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2024 Volume 40 Issue 11
2024, 40(11): 2041-2062
doi: 10.11862/CJIC.20240161
Abstract:
Zirconium‐based metal-organic frameworks (Zr-MOFs) have emerged as one of the most promising crystalline porous framework materials for various applications, owing to their abundant structural varieties, excellent thermal and chemical stability as well as diverse functionalities. Incorporating organic ligands with tailored functional groups into the Zr-MOFs system via various methods such as one‐pot synthesis and post-synthetic modification enables the construction of multicomponent zirconium‐based metal-organic frameworks (MC-Zr-MOFs), allowing precise regulation over their pore environment for particular requirements. MC-Zr-MOFs have found extensive utility in gas adsorption/separation, guest molecule/ion adsorption in the solution phase, multiphase catalysis, chemical sensing, and optical materials for instance while exhibiting remarkable performance. This review aims to carefully investigate the recent advances in the synthetic strategies and novel applications of MC-Zr-MOFs, along with prospects for their future development.
Zirconium‐based metal-organic frameworks (Zr-MOFs) have emerged as one of the most promising crystalline porous framework materials for various applications, owing to their abundant structural varieties, excellent thermal and chemical stability as well as diverse functionalities. Incorporating organic ligands with tailored functional groups into the Zr-MOFs system via various methods such as one‐pot synthesis and post-synthetic modification enables the construction of multicomponent zirconium‐based metal-organic frameworks (MC-Zr-MOFs), allowing precise regulation over their pore environment for particular requirements. MC-Zr-MOFs have found extensive utility in gas adsorption/separation, guest molecule/ion adsorption in the solution phase, multiphase catalysis, chemical sensing, and optical materials for instance while exhibiting remarkable performance. This review aims to carefully investigate the recent advances in the synthetic strategies and novel applications of MC-Zr-MOFs, along with prospects for their future development.
2024, 40(11): 2063-2074
doi: 10.11862/CJIC.20240195
Abstract:
Multivariate two-dimensional conjugated metal-organic frameworks (MTV 2D c-MOFs) represent a novel class of porous crystalline materials constructed by coordinating multiple organic ligands and metal nodes. These advantages include predictable topology, tunable porosity, high conductivity, and high electrocatalytic activity, making them widely applicable in electrocatalysis, energy storage, and gas sensing. By leveraging the synergistic effects of multiple metal ions or organic ligands, the electrochemical activity and selectivity of MTV 2D c-MOFs can be efficiently optimized, resulting in superior conductivity and catalytic performance compared to traditional two-component 2D c-MOFs. In this mini-review, we first outline several common construction strategies for MTV 2D c-MOFs and provide a detailed comparison with two-component 2D c-MOFs. In addition, we discuss the promising application prospects of MTV 2D c-MOFs across various fields. Finally, we address the current challenges hindering the development of MTV 2D c-MOFs, highlighting directions for future research and improvement.
Multivariate two-dimensional conjugated metal-organic frameworks (MTV 2D c-MOFs) represent a novel class of porous crystalline materials constructed by coordinating multiple organic ligands and metal nodes. These advantages include predictable topology, tunable porosity, high conductivity, and high electrocatalytic activity, making them widely applicable in electrocatalysis, energy storage, and gas sensing. By leveraging the synergistic effects of multiple metal ions or organic ligands, the electrochemical activity and selectivity of MTV 2D c-MOFs can be efficiently optimized, resulting in superior conductivity and catalytic performance compared to traditional two-component 2D c-MOFs. In this mini-review, we first outline several common construction strategies for MTV 2D c-MOFs and provide a detailed comparison with two-component 2D c-MOFs. In addition, we discuss the promising application prospects of MTV 2D c-MOFs across various fields. Finally, we address the current challenges hindering the development of MTV 2D c-MOFs, highlighting directions for future research and improvement.
2024, 40(11): 2075-2090
doi: 10.11862/CJIC.20240196
Abstract:
Copper nanoclusters (Cu NCs) have made remarkable progress in the field of luminescence due to their excellent photophysical properties. However, due to the easy oxidation of copper, it is difficult to obtain Cu NCs with stable structure and high-intensity luminescence. It is one of the most feasible strategies to combine Cu NCs with other components to construct multi-component systems to improve stability and luminescence performance. Such systems can not only effectively make up for the defects of Cu NCs, but also realize the functional diversification of the luminous properties, which is conducive to the practical application of luminous materials. Based on this, this review will give a brief survey of the current study in this field, with first an introduction to the basic structure and effects on the luminescence of Cu NCs, and then a summary of the current strategies and applications of luminous multi-component systems constructed from Cu NCs.
