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2025 Volume 41 Issue 4
2025, 41(4): 625-638
doi: 10.11862/CJIC.20240358
Abstract:
An efficient interlocking process was developed, including acid leaching, co-precipitation, and heat treatment, to regenerate waste LiNi0.5Co0.2Mn0.3O2 (NCM523) materials. DL-tartaric acid and formic acid were used as leaching systems, and the leaching efficiencies of Li, Ni, Co, and Mn reached about 98%. The leaching solution was added to the oxalic acid solution for a co-precipitation reaction, and then the regeneration of the material was realized through heat treatment. The regenerated NCM523 material exhibited an excellent layered structure and uniform elemental distribution. When employed as a cathode material for LIBs, the regenerated NCM523 exhibited a discharge-specific capacity of 168.5 mAh·g-1 at 0.1C (18 mA·g-1), which is comparable to the performance of fresh NCM523. Furthermore, the regenerated NCM523 demonstrated a capacity retention of 93.09% after 100 cycles at 0.5C.
An efficient interlocking process was developed, including acid leaching, co-precipitation, and heat treatment, to regenerate waste LiNi0.5Co0.2Mn0.3O2 (NCM523) materials. DL-tartaric acid and formic acid were used as leaching systems, and the leaching efficiencies of Li, Ni, Co, and Mn reached about 98%. The leaching solution was added to the oxalic acid solution for a co-precipitation reaction, and then the regeneration of the material was realized through heat treatment. The regenerated NCM523 material exhibited an excellent layered structure and uniform elemental distribution. When employed as a cathode material for LIBs, the regenerated NCM523 exhibited a discharge-specific capacity of 168.5 mAh·g-1 at 0.1C (18 mA·g-1), which is comparable to the performance of fresh NCM523. Furthermore, the regenerated NCM523 demonstrated a capacity retention of 93.09% after 100 cycles at 0.5C.
2025, 41(4): 729-740
doi: 10.11862/CJIC.20240404
Abstract:
In this study, ZnSnO3/NiO heterostructures were synthesized using a co-precipitation method followed by an annealing process. The gas-sensitive characteristics of the sensors based on these samples were evaluated. The results indicate that the sensor performance was optimized when the molar ratio of Ni to Zn was 1∶2. Specifically, the response values of the ZnSnO3/NiO-2-based sensor to 100 μL·L-1 triethylamine (TEA) gas at 220 ℃ reached 70.6, which were 6.1 times higher than that of the pure ZnSnO3 based sensor. The findings demonstrate that ZnSnO3/NiO heterostructures exhibited not only short response and recovery times (1 s/18 s) but also good gas selectivity, repeatability, and long-term stability. The enhanced sensing mechanism has been investigated in detail.
In this study, ZnSnO3/NiO heterostructures were synthesized using a co-precipitation method followed by an annealing process. The gas-sensitive characteristics of the sensors based on these samples were evaluated. The results indicate that the sensor performance was optimized when the molar ratio of Ni to Zn was 1∶2. Specifically, the response values of the ZnSnO3/NiO-2-based sensor to 100 μL·L-1 triethylamine (TEA) gas at 220 ℃ reached 70.6, which were 6.1 times higher than that of the pure ZnSnO3 based sensor. The findings demonstrate that ZnSnO3/NiO heterostructures exhibited not only short response and recovery times (1 s/18 s) but also good gas selectivity, repeatability, and long-term stability. The enhanced sensing mechanism has been investigated in detail.
2025, 41(4): 741-752
doi: 10.11862/CJIC.20240403
Abstract:
The Z-scheme heterojunction Cu2O/Bi2CrO6 photocatalyst was successfully prepared by introducing Cu2O on the Bi2CrO6 surface using a coprecipitation method. The photocatalytic degradation of tetracycline (TC) on Cu2O/Bi2CrO6 under visible light irradiation was investigated. It was found that the Cu2O/Bi2CrO6 photocatalyst had the best photocatalytic activity when the mass ratio of Cu2O to Bi2CrO6 was 20%, and the TC could be degraded by 87.5% within 100 min, which was about 1.8 times and 1.3 times higher than that of pure Bi2CrO6 and pure Cu2O, respectively. Besides, the Cu2O/Bi2CrO6 photocatalyst also showed good stability and reusability. The Z scheme heterojunction structure of Cu2O/Bi2CrO6 provided increased active sites, enhanced interfacial charge separation, and improved separation efficiency of photogenerated electro-hole (e--h+) pairs, leading to enhanced photocatalytic properties. Electron paramagnetic resonance (EPR) measurement confirmed that the superoxide radical (·O2-), hydroxyl radical (·OH), and h+ were the primary active species during photocatalysis.
The Z-scheme heterojunction Cu2O/Bi2CrO6 photocatalyst was successfully prepared by introducing Cu2O on the Bi2CrO6 surface using a coprecipitation method. The photocatalytic degradation of tetracycline (TC) on Cu2O/Bi2CrO6 under visible light irradiation was investigated. It was found that the Cu2O/Bi2CrO6 photocatalyst had the best photocatalytic activity when the mass ratio of Cu2O to Bi2CrO6 was 20%, and the TC could be degraded by 87.5% within 100 min, which was about 1.8 times and 1.3 times higher than that of pure Bi2CrO6 and pure Cu2O, respectively. Besides, the Cu2O/Bi2CrO6 photocatalyst also showed good stability and reusability. The Z scheme heterojunction structure of Cu2O/Bi2CrO6 provided increased active sites, enhanced interfacial charge separation, and improved separation efficiency of photogenerated electro-hole (e--h+) pairs, leading to enhanced photocatalytic properties. Electron paramagnetic resonance (EPR) measurement confirmed that the superoxide radical (·O2-), hydroxyl radical (·OH), and h+ were the primary active species during photocatalysis.
