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2025 Volume 41 Issue 8
2025, 41(8): 1465-1482
doi: 10.11862/CJIC.20240430
Abstract:
Two-dimensional transition metal carbon/nitrides or carbonitrides (MXenes) have shown wide application potential in many fields such as electricity, optics, catalysis, and environment due to their unique physical and chemical properties. These unique properties lay a solid foundation for the innovative application of MXene materials in various fields. In recent years, the interface control strategy of 2D MXenes nanomaterials has received extensive attention. Researchers have conducted in-depth modification studies on MXenes using various methods, including surface group control, surface adsorption, surface compounding, and crosslinking. This paper reviews the interface regulation strategies of MXenes and their applications in energy storage, catalysis, photoelectric detection, electromagnetic shielding, pollutant adsorption, and biomedicine.
Two-dimensional transition metal carbon/nitrides or carbonitrides (MXenes) have shown wide application potential in many fields such as electricity, optics, catalysis, and environment due to their unique physical and chemical properties. These unique properties lay a solid foundation for the innovative application of MXene materials in various fields. In recent years, the interface control strategy of 2D MXenes nanomaterials has received extensive attention. Researchers have conducted in-depth modification studies on MXenes using various methods, including surface group control, surface adsorption, surface compounding, and crosslinking. This paper reviews the interface regulation strategies of MXenes and their applications in energy storage, catalysis, photoelectric detection, electromagnetic shielding, pollutant adsorption, and biomedicine.
2025, 41(8): 1483-1494
doi: 10.11862/CJIC.20250031
Abstract:
A novel cyclometalated iridium complex, CycIr-DHA, was successfully synthesized by incorporating the natural product dehydroabietic acid (DHA) into the cyclometalated iridium framework, and the ligand and complex were characterized by 1H NMR. The complex showed strong antitumor effects on various cancer cells, especially michigan cancer foundation-7 (MCF-7) cells, with a half maximal inhibitory concentration (IC50) of 2.5 μmol·L-1, superior to that of the traditional chemotherapeutic drug cisplatin. Experimental results indicated that CycIr-DHA primarily accumulated in the mitochondria of MCF-7, leading to a significant increase in intracellular reactive oxy- gen species levels and subsequent mitochondrial dysfunction. Furthermore, the complex modulated the expression of apoptosis - related proteins (Bax and Bcl - 2), promoting apoptosis, and upregulates LC3 - Ⅱ protein, inducing autophagy. In a 3D cell spheroid model, CycIr-DHA significantly inhibited the growth of the spheroids.
A novel cyclometalated iridium complex, CycIr-DHA, was successfully synthesized by incorporating the natural product dehydroabietic acid (DHA) into the cyclometalated iridium framework, and the ligand and complex were characterized by 1H NMR. The complex showed strong antitumor effects on various cancer cells, especially michigan cancer foundation-7 (MCF-7) cells, with a half maximal inhibitory concentration (IC50) of 2.5 μmol·L-1, superior to that of the traditional chemotherapeutic drug cisplatin. Experimental results indicated that CycIr-DHA primarily accumulated in the mitochondria of MCF-7, leading to a significant increase in intracellular reactive oxy- gen species levels and subsequent mitochondrial dysfunction. Furthermore, the complex modulated the expression of apoptosis - related proteins (Bax and Bcl - 2), promoting apoptosis, and upregulates LC3 - Ⅱ protein, inducing autophagy. In a 3D cell spheroid model, CycIr-DHA significantly inhibited the growth of the spheroids.
2025, 41(8): 1495-1504
doi: 10.11862/CJIC.20250144
Abstract:
This article reports the rational design of a chemodynamic prodrug, FcNH-SeNBD. The prodrug was constructed by coupling ferrocene with benzoselenadiazole (SeNBD). By taking advantage of the elevated level of H2O2 in cancer cells, FcNH-SeNBD could generate cytotoxic ·OH radicals to induce cancer cell apoptosis and remain non-toxic in normal cells. In the meantime, the oxidation of ferrocene may interrupt its photo-induced electron transfer to SeNBD and facilitate the fluorescence recovery, thereby enabling FcNH-SeNBD for cancer cell imaging. FcNH-SeNBD was cytotoxic against liver cancer cell line HepG2 [IC50=(7.95±0.98) μg·mL-1] and colon cancer cell line HCT116 [IC50=(15.74±1.5) μg·mL-1], while displayed minimum toxicity to normal epithelial colonic cell line NCM- 460 (IC50>100 μg·mL-1), demonstrating its selective toxicity to cancer cell line. Mechanistic investigations revealed that FcNH-SeNBD was able to induce cancer cell apoptosis through caspase-3-dependent pathways. Moreover, a cell imaging study confirmed the strong red fluorescence signal of FcNH-SeNBD upon internalization and subsequent activation in tumor cells.
This article reports the rational design of a chemodynamic prodrug, FcNH-SeNBD. The prodrug was constructed by coupling ferrocene with benzoselenadiazole (SeNBD). By taking advantage of the elevated level of H2O2 in cancer cells, FcNH-SeNBD could generate cytotoxic ·OH radicals to induce cancer cell apoptosis and remain non-toxic in normal cells. In the meantime, the oxidation of ferrocene may interrupt its photo-induced electron transfer to SeNBD and facilitate the fluorescence recovery, thereby enabling FcNH-SeNBD for cancer cell imaging. FcNH-SeNBD was cytotoxic against liver cancer cell line HepG2 [IC50=(7.95±0.98) μg·mL-1] and colon cancer cell line HCT116 [IC50=(15.74±1.5) μg·mL-1], while displayed minimum toxicity to normal epithelial colonic cell line NCM- 460 (IC50>100 μg·mL-1), demonstrating its selective toxicity to cancer cell line. Mechanistic investigations revealed that FcNH-SeNBD was able to induce cancer cell apoptosis through caspase-3-dependent pathways. Moreover, a cell imaging study confirmed the strong red fluorescence signal of FcNH-SeNBD upon internalization and subsequent activation in tumor cells.
