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1. Implications of Defect Density and Polymer Interactions for CO ₂ Capture on Amine‐Functionalized MIL‐101(Cr)

   https://doi.org/10.1002/cssc.202400249  

   Yang, Rachel A; Cho, Stanley; Hughes, Sydney N; Sarazen, Michele L (May 2024, ChemSusChem)

   Abstract Rising anthropogenic carbon emissions have dire environmental consequences, necessitating remediative approaches, which includes use of solid sorbents. Here, aminopolymers (poly(ethylene imine) (PEI) and poly(propylene imine) (PPI)) are supported within solid mesoporous MIL‐101(Cr) to examine effects of support defect density on aminopolymer‐MOF interactions for CO₂uptake and stability during uptake‐regeneration cycles. Using simulated flue gas (10 % CO₂in He), MIL‐101(Cr)‐ρ_high(higher defect density) shows 33 % higher uptake capacity per gram adsorbent than MIL‐101(Cr)‐ρ_low(lower defect density) at 308 K, consistent with increased availability of undercoordinated Cr adsorption sites at missing linker defects. Increasing aminopolymer weight loadings (10–50 wt.%) within MIL‐101(Cr)‐ρ_lowand MIL‐101(Cr)‐ρ_highincreases amine efficiencies and CO₂uptake capacities relative to bare MOFs, though both incur CO₂diffusion limitations through confined, viscous polymer phases at higher (40–50 wt.%) loadings. Benchmarked against SBA‐15, lower polymer packing densities (PPI>PEI), weaker and less abundant van der Waals interactions between aminopolymers and pore walls, and open framework topology increase amine efficiencies. Interactions between amines and Cr defect sites incur amine efficiency losses but grant higher thermal and oxidative stability during uptake‐regeneration cycling. Finally, >25 % higher CO₂uptake capacities are achieved for aminopolymer/MIL‐101(Cr)‐ρ_highunder humid conditions, demonstrating promise for realistic applications. 

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2. Platinum and cobalt intermetallic nanoparticles confined within MIL-101(Cr) for enhanced selective hydrogenation of the carbonyl bond in α,β-unsaturated aldehydes: synergistic effects of electronically modified Pt sites and Lewis acid sites

   https://doi.org/10.1039/D0CY02082F  

   Zahid, Muhammad; Li, Jiang; Ismail, Ahmed; Zaera, Francisco; Zhu, Yujun (April 2021, Catalysis Science & Technology)

   Precious metals have been shown to play a vital role in the selective hydrogenation of α,β-unsaturated aldehydes, but still suffer from challenges to control selectivity. Herein, we have advanced the design of catalysts made out of Pt–Co intermetallic nanoparticles (IMNs) supported on a MIL-101(Cr) MOF (3%Pt y %Co/MIL-101(Cr)), prepared by using a polyol reduction method, as an effective approach to enhance selectivity toward the production of α,β-unsaturated alcohol, the desired product. XRD, N 2 adsorption–desorption, FTIR spectroscopy, SEM, TEM, XPS, CO adsorption, NH 3 -TPD, XANES and EXAFS measurements were used to investigate the structure and surface properties of our 3%Pt y %Co/MIL-101(Cr) catalysts. It was found that the Co-modified 3%Pt y %Co/MIL-101(Cr) catalysts can indeed improve the hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL), reaching a higher selectivity under mild conditions than the monometallic Pt/MIL-101(Cr) catalysts: 95% conversion of CAL with 91% selectivity to COL can be reached with 3%Pt3%Co/MIL-101(Cr). Additionally, high conversion of furfural (97%) along with high selectivity to furfural alcohol (94%) was also attained with the 3%Pt3%Co/MIL-101(Cr) catalyst. The enhanced activity and selectivity toward the unsaturated alcohols are attributed to the electronic and geometric effects derived from the partial charge transfer between Co and Pt through the formation of uniformly dispersed Pt–Co IMNs. Moreover, various characterization results revealed that the addition of Co to the IMPs can promote the Lewis acid sites that facilitate the polarization of the charge-rich CO bonds and their adsorption via their oxygen atom, and also generate new interfacial acid sites. 

