Water-based synthesis of nanoscale hierarchical metal-organic frameworks:Boosting adsorption and catalytic performance

The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.

Recent advancements in metal-organic frameworks for green applications

A series of environmental and energy issues,such as global warming,water pollution,acid rain,and energy shortage,have to be settled urgently.Metal-organic frameworks(MOFs)are compounds consisting of metal ions or clusters coordinated to organic ligands,which show great promise for alleviating or mitigating these challenges owing to their outstanding physical and chemical properties.In this review,we summarize the recent advances of MOFs in the fields of green applications,including carbon capture,harmful gas removal,sewage treatment,and green energy storage.In addition,the challenges and prospects of the large-scale commercialized use of MOFs in handling environmental issues are also discussed.

Recent advances in the synthesis of nanoscale hierarchically porous metal–organic frameworks

Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.

Highly selective separation of propylene/propane mixture on cost-effectively four-carbon linkers based metal-organic frameworks

The separation of propylene and propane is an important but challenging process,primarily achieved through energy-intensive distillation technology in the petrochemical industry.Here,we reported two natural C4linkers based metal–organic frameworks(MIP-202 and MIP-203)for C_(3)H_(6)/C_(3)H_(8)separation.Adsorption isotherms and selectivity calculations were performed to study the adsorption performance for C_(3)H_(6)/C_(3)H_(8)separation.Results show that C_(3)H_(6)/C_(3)H_(8)uptake ratios(298 K,100 kPa)for MIP-202 and MIP-203 are 2.34 and 7.4,respectively.C_(3)H_(6)/C_(3)H_(8)uptake ratio(303 K,100 k Pa)for MIP-203 is up to50.0.The mechanism for enhanced separation performance of C_(3)H_(6)/C_(3)H_(8)on MIP-203 at higher temperature(303 K)was revealed by the in situ PXRD characterization.The adsorption selectivities of C_(3)H_(6)/C_(3)H_(8)on MIP-202 and MIP-203(298 K,100 k Pa)are 8.8 and 551.4,respectively.The mechanism for the preferential adsorption of C_(3)H_(6)over C_(3)H_(8)in MIP-202 and MIP-203 was revealed by the Monte Carlo simulation.The cost of organic ligands for MIP-202 and MIP-203 was lower than that of organic ligands for those top-performance MOFs.Our work sets a new benchmark for C_(3)H_(6)sorbents with high adsorption selectivities.

Synthesis of hierarchical porous carbon with high surface area by chemical activation of(NH_(4))_(2)C_(2)O_(4) modified hydrochar for chlorobenzene adsorption

In this work,hydrothermal technique combined with KOH activation were employed to develop a series of porous carbons (NPCK-x) using tobacco stem as a low-cost carbon source and (NH_(4))_(2)C_(2)O_(4)as a novel nitrogen-doping agent.Physicochemical properties of NPCK-x were characterized by Brunauer-Emmett-Teller,field emission scanning electron microscopy,X-ray diffraction,Raman microscope,elemental analysis,and X-ray photoelectron spectroscopy.Results showed that the NPCK-x samples possessed large surface areas (maximum:2875 m^(2)/g),hierarchical porous structures,and high degree of disorder.N-containing functional groups decomposed during activation process,which could be the dominant reason for appearance of abundant mesopores and well-developed pore structure.Dynamic chlorobenzene adsorption experiments demonstrated that carbon materials with(NH_(4))_(2)C_(2)O_(4)modification exhibited higher adsorption capacity (maximum:1053 mg/g) than those without modification (maximum:723 mg/g).The reusability studies of chlorobenzene indicated that the desorption efficiency of (NH_(4))_(2)C_(2)O_(4)modified porous carbon reached90.40%after thermal desorption at 100℃ under N2atmosphere.Thomas model fitting results exhibited that the existence of mesopores accelerated the diffusion rate of chlorobenzene in porous carbon.Moreover,Grand Canonical Monte Carlo simulation was conducted to verify that micropores with pore sizes of 1.2–2 nm of the optimized porous carbon were the best adsorption sites for chlorobenzene and mesopores with pore sizes of 2–5 nm were also highly active sites for chlorobenzene adsorption.

Water-based routes for synthesis of metal-organic frameworks:A review

Although metal-organic frameworks(MOFs)show numerous advantages over other crystalline materials,their industrial relevances have been impeded owing to their many drawbacks such as environmental impacts and economic costs of their synthesis.A green preparation pathway could greatly reduce the environmental costs,energy,and the need for toxic organic solvents,and consequently reduce the production cost.Thus,the most desirable synthesis route is the replacement of harsh organic solvents with aqueous solutions to abate environmental and economic impacts.This review summarizes recent research advancements of water-based routes for MOF synthesis and gives a brief outline of the most prominent examples.The challenges and prospects of the commercialization of promising MOFs in the future are also presented.This study aims to offer necessary information regarding the green,sustainable,and industrially acceptable fabrication of MOFs for their commercial applications in the future.

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.

Recent advances in the synthesis of monolithic metal–organic frameworks

Although considerable achievements have been realized in recent years with respect to the syntheses of metal–organic frameworks(MOFs),majority of the developed MOFs are in the form of polydisperse microcrystalline powders,which cause dustiness,abrasion,and clogging and decrease pressure when used in industrial applications.Monolithic MOFs overcome these drawbacks and exhibit various promising characteristics.In this review,we present the recent advances associated with monolithic MOFs based on metal centers and a brief outline of the most prominent examples.Furthermore,the challenges and prospects associated with monolithic MOFs in terms of large-scale production and engineering applicability are analyzed based on our knowledge to conclude this review.

Effect of textural property of coconut shell-based activated carbon on desorption activation energy of benzothiophene

In this work,the effect of the textural property of activated carbons on desorption activation energy and adsorption capacity for benzothiophene(BT)was investigated.BET surface areas and the textural parameters of three kinds of the activated carbons,namely SY-6,SY-13 and SY-19,were measured with an ASAP 2010 instrument.The desorption activation energies of BT on the activated carbons were determined by temperature-programmed desorption(TPD).Static adsorption experiments were carried out to determine the isotherms of BT on the activated carbons.The influence of the textural property of the activated carbons on desorption activation energy and the adsorption capacity for BT was discussed.Results showed that the BET surface areas of the activated carbons,SY-6,SY-13 and SY-19 were 1106,1070 and 689 m2·g^(-1),respectively,and their average pore diameters were 1.96,2.58 and 2.16 nm,respectively.The TPD results indicated that the desorption activation energy of BT on the activated carbons,SY-6,SY-19 and SY-13 were 58.84,53.02 and 42.57 KJ/mol,respectively.The isotherms showed that the amount of BT adsorbed on the activated carbons followed the order of SY-6>SY-19>SY-13.The smaller the average pore diameter of the activated carbon,the stronger its adsorption for BT and the higher the activation energy required for BT desorption on its surface.The Freundlich adsorption isotherm model can be properly used to formulate the adsorption behavior of BT on the activated carbons.