A purely green approach to low-cost mass production of zeolitic imidazolate frameworks

Although zeolitic imidazolate frameworks(ZIFs)have bright prospects in wide fields like gas storage/separation,catalysis and medicine,etc.,their large-scale applications are bottlenecked by the absence of their low-cost commercial production technique.Here,we report an uncon ventional method suitable for environmentally friendly and low-cost mass-production of ZIFs.In this method,taking the synthesis of ZIF-8 as an example,ZnO was used instead of Zn(NO_(3))_(2) in traditional solvent synthesis methods and CO_(2) was introduced to dissolve ZnO in aqueous solution of 2-methylimidazole(HMeim)and form water soluble salt([ZnMeim]^(+)[MeimCOO]^(-))at room temperature.Then,by removing CO_(2) through heating or vacuuming,Meim-ions are produced and instantaneously assemble with[ZnMeim]^(+)s to generate ZIF-8 without any by product.Due to the absence of strong acid anions(such as NO^(-)_(3) and Cl^(-) et al.)in solution,the washing of filter cake required in the conventional approaches could be omitted and the filtrate containing only water and HMeim could be reused completely.This method is really green as no waste gas or liquid generates because CO_(2) and water could be recycled perfectly.It overcomes almost all bottlenecks occurred in commercial production of ZIF-8 when using traditional methods.A pilot plant was established for mass-production of ZIF-8 and hundreds kilograms of ZIF-8 was produced,which indicates that the new method is not only environmentally friendly but also low cost and commercial accessibility.It is expected that the new method would open an avenue for commercial applications of ZIFs.

Preparation of hybridizing zeolitic imidazolate frameworks with carboxymethylcellulose for adsorption separation of n-hexane/3-methylpentane

A novel ZIF-8-CMC hybrid material was fabricated from the hybridization of ZIF-8 and carboxymethylcellulose(CMC) by impregnation method for n-hexane/3-methylpentane separation.The surface properties of ZIF-8 were tailored by introducing CMC into ZIF-8 nanoparticles.In this work,adsorption separation of n-hexane(nHEX) and 3-methylpentane(3 MP) on ZIF-8-CMC were investigated by batch vapor-phase adsorption and liquid-phase breakthrough adsorption.The adsorption selectivity of nHEX/3 MP reversed from preferable adsorption of nHEX to preferable adsorption of 3 MP upon the increasing of CMC containing in the hybrid materials.As the temperature increases,the adsorption amounts of nHEX and 3 MP decrease.With the increasing of CMC contents,the nHEX uptake decreased,the uptake capacity of 3 MP increased gradually.For liquid-phase breakthrough adsorption,the dynamic adsorption capacity of nHEX also decreased with the increasing of temperature.

Rapid room-temperature synthesis of hierarchical porous zeolitic imidazolate frameworks with high space-time yield

Hierarchical porous zeolitic imidazolate frameworks （ZIFs） have potential for adsorption, catalysis and chemical sensing applications. Ultrafast synthesis of ZIFs at room temperature and pressure is particularly desirable for large-scale industrial production. Here, we developed a green and versatile method using organic amines as supramolecular templates （organic amine-template） to rapidly synthesize hierarchical porous ZIFs （ZIF-8, ZIF-61 and ZIF-90） at room temperature and pressure. The synthesis time was reduced dramatically to within 1 min, and the resulting ZIFs had multimodal hierarchical porous structures with mesopores/ macropores interconnected with micropores. Notably, the space-time yield （STY） of hierarchical porous ZIF-8 was up to 1.29×10^4 kg m^-3 d^-1, which is more than three times higher than that reported using other methods. Furthermore, the morphologies and porosities of the produced ZIFs could be readily tuned by controlling the synthesis time or type of organic amine. The organic amine played two roles in the synthesis： （1） a protonation agent to deprotonate organic ligands, facilitating the formation of ZIF crystals, and （2） an structure directing agent to direct mesopore/macropore formation. The resulting hierarchical porous ZIF-8 exhibited enhanced uptake capacities and diffusion rates for guest molecules relative to its microporous counterpart. This work provides a new direction for the green and efficient synthesis of various hierarchical porous ZIFs with high STYs for a wide range of applications.