2025, 41(4): 753-760
doi: 10.11862/CJIC.20240399
Abstract:
A Zn(Ⅱ)-based coordination polymer (CP), {[Zn2(bdc)2(mfdp)]2·4DMA·2Me2NH·3H2O}n (1), was synthesized by solvothermal method based on H2bdc and mfdp, where H2bdc=1, 4-benzenedicarboxylic acid, mfdp=2, 7-bis (4-pyridyl)-9, 9-dimethylfluorene, and DMA=N, N-dimethylacetamide. It was characterized by FTIR, elemental analysis, TGA, and single-crystal X-ray diffraction. In 1, two adjacent zinc ions lie in the same {ZnNO4} geometrical configurations, forming a paddle-wheel building block. Complex 1 displays 2-fold interpenetrating frameworks with {412· 63} topology and with the emission peak situated at 385 nm, which offers a good foundation to be integrated as a chemical sensor. The fluorescence sensing experiments showed that the LOD (limit of detection) of 2, 4, 6-trinitrophenol (TNP) was 0.164 μmol·L-1, and the quenching constant (KSV) was 6.65×104 L·mol-1, indicating the excellent detection ability of trace analytes in DMA.
A Zn(Ⅱ)-based coordination polymer (CP), {[Zn2(bdc)2(mfdp)]2·4DMA·2Me2NH·3H2O}n (1), was synthesized by solvothermal method based on H2bdc and mfdp, where H2bdc=1, 4-benzenedicarboxylic acid, mfdp=2, 7-bis (4-pyridyl)-9, 9-dimethylfluorene, and DMA=N, N-dimethylacetamide. It was characterized by FTIR, elemental analysis, TGA, and single-crystal X-ray diffraction. In 1, two adjacent zinc ions lie in the same {ZnNO4} geometrical configurations, forming a paddle-wheel building block. Complex 1 displays 2-fold interpenetrating frameworks with {412· 63} topology and with the emission peak situated at 385 nm, which offers a good foundation to be integrated as a chemical sensor. The fluorescence sensing experiments showed that the LOD (limit of detection) of 2, 4, 6-trinitrophenol (TNP) was 0.164 μmol·L-1, and the quenching constant (KSV) was 6.65×104 L·mol-1, indicating the excellent detection ability of trace analytes in DMA.
2025, 41(4): 761-772
doi: 10.11862/CJIC.20240344
Abstract:
Two new binuclear Gd2 complexes with the molecular formula [Gd2(L)(H2L)]·2CH3OH·CH3CN (1) and [Gd2(H2L)2(dbm)2]·6CH3CN (2) (Hdbm=dibenzoylmethane) have been obtained by using a large conjugated diacylhydrazone organic ligand N′, N‴-(1E, 1′E)-(1, 10-phenanthroline-2, 9-diyl)bis(methaneylylidene) bis (2-hydroxy-benzohydrazide) (H4L) reacting with Gd(NO3)3·6H2O or Gd(dbm)3·2H2O. Structure studies reveal that Gd2 complexes 1 and 2 belong to a triclinic crystal system with space group P1. Nevertheless, they show different molecule structures. 1 displays a cattail leaf fan shape, while 2 displays a pinwheel-shaped cage. Magnetic properties researches suggest that the two Gd2 complexes displayed different magnetic refrigeration (-ΔSm=23.35 and 15.09 J·kg-1·K-1 for 1 and 2, respectively). In addition, the synergistic interaction between ligand and Ln(Ⅲ) ions, promotes the two Gd2 complexes showing excellent antibacterial activity. When the Gd2 complexes interact with DNA, the Gd2 complexes mainly insert or cut DNA.
Two new binuclear Gd2 complexes with the molecular formula [Gd2(L)(H2L)]·2CH3OH·CH3CN (1) and [Gd2(H2L)2(dbm)2]·6CH3CN (2) (Hdbm=dibenzoylmethane) have been obtained by using a large conjugated diacylhydrazone organic ligand N′, N‴-(1E, 1′E)-(1, 10-phenanthroline-2, 9-diyl)bis(methaneylylidene) bis (2-hydroxy-benzohydrazide) (H4L) reacting with Gd(NO3)3·6H2O or Gd(dbm)3·2H2O. Structure studies reveal that Gd2 complexes 1 and 2 belong to a triclinic crystal system with space group P1. Nevertheless, they show different molecule structures. 1 displays a cattail leaf fan shape, while 2 displays a pinwheel-shaped cage. Magnetic properties researches suggest that the two Gd2 complexes displayed different magnetic refrigeration (-ΔSm=23.35 and 15.09 J·kg-1·K-1 for 1 and 2, respectively). In addition, the synergistic interaction between ligand and Ln(Ⅲ) ions, promotes the two Gd2 complexes showing excellent antibacterial activity. When the Gd2 complexes interact with DNA, the Gd2 complexes mainly insert or cut DNA.
