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-co...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.展开更多
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 t...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.展开更多
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,catalysi...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.展开更多
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 polyhedr...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.展开更多
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 tail...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.展开更多
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 abilit...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.展开更多
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 u...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.展开更多
The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient s...The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.展开更多
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 ...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.展开更多
Hybrid metal-organic framework(MOF)derivatives play a significant role in the novel catalyst development in energy conversion reactions.Here,we demonstrated the low-temperature fully fluorinated zeolitic imidazole fra...Hybrid metal-organic framework(MOF)derivatives play a significant role in the novel catalyst development in energy conversion reactions.Here,we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework(ZIF)coupled with a three-dimensional open framework Prussian blue analog(PBA)with combined advantages for electrocatalytic oxygen evolution reaction(OER)in water splitting reaction.The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism.Because of good conductivity improvement by Ndoped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives,good catalytic performance was obtained on the optimal catalyst of Co Ni ZIF/Co Fe-PBAF-300,which required a low overpotential of 250 m V to reach 10 m A/cm^(2)loaded on the glassy carbon electrode,with Tafel slope of 47.4 m V/dec,and very high dynamic and steady stability.In addition,the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis.The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives,which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.展开更多
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 ...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%.展开更多
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,robus...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.展开更多
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 des...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.展开更多
Developing high efficient bifunctional oxygen electrocatalysts for clean energy applications like Zin-air battery(ZAB)is highly desired,because it would reduce the cost and speed up the practical application of ZAB.He...Developing high efficient bifunctional oxygen electrocatalysts for clean energy applications like Zin-air battery(ZAB)is highly desired,because it would reduce the cost and speed up the practical application of ZAB.Here we use a dual metal-organic framework(MOF)synthesis strategy to prepare the N-doped carbon supported bimetallic FeCo nanoparticle catalysts(marked as FeCo@NC)by pyrolysis of Zn CoZIF/MIL-101(Fe)composite.The FeCo@NC exhibits remarkable electrocatalytic activity for ORR with half-wave potential of 0.89 V vs.the reversible hydrogen electrode(RHE)and robust durability for both ORR and OER(oxygen reduction reaction and oxygen evolution reaction),which is attributed to the generation of Fe_(0.26)Co_(0.74) crystalline phase and mesopores due to the dual-MOF synthesis strategy.The rechargeable ZAB based on FeCo@NC air electrode shows a maximum energy density of139.6 mW·cm^(-2) and excellent cyclic stability over 130 h,significantly surpassing the Pt and Ir-based ZAB.The present work provides a useful dual-MOF synthesis strategy for preparing high-performance multifunctional catalysts for ORR,OER and hydrogen evolution reaction(HER).展开更多
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 effi...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.展开更多
Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. H...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.展开更多
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....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.展开更多
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. ...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.展开更多
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 s...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.展开更多
Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity i...Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries.展开更多
基金supports received from the National Natural Science Foundation of China (21776301,21636009)are gratefully acknowledged.
文摘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.
基金the financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2023b0145)Guangdong Provincial International Joint Research Center for Energy Storage Materials(2023A0505090009)。
文摘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.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.51603052 and 51573216)the Fundamental Research Funds for the Central Universities(Grant Nos.18lgpy02 and 16lgjc66).
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.52102100)the Natural Science Foundation of Jiangsu Province(No.BK20181469)the Guangdong Basic and Applied Basic Research Foundation,China(No.2020A1515110035)。
文摘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.
基金supported by the National Natural Science Foundation of China (Nos. 11775037 and 21676030)the Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology (BM212110)The Postgraduate Innovation Project of Changzhou University (KYCX19_1782)。
文摘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.
基金supported by the Excellent Youth Foundation of Henan Scientific Committee,China(222300420018)Key Scientific Research Projects in Universities of Henan Province,China(21zx006)。
文摘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.
基金This work was supported by the National Natural Science Foundation of China(Nos.30800705 and 31101599)the Provincial Natural Science Foundation of Zhejiang(Nos.LY15C150004 and LY18C150007)the Key Research and Devel opment Projects of Social Development of Jinhua Science and Technology Program(No.2021C22750).
文摘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.
基金supported by the Beijing Natural Science Foundation (2222004)。
文摘The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.
文摘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.
基金the finical support of the National Natural Science Foundation of China(Nos.21972124,22272148)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institution。
文摘Hybrid metal-organic framework(MOF)derivatives play a significant role in the novel catalyst development in energy conversion reactions.Here,we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework(ZIF)coupled with a three-dimensional open framework Prussian blue analog(PBA)with combined advantages for electrocatalytic oxygen evolution reaction(OER)in water splitting reaction.The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism.Because of good conductivity improvement by Ndoped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives,good catalytic performance was obtained on the optimal catalyst of Co Ni ZIF/Co Fe-PBAF-300,which required a low overpotential of 250 m V to reach 10 m A/cm^(2)loaded on the glassy carbon electrode,with Tafel slope of 47.4 m V/dec,and very high dynamic and steady stability.In addition,the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis.The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives,which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.