From Zeolitic Imidazolate Framework-8 to Metal-Organic Frameworks (MOFs): Representative Substance for the General Study of Pioneering MOF Applications

Metal-organic frameworks(MOFs)have been intensely studied for the past few decades as an enormous family of highly tunable porous materials with promisingly applicable functionalities in adsorption,separation,catalysis,sensing,electrochemistry,and a great number of emerging purposes.As a classic MOF,zeolitic imidazolate framework-8(ZIF-8)is conventionally one of the very few MOF members that has been commercialized with considerable production.

Regulation of surface carbides on palladium nanocubes with zeolitic imidazolate frameworks for propyne selective hydrogenation

The selective hydrogenation of propyne to propylene has attracted great attention in chemical industry for removing trace amount of propyne for producing polymer-grade propylene. As the state-of-the-art catalyst, Pd suffers from the disadvantage of poor propylene selectivity due to the over-hydrogenation of propylene to propane. We here demonstrate that Pd nanocubes (NCs) coated by zeolitic imidazolate frameworks (i.e., Pd NCs@ZIF-8) can serve as highly active and selective catalysts for propyne selective hydrogenation (PSH). Benefitting from the unique properties and abundant groups of ZIF-8, Pd carbide (Pd-C) is formed on the surface of Pd NCs after thermal treatment, which acts the active sites for PSH to propylene. More importantly, the content of Pd-C can be precisely controlled by altering the calcination temperature without aggregation of Pd NCs and obvious changes in the framework of ZIF-8. The formation of Pd-C on Pd NCs@ZIF-8 can strongly suppress the H2 adsorption, and thus selectively catalyze propyne to propylene. Consequently, the optimized catalyst (i.e., Pd NCs@ZIF-8-100) exhibits a propylene selectivity of 96.4% at a propyne conversion of 93.3% at 35 °C and atmospheric pressure. This work may not only provide an efficient catalyst for PSH, but also shed a new light on the catalytic application of ZIFs.

High-throughput model-building and screening of zeolitic imidazolate frameworks for CO2 capture from flue gas

To find potential zeolitic imidazolate frameworks(ZIFs)for CO2 capture from flue gas,we built 169,898 ZIF models from 84,949 hypothetical zeolite networks.By calculating their lattice energies,accessible volumes to CO2,the isosteric adsorption heat(Qst)of H2 O,Henry’s constant ratio(SKH)of CO2/N2,percent regenerability(R%),CO2 working capacity(ΔNCO2),CO2/N2 adsorption selectivity(SCO2/N2))and adsorbent performance score(APS),we identi fied 49 hydrophobic ZIF structures that might outplay already-realised ZIFs built from the same imidazolate linkers for CO2 capture from flue gas.

Synergistic effects of zeolitic imidazolate frameworks(ZIFs)with different transition metals on intumescent flame-retarded polypropylene composites:A comparative study

The use of intumescent flame retardants(IFRs)is considered an environmentally friendly and cost-effective strategy to suppress potential fire hazards from synthetic polymers.However,some conventional IFRs are neither efficient in developing a thermally stable char layer nor reducing the release of toxic byproducts during polymer combustion.In this work,we aim to discuss the effects of zeolitic imidazolate frameworks(ZIFs)on synergistically improving the flame retardancy behaviors in polypropylene(PP)composites,including thermal degradation(evolved gas analysis),free radical reactions in the gaseous phase(in-situ chemiluminescent image analysis),and carbonaceous structure in the condensed phase(micro-morphology and composition analysis).It is found that the transition metals in ZIFs can catalytically accelerate the crosslinking reaction at a lower initial temperature and decrease the amount of hydrocarbon volatiles in the gaseous phase.Once ignited,the embedded ZIFs can firstly bridge adjacent phosphorus chains in the polymer matrix to expand crosslinking degrees and then they are anchored in the developed N-doped phospho-carbonaceous networks after pyrolysis.As a result,more compact char residue structures are observed in the condensed phase for ZIF-reinforced composites.For example,by replacing 2 wt%of IFR with ZIF-67,the peak heat release rate,peak smoke production rate,and peak CO production rate are reduced by 69%,80%,and 72%,respectively,when compared to the conventional composite.These results indicate an excellent solution to resolve inherent fire hazards associated with IFRs in polymers and achieve necessary efficiency for industrial applications.It also provides a new strategy for determining flammability characteristics and combustion mechanisms of polymer composites using in-situ chemiluminescence analysis.

Unveiling the tailorable electrochemical properties of zeolitic imidazolate framework-derived Ni-doped LiCoO_(2) for lithium-ion batteries in half/full cells

As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.

