Polyimide/Ionic Liquids Hybrid Membranes with NH3-Philic Channels for Ammonia-Based CO2 Separation Processes.

An efficient separation technology involving ammonia (NH3) and carbon dioxide (CO2) is of great importance for achieving low-carbon economy, environmental protection, and resource utilization. However, directly separating NH3 and CO2 for ammonia-based CO2 capture processes is still a great challenge. Herein, we propose a new strategy for selective separation of NH3 and CO2 by functional hybrid membranes that integrate polyimide (PI) and ionic liquids (ILs). The incorporated protic IL [Bim][NTf2] is confined in the interchain segment of PI, which decreases the fractional free volume and narrows the gas transport channel, benefiting the high separation selectivity of hybrid membranes. At the same time, the confined IL also provides high NH3 affinity for transport channels, promoting NH3 selective and fast transport owing to strong hydrogen bonding interaction between [Bim][NTf2] and NH3 molecules. Thus, the optimal hybrid membrane exhibits an ultrahigh NH3/CO2 ideal selectivity of up to 159 at 30 °C without sacrificing permeability, which is 60 times higher than that of the neat PI membrane and superior to the state-of-the art reported values. Moreover, the introduction of [Bim][NTf2] also reduces the permeation active energy of NH3 and reverses the hybrid membrane toward "NH3 affinity", as understood by studying the effect of temperature. Also, NH3 molecules are much easier to transport at high temperature, showing great application potential in direct NH3/CO2 separation. Overall, this work provides a promising ultraselective membrane material for ammonia-based CO2 capture processes.

Sulfidated microscale zero-valent iron/reduced graphene oxide composite (S-mZVI/rGO) for enhanced degradation of trichloroethylene: The role of hydrogen spillover.

Atomic hydrogen (H*) has long been thought to play an important role in the dechlorination of trichloroethylene (TCE) by carbon-supported zero-valent iron (ZVI), which offers an alternative pathway for TCE dechlorination. Herein, we demonstrate that the reductive dechlorination of TCE by sulfidated microscale ZVI (S-mZVI) can be further enhanced by promoting the formation of H* through the introduction of reduced graphene oxide (rGO). The completely degradation of 10 mg/L TCE can be achieved by S-mZVI/rGO within 24 h, which was 3.3 times faster than that of S-mZVI. The change in the distribution of TCE degradation products over time suggests that the introduction of rGO leads to a change in the dechlorination pathway. The percentage of ethane in the final products of TCE degradation by S-mZVI/rGO was 34.3 %, while that of S-mZVI was only 21.9 %. The electrochemical tests confirmed the occurrence of hydrogen spillover in the S-mZVI/rGO composite, which promoted the reductive dechlorination of TCE by H*. Although the S-mZVI/rGO composite had stronger hydrogen evolution propensity than S-mZVI, the S-mZVI/rGO composite still exhibited higher electron utilization efficiency than S-mZVI thanks to the increased utilization of hydrogen.

Interface-Confined Channels Facilitating Water Transport through an IL-Enriched Nanocomposite Membrane.

Improving the permeance of the polyamide (PA) membrane while maintaining the rejection is crucial for promoting the development of membrane separation technology in the practical water-treatment industry. Herein, a novel metal-ionic liquid (Zn-IL) coordination compound was synthesized by in situ growth to improve the water permeance of PA nanofiltration membranes, using an amine-functionalized IL (1-aminopropyl-3-methylimidazolium chloride, [AEMIm][Cl]) as a ligand to react with Zn(NO3)2·6H2O. Piperazine (PIP) and trimesoyl chloride (TMC) were adopted to prepare the PA layer covering the Zn-IL complex. Due to the unique property of the Zn-IL complex, the Zn-IL/PIP-TMC absorbing force to water was increased, enabling the fast transport of water molecules through the membrane pore channels in the form of free water. The resulting Zn-IL/PIP-TMC nanocomposite membrane exhibited a high permeance of up to 26.5 L m-2 h-1 bar-1, which is 3 times that of the PIP-TMC membrane (8.8 L m-2 h-1 bar-1), combined with rejection above 99% for dyes such as methyl blue.

