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2025 Volume 41 Issue 10
2025, 41(10): 1-2
Abstract:
2025, 41(10): 1929-1952
doi: 10.11862/CJIC.20250122
Abstract:
Inorganic X-ray nanoscintillators have attracted considerable attention from researchers due to their outstanding optical properties and solution processability, offering promising prospects for applications in flexible scintillating screens, bioimaging, disease theranostics, and related fields. This review highlights recent advancements in inorganic X-ray nanoscintillators, focusing on transition metal ion-doped nanocrystals, quantum dots, clusters, and nanoscale metal-organic framework scintillator materials, along with their scintillation mechanisms. Additionally, the paper reviews the latest achievements in applying inorganic nanoscintillators to areas such as detection, information storage, bioimaging, and therapy. Finally, future development directions are discussed, emphasizing their enormous potential in three-dimensional flexible detectors and near-infrared Ⅱ fluorescence imaging.
Inorganic X-ray nanoscintillators have attracted considerable attention from researchers due to their outstanding optical properties and solution processability, offering promising prospects for applications in flexible scintillating screens, bioimaging, disease theranostics, and related fields. This review highlights recent advancements in inorganic X-ray nanoscintillators, focusing on transition metal ion-doped nanocrystals, quantum dots, clusters, and nanoscale metal-organic framework scintillator materials, along with their scintillation mechanisms. Additionally, the paper reviews the latest achievements in applying inorganic nanoscintillators to areas such as detection, information storage, bioimaging, and therapy. Finally, future development directions are discussed, emphasizing their enormous potential in three-dimensional flexible detectors and near-infrared Ⅱ fluorescence imaging.
2025, 41(10): 1953-1972
doi: 10.11862/CJIC.20250160
Abstract:
With the rapid development of technology, electrochemical sensors have been widely applied in fields such as disease diagnosis, environmental monitoring, and food safety due to their high sensitivity, good selectivity, low cost, and simple operation. Although traditional sensing materials (such as noble metals, carbon-based materials, or conductive polymers) have made remarkable progress, their limited active site density, low porosity, and non-tunable electronic structures restrict their detection performance in complex systems. In recent years, electrically conductive metal-organic frameworks (EC-MOFs) have offered brand-new research opportunities and development directions for the field of electrochemical sensing. This is attributed to their high specific surface area, abundant pore structure, flexible tunable design characteristics, as well as excellent catalytic performance, efficient electron transport capability, and significant signal amplification effect. This review systematically summarizes the latest research progress of EC-MOFs materials in the field of electrochemical sensing, focusing on the design and synthesis strategies of working electrodes for EC-MOFs-based electrochemical sensors, including in-situ synthesis, ex-situ synthesis, and combined in-situ and ex-situ strategies. Additionally, it provides a detailed review of their breakthrough applications in biomolecular recognition, environmental pollutant monitoring, etc. Meanwhile, the review provides a deep analysis of the key challenges faced by EC-MOFs in the field of electrochemical sensing and outlines their future development directions.
With the rapid development of technology, electrochemical sensors have been widely applied in fields such as disease diagnosis, environmental monitoring, and food safety due to their high sensitivity, good selectivity, low cost, and simple operation. Although traditional sensing materials (such as noble metals, carbon-based materials, or conductive polymers) have made remarkable progress, their limited active site density, low porosity, and non-tunable electronic structures restrict their detection performance in complex systems. In recent years, electrically conductive metal-organic frameworks (EC-MOFs) have offered brand-new research opportunities and development directions for the field of electrochemical sensing. This is attributed to their high specific surface area, abundant pore structure, flexible tunable design characteristics, as well as excellent catalytic performance, efficient electron transport capability, and significant signal amplification effect. This review systematically summarizes the latest research progress of EC-MOFs materials in the field of electrochemical sensing, focusing on the design and synthesis strategies of working electrodes for EC-MOFs-based electrochemical sensors, including in-situ synthesis, ex-situ synthesis, and combined in-situ and ex-situ strategies. Additionally, it provides a detailed review of their breakthrough applications in biomolecular recognition, environmental pollutant monitoring, etc. Meanwhile, the review provides a deep analysis of the key challenges faced by EC-MOFs in the field of electrochemical sensing and outlines their future development directions.
2025, 41(10): 2011-2028
doi: 10.11862/CJIC.20250185
Abstract:
The electrocatalytic oxygen evolution reaction (OER), serving as a crucial half-reaction in clean energy technologies such as water splitting and metal-air batteries, plays a significant role in addressing energy crises and solving environmental pollution problems. However, the intricate electron/proton transfer mechanisms and sluggish reaction kinetics of OER result in high overpotentials that significantly limit energy conversion efficiency. The development of highly efficient and stable OER electrocatalysts is therefore urgently required. Metal-organic frameworks (MOFs) have emerged as promising electrocatalysts due to their abundant metal centers, large specific surface areas, and tunable structural configurations. This review systematically summarizes the design strategies for high-performance MOF-based electrocatalysts, while also discussing current challenges and future research directions in this field.
