Key Laboratory for Green Chemical Technology of State Education Ministry, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China.
Phys Chem Chem Phys. 2011 Sep 14;13(34):15589-96. doi: 10.1039/c1cp21299k. Epub 2011 Jul 27.
Bulk modified phosphorus alumina samples were prepared by gel method (GPA) and hydrolysis of phosphide aluminum (HPA). The γ-Al(2)O(3) impregnated by phosphates precursor (IPA) was also compared. The basicity of the samples has been investigated through the CO(2) adsorption/desorption processes by in situ DRIFT and temperature programmed desorption experiments. It was found that the surface basicity can be adjusted by different location of phosphates species. For the GPA sample, the phosphates species tends to be located in the grain boundaries as they were not stable enough to overcome the structure rearrangement at high temperatures. In contrast, phosphorus was stably anchored in the crystal lattice of HPA sample. Considering the synthesis process of HPA samples, phosphorus changed its valence state from P(-3) to P(+5) and migrated from anion to cation sites. The anion vacancies left in the lattice facilitated the formation of unsaturated oxygen ions and results in the enhanced basicity.
采用凝胶法(GPA)和磷化铝水解(HPA)制备了负载型磷酸铝样品。此外,还比较了磷酸盐前体浸渍γ-Al2O3(IPA)样品。通过原位 DRIFT 和程序升温脱附实验研究了样品的碱性。结果表明,通过不同位置的磷酸盐物种可以调节表面碱性。对于 GPA 样品,磷酸盐物种倾向于位于晶界处,因为它们不够稳定,无法在高温下克服结构重排。相比之下,磷在 HPA 样品的晶格中稳定地固定。考虑到 HPA 样品的合成过程,磷的价态从 P(-3)变为 P(+5),并从阴离子位迁移到阳离子位。晶格中留下的阴离子空位有利于不饱和氧离子的形成,从而增强了碱性。