2025, 41(8): 1505-1512
doi: 10.11862/CJIC.20250125
Abstract:
The cluster precursor [Ag9(Tab) 8(MeCN)8]2(PF6)18·4MeCN (Ag18, Tab=4-(trimethylammonio)benzenethio- late), MeCN=acetonitrile) was subjected to solid-state grinding reactions with two phosphine ligands, triphenylphos- phine (L1) and diphenyl- 2-pyridylphosphine (L2), respectively. The obtained solid powders were dissolved in DMF/ EtOH solvents, followed by centrifugal separation. Two silver thiolate clusters protected by phosphine ligands were obtained from the supernatant through Et2O diffusion crystallization: [Ag7(Tab)6(L1)6Cl] (PF6)6·8DMF (1) and [Ag17(Tab)20(L2) 2](PF 6)17·32DMF (2). Both compounds were thoroughly characterized via single-crystal X-ray diffrac- tion, powder X -ray diffraction, infrared spectroscopy, ultraviolet- visible spectroscopy, thermogravimetric, and ele- mental analysis. Single-crystal X-ray diffraction analysis revealed that both clusters are stabilized by a combination of phosphine and Tab ligands, with the diphenyl-2-pyridylphosphine ligand in 2 exhibiting simultaneous coordina- tion through both phosphorus and nitrogen atoms. Z-scan measurements demonstrated that both compounds in solu- tion exhibit notable third-order nonlinear optical responses.
The cluster precursor [Ag9(Tab) 8(MeCN)8]2(PF6)18·4MeCN (Ag18, Tab=4-(trimethylammonio)benzenethio- late), MeCN=acetonitrile) was subjected to solid-state grinding reactions with two phosphine ligands, triphenylphos- phine (L1) and diphenyl- 2-pyridylphosphine (L2), respectively. The obtained solid powders were dissolved in DMF/ EtOH solvents, followed by centrifugal separation. Two silver thiolate clusters protected by phosphine ligands were obtained from the supernatant through Et2O diffusion crystallization: [Ag7(Tab)6(L1)6Cl] (PF6)6·8DMF (1) and [Ag17(Tab)20(L2) 2](PF 6)17·32DMF (2). Both compounds were thoroughly characterized via single-crystal X-ray diffrac- tion, powder X -ray diffraction, infrared spectroscopy, ultraviolet- visible spectroscopy, thermogravimetric, and ele- mental analysis. Single-crystal X-ray diffraction analysis revealed that both clusters are stabilized by a combination of phosphine and Tab ligands, with the diphenyl-2-pyridylphosphine ligand in 2 exhibiting simultaneous coordina- tion through both phosphorus and nitrogen atoms. Z-scan measurements demonstrated that both compounds in solu- tion exhibit notable third-order nonlinear optical responses.
2025, 41(8): 1513-1522
doi: 10.11862/CJIC.20250113
Abstract:
The phosphine-anthracene ligand 1, 8-bis(diphenylphosphine) anthracene (Hbdpa) and its complexes[Au(Hbdpa)2]PF6 (1) and [Ir(tpy)(bdpa)](PF6)2 (2) were synthesized, where tpy=2, 2′∶6′, 2″-tripyridine. Upon light irradiation, these compounds underwent photoreaction, yielding Hbdpa-2O, [Au(Hbdpa-O)2]PF6 (1-O) and [Ir(tpy)(bdpa-OH)](PF6)2 (2-OH). NMR, mass spectrometry, and X-ray crystallography characterized the structures of these compounds. We discussed the photoreaction characteristics of compounds Hbdpa, 1, and 2, as well as the associated luminescence modulation. We found that the coordination with Au(Ⅰ) or Ir(Ⅲ) enhanced the photoreaction activity of the ligand Hbdpa. Moreover, complex 2 is the first Ir(Ⅲ) complex in which an anthracene unit participates in coordination and exhibits a light-induced dearomatization reaction, leading to the formation of complex 2-OH.
The phosphine-anthracene ligand 1, 8-bis(diphenylphosphine) anthracene (Hbdpa) and its complexes[Au(Hbdpa)2]PF6 (1) and [Ir(tpy)(bdpa)](PF6)2 (2) were synthesized, where tpy=2, 2′∶6′, 2″-tripyridine. Upon light irradiation, these compounds underwent photoreaction, yielding Hbdpa-2O, [Au(Hbdpa-O)2]PF6 (1-O) and [Ir(tpy)(bdpa-OH)](PF6)2 (2-OH). NMR, mass spectrometry, and X-ray crystallography characterized the structures of these compounds. We discussed the photoreaction characteristics of compounds Hbdpa, 1, and 2, as well as the associated luminescence modulation. We found that the coordination with Au(Ⅰ) or Ir(Ⅲ) enhanced the photoreaction activity of the ligand Hbdpa. Moreover, complex 2 is the first Ir(Ⅲ) complex in which an anthracene unit participates in coordination and exhibits a light-induced dearomatization reaction, leading to the formation of complex 2-OH.