2025, 41(4): 773-785
doi: 10.11862/CJIC.20250015
Abstract:
A novel porous silicon composite material (pSi/Ge@Gr/CNTs) was successfully fabricated by utilizing high-energy ball milling and electrostatic assembly techniques. This material starts with a commercial Al60Si40 alloy as the raw material. Through a simple acid etching process, a porous silicon (pSi) matrix was produced. Germanium (Ge) was then introduced into the matrix via ball milling. Finally, with the aid of electrostatic assembly, a dual coating of graphene (Gr) and carbon nanotubes (CNTs) was achieved, endowing the material with a unique structure. The incorporation of Ge introduction effectively augments the conductivity and ion transport characteristics of pSi, substantially bolstering the reversible capacity of the entire electrode. The hybrid encapsulation with Gr and CNTs further fortifies the stability, mechanical robustness, and electrical conductivity of the electrode. When utilized as anodes in LIBs, the pSi/Ge@Gr/CNTs electrode demonstrated outstanding electrochemical performance, achieving a reversible discharge specific capacity exceeding 700 mAh·g-1 after 100 cycles at a current density of 0.2 A·g-1, accompanied by a remarkably enhanced rate performance.
A novel porous silicon composite material (pSi/Ge@Gr/CNTs) was successfully fabricated by utilizing high-energy ball milling and electrostatic assembly techniques. This material starts with a commercial Al60Si40 alloy as the raw material. Through a simple acid etching process, a porous silicon (pSi) matrix was produced. Germanium (Ge) was then introduced into the matrix via ball milling. Finally, with the aid of electrostatic assembly, a dual coating of graphene (Gr) and carbon nanotubes (CNTs) was achieved, endowing the material with a unique structure. The incorporation of Ge introduction effectively augments the conductivity and ion transport characteristics of pSi, substantially bolstering the reversible capacity of the entire electrode. The hybrid encapsulation with Gr and CNTs further fortifies the stability, mechanical robustness, and electrical conductivity of the electrode. When utilized as anodes in LIBs, the pSi/Ge@Gr/CNTs electrode demonstrated outstanding electrochemical performance, achieving a reversible discharge specific capacity exceeding 700 mAh·g-1 after 100 cycles at a current density of 0.2 A·g-1, accompanied by a remarkably enhanced rate performance.
2025, 41(4): 786-796
doi: 10.11862/CJIC.20240329
Abstract:
Herein, a mesoporous magnetic nanocarrier containing disulfide bonds (NH2-SMNPs) was developed to improve the efficacy of tumor treatment and reduce side effects. After loading the carrier with doxorubicin (DOX), a nontoxic pullulan oxide was used as a gating material to form the oSMNPs/DOX nanodrug. This nanodrug exhibited uniform dispersion, good drug-loading capacity, and high saturation magnetization, enabling pH/glutathione (GSH) dual-responsive drug release in the tumor microenvironment, with a release rate as high as 81.53%. Furthermore, this nanodrug demonstrated good biocompatibility, effective capability to kill cancer cells, and competent cellular uptake ability.
Herein, a mesoporous magnetic nanocarrier containing disulfide bonds (NH2-SMNPs) was developed to improve the efficacy of tumor treatment and reduce side effects. After loading the carrier with doxorubicin (DOX), a nontoxic pullulan oxide was used as a gating material to form the oSMNPs/DOX nanodrug. This nanodrug exhibited uniform dispersion, good drug-loading capacity, and high saturation magnetization, enabling pH/glutathione (GSH) dual-responsive drug release in the tumor microenvironment, with a release rate as high as 81.53%. Furthermore, this nanodrug demonstrated good biocompatibility, effective capability to kill cancer cells, and competent cellular uptake ability.
2025, 41(4): 797-808
doi: 10.11862/CJIC.20240328
Abstract:
Under hydrothermal conditions, semi-rigid 4-(1-carboxyethoxy)benzoic acid (H2cba) and Ni(Ⅱ) ions reacted with imidazole derivatives 1,4-di(1H-imidazol-1-yl)benzene (1,4-dib) and 4,4'-di(1H-imidazol-1-yl)-1,1'-biphenyl (4, 4' dib) to form complexes {[Ni(cba)(1, 4 dib)(H2O)0.5] ·0.5H2O}n (HU21) and {[Ni(cba)(4, 4' dib)(H2O)0.5] · 0.5H 2O}n (HU22), respectively. Singlecrystal X-ray diffraction analysis revealed that both complexes HU21 and HU22 contain binuclear [Ni2(CO2)2(H2O)]2+ units, which are further bridged together via cba2- anions to form 1D [Ni2(H2O)(cba)2]n chains in HU21 and HU22. In addition to the [Ni2(H2O)(cba)2]n chains, large right-handed and lefthanded helical chains were constructed by Ni(Ⅱ) ions, water molecules, and 1,4-dib ligands in HU21, with diameters of up to 1.6 nm along the b-axis. These helical chains are further joined together in a 1∶1 ratio to form a 3D framework. Subsequently, the [Ni2(H2O)(cba)2]n chains are incorporated into the 3D framework to build a six-connected dense network with a point symbol of (44.611) in HU21. In complex HU22, left-and right-handed helical chains were also observed. However, unlike the 3D framework constructed by helical chains in HU21, these helical chains in HU22 can only form a 2D layer. Adjacent layers are packed together in an ABAB pattern to form a six-connected framework in the presence of [Ni2(H2O) (cba)2]n chains. UV-Vis absorption experiments indicated that complexes HU21 and HU22 are semiconductor materials with strong light absorption capacities in the ultraviolet and visible regions. Moreover, magnetic experiments showed that HU21 and HU22 exhibit similar antiferromagnetic behaviors.