The electrocatalytic oxygen evolution reaction (OER), serving as a crucial half-reaction in clean energy technologies such as water splitting and metal-air batteries, plays a significant role in addressing energy crises and solving environmental pollution problems. However, the intricate electron/proton transfer mechanisms and sluggish reaction kinetics of OER result in high overpotentials that significantly limit energy conversion efficiency. The development of highly efficient and stable OER electrocatalysts is therefore urgently required. Metal-organic frameworks (MOFs) have emerged as promising electrocatalysts due to their abundant metal centers, large specific surface areas, and tunable structural configurations. This review systematically summarizes the design strategies for high-performance MOF-based electrocatalysts, while also discussing current challenges and future research directions in this field.
2025, 41(10): 2029-2038
doi: 10.11862/CJIC.20250186
Abstract:
Supercapacitors are highly efficient electrochemical energy storage devices, and the electrode material is a key factor affecting their performance. In recent years, metal-organic framework (MOF) materials have become an ideal choice for enhancing the performance of supercapacitors owing to their unique structure and properties. Especially nickel MOF (Ni-MOF) materials, due to their excellent stability and appropriate reaction potential, exhibit great electrochemical energy storage performance. However, they are still faced with some problems in practical applications. It is expected to further enhance their electrochemical performance through material compounding or derivatization. This paper reviews the applications of Ni-MOF and its composites and derivatives in supercapacitors, providing new ideas for developing high-performance energy storage devices.
Supercapacitors are highly efficient electrochemical energy storage devices, and the electrode material is a key factor affecting their performance. In recent years, metal-organic framework (MOF) materials have become an ideal choice for enhancing the performance of supercapacitors owing to their unique structure and properties. Especially nickel MOF (Ni-MOF) materials, due to their excellent stability and appropriate reaction potential, exhibit great electrochemical energy storage performance. However, they are still faced with some problems in practical applications. It is expected to further enhance their electrochemical performance through material compounding or derivatization. This paper reviews the applications of Ni-MOF and its composites and derivatives in supercapacitors, providing new ideas for developing high-performance energy storage devices.
2025, 41(10): 1973-2010
doi: 10.11862/CJIC.20250175
Abstract:
The selective hydrogenation of α, β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule. This approach serves as a critical strategy for the directional synthesis of high-value molecules. However, achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds in α, β-unsaturated systems. Consequently, constructing precisely targeted catalytic systems is essential to overcome these limitations, offering both fundamental scientific significance and industrial application potential. Metal-organic frameworks (MOFs) and their derivatives have emerged as innovative platforms for designing such systems, owing to their programmable topology, tunable pore microenvironments, spatially controllable active sites, and modifiable electronic structures. This review systematically summarizes the research progress of MOF-based catalysts for selective hydrogenation of α, β-unsaturated aldehydes/ketones in the last decade, with emphasis on the design strategy, conformational relationship, and catalytic mechanism, aiming to provide new ideas for the design of targeted catalytic systems for the selective hydrogenation of α, β-unsaturated aldehydes/ketones.
The selective hydrogenation of α, β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule. This approach serves as a critical strategy for the directional synthesis of high-value molecules. However, achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds in α, β-unsaturated systems. Consequently, constructing precisely targeted catalytic systems is essential to overcome these limitations, offering both fundamental scientific significance and industrial application potential. Metal-organic frameworks (MOFs) and their derivatives have emerged as innovative platforms for designing such systems, owing to their programmable topology, tunable pore microenvironments, spatially controllable active sites, and modifiable electronic structures. This review systematically summarizes the research progress of MOF-based catalysts for selective hydrogenation of α, β-unsaturated aldehydes/ketones in the last decade, with emphasis on the design strategy, conformational relationship, and catalytic mechanism, aiming to provide new ideas for the design of targeted catalytic systems for the selective hydrogenation of α, β-unsaturated aldehydes/ketones.
2025, 41(10): 2039-2053
doi: 10.11862/CJIC.20250036
Abstract:
Hollow multi-shelled structure (HoMS) is the novel multifunctional structural system, which are constructed with nanoparticles as structural units, featuring two or more shells, multiple interfaces, and numerous channels and demonstrating outstanding properties in energy conversion and mass transfer. In recent years, owing to the breakthroughs in synthetic methods, the diversity of composition and structure of HoMS has been greatly enriched, showing broad application prospects in energy, catalysis, environment and other fields. This review focuses on the research status of HoMS for catalytic applications. Firstly, the new synthesis method for HoMS, namely the sequential templating approach, is introduced from both practical and theoretical perspectives. Then, it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance. The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed. Finally, it looks forward to the opportunities and challenges in the development of HoMS.
