A new strategy was developed to introduce active site K+ into the pores of MOF precursors, and various N-doped hierarchical porous carbons were prepared in a one-step synthetic route. The effect of K+in situ activation on the textural properties of the derived porous carbons was studied systematically, and the CO2 capture properties and electrochemical performance of these porous carbons were enhanced for their application in supercapacitors. The KBM-700 sample derived from K@bio-MOF-1 (potassium-ion-exchanged bio-MOF-1), which had high nitrogen content (10.16%) and micropore volume (73%), exhibited good CO2 uptakes (4.75 mmol g−1), and high adsorption selectivity for CO2/N2 at 298 K and 1 bar (Sads = 99.1) as well as high specific capacitance (230 F g−1) and excellent electrochemical cycling stability (97% retention after cycling 10 000 times).

A stable MOF membrane with guest molecules encapsulated in the pores by in situ synthesis has been successfully fabricated. The in situ confinement of linkers in the channels of the MOF membrane improves its gas separation properties, which may provide a general method for fine-tuning the pore size of MOF membranes and develop the functional applications of porous MOF materials.

Coordination complexes are ideal sacrificial templates for fabricating their respective derivatives by changing the thermal conditions. In this study, nitrogen-doped hierarchical porous carbons anchored with nickel nanoparticles (Ni NPs) were prepared by using rod-like nickel dimethylglyoximate [Ni(dmg)2] as a sacrificial template under nitrogen flow at different temperatures. The structure, morphology and properties of the products were characterised by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), N2 adsorption–desorption measurements and ultraviolet-visible (UV-vis) spectrophotometry. The optimised Ni@NC-700 sample exhibited an excellent ability to reduce 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 in an aqueous solution, which shortened the reduction time to 3.0 min with a conversion of nearly 100%. In addition, Ni@NC-700 possessed magnetic properties, which provided efficient separation by an external magnetic field. The present report may provide a potential and favourable method for preparing magnetically reusable Ni NP anchored N-doped porous carbon catalysts derived from a simple coordination complex.

•A rarely used mixed donor ligand is as linker with outstanding coordinated ability which leads to unforeseen structural patterns.•The using rigid linker can be regarded as a partially flexible ligand for the rotation of the different units.•The properties of the two MOFs indicate that they may be good candidates for multifunctional materials.The self-assembly of a prominent ligand, 5-(4-(1H-tetrazolyl)phen)isophthalic acid (H3TZPI), with Zn2 +/Cu2 + centres generates two new MOFs, [Zn2(TZPI)(μ3-OH)(H2O)2]·2H2O (JUC-161) and [Cu(HTZPI)(μ2-H2O)0.5(H2O)1.5]·5(H2O) (JUC-162). JUC-161 exhibits fascinating three-dimensional structures containing rectangular channels with dimensions of 6.5 × 3.0 Å2, and JUC-162 displays 3D supramolecular structures with 12.5 × 14.6 Å2 hexagonal channels. The observed structural diversity in these frameworks is due to the two distinct coordinating moieties of the H3TZPI ligand. The photoluminescence of JUC-161 and the magnetic properties of JUC-162 are also measured at room temperature. Photoluminescence investigations reveal that JUC-161 displays a strong main emission spectrum peak at 388 nm. JUC-162 is found to exhibit an antiferromagnetic interaction between Cu2 + ions.The self-assembly of one prominent ligand, 5-(4-(1H-tetrazolyl)phen)isophthalic acid (H3TZPI), with Zn2 +/Cu2 + centres generates two new MOFs named JUC-161 and JUC-162 (JUC = Jilin University, China). Due to the rotation of different motifs in the ligand and its varied coordination modes, JUC-161 and JUC-162 exhibit fascinating 3D frameworks containing distinct channels. The fluorescence property of JUC-161 and the magnetic property of JUC-162 indicate that these MOFs may be good candidates for multifunctional materials.