Mesoporous Zeolitic Imidazolate Frameworks

The zeolitic imidazolate frameworks(ZIFs)with threedimensional perio dic micropores encounter the barrier of mass transfer in the diffusion-limited processes.To solve this problem,fabricating the ZIFs combined intrinsic micropores with ordered mesopores(mZIFs)is highly desirable.Herein,mZIFs were synthesized for the first time,achieved by employing a polymer-micelle template strategy.

In-situ incorporation of halloysite nanotubes with 2D zeolitic imidazolate framework-L based membrane for dye/salt separation

Layered assembled membranes of 2D leaf-like zeolitic imidazolate frameworks(ZIF-L)nanosheets have received great attention in the field of water treatment due to the porous structure and excellent antibacterial ability,but the dense accumulation on the membrane surface and the low permeate flux greatly hinder their application.Herein,we synthesized m HNTs(modified halloysite nanotubes)/ZIF-L nanocomposites on modified m HNTs by in situ growth method.Interestingly,due to the different size of m HNTs and ZIF-L,m HNTs were packed in ZIF-L nanosheets.The hollow m HNTs provided additional transport channels for water molecules,and the accumulation of the ZIF-L nanosheets was decreased after assembling m HNTs/ZIF-L nanocomposites into membrane by filtration.The prepared m HNTs/ZIF-L membrane presented high permeate flux(59.6 L·m^(-2)·h^(-1)),which is 2-4 times of the ZIF-L membranes(14.8 L·m^(-2)·h^(-1)).Moreover,m HNTs/ZIF-L membranes are intrinsically antimicrobial,which exhibit extremely high bacterial resistance.We provide a controllable strategy to improve 2D ZIF-L assembles,and develops novel membranes using 2D package structure as building units.

KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage

To solve low efficiency,environmental pollution,and toxicity for synthesizing zeolitic imidazolate frameworks(ZIFs)in organic solvents,a KOH-assisted aqueous strategy is proposed to synthesize bimetallic ZIFs polyhedrons,which are used as precursors to prepare bimetallic selenide and N-doped carbon(NC)composites.Among them,Fe–Co–Se/NC retains the three-dimensional(3D)polyhedrons with mesoporous structure,and Fe–Co–Se nanoparticles are uniform in size and evenly distributed.When assessed as anode material for lithium-ion batteries,Fe–Co–Se/NC achieves an excellent initial specific capacity of 1165.9 m Ah·g^(-1)at 1.0 A·g^(-1),and the reversible capacity of Fe–Co–Se/NC anode is 1247.4 m Ah·g^(-1)after 550 cycles.It is attributed to that the uniform composite of bimetallic selenides and N-doped carbon can effectively tune redox active sites,the stable 3D structure of Fe–Co–Se/NCs guarantees the structural stability and wettability of the electrolyte,and the uniform distribution of Fe–Co–S nanoparticles in size esuppresses the volume expansion and accelerates the electrochemical reaction kinetics.

Hydrophobic CHA-ZIFs with a junctional trap between cha and d6r cages for adsorption of 2,3-butanediol in aqueous solution

The adsorption and separation of diols from dilute aqueous solution using hydrophobic materials is very challenging due to the strong diol-water hydrogen-bonding interactions. Herein, we screened hydrophobic zeolitic imidazolate frameworks(ZIFs) with chabazite(CHA) topology for separation of 2,3-butanediol(2,3-BDO) and 1,3-propanediol(1,3-PDO), which had junctional and hydrophobic traps matching the two end methyl groups of the 2,3-BDO molecule. Based on CHA-ZIFs with the same small-sized ligand 2-methylimidazole(mIm) and different large-sized ligand benzimidazole derivatives(RbIm),CHA-ZIFs with larger surface areas were obtained by the addition of excess small-sized ligand mIm in the synthesis process. We showed that all of the hydrophobic CHA-ZIFs preferentially adsorbed 2,3-BDO over 1,3-PDO by static batch adsorption and dynamic column adsorption experiments. But ZIF-301 and ZIF-300 with halogen groups exhibited better adsorptive separation performance for 2,3-BDO/1,3-PDO than ZIF-302 with methyl groups. For a typical ZIF-301, its adsorption capacity for 2,3-BDO was 116.4 mg·g^(-1)and selectivity for 2,3-BDO/1,3-PDO was 3.8 in dynamic column adsorption of the binary-component system(2,3-BDO/1,3-PDO: 50 g·L^(-1)/50 g·L^(-1)). Computational simulations revealed that 2,3-BDO preferentially adsorbed in a trap at the junction between the cha and d6r cages of CHA-ZIFs,meaning the strong host-guest interactions. Therefore, the hydrophobic CHA-ZIFs with a junctional trap were promising candidate materials for adsorbing 2,3-BDO, which also provided a new perspective for separating diols in dilute aqueous solutions.