Hollow multi-shelled structure (HoMS) is the novel multifunctional structural system, which are constructed with nanoparticles as structural units, featuring two or more shells, multiple interfaces, and numerous channels and demonstrating outstanding properties in energy conversion and mass transfer. In recent years, owing to the breakthroughs in synthetic methods, the diversity of composition and structure of HoMS has been greatly enriched, showing broad application prospects in energy, catalysis, environment and other fields. This review focuses on the research status of HoMS for catalytic applications. Firstly, the new synthesis method for HoMS, namely the sequential templating approach, is introduced from both practical and theoretical perspectives. Then, it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance. The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed. Finally, it looks forward to the opportunities and challenges in the development of HoMS.
2025, 41(10): 2054-2062
doi: 10.11862/CJIC.20250096
Abstract:
In this study, an aluminium-based porphyrin metal-organic framework (Al-TCPP) with slit-shaped pores was prepared by a solvothermal method, and its adsorptive separation and recovery properties of electronic specialty gas C3F8 were investigated. The synthesized Al-TCPP has a narrow slit pore structure with a pore size of 0.6 nm×1.1 nm, which is slightly larger than the molecular size of C3F8 (0.57 nm×0.52 nm). Meanwhile, the densely packed C—H bonds and μ-OH groups in the Al-TCPP pores can form multiple hydrogen bonding sites with the F atoms of C3F8, which further enhances the affinity for C3F8. Adsorption experiments showed that the adsorption amount of C3F8 in Al-TCPP was up to 96.1 cm3·g-1 at 298 K and 100 kPa, while the N2 adsorption amount was only 6.1 cm3·g-1, affording a record C3F8/N2 selectivity of 244.8, which exceeded that of all the adsorbents reported so far. Meanwhile, the heat of adsorption of C3F8 in the low-pressure region was 50.6 kJ·mol-1, which was much higher than that of N2 (16.5 kJ·mol-1). Density functional theory (DFT) calculations also showed that multiple H atoms in the adjacent porphyrin units of Al-TCPP can form strong interactions with the F atoms of C3F8 by hydrogen bonding. Breakthrough experiments confirmed that Al-TCPP could achieve the effective separation of C3F8/N2 mixtures, and high-purity C3F8 could be recovered by the desorption process.
In this study, an aluminium-based porphyrin metal-organic framework (Al-TCPP) with slit-shaped pores was prepared by a solvothermal method, and its adsorptive separation and recovery properties of electronic specialty gas C3F8 were investigated. The synthesized Al-TCPP has a narrow slit pore structure with a pore size of 0.6 nm×1.1 nm, which is slightly larger than the molecular size of C3F8 (0.57 nm×0.52 nm). Meanwhile, the densely packed C—H bonds and μ-OH groups in the Al-TCPP pores can form multiple hydrogen bonding sites with the F atoms of C3F8, which further enhances the affinity for C3F8. Adsorption experiments showed that the adsorption amount of C3F8 in Al-TCPP was up to 96.1 cm3·g-1 at 298 K and 100 kPa, while the N2 adsorption amount was only 6.1 cm3·g-1, affording a record C3F8/N2 selectivity of 244.8, which exceeded that of all the adsorbents reported so far. Meanwhile, the heat of adsorption of C3F8 in the low-pressure region was 50.6 kJ·mol-1, which was much higher than that of N2 (16.5 kJ·mol-1). Density functional theory (DFT) calculations also showed that multiple H atoms in the adjacent porphyrin units of Al-TCPP can form strong interactions with the F atoms of C3F8 by hydrogen bonding. Breakthrough experiments confirmed that Al-TCPP could achieve the effective separation of C3F8/N2 mixtures, and high-purity C3F8 could be recovered by the desorption process.
2025, 41(10): 2063-2068
doi: 10.11862/CJIC.20250020
Abstract:
Ammonia, a toxic gas, poses significant risks to human health and the environment. Developing cost- effective and eco-friendly adsorbents for ammonia capture is crucial. In this study, a La3+-based metal-organic framework {[La4(QS)6(H2O)6]·18H2O}n (MOF-LaQS) was synthesized via a simple low-temperature hydrothermal method using inexpensive 8-hydroxyquinoline-5-sulfonic acid (H2QS) as organic ligand. The material exhibited structural stability, low synthesis costs, and exceptional ammonia adsorption capacities of 228 cm3·g-1 (10.2 mmol·g-1) at 273 K (101 kPa) and 48 cm3·g-1 (2.14 mmol·g-1) at ultra-low pressure (0.101 kPa). In situ infrared spectroscopy and DFT calculations revealed that open La3+ sites are key to its ammonia adsorption, thereby elucidating the mechanism underlying its high ammonia uptake.