Peracetic acid integrated catalytic ceramic membrane filtration for enhanced membrane fouling control: Performance evaluation and mechanism analysis.

Endowing ceramic membrane (CM) catalytic reactivity can enhance membrane fouling control in the aid of in situ oxidation process. Peracetic acid (PAA) oxidant holds great prospect to integrate with CM for membrane fouling control, owing to the prominent advantages of high oxidation efficacy and easy activation. Herein, this study, for the first time, presented a PAA/CM catalytic filtration system achieving highly-efficient protein fouling alleviation. A FeOCl functionalized CM (FeOCl-CM) was synthesized, possessing high hydrophilicity, low surface roughness, and highly-efficient activation towards PAA oxidation. Using bovine serum albumin (BSA) as the model protein foulant, the PAA/FeOCl-CM catalytic filtration notably alleviated fouling occurring in both membrane pores and surface, and halved the flux reduction degree as compared with the conventional CM filtration. The PAA/FeOCl-CM catalytic oxidation allows quick and complete disintegration of BSA particles, via the breakage of the amide I and II bands and the ring opening of the aromatic amino acids (e.g., Tryptophan, Tyrosine). In-depth investigation revealed that the in situ generated •OH and 1O2 were the key reactive species towards BSA degradation during catalytic filtration, while the organic radical oxidation and the direct electron transfer pathway from BSA to PAA via FeOCl-CM played minor roles. Overall, our findings highlight a new PAA/CM catalytic filtration strategy for achieving highly-efficient membrane fouling control and provide an understanding of the integrated PAA catalytic oxidation - membrane filtration behaviors.

Ni2P nanocrystals embedded Ni-MOF nanosheets supported on nickel foam as bifunctional electrocatalyst for urea electrolysis.

It's highly desired but challenging to synthesize self-supporting nanohybrid made of conductive nanoparticles with metal organic framework (MOF) materials for the application in the electrochemical field. In this work, we report the preparation of Ni2P embedded Ni-MOF nanosheets supported on nickel foam through partial phosphidation (Ni2P@Ni-MOF/NF). The self-supporting Ni2P@Ni-MOF/NF was directly tested as electrode for urea electrolysis. When served as anode for urea oxidation reaction (UOR), it only demands 1.41 V (vs RHE) to deliver a current of 100 mA cm-2. And the overpotential of Ni2P@Ni-MOF/NF to reach 10 mA cm-2 for hydrogen evolution reaction HER was only 66 mV, remarkably lower than Ni2P/NF (133 mV). The exceptional electrochemical performance was attributed to the unique structure of Ni2P@Ni-MOF and the well exposed surface of Ni2P. Furthermore, the Ni2P@Ni-MOF/NF demonstrated outstanding longevity for both HER and UOR. The electrolyzer constructed with Ni2P@Ni-MOF/NF as bifunctional electrode can attain a current density of 100 mA cm-2 at a cell voltage as low as 1.65 V. Our work provides new insights for prepare MOF based nanohydrid for electrochemical application.

The Ionic Liquid-H2O Interface: A New Platform for the Synthesis of Highly Crystalline and Molecular Sieving Covalent Organic Framework Membranes.