A customized zeolitic imidazolate framework enabling bionic preconcentration of ultralow CO_(2)

Advancing our understanding of global climate,particularly in polar regions,requires accurate detection of carbon dioxide(CO_(2))in ice cores and deep sea environments.However,detecting trace levels of CO_(2)in these areas presents significant challenges.We introduce a novel preconcentration approach using functionalized zeolitic imidazolate framework,ZIF-8(CN),for the detection of ultra-low CO_(2).ZIF-8(CN)has small pores(4.4■and cyano groups(–CN),enabling highly selective adsorption of CO_(2)(36.2 cm^(3)g^(−1))over N_(2)(1.6 cm^(3)g^(−1))at 298 K.The mechanism involves unique–CN···CO_(2)···–CN interactions within the pore structure.When cast into a film on an aluminum substrate,ZIF-8(CN)demonstrates exceptional CO_(2)preconcentration capability(1 ppm in N_(2))with an extraordinary preconcentration factor of 748,outperforming traditional ZIF and zeolite materials.Additionally,a ZIF-8(CN)preconcentrator is designed and fabricated with bionic gas flow of fractal structure which optimizes the gas-film contact,and thus its performance is further improved by 115%.

Transition metal-nitrogen sites for electrochemical carbon dioxide reduction reaction

Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.

Coordination and interface engineering to boost catalytic property of two-dimensional ZIFs for wearable Zn-air batteries

Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. Herein, by incorporating the cobalt-oxide bonds and polyaniline(PANI) with two-dimension zeolitic imidazolate frameworks(ZIFs), a novel bifunctional catalyst(Co-O-ZIF/PANI) for Zn-air battery was designed based on a facile and eco-friendly method. This Co-O-ZIF/PANI with optimized surface adsorption effect and suitable Co^(3+)/Co^(2+)ratio, exhibits eminent electrocatalytic activity toward both oxygen reduction and evolution reaction. The as-assembled liquid ZABs based on Co-O-ZIF/PANI achieves a remarkable maximum power density of 123.1 m W cm^(-2) and low discharge-charge voltage gap of 0.81 V at 5 m A cm^(-2) for over 300 cycles. Operando Raman spectroscopy reveals that the excellent performance origins from the optimized surface chemisorption property of O_(2) and H_(2)O brought by Co–O bonds and PANI. This work provides a novel prospect to develop efficient MOF derived bifunctional electrocatalysts by optimizing surface chemisorption properties.

Two-step pyrolysis of ZIF-8 functionalized with ammonium ferric citrate for efficient oxygen reduction reaction

Zeolitic imidazolate frameworks（ZIFs） are widely employed in catalyst synthesis as parental materials for electrochemical energy storage and conversion. Herein, we have demonstrated a facile synthesis of highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic medium, which is derived from ZIF-8 functionalized with ammonium ferric citrate via two-step pyrolysis in Ar and NHatmosphere.The results reveal that the catalytic activity improvement after NH3 pyrolysis benefits from mesoporedominated morphology and high utilization of Fe-containing active sites. The optimum catalyst shows excellent performance in zinc-air battery and polymer electrolyte membrane fuel cell tests.

Ultra-small platinum nanoparticles segregated by nickle sites for efficient ORR and HER processes

In the electrochemical process,Pt nanoparticles(NPs)in Pt-based catalysts usually agglomerate due to Oswald ripening or lack of restraint,ultimately resulting in reduction of the active sites and catalytic efficiency.How to uniformly disperse and firmly fix Pt NPs on carbon matrix with suitable particle size for catalysis is still a big challenge.Herein,to prevent the agglomeration and shedding of Pt NPs,Ni species is introduced and are evenly dispersed in the surface of carbon matrix in the form of Ni-N-C active sites(Ni ZIF-NC).The Ni sites can be used to anchor Pt NPs,and then effectively limit the further growth and agglomeration of Pt NPs during the reaction process.Compared with commercial Pt/C catalyst,Pt@Ni ZIF-NC,with ultralow Pt loading(7 wt%)and ideal particle size(2.3 nm),not only increases the active center,but also promotes the catalysis kinetics,greatly improving the ORR and HER catalytic activity.Under acidic conditions,its half-wave potential(0.902 V)is superior to commercial Pt/C(0.861 V),and the mass activity(0.38 A per mg Pt)at 0.9 V is 4.7 times that of Pt/C(0.08 A per mg Pt).Besides,it also shows outstanding HER performance.At 20 and 30 mV,its mass activity is even 2 and 6 times that of Pt/C,respectively.Whether it is under ORR or HER conditions,it still shows excellent durability.These undoubtedly indicate the realization of dual-functional catalysts with low-Pt and high-efficiency properties.