Copper nanoclusters (Cu NCs) have made remarkable progress in the field of luminescence due to their excellent photophysical properties. However, due to the easy oxidation of copper, it is difficult to obtain Cu NCs with stable structure and high-intensity luminescence. It is one of the most feasible strategies to combine Cu NCs with other components to construct multi-component systems to improve stability and luminescence performance. Such systems can not only effectively make up for the defects of Cu NCs, but also realize the functional diversification of the luminous properties, which is conducive to the practical application of luminous materials. Based on this, this review will give a brief survey of the current study in this field, with first an introduction to the basic structure and effects on the luminescence of Cu NCs, and then a summary of the current strategies and applications of luminous multi-component systems constructed from Cu NCs.
2024, 40(11): 2091-2104
doi: 10.11862/CJIC.20240265
Abstract:
Developing asymmetric catalysts derived solely from octahedral centrochirality has garnered significant attention in the scientific community. Chiral-octahedral metal complexes can be classified into stereogenic-only-at-metal complexes and stereogenic-at-metal complexes with chiral ligands. This review introduces the design and syn-thesis of chiral-octahedral iridium and ruthenium complexes, which can be fine-tuned by altering the metal center, ligand combinations, and the chirality or achirality of the ligands. The applications of these complexes in asymmetric catalysis are then explored, considering catalysis via metal binding and catalysis via the ligand sphere. Addition-ally, the potential of using octahedral chiral metal complexes as building units for supramolecular structures and their integration with asymmetric catalysis are discussed, suggesting promising perspectives for broader applications.
Developing asymmetric catalysts derived solely from octahedral centrochirality has garnered significant attention in the scientific community. Chiral-octahedral metal complexes can be classified into stereogenic-only-at-metal complexes and stereogenic-at-metal complexes with chiral ligands. This review introduces the design and syn-thesis of chiral-octahedral iridium and ruthenium complexes, which can be fine-tuned by altering the metal center, ligand combinations, and the chirality or achirality of the ligands. The applications of these complexes in asymmetric catalysis are then explored, considering catalysis via metal binding and catalysis via the ligand sphere. Addition-ally, the potential of using octahedral chiral metal complexes as building units for supramolecular structures and their integration with asymmetric catalysis are discussed, suggesting promising perspectives for broader applications.
2024, 40(11): 2105-2123
doi: 10.11862/CJIC.20240126
Abstract:
Quantum dot materials have excellent optical properties related to size, such as tunable emission wavelength, narrow full width at half maximum, and wide excitation range, and have a wide range of applications. However, currently, mainstream quantum dots generally contain elements such as cadmium and lead, which is not conducive to the development of commercial products. Indium phosphide (InP) quantum dots have no heavy metal toxicity, and their spectral range can cover the entire visible light region. They have luminescence and optoelectronic properties comparable to cadmium‐based quantum dots and are gradually gaining attention. This article reviews the progress of research in the synthesis methods and applications of InP quantum dots in recent years. Firstly, the advantages and disadvantages of InP quantum dot synthesis methods such as hot injection, heating, crystal nucleus growth, and cation exchange are discussed. Then, the current application achievements of InP quantum dots in fields such as illumination display, photovoltaics, photocatalysis, and optical labeling imaging are highlighted. Finally, the challenges and possible solutions for the development of InP quantum dots are proposed from the perspectives of material synthesis and device applications, to promote the research and application of InP quantum dots and provide new ideas for the development of the optoelectronic field.
Quantum dot materials have excellent optical properties related to size, such as tunable emission wavelength, narrow full width at half maximum, and wide excitation range, and have a wide range of applications. However, currently, mainstream quantum dots generally contain elements such as cadmium and lead, which is not conducive to the development of commercial products. Indium phosphide (InP) quantum dots have no heavy metal toxicity, and their spectral range can cover the entire visible light region. They have luminescence and optoelectronic properties comparable to cadmium‐based quantum dots and are gradually gaining attention. This article reviews the progress of research in the synthesis methods and applications of InP quantum dots in recent years. Firstly, the advantages and disadvantages of InP quantum dot synthesis methods such as hot injection, heating, crystal nucleus growth, and cation exchange are discussed. Then, the current application achievements of InP quantum dots in fields such as illumination display, photovoltaics, photocatalysis, and optical labeling imaging are highlighted. Finally, the challenges and possible solutions for the development of InP quantum dots are proposed from the perspectives of material synthesis and device applications, to promote the research and application of InP quantum dots and provide new ideas for the development of the optoelectronic field.