Covalent organic frameworks (COFs) are highly porous crystalline polymers with uniform pores and large surface areas. Combined with their modular design principle and excellent properties, COFs are an ideal candidate for separation membranes. Liquid-liquid interfacial polymerization is a well-known approach to synthesize membranes by reacting two monomers at the interface. However, volatile organic solvents are usually used, which may disturb the liquid-liquid interface and affect the COF membrane crystallinity due to solvent evaporation. Simultaneously, the domain size of the organic solvent-water interface, named the reaction zone, can hardly be regulated, and the diffusion control of monomers for favorable crystallinity is only achieved in the water phase. These drawbacks may limit the widespread applications of liquid-liquid interfacial polymerization to synthesize diverse COF membranes with different functionalities. Here, we report a facile strategy to synthesize a series of imine-linked freestanding COF membranes with different thicknesses and morphologies at tunable ionic liquid (IL)-H2O interfaces. Due to the H-bonding of the catalysts with amine monomers and the high viscosity of the ILs, the diffusion of the monomers was simultaneously controlled in water and in ILs. This resulted in the exceptionally high crystallinity of freestanding COF membranes with a Brunauer-Emmett-Teller (BET) surface area up to 4.3 times of that synthesized at a dichloromethane-H2O interface. By varying the alkyl chain length of cations in the ILs, the interfacial region size and interfacial tension could be regulated to further improve the crystallinity of the COF membranes. As a result, the as-fabricated COF membranes exhibited ultrahigh permeance toward water and organic solvents and excellent selective rejection of dyes.

Highly Selective Oxygen/Nitrogen Separation Membrane Engineered Using a Porphyrin-Based Oxygen Carrier.

Air separation is very important from the viewpoint of the economic and environmental advantages. In this work, defect-free facilitated transport membranes based on poly(amide-12-b-ethylene oxide) (Pebax-2533) and tetra(p-methoxylphenyl)porphyrin cobalt chloride (T(p-OCH3)PPCoCl) were fabricated in systematically varied compositions for O2/N2 separation. T(p-OCH3)PPCoCl was introduced as carriers that selectively and reversibly interacted with O2 and facilitated O2 transport in the membrane. The T(p-OCH3)PPCoCl had good compatibility with the Pebax-2533 via the hydrogen bond interaction and formed a uniform and thin selective layer on the substrate. The O2 separation performance of the thin film composite (TFC) membranes was improved by adding a small amount of the T(p-OCH3)PPCoCl and decreasing the feed pressure. At the pressure of 0.035 MPa, the O2 permeability and O2/N2 selectivity of the 0.6 wt % T(p-OCH3)PPCoCl/Pebax-2533 was more than 3.5 times that of the Pebax-2533 TFC membrane, which reached the 2008 Robeson upper bound. It provides a candidate membrane material for O2/N2 efficient separation in moderate conditions.

Interaction Analysis between Gravity-Driven Ceramic Membrane and Smaller Organic Matter: Implications for Retention and Fouling Mechanism in Ultralow Pressure-Driven Filtration System.

Gravity-driven membranes (GDM) generally achieve high retention performance in filtration of organic matter with a smaller size than the membrane pore, yet the in-depth mechanism remains unclear. Thorough analysis of the retention mechanism is crucial for optimizing GDM properties and improving GDM filtration performance. The performance and interaction mechanism of gravity-driven ceramic membrane (GDCM) filtrating smaller organic matter (SOM) were systematically studied. Rejection rate grew noticeably for like-charged foulant, whereas it only grew slightly for opposite-charged foulant as operation height decreased. Flux declined more seriously at lower operation height, probably due to heavier cake fouling caused by the rejected foulant. Interactions of ceramic membrane-SOM were analyzed through extended Derjaguin-Landau-Verwey-Overbeek theory (XDLVO) and hydrodynamic permeation drag (PD). Among van der Waals (LW), acid-base (AB), and electrostatic (EL) forces in XDLVO, EL played a significant role on GDCM filtrating SOM, and altering membrane electrostatic property could greatly influence SOM filtration. Furthermore, the rising PD force largely weakened the EL dominant zone with operation height increasing, while barely influencing the LW and AB dominant zones. Therefore, the weakened EL-dominant repulsive zone caused less rejection of like-charged foulant with operation height increasing. Fe2O3- and MnO2-modified membranes further validated the comprehensive influence of LW, AB, EL, and PD interactions on GDCM filtration. The possible "trade-off" of pore blocking-cake fouling with operation height decreasing demonstrated potential enhancement for both rejection and antifouling performance by electrically modified membrane under ultralow pressure. This study provides insight on membrane selection/preparation/modification and performance control of ultralow pressure-driven filtration.

