Breckner Christian J, Pham Hien N, Dempsey Michael G, Perez-Ahuatl Michelle A, Kohl Alyssa C, Lytle Corryn N, Datye Abhaya K, Miller Jeffrey T
Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA.
Department of Chemical and Biological Engineering and Center for Microengineered Materials, University of New Mexico, Albuquerque, NM, 87137, USA.
Chemphyschem. 2023 Jul 17;24(14):e202300244. doi: 10.1002/cphc.202300244. Epub 2023 Jun 9.
Olefin oligomerization by γ-Al O has recently been reported, and it was suggested that Lewis acid sites are catalytic. The goal of this study is to determine the number of active sites per gram of alumina to confirm that Lewis acid sites are indeed catalytic. Addition of an inorganic Sr oxide base resulted in a linear decrease in the propylene oligomerization conversion at loadings up to 0.3 wt %; while, there is a >95 % loss in conversion above 1 wt % Sr. Additionally, there was a linear decrease in the intensity of the Lewis acid peaks of absorbed pyridine in the IR spectra with an increase in Sr loading, which correlates with the loss in propylene conversion, suggesting that Lewis acid sites are catalytic. Characterization of the Sr structure by XAS and STEM indicates that single Sr ions are bound to the γ-Al O surface and poison one catalytic site per Sr ion. The maximum loading needed to poison all catalytic sites, assuming uniform surface coverage, was ∼0.4 wt % Sr, giving an acid site density of ∼0.2 sites per nm of γ-Al O , or approximately 3 % of the alumina surface.
最近有报道称γ-Al₂O₃可催化烯烃齐聚反应,并且认为路易斯酸位点具有催化活性。本研究的目的是确定每克氧化铝的活性位点数量,以证实路易斯酸位点确实具有催化作用。添加无机Sr氧化物碱后,在负载量高达0.3 wt %时,丙烯齐聚反应转化率呈线性下降;而当Sr含量高于1 wt %时,转化率损失超过95 %。此外,随着Sr负载量的增加,红外光谱中吸附吡啶的路易斯酸峰强度呈线性下降,这与丙烯转化率的损失相关,表明路易斯酸位点具有催化作用。通过X射线吸收光谱(XAS)和扫描透射电子显微镜(STEM)对Sr结构进行表征表明,单个Sr离子与γ-Al₂O₃表面结合,每个Sr离子会使一个催化位点失活。假设表面均匀覆盖,使所有催化位点失活所需的最大负载量约为0.4 wt % Sr,这给出了γ-Al₂O₃每纳米约0.2个位点的酸位点密度,约占氧化铝表面的3 %。