2024, 40(11): 2124-2132
doi: 10.11862/CJIC.20240158
Abstract:
Solvothermal reactions of 3, 5‐dinitrobenzoic acid (3, 5‐HDNBA), 4‐pyrazolecarboxylic acid (4‐H2PyC) or 4‐ethylbenzoic acid (4‐HEBA) with Zn(NO3)2·6H2O and 1, 2, 4, 5‐tetrakis(4‐vinylpyridyl) benzene (tkpvb) gave rise to three kinds of coordination polymers (CPs), [Zn(tkpvb)(3, 5‐DNBA)2]n (CP1), {[Zn(tkpvb)(4‐PyC)]·2H2O]}n (CP2), and {[Zn(tkpvb)0.5(4‐EBA)2]·H2O}n (CP3). CP1 has a 1D zigzag chain structure composed of Zn(Ⅱ), tkpvb, and 4‐EBA ligands. CP2 is a 3D topological structure that can be seen constructed from 2D [Zn(4‐PyC)3]n layers connected by tkpvb ligands. CP3 holds a 4 ‐ connected 3D topological structure, where 1D channels are present. CP1‐CP3 showed a fluorescence emission phenomenon, and they had certain responses to inorganic metal ions. Among them, Fe3+ ions had the greatest impact on the fluorescence intensity of CP1. In addition, after the addition of Fe3+, the fluorescence lifetime and fluorescence quantum yield of CP1 were significantly enhanced compared to CP2 and CP3, with a detection limit of 0.020 μmol·L-1. This may be due to the interaction between Fe3+ and the uncoordinated pyridine groups in CP1.
Solvothermal reactions of 3, 5‐dinitrobenzoic acid (3, 5‐HDNBA), 4‐pyrazolecarboxylic acid (4‐H2PyC) or 4‐ethylbenzoic acid (4‐HEBA) with Zn(NO3)2·6H2O and 1, 2, 4, 5‐tetrakis(4‐vinylpyridyl) benzene (tkpvb) gave rise to three kinds of coordination polymers (CPs), [Zn(tkpvb)(3, 5‐DNBA)2]n (CP1), {[Zn(tkpvb)(4‐PyC)]·2H2O]}n (CP2), and {[Zn(tkpvb)0.5(4‐EBA)2]·H2O}n (CP3). CP1 has a 1D zigzag chain structure composed of Zn(Ⅱ), tkpvb, and 4‐EBA ligands. CP2 is a 3D topological structure that can be seen constructed from 2D [Zn(4‐PyC)3]n layers connected by tkpvb ligands. CP3 holds a 4 ‐ connected 3D topological structure, where 1D channels are present. CP1‐CP3 showed a fluorescence emission phenomenon, and they had certain responses to inorganic metal ions. Among them, Fe3+ ions had the greatest impact on the fluorescence intensity of CP1. In addition, after the addition of Fe3+, the fluorescence lifetime and fluorescence quantum yield of CP1 were significantly enhanced compared to CP2 and CP3, with a detection limit of 0.020 μmol·L-1. This may be due to the interaction between Fe3+ and the uncoordinated pyridine groups in CP1.
2024, 40(11): 2133-2140
doi: 10.11862/CJIC.20240282
Abstract:
The combination of hygroscopic salt with metal-organic framework (MOF) material and in-situ modified moulding method can be used to rapidly prepare hygroscopic salt-loaded CaCl2@MOF-808 composite moulded particles. Based on the high porosity and high specific surface area of MOF-808, CaCl2 could be dispersed in the pore channels of MOF-808, and water molecules were adsorbed under the joint action of the rich pore environment and the hygroscopic salt, which enhances the water harvesting ability of the molded particles under low pressure. Characterization techniques such as X-ray powder diffraction, scanning electron microscopy, N2 adsorption-desorption, and water adsorption tests were used to observe the physical phase and properties of the formed particles. The test results showed that the mechanical strength of CaCl2@MOF-808 molded adsorbent reached 25 N, which meets the compressive level of the application. At a temperature of 25 ℃ and a relative humidity (RH) of 30%, the maximum value of its water adsorption rate was 0.43 g·g-1, which was five times higher than that of the original MOF-808.
The combination of hygroscopic salt with metal-organic framework (MOF) material and in-situ modified moulding method can be used to rapidly prepare hygroscopic salt-loaded CaCl2@MOF-808 composite moulded particles. Based on the high porosity and high specific surface area of MOF-808, CaCl2 could be dispersed in the pore channels of MOF-808, and water molecules were adsorbed under the joint action of the rich pore environment and the hygroscopic salt, which enhances the water harvesting ability of the molded particles under low pressure. Characterization techniques such as X-ray powder diffraction, scanning electron microscopy, N2 adsorption-desorption, and water adsorption tests were used to observe the physical phase and properties of the formed particles. The test results showed that the mechanical strength of CaCl2@MOF-808 molded adsorbent reached 25 N, which meets the compressive level of the application. At a temperature of 25 ℃ and a relative humidity (RH) of 30%, the maximum value of its water adsorption rate was 0.43 g·g-1, which was five times higher than that of the original MOF-808.