Ammonia, a toxic gas, poses significant risks to human health and the environment. Developing cost- effective and eco-friendly adsorbents for ammonia capture is crucial. In this study, a La3+-based metal-organic framework {[La4(QS)6(H2O)6]·18H2O}n (MOF-LaQS) was synthesized via a simple low-temperature hydrothermal method using inexpensive 8-hydroxyquinoline-5-sulfonic acid (H2QS) as organic ligand. The material exhibited structural stability, low synthesis costs, and exceptional ammonia adsorption capacities of 228 cm3·g-1 (10.2 mmol·g-1) at 273 K (101 kPa) and 48 cm3·g-1 (2.14 mmol·g-1) at ultra-low pressure (0.101 kPa). In situ infrared spectroscopy and DFT calculations revealed that open La3+ sites are key to its ammonia adsorption, thereby elucidating the mechanism underlying its high ammonia uptake.
2025, 41(10): 2069-2077
doi: 10.11862/CJIC.20250129
Abstract:
Using (Et4N)[Tp*WS3(CuCl)3] (A) (Tp*=tris(3, 5-dimethylpyrazolyl)hydroborate) as a precursor cluster, a dechlorination reaction with Ag(OTf) was performed, followed by self-assembly with two bidentate pyridine ligands: 1, 3-bis[4-(pyridin-4-ylethynyl)phenyl]propane (L1) and 1, 3-bis[4-(pyridin-4-ylethynyl)phenyl]propan-2-one (L2). This led to the construction of two W/Cu/S cluster-based supramolecular rectangular macrocycles, [(Tp*WS3Cu2Cl)4(L1)2]·6CH2Cl2 (1·6CH2Cl2) and [(Tp*WS3Cu2Cl)4(L2)2]·6CH2Cl2 (2·6CH2Cl2). During their assembly process, one cycloaddition reaction between one alkynyl group of L1 or L2 and two S atoms of A occurred, which exerted an important impact on the formation of both supramolecular rectangular macrocycles. In addition, by introducing pyridine (Py) as a second ligand into the reaction systems of 1·6CH2Cl2 and 2·6CH2Cl2, a novel cluster [Tp*WS3Cu3(μ3-Cl)(Py)3](OTf) (3) was obtained. The three compounds were systematically characterized using single-crystal X-ray diffraction, electrospray ionization mass spectrometry, IR, and UV-Vis spectroscopy. Single crystal X-ray diffraction results confirmed that 1·6CH2Cl2 and 2·6CH2Cl2 have supramolecular rectangular macrocycle structures formed by two bidentate ligands (L1 or L2) bridging four [Tp*WS3Cu2Cl] cluster units. Cluster 3 has a cationic cubane-like structure with three pyridine molecules coordinating at three Cu(Ⅰ) centers of the [Tp*WS3Cu3(μ3-Cl)]+ core. The Z-scan technique revealed that the solutions of 1·6CH2Cl2, 2·6CH2Cl2, and 3 showed good third-order nonlinear optical responses.
Using (Et4N)[Tp*WS3(CuCl)3] (A) (Tp*=tris(3, 5-dimethylpyrazolyl)hydroborate) as a precursor cluster, a dechlorination reaction with Ag(OTf) was performed, followed by self-assembly with two bidentate pyridine ligands: 1, 3-bis[4-(pyridin-4-ylethynyl)phenyl]propane (L1) and 1, 3-bis[4-(pyridin-4-ylethynyl)phenyl]propan-2-one (L2). This led to the construction of two W/Cu/S cluster-based supramolecular rectangular macrocycles, [(Tp*WS3Cu2Cl)4(L1)2]·6CH2Cl2 (1·6CH2Cl2) and [(Tp*WS3Cu2Cl)4(L2)2]·6CH2Cl2 (2·6CH2Cl2). During their assembly process, one cycloaddition reaction between one alkynyl group of L1 or L2 and two S atoms of A occurred, which exerted an important impact on the formation of both supramolecular rectangular macrocycles. In addition, by introducing pyridine (Py) as a second ligand into the reaction systems of 1·6CH2Cl2 and 2·6CH2Cl2, a novel cluster [Tp*WS3Cu3(μ3-Cl)(Py)3](OTf) (3) was obtained. The three compounds were systematically characterized using single-crystal X-ray diffraction, electrospray ionization mass spectrometry, IR, and UV-Vis spectroscopy. Single crystal X-ray diffraction results confirmed that 1·6CH2Cl2 and 2·6CH2Cl2 have supramolecular rectangular macrocycle structures formed by two bidentate ligands (L1 or L2) bridging four [Tp*WS3Cu2Cl] cluster units. Cluster 3 has a cationic cubane-like structure with three pyridine molecules coordinating at three Cu(Ⅰ) centers of the [Tp*WS3Cu3(μ3-Cl)]+ core. The Z-scan technique revealed that the solutions of 1·6CH2Cl2, 2·6CH2Cl2, and 3 showed good third-order nonlinear optical responses.
