results showed that the addition of B imparted an increase in electron density and affected the reducibility of Pt sites. In addition, incorporating B on SiO created anchoring sites for Pt ALD. The amount of Pt deposited on B/SiO was 2.2 times that on SiO. Catalytic activity results revealed the addition of B did not change the initial activity of Pt sites significantly, but improved propylene selectivity from 80% to 87% and stability almost threefold. The enhanced selectivity and stability of PtB/SiO is most presumably due to favored desorption of propylene and mitigating coke formation under reaction conditions, respectively.
使用铂基负载型催化剂将丙烷非氧化脱氢制丙烯是催化领域一个活跃的研究方向,因为通过精心设计活性位点可以控制铂位点的催化剂属性。实现这一点的一种方法是添加第二种金属,这可能会改变活性位点的电子密度,进而影响催化性能。在本研究中,使用原子层沉积(ALD)将双金属铂和硼位点沉积在粉末状二氧化硅上。首先使用硼酸三异丙酯作为硼源,通过半周期ALD将硼沉积在二氧化硅上。煅烧后,使用三甲基(甲基环戊二烯基)铂(IV)作为铂源,通过半周期ALD进行铂沉积。合成的催化剂在550℃的氢气气氛下还原,并使用电感耦合等离子体发射光谱进行元素分析、吸附一氧化碳的漫反射红外傅里叶变换光谱来研究铂的性质,以及时间分辨X射线吸收近边结构光谱来研究铂位点还原度的变化。然后使用固定床活塞流反应器在550℃下对样品进行丙烷非氧化脱氢测试,以研究硼对催化性能的作用。表征结果表明,硼的添加使电子密度增加,并影响了铂位点的还原度。此外,在二氧化硅上引入硼为铂的ALD创造了锚定位点。沉积在B/SiO上的铂量是沉积在SiO上的2.2倍。催化活性结果表明,硼的添加并没有显著改变铂位点的初始活性,但将丙烯选择性从80%提高到了87%,稳定性提高了近三倍。PtB/SiO选择性和稳定性的提高最可能分别是由于丙烯脱附更有利以及在反应条件下减轻了积炭的形成。