2024, 40(11): 2141-2154
doi: 10.11862/CJIC.20240085
Abstract:
Herein, a one-step hydrothermal method was used to synthesize nickel foam (NF) self-supported Co9S8/Ni3S2@NF heterojunction nanorod arrays, which can be used as bifunctional catalysts for urea oxidation reaction (UOR) and hydrogen precipitation reaction (HER). The results of physical phase analysis, morphological characterization, and electrochemical tests showed that the Co9S8/Ni3S2@NF heterojunction hybridized nanorod arrays facilitated the electron transfer through the coupled hetero-interface between Co9S8 and Ni3S2, and improved the charge transfer rate. Meanwhile, the rough surface of the catalyst enabled it to exhibit excellent superhydrophilicity and superhydrophobicity, which facilitated gas transport as well as electrolyte diffusion. The catalyst was able to achieve current densities of 100 and 10 mA·cm-2 at low overpotentials of 120 and 103 mV in UOR and HER, respectively. In addition, using the synthesized Co9S8/Ni3S2@NF electrodes as cathode and anode, the operation of the two-electrode electrolytic cell required only a low voltage of 1.57 V when the current density reached 100 mA·cm-2 and operated stably for 27 h at a current density of 20 mA·cm-2 without significant activity decay.
Herein, a one-step hydrothermal method was used to synthesize nickel foam (NF) self-supported Co9S8/Ni3S2@NF heterojunction nanorod arrays, which can be used as bifunctional catalysts for urea oxidation reaction (UOR) and hydrogen precipitation reaction (HER). The results of physical phase analysis, morphological characterization, and electrochemical tests showed that the Co9S8/Ni3S2@NF heterojunction hybridized nanorod arrays facilitated the electron transfer through the coupled hetero-interface between Co9S8 and Ni3S2, and improved the charge transfer rate. Meanwhile, the rough surface of the catalyst enabled it to exhibit excellent superhydrophilicity and superhydrophobicity, which facilitated gas transport as well as electrolyte diffusion. The catalyst was able to achieve current densities of 100 and 10 mA·cm-2 at low overpotentials of 120 and 103 mV in UOR and HER, respectively. In addition, using the synthesized Co9S8/Ni3S2@NF electrodes as cathode and anode, the operation of the two-electrode electrolytic cell required only a low voltage of 1.57 V when the current density reached 100 mA·cm-2 and operated stably for 27 h at a current density of 20 mA·cm-2 without significant activity decay.
2024, 40(11): 2155-2162
doi: 10.11862/CJIC.20240147
Abstract:
A series of h-MoO3/SiO2 catalysts for the synthesis of pentaerythritol tetra(2-ethylthylhexoate)(POE) from pentaerythritol (PER) and 2-ethylhexanoic acid (i-EHA) were prepared by solid-phase milling and characterized and tested by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, scanning electron microscope (SEM) and transmission electron microscope (TEM). The results showed that (200) crystalline facet-selectively oriented h-MoO3/SiO2 with h-MoO3 loading of 15% is an excellent catalyst for the synthesis of POE. Under the suitable reaction process conditions (ni-EHA/nPER=4.3, mh-MoO3/SiO2/mPER=0.003, T=220 ℃, t=4 h), the esterification rate was up to 90.83% and the selectivity of POE was up to 100%.
A series of h-MoO3/SiO2 catalysts for the synthesis of pentaerythritol tetra(2-ethylthylhexoate)(POE) from pentaerythritol (PER) and 2-ethylhexanoic acid (i-EHA) were prepared by solid-phase milling and characterized and tested by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, scanning electron microscope (SEM) and transmission electron microscope (TEM). The results showed that (200) crystalline facet-selectively oriented h-MoO3/SiO2 with h-MoO3 loading of 15% is an excellent catalyst for the synthesis of POE. Under the suitable reaction process conditions (ni-EHA/nPER=4.3, mh-MoO3/SiO2/mPER=0.003, T=220 ℃, t=4 h), the esterification rate was up to 90.83% and the selectivity of POE was up to 100%.
