Design and Synthesis of N-Doped Porous Carbons for the Selective Carbon Dioxide Capture under Humid Flue Gas Conditions.

The design of novel porous solid sorbents for carbon dioxide capture is critical in developing carbon capture and storage technology (CCS). We have synthesized a series of nitrogen-rich porous organic polymers (POPs) from crosslinking melamine and pyrrole monomers. The final polymer's nitrogen content was tuned by varying the melamine ratio compared to pyrrole. The resulting polymers were then pyrolyzed at 700 °C and 900 °C to produce high surface area nitrogen-doped porous carbons (NPCs) with different N/C ratios. The resulting NPCs showed good BET surface areas reaching 900 m2 g-1. Owing to the nitrogen-enriched skeleton and the micropore nature of the prepared NPCs, they exhibited CO2 uptake capacities as high as 60 cm3 g-1 at 273 K and 1 bar with significant CO2/N2 selectivity. The materials showed excellent and stable performance over five adsorption/desorption cycles in the dynamic separation of the ternary mixture of N2/CO2/H2O. The method developed in this work and the synthesized NPCs' performance towards CO2 capture highlight the unique properties of POPs as precursors for synthesizing nitrogen-doped porous carbons with a high nitrogen content and high yield.

Azo-Linked Porous Organic Polymers for Selective Carbon Dioxide Capture and Metal Ion Removal.

The facile and environmentally friendly synthesis of porous organic polymers with designed polar functionalities decorating the interior frameworks as an excellent adsorbent for selective carbon dioxide capture and metal ion removal is a target worth pursuing for environmental applications. In this regard, two azo-linked porous organic polymers denoted man-Azo-P1 and man-Azo-P2 were synthesized in water by the azo-linking of 4,4'-diaminobiphenyl (benzidine) and 4,4'-methylenedianiline, respectively, with 1,3,5-trihydroxybenzene. The resulting polymers showed good BET surface areas of 290 and 78 m2 g-1 for man-Azo-P1 and man-Azo-P2, respectively. Due to the enriched core functionality of the azo (-N=N-) and hydroxyl groups along with the porous frameworks, man-Azo-P1 exhibited a good CO2 uptake capacity of 32 cm3 g-1 at 273 K and 1 bar, in addition to the remarkable removal of lead (Pd), chromium (Cr), arsenic (As), nickel (Ni), copper (Cu), and mercury (Hg) ions. This performance of the synthesized man-Azo-P1 and man-Azo-P2 in the dual application of CO2 capture and heavy metal ion removal highlights the unique properties of azo-linked POPs as excellent and stable sorbent materials for the current challenging environmental applications.

Experimental and Theoretical Study on the Interchange between Zr and Ti within the MIL-125-NH2 Metal Cluster.

This study aims to investigate the effect of replacing Ti with Zr in the SBU of MIL-125-NH2 . We were able to replace Ti with Zr in the mixed metal synthesis of MIL-125-NH2 , for the first time. After experimentally confirming the consistency in their framework structure and comparing their morphology, we related the femtosecond light dynamics with photocatalytic CO2 visible light conversion yield of the different variants in order to establish the composition-function relation in MIL-125 vis a vis CO2 reduction. Introducing Zr to the system was found to cause structure defects due to missing linkers. The lifetime of the charge carriers for the mixed metal samples were shorter than that of the MIL-125-NH2 . The study of CO2 photocatalytic reduction under visible light indicated that the NH2 group enhances the photocatalytic activity while the Zr incorporation inside the MIL framework introduces no significant improvements. In addition, the material systems were modelled and simulated through DFT calculations which concluded that the decrease of the photocatalytic activity is not related to the system electronic structure, insinuating that defects are the culprit.

Trends and Prospects in UiO-66 Metal-Organic Framework for CO2 Capture, Separation, and Conversion.

Among thousands of known metal-organic frameworks (MOFs), the University of Oslo's MOF (UiO-66) exhibits unique structure topology, chemical and thermal stability, and intriguing tunable properties, that have gained incredible research interest. This paper summarizes the structural advancement of UiO-66 and its role in CO2 capture, separation, and transformation into chemicals. The first part of the review summarizes the fast-growing literature related to the CO2 capture reported by UiO-66 during the past ten years. The second part provides an overview of various advancements in UiO-66 membranes in CO2 purification. The third part describes the role of UiO-66 and its composites as catalysts for CO2 conversion into useful products. Despite many achievements, significant challenges associated with UiO-66 are addressed, and future perspectives are comprehensively presented to forecast how UiO-66 might be used further for CO2 management.

Sulfone-containing Conjugated Polyimide 2D Nanosheets for Efficient Water Oxidation.

Water oxidation is a bottleneck in artificial photosynthesis that impedes its practicality for solar energy conversion and utilization. It is highly desired to significantly improve the efficacy of the existing catalysts or to rationally design new catalysts with improved performance. We report a novel conjugated and sulfone containing polyimide as a metal-free photocatalyst synthesized via a two-step method: (i) synthesis of precursor poly(amic acid) (PAA) (ii) solvothermal synthesis of polyimide through thermal imidization. The synthesis of the polyimide photocatalyst was demonstrated by the amide linkage in the FTIR spectrum. The obtained photocatalyst was semicrystalline in nature and possessed sheet-like morphology as illustrated by the diffraction pattern and the electron micrographic images, respectively. The thermogravimetric analysis of the polyimide nanosheets validated a thermally stable structure. The DFT calculations were performed which showed a suitable HOMO band position, favorable for water oxidation. The photoelectrocatalytic (PEC) performance of the polyimide nanosheets evaluated by studying water oxidation reaction without any sacrificial agent under 1-SUN showed enhanced PEC performance and good stability towards water oxidation at 0 V versus SCE.