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3. Fabrication of a freestanding metal organic framework predominant hollow fiber mat and its potential applications in gas separation and catalysis

   https://doi.org/10.1039/c9ta11701f  

   Dai, Zijian; Lee, Dennis T.; Shi, Kaihang; Wang, Siyao; Barton, Heather F.; Zhu, Jie; Yan, Jiaqi; Ke, Qinfei; Parsons, Gregory N. (February 2020, Journal of Materials Chemistry A)

   Recently, metal–organic framework (MOF)-based polymeric substrates show promising performance in many engineering and technology fields. However, a commonly known drawback of MOF/polymer composites is MOF crystal encapsulation and reduced surface area. This work reports a facile and gentle strategy to produce self-supported MOF predominant hollow fiber mats. A wide range of hollow MOFs including MIL-53(Al)–NH 2 , Al-PMOF, and ZIF-8 are successfully fabricated by our synthetic method. The synthetic strategy combines atomic layer deposition (ALD) of metal oxides onto polymer fibers and subsequent selective removal of polymer components followed by conversion of remaining hollow metal oxides into freestanding MOF predominant hollow fiber structures. The hollow MOFs show boosted surface area, superb porosity, and excellent pore accessibility, and exhibit a significantly improved performance in CO 2 adsorption (3.30 mmol g −1 ), CO 2 /N 2 separation selectivity (24.9 and 21.2 for 15/85 and 50/50 CO 2 /N 2 mixtures), and catalytic removal of HCHO (complete oxidation of 150 ppm within 60 min). 

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4. Optimization of batch and packed-bed column Cr( vi ) adsorption of an amine-rich chitosan/polyethyleneimine composite: application in electroplating wastewater treatment

   https://doi.org/10.1039/d4ew00123k  

   Ansari, Ali; Silva_Jacovone, Raynara Maria; Nadres, Enrico Tapire; Đỗ, Minh; Rodrigues, Debora Frigi (June 2024, Environmental Science: Water Research & Technology)

   Toxic oxyanions of Cr(VI) can be potentially removed by adsorbents with positively charged surfaces. In this study, we synthesized a stable and insoluble amine-rich polymer composite (CS–PEI–GLA) by crosslinking polyethyleneimine (PEI), a soluble amine-rich synthetic polymer, and chitosan (CS) with glutaraldehyde (GLA). The positively charged amine groups were the main adsorption sites. The batch investigation demonstrated that the adsorbent was able to remove ≥90% of chromium at pH ranging from 2 to 8. Due to deprotonation of the amine groups, chromium removal decreased at higher pH values. The adsorption was fast and reached equilibrium after 45 min. The maximum adsorption capacity was 500 mg g−1 according to the Langmuir isotherm and did not decrease in the presence of monovalent anions. In the column study, the adsorption capacity was the highest when the flow rate was the lowest (5 mL min−1), influent concentration was medium (225 mg L−1), and the bed height was the shortest (3.5 cm). NaOH was the best recovery reagent with recovery of 67% in batch and 31% in the column. The CS–PEI–GLA composite was able to remove 97.1 ± 0.1% chromium in batch and treat 750 mL of electroplating wastewater with a 3.5 cm packed-bed column. 

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5. Vapor-Phase-Infiltrated AlO _x /PIM-1 “Hybrid Scaffolds” as Solution-Processable Amine Supports for CO ₂ Adsorption

   https://doi.org/10.1021/acsapm.1c00452  

   Zhang, Fengyi; McGuinness, Emily K.; Ma, Yao; Ren, Yi; Leisen, Johannes E.; Losego, Mark D.; Lively, Ryan P. (January 2021, ACS Applied Polymer Materials)

   null (Ed.)

   Energy-efficient adsorptive CO2 capture requires both adsorbent materials with high CO2 capacity and structured adsorption contactors possessing fast mass transfer kinetics and low pressure drop. The state-of-the-art research primarily focuses on “hard” adsorbents such as mesoporous zeolites and metal–organic frameworks, which exhibit high CO2 capacities but are challenging to translate into structured contactors. Polymer of intrinsic microporosity 1 (PIM-1), a solution-processable microporous polymer, is a “softer” alternative that can be easily fabricated into structured adsorption contactors. In prior research, PIM-1 has been utilized as a “molecular basket” for poly(ethylene imine) (PEI). Despite nanoscale amine dispersion and excellent processability, PEI/PIM-1 composites possess an unstable micropore structure, which collapses at high PEI loadings (∼30%) and results in lower CO2 adsorption capacity than PEI-loaded hard oxides. Here, we applied a post-fabrication polymer stabilization method, vapor phase infiltration (VPI), to improve the CO2 capacity of the PEI/PIM-1 composite without sacrificing its processibility. PIM-1 is fabricated into structured adsorption contactors and then reinforced with amorphous aluminum oxyhydroxide (AlOx) nanostrands via VPI. The resulting AlOx/PIM-1 is a stable, hierarchically porous support, which can be loaded with 40% PEI without pore collapse. Owing to the combination of processibility, comparable CO2 capacity, and high amine efficiency, PEI/AlOx/PIM-1 composites are a promising alternative to PEI-loaded mesoporous oxides. 

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