2024, 40(11): 2163-2174
doi: 10.11862/CJIC.20240204
Abstract:
The relatively cheap nickel vanadate anode material (NVO-NBA) was prepared through an improved co-precipitation method with Ni(NO3)2·6H2O as nickel source, NH4VO3 as vanadium source, and deionized water as a green solvent. The specific surface area and particle dispersion were improved by adjusting the pH value of precipitation with sodium carbonate solution and drying with n-butanol. The effects of the enhanced co-precipitation method on the texture properties of nickel vanadate electrode materials were investigated by testing the microstructure, specific surface area, pore size, and surface element distribution. The results show that the specific surface area, pore size, microstructure, and particle dispersion of the material are significantly affected by the precise adjustment of the pH value of the solution during the precipitation process and the drying method of the subsequent addition of alcohol solvents with smaller surface tension. The typical sample NVO-8-NBA obtained by precipitation at pH=8 and subsequent addition of n-butanol-assisted drying possessed the largest specific surface area (86 m2·g-1), and the material's morphology was spherical nanoparticles with higher dispersion and a smaller diameter. The specific surface area of the vanadate materials obtained by adding alcohol solvents such as ethanol, n-butanol, and n-hexanol for subsequent drying was significantly higher than that of the sample without alcohol treatment, while the samples treated with n-butanol had the best effect, indicating that the alcohol solvent with smaller surface tension can effectively protect the pore system generated by the co-precipitation process and can make the particles disperse more evenly, and the carbon chain length of the alcohol also has a significant effect on its properties. The specific surface area of the sample NVO-8 without alcohol treatment was only 20 m2·g-1, and its morphology was a large block of aggregation. The prepared nickel vanadate material was used as the anode material of the lithium-ion battery. At a current density of 0.3 A·g-1, the first cycle discharge capacity of NVO-8-NBA can reach 1 519 mAh·g-1, while that for NVO-8 was only 536 mAh·g-1. NVO-8-NBA maintained a stable specific capacity of 223 mAh·g-1 after 100 cycles at a current density of 0.3 A·g-1, while that for NVO- 8 was only 45.8 mAh·g-1 and still had a downward trend, indicating the potential advantages of the improved co-precipitation synthesis of vanadate materials in this paper.
The relatively cheap nickel vanadate anode material (NVO-NBA) was prepared through an improved co-precipitation method with Ni(NO3)2·6H2O as nickel source, NH4VO3 as vanadium source, and deionized water as a green solvent. The specific surface area and particle dispersion were improved by adjusting the pH value of precipitation with sodium carbonate solution and drying with n-butanol. The effects of the enhanced co-precipitation method on the texture properties of nickel vanadate electrode materials were investigated by testing the microstructure, specific surface area, pore size, and surface element distribution. The results show that the specific surface area, pore size, microstructure, and particle dispersion of the material are significantly affected by the precise adjustment of the pH value of the solution during the precipitation process and the drying method of the subsequent addition of alcohol solvents with smaller surface tension. The typical sample NVO-8-NBA obtained by precipitation at pH=8 and subsequent addition of n-butanol-assisted drying possessed the largest specific surface area (86 m2·g-1), and the material's morphology was spherical nanoparticles with higher dispersion and a smaller diameter. The specific surface area of the vanadate materials obtained by adding alcohol solvents such as ethanol, n-butanol, and n-hexanol for subsequent drying was significantly higher than that of the sample without alcohol treatment, while the samples treated with n-butanol had the best effect, indicating that the alcohol solvent with smaller surface tension can effectively protect the pore system generated by the co-precipitation process and can make the particles disperse more evenly, and the carbon chain length of the alcohol also has a significant effect on its properties. The specific surface area of the sample NVO-8 without alcohol treatment was only 20 m2·g-1, and its morphology was a large block of aggregation. The prepared nickel vanadate material was used as the anode material of the lithium-ion battery. At a current density of 0.3 A·g-1, the first cycle discharge capacity of NVO-8-NBA can reach 1 519 mAh·g-1, while that for NVO-8 was only 536 mAh·g-1. NVO-8-NBA maintained a stable specific capacity of 223 mAh·g-1 after 100 cycles at a current density of 0.3 A·g-1, while that for NVO- 8 was only 45.8 mAh·g-1 and still had a downward trend, indicating the potential advantages of the improved co-precipitation synthesis of vanadate materials in this paper.
2024, 40(11): 2175-2185
doi: 10.11862/CJIC.20240165
Abstract:
A simple strategy was adopted to prepare single-atom catalysts (SACs) using mesoporous silica KIT- 6 (TOK) without templating agent removal as a carrier and utilizing the confined space between the templating agent and the silica wall. After the Mn-containing precursor was introduced into the confined space of TOK by solid-phase milling, Mn SACs can be rapidly generated during the calcination. Density functional theory calculations and experimental data indicate that the Mn atoms are anchored by Si—OH groups on the carriers and exist as Mn—O—Si. The obtained Mn SACs were applied to the electrocatalytic oxygen evolution reaction, and the experimental results show that the Mn SACs exhibit better catalytic performance than the comparison samples synthesized in a carrier without confined space.
A simple strategy was adopted to prepare single-atom catalysts (SACs) using mesoporous silica KIT- 6 (TOK) without templating agent removal as a carrier and utilizing the confined space between the templating agent and the silica wall. After the Mn-containing precursor was introduced into the confined space of TOK by solid-phase milling, Mn SACs can be rapidly generated during the calcination. Density functional theory calculations and experimental data indicate that the Mn atoms are anchored by Si—OH groups on the carriers and exist as Mn—O—Si. The obtained Mn SACs were applied to the electrocatalytic oxygen evolution reaction, and the experimental results show that the Mn SACs exhibit better catalytic performance than the comparison samples synthesized in a carrier without confined space.