2025, 41(8): 1523-1532
doi: 10.11862/CJIC.20250073
Abstract:
Two metal complexes [In(HL)(NO3)3] (1) and [Dy(L)(CH3OH)0.89(H2O)1.11(NO3)2]·0.11H2O (2) were synthesized with N′-[(1E)-pyridine-2-methylene]pyridine-4-carbon hydrazide (HL) ligand and indium /dysprosium ions. The single-crystal X-ray diffraction results show that complexes 1 and 2 have a zero-dimensional mononuclear structure formed by one ligand connecting one metal ion. Powder X-ray diffraction shows that the sample purity ofcomplexes 1 and 2 is high, and thermogravimetric analysis shows that both complexes have good thermal stability. The in vitro antiproliferative activity study shows that complex 1 has better antitumor activity than cisplatin against human hepatocellular carcinoma cell line SMMC-7721, human breast cancer cell line MDA-MB-231, and human non-small cell lung cancer cell line A549; complex 2 has better anti-tumor activity than cisplatin against SMMC-7721 and A549 cells. In comparison, the toxicity of complexes 1 and 2 to normal cells (HK-2) is lower than that of cisplatin. The wound healing experiment shows that complexes 1 and 2 can inhibit the migration ability of A549 cells in a concentration-dependent manner. In addition, complex 2 has a significant antibacterial effect on Escherichia coli, with an inhibition zone diameter of 22 mm.
Two metal complexes [In(HL)(NO3)3] (1) and [Dy(L)(CH3OH)0.89(H2O)1.11(NO3)2]·0.11H2O (2) were synthesized with N′-[(1E)-pyridine-2-methylene]pyridine-4-carbon hydrazide (HL) ligand and indium /dysprosium ions. The single-crystal X-ray diffraction results show that complexes 1 and 2 have a zero-dimensional mononuclear structure formed by one ligand connecting one metal ion. Powder X-ray diffraction shows that the sample purity ofcomplexes 1 and 2 is high, and thermogravimetric analysis shows that both complexes have good thermal stability. The in vitro antiproliferative activity study shows that complex 1 has better antitumor activity than cisplatin against human hepatocellular carcinoma cell line SMMC-7721, human breast cancer cell line MDA-MB-231, and human non-small cell lung cancer cell line A549; complex 2 has better anti-tumor activity than cisplatin against SMMC-7721 and A549 cells. In comparison, the toxicity of complexes 1 and 2 to normal cells (HK-2) is lower than that of cisplatin. The wound healing experiment shows that complexes 1 and 2 can inhibit the migration ability of A549 cells in a concentration-dependent manner. In addition, complex 2 has a significant antibacterial effect on Escherichia coli, with an inhibition zone diameter of 22 mm.
2025, 41(8): 1533-1544
doi: 10.11862/CJIC.20250063
Abstract:
Four binary Li2O-GeO2 crystals, Li4GeO4, Li6Ge2O7, Li2GeO3, and Li2Ge2O5, were synthesized through solid-state sintering. In situ high-temperature Raman spectroscopy, combined with theoretical calculations, was employed to qualitatively and quantitatively analyze the structure evolution from the crystalline to the molten state, as well as the melt microstructure. The study reveals that the melts of Li4GeO4, Li6Ge2O7, and Li2GeO3 are composed of [GeO4]4-, [Ge2O7]6-, and [GeO3]2- units, respectively, along with Li+ ions. In contrast, Li2Ge2O5 crystal undergoes a gradual transition from a three-dimensional network structure formed by [GeO4]4- tetrahedra to smaller [Ge3O9]6- three-membered rings as the temperature increases towards the melting point. The microstructure units and a series of model clusters have been designed, optimized, and calculated by quantum chemistry ab initio calculations. The computational simulation, in conjunction with the experiments, presents a novel method for correcting the experimental Raman spectra of the melts. By introducing the concept of delicate structure and employing Gaussian functions to deconvolute the stretching vibration band of non-bridging oxygen in [GeO4]4- tetrahedra within Raman spectra, we quantitatively determined the distribution of structure units (Qi, where i denotes the number of bridging oxygens in each [GeO4]4- tetrahedron, i=0-4) for these four crystals in their molten state.
Four binary Li2O-GeO2 crystals, Li4GeO4, Li6Ge2O7, Li2GeO3, and Li2Ge2O5, were synthesized through solid-state sintering. In situ high-temperature Raman spectroscopy, combined with theoretical calculations, was employed to qualitatively and quantitatively analyze the structure evolution from the crystalline to the molten state, as well as the melt microstructure. The study reveals that the melts of Li4GeO4, Li6Ge2O7, and Li2GeO3 are composed of [GeO4]4-, [Ge2O7]6-, and [GeO3]2- units, respectively, along with Li+ ions. In contrast, Li2Ge2O5 crystal undergoes a gradual transition from a three-dimensional network structure formed by [GeO4]4- tetrahedra to smaller [Ge3O9]6- three-membered rings as the temperature increases towards the melting point. The microstructure units and a series of model clusters have been designed, optimized, and calculated by quantum chemistry ab initio calculations. The computational simulation, in conjunction with the experiments, presents a novel method for correcting the experimental Raman spectra of the melts. By introducing the concept of delicate structure and employing Gaussian functions to deconvolute the stretching vibration band of non-bridging oxygen in [GeO4]4- tetrahedra within Raman spectra, we quantitatively determined the distribution of structure units (Qi, where i denotes the number of bridging oxygens in each [GeO4]4- tetrahedron, i=0-4) for these four crystals in their molten state.
2025, 41(8): 1545-1554
doi: 10.11862/CJIC.20250046
Abstract:
This work focuses on fabricating multifunctional electrode materials and reaction systems for the highly efficient 5-hydroxymethylfurfural (HMF) oxidation under mild conditions. Bimetallic metal-organic framework materials (BMOF) and their derivatives were synthesized for the electrocatalytic oxidation of HMF at low voltage. Bimetallic CoNi-MOF-74 was synthesized using the solvothermal method. Two methods were used to transform the MOF material into electrode materials. Firstly, the CoNi alloy particles stabilized by porous carbon matrix (denoted asCoNi@C) were obtained by pyrolysis of CoNi-MOF-74. Secondly, the CoNi(OH)2 was in situ and obtained through the hydrolysis of CoNi-MOF-74 under an alkaline electrolyte during electrocatalysis. Interestingly, the optimal Co1Ni3@C derived from Co1Ni3-MOF-74 via pyrolysis at 800 ℃ exhibited excellent catalytic activity and high 2, 5- furandicarboxylic acid (FDCA) selectivity (87.26%) for HMF electrooxidation at low potential. The Co0.5Ni0.5(OH)2 generated in situ during electrolysis of Co1Ni1-MOF-74 displayed high selectivity (88.59%) for the intermediate product of 5-(hydroxymethyl) furano-2-carboxylic acid (HMFCA). The superior performance is mainly attributed to the pore structure of the catalytic materials, the synergistic effect between Co and Ni, and the good electrical conductivity of graphitic carbon.
