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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:
通过Sr、Ni共掺杂PrBaFe2O5+δ(PBF)制备了中温固体氧化物燃料电池PrBa0.5Sr0.5Fe1.6Ni0.4O5+δ(PBSFN)阴极，并对其性能进行测试。X射线衍射(XRD)图表明，高温煅烧的PBSFN阴极形成了立方钙钛矿结构。在950℃下，混合共烧的PBSFN阴极与La0.9Sr0.1Ga0.83Mg0.17O3-δ(LSGM)电解质表现出良好的化学兼容性。350℃时，在空气气氛下，PBSFN电极材料的电导率最大，其值为681 S·cm-1。800℃时，在空气气氛下，PBSFN阴极在LSGM电解质上的极化阻抗为0.033 Ω·cm2。Sr、Ni掺杂PBSFN阴极的高频阻抗(R1)仅为低频阻抗(R2)的6.4%，表明Sr、Ni掺杂PBSFN提高了阴极的电荷转移效率。此外，该阻抗特性与密度泛函理论计算的PBSFN氧空位形成能结论一致。800℃时，以H2为燃料测试的单电池的最大功率密度为647 mW·cm-2。特别地，采用PBSFN为阴极的单电池在100 h内保持了良好的功率稳定性。
通过Sr、Ni共掺杂PrBaFe2O5+δ(PBF)制备了中温固体氧化物燃料电池PrBa0.5Sr0.5Fe1.6Ni0.4O5+δ(PBSFN)阴极，并对其性能进行测试。X射线衍射(XRD)图表明，高温煅烧的PBSFN阴极形成了立方钙钛矿结构。在950℃下，混合共烧的PBSFN阴极与La0.9Sr0.1Ga0.83Mg0.17O3-δ(LSGM)电解质表现出良好的化学兼容性。350℃时，在空气气氛下，PBSFN电极材料的电导率最大，其值为681 S·cm-1。800℃时，在空气气氛下，PBSFN阴极在LSGM电解质上的极化阻抗为0.033 Ω·cm2。Sr、Ni掺杂PBSFN阴极的高频阻抗(R1)仅为低频阻抗(R2)的6.4%，表明Sr、Ni掺杂PBSFN提高了阴极的电荷转移效率。此外，该阻抗特性与密度泛函理论计算的PBSFN氧空位形成能结论一致。800℃时，以H2为燃料测试的单电池的最大功率密度为647 mW·cm-2。特别地，采用PBSFN为阴极的单电池在100 h内保持了良好的功率稳定性。
2025, 41(4): 650-660
doi: 10.11862/CJIC.20240386
Abstract:
以锌基沸石咪唑酯骨架(Zn-based zeolitic imidazolate framework，Zn-ZIF)为前驱体，通过简单的一步热解策略制备出锌纳米粒子修饰的氮掺杂多孔碳(N-C)催化剂(Zn@N-C)，进一步将其负载的Zn纳米粒子通过硒化反应转化为ZnSe纳米颗粒，构建出ZnSe@N-C异质结催化剂。采用X射线衍射(XRD)、拉曼(Raman)光谱、X射线光电子能谱(XPS)、场发射扫描电子显微镜(FESEM)和透射电子显微镜(TEM)对催化剂的组分、结构和形貌进行了表征，并通过电化学测试系统评估了2种催化剂在析氢反应(hydrogen evolution reaction，HER)中的催化活性和稳定性。结果表明：通过硒化处理，催化剂的形貌由规整的菱形十二面体(Zn@N-C)转变为结构塌陷、褶皱变形的十二面体(ZnSe@N-C)，这增加了结构缺陷，从而引入了更多的催化活性位点。同时ZnSe和N-C基底间存在异质界面结构，这促进了电子的传输，提高了催化剂的活性。ZnSe@N-C在碱性HER过程中，在10 mA·cm-2的电流密度下获得了165.8 mV的过电位，优于Zn@N-C (190.8 mV)。此外，ZnSe@N-C在碱性溶液中具有良好的电化学稳定性。
