By adjusting the stretch state of a triethylenetetramine (TETA) chain in an amine-functionalized porous organic polymer (POP), two adsorbents were designed to study the rational microenvironment for heavy metal ion removal. The quantum calculation elucidated that the hooped amino chains in FC-POP-CH2TETA-H exhibited stronger interactions with Pb­(II) than the extended one in FC-POP-CH2TETA-E, not only through metal–ligand chelation but also metal coordination. The high binding energy of −2624 kJ mol–1 as well as the constructed microenvironment by the hooped amino chains ensured an extremely high Pb­(II) capacity of 1134 mg g–1 on FC-POP-CH2TETA-H. Meanwhile, no more than 5 min to approach adsorption equilibrium revealed its ultrafast adsorption rate. It also showed excellent broad removal capability for multiple metal ions and nonsensitivity to pH. Therefore, by controlling the microenvironmental structures with suitable porosity, functional group stretching states, and coordination modes, the removal efficiency of heavy metal ions would be significantly enhanced, which further provided a promising strategy for designing a rational microenvironment to improve the task-specific separation properties.

A Pickering emulsion catalytic system was proposed to reduce the transfer limitation between two immiscible reactant phases for enhancing the kinetics of heterogenetic oxidative desulfurization (ODS). By loading phosphotungstic acid (HPW) nanoparticles on a novel pyridine-based porous organic polymer of P[tVPB-VP x ], the amphiphilic catalysts were produced and used as the stabilizer for Pickering emulsions. Specifically, an ultrafast ODS rate was realized in the HPW/P[tVPB-VP 1 ]-stabilized Pickering emulsion catalytic system, and just within 15 min, 100 ppm dibenzothiophene (DBT) was completely oxidized by H 2 O 2 . Because the obtained hierarchical porous HPW/P[tVPB-VP x ] catalysts showed both high adsorption capacity of DBT and excellent catalytic ODS performance, the catalysts assembling at the interface of emulsions provided this fastest reaction dynamics. Playing three roles of catalyst, emulsion stabilizer, and adsorbent, the synergistic functional catalytic emulsions can be a promising approach to significantly boost the heterogeneous catalytic ODS performance.

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