This work focuses on fabricating multifunctional electrode materials and reaction systems for the highly efficient 5-hydroxymethylfurfural (HMF) oxidation under mild conditions. Bimetallic metal-organic framework materials (BMOF) and their derivatives were synthesized for the electrocatalytic oxidation of HMF at low voltage. Bimetallic CoNi-MOF-74 was synthesized using the solvothermal method. Two methods were used to transform the MOF material into electrode materials. Firstly, the CoNi alloy particles stabilized by porous carbon matrix (denoted asCoNi@C) were obtained by pyrolysis of CoNi-MOF-74. Secondly, the CoNi(OH)2 was in situ and obtained through the hydrolysis of CoNi-MOF-74 under an alkaline electrolyte during electrocatalysis. Interestingly, the optimal Co1Ni3@C derived from Co1Ni3-MOF-74 via pyrolysis at 800 ℃ exhibited excellent catalytic activity and high 2, 5- furandicarboxylic acid (FDCA) selectivity (87.26%) for HMF electrooxidation at low potential. The Co0.5Ni0.5(OH)2 generated in situ during electrolysis of Co1Ni1-MOF-74 displayed high selectivity (88.59%) for the intermediate product of 5-(hydroxymethyl) furano-2-carboxylic acid (HMFCA). The superior performance is mainly attributed to the pore structure of the catalytic materials, the synergistic effect between Co and Ni, and the good electrical conductivity of graphitic carbon.
2025, 41(8): 1555-1564
doi: 10.11862/CJIC.20250040
Abstract:
A one-step activation-carbonization method was adopted to prepare waste cotton fabric-based carbon wave-absorption materials (CCF) with a porous structure using waste cotton fabrics as raw materials and ZnCl2 as the activation agent. The impact of different ZnCl2 mass fraction on the wave absorption performance of CCF was explored. The results showed that ZnCl2 could effectively enrich the pore structure of CCF and enhance its wave-absorption property. The specific surface area of CCF-10 prepared at a carbonization temperature of 700 ℃ (under N2 atmosphere) and a ZnCl2 mass concentration of 10% was as high as 1 310 m2·g-1, and its minimum reflection loss at a thickness of 2.0 mm reached -35.02 dB with an effective absorption bandwidth of 5.6 GHz.
A one-step activation-carbonization method was adopted to prepare waste cotton fabric-based carbon wave-absorption materials (CCF) with a porous structure using waste cotton fabrics as raw materials and ZnCl2 as the activation agent. The impact of different ZnCl2 mass fraction on the wave absorption performance of CCF was explored. The results showed that ZnCl2 could effectively enrich the pore structure of CCF and enhance its wave-absorption property. The specific surface area of CCF-10 prepared at a carbonization temperature of 700 ℃ (under N2 atmosphere) and a ZnCl2 mass concentration of 10% was as high as 1 310 m2·g-1, and its minimum reflection loss at a thickness of 2.0 mm reached -35.02 dB with an effective absorption bandwidth of 5.6 GHz.
2025, 41(8): 1565-1573
doi: 10.11862/CJIC.20250054
Abstract:
MoO3 nanosheets were composited with TEMPO-oxidized cellulose nanofibers (TEMPO-CNF), and the mixture was subsequently subjected to a high-temperature carbonization process to prepare a MoO3/T-CNF carbonized composite aerogel material, where T-CNF refers to the porous carbonaceous material obtained through carbonization of TEMPO-CNT. The MoO3/T-CNF material exhibited high electrical conductivity, a well-developed porous structure, and a large specific surface area. When employed as a cathode in lithium-sulfur batteries, it effectively adsorbs polysulfides, suppresses the shuttle effect, and mitigates volume expansion during charge/discharge cycles. Specifically, the optimal sample, MoO3/T-CNF-3, delivered a maximum discharge specific capacity of 1 721.8 mAh· g-1 at 0.1C. Furthermore, after 200 cycles, it maintained a high capacity retention rate of 84.8% and a Coulombic efficiency of 99.6%.
MoO3 nanosheets were composited with TEMPO-oxidized cellulose nanofibers (TEMPO-CNF), and the mixture was subsequently subjected to a high-temperature carbonization process to prepare a MoO3/T-CNF carbonized composite aerogel material, where T-CNF refers to the porous carbonaceous material obtained through carbonization of TEMPO-CNT. The MoO3/T-CNF material exhibited high electrical conductivity, a well-developed porous structure, and a large specific surface area. When employed as a cathode in lithium-sulfur batteries, it effectively adsorbs polysulfides, suppresses the shuttle effect, and mitigates volume expansion during charge/discharge cycles. Specifically, the optimal sample, MoO3/T-CNF-3, delivered a maximum discharge specific capacity of 1 721.8 mAh· g-1 at 0.1C. Furthermore, after 200 cycles, it maintained a high capacity retention rate of 84.8% and a Coulombic efficiency of 99.6%.