2025, 41(10): 2078-2086
doi: 10.11862/CJIC.20250167
Abstract:
One metal-organic framework [Zn3(NTB)2(bipy)]·4H2O (1) with charge transfer characteristic and 3D polyrotaxane structure was synthesized by the reaction of 4, 4′, 4″-nitrilotribenzoic acid (H3NTB) as electron donor, 4, 4′-bipyridine (bipy) as electron acceptor and Zn(NO3)2·6H2O under solvothermal method. Its crystal structure, phase purity, and thermal stability were characterized by X-ray single-crystal diffraction, powder X-ray diffraction, and thermogravimetric analysis. Complex 1 crystallizes in triclinic system, P1 space group with cell parameters: a=1.374 87(15) nm, b=1.376 65(15) nm, c=1.795 50(18) nm, α=86.994(9)°, β=82.384(9)°, γ=64.835(11)°. It emitted bright yellow emission peaking at 575 nm with lifetime of 16.01 ns under room temperature. The temperature- dependent photoluminescence shows that 1 could maintain 92.05% of its initial emission intensity after being heated to 150 ℃, higher than several silicates and borate based inorganic phosphors.
One metal-organic framework [Zn3(NTB)2(bipy)]·4H2O (1) with charge transfer characteristic and 3D polyrotaxane structure was synthesized by the reaction of 4, 4′, 4″-nitrilotribenzoic acid (H3NTB) as electron donor, 4, 4′-bipyridine (bipy) as electron acceptor and Zn(NO3)2·6H2O under solvothermal method. Its crystal structure, phase purity, and thermal stability were characterized by X-ray single-crystal diffraction, powder X-ray diffraction, and thermogravimetric analysis. Complex 1 crystallizes in triclinic system, P1 space group with cell parameters: a=1.374 87(15) nm, b=1.376 65(15) nm, c=1.795 50(18) nm, α=86.994(9)°, β=82.384(9)°, γ=64.835(11)°. It emitted bright yellow emission peaking at 575 nm with lifetime of 16.01 ns under room temperature. The temperature- dependent photoluminescence shows that 1 could maintain 92.05% of its initial emission intensity after being heated to 150 ℃, higher than several silicates and borate based inorganic phosphors.
2025, 41(10): 2087-2094
doi: 10.11862/CJIC.20250182
Abstract:
A lanthanide-based metal-organic framework Eu0.52Tb0.48-TCPP was synthesized under solvothermal conditions, where H4TCPP=4,4′, 4″,4‴-(pyrazine-2, 3, 5, 6-tetrayl)-tetrabenzoic acid. The structure and composition were characterized by powder X-ray diffraction, thermogravimetric analysis, infrared spectroscope, and elemental analysis. Eu0.52Tb0.48-TCPP showed excellent chemical stability, thermal stability, and good fluorescence sensing performance, which realized efficient and sensitive detection of 2, 4, 6-trinitrophenol (TNP). The detection limit was 0.49 μmol·L-1. In addition, the fluorescence sensing mechanism of TNP detected by Eu0.52Tb0.48-TCPP was explored and a portable fluorescence test papers and composite films were successfully prepared for the real-time and on-site inspection of TNP.
A lanthanide-based metal-organic framework Eu0.52Tb0.48-TCPP was synthesized under solvothermal conditions, where H4TCPP=4,4′, 4″,4‴-(pyrazine-2, 3, 5, 6-tetrayl)-tetrabenzoic acid. The structure and composition were characterized by powder X-ray diffraction, thermogravimetric analysis, infrared spectroscope, and elemental analysis. Eu0.52Tb0.48-TCPP showed excellent chemical stability, thermal stability, and good fluorescence sensing performance, which realized efficient and sensitive detection of 2, 4, 6-trinitrophenol (TNP). The detection limit was 0.49 μmol·L-1. In addition, the fluorescence sensing mechanism of TNP detected by Eu0.52Tb0.48-TCPP was explored and a portable fluorescence test papers and composite films were successfully prepared for the real-time and on-site inspection of TNP.