基金supported by the National Natural Science Foundation of China(22375031,22131004,U21A20330,U22A20184 and 22208224)National Key R&D Program of China(2022YFB3805902 and 2023YFC2812603)+4 种基金“111”Program(B18012)Jilin Natural Science Fund for Excellent Young Scholars(20230508116RC)Science&Technology Department of Jilin Province(20230101023JC)Fundamental Research Funds for the Central Universities(JGPY202103 and 2412023YQ001)Excellent Youth Lift Plan from Shenyang University of Chemical Technology(2022YQ003)。
文摘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%.
基金supported by the National Key R&D Program of China(2017YFA0700102)the National Natural Science Foundation of China(21573222 and 91545202)+1 种基金the Outstanding Youth Talent Project of Dalian(2017RJ03)the DMTO Project of Dalian Institute of Chemical Physics,CAS(DICP DMTO201702),the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020200),the Youth Innovation Promotion Association,CAS(2015145)~~
文摘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.
基金supported by the National Natural Science Foundation of China (21576094)SRFDP (20130172110012)the Fundamental Research Funds for the Central Universities (2015ZM046)
文摘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.
基金supported by the National Key Research and Development Program of China(2019YFA0210300)the National Natural Science Foundation of China(21905016)。
文摘Developing high efficient bifunctional oxygen electrocatalysts for clean energy applications like Zin-air battery(ZAB)is highly desired,because it would reduce the cost and speed up the practical application of ZAB.Here we use a dual metal-organic framework(MOF)synthesis strategy to prepare the N-doped carbon supported bimetallic FeCo nanoparticle catalysts(marked as FeCo@NC)by pyrolysis of Zn CoZIF/MIL-101(Fe)composite.The FeCo@NC exhibits remarkable electrocatalytic activity for ORR with half-wave potential of 0.89 V vs.the reversible hydrogen electrode(RHE)and robust durability for both ORR and OER(oxygen reduction reaction and oxygen evolution reaction),which is attributed to the generation of Fe_(0.26)Co_(0.74) crystalline phase and mesopores due to the dual-MOF synthesis strategy.The rechargeable ZAB based on FeCo@NC air electrode shows a maximum energy density of139.6 mW·cm^(-2) and excellent cyclic stability over 130 h,significantly surpassing the Pt and Ir-based ZAB.The present work provides a useful dual-MOF synthesis strategy for preparing high-performance multifunctional catalysts for ORR,OER and hydrogen evolution reaction(HER).
基金supported by the National Natural Science Foundation of China(Grants 21573222,21622607,91545202 and U1532117)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB17020200)+1 种基金CAS Youth Innovation PromotionK.C.Wong Education Foundation in Ningbo University
文摘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.
基金financially supported by the National Natural Science Foundation of China (51772135 and 51872124)the Ministry of Education of China (6141A02022516)+6 种基金the Natural Science Foundation of Guangdong Province (2014A030306010)the Natural Science Foundation of Guangdong Province (2021A1515010504)the Natural Science Key Foundation of Guangdong Province (2019B1515120056)the Natural Science Foundation of Guangzhou (201904010049)the Jinan University (88016105)the Innovation Team Project of Foshan City (FS0AA-KJ919-4402-0086)the Fundamental Research Foundation for the Central Universities(21617326 and 11619103)。
文摘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.
基金supported by the National Natural Science Foundation of China(22075223,51701146)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2021-ZD-4)。
文摘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.
文摘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.
基金This work was supported by the National Natural Science Foundation of China (Nos. 21703146 and 51802206)Natural Science Foundation of Jiangsu Province (No. BK20180846)+1 种基金We also acknowledge the financial support from the 111 Project, Joint International Research Laboratory of Carbon-Based Functional Materials and Devices, Collaborative Innovation Center of Suzhou Nano Science and Technology (NANO-CIC)the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD),SWC for Synchrotron Radiation. Yong Xu acknowledges the financial support from Guangdong University of Technology.
文摘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.
基金supported by the National Natural Science Foundation of China(22171266)the FJIRSM&IUE Joint Research Fund(RHZX-2019-002)+2 种基金the STS Project(KFJ-STS-QYZD-2021-09002)the National Key Basic Research Program of China(2017YFA0403402)the Project of the National Natural Science Foundation of China(U1932119)。
文摘Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries.