Porous framework materials for energy&environment relevant applications:A systematic review

Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and efficiency reinforcement,carbon capture,and pollutant gas treatment is in highly imperious demand.The emerging porous framework materials such as metal–organic frameworks(MOFs),covalent organic frameworks(COFs)and hydrogen-bonded organic frameworks(HOFs),owing to the permanent porosity,tremendous specific surface area,designable structure and customizable functionality,have shown great potential in major energy-consuming industrial processes,including sustainable energy gas catalytic conversion,energy-efficient industrial gas separation and storage.Herein,this manuscript presents a systematic review of porous framework materials for global and comprehensive energy&environment related applications,from a macroscopic and application perspective.

Photocatalytic synthesis of small-molecule drugs by porous framework materials

Small-molecule drugs are widely used in daily life.There are still issues with the current industrial synthesis techniques for small-molecule drugs,such as the use of expensive metal catalysts,convoluted reaction processes,and non-recyclable catalysts.The benefits of photocatalytic organic synthesis over conventional techniques are mild conditions,environmental friendliness,and great selectivity.Porous framework materials can precisely modulate catalytic sites'electronic state and ligand structure to improve photocatalytic performance.In particular,MOFs,COFs and PCCs based photocatalysts have received extensive research interest due to their unique morphology,structural adjustability,high photocatalytic performance,unique recyclability,excellent chemical stability,easy synthesis and low cost.Therefore,a key area for future research is the development of porous framework materials as photocatalysts for the synthesis of small-molecule drugs or drug precursors.

Rational design of new in situ reduction of Ni(II)catalytic system for low-cost and large-scale preparation of porous aromatic frameworks

Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.

Construction of 3D porous Cu_(1.81)S/nitrogen-doped carbon frameworks for ultrafast and long-cycle life sodium-ion storage

Transition metal sulfides have great potential as anode mterials for sodium-ion batteries(SIBs)due to their high theoretical specific capacities.However,the inferior intrinsic conductivity and large volume variation during sodiation-desodiation processes seriously affect its high-rate and long-cyde performance,unbeneficial for the application as fast-charging and long-cycling SIBs anode.Herein,the three-dimensional porous Cu_(1.81)S/nitrogen-doped carbon frameworks(Cu_(1.81)S/NC)are synthesized by the simple and facile sol-gel and annealing processes,which can accommodate the volumetric expansion of Cu_(1.81)S nanoparticles and accelerate the transmission of ions and electrons during Na^(+)insertion/extraction processes,exhibiting the excellent rate capability(250.6 mA·g^(-1)at 20.0 A·g^(-1))and outstanding cycling stability(70% capacity retention for 6000 cycles at 10.0 A·g^(-1))for SIBs.Moreover,the Na-ion full cells coupled with Na_(3)V_(2)(PO_(4))_(3)/C cathode also demonstrate the satisfactory reversible specific capacity of 330.5 mAh·g^(-1)at 5.0 A·g^(-1)and long-cycle performance with the 86.9% capacity retention at 2.0 A·g^(-1)after 750 cycles.This work proposes a promising way for the conversionbased metal sulfides for the applications as fast-charging sodium-ion battery anode.

A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide:Hybrid material‐confined Co for ammonia borane methanolysis

The rational synthesis of a two-dimensional(2D)porous aromatic framework(PAF)with a controllable growth direction remains a challenge to overcome the limitation of traditional stacked 2D materials.Herein,a step-growth strategy is developed to fabricate a vertically oriented nitrogen-rich porous aromatic framework on graphene oxide(V-PAF-GO)using monolayer benzidine-functionalized GO(BZ-GO)as a molecular pillar.Then,the confined Co nanoparticle(NP)catalysts are synthesized by encapsulating ultra-small Co into the slit pores of V-PAF-GO.Due to the high nitrogen content,large specific surface area,and adequate slit pores,the optimized vertical nanocomposites V-PAF-GO provide abundant anchoring sites for metal NPs,leading to ultrafine Co NPs(1.4 nm).The resultant Co/V-PAF-GO catalyst shows an extraordinary catalytic activity for ammonia borane(AB)methanolysis,yielding a turnover frequency value of 47.6 min−1 at 25°C,comparable to the most effective non-noble-metal catalysts ever reported for AB methanolysis.Experimental and density functional theory studies demonstrate that the electron-donating effect of N species of PAF positively corresponds to the low barrier in methanol molecule activation,and the cleavage of the O–H bond in CH3OH has been proven to be the rate-determining step for AB methanolysis.This work presents a versatile step-growth strategy to prepare a vertically oriented PAF on GO to solve the stacking problem of 2D materials,which will be used to fabricate other novel 2D or 2D–2D materials with controllable orientation for various 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.

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.

A Porous Organic-inorganic Hybrid Compound Constructed from Polyoxovanadium Borate Anions,Dinuclear Na Sites and Metal-organic Units

A polyoxovanadium borate [Na（H2O）]2[Na（H2O）2]2[Cu（en）2][V12B18O54（OH）6]·（H3O）2·（H2O）18 1（en = ethylenediamine） has been hydrothermally synthesized and characterized by IR,two-dimensional infrared（2D IR） correlation spectroscopy with magnetic and thermal perturba-tion,thermal IR spectroscopy,thermal gravimetric analysis and single-crystal X-ray diffraction.It crystallizes in triclinic,space group P with a = 12.981（3）,b = 13.044（3）,c = 14.208（3） ,α = 63.98（3）,β = 77.17（3）,γ = 14.208（3）°,V = 2001.0（8） 3,Z = 1,Mr = 2518.05,Dc = 2.090 g/cm-1,F（000） = 1255.0,Mu（mm-1） = 1.756,λ（MoKα） = 0.71073 ,R = 0.0625 and wR = 0.1952.In 1,the [V12B18O54（OH）6]8- units are connected by [Cu（en）2]2＋,binuclear Na（1） and Na（2） to form a three-dimensional porous framework.

Tuning Interface Bridging Between MoSe2 and Three‑Dimensional Carbon Framework by Incorporation of MoC Intermediate to Boost Lithium Storage Capability

Interface engineering has been widely explored to improve the electrochemical performances of composite electrodes,which governs the interface charge transfer,electron transportation,and structural stability.Herein,MoC is incorporated into MoSe2/C composite as an intermediate phase to alter the bridging between MoSe2-and nitrogen-doped three-dimensional(3D)carbon framework as MoSe2/MoC/N–C connection,which greatly improve the structural stability,electronic conductivity,and interfacial charge transfer.Moreover,the incorporation of MoC into the composites inhibits the overgrowth of MoSe2 nanosheets on the 3D carbon framework,producing much smaller MoSe2 nanodots.The obtained MoSe2 nanodots with fewer layers,rich edge sites,and heteroatom doping ensure the good kinetics to promote pseudo-capacitance contributions.Employing as anode material for lithium-ion batteries,it shows ultralong cycle life(with 90%capacity retention after 5000 cycles at 2 A g−1)and excellent rate capability.Moreover,the constructed LiFePO4//MoSe2/MoC/N–C full cell exhibits over 86%capacity retention at 2 A g−1 after 300 cycles.The results demonstrate the effectiveness of the interface engineering by incorporation of MoC as interface bridging intermediate to boost the lithium storage capability,which can be extended as a potential general strategy for the interface engineering of composite materials.

Bioinspired urchin-like murray carbon nanostructure with protection shell for advanced lithium-sulfur batteries

Commercial application of lithium-sulfur(Li-S) batteries is hindered by the insulating nature of sulfur and the dissolution of polysulfides. Here, a bioinspired 3D urchin-like N-doped Murray's carbon nanostructure(N-MCN) with interconnected micro-meso-macroporous structure and a polydopamine protection shell has been designed as an effective sulfur host for high-performance Li-S batteries. The advanced 3D hierarchically porous framework with the characteristics of the generalized Murray's law largely improves electrolyte diffusion, facilitates electrons/ions transfer and provides strong chemisorption for active species, leading to the synergistic structural and chemical confinement of polysulfides. As a result,the obtained P@S/N-MCN electrode with high areal sulfur loading demonstrates high capacity at high current densities after long cycles. This work reveals that following the generalized Murray's law is feasible to design high-performance sulfur cathode materials for potentially practical Li-S battery applications.

Silver-anchored porous aromatic framework for efficient conversion of propargylic alcohols with CO_(2) at ambient pressure

The conversion of propargylic alcohols and carbon dioxide(CO_(2)) into fine chemicals suffers from issues of harsh reaction conditions and difficult catalyst recovery. To achieve efficient CO_(2)activation at low energy consumption, a silver-anchored porous aromatic framework catalyst Ag@PAF-DAB with high active phase density and CO_(2)adsorption capacity was proposed. Since Ag@PAF-DAB has the dual functions of CO_(2)capture and conversion, propargylic alcohols were completely converted into α-alkylidene cyclic carbonate or α–hydroxy ketone as high value-added product under atmospheric pressure(CO_(2), 0.1 MPa) and low silver equivalent(0.5 mol%). Notably, Ag@PAF-DAB exhibited broad substrate diversity, high stability,and excellent reusability. By applying FTIR and GC, the key to green synthetic route of α–hydroxy ketone was confirmed to lie in the further hydration of α-alkylidene cyclic carbonate.