Under hydrothermal conditions, semi-rigid 4-(1-carboxyethoxy)benzoic acid (H2cba) and Ni(Ⅱ) ions reacted with imidazole derivatives 1,4-di(1H-imidazol-1-yl)benzene (1,4-dib) and 4,4'-di(1H-imidazol-1-yl)-1,1'-biphenyl (4, 4' dib) to form complexes {[Ni(cba)(1, 4 dib)(H2O)0.5] ·0.5H2O}n (HU21) and {[Ni(cba)(4, 4' dib)(H2O)0.5] · 0.5H 2O}n (HU22), respectively. Singlecrystal X-ray diffraction analysis revealed that both complexes HU21 and HU22 contain binuclear [Ni2(CO2)2(H2O)]2+ units, which are further bridged together via cba2- anions to form 1D [Ni2(H2O)(cba)2]n chains in HU21 and HU22. In addition to the [Ni2(H2O)(cba)2]n chains, large right-handed and lefthanded helical chains were constructed by Ni(Ⅱ) ions, water molecules, and 1,4-dib ligands in HU21, with diameters of up to 1.6 nm along the b-axis. These helical chains are further joined together in a 1∶1 ratio to form a 3D framework. Subsequently, the [Ni2(H2O)(cba)2]n chains are incorporated into the 3D framework to build a six-connected dense network with a point symbol of (44.611) in HU21. In complex HU22, left-and right-handed helical chains were also observed. However, unlike the 3D framework constructed by helical chains in HU21, these helical chains in HU22 can only form a 2D layer. Adjacent layers are packed together in an ABAB pattern to form a six-connected framework in the presence of [Ni2(H2O) (cba)2]n chains. UV-Vis absorption experiments indicated that complexes HU21 and HU22 are semiconductor materials with strong light absorption capacities in the ultraviolet and visible regions. Moreover, magnetic experiments showed that HU21 and HU22 exhibit similar antiferromagnetic behaviors.
2025, 41(4): 809-820
doi: 10.11862/CJIC.20240171
Abstract:
A cadmium-based coordination polymer [Cd4(L)4(1,4-bib)4]·2DMA (CP1) was synthesized under solvothermal conditions, where H2L=2 hydroxyterephthalic acid, 1, 4 bib=1, 4 bis(imidazol1 ylmethyl) benzene, and DMA=N,N-dimethylacetamide. The structure was characterized by thermogravimetric analysis, elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. The single crystal structure shows that CP1 belongs to the orthorhombic system, the space group Pna21, Cd(Ⅱ) forms a 2D plane structure through L2-, and the 2D plane structure forms a 3D network with pcu topology through 1,4-bib. CP1 shows good fluorescence sensing performance and thermal stability and realizes efficient and sensitive detection of 2,4,6-trinitrophenol (TNP), Fe3+, and fluridine (FLU). The detection limits were 0.051 μmol·L-1 (TNP), 0.65 μmol·L-1 (Fe3+), and 0.14 μmol·L-1 (FLU), respectively. In addition, the mechanism of fluorescence detection of pollutant detection was explored and a portable test paper was successfully prepared. A portable test paper could not only selectively detect FLU, but also showed different fluorescence colors in different concentrations of FLU.
A cadmium-based coordination polymer [Cd4(L)4(1,4-bib)4]·2DMA (CP1) was synthesized under solvothermal conditions, where H2L=2 hydroxyterephthalic acid, 1, 4 bib=1, 4 bis(imidazol1 ylmethyl) benzene, and DMA=N,N-dimethylacetamide. The structure was characterized by thermogravimetric analysis, elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. The single crystal structure shows that CP1 belongs to the orthorhombic system, the space group Pna21, Cd(Ⅱ) forms a 2D plane structure through L2-, and the 2D plane structure forms a 3D network with pcu topology through 1,4-bib. CP1 shows good fluorescence sensing performance and thermal stability and realizes efficient and sensitive detection of 2,4,6-trinitrophenol (TNP), Fe3+, and fluridine (FLU). The detection limits were 0.051 μmol·L-1 (TNP), 0.65 μmol·L-1 (Fe3+), and 0.14 μmol·L-1 (FLU), respectively. In addition, the mechanism of fluorescence detection of pollutant detection was explored and a portable test paper was successfully prepared. A portable test paper could not only selectively detect FLU, but also showed different fluorescence colors in different concentrations of FLU.
2025, 41(4): 821-832
doi: 10.11862/CJIC.20240148
Abstract:
MoS2/Ag/g-C3N4 composite photocatalysts were prepared via hydrothermal synthesis, and a series of analytical methods were employed for systematic characterization. The results indicate that the significant enhancement in catalytic degradation activity is attributed to the formation of Z-scheme heterojunction, which effectively facilitates the transport and separation of photogenerated charge carriers while suppressing the recombination of photogenerated electron and hole pairs. Degradation experiments demonstrated that the prepared composite material achieved a degradation rate of up to 98% for rhodamine B (RhB) within 120 min, exhibiting superior photocatalytic performance compared to individual photocatalysts. Furthermore, capture experiments and electron paramagnetic resonance (EPR) results revealed that superoxide radicals (·O2-) and photogenerated holes (h+) were the key active species in the photocatalytic degradation of RhB. Finally, an in-depth discussion of the photocatalytic degradation mechanism of the composite material was conducted.
MoS2/Ag/g-C3N4 composite photocatalysts were prepared via hydrothermal synthesis, and a series of analytical methods were employed for systematic characterization. The results indicate that the significant enhancement in catalytic degradation activity is attributed to the formation of Z-scheme heterojunction, which effectively facilitates the transport and separation of photogenerated charge carriers while suppressing the recombination of photogenerated electron and hole pairs. Degradation experiments demonstrated that the prepared composite material achieved a degradation rate of up to 98% for rhodamine B (RhB) within 120 min, exhibiting superior photocatalytic performance compared to individual photocatalysts. Furthermore, capture experiments and electron paramagnetic resonance (EPR) results revealed that superoxide radicals (·O2-) and photogenerated holes (h+) were the key active species in the photocatalytic degradation of RhB. Finally, an in-depth discussion of the photocatalytic degradation mechanism of the composite material was conducted.