2025, 41(10): 2095-2102
doi: 10.11862/CJIC.20250025
Abstract:
Ultrafine, highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74. Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms, the obtained Pt-on-Co/C400 catalysts exhibited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency (TOF) value of 3 022 min-1 at 303 K. Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability, and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
Ultrafine, highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74. Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms, the obtained Pt-on-Co/C400 catalysts exhibited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency (TOF) value of 3 022 min-1 at 303 K. Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability, and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
2025, 41(10): 2103-2114
doi: 10.11862/CJIC.20250110
Abstract:
Perfluoroalkyl acids of different chain lengths, including trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid, were used as second ligands to replace the formic acid on the Zr6 clusters in MOF-808. This led to the formation of a series of MOF-808-R materials (R=F3, F7, F9, corresponding to trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid) with multiple ligands, and we investigated the impact of the second ligand modification on pore size and pore environment. The loading amount of the second ligand was determined using NMR and other methods. We conducted adsorption tests for acetylene and carbon dioxide at different temperatures on both MOF-808 and MOF-808-R to explore the effects of the ligand diversification on acetylene separation performance. It was found that MOF-808-F7 exhibited the best performance in acetylene-carbon dioxide separation.
Perfluoroalkyl acids of different chain lengths, including trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid, were used as second ligands to replace the formic acid on the Zr6 clusters in MOF-808. This led to the formation of a series of MOF-808-R materials (R=F3, F7, F9, corresponding to trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid) with multiple ligands, and we investigated the impact of the second ligand modification on pore size and pore environment. The loading amount of the second ligand was determined using NMR and other methods. We conducted adsorption tests for acetylene and carbon dioxide at different temperatures on both MOF-808 and MOF-808-R to explore the effects of the ligand diversification on acetylene separation performance. It was found that MOF-808-F7 exhibited the best performance in acetylene-carbon dioxide separation.
2025, 41(10): 2115-2126
doi: 10.11862/CJIC.20250139
Abstract:
In the paper, we report a highly robust and porous bimetallic Ti-MOF (designated Mg2Ti-ABTC) by utilizing a trinuclear [Mg2TiO(COO)6] cluster and a tetradentate H4ABTC (3, 3′, 5, 5′-azobenzene tetracarboxylic acid) ligand. Mg2Ti-ABTC exhibited permanent porosity for N2, CO2, CH4, C2H2, C2H4, and C2H6 gas adsorption. Furthermore, Mg2Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corresponding sulfoxides under ambient air conditions. Mechanism studies reveal that photoinduced holes (h+), the superoxide radical (•O2-), and singlet oxygen (1O2) are pivotal species involved in the photocatalytic oxidation reaction.
In the paper, we report a highly robust and porous bimetallic Ti-MOF (designated Mg2Ti-ABTC) by utilizing a trinuclear [Mg2TiO(COO)6] cluster and a tetradentate H4ABTC (3, 3′, 5, 5′-azobenzene tetracarboxylic acid) ligand. Mg2Ti-ABTC exhibited permanent porosity for N2, CO2, CH4, C2H2, C2H4, and C2H6 gas adsorption. Furthermore, Mg2Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corresponding sulfoxides under ambient air conditions. Mechanism studies reveal that photoinduced holes (h+), the superoxide radical (•O2-), and singlet oxygen (1O2) are pivotal species involved in the photocatalytic oxidation reaction.
2025, 41(10): 2127-2137
doi: 10.11862/CJIC.20250149
Abstract:
To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis, two new lanthanum phosphite-oxalates with 3D frameworks, designated as [La(HPO3)(C2O4)0.5(H2O)2] (La-1) and (C6H16N2)(H3O)[La2(H2PO3)3(C2O4)3(H2O)] (La-2) (C6H14N2=cis-, 6-dimethylpiperazine), were prepared by hydrothermal and solvothermal conduction, respectively. La-1 was constructed with lanthanum phosphite 2D layers and C2O42- groups, whereas La-2 was constructed with lanthanum oxalate 2D layers and H2PO3- groups. Alternating current (AC) impedance spectra indicate that the proton conductivities of both compounds could reach 10-4 S•cm-1 and remain highly durable at 75 ℃ and 98% of relative humidity (RH). Due to the abundance of H-bonds in La-2, the σ of La-2 was higher than that of La-1. La-1 exhibited excellent water and pH stability.
To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis, two new lanthanum phosphite-oxalates with 3D frameworks, designated as [La(HPO3)(C2O4)0.5(H2O)2] (La-1) and (C6H16N2)(H3O)[La2(H2PO3)3(C2O4)3(H2O)] (La-2) (C6H14N2=cis-, 6-dimethylpiperazine), were prepared by hydrothermal and solvothermal conduction, respectively. La-1 was constructed with lanthanum phosphite 2D layers and C2O42- groups, whereas La-2 was constructed with lanthanum oxalate 2D layers and H2PO3- groups. Alternating current (AC) impedance spectra indicate that the proton conductivities of both compounds could reach 10-4 S•cm-1 and remain highly durable at 75 ℃ and 98% of relative humidity (RH). Due to the abundance of H-bonds in La-2, the σ of La-2 was higher than that of La-1. La-1 exhibited excellent water and pH stability.