2025, 41(8): 1574-1588
doi: 10.11862/CJIC.20250032
Abstract:
Based on the study of the characteristics and mechanism of ammonia nitrogen (NH4+) adsorption by biogas residue biochar, we focused on the thermal regeneration of saturated biogas residue biochar, and investigated the influence mechanism of thermal regeneration parameters (regeneration temperature, regeneration time, heating rate, protective gas, and gas flow rate) on the adsorption performance of biochar. The adsorption capacity of NH4+ by biogas residue biochar could reach 19.12 mg·g-1, which was in line with the Langmuir model. The adsorption mechanism was mainly surface coordination and ion exchange reaction. Optimal hot regeneration parameters were as fllowed: the temprepure was 200 ℃, the protective gas was N2, the flow rate was 0.5 L·min-1, and the regeneration was carried out at a heating rate of 5 ℃ ·min-1 for 1 h. The initial adsorption and regeneration rate was 99.59%. After 10 adsorption-regeneration cycles, the adsorption and regeneration rate still reached 89.55%, and the weight loss rate was less than 5%. Characterization was carried out through various technical means such as thermogravi-metric infrared spectroscopy (TG-IR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), specific surface area and porosity analysis, and scanning electron microscopy (SEM). The results showed that multiple cycles of thermal regeneration could destroy the oxygen-containing functional groups such as C=O, —OH, and —COOH on the surface of saturated biochar. Meanwhile, some adsorption sites were permanently occupied, resulting in a gradual decrease in the adsorption regeneration rate. Hot regeneration could achieve the thermal desorption of the vast majority of ammonia nitrogen in saturated biochar, effectively restoring the pore structure and adsorption sites of oxygen-containing functional groups on the surface of biochar.
Based on the study of the characteristics and mechanism of ammonia nitrogen (NH4+) adsorption by biogas residue biochar, we focused on the thermal regeneration of saturated biogas residue biochar, and investigated the influence mechanism of thermal regeneration parameters (regeneration temperature, regeneration time, heating rate, protective gas, and gas flow rate) on the adsorption performance of biochar. The adsorption capacity of NH4+ by biogas residue biochar could reach 19.12 mg·g-1, which was in line with the Langmuir model. The adsorption mechanism was mainly surface coordination and ion exchange reaction. Optimal hot regeneration parameters were as fllowed: the temprepure was 200 ℃, the protective gas was N2, the flow rate was 0.5 L·min-1, and the regeneration was carried out at a heating rate of 5 ℃ ·min-1 for 1 h. The initial adsorption and regeneration rate was 99.59%. After 10 adsorption-regeneration cycles, the adsorption and regeneration rate still reached 89.55%, and the weight loss rate was less than 5%. Characterization was carried out through various technical means such as thermogravi-metric infrared spectroscopy (TG-IR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), specific surface area and porosity analysis, and scanning electron microscopy (SEM). The results showed that multiple cycles of thermal regeneration could destroy the oxygen-containing functional groups such as C=O, —OH, and —COOH on the surface of saturated biochar. Meanwhile, some adsorption sites were permanently occupied, resulting in a gradual decrease in the adsorption regeneration rate. Hot regeneration could achieve the thermal desorption of the vast majority of ammonia nitrogen in saturated biochar, effectively restoring the pore structure and adsorption sites of oxygen-containing functional groups on the surface of biochar.
2025, 41(8): 1589-1600
doi: 10.11862/CJIC.20250011
Abstract:
Flower-like Fe-doped ZnO (ZnFeO) microspheres were synthesized via a hydrothermal method, and Mn-doped carbon quantum dots (Mn-CQDs) were uniformly loaded onto the surface of ZnFeO through physical deposition, successfully constructing Mn-CQDs/ZnFeO heterojunction composites. The relationship between the structure and photocatalytic performance of Mn-CQDs/ZnFeO was investigated using X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet visible diffuse reflection spectroscopy (UV-Vis DRS), and N2 adsorption-desorption analysis. The results showed that Mn doping significantly enhanced the light absorption range and photoluminescence (PL) stability of CQDs. The synergistic interaction between Mn-doped CQDs and Fe-doped ZnO extended the visible-light absorption edge of Mn-CQDs/ZnFeO, improved absorption intensity, and promoted the separation of photogenerated electron (e-)-hole (h+) pairs between the interfaces of heterojunction, leading to enhanced photocatalytic performance. Under xenon lamp irradiation for 80 min, the degradation rate of methyl orange (MO) reached 91.4%, and remained at 80.7% after four consecutive cycles over Mn-CQDs/ZnFeO heterojunction. The radical capture experiment confirmed that the main active species that participated in MO degradation were both the photogenerated h+ and superoxide radical (·O2-).
Flower-like Fe-doped ZnO (ZnFeO) microspheres were synthesized via a hydrothermal method, and Mn-doped carbon quantum dots (Mn-CQDs) were uniformly loaded onto the surface of ZnFeO through physical deposition, successfully constructing Mn-CQDs/ZnFeO heterojunction composites. The relationship between the structure and photocatalytic performance of Mn-CQDs/ZnFeO was investigated using X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet visible diffuse reflection spectroscopy (UV-Vis DRS), and N2 adsorption-desorption analysis. The results showed that Mn doping significantly enhanced the light absorption range and photoluminescence (PL) stability of CQDs. The synergistic interaction between Mn-doped CQDs and Fe-doped ZnO extended the visible-light absorption edge of Mn-CQDs/ZnFeO, improved absorption intensity, and promoted the separation of photogenerated electron (e-)-hole (h+) pairs between the interfaces of heterojunction, leading to enhanced photocatalytic performance. Under xenon lamp irradiation for 80 min, the degradation rate of methyl orange (MO) reached 91.4%, and remained at 80.7% after four consecutive cycles over Mn-CQDs/ZnFeO heterojunction. The radical capture experiment confirmed that the main active species that participated in MO degradation were both the photogenerated h+ and superoxide radical (·O2-).