2025, 41(4): 639-649
doi: 10.11862/CJIC.20240397
Abstract:
Sr, Ni co-doped PrBaFe2O5+δ (PBF) was employed to prepare the PrBa0.5Sr0.5Fe1.6Ni0.4O5+δ (PBSFN) cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs), and the performance of cathode was evaluated. X-ray diffraction (XRD) analysis revealed that the PBSFN cathode formed a cubic perovskite structure after being calcined at high temperatures. PBSFN cathode and La0.9Sr0.1Ga0.83Mg0.17O3-δ (LSGM) electrolyte exhibited good chemical compatibility after being co-calcined at 950 ℃. In an air atmosphere, the conductivity of the PBSFN cathode reached a maximum value of 681 S·cm-1 at 350 ℃. At 800 ℃, the polarization resistance of the PBSFN cathode on the LSGM electrolyte was 0.033 Ω·cm2 in an air atmosphere. The high-frequency resistance (R1) is only 6.4% more than that of low-frequency resistance (R2), indicating Sr, Ni doped significantly improves the efficiency of charge transfer. The polarization resistance (Rp) result is consistent with the oxygen vacancy formation energy of PBSFN by density function theory calculations. At 800 ℃, using H2 as the fuel, the maximum power density of the single cell reached 647 mW·cm-2. In particular, the output power of the single cell with the PBSFN cathode maintained good stability over 100 h.
Sr, Ni co-doped PrBaFe2O5+δ (PBF) was employed to prepare the PrBa0.5Sr0.5Fe1.6Ni0.4O5+δ (PBSFN) cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs), and the performance of cathode was evaluated. X-ray diffraction (XRD) analysis revealed that the PBSFN cathode formed a cubic perovskite structure after being calcined at high temperatures. PBSFN cathode and La0.9Sr0.1Ga0.83Mg0.17O3-δ (LSGM) electrolyte exhibited good chemical compatibility after being co-calcined at 950 ℃. In an air atmosphere, the conductivity of the PBSFN cathode reached a maximum value of 681 S·cm-1 at 350 ℃. At 800 ℃, the polarization resistance of the PBSFN cathode on the LSGM electrolyte was 0.033 Ω·cm2 in an air atmosphere. The high-frequency resistance (R1) is only 6.4% more than that of low-frequency resistance (R2), indicating Sr, Ni doped significantly improves the efficiency of charge transfer. The polarization resistance (Rp) result is consistent with the oxygen vacancy formation energy of PBSFN by density function theory calculations. At 800 ℃, using H2 as the fuel, the maximum power density of the single cell reached 647 mW·cm-2. In particular, the output power of the single cell with the PBSFN cathode maintained good stability over 100 h.
2025, 41(4): 650-660
doi: 10.11862/CJIC.20240386
Abstract:
Zn nanoparticles-modified nitrogen-doped porous carbon (N-C) catalysts (Zn@N-C) were prepared by a simple one-step pyrolysis strategy using Zn-based zeolite imidazolate framework (Zn-ZIF) as the precursor. Subsequently, the Zn nanoparticles were further converted to the ZnSe nanoparticles by using a selenization strategy; meanwhile, the heterostructure between the ZnSe and N-C was constructed to enhance the catalytic activity of the catalysts. The components, structures, and morphologies of as-prepared catalysts were characterized by using X-ray diffraction (XRD), Raman, X - ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). Electrochemical tests in water splitting systematically evaluated the hydrogen evolution reaction (HER) catalytic activity and stability of the catalysts. Results showed that the morphology of the catalyst was transformed from a regular rhombic dodecahedron (Zn@N-C) to a structurally collapsed, folded, and deformed dodecahedron (ZnSe@N-C) by selenization, which increased the structural defects and introduced more catalytic active sites. Meanwhile, the existence of a heterogeneous interfacial structure between the ZnSe and N-C substrates was beneficial to the electron transport and improved the catalytic activity of the catalysts. ZnSe@N-C yielded a low overpotential of 165.8 mV at a current density of 10 mA·cm-2 in the HER process, which was superior to that of Zn@N-C (190.8 mV). ZnSe@N-C also demonstrated good electrochemical stability in an alkaline solution.
Zn nanoparticles-modified nitrogen-doped porous carbon (N-C) catalysts (Zn@N-C) were prepared by a simple one-step pyrolysis strategy using Zn-based zeolite imidazolate framework (Zn-ZIF) as the precursor. Subsequently, the Zn nanoparticles were further converted to the ZnSe nanoparticles by using a selenization strategy; meanwhile, the heterostructure between the ZnSe and N-C was constructed to enhance the catalytic activity of the catalysts. The components, structures, and morphologies of as-prepared catalysts were characterized by using X-ray diffraction (XRD), Raman, X - ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). Electrochemical tests in water splitting systematically evaluated the hydrogen evolution reaction (HER) catalytic activity and stability of the catalysts. Results showed that the morphology of the catalyst was transformed from a regular rhombic dodecahedron (Zn@N-C) to a structurally collapsed, folded, and deformed dodecahedron (ZnSe@N-C) by selenization, which increased the structural defects and introduced more catalytic active sites. Meanwhile, the existence of a heterogeneous interfacial structure between the ZnSe and N-C substrates was beneficial to the electron transport and improved the catalytic activity of the catalysts. ZnSe@N-C yielded a low overpotential of 165.8 mV at a current density of 10 mA·cm-2 in the HER process, which was superior to that of Zn@N-C (190.8 mV). ZnSe@N-C also demonstrated good electrochemical stability in an alkaline solution.