2024, 40(11): 2186-2192
doi: 10.11862/CJIC.20240177
Abstract:
Different solvothermal reactions of ZnC2O4 with oxalic acid (H2ox) and 1, 2, 4-triazole (Htrz) successfully gave a new quaternary (NJTU-Bai83, NJTU-Bai=Nanjing Tech University Bai's group) and a new quinary (NJTU- Bai84) anionic metal-organic frameworks (MOFs), where NJTU-Bai83=(Me2NH2)2[Zn3(trz)2(ox)3]·2H2O and NJTU-Bai84=(Me2NH2)[Zn3(trz)3(ox)2]·H2O, respectively. With the [Zn2(ox)4(trz)2] secondary building unit (SBU) in NJTU- Bai83 replaced by the [Zn3(ox)2(trz)6] and planar [Zn(ox)2(trz)2] ones in NJTU-Bai84, 2D supramolecular building layers (SBLs) are changed from the A-layer and B-layer to another A-layer, while pillars are transformed from the tetrahedral [Zn(ox)2(trz)2] SBU to the irregular tetrahedral [Zn(ox)2(trz)2] and planar [Zn(ox)2(trz)2] SBUs. Thus, cdq-topological quaternary NJTU-Bai83 is tuned to (4, 4, 8)-c new topological quinary NJTU-Bai84. Two MOFs were well characterized by powder X-ray diffraction, thermogravimetric analysis, elemental analysis, etc.
Different solvothermal reactions of ZnC2O4 with oxalic acid (H2ox) and 1, 2, 4-triazole (Htrz) successfully gave a new quaternary (NJTU-Bai83, NJTU-Bai=Nanjing Tech University Bai's group) and a new quinary (NJTU- Bai84) anionic metal-organic frameworks (MOFs), where NJTU-Bai83=(Me2NH2)2[Zn3(trz)2(ox)3]·2H2O and NJTU-Bai84=(Me2NH2)[Zn3(trz)3(ox)2]·H2O, respectively. With the [Zn2(ox)4(trz)2] secondary building unit (SBU) in NJTU- Bai83 replaced by the [Zn3(ox)2(trz)6] and planar [Zn(ox)2(trz)2] ones in NJTU-Bai84, 2D supramolecular building layers (SBLs) are changed from the A-layer and B-layer to another A-layer, while pillars are transformed from the tetrahedral [Zn(ox)2(trz)2] SBU to the irregular tetrahedral [Zn(ox)2(trz)2] and planar [Zn(ox)2(trz)2] SBUs. Thus, cdq-topological quaternary NJTU-Bai83 is tuned to (4, 4, 8)-c new topological quinary NJTU-Bai84. Two MOFs were well characterized by powder X-ray diffraction, thermogravimetric analysis, elemental analysis, etc.
2024, 40(11): 2193-2202
doi: 10.11862/CJIC.20240176
Abstract:
Electro-copolymerized film containing ruthenium complexes as electron-transfer (or redox) mediators and water-oxidation catalysts by an oxidative copolymerization method is presented. The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV. The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s-1 and an initial turnover frequency of 1.01 s-1 in 1 000 s by potential electrolysis at 1.7 V applied bias vs NHE (normal hydrogen electrode). The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.
Electro-copolymerized film containing ruthenium complexes as electron-transfer (or redox) mediators and water-oxidation catalysts by an oxidative copolymerization method is presented. The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV. The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s-1 and an initial turnover frequency of 1.01 s-1 in 1 000 s by potential electrolysis at 1.7 V applied bias vs NHE (normal hydrogen electrode). The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.
2024, 40(11): 2203-2211
doi: 10.11862/CJIC.20240209
Abstract:
By virtue of a 3∶1 complementary coordination strategy, a chiral heteroleptic metal-organic cage that contains divergent functional units, Pd-R(Zn), was precisely constructed via self-assembly of monodentate variational Znsalen ligands RZn and NADH (reduced nicotinamide adenine dinucleotide) mimic modified tridentate ligands with square-planar Pd ions. UV-Vis and luminescence spectra experiments reveal that different anions could selectively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound, by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts. Compared to other anions, the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd-R(Zn), meanwhile, the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease, and the metal-to-ligand induced peak displayed a blue shift effect. Circular dichroism and 1H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.
By virtue of a 3∶1 complementary coordination strategy, a chiral heteroleptic metal-organic cage that contains divergent functional units, Pd-R(Zn), was precisely constructed via self-assembly of monodentate variational Znsalen ligands RZn and NADH (reduced nicotinamide adenine dinucleotide) mimic modified tridentate ligands with square-planar Pd ions. UV-Vis and luminescence spectra experiments reveal that different anions could selectively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound, by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts. Compared to other anions, the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd-R(Zn), meanwhile, the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease, and the metal-to-ligand induced peak displayed a blue shift effect. Circular dichroism and 1H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.
