RESUMO
Hierarchical porous carbons equipped with heteroatoms and diffusion pores have a wide application prospect in adsorption. Herein, we report N-autodoped porous carbons (PTPACs), which were derived from rigid N-rich conjugated microporous poly(aniline)s (CMPAs) and show their all-around applicability in heavy metal adsorption. Their molecular structure could be delicately tuned from 3D organic networks to graphitic carbons through simply adjusting the pyrolysis temperature, affording unique hybrid features of hierarchical micro-meso-macroporosity and amount-tunable nitrogen defects, as validated by the enhanced CO2 adsorption capacities reaching 5.0 mmol g-1, a 230% increase compared to the precursor (2.15 mmol g-1). They therefore show promising a Langmuir adsorption capacity of 434.8 mg g-1 toward mercury ions, which could be rapidly achieved within a short 20 min. Based on the comprehensive experimental, characterization, and DFT calculation studies, we rationally reveal these impressive adsorptions arise from the hybrid function of chemisorption contributed by populated nitrogen defects and physical adsorption achieved by synergistic functions in the diffusion and storage pores. Outcomes mark the high merits of PTPACs in addressing recent global challenges in environmental engineering.
RESUMO
The use of conjugated microporous polymers (CMPs) in practical wastewater treatment demands further design on the pore structure, otherwise their adsorption capacities toward heavy-metal ions were moderate. Here, we report a rational design approach, which produces hybrid molecular pores in conjugated microporous poly(aniline)s (CMPAs) for mercury removal. It is achieved through a delicate interval introduction of linkers with differential molecular lengths during polymerization, acquiring both diffusion channels and storage pores for radical enhancement of mass transfer and adsorption storage. The resulting CMPA-M featured a large adsorption capacity of 975 mg g-1 and rapid kinetics that could remove 94.8% of 50 mg g-1 of mercury(II) within a very short contact time of 48 s, with a promising initial adsorption rate h as high as 113 mg g-1 min-1, which was 2.54-fold larger in the adsorption capacity and 45.2-fold faster in the adsorption efficiency compared with the undeveloped CMPAs. More importantly, our CMPA-M-2, with robust stability and easy reusability, was able to scavenge over 99.9% of mercury(II) from the actual wastewater in a harsh condition with a very low pH of 0.77, extremely high salinity of 53,157 mg L-1, and complex impurities, featuring exceptional selectivity that allows us to extract and recycle a high purity of 99.1% of mercury from the wastewater. These outcomes demonstrate the unprecedented potential of CMPs for environmental remediation and real-world mercury extraction and present benchmarks for CMP-based mercury adsorbents.