Mean Residence Time of CO2 Molecules in Flexible ZIF-8 Cages Explored by Molecular Dynamics Simulations

The adsorption sites and diffusion mechanism of CO2 molecules in the flexible Zn（MeIM）2 （MeIM=2-methylimidazole） （ZIF-8） have been investigated by grand canonical Monte Carlo and molecular dynamics simulations. A reasonable time correlation function is for the first time constructed to explore the mean residence time of CO2 molecules in the ZIF-8 cages, suggesting that C02 molecules can remain in the same cage for up to several tens of picoseconds. Furthermore, we find that the mean residence time almost linearly increases with the increasing pressure （or loading） at 273 and 298 K.

Co NP/NC hollow nanoparticles derived from yolk-shell structured ZIFs@polydopamine as bifunctional electrocatalysts for water oxidation and oxygen reduction reactions

The pyrolysis under inert atmosphere has been widely used for the synthesis of metal containing heteroatoms doped carbon materials, versatile catalysts for various reactions. However, it is difficult to prevent metal nanoparticles aggregation during pyrolysis process. Herein, we reported the efficient synthesis of nitrogen doped carbon hollow nanospheres with cobalt nanoparticles （Co NP, ca. 10nm in size） distributed uniformly in the shell via pyrolysis of yolk-shell structured Zn-Co-ZIFs@polydopamine （PDA）. PDA acted as both protection layer and carbon source, which successfully prevented the aggregation of cobalt nanoparticles during high-temperature pyrolysis process. The Co NP and N containing carbon （Co NP/NC） hollow nanospheres were active for both oxygen evolution reaction （OER） and oxygen reduction reaction （ORR）, affording overpotential of 430 mV at 10 mA/cm2 for OER in 1 M KOH and comparable half-wave potential to that of Pt/C （0.80V vs RHE） for ORR in 0.1 M KOH. The superior performance of carbon hollow nanospheres for both OER and ORR was mainly attributed to its small metal nanoparticles, N-doping and hollow nanostructure. The protection and confinement effect that originated from PDA coating strategy could be extended to the synthesis of other hollow structured carbon materials, especially the ones with small metal nanoparticles.

Effects of zeolite imidazole frameworks on rice seedlings (Oryza sativa L.): Phytotoxicity, transformation, and bioaccumulation

Zeolite imidazole frameworks(ZIFs),a class of the metal organic framework,have been extensively studied in environmental applications.However,their environmental fate and potential ecological impact on plants remain unknown.Here,we investigated the phytotoxicity,transformation,and bioaccumulation processes of two typical ZIFs(ZIF-8 and ZIF-67)in rice(Oryza sativa L.)under hydroponic conditions.ZIF-8 and ZIF-67 in the concentration of 50 mg/L decreased root and shoot dry weight maximally by 55.2%and 27.5%,53.5%and 37.5%,respectively.The scanning electron microscopy(SEM)imaging combined with X-ray diffraction(XRD)patterns revealed that ZIFs on the root surface gradually collapsed and transformed into nanosheets with increasing cultivation time.The fluorescein isothiocyanate(FITC)labeled ZIFs were applied to trace the uptake and translocation of ZIFs in rice.The results demonstrated that the transformed ZIFs were mainly distributed in the intercellular spaces of rice root,while they cannot be transported to culms and leaves.Even so,the Co and Zn contents of rice roots and shoots in the ZIFs treated groups were increased by 1145%and 1259%,145%and 259%,respectively,compared with the control groups.These findings suggested that the phytotoxicity of ZIFs are primarily attributed to the transformed ZIFs and to a less extent,the metal ions and their ligands,and they were internalized by rice root and increased the Co and Zn contents of shoots.This study reported the transformation of ZIFs and their biological effectiveness in rice,highlighting the potential environmental hazards and risks of ZIFs to crop plants.