2024, 40(11): 2212-2220
doi: 10.11862/CJIC.20240131
Abstract:
This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives: bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether (L1), bis-[4-(2-pyridylmethyleneamino)-phenyl]ether (L2), and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane (L3). Single-crystal X-ray diffraction analysis reveals that the complexes [Co2(L1)3](ClO4)4·2CH3CN (1), [Co2(L2)3](ClO4)4·2CH3OH (2), and [Co2(L3)3](ClO4)4·2CH3OH (3) all exhibit a dinuclear structure. Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K, with the average Co—N bond length increasing from 0.213 9(3) to 0.215 3(3) nm. Meanwhile, the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2. Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.
This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives: bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether (L1), bis-[4-(2-pyridylmethyleneamino)-phenyl]ether (L2), and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane (L3). Single-crystal X-ray diffraction analysis reveals that the complexes [Co2(L1)3](ClO4)4·2CH3CN (1), [Co2(L2)3](ClO4)4·2CH3OH (2), and [Co2(L3)3](ClO4)4·2CH3OH (3) all exhibit a dinuclear structure. Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K, with the average Co—N bond length increasing from 0.213 9(3) to 0.215 3(3) nm. Meanwhile, the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2. Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.
2024, 40(11): 2221-2231
doi: 10.11862/CJIC.20240234
Abstract:
Under solvothermal conditions, six new coordination polymers (CPs) [Mn(L) (phen) (H2O)]n (1), [Co(L) (phen)(H2O)]n (2), [Cu(L)(phen)(H2O)]n (3), [Zn2(L)2(phen)2(H2O)]n (4), [Zn(L)(phen)]n (5), and [Cd(L)(phen)2]n (6) were synthesized by reactions of dicarboxylate ligand 2, 2'-(1, 2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid (H2L) and 1, 10-phenanthroline (phen) with the corresponding metal salts. Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, IR, thermogravimetric analysis, and powder X-ray diffraction. The structures of 1-6 are 1D chains, which are further connected by hydrogen bonding interactions to form 3D supramolecular structures. Among them, 1 and 2 are isomorphic with L2- of syn-conformation, while L2- shows anti-conformation in 3-6. In addition, the solid-state photoluminescence property of 4-6 was investigated.
Under solvothermal conditions, six new coordination polymers (CPs) [Mn(L) (phen) (H2O)]n (1), [Co(L) (phen)(H2O)]n (2), [Cu(L)(phen)(H2O)]n (3), [Zn2(L)2(phen)2(H2O)]n (4), [Zn(L)(phen)]n (5), and [Cd(L)(phen)2]n (6) were synthesized by reactions of dicarboxylate ligand 2, 2'-(1, 2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid (H2L) and 1, 10-phenanthroline (phen) with the corresponding metal salts. Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, IR, thermogravimetric analysis, and powder X-ray diffraction. The structures of 1-6 are 1D chains, which are further connected by hydrogen bonding interactions to form 3D supramolecular structures. Among them, 1 and 2 are isomorphic with L2- of syn-conformation, while L2- shows anti-conformation in 3-6. In addition, the solid-state photoluminescence property of 4-6 was investigated.
2024, 40(11): 2232-2240
doi: 10.11862/CJIC.20240236
Abstract:
TiO2 nanobelts and Co3O4/TiO2 catalytic materials were prepared using the hydrothermal method. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray electron spectroscopy, and fluorescence spectroscopy. At room temperature, with a relative humidity of 50.0%, the total gas flow rate of 1.0 L·min-1, the space velocity of 1.05×104 h-1, and toluene volume concentration of 25.0 μL·L-1, two 6 W vacuum ultraviolet lamps were used as light sources to catalyze, degrade, and mineralize toluene. The results show that the prepared catalyst is in the shape of nano-ribbons. The loading of Co3O4 inhibits the recombination of photogenerated electrons and holes and can effectively improve the catalytic performance. The Co3O4/TiO2 with a load of 6.0% Co3O4 has the best catalytic effect. When N2 was used as a carrier gas, the degradation rate of toluene was only 34.7%. The toluene degradation is mainly due to the photolysis of vacuum ultraviolet light. When air was used as a carrier gas, O3 was produced. The Co3O4/TiO2 with a load of 6.0% and vacuum ultraviolet synergistically promote toluene degradation. The highest degradation rate of toluene was 91.7% and the mineralization rate was 74.6%. The degradation rate of toluene was 2.6 times that of nitrogen as a carrier gas.