以锌基沸石咪唑酯骨架(Zn-based zeolitic imidazolate framework，Zn-ZIF)为前驱体，通过简单的一步热解策略制备出锌纳米粒子修饰的氮掺杂多孔碳(N-C)催化剂(Zn@N-C)，进一步将其负载的Zn纳米粒子通过硒化反应转化为ZnSe纳米颗粒，构建出ZnSe@N-C异质结催化剂。采用X射线衍射(XRD)、拉曼(Raman)光谱、X射线光电子能谱(XPS)、场发射扫描电子显微镜(FESEM)和透射电子显微镜(TEM)对催化剂的组分、结构和形貌进行了表征，并通过电化学测试系统评估了2种催化剂在析氢反应(hydrogen evolution reaction，HER)中的催化活性和稳定性。结果表明：通过硒化处理，催化剂的形貌由规整的菱形十二面体(Zn@N-C)转变为结构塌陷、褶皱变形的十二面体(ZnSe@N-C)，这增加了结构缺陷，从而引入了更多的催化活性位点。同时ZnSe和N-C基底间存在异质界面结构，这促进了电子的传输，提高了催化剂的活性。ZnSe@N-C在碱性HER过程中，在10 mA·cm-2的电流密度下获得了165.8 mV的过电位，优于Zn@N-C (190.8 mV)。此外，ZnSe@N-C在碱性溶液中具有良好的电化学稳定性。
2025, 41(4): 661-674
doi: 10.11862/CJIC.20240363
Abstract:
通过溶剂热并辅以硫化法制备了金属有机骨架(MOF)基镍钴双金属硫化物微球，并通过高温热解有机碳源盐酸多巴胺制备了痕量氮掺杂碳包覆(NC)的Ni-Co-S@NC钠离子电池负极材料。这种改性能够有效提高电极材料的导电性以及结构和界面的稳定性，从而提高材料的循环稳定性。其中表面包覆约5 nm碳层的Ni-Co-S@NC-0.5微球具有出色的长循环寿命，其在1A·g-1下循环1 000圈后，仍有381.8 mAh·g-1的放电比容量和75.2%的容量保持率，相应地每圈循环的容量衰减量仅为0.126mAh·g-1；Ni-Co-S@NC-0.5||NVP/C (NVP：Na3V2(PO4)3)钠离子全电池在1 A·g-1下经过100次循环后，可逆放电比容量为386.2mAh·g-1，容量保持率为88.6%，库仑效率稳定在98.1%左右。动力学研究表明，Ni-Co-S@NC-0.5的储钠过程以赝电容行为控制为主，钠离子扩散系数在10-11~10-13 cm2·s-1之间，同时具有相对小的电荷转移阻抗(36.7 Ω)。
通过溶剂热并辅以硫化法制备了金属有机骨架(MOF)基镍钴双金属硫化物微球，并通过高温热解有机碳源盐酸多巴胺制备了痕量氮掺杂碳包覆(NC)的Ni-Co-S@NC钠离子电池负极材料。这种改性能够有效提高电极材料的导电性以及结构和界面的稳定性，从而提高材料的循环稳定性。其中表面包覆约5 nm碳层的Ni-Co-S@NC-0.5微球具有出色的长循环寿命，其在1A·g-1下循环1 000圈后，仍有381.8 mAh·g-1的放电比容量和75.2%的容量保持率，相应地每圈循环的容量衰减量仅为0.126mAh·g-1；Ni-Co-S@NC-0.5||NVP/C (NVP：Na3V2(PO4)3)钠离子全电池在1 A·g-1下经过100次循环后，可逆放电比容量为386.2mAh·g-1，容量保持率为88.6%，库仑效率稳定在98.1%左右。动力学研究表明，Ni-Co-S@NC-0.5的储钠过程以赝电容行为控制为主，钠离子扩散系数在10-11~10-13 cm2·s-1之间，同时具有相对小的电荷转移阻抗(36.7 Ω)。
2025, 41(4): 675-682
doi: 10.11862/CJIC.20240339
Abstract:
通过一步水热法成功制备了一种水系锌离子电池正极材料——富1T相的MoS2(1T′-MoS2)。表征结果与密度泛函理论(DFT)模拟计算表明，1T′-MoS2的电导率明显高于2H-MoS2，并且含有丰富的硫缺陷。这有助于大幅提升离子扩散速率和电荷转移速率，优化材料的电化学和动力学性能。因此，采用1T′-MoS2组装的电池在0.1 A·g-1的电流密度下，首次放电容量高达202 mAh·g-1。此外，在大电流密度下(1 A·g-1)，其经过500次恒电流充放电循环后，电池的容量保持率为92%，显示出较高的容量和长循环稳定性。
通过一步水热法成功制备了一种水系锌离子电池正极材料——富1T相的MoS2(1T′-MoS2)。表征结果与密度泛函理论(DFT)模拟计算表明，1T′-MoS2的电导率明显高于2H-MoS2，并且含有丰富的硫缺陷。这有助于大幅提升离子扩散速率和电荷转移速率，优化材料的电化学和动力学性能。因此，采用1T′-MoS2组装的电池在0.1 A·g-1的电流密度下，首次放电容量高达202 mAh·g-1。此外，在大电流密度下(1 A·g-1)，其经过500次恒电流充放电循环后，电池的容量保持率为92%，显示出较高的容量和长循环稳定性。
