Recovering noble metals from waste streams using porous organic frameworks for heterogeneous catalysis

Recovering noble metals from waste resources and incorporating them into catalysts stands out as a promising strategy for advancing sustainability within the catalysis field. This review provides a comprehensive overview of recent investigations into noble metal recovery from waste streams, specifically employing porous organic frameworks(POFs). Additionally, the study delves into the utilization of the resultant composites, enriched with noble metals, in heterogeneous catalysis. Moreover, we offer insights into the challenges faced and outline prospects for the practical implementation of extracting noble metal catalysts from waste streams using POFs, aiming to develop cost-effective, sustainable, and efficient heterogeneous catalysts.

Porous Organic Frameworks-derived Porous Carbons with Outstanding Gas Adsorption Performance

A series of porous carbon materials was synthesized via high temperature pyrolysis from well-defined and thermally stable precursors, namely porous organic frameworks（POFs）, in inert atmosphere. The porous carbon materials showed enhanced gas adsorption capacities together with increased heat of adsorption and stronger affinity between the frameworks and the gases as compared to the precursor materials. To exemplify, sample C-POF-TBBP-1000 with a high BET surface area of 1290 m^2/g can adsorb 2.8 mmol/g CH4（273 K, 101.325 kPa）, 5.4 mmol/g CO2（273 K, 101.325 kPa） and 2.2% H2（mass fraction, 77 K, 101.325 kPa）, thereby surpassing most other porous adsorbent materials reported till date. The study highlights the potential of porous carbons derived from novel porous organic framework structures for gas adsorption applications.

Recent Advances in Multifunctional Reticular Framework Nanoparticles:A Paradigm Shift in Materials Science Road to a Structured Future

Porous organic frameworks(POFs)have become a highly sought-after research domain that offers a promising avenue for developing cutting-edge nanostructured materials,both in their pristine state and when subjected to various chemical and structural modifications.Metal–organic frameworks,covalent organic frameworks,and hydrogen-bonded organic frameworks are examples of these emerging materials that have gained significant attention due to their unique properties,such as high crystallinity,intrinsic porosity,unique structural regularity,diverse functionality,design flexibility,and outstanding stability.This review provides an overview of the state-of-the-art research on base-stable POFs,emphasizing the distinct pros and cons of reticular framework nanoparticles compared to other types of nanocluster materials.Thereafter,the review highlights the unique opportunity to produce multifunctional tailoring nanoparticles to meet specific application requirements.It is recommended that this potential for creating customized nanoparticles should be the driving force behind future synthesis efforts to tap the full potential of this multifaceted material category.

An Ultrastable π-π Stacked Porous Organic Molecular Framework as a Crystalline Sponge for Rapid Molecular Structure Determination

The crystalline sponge method is a pragmatic and promising strategy for molecular structure determination.However,the dominant metal-organic framework crystal sponge platforms always face poor chemical stability,especially solvent instability,hampering their application in a vaster domain.Herein,we report an ultrastable π-π stacked porous organic molecular framework which exhibits permanent porosity,high thermal stability,and good chemical resistance.It can efficiently implement an approach to molecular structure determination via a single-crystal-to-single-crystal transformation.This is the first example utilizing π-π stacked porous organic molecular framework as“crystalline sponge”to determine a wide variety of guests,ranging from hydrophilic to hydrophobic,and from aliphatic to aromatic,which complements the crystalline sponges based on the famous metal-organic frameworks.More importantly,it can achieve rapid structure determination of small molecules within 3 h.

Efficient separation between trivalent americium and lanthanides enabled by a phenanthroline-based polymeric organic framework