TiO2 nanobelts and Co3O4/TiO2 catalytic materials were prepared using the hydrothermal method. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray electron spectroscopy, and fluorescence spectroscopy. At room temperature, with a relative humidity of 50.0%, the total gas flow rate of 1.0 L·min-1, the space velocity of 1.05×104 h-1, and toluene volume concentration of 25.0 μL·L-1, two 6 W vacuum ultraviolet lamps were used as light sources to catalyze, degrade, and mineralize toluene. The results show that the prepared catalyst is in the shape of nano-ribbons. The loading of Co3O4 inhibits the recombination of photogenerated electrons and holes and can effectively improve the catalytic performance. The Co3O4/TiO2 with a load of 6.0% Co3O4 has the best catalytic effect. When N2 was used as a carrier gas, the degradation rate of toluene was only 34.7%. The toluene degradation is mainly due to the photolysis of vacuum ultraviolet light. When air was used as a carrier gas, O3 was produced. The Co3O4/TiO2 with a load of 6.0% and vacuum ultraviolet synergistically promote toluene degradation. The highest degradation rate of toluene was 91.7% and the mineralization rate was 74.6%. The degradation rate of toluene was 2.6 times that of nitrogen as a carrier gas.
2024, 40(11): 2241-2249
doi: 10.11862/CJIC.20240219
Abstract:
A simple two-step hydrothermal method synthesized four different CdS/Fe3O4 photocatalysts with varying ratios of mass of CdS to Fe3O4. The composition and morphology of the prepared samples were investigated using X-ray diffraction (XRD), Raman spectrum, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Solid UV reflectance spectra testing found that CdS/Fe3O4 nanocomposites had good light absorption throughout the spectral range, promoting their photocatalytic properties. Under visible light irradiation, CdS/Fe3O4 (2:5) with a mass ratio of 2:5 exhibited excellent photocatalytic performance, with a degradation rate of 98.8% for rhodamine B. Furthermore, after five cycles of photocatalytic degradation reaction, the rhodamine B degradation rate remained at 96.2%, indicating that the photocatalysts have good photocatalytic stability.
A simple two-step hydrothermal method synthesized four different CdS/Fe3O4 photocatalysts with varying ratios of mass of CdS to Fe3O4. The composition and morphology of the prepared samples were investigated using X-ray diffraction (XRD), Raman spectrum, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Solid UV reflectance spectra testing found that CdS/Fe3O4 nanocomposites had good light absorption throughout the spectral range, promoting their photocatalytic properties. Under visible light irradiation, CdS/Fe3O4 (2:5) with a mass ratio of 2:5 exhibited excellent photocatalytic performance, with a degradation rate of 98.8% for rhodamine B. Furthermore, after five cycles of photocatalytic degradation reaction, the rhodamine B degradation rate remained at 96.2%, indicating that the photocatalysts have good photocatalytic stability.
2024, 40(11): 2250-2258
doi: 10.11862/CJIC.20240104
Abstract:
The electronic structure, magnetic, and optical properties of two-dimensional(2D) GaSe doped with rare earth elements X (X=Sc, Y, La, Ce, Eu) were calculated using the first-principles plane wave method based on density functional theory. The results show that intrinsic 2D GaSe is a p-type nonmagnetic semiconductor with an indirect bandgap of 2.661 1 eV. The spin-up and spin-down channels of Sc-, Y-, and La-doped 2D GaSe are symmetric, they are non-magnetic semiconductors. The magnetic moments of Ce- and Eu- doped 2D GaSe are 0.908μB and 7.163μB, which are magnetic semiconductors. Impurity energy levels appear in both spin-up and spin-down channels of Eu-doped 2D GaSe, which enhances the probability of electron transition. Compared with intrinsic 2D GaSe, the static dielectric constant of the doped 2D GaSe increases, and the polarization ability is strengthened. The absorption spectrum of the doped 2D GaSe shifts in the low-energy direction, and the red-shift phenomenon occurs, which extends the absorption spectral range. The optical reflection coefficient of the doped 2D GaSe is improved in the low energy region, and the improvement of Eu-doped 2D GaSe is the most obvious.
The electronic structure, magnetic, and optical properties of two-dimensional(2D) GaSe doped with rare earth elements X (X=Sc, Y, La, Ce, Eu) were calculated using the first-principles plane wave method based on density functional theory. The results show that intrinsic 2D GaSe is a p-type nonmagnetic semiconductor with an indirect bandgap of 2.661 1 eV. The spin-up and spin-down channels of Sc-, Y-, and La-doped 2D GaSe are symmetric, they are non-magnetic semiconductors. The magnetic moments of Ce- and Eu- doped 2D GaSe are 0.908μB and 7.163μB, which are magnetic semiconductors. Impurity energy levels appear in both spin-up and spin-down channels of Eu-doped 2D GaSe, which enhances the probability of electron transition. Compared with intrinsic 2D GaSe, the static dielectric constant of the doped 2D GaSe increases, and the polarization ability is strengthened. The absorption spectrum of the doped 2D GaSe shifts in the low-energy direction, and the red-shift phenomenon occurs, which extends the absorption spectral range. The optical reflection coefficient of the doped 2D GaSe is improved in the low energy region, and the improvement of Eu-doped 2D GaSe is the most obvious.