2025, 41(4): 661-674
doi: 10.11862/CJIC.20240363
Abstract:
Metal-organic framework (MOF)-based nickel-cobalt bimetallic sulfides microspheres were prepared by solvothermal and sulfurization methods, and trace nitrogen-doped carbon (NC)-coated Ni-Co-S@NC anode for sodium-ion batteries were further synthesized by high-temperature pyrolysis using dopamine hydrochloride as the organic carbon source. This surface modification can effectively improve the conductivity, structure, and interface stability of the synthesized materials, which helps to enhance the cycling stability of the materials, thereby improving the cycling stability and thermal stability. The Ni-Co-S@NC-0.5 anode with a carbon layer thickness of about 5 nm had an excellent long cycling performance with a 381.8 mAh·g-1 reversible capacity at 1 A·g-1 after 1 000 cycles, a capacity retention rate of 75.2%, and correspondingly the capacity decay per cycle was only 0.126 mAh·g-1. The Ni-Co-S@NC-0.5||NVP/C (NVP: Na3V2(PO4)3) full cell assembled had a reversible specific capacity of 386.2 mAh· g-1 with 88.6 % capacity retention at 1 A·g-1 after 100 cycles, and a stable Coulombic efficiency of 98.1%. It is found for the sodium ion dynamics behavior that the sodium storage mechanism of the Ni-Co-S@NC-0.5 anode is mainly controlled by pseudocapacitive behavior, indicating that the sodium ion storage process is more biased towards surface reactions, which is conducive to the shortening of the ion transport path and the realization of rapid sodium storage. The diffusion coefficients of sodium ions were between 10-11~10-13 cm2·s-1, and the charge transfer impedance value was a relatively minimum (36.7 Ω) of all.
Metal-organic framework (MOF)-based nickel-cobalt bimetallic sulfides microspheres were prepared by solvothermal and sulfurization methods, and trace nitrogen-doped carbon (NC)-coated Ni-Co-S@NC anode for sodium-ion batteries were further synthesized by high-temperature pyrolysis using dopamine hydrochloride as the organic carbon source. This surface modification can effectively improve the conductivity, structure, and interface stability of the synthesized materials, which helps to enhance the cycling stability of the materials, thereby improving the cycling stability and thermal stability. The Ni-Co-S@NC-0.5 anode with a carbon layer thickness of about 5 nm had an excellent long cycling performance with a 381.8 mAh·g-1 reversible capacity at 1 A·g-1 after 1 000 cycles, a capacity retention rate of 75.2%, and correspondingly the capacity decay per cycle was only 0.126 mAh·g-1. The Ni-Co-S@NC-0.5||NVP/C (NVP: Na3V2(PO4)3) full cell assembled had a reversible specific capacity of 386.2 mAh· g-1 with 88.6 % capacity retention at 1 A·g-1 after 100 cycles, and a stable Coulombic efficiency of 98.1%. It is found for the sodium ion dynamics behavior that the sodium storage mechanism of the Ni-Co-S@NC-0.5 anode is mainly controlled by pseudocapacitive behavior, indicating that the sodium ion storage process is more biased towards surface reactions, which is conducive to the shortening of the ion transport path and the realization of rapid sodium storage. The diffusion coefficients of sodium ions were between 10-11~10-13 cm2·s-1, and the charge transfer impedance value was a relatively minimum (36.7 Ω) of all.
2025, 41(4): 675-682
doi: 10.11862/CJIC.20240339
Abstract:
A cathode material rich in 1T-MoS2 (1T′-MoS2) for aqueous zinc ion batteries was successfully synthesized via a one-step hydrothermal method. The characterization results and density functional theory (DFT) simulation calculations indicated that the conductivity of 1T′-MoS2 was significantly higher than that of 2H-MoS2, and 1T′-MoS2 contained abundant sulfur vacancies. That substantially enhances the ion diffusion and charge transfer rates, as well as the electrochemical and kinetic characteristics of the material. Therefore, the initial discharge capacity of the battery assembled with 1T′-MoS2 was as high as 202 mAh·g-1 at a current density of 0.1 A·g-1. In addition, at a high current density (1 A·g-1), the capacity retention rate was 92% after 500 cycles, showing good high capacity and long-cycle stability.
A cathode material rich in 1T-MoS2 (1T′-MoS2) for aqueous zinc ion batteries was successfully synthesized via a one-step hydrothermal method. The characterization results and density functional theory (DFT) simulation calculations indicated that the conductivity of 1T′-MoS2 was significantly higher than that of 2H-MoS2, and 1T′-MoS2 contained abundant sulfur vacancies. That substantially enhances the ion diffusion and charge transfer rates, as well as the electrochemical and kinetic characteristics of the material. Therefore, the initial discharge capacity of the battery assembled with 1T′-MoS2 was as high as 202 mAh·g-1 at a current density of 0.1 A·g-1. In addition, at a high current density (1 A·g-1), the capacity retention rate was 92% after 500 cycles, showing good high capacity and long-cycle stability.