Separation of the minor actinides(Am and Cm)from lanthanides in high-level liquid wastes(HLLW)is one of the most challenging chemical separation tasks known owing to their chemical similarities and is highly significant in nuclear fuel reprocessing plants because it could practically lead to sustainable nuclear energy by closing the nuclear fuel cycle.The solid phase extraction is proposed to be a possible strategy but all reported sorbent materials severely suffer from limited stability and/or efficiency caused by the harsh conditions of high acidity coupled with intense irradiation.Herein,a phenanthroline-based polymeric organic framework(PhenTAPB-POF)was designed and tested for the separation of trivalent americium from lanthanides for the first time.Due to its fully conjugated structure,PhenTAPB-POF exhibits previously unachieved stability under the combined extreme conditions of strong acids and high irradiation field.The americium partitioning experiment indicates that PhenTAPB-POF possesses an ultrahigh adsorption selectivity towards Am(Ⅲ)over lanthanides(e.g.,SFAm(Ⅲ)/Eu(Ⅲ)=3326)in highly acidic simulated HLLW and relatively fast adsorption kinetics in both static and dynamic experiments.Am(Ⅲ)can be almost quantitatively eluted from the PhenTAPB-POF packed-column using a concentrated nitric acid elution.The high stability and superior separation performance endow PhenTAPB-POF with the promising alternative for separating minor actinides over lanthanides from highly acidic HLLW streams.

Applications of covalent organic frameworks(COFs)：From gas storage and separation to drug delivery

Covalent organic frameworks（COFs） are an emerging class of porous covalent organic structures whose backbones were composed of light elements（B,C,N,O,Si） and linked by robust covalent bonds to endow such material with desirable properties,i.e.,inherent porosity,well-defined pore aperture,ordered channel structure,large surface area,high stability,and multi-dimension.As expected,the abovementioned properties of COFs broaden the applications of this class of materials in various fields such as gas storage and separation,catalysis,optoelectronics,sensing,small molecules adsorption,and drug delivery.In this review,we outlined the synthesis of COFs and highlighted their applications ranging from the initial gas storage and separation to drug delivery.

Assemblies of covalent organic framework microcrystals:multiple-dimensional manipulation for enhanced applications

Covalent organic frameworks (COFs) are well known as the next generation of shape-persistent zeolite analogues, which have brought new impetus to the development of porous organic materials as well as two-dimensional polymers. Since the advent of COFs in 2005, many striking findings have definitely proven their great potentials expanding applications across energy,environment and healthcare fields. With thorough exploration over a decade, research interest has been drawn on the scientific challenges on chemistry, while making full play of COF values has remained far from satisfactory yet. Thus opening an avenue to modulating COF assemblies on the multi-scale is no longer just an option, but a necessity for matching the application requirements with enhanced performances. In this mini-review, we summarize the recent progress on design of nanoscale COFs with varying forms. Detailed description is concentrated on the synthetic strategies of COF assemblies such as spheres, fibers,tubes, coatings and films, thereby shedding light on the flexible manipulation over dimensions, compositions and morphologies.Meanwhile, the advanced applications of nanoscale COFs have been discussed here with comparison of their bulky counterparts.

Tuning the primary selective nanochannels of MOF thin-film nanocomposite nanofiltration membranes for efficient removal of hydrophobic endocrine disrupting compounds

Metal organic framework(MOF)incorporated thin-film nanocomposite(TFN)membranes have the potential to enhance the removal of endocrine disrupting compounds(EDCs).In MOF-TFN membranes,water transport nanochannels include(i)pores of polyamide layer,(ii)pores in MOFs and(iii)channels around MOFs(polyamide-MOF interface).However,information on how to tune the nanochannels to enhance EDCs rejection is scarce,impeding the refinement of TFN membranes toward efficient removal of EDCs.In this study,by changing the polyamide properties,the water transport nanochannels could be confined primarily in pores of MOFs when the polyamide layer became dense.Interestingly,the improved rejection of EDCs was dependent on the water transport channels of the TFN membrane.At low monomer concentration(i.e.,loose polyamide structure),the hydrophilic nanochannels of MIL-101(Cr)in the polyamide layer could not dominate the membrane separation performance,and hence the extent of improvement in EDCs rejection was relatively low.In contrast,at high monomer concentration(i.e.,dense polyamide structure),the hydrophilic nanochannels of MIL-101(Cr)were responsible for the selective removal of hydrophobic EDCs,demonstrating that the manipulation of water transport nanochannels in the TFN membrane could successfully overcome the permeability and EDCs rejection trade-off.Our results highlight the potential of tuning primary selective nanochannels of MOF-TFN membranes for the efficient removal of EDCs.