2025, 41(8): 1601-1609
doi: 10.11862/CJIC.20250012
Abstract:
Di(o-fluorobenzyl)tin-2, 2′-bipyridine-6, 6′-dicarboxylic acid complex [Sn(o-F-C6H4CH2)2(bpdc)(H2O)]2·H2O (1) and di-n-butyltin-2, 2′-bipyridine-6, 6′-dicarboxylic acid complex [Sn(n-C4H9)2(bpdc)(H2O)]·H2O (2) were synthesized via a solvothermal method using anhydrous ethanol as the solvent. The complexes were characterized by elemental analysis, IR spectroscopy, NMR(1H, 13C, and 119Sn), and thermogravimetric analysis. The crystal structures of the complexes were determined by the single-crystal X-ray diffraction method. The complexes are all single tin core molecules, belonging to the orthorhombic(Pbca) and monoclinic(P21/c) crystal systems, respectively. The central tin atoms are in a pentagonal bipyramidal configuration with seven coordination. The in vitro antitumor activities of the complexes against human gastric adenocarcinoma (AGS), acute lymphoblastic leukemia (MOLT4), and breast cancer (MDA-MB-231) cell lines were evaluated using the CCK-8 assay. Complex 1 demonstrated potent inhibitory effects across all tested cell lines, while complex 2 showed strong activity against AGS and MOLT4 but significantly reduced efficacy toward MDA-MB-231.
Di(o-fluorobenzyl)tin-2, 2′-bipyridine-6, 6′-dicarboxylic acid complex [Sn(o-F-C6H4CH2)2(bpdc)(H2O)]2·H2O (1) and di-n-butyltin-2, 2′-bipyridine-6, 6′-dicarboxylic acid complex [Sn(n-C4H9)2(bpdc)(H2O)]·H2O (2) were synthesized via a solvothermal method using anhydrous ethanol as the solvent. The complexes were characterized by elemental analysis, IR spectroscopy, NMR(1H, 13C, and 119Sn), and thermogravimetric analysis. The crystal structures of the complexes were determined by the single-crystal X-ray diffraction method. The complexes are all single tin core molecules, belonging to the orthorhombic(Pbca) and monoclinic(P21/c) crystal systems, respectively. The central tin atoms are in a pentagonal bipyramidal configuration with seven coordination. The in vitro antitumor activities of the complexes against human gastric adenocarcinoma (AGS), acute lymphoblastic leukemia (MOLT4), and breast cancer (MDA-MB-231) cell lines were evaluated using the CCK-8 assay. Complex 1 demonstrated potent inhibitory effects across all tested cell lines, while complex 2 showed strong activity against AGS and MOLT4 but significantly reduced efficacy toward MDA-MB-231.
2025, 41(8): 1610-1616
doi: 10.11862/CJIC.20240444
Abstract:
Ni-doped WP2 nanowirearrays were successfully prepared on carbon cloth(CC)by the hydrothermal method, and then phosphorized using the high vacuum solid-phase phosphorization method to obtain CC surface-grown Ni-doped WP2 nanowire composite material (Ni-WP2 NWs/CC). The electrochemical test results show that after Ni doping, the overpotential of the hydrogen evolution reaction in the alkaline environment was reduced. When the molar ratio of Ni and W was 10%, the 10%Ni-WP2 NWs/CCexhibited the best catalytic performance. Under alkaline conditions, when the current density was 10 and 100 mA·cm-2, the required overpotentials for 10%Ni-WP2 NWs/CC were 115 and 190 mV, respectively. After Ni doping, the electrochemically active surface area of 10%Ni-WP2 NWs/CC significantly increased. In addition, the catalyst maintained good working stability under long-term electrocatalytic conditions.
Ni-doped WP2 nanowirearrays were successfully prepared on carbon cloth(CC)by the hydrothermal method, and then phosphorized using the high vacuum solid-phase phosphorization method to obtain CC surface-grown Ni-doped WP2 nanowire composite material (Ni-WP2 NWs/CC). The electrochemical test results show that after Ni doping, the overpotential of the hydrogen evolution reaction in the alkaline environment was reduced. When the molar ratio of Ni and W was 10%, the 10%Ni-WP2 NWs/CCexhibited the best catalytic performance. Under alkaline conditions, when the current density was 10 and 100 mA·cm-2, the required overpotentials for 10%Ni-WP2 NWs/CC were 115 and 190 mV, respectively. After Ni doping, the electrochemically active surface area of 10%Ni-WP2 NWs/CC significantly increased. In addition, the catalyst maintained good working stability under long-term electrocatalytic conditions.
2025, 41(8): 1617-1631
doi: 10.11862/CJIC.20240420
Abstract:
CeO2 non-homogeneous Fenton catalyst (ST-CeO2) was prepared from Ce(NO3)3·6H2O and soluble starch (ST) via the biotemplating method. It was characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, solid UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), and X-ray photoelectron spectroscopy (XPS). FTIR and Raman spectra confirmed Ce—O bonds and oxygen vacancies. UV-Vis DRS showed strong absorption in the UV and visible light regions. XPS revealed mixed Ce3+ and Ce4+ valence states on the surface, benefiting charge separation and H2O2 activation. MO degradation tests showed that under UV light for 60 min, ST-CeO2 achieved an 82.8% MO degradation rate. With H2O2 added, the 60-min degradation rate reached 99.7%, and it still maintained excellent catalytic performance after recycling five times. Radical scavenging tests proved that hole (h+) and hydroxyl radical (·OH) were the main active species in MO degradation, with superoxide radical (·O2-) playing a secondary role. Also, the mechanism of ST-CeO2 in MO-dye photocatalytic Fenton degradation was explored.