2025, 41(4): 683-694
doi: 10.11862/CJIC.20240291
Abstract:
本研究通过预修饰和后修饰2种策略分别合成了官能化锆基金属有机骨架(MOF)材料UiO-66-CHO和UiO-66-CH=C (CN)2，用于去除水中的四环素(TC)。采用粉末X射线衍射、FTIR、1H NMR、热重分析、扫描电子显微镜和N2吸附-脱附等测试手段对合成的MOFs进行了表征。UiO-66-CHO较UiO-66-CH=C (CN)2比表面积大，吸附性能更好。实验数据证实，2种MOFs对TC的吸附符合准二级动力学和Langmuir等温线模型，是单层的化学吸附。在pH=9.0时，UiO-66-CHO和UiO-66-CH=C (CN)2的理论最大吸附量分别为199.28和62.61 mg·g-1，平衡时间为150 min。热力学分析表明，UiO-66-CHO吸附TC是一个自发的吸热过程。UiO-66-CHO在重复5次循环吸附后，对TC去除率仍达75%以上。
本研究通过预修饰和后修饰2种策略分别合成了官能化锆基金属有机骨架(MOF)材料UiO-66-CHO和UiO-66-CH=C (CN)2，用于去除水中的四环素(TC)。采用粉末X射线衍射、FTIR、1H NMR、热重分析、扫描电子显微镜和N2吸附-脱附等测试手段对合成的MOFs进行了表征。UiO-66-CHO较UiO-66-CH=C (CN)2比表面积大，吸附性能更好。实验数据证实，2种MOFs对TC的吸附符合准二级动力学和Langmuir等温线模型，是单层的化学吸附。在pH=9.0时，UiO-66-CHO和UiO-66-CH=C (CN)2的理论最大吸附量分别为199.28和62.61 mg·g-1，平衡时间为150 min。热力学分析表明，UiO-66-CHO吸附TC是一个自发的吸热过程。UiO-66-CHO在重复5次循环吸附后，对TC去除率仍达75%以上。
2025, 41(4): 695-701
doi: 10.11862/CJIC.20240302
Abstract:
采用密度泛函理论构建了不同卤族轴向配位原子修饰的碳载Fe-N4位点(Fe原子与同一水平面的4个N原子配位成键)模型(Fe-N4-F/C、Fe-N4-Cl/C和Fe-N4-Br/C)，通过计算上述模型的态密度、Mulliken电荷、氧还原中间体吸附能以及氧还原自由能，深入研究卤族轴向配位原子对Fe中心电子结构和吸附行为的调控机理，明确不同卤族轴向原子与Fe-N4位点氧还原活性之间的构效关系。计算结果发现，引入Br作为轴向配位原子可以有效优化Fe原子的电子结构，从而适当降低Fe中心对OH*中间体的吸附强度，促进OH*解吸反应顺利进行。与Fe-N4/C模型相比，Fe-N4-Br/C模型具有更低的决速步骤(即OH*解吸)反应能垒。因此预测卤族轴向配位原子修饰策略能够改善Fe-N4位点的氧还原本征催化活性。
采用密度泛函理论构建了不同卤族轴向配位原子修饰的碳载Fe-N4位点(Fe原子与同一水平面的4个N原子配位成键)模型(Fe-N4-F/C、Fe-N4-Cl/C和Fe-N4-Br/C)，通过计算上述模型的态密度、Mulliken电荷、氧还原中间体吸附能以及氧还原自由能，深入研究卤族轴向配位原子对Fe中心电子结构和吸附行为的调控机理，明确不同卤族轴向原子与Fe-N4位点氧还原活性之间的构效关系。计算结果发现，引入Br作为轴向配位原子可以有效优化Fe原子的电子结构，从而适当降低Fe中心对OH*中间体的吸附强度，促进OH*解吸反应顺利进行。与Fe-N4/C模型相比，Fe-N4-Br/C模型具有更低的决速步骤(即OH*解吸)反应能垒。因此预测卤族轴向配位原子修饰策略能够改善Fe-N4位点的氧还原本征催化活性。
2025, 41(4): 702-708
doi: 10.11862/CJIC.20240281
Abstract:
针对二维单层BiOI纳米片的晶格热导率及其声子输运性质进行了深入探究。通过结合第一性原理计算和玻尔兹曼输运理论，系统地分析了单层BiOI纳米片在不同温度下的声子群速度、格林艾森参数、三声子散射率和散射相空间等关键物理量。计算结果显示，单层BiOI纳米片在室温下的本征晶格热导率约为4.71 W·m-1·K-1，当温度升高至800 K时，其热导率显著降低至1.74 W·m-1·K-1。面外声学支(ZA)、横向声学支(TA)和纵向声学支(LA)声子模式在所研究的温度范围内对晶格热导率的贡献几乎相等。低晶格热导率的物理根源归结于低声子群速度、强烈的声子-声子散射过程以及较低的德拜温度。此外，还探讨了单层BiOI纳米片的电子结构，确认了其具有半导体特性，并且间接带隙约为2.16 eV。
针对二维单层BiOI纳米片的晶格热导率及其声子输运性质进行了深入探究。通过结合第一性原理计算和玻尔兹曼输运理论，系统地分析了单层BiOI纳米片在不同温度下的声子群速度、格林艾森参数、三声子散射率和散射相空间等关键物理量。计算结果显示，单层BiOI纳米片在室温下的本征晶格热导率约为4.71 W·m-1·K-1，当温度升高至800 K时，其热导率显著降低至1.74 W·m-1·K-1。面外声学支(ZA)、横向声学支(TA)和纵向声学支(LA)声子模式在所研究的温度范围内对晶格热导率的贡献几乎相等。低晶格热导率的物理根源归结于低声子群速度、强烈的声子-声子散射过程以及较低的德拜温度。此外，还探讨了单层BiOI纳米片的电子结构，确认了其具有半导体特性，并且间接带隙约为2.16 eV。
2025, 41(4): 709-718
doi: 10.11862/CJIC.20240280
Abstract:
以生物质橙子皮为原料，通过简单的一步水热法制备了橙子皮基碳量子点(orange peel-based carbon quantum dots，OP-CQDs)，并用荧光分析法对其性质进行了研究。结果表明，OP-CQDs水溶性好、荧光强、在生理pH范围内性能稳定。OP-CQDs对铁离子(Fe3+)有特异性猝灭反应且灵敏度高，同时，L-抗坏血酸(L-ascorbic acid，L-AA)能够使OP-CQDs-Fe3+体系的荧光部分恢复，形成了“开-关-开”的荧光检测体系。Fe3+和L-AA的检出限分别为1.1和31.8 μmol·L-1。
以生物质橙子皮为原料，通过简单的一步水热法制备了橙子皮基碳量子点(orange peel-based carbon quantum dots，OP-CQDs)，并用荧光分析法对其性质进行了研究。结果表明，OP-CQDs水溶性好、荧光强、在生理pH范围内性能稳定。OP-CQDs对铁离子(Fe3+)有特异性猝灭反应且灵敏度高，同时，L-抗坏血酸(L-ascorbic acid，L-AA)能够使OP-CQDs-Fe3+体系的荧光部分恢复，形成了“开-关-开”的荧光检测体系。Fe3+和L-AA的检出限分别为1.1和31.8 μmol·L-1。
2025, 41(4): 719-728
doi: 10.11862/CJIC.20250023
Abstract:
为解决锂离子电池(LIBs)低温性能较差的问题，提出了一种通过调节电解质添加剂配方，提高电池低温性能的有效方法。其中，四氟硼酸锂(LiBF4)+碳酸亚乙烯酯(VC)+1，3-丙烷磺酸内酯(PS)+氟代碳酸乙烯酯(FEC)的添加剂配方对电极有较好的保护作用，能够提高电化学性能。结果表明，目标电解液具有良好的低温性能，在-20和-40℃条件下电极的首圈放电比容量(0.2C)分别为144.65和133.05 mAh·g-1，且具有良好的循环稳定性。研究表明，使用多功能添加剂可以显著提高锂离子的扩散速率，促进其在电极表面的释放。同时，添加剂较好的成膜性能还可以减少电池的极化，最终实现低温条件下高容量、高稳定的电池性能。
为解决锂离子电池(LIBs)低温性能较差的问题，提出了一种通过调节电解质添加剂配方，提高电池低温性能的有效方法。其中，四氟硼酸锂(LiBF4)+碳酸亚乙烯酯(VC)+1，3-丙烷磺酸内酯(PS)+氟代碳酸乙烯酯(FEC)的添加剂配方对电极有较好的保护作用，能够提高电化学性能。结果表明，目标电解液具有良好的低温性能，在-20和-40℃条件下电极的首圈放电比容量(0.2C)分别为144.65和133.05 mAh·g-1，且具有良好的循环稳定性。研究表明，使用多功能添加剂可以显著提高锂离子的扩散速率，促进其在电极表面的释放。同时，添加剂较好的成膜性能还可以减少电池的极化，最终实现低温条件下高容量、高稳定的电池性能。