Facile Synthesis of a Pentiptycene-Based Highly Microporous Organic Polymer for Gas Storage and Water Treatment.

Rigid H-shaped pentiptycene units, with an intrinsic hierarchical structure, were employed to fabricate a highly microporous organic polymer sorbent via Friedel-Crafts reaction/polymerization. The obtained microporous polymer exhibits good thermal stability, a high Brunauer-Emmett-Teller surface area of 1604 m2 g-1, outstanding CO2, H2, and CH4 storage capacities, as well as good adsorption selectivities for the separation of CO2/N2 and CO2/CH4 gas pairs. The CO2 uptake values reached as high as 5.00 mmol g-1 (1.0 bar and 273 K), which, along with high adsorption selectivity values (e.g., 47.1 for CO2/N2), make the pentiptycene-based microporous organic polymer (PMOP) a promising sorbent material for carbon capture from flue gas and natural gas purification. Moreover, the PMOP material displayed superior absorption capacities for organic solvents and dyes. For example, the maximum adsorption capacities for methylene blue and Congo red were 394 and 932 mg g-1, respectively, promoting the potential of the PMOP as an excellent sorbent for environmental remediation and water treatment.

Highly Proton Conducting Polyelectrolyte Membranes with Unusual Water Swelling Behavior Based on Triptycene-containing Poly(arylene ether sulfone) Multiblock Copolymers.

Multiblock poly(arylene ether sulfone) copolymers are attractive for polyelectrolyte membrane fuel cell applications due to their reportedly improved proton conductivity under partially hydrated conditions and better mechanical/thermal stability compared to Nafion. However, the long hydrophilic sequences required to achieve high conductivity usually lead to excessive water uptake and swelling, which degrade membrane dimensional stability. Herein, we report a fundamentally new approach to address this grand challenge by introducing shape-persistent triptycene units into the hydrophobic sequences of multiblock copolymers, which induce strong supramolecular chain-threading and interlocking interactions that effectively suppress water swelling. Consequently, unlike previously reported multiblock copolymer systems, the water swelling of the triptycene-containing multiblock copolymers did not increase proportionally with water uptake. This combination of high water uptake and low swelling behavior of these copolymers resulted in excellent proton conductivity and membrane dimensional stability under fully hydrated conditions. In particular, the triptycene-containing multiblock copolymer film with the longest hydrophilic block length (i.e., BPSH100-TRP0-15k-15k) had a water uptake of 105%, an excellent proton conductivity of 0.150 S/cm, and a volume swelling ratio of just 29% (more than 42% reduction compared to Nafion 212).

Single chains of strong polyelectrolytes in aqueous solutions at extreme dilution: Conformation and counterion distribution.

The molecular conformation of two typical polyelectrolytes, sodium polystyrene sulfonate (NaPSS) and quarternized poly-4-vinylpyridine (QP4VP), was studied in aqueous solutions without salt addition at the single molecular level. By fluorescence correlation spectroscopy, the hydrodynamic radius (Rh) of NaPSS and QP4VP with the molecular weight ranging more than one order of magnitude was measured. The scaling analysis of Rh exhibits scaling exponent of 0.70 and 0.86 for NaPSS and QP4VP in solutions without added salts, respectively, showing the conformation is much more expanded than random coil. Numerical fittings using the model of diffusion of a rod molecule agree with the data well, indicating that the polyelectrolyte chains take the rod-like conformation under the condition without salt addition. Further investigations by determining the electric potential of single PSS- chains using the photon counting histogram technique demonstrate the enhanced counterion adsorption to the charged chain at higher molecular weight.

Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.