2025, 41(10): 2138-2148
doi: 10.11862/CJIC.20250154
Abstract:
We report a robust pillar-layered metal-organic framework, Zn-tfbdc-dabco (tfbdc: tetrafluoroterephthalate, dabco: 1, 4-diazabicyclo[2.2.2]octane), featuring the fluorinated pore environment, for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture. The inverse propane-selective performance of Zn-tfbdc-dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms, isosteric enthalpy of adsorption calculations, ideal adsorbed solution theory calculations, along with the breakthrough experiment. The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane, as unveiled by the simulation studies at the molecular level. With the advantage of inverse propane-selective adsorption behavior, high adsorption capacity, good cycling stability, and low isosteric enthalpy of adsorption, Zn-tfbdc-dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.
We report a robust pillar-layered metal-organic framework, Zn-tfbdc-dabco (tfbdc: tetrafluoroterephthalate, dabco: 1, 4-diazabicyclo[2.2.2]octane), featuring the fluorinated pore environment, for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture. The inverse propane-selective performance of Zn-tfbdc-dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms, isosteric enthalpy of adsorption calculations, ideal adsorbed solution theory calculations, along with the breakthrough experiment. The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane, as unveiled by the simulation studies at the molecular level. With the advantage of inverse propane-selective adsorption behavior, high adsorption capacity, good cycling stability, and low isosteric enthalpy of adsorption, Zn-tfbdc-dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.
2025, 41(10): 2149-2156
doi: 10.11862/CJIC.20250177
Abstract:
Herein, we report the synthesis and third-order nonlinear optical (NLO) properties of a novel cage-based 2D metal-organic framework constructed from Ti4L6 (L4-=embonate) cage combined with Mg2+ and tris[4-(1H-imidazol-1-yl)phenyl]amine (tipa) ligand, whose molecular formula is (Me2CH2)2[Mg3(Ti4L6)(tipa)(H2O)12] (PTC-378). The Ti4L6 tetrahedral cages serve as robust building units, while the Mg2+ ions and tipa ligands provide structural stability and tunable optical properties. The resulting PTC-378 film exhibited intriguing third-order NLO property, which was systematically investigated using Z-scan techniques. Our results demonstrate that the synergistic interaction between Ti4L6 cages and π-conjugated ligands significantly enhances the NLO performance of the materials.
Herein, we report the synthesis and third-order nonlinear optical (NLO) properties of a novel cage-based 2D metal-organic framework constructed from Ti4L6 (L4-=embonate) cage combined with Mg2+ and tris[4-(1H-imidazol-1-yl)phenyl]amine (tipa) ligand, whose molecular formula is (Me2CH2)2[Mg3(Ti4L6)(tipa)(H2O)12] (PTC-378). The Ti4L6 tetrahedral cages serve as robust building units, while the Mg2+ ions and tipa ligands provide structural stability and tunable optical properties. The resulting PTC-378 film exhibited intriguing third-order NLO property, which was systematically investigated using Z-scan techniques. Our results demonstrate that the synergistic interaction between Ti4L6 cages and π-conjugated ligands significantly enhances the NLO performance of the materials.
2025, 41(10): 2157-2164
doi: 10.11862/CJIC.20250179
Abstract:
To obtain materials capable of efficiently separating acetylene (C2H2) from carbon dioxide (CO2) and ethylene (C2H4), In this work, based on the pore space partition strategy, a pacs-metal-organic framework (MOF): (NH2Me2)2[Fe3(μ3-O)(bdc)3][In(FA)3Cl3] (Fe-FAIn-bdc) was synthesized successfully by using the metal-formate complex [In(FA)3Cl3]3- as the pore partition units, where bdc2-=terephthalate, FA-=formate. Owing to the pore partition effect of this metal-organic building block, fruitful confined spaces are formed in the network of Fe-FAIn-bdc, endowing this MOF with superior separation performance of acetylene and carbon dioxide. According to the adsorption test, this MOF exhibited a high adsorption capacity for C2H2 (50.79 cm3·g-1) at 298 K and 100 kPa, which was much higher than that for CO2 (29.99 cm3·g-1) and C2H4 (30.94 cm3·g-1) under the same conditions. Ideal adsorbed solution theory (IAST) calculations demonstrate that the adsorption selectivity of Fe-FAIn-bdc for the mixture of C2H2/CO2 and C2H2/C2H4 in a volume ratio of 50∶50 was 3.08 and 3.65, respectively, which was higher than some reported MOFs such as NUM-11 and SNNU-18.