The self-assembly of a prominent mixed-donor ligand, 5-[4-(1H-tetrazolyl)phen]isophthalic acid(H3TZPI), with a Cd2+ center generates two new metal-organic frameworks: [Cd(H2TZPI)2(H2O)2]n(JUC-163) and [Cd2(TZPI)(μ3-OH)(H2O)2]·H2O·DMF(JUC-164). The two complexes demonstrate different structures for the ligand’s different coordination modes and configurations. JUC-163 shows a 2D layer structure and further forms into a 3D supramolecular framework by noncovalent interactions(C―H···O, O―H···N and π···π interactions), whereas JUC-164 exhibits a fascinating 3D framework for the outstanding coordination modes and configurations of the ligand, which are fit for the complex structure. And also, the factor of different cadmium salts(chloride and nitrate) which are used in synthesis progress is worth to notice for the construction of the two distinct structures. The luminescent properties of these metal-organic frameworks are also investigated.

Mixed transition metal oxides have attracted much attention recently due to their potential application in energy and environmental sciences. The emergence of multivariate MOFs recently has attracted great research attention and provides an opportunity for multivariate mixed-metal oxides. In this work, five isostructural, single-phase MOF-74 structures with different divalent metals (MOF-74–Co, MOF-74–Ni, MOF-74–NiCo1, MOF-74–NiCo2 and MOF-74–NiCo4) were synthesised by varying the mole ratios of Ni/Co mixed-metal ions. After annealing at the appropriate temperature, Co3O4, NiO and three kinds of NixCo3−xO4 mixed-metal oxide nanoparticles with high surface area were easily obtained and the metal ratio was readily controlled, enabling us to systematically investigate the effect of different metal species amounts on the electrochemical properties of the mixed-metal oxide materials. When these metal oxides were used as electrode materials for supercapacitors, we found that the mixed-metal oxides NixCo3−xO4 obtained from bimetallic MOF-74–NiCo structures had obvious advantages compared with the monometallic oxides of MOF-74–Ni and MOF-74–Co. In particular, the NixCo3−xO4-1 with the Ni/Co metal ratio 1:1 exhibited the highest capacitance of 797 F g−1 and excellent cycling stability.

•A composite material by incorporating MWCNTs into MOF nanoparticles (JUC-32) were synthesized successfully in situ.•The presence of carboxyl decorated on the MWCNTs promoted the nuclearity and growth of JUC-32 nanocrystals on their surfaces.•The adsorption enthalpies of CO2 and CH4 for hybrid materials had significantly increased compared with the original JUC-32.Two hybrid materials composed of metal-organic framework (JUC-32) nanoparticles and carboxyl-modified multi-wall carbon nanotubes (MWCNTs) were synthesised successfully in situ and characterized by TEM, PXRD, and TGA. The gas adsorption properties of these two hybrid materials were compared with the original JUC-32 material and a physical mixture of JUC-32 and MWCNTs. The results indicated that the composite materials absorbed larger amounts of CO2 and CH4 per specific surface area than the original materials, and that the adsorption enthalpies of CO2 and CH4 had significantly increased.Two hybrid materials composed of metal-organic framework (named JUC-32, JUC = Jilin University, China) nanoparticles and carboxyl-modified multi-wall carbon nanotubes (MWCNTs) were synthesised successfully in situ. And the CO2 adsorption enthalpy of MWCNTs/JUC32-2 was enhanced to 33.8 kJ·mol− 1, compared to 23.4 kJ·mol− 1 for the original JUC-32.

Two tailor-made microporous metal–organic framework (MOF) membranes were successfully fabricated on nickel screens by secondary growth. The effect of pore structures on gas separation was examined by means of single and binary gas permeation tests. The MOF JUC-150 membrane with its ultra-micropores showed marked preferential permeance to H2 relative to other gas molecules. The selectivity factors of this membrane were 26.3, 17.1 and 38.7 for H2/CH4, H2/N2 and H2/CO2, respectively, at room temperature. To the best of our knowledge, these values represent unprecedentedly high separation selectivity among those for all MOF membranes reported to date. The JUC-150 membrane also shows high thermal stability and outstanding separation performance at a high temperature of 200 °C. The separation performance of these membranes persists even after more than 1 year exposure to air. The superiority of the tailored pore size, high selectivity for H2 over other gases, significant stability and recyclability make these materials potential candidates for industrial H2 recycling applications.