Frustrated Lewis pairs in situ formation in B-based porous aromatic frameworks for efficient o-phenylenediamine cyclization

Benzimidazoles are very important chemical materials in the pharmaceutical industry,and the most common synthetic route is cyclization of o-phenylenediamine with carbon sources,in which utilization of inexpensive and abundant CO_(2)as C1 source is very impressive.Porous aromatic frameworks(PAFs)with highly desired skeletons have attracted great attentions in gas capture and catalysis.Herein,B-based PAF-165 and PAF-166 are designed and synthesized via Friedel-Crafts alkylation reaction,which present high surface areas as well as high stability.Benefiting from the abundant electron-deficient B centers,both PAFs exhibit excellent selective CO_(2)adsorption abilities.The presence of sterically hindered B units in PAFs can act as Lewis acid active sites for the frustrated Lewis pairs(FLPs)in situ formation with ophenylenediamine,thus promoting the synthesis of benzimidazole.The optimal reaction conditions for o-phenylenediamine cyclization with PAF catalysts are explored,and the reaction mechanism is also proposed.This work provides feasible ideas for incorporating FLPs within porous materials as reusable heterogeneous catalysts for CO_(2)capture and conversion.

Two pseudo-polymorphic porous POM-pillared MOFs for sulfide-sulfoxide transformation: Efficient synergistic effects of POM precursors, metal sites and microstructures

Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous polyoxometalate-pillared metal-organic frameworks,formulated as H_(3n)[Cu_(3)(pidc)_(2)(H_(2)O)_(2.5)]_(2)[PW_(12)O_(40)]_n·x H_(2)O (n=1.5,x=6 for 1,n=1,x=12 for 2;and H_(3)pidc=2-(3-pyridinyl)-1H-imidazole-4,5-dicarboxylic acid),were consciously manufacture and employed for heterogeneously catalyzed sulfide-sulfoxide transformation.Structural analysis shows that 1 and 2 exhibit similar porous frameworks with nearly identical two-dimensional metal-organic layers further pillared by tetradentate POM ligands with different coordination modes,which also result in the porosity of 1 being almost twice that of 2.In catalyzing the conversion of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO),1 can convert nearly 100%of MPS into MPSO within 30 min,while 2 achieved the similar results requires 50 min.The higher activity of 1 may be attributed to its larger channel that can provide more active sites and more efficient mass transfer process.Systematic structure-activity analyses and mechanistic studies revealed dual-reaction pathways driven by POM sites and metal sites assisted by the structural microenvironment.

Application of hierarchically porous metal-organic frameworks in heterogeneous catalysis:A review

Hierarchically porous metal-organic frameworks(H-MOFs)with micro-,meso-and macropores have emerged as a popular class of crystalline porous materials that have attracted extensive interests,and they have been studied in diverse applications,especially in heterogeneous catalysis.The hierarchical structures enable sufficient diffusion and accessibility to the active sites of the molecules and permit the encapsulation of catalytic guest molecules to exploit more possibilities with enhanced catalytic performance.In this review,we have summarized the recent representative developments of H-MOFs in the field of heterogeneous catalysis,which includes oxidation reaction,hydrogenation reaction,and condensation reaction.Emphasis is placed on the multiple functions of hierarchical structures,and the catalytic activity,selectivity,stability,recyclability,etc.of the industrial utility of H-MOFs.Finally,the prospects and challenges of H-MOFs in heterogeneous catalysis and the remaining issues in this field are presented.

Integration of enzyme immobilization and biomimetic catalysis in hierarchically porous metal-organic frameworks for multi-enzymatic cascade reactions

Multiple enzymes-induced biological cascade catalysis is indispensable in biotechnology and industrial processes. Nevertheless,the drawbacks of most natural enzymes, including poor stability and recyclability and sensitivity to the environment, have hindered their broader application. Here, we report a facile strategy to prepare a biomimetic cascade reaction system by combining the advantages of enzyme immobilization and biomimetic catalysis in a one-pot reaction system based on the hierarchically porous metal-organic frameworks(HP-MOFs). The hierarchically porous zirconium-porphyrin-based MOF(HPPCN-222(Fe)) synthesized by modulator-induced strategy possessed tunable hierarchical porous and peroxidase-like activity,permitting them to act as not only an efficient immobilization matrix for glucose oxidase(GOx) but also peroxidase mimics to catalyze the cascade for glucose detection. A stable, anti-interference and reusable colorimetric biosensor for glucose detection was successfully established through GOx@HP-PCN-222(Fe) on the basis of the artificial tandem catalysis. Moreover, the GOx@HP-PCN-222(Fe)-fabricated electrode was available for glucose detection by electrochemical method. This work provides a potentially universal method to design functional multi-enzymatic cascade reaction systems by integrating the merits of enzyme encapsulation and biomimetic catalysis in HP-MOFs.

