In the late 1970s, it was found that post-modification with a phosphorus precursor can change the acidic and shape-selective properties of zeolites. The most notable phosphorus-containing precursor is H3PO4, which is added to a zeolite by wet impregnation. After this step, the zeolite is thermally treated in air/oxygen, a process better known as calcination, which decomposes phosphorus precursors into (poly)phosphates and phosphorus pentoxide. It has been found that phosphorus can act towards zeolites either as a promoter, e.g., in the fluid catalytic cracking (FCC) process and the methanol-to-hydrocarbons (MTH) reaction, or as a poison, as in ammonia selective catalytic reduction (NH3-SCR) of exhaust gases, i.e., NOx.27,31,32
As a promoter, phosphorus is well known to improve the hydrothermal stability of zeolite H-ZSM-5. At the same time, phosphorus interacts with the acid sites of zeolites, leading to a reduction in the number and strength of acid sites. Furthermore, if phosphorus is located in the micropores of a zeolite, it can either favourably alter its shape-selective effects or block the micropores and reduce the overall accessibility of the zeolite material.36 Although the presence of phosphorus can be beneficial, for example in the MTH reaction where it boosts selectivity towards light olefins and especially towards propylene, it is deleterious for NH3-SCR nitrogen oxide-removing applications.