•ZIF-78 membrane was synthesized on porous silica support by secondary growth method.•Amorphous precursors were used as seeds for the growth of ZIF-78 membrane.•MOF membrane was applied for the first time in cyclohexanone/cyclohexanol separation.Cyclohexanone and cyclohexanol are products of selective oxidation of cyclohexane. They are important industrial intermediates and difficult to be separated due to their close boiling points. In this work, well-intergrown ZIF-78 membrane was successfully synthesized on the porous silica substrate by secondary growth method and applied for separation of cyclohexanone/cyclohexanol mixture for the first time. Meanwhile, a facile method for seeding procedure was developed by utilizing the amorphous ZIF-78 precursors to provide better-distributed nucleation sites. Both XRD and SEM results confirmed the good quality of the membrane. The pervaporation separation of cyclohexanone/cyclohexanol mixture were carried out at room temperature with permselectivity of 1:2 and total flux around 8.7 × 10−2 kg m−2 h−1.Amorphous precursors based ZIF-78 membrane was synthesized on porous SiO2 support and was explored for the separation of cyclohexanone/cyclohexanol mixture for the first time.

A homochiral MOF membrane was successfully and facilely synthesized using an in situ growth method, which had the advantages of cheap raw materials, simple operation and high thermal stability. A diol isomer mixture was used to test the separation efficiency of the membrane at different temperatures and pressures.

Two 3D multifunctional lanthanide metal-organic frameworks(MOFs), Pr(HTCPS)(H2O)·2DMF·C2H5OH·5H2O(JUC-93) and Pr3(TCPS)2(NO3)(H2O)4(DMA)2·2DMA·C2H5OH·3H2O(JUC-94)[H4TCPS=tetrakis(4-carboxyphenyl)silane, DMF=N,N′-dimethylformamide, DMA=N,N′-dimethylacetamide and JUC=Jilin University China] were synthesized by the self-assembly of a rigid silicon-centered tetrahedral carboxylate ligand H4TCPS and Pr(III) ions in different solvothermal reactions. X-Ray crystallography revealed that they exhibited a rare CaF2 topology framework, constructed from the 4-connected tetrahedral TCPS unit with the 8-connected dinuclear praseodymium cluster unit and trinuclear praseodymium cluster unit, respectively. In addition, the luminescent and magnetic properties of the two compounds were investigated.

Three new metal–organic frameworks (MOFs), [Zn2(TZI)(μ3-OH)(H2O)2]·(CH3)2NH (JUC-165), [Cd5(TZI)3(μ3-OH)(H2O)7]·4H2O (JUC-166), and [Cd(TZI)]·(CH3)2NH2·H2O (JUC-167) (JUC = Jilin University China) have been synthesized by self-assembly of Zn2+/Cd2+ ions and a prominent ligand, 5-tetrazolylisophthalic acid (H3TZI). JUC-165 exhibits fascinating three-dimensional (3D) structure containing 1D rectangular channels with dimensions of 6.5 × 3.0 Å2 and it performs (5,5)-connected topology with a Schläfli symbol of 4664, JUC-166 displays a 2D sandwich-layer which further forms into a 3D supermolecular structure by H-bonds reactions and JUC-167 exhibits (4,4)-connected 3D frameworks with a Schläfli symbol of 42638. Furthermore, we research the fluorescence properties of these new MOFs measured at room temperature, and the results reveal that JUC-165, JUC-166 and JUC-167 display strong main emission spectra peaks at 410, 437 and 415 nm, respectively.Three new MOFs comprising one mixed-donor ligand (5-tetrazolylisophthalic acid, H3TZI) are synthesized and structurally characterized. JUC-165 features 3D frameworks including 1D rectangular channels and it performs (5,5)-connected frameworks with a Schläfli symbol of 4664, JUC-166 shows a 2D rarely sandwich-like tri-layer, and JUC-167 exhibits (4,4)-connected 3D frameworks with a Schläfli symbol of 42638. The fluorescence properties of these three new MOFs were measured at room temperature.