CeO2 non-homogeneous Fenton catalyst (ST-CeO2) was prepared from Ce(NO3)3·6H2O and soluble starch (ST) via the biotemplating method. It was characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, solid UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), and X-ray photoelectron spectroscopy (XPS). FTIR and Raman spectra confirmed Ce—O bonds and oxygen vacancies. UV-Vis DRS showed strong absorption in the UV and visible light regions. XPS revealed mixed Ce3+ and Ce4+ valence states on the surface, benefiting charge separation and H2O2 activation. MO degradation tests showed that under UV light for 60 min, ST-CeO2 achieved an 82.8% MO degradation rate. With H2O2 added, the 60-min degradation rate reached 99.7%, and it still maintained excellent catalytic performance after recycling five times. Radical scavenging tests proved that hole (h+) and hydroxyl radical (·OH) were the main active species in MO degradation, with superoxide radical (·O2-) playing a secondary role. Also, the mechanism of ST-CeO2 in MO-dye photocatalytic Fenton degradation was explored.
2025, 41(8): 1632-1640
doi: 10.11862/CJIC.20240398
Abstract:
We used ZIF-8 as a sacrificial template and utilized its inherent polyhedral spatial structure to suppress the stacking and aggregation behavior of nanoparticle catalysts. At the same time, we further introduced transition metal nickel (Ni) element to doping ruthenium dioxide (RuO2) to optimize the electronic structure of the material and improve the intrinsic activity of active sites. As a result, the high-performance oxygen evolution electrocatalyst (Ni-RuO2) with a particle size of 8-10 nm was prepared. The results indicated that Ni-RuO2 had excellent oxygen evolution reaction (OER) catalytic performance, surpassing commercial RuO2. When Ni-RuO2 was used as the anode for overall water splitting testing, only a decomposition voltage of 1.476 V was required at a current density of 10 mA·cm-2.
We used ZIF-8 as a sacrificial template and utilized its inherent polyhedral spatial structure to suppress the stacking and aggregation behavior of nanoparticle catalysts. At the same time, we further introduced transition metal nickel (Ni) element to doping ruthenium dioxide (RuO2) to optimize the electronic structure of the material and improve the intrinsic activity of active sites. As a result, the high-performance oxygen evolution electrocatalyst (Ni-RuO2) with a particle size of 8-10 nm was prepared. The results indicated that Ni-RuO2 had excellent oxygen evolution reaction (OER) catalytic performance, surpassing commercial RuO2. When Ni-RuO2 was used as the anode for overall water splitting testing, only a decomposition voltage of 1.476 V was required at a current density of 10 mA·cm-2.
2025, 41(8): 1641-1649
doi: 10.11862/CJIC.20250152
Abstract:
A novel 3D metal-organic framework (MOF) [Pr2(L)3(H2O)5·H2O]n (Pr-1), (H2L=4, 4′-oxybis(benzoic acid)) with a rare structure of broken layer net, was constructed under the condition of solvothermal synthesis. The structure and crystal net were analyzed and characterized. This rod net of Pr-1 is new to both RCSR and ToposPro databases, and is named as rn-12 as suggested. Due to the luminescent properties of H2L and Pr(Ⅲ), the solid-state fluorescence property and sensing performance (solvents and metal ions) of Pr-1 were investigated. The sensing experiments indicated that Pr-1 could act as a fluorescence sensor to detect Cd2+ ions with good sensitivity. In addition, antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Bacillus subtilis (B. subtilis) compared to synthetic materials.
A novel 3D metal-organic framework (MOF) [Pr2(L)3(H2O)5·H2O]n (Pr-1), (H2L=4, 4′-oxybis(benzoic acid)) with a rare structure of broken layer net, was constructed under the condition of solvothermal synthesis. The structure and crystal net were analyzed and characterized. This rod net of Pr-1 is new to both RCSR and ToposPro databases, and is named as rn-12 as suggested. Due to the luminescent properties of H2L and Pr(Ⅲ), the solid-state fluorescence property and sensing performance (solvents and metal ions) of Pr-1 were investigated. The sensing experiments indicated that Pr-1 could act as a fluorescence sensor to detect Cd2+ ions with good sensitivity. In addition, antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Bacillus subtilis (B. subtilis) compared to synthetic materials.
2025, 41(8): 1650-1660
doi: 10.11862/CJIC.20250143
Abstract:
Two metal-organic frameworks (MOFs), trans-[Co(L)(μ2-H2O)(H2O)2]·2H2O (1) and cis-[Mn(L)(Bipy)] (2) (H2L=2, 2′-dimethyl-4, 4′-biphenyldicarboxylic acid, Bipy=4, 4′-bipyridine), have been synthesized and characterized by FTIR, thermogravimetric analysis (TGA), powder and single crystal X-ray diffraction. MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Co(Ⅱ) ions. Each trans-[CoO6] octahedron is connected by μ2-H2O and L2- ligand with a bis(unidentate) coordination mode to produce a 2D sql topological network. MOF 2 crystallizes in the monoclinic system with a C2/c space group. The Mn(Ⅱ) cation adopts a cis-[MnO4N2] octahedron as a 6-connected node and is linked by L2- ligand as a 4-connected node to generate a binodal (4, 6)-connected 3D fsc framework. The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1, and H…H and C…H/H…C contacts in 2. The TGA indicated that 1 and 2 were stable below 390 and 370 ℃, respectively.
Two metal-organic frameworks (MOFs), trans-[Co(L)(μ2-H2O)(H2O)2]·2H2O (1) and cis-[Mn(L)(Bipy)] (2) (H2L=2, 2′-dimethyl-4, 4′-biphenyldicarboxylic acid, Bipy=4, 4′-bipyridine), have been synthesized and characterized by FTIR, thermogravimetric analysis (TGA), powder and single crystal X-ray diffraction. MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Co(Ⅱ) ions. Each trans-[CoO6] octahedron is connected by μ2-H2O and L2- ligand with a bis(unidentate) coordination mode to produce a 2D sql topological network. MOF 2 crystallizes in the monoclinic system with a C2/c space group. The Mn(Ⅱ) cation adopts a cis-[MnO4N2] octahedron as a 6-connected node and is linked by L2- ligand as a 4-connected node to generate a binodal (4, 6)-connected 3D fsc framework. The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1, and H…H and C…H/H…C contacts in 2. The TGA indicated that 1 and 2 were stable below 390 and 370 ℃, respectively.
