当前位置: X-MOL 学术Ind. Eng. Chem. Res. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
First-Principles Study of Interaction between Molecules and Lewis Acid Zeolites Manipulated by Injection of Energized Charge Carriers
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2021-09-22 , DOI: 10.1021/acs.iecr.1c02808
Tien Le 1 , Bin Wang 1
Affiliation  

Metal dopants in Lewis acid zeolites can be applied to manipulate the interaction between the active sites and molecular reactants. However, only a few elements can be introduced into the zeolite framework to generate strong Lewis acid sites. In this study, we propose an alternative approach to tune the interaction between zeolite and molecules by introducing energized charge carriers that are photoexcited in a complex of plasmonic metal and zeolites. Through density functional theory (DFT) calculations, we show that although the energized electrons do not impact the adsorption of ammonia, which is used as a probe molecule, on Zr- and Si-BEA, ammonia’s heat of adsorption can be reduced up to 60% on Sn-BEA and 20% on Ti-BEA, respectively, because of the localized population of the electrons at the Sn and Ti center. This most pronounced effect in Sn-BEA is attributed to the Sn-induced midgap states and the strong electronegativity of Sn atoms. In contrast, the energized holes can strengthen the interaction between zeolites and ammonia by at least 10%. Particularly, if an energized hole is present in the system, the heat of adsorption of ammonia within Si-BEA can increase 3-fold, shifting from weak to moderate interaction. We find that, similar to closed sites, the effect of energized charge carriers can also be extended to open sites of Lewis acid zeolites. Our study provides fundamental insights for unlocking the potentials of integrating plasmonic metals with zeolites and brings an additional degree of control to tune the interfacial interaction.

中文翻译:

通过注入带电载流子操纵分子与路易斯酸沸石相互作用的第一性原理研究

路易斯酸沸石中的金属掺杂剂可用于控制活性位点和分子反应物之间的相互作用。然而,只有少数元素可以引入沸石骨架以产生强路易斯酸位点。在这项研究中,我们提出了一种替代方法,通过引入在等离子体金属和沸石的复合物中光激发的带电载流子来调节沸石和分子之间的相互作用。通过密度泛函理论 (DFT) 计算,我们表明虽然带电的电子不影响用作探针分子的氨的吸附,但在 Zr-和 Si-BEA 上,氨的吸附热可降低至 60由于电子在 Sn 和 Ti 中心的局部分布,Sn-BEA 的百分比和 Ti-BEA 的百分比分别为 20%。Sn-BEA 中这种最显着的效应归因于 Sn 诱导的中带隙状态和 Sn 原子的强电负性。相比之下,通电空穴可以将沸石和氨之间的相互作用增强至少 10%。特别是,如果系统中存在通电空穴,Si-BEA 内氨的吸附热可以增加 3 倍,从弱相互作用转变为中等相互作用。我们发现,类似于封闭位点,带电载流子的作用也可以扩展到路易斯酸沸石的开放位点。我们的研究为释放将等离子体金属与沸石相结合的潜力提供了基本见解,并带来了额外的控制程度来调整界面相互作用。通电空穴可将沸石与氨之间的相互作用增强至少 10%。特别是,如果系统中存在通电空穴,Si-BEA 内氨的吸附热可以增加 3 倍,从弱相互作用转变为中等相互作用。我们发现,类似于封闭位点,带电载流子的作用也可以扩展到路易斯酸沸石的开放位点。我们的研究为释放将等离子体金属与沸石相结合的潜力提供了基本见解,并带来了额外的控制程度来调整界面相互作用。通电空穴可将沸石与氨之间的相互作用增强至少 10%。特别是,如果系统中存在通电空穴,Si-BEA 内氨的吸附热可以增加 3 倍,从弱相互作用转变为中等相互作用。我们发现,类似于封闭位点,带电载流子的作用也可以扩展到路易斯酸沸石的开放位点。我们的研究为释放将等离子体金属与沸石结合的潜力提供了基本见解,并带来了额外的控制程度来调整界面相互作用。从弱相互作用转向中等相互作用。我们发现,类似于封闭位点,带电载流子的作用也可以扩展到路易斯酸沸石的开放位点。我们的研究为释放将等离子体金属与沸石相结合的潜力提供了基本见解,并带来了额外的控制程度来调整界面相互作用。从弱相互作用转向中等相互作用。我们发现,类似于封闭位点,带电载流子的作用也可以扩展到路易斯酸沸石的开放位点。我们的研究为释放将等离子体金属与沸石相结合的潜力提供了基本见解,并带来了额外的控制程度来调整界面相互作用。
更新日期:2021-10-06
down
wechat
bug