Synthetic subnanochannels in porous aromatic frameworks accelerate selective water permeation in membrane desalination

Creation of freeways in a membrane accelerates water transport for efficient desalination;however,the synthesis of target membrane materials is very challenging.In the present study,the molecular-design strategy is developed for the synthesis of porous aromatic framework(PAF)membranes with rigid and open networks to regulate water transport.Nitrile-based monomers in triangle shape are designed for the construction of PAF-98 and its sister frameworks,and these PAF membranes are formed through trifluoromethanesulfonic acid catalysis.The rigidity and geometry of the monomers endow PAFs with unique structures of connected pores with edging size(4.5–6.7Å)between water(2.8Å)and hydrated sodium molecules(7.2Å),enabling effective differentiation of water and salt.The fabricated membranes with high flexibility and continuity are ideal for water desalination,and reverse osmosis experiments demonstrate that the three PAF membranes are selective for permeation of water molecules over hydrated sodium cations.Unprecedented water flux of 547.1 L m^(-2) h^(-1) and high rejection degree of 90%are obtained on a representative membrane of PAF-98-E;and the desalination performance is superior to currently available membrane materials.Furthermore,PAF-98-E membrane is capable of rejecting various cations with high efficiency in real seawater,holding great promise in practical water desalination application.

Novel Porous Aromatic Framework with Excellent Separation Capability of CO2 in N2 or CH4

A novel porous aromatic framework, PAF-52, was obtained via the polymerization of tetrahedral mono- mer tetrakis（4-cyanodiphenyl） methane（TCDPM） with the aid of a facile ionothermal method. PAF-52 has a surface area of 1159 m2/g（BET）, and shows a considerable high separation ability of CO2 in N2 or CH4 respectively at room temperature, using gas-chromatography experiments as evidence,

Targeted synthesis of novel porous aromatic frameworks with selective separation of CO_2/CH_4and CO_2/N_2

Novel porous aromatic frameworks（PAF-53 and PAF-54） have been obtained by the polymerization of amino compound（p-phenylenediamine and melamine） and cyanuric chloride. They display a certain amount of CO2 adsorption capacity and highly selective separation of CO2/CH4 and CO2/N2 as 18.1 and83 by Henry Law respectively. They may be applied as ideal adsorbents to separate and capture CO2.

High energy and insensitive explosives based on energetic porous aromatic frameworks

The design and synthesis of energetic materials with a compatibility of high energy and insensitivity have always been the research fronts in military and civilian fields.Considering excellent performances of porous organic frameworks and the lack of research in the field of energetic materials,in this study,a new concept named energetic porous aromatic frameworks(EPAFs)is proposed.The strategy of coating high energy explosives such as 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20)and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)in the EPAFs by wet-infiltration method has successfully realized the assembly of target energetic composite materials.The results show that the 75 wt.%CL-20@EPAF-1 possesses the safer impact sensitivity of 31.4 J than that of CL-20(4.0 J).Notably,for 75 wt.%CL-20@EPAF-1,in addition to the superior detonation performances of the detonation velocity(8,761 m·s^(-1))and detonation pressure(31.27 GPa),the synergistic effect of the nitrogen-rich EPAFs and the nitramines high energy explosives results in a higher heat of detonation that surpasses the most of pristine high explosives and reported novel energetic materials.In prospect,energetic porous aromatic frameworks could be a promising and inspiring strategy to build high energy insensitive energetic materials.

Synthesis of porous aromatic framework with Friedel–Crafts alkylation reaction for CO_2 separation

A novel porous aromatic framework, PAF-8, derived from tetraphenylsilane as basic building unit, was successfully synthesized via Friedel-Crafts alkylation reaction. This PAF material had high thermal stability as well as high surface area （785 m^2 g^-1） calculated from the Brunauer-Emmett-Teller （BET） model. Meanwhile, PAF-8 possessed high performances in gas sorption and especially for CO2 separation.