2025, 41(8): 1661-1671
doi: 10.11862/CJIC.20250075
Abstract:
A functional interlayer based on two-dimensional (2D) porous modified vermiculite nanosheets (PVS) was obtained by acid-etching vermiculite nanosheets. The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m2•g-1 and rich surface active sites, which help restrain polysulfides (LiPSs) through good physical and chemical adsorption, while simultaneously accelerating the nucleation and dissolution kinetics of Li2S, effectively suppressing the shuttle effect. The assembled lithium-sulfur batteries (LSBs) employing the PVS-based interlayer delivered a high initial discharge capacity of 1 386 mAh•g-1 at 0.1C (167.5 mAh•g-1), long-term cycling stability, and good rate property.
A functional interlayer based on two-dimensional (2D) porous modified vermiculite nanosheets (PVS) was obtained by acid-etching vermiculite nanosheets. The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m2•g-1 and rich surface active sites, which help restrain polysulfides (LiPSs) through good physical and chemical adsorption, while simultaneously accelerating the nucleation and dissolution kinetics of Li2S, effectively suppressing the shuttle effect. The assembled lithium-sulfur batteries (LSBs) employing the PVS-based interlayer delivered a high initial discharge capacity of 1 386 mAh•g-1 at 0.1C (167.5 mAh•g-1), long-term cycling stability, and good rate property.
2025, 41(8): 1672-1680
doi: 10.11862/CJIC.20250013
Abstract:
One Yb(Ⅲ)-based coordination polymer, {[Yb(H2dhtp)1.5(H2O)4]·3H2O}n (1) (H4dhtp=2, 5-dihydroxyterephthalic acid), was fabricated and structurally characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction, X-ray diffraction, and elemental analysis. Complex 1 displays a 1D chain structure, and belongs to P1 group. The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm (λex=408 nm). It exhibited the emission characteristic of the H4dhtp ligand. The fluorescence of 1 in water displayed the strongest intensity. In detecting various metal ions, adding Zr4+ led to a blue shift in fluorescence, accompanied by an increase in intensity, whereas the presence of Fe3+ resulted in a decrease in luminescence. The changes observed in the IR spectrum indicate an interaction between Fe3+/Zr4+ and complex 1, resulting in the variation of luminescence properties.
One Yb(Ⅲ)-based coordination polymer, {[Yb(H2dhtp)1.5(H2O)4]·3H2O}n (1) (H4dhtp=2, 5-dihydroxyterephthalic acid), was fabricated and structurally characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction, X-ray diffraction, and elemental analysis. Complex 1 displays a 1D chain structure, and belongs to P1 group. The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm (λex=408 nm). It exhibited the emission characteristic of the H4dhtp ligand. The fluorescence of 1 in water displayed the strongest intensity. In detecting various metal ions, adding Zr4+ led to a blue shift in fluorescence, accompanied by an increase in intensity, whereas the presence of Fe3+ resulted in a decrease in luminescence. The changes observed in the IR spectrum indicate an interaction between Fe3+/Zr4+ and complex 1, resulting in the variation of luminescence properties.
2025, 41(8): 1681-1688
doi: 10.11862/CJIC.20250004
Abstract:
Six coordination polymers based on 9, 10-di(pyridine-4-yl)-anthracene (DPA) and 1, 6-di(1H-imidazol-1-yl)pyrene (DIP) were obtained by solvothermal reactions. {[Zn(DPA)Cl2]·DMF·2H2O}n (1) and {[Zn1.5(DPA)1.5Cl3]·5H2O}n (2) are framework isomers, which both contain zigzag chains formed by DPA, Zn2+, and Cl-. The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers, and these layers exhibit two different orientations, displaying a rare 2D to 3D interpenetration mode. The zigzag chains in 2 are parallelly arranged. {[Zn3(DPA)3Br6]·2DMF·1.5H2O}n (3) is isostructural to 2. 3 was obtained using ZnBr2 instead of ZnCl2.[M(DPA) (formate)2(H2O)2]n[M=Co (4), Cu (5)] are isostructural, contain chain structures formed by DPA, Cu2+/Co2+, and formate ions, which were formed in situ in the solvothermal reaction. {[Zn(DIP)2Cl]ClO4}n (6) contains a layer structure formed by DIP and Zn2+. Free DPA and DIP ligands exhibited high fluorescence at room temperature, and coordination polymers 3 and 6 displayed enhanced fluorescent emissions.
Six coordination polymers based on 9, 10-di(pyridine-4-yl)-anthracene (DPA) and 1, 6-di(1H-imidazol-1-yl)pyrene (DIP) were obtained by solvothermal reactions. {[Zn(DPA)Cl2]·DMF·2H2O}n (1) and {[Zn1.5(DPA)1.5Cl3]·5H2O}n (2) are framework isomers, which both contain zigzag chains formed by DPA, Zn2+, and Cl-. The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers, and these layers exhibit two different orientations, displaying a rare 2D to 3D interpenetration mode. The zigzag chains in 2 are parallelly arranged. {[Zn3(DPA)3Br6]·2DMF·1.5H2O}n (3) is isostructural to 2. 3 was obtained using ZnBr2 instead of ZnCl2.[M(DPA) (formate)2(H2O)2]n[M=Co (4), Cu (5)] are isostructural, contain chain structures formed by DPA, Cu2+/Co2+, and formate ions, which were formed in situ in the solvothermal reaction. {[Zn(DIP)2Cl]ClO4}n (6) contains a layer structure formed by DIP and Zn2+. Free DPA and DIP ligands exhibited high fluorescence at room temperature, and coordination polymers 3 and 6 displayed enhanced fluorescent emissions.