Various N-doped hierarchical porous carbons were prepared by using a new mixed-ligand ZIF (zeolitic imidazolate framework) (JUC-160) as the precursor in a one-step synthetic route without any additional carbon sources or purification steps. The effect of the ZIF precursor crystal size on the textural properties of the derived porous carbons was systematically studied. Microporosity was dominant in micron-sized JUC-160 crystal derived porous carbons, while more mesopore volume was present in porous carbons obtained from nanometre-sized JUC-160 crystals. The mJUC160-900 sample, which had a high nitrogen content and micropore volume, exhibited the highest CO2 uptake, which is 5.50 and 3.50 mmol g−1 at 273 and 298 K, respectively. Moreover, the analysis based on the ideal adsorbed solution theory (IAST) exhibited a high adsorption selectivity for CO2/N2 at 298 K and 1 bar (Sads = 29). Introduction to the international collaboration State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, at Jilin University China, has a long term cooperation with the Laboratory of Catalysis and Spectroscopy in Caen, at CNRS-France. Recently, Prof. Shilun Qiu's group and Prof. Valentin Valtchev's group had an international collaborative researching project entitled “Microporous materials: green synthesis for green applications”, which was supported by the National Natural Science Foundation of China (21261130584) and the French Science Foundation (ANR-12-IS08-0001-01). This project is focused on the design and synthesis of porous materials such as zeolites, metal organic frameworks (MOFs), covalent organic frameworks (COFs), porous aromatic frameworks (PAFs) and porous carbon materials that can find applications for clean energy storage, carbon capture, catalysis, and molecular selective sorption and separation.

Mixed transition metal oxides have attracted much attention recently due to their potential application in energy and environmental sciences. The emergence of multivariate MOFs recently has attracted great research attention and provides an opportunity for multivariate mixed-metal oxides. In this work, five isostructural, single-phase MOF-74 structures with different divalent metals (MOF-74–Co, MOF-74–Ni, MOF-74–NiCo1, MOF-74–NiCo2 and MOF-74–NiCo4) were synthesised by varying the mole ratios of Ni/Co mixed-metal ions. After annealing at the appropriate temperature, Co3O4, NiO and three kinds of NixCo3−xO4 mixed-metal oxide nanoparticles with high surface area were easily obtained and the metal ratio was readily controlled, enabling us to systematically investigate the effect of different metal species amounts on the electrochemical properties of the mixed-metal oxide materials. When these metal oxides were used as electrode materials for supercapacitors, we found that the mixed-metal oxides NixCo3−xO4 obtained from bimetallic MOF-74–NiCo structures had obvious advantages compared with the monometallic oxides of MOF-74–Ni and MOF-74–Co. In particular, the NixCo3−xO4-1 with the Ni/Co metal ratio 1:1 exhibited the highest capacitance of 797 F g−1 and excellent cycling stability.

A homochiral MOF membrane was successfully and facilely synthesized using an in situ growth method, which had the advantages of cheap raw materials, simple operation and high thermal stability. A diol isomer mixture was used to test the separation efficiency of the membrane at different temperatures and pressures.

A new strategy was developed to introduce active site K+ into the pores of MOF precursors, and various N-doped hierarchical porous carbons were prepared in a one-step synthetic route. The effect of K+in situ activation on the textural properties of the derived porous carbons was studied systematically, and the CO2 capture properties and electrochemical performance of these porous carbons were enhanced for their application in supercapacitors. The KBM-700 sample derived from K@bio-MOF-1 (potassium-ion-exchanged bio-MOF-1), which had high nitrogen content (10.16%) and micropore volume (73%), exhibited good CO2 uptakes (4.75 mmol g−1), and high adsorption selectivity for CO2/N2 at 298 K and 1 bar (Sads = 99.1) as well as high specific capacitance (230 F g−1) and excellent electrochemical cycling stability (97% retention after cycling 10000 times).