Halawy Samih A, Osman Ahmed I, Abdelkader Adel, Nasr Mahmoud, Rooney David W
Nanocomposite Catalysts Lab., Chemistry Department, Faculty of Science at Qena, South Valley University, Qena, 83523, Egypt.
School of Chemistry and Chemical Engineering, Queen's University Belfast, David Keir Building, Belfast, BT9 5AG, UK.
ChemistryOpen. 2022 Mar;11(3):e202200021. doi: 10.1002/open.202200021.
Measuring the Lewis-acidic surface sites in catalysis is problematic when the material's surface area is very low (S ≤1 m ⋅ g ). For the first time, a quantitative assessment of total acidic surface sites of very small surface area catalysts (MoO as pure and mixed with 5-30 % CdO (wt/wt), as well as CdO for comparison) was performed using a smart new probe molecule, tetrahydrofuran (THF). The results were nearly identical compared to using another commonly used probe molecule, pyridine. This audition is based on the limited values of the surface area of these samples that likely require a relatively moderate basic molecule as THF with pK =16.08, rather than strong basic molecules such as NH (pK =4.75) or pyridine (pK =8.77). We propose mechanisms for the interaction of vapour phase molecules of THF with the Lewis-cationic Mo and Cd atoms of these catalysts. Besides, dehydration of isopropyl alcohol was used as a probe reaction to investigate the catalytic activity of these catalysts to further support our findings in the case of THF in a temperature range of 175-300 °C. A good agreement between the obtained data of sample MoO -10 % CdO, which is characterised by the highest surface area value, the population of Lewis-acidic sites and % selectivity of propylene at all the applied reaction temperatures was found.
当材料的表面积非常低(S≤1 m²·g⁻¹)时,测量催化过程中路易斯酸性表面位点存在问题。首次使用一种新型智能探针分子四氢呋喃(THF)对表面积非常小的催化剂(纯MoO₃以及与5 - 30% CdO(重量/重量)混合的MoO₃,以及作为对照的CdO)的总酸性表面位点进行了定量评估。与使用另一种常用探针分子吡啶相比,结果几乎相同。这种选择是基于这些样品有限的表面积值,这可能需要一个相对中等碱性的分子如THF(pKₐ = 16.08),而不是强碱性分子如NH₃(pKₐ = 4.75)或吡啶(pKₐ = 8.77)。我们提出了THF气相分子与这些催化剂的路易斯阳离子Mo和Cd原子相互作用的机制。此外,异丙醇脱水被用作探针反应,以研究这些催化剂的催化活性,从而在175 - 300°C的温度范围内进一步支持我们在THF情况下的研究结果。发现以最高表面积值为特征的样品MoO₃ - 10% CdO在所有应用反应温度下获得的数据、路易斯酸性位点数量和丙烯的%选择性之间有良好的一致性。