2025, 41(4): 683-694
doi: 10.11862/CJIC.20240291
Abstract:
In this study, UiO-66-CHO and UiO-66-CH=C(CN)2 were synthesized using pre-synthetic and postsynthetic modification methods, for the adsorption of tetracycline (TC) from aqueous solution. The powder X-ray diffraction patterns of these functional MOFs exhibit that they have the same frameworks with UiO-66 and good crystallinity. FTIR and 1H NMR spectroscopy powerfully suggested that the formyl and the cyano were successfully introduced to the frameworks. Compared to UiO-66, UiO-66-CHO and UiO-66-CH=C(CN)2 exhibit slightly diminished thermal stability in the thermogravimetric analysis and the absence of organic linkers. The Brunauer-Emmett-Teller (BET) specific surface area calculated from the N2 adsorption and desorption experiment data shows that all modified materials also preserve porousness. The three materials in the scanning electron microscope showed similar morphology at the microscopic level, and uniform particle size may be favorable for TC adsorption. A series of experiments were conducted on UiO-66-CHO and UiO-66-CH=C(CN)2 for the adsorption of TC in water. For the two functional MOFs, adsorption experiment data confirmed that the adsorption occurs via chemisorption on a monolayer, aligning with the pseudo-second-order kinetic and Langmuir isotherm models. UiO-66-CHO and UiO-66-CH=C (CN)2 exhibited a higher theoretical maximum adsorption capacity of 199.28 and 62.61 mg·g-1 at pH 9.0 than UiO-66 and shorter adsorption equilibrium time of about 150 min. Thermodynamic experiments have shown that the uptake of TC is both endothermic and spontaneous, leading to an increased disorder at the solid-solution interface. It is worth noting that UiO-66-CHO could preserve the 75% removal efficiency in the fifth adsorption cycle.
In this study, UiO-66-CHO and UiO-66-CH=C(CN)2 were synthesized using pre-synthetic and postsynthetic modification methods, for the adsorption of tetracycline (TC) from aqueous solution. The powder X-ray diffraction patterns of these functional MOFs exhibit that they have the same frameworks with UiO-66 and good crystallinity. FTIR and 1H NMR spectroscopy powerfully suggested that the formyl and the cyano were successfully introduced to the frameworks. Compared to UiO-66, UiO-66-CHO and UiO-66-CH=C(CN)2 exhibit slightly diminished thermal stability in the thermogravimetric analysis and the absence of organic linkers. The Brunauer-Emmett-Teller (BET) specific surface area calculated from the N2 adsorption and desorption experiment data shows that all modified materials also preserve porousness. The three materials in the scanning electron microscope showed similar morphology at the microscopic level, and uniform particle size may be favorable for TC adsorption. A series of experiments were conducted on UiO-66-CHO and UiO-66-CH=C(CN)2 for the adsorption of TC in water. For the two functional MOFs, adsorption experiment data confirmed that the adsorption occurs via chemisorption on a monolayer, aligning with the pseudo-second-order kinetic and Langmuir isotherm models. UiO-66-CHO and UiO-66-CH=C (CN)2 exhibited a higher theoretical maximum adsorption capacity of 199.28 and 62.61 mg·g-1 at pH 9.0 than UiO-66 and shorter adsorption equilibrium time of about 150 min. Thermodynamic experiments have shown that the uptake of TC is both endothermic and spontaneous, leading to an increased disorder at the solid-solution interface. It is worth noting that UiO-66-CHO could preserve the 75% removal efficiency in the fifth adsorption cycle.
2025, 41(4): 695-701
doi: 10.11862/CJIC.20240302
Abstract:
A series of halogen axial coordination atoms-modified Fe-N4 (Fe atoms coordinated with four N atoms on the same horizontal plane to form bonds) models (Fe-N4-F/C, Fe-N4-Cl/C, and Fe-N4-Br/C) were constructed based on the density functional theory. All density functional theory (DFT) calculations were carried out using the Dmol3 code in the Materials Studio package. By calculating the partial density of states, Mulliken charge, adsorption energy of intermediates, and free energy of oxygen reduction reaction (ORR), the regulation mechanism of halogen axial coordination atoms on the electronic structure and adsorption behavior of Fe atoms was studied. The structure-activity relationship between halogen axial coordination atoms and the catalytic activity of the Fe-N4 site was also investigated. The results of calculations reveal that the introduction of Br as the halogen axial coordination atoms can optimize the electronic structure of the Fe atom, thus weakening the bonding strength of OH* intermediates on the Fe center. As a result, the Fe-N4-Br/C possesses a lower energy barrier of the rate-determining step (desorption of OH* intermediates) compared to Fe-N4/C, indicating better ORR kinetics process and intrinsic activity of the Fe-N4-Br/C. Therefore, it is speculated that the introduction of halogen axial coordination atoms can improve the catalytic activity of Fe-N4 sites for ORR.
A series of halogen axial coordination atoms-modified Fe-N4 (Fe atoms coordinated with four N atoms on the same horizontal plane to form bonds) models (Fe-N4-F/C, Fe-N4-Cl/C, and Fe-N4-Br/C) were constructed based on the density functional theory. All density functional theory (DFT) calculations were carried out using the Dmol3 code in the Materials Studio package. By calculating the partial density of states, Mulliken charge, adsorption energy of intermediates, and free energy of oxygen reduction reaction (ORR), the regulation mechanism of halogen axial coordination atoms on the electronic structure and adsorption behavior of Fe atoms was studied. The structure-activity relationship between halogen axial coordination atoms and the catalytic activity of the Fe-N4 site was also investigated. The results of calculations reveal that the introduction of Br as the halogen axial coordination atoms can optimize the electronic structure of the Fe atom, thus weakening the bonding strength of OH* intermediates on the Fe center. As a result, the Fe-N4-Br/C possesses a lower energy barrier of the rate-determining step (desorption of OH* intermediates) compared to Fe-N4/C, indicating better ORR kinetics process and intrinsic activity of the Fe-N4-Br/C. Therefore, it is speculated that the introduction of halogen axial coordination atoms can improve the catalytic activity of Fe-N4 sites for ORR.
