The high carbon dioxide emission levels due to the increased consumption of fossil fuels has led to various environmental problems. Efficient strategies for the capture and storage of greenhouse gases, such as carbon dioxide are crucial in reducing their concentrations in the environment. Considering this, herein, three novel heteroatom-doped porous-organic polymers (POPs) containing phosphate units were synthesized in high yields from the coupling reactions of phosphate esters and 1,4-diaminobenzene (three mole equivalents) in boiling ethanol using a simple, efficient, and general procedure. The structures and physicochemical properties of the synthesized POPs were established using various techniques. Field emission scanning electron microscopy (FESEM) images showed that the surface morphologies of the synthesized POPs were similar to coral reefs. They had grooved networks, long range periodic macropores, amorphous surfaces, and a high surface area (SBET = 82.71–213.54 m2/g). Most importantly, they had considerable carbon dioxide storage capacity, particularly at high pressure. The carbon dioxide uptake at 323 K and 40 bar for one of the POPs was as high as 1.42 mmol/g (6.00 wt %). The high carbon dioxide uptake capacities of these materials were primarily governed by their geometries. The POP containing a meta-phosphate unit leads to the highest CO2 uptake since such geometry provides a highly distorted and extended surface area network compared to other POPs.
