Chi Heng-Yu, Chen Cailing, Zhao Kangning, Villalobos Luis Francisco, Schouwink Pascal Alexander, Piveteau Laura, Marshall Kenneth Paul, Liu Qi, Han Yu, Agrawal Kumar Varoon
Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Rue de l'Industrie 17, 1950, Sion, Switzerland.
Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955, Saudi Arabia.
Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202207457. doi: 10.1002/anie.202207457. Epub 2022 Aug 25.
Poly(triazine imide) or PTI is an ordered graphitic carbon nitride hosting Å-scale pores attractive for selective molecular transport. AA'-stacked PTI layers are synthesized by ionothermal route during which ions occupy the framework and occlude the pores. Synthesis of ion-free PTI hosting AB-stacked layers has been reported, however, pores in this configuration are blocked by the neighboring layer. The unavailability of open pore limits application of PTI in molecular transport. Herein, we demonstrate acid treatment for ion depletion which maintains AA' stacking and results in open pore structure. We provide first direct evidence of ion-depleted open pores by imaging with the atomic resolution using integrated differential phase-contrast scanning transmission electron microscopy. Depending on the extent of ion-exchange, AA' stacking with open channels and AB stacking with closed channels are obtained and imaged for the first time. The accessibility of open channels is demonstrated by enhanced proton transport through ion depleted PTI.
聚(三嗪酰亚胺)或PTI是一种有序的石墨相氮化碳,具有吸引选择性分子传输的埃级孔隙。AA'堆叠的PTI层通过离子热法合成,在此过程中离子占据骨架并堵塞孔隙。然而,已报道了具有AB堆叠层的无离子PTI的合成,但是这种构型的孔隙被相邻层堵塞。开放孔隙的不可用限制了PTI在分子传输中的应用。在此,我们展示了用于离子耗尽的酸处理,该处理保持AA'堆叠并导致开放孔隙结构。我们使用集成差分相衬扫描透射电子显微镜以原子分辨率成像,首次提供了离子耗尽的开放孔隙的直接证据。根据离子交换的程度,首次获得并成像了具有开放通道的AA'堆叠和具有封闭通道的AB堆叠。通过离子耗尽的PTI中质子传输的增强证明了开放通道的可及性。