2025, 41(4): 702-708
doi: 10.11862/CJIC.20240281
Abstract:
This paper conducts an in-depth study of the lattice thermal conductivity and phonon transport properties of two-dimensional single-layer BiOI nanosheets. Combining first-principles calculations and Boltzmann transport theory, we systematically analyzed the phonon group velocity, Greeneisen parameter, three-phonon scattering rate, and scattering phase space of single-layer BiOI nanosheets at different temperatures and other key physical quantities. Calculation results show that the intrinsic lattice thermal conductivity of single-layer BiOI nanosheets at room temperature was approximately 4.71 W·m-1·K-1, significantly decreasing to 1.74 W·m-1·K-1, as the temperature increased to 800 K. The out-of-plane acoustic (ZA), transverse acoustic (TA), and longitudinal acoustic (LA) phonon modes contribute almost equally to the lattice thermal conductivity in the studied temperature range. The physical origin of low lattice thermal conductivity is attributed to low phonon group velocity, strong phonon-phonon scattering process, and low Debye temperature. In addition, we also explored the electronic structure and confirmed that the single-layer BiOI nanosheet has semiconductor properties and an indirect band gap of approximately 2.16 eV.
This paper conducts an in-depth study of the lattice thermal conductivity and phonon transport properties of two-dimensional single-layer BiOI nanosheets. Combining first-principles calculations and Boltzmann transport theory, we systematically analyzed the phonon group velocity, Greeneisen parameter, three-phonon scattering rate, and scattering phase space of single-layer BiOI nanosheets at different temperatures and other key physical quantities. Calculation results show that the intrinsic lattice thermal conductivity of single-layer BiOI nanosheets at room temperature was approximately 4.71 W·m-1·K-1, significantly decreasing to 1.74 W·m-1·K-1, as the temperature increased to 800 K. The out-of-plane acoustic (ZA), transverse acoustic (TA), and longitudinal acoustic (LA) phonon modes contribute almost equally to the lattice thermal conductivity in the studied temperature range. The physical origin of low lattice thermal conductivity is attributed to low phonon group velocity, strong phonon-phonon scattering process, and low Debye temperature. In addition, we also explored the electronic structure and confirmed that the single-layer BiOI nanosheet has semiconductor properties and an indirect band gap of approximately 2.16 eV.
2025, 41(4): 709-718
doi: 10.11862/CJIC.20240280
Abstract:
Orange peel-based carbon quantum dots (OP-CQDs) were prepared by a simple one-step hydrothermal method. The properties of OP-CQDs were studied through fluorescence analysis. The results show that OP-CQDs have good water solubility, strong fluorescence, and stable performance in the physiological pH range. OP-CQDs exhibit a specific quenching reaction towards iron ions (Fe3+) with high sensitivity. At the same time, L-ascorbic acid (L-AA) can partially restore the fluorescence of the OP-CQDs-Fe3+ system to form an"on-off-on"fluorescence detection system. The detection limits of Fe3+ and L-AA were 1.1 and 31.8 μmol·L-1, respectively.
Orange peel-based carbon quantum dots (OP-CQDs) were prepared by a simple one-step hydrothermal method. The properties of OP-CQDs were studied through fluorescence analysis. The results show that OP-CQDs have good water solubility, strong fluorescence, and stable performance in the physiological pH range. OP-CQDs exhibit a specific quenching reaction towards iron ions (Fe3+) with high sensitivity. At the same time, L-ascorbic acid (L-AA) can partially restore the fluorescence of the OP-CQDs-Fe3+ system to form an"on-off-on"fluorescence detection system. The detection limits of Fe3+ and L-AA were 1.1 and 31.8 μmol·L-1, respectively.
2025, 41(4): 719-728
doi: 10.11862/CJIC.20250023
Abstract:
To solve the problem of poor low-temperature performance of lithium-ion batteries (LIBs), an effective method was proposed to improve the low-temperature performance of batteries by adjusting the electrolyte additive formulation. Among them, the additive formulation of lithium tetrafluoroborate (LiBF4)+vinylidene carbonate (VC)+1, 3-propane sulfonate lactone (PS)+fluorinated ethylene carbonate (FEC) had a better protection effect on the electrode. It can improve the electrochemical performance of the battery. The results showed that the target electrolyte had good low-temperature performance, with 0.2C first discharge specific capacities of 144.65 and 133.05 mAh·g-1 for the electrode at -20 and -40 ℃, respectively, and good cycling stability. It is shown that the use of multifunctional additives can significantly improve the diffusion rate of lithium ions and promote the release of lithium ions on the electrode surface. Meanwhile, the better film-forming performance can also reduce the polarization of the battery and ultimately achieve high-capacity and high-stability battery performance under low-temperature conditions.
To solve the problem of poor low-temperature performance of lithium-ion batteries (LIBs), an effective method was proposed to improve the low-temperature performance of batteries by adjusting the electrolyte additive formulation. Among them, the additive formulation of lithium tetrafluoroborate (LiBF4)+vinylidene carbonate (VC)+1, 3-propane sulfonate lactone (PS)+fluorinated ethylene carbonate (FEC) had a better protection effect on the electrode. It can improve the electrochemical performance of the battery. The results showed that the target electrolyte had good low-temperature performance, with 0.2C first discharge specific capacities of 144.65 and 133.05 mAh·g-1 for the electrode at -20 and -40 ℃, respectively, and good cycling stability. It is shown that the use of multifunctional additives can significantly improve the diffusion rate of lithium ions and promote the release of lithium ions on the electrode surface. Meanwhile, the better film-forming performance can also reduce the polarization of the battery and ultimately achieve high-capacity and high-stability battery performance under low-temperature conditions.