To obtain materials capable of efficiently separating acetylene (C2H2) from carbon dioxide (CO2) and ethylene (C2H4), In this work, based on the pore space partition strategy, a pacs-metal-organic framework (MOF): (NH2Me2)2[Fe3(μ3-O)(bdc)3][In(FA)3Cl3] (Fe-FAIn-bdc) was synthesized successfully by using the metal-formate complex [In(FA)3Cl3]3- as the pore partition units, where bdc2-=terephthalate, FA-=formate. Owing to the pore partition effect of this metal-organic building block, fruitful confined spaces are formed in the network of Fe-FAIn-bdc, endowing this MOF with superior separation performance of acetylene and carbon dioxide. According to the adsorption test, this MOF exhibited a high adsorption capacity for C2H2 (50.79 cm3·g-1) at 298 K and 100 kPa, which was much higher than that for CO2 (29.99 cm3·g-1) and C2H4 (30.94 cm3·g-1) under the same conditions. Ideal adsorbed solution theory (IAST) calculations demonstrate that the adsorption selectivity of Fe-FAIn-bdc for the mixture of C2H2/CO2 and C2H2/C2H4 in a volume ratio of 50∶50 was 3.08 and 3.65, respectively, which was higher than some reported MOFs such as NUM-11 and SNNU-18.
2025, 41(10): 2165-2174
doi: 10.11862/CJIC.20250190
Abstract:
Herein, a luminescent europium-based metal-organic framework (Eu-MOF, [Eu3(L)(HL)(NO3)2(DMF)2]·4DMF·5H2O, H4L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid, DMF=N,N-dimethylformamide) was developed for the dual-functional detection of environmental pollutants. This fluorescence-quenching-based sensor exhibited exceptional sensitivity for both 2,4,6-trinitrophenol (TNP) and tetracycline (TC), achieving remarkably low detection limits of 1.96×10-6 and 1.71×10-7 mol·L-1, respectively. Notably, the system exhibited 99% fluorescence quenching efficiency for TC, indicating ultra-efficient analyte recognition. The detection performance surpasses most reported luminescent MOF sensors, attributed to synergistic mechanisms of fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET).
Herein, a luminescent europium-based metal-organic framework (Eu-MOF, [Eu3(L)(HL)(NO3)2(DMF)2]·4DMF·5H2O, H4L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid, DMF=N,N-dimethylformamide) was developed for the dual-functional detection of environmental pollutants. This fluorescence-quenching-based sensor exhibited exceptional sensitivity for both 2,4,6-trinitrophenol (TNP) and tetracycline (TC), achieving remarkably low detection limits of 1.96×10-6 and 1.71×10-7 mol·L-1, respectively. Notably, the system exhibited 99% fluorescence quenching efficiency for TC, indicating ultra-efficient analyte recognition. The detection performance surpasses most reported luminescent MOF sensors, attributed to synergistic mechanisms of fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET).
2025, 41(10): 2175-2185
doi: 10.11862/CJIC.20250218
Abstract:
Through employing zeolitic imidazolate framework-67 (ZIF-67) templates, the straightforward hydrothermal and electrodeposition methods were applied to synthesize FeOOH@CoMoO4 heterostructure attached to the surface of nickel foam (NF). The specific structure of the as-prepared FeOOH@CoMoO4/NF-400s provided pronounced porosity and extensive surface area, enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions. Furthermore, the introduction of FeOOH, which induces electron transfer from FeOOH to CoMoO4, confirms their strong electronic interaction, thereby leading to an accelerated surface catalytic reaction. Consequently, the constructed FeOOH@CoMoO4/NF-400s heterostructure demonstrated exceptional oxygen evolution reaction (OER) activity, requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm-2, coupled with the superior Tafel slope value of 49.56 mV·dec-1 and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm-2.
Through employing zeolitic imidazolate framework-67 (ZIF-67) templates, the straightforward hydrothermal and electrodeposition methods were applied to synthesize FeOOH@CoMoO4 heterostructure attached to the surface of nickel foam (NF). The specific structure of the as-prepared FeOOH@CoMoO4/NF-400s provided pronounced porosity and extensive surface area, enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions. Furthermore, the introduction of FeOOH, which induces electron transfer from FeOOH to CoMoO4, confirms their strong electronic interaction, thereby leading to an accelerated surface catalytic reaction. Consequently, the constructed FeOOH@CoMoO4/NF-400s heterostructure demonstrated exceptional oxygen evolution reaction (OER) activity, requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm-2, coupled with the superior Tafel slope value of 49.56 mV·dec-1 and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm-2.
