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无机化学学报
Chinese Journal of Inorganic Chemistry
主管 : 中国科学技术协会
刊期 : 月刊主编 : 游效曾
语种 : 中文主办 : 中国化学会
ISSN : 1001-4861 CN : 32-1185/O6展开 >《无机化学学报》由中国化学会主办，是展示我国无机化学研究成果的学术性期刊，月刊。1985年由化学前辈戴安邦院士（发起）创刊，现任主编游效曾院士。编辑部设在南京大学化学化工学院化学楼。报道我国无机化学领域的基础研究和应用基础研究的创新成果，内容涉及固体无机化学、配位化学、无机材料化学、生物无机化学、有机金属化学、理论无机化学、超分子化学和应用无机化学、催化等，着重报道新的和已知化合物的合成、热力学、动力学性质、谱学、结构和成键等。设有综述、研究快报及论文等栏目。
本刊所刊论文均为美国《科学引文索引》（SCI）网络版、美国《化学文摘》(CA)、《中国学术期刊文摘》（中、英文版）、《中国科技论文与引文数据库（CSTPCD）》、《中国科学引文数据库》、《中文科技期刊数据库》、《中国期刊全文数据库》、《中国核心期刊（遴选）数据库》、中国台湾华艺《中文电子期刊服务》等国内外多种著名检索刊物和文献数据库摘引和收录。
《无机化学学报》2011年每期200页，定价28.00元、全年定价336.00元。本刊由各地邮局征订，邮发代号28-133。也可直接向编辑部订阅。
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期刊内热点文章
2024, 40(10): 1825-1839
doi: 10.11862/CJIC.20240225
摘要:
双金属有机骨架(BMOFs)是以2种不同的金属离子作为节点与有机配体通过配位键连接起来的一类新型杂化材料。BMOFs具有比表面积大、负载量高、组成及孔径可调等优点，可以用作合成具有可控的尺寸、组成和结构的功能纳米材料的模板或前驱体。与单金属MOFs相比，BMOFs在生物医学领域具有更好的离子协同效应、催化选择性和结构稳定性。本综述总结了BMOFs用于肿瘤单一治疗和联合治疗以及在磁共振成像等方面应用的最新研究进展。最后讨论了BMOFs在肿瘤诊疗中存在的挑战和未来发展趋势。
双金属有机骨架(BMOFs)是以2种不同的金属离子作为节点与有机配体通过配位键连接起来的一类新型杂化材料。BMOFs具有比表面积大、负载量高、组成及孔径可调等优点，可以用作合成具有可控的尺寸、组成和结构的功能纳米材料的模板或前驱体。与单金属MOFs相比，BMOFs在生物医学领域具有更好的离子协同效应、催化选择性和结构稳定性。本综述总结了BMOFs用于肿瘤单一治疗和联合治疗以及在磁共振成像等方面应用的最新研究进展。最后讨论了BMOFs在肿瘤诊疗中存在的挑战和未来发展趋势。
2024, 40(10): 1840-1849
doi: 10.11862/CJIC.20240216
摘要:
A 3D nitrogen-doped graphene/multi-walled carbon nanotube (CS-GO-NCNT) crosslinked network material was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources, concomitant with the incorporation of multi-wall carbon nanotubes and employing freeze drying technology. The material amalgamates the merits of 1D/2D hybrid carbon materials, wherein 1D carbon nanotubes confer robustness and expedited electron transport pathways, while 2D graphene sheets facilitate rapid ion migration. Furthermore, the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage. When served as an anode material for lithium-ion batteries, the CS-GO-NCNT electrode delivered a reversible capacity surpassing 500 mAh·g-1, markedly outperforming commercial graphite anodes. Even after 300 cycles at a high current density of 1 A·g-1, it remained a reversible capacity of up to 268 mAh·g-1.
A 3D nitrogen-doped graphene/multi-walled carbon nanotube (CS-GO-NCNT) crosslinked network material was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources, concomitant with the incorporation of multi-wall carbon nanotubes and employing freeze drying technology. The material amalgamates the merits of 1D/2D hybrid carbon materials, wherein 1D carbon nanotubes confer robustness and expedited electron transport pathways, while 2D graphene sheets facilitate rapid ion migration. Furthermore, the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage. When served as an anode material for lithium-ion batteries, the CS-GO-NCNT electrode delivered a reversible capacity surpassing 500 mAh·g-1, markedly outperforming commercial graphite anodes. Even after 300 cycles at a high current density of 1 A·g-1, it remained a reversible capacity of up to 268 mAh·g-1.
2024, 40(10): 1975-1985
doi: 10.11862/CJIC.20240180
摘要:
Three coordination polymers [Mn(epda)(2,2′-bipy)(H2O)] (1), [Mn(epda)(phen)] (2), and [Co2(epda)2(bpe)2(H2O)4]·5H2O (3) (H2epda=5-ethyl-pyridine-2,3-dicarboxylic acid, 2,2′-bipy=2,2′-bipyridine, phen=phenanthroline, bpe=1,2-bis(4-pyridyl) ethylene) were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. 1 displays a 1D chain structure, and these chains are joined by O—H…O hydrogen bonding and π-π stacking interactions to generate a 2D layer structure. 2 displays a 2D layer structure, and adjacent layers are generated 3D architecture through π-π stacking interactions. 3 displays a 1D chain structure, and adjacent chains are generated double layer structure through O—H…O hydrogen bonding. The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor. 1 was highly selective and sensitive towards o-nitrophenol through different detection mechanisms, however, 3 was highly selective and sensitive towards 2,4,6-trinitrophenol. In addition, the magnetic behavior of 2 has also been investigated.
Three coordination polymers [Mn(epda)(2,2′-bipy)(H2O)] (1), [Mn(epda)(phen)] (2), and [Co2(epda)2(bpe)2(H2O)4]·5H2O (3) (H2epda=5-ethyl-pyridine-2,3-dicarboxylic acid, 2,2′-bipy=2,2′-bipyridine, phen=phenanthroline, bpe=1,2-bis(4-pyridyl) ethylene) were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. 1 displays a 1D chain structure, and these chains are joined by O—H…O hydrogen bonding and π-π stacking interactions to generate a 2D layer structure. 2 displays a 2D layer structure, and adjacent layers are generated 3D architecture through π-π stacking interactions. 3 displays a 1D chain structure, and adjacent chains are generated double layer structure through O—H…O hydrogen bonding. The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor. 1 was highly selective and sensitive towards o-nitrophenol through different detection mechanisms, however, 3 was highly selective and sensitive towards 2,4,6-trinitrophenol. In addition, the magnetic behavior of 2 has also been investigated.
2024, 40(10): 1986-1994
doi: 10.11862/CJIC.20240153
摘要:
A novel compound (H2L)SCN (5-methyl-3-phenyl-2H-pyrazol-1-ium thiocyanate) has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol. Two zinc(Ⅱ) complexes [Zn(HL)2(NCS)(CH3COO)] (1) and [Zn2(L)2(HL)2(NCS)2]2·2CH3OH (2) have been synthesized by the coordination reactions of Zn(OAc)2·2H2O or ZnCl2 with (H2L)SCN under reflux conditions. Elemental analyses and single-crystal X-ray diffraction have confirmed the structures of the synthesized compounds. The (H2L)SCN ligand and complex 1 pertain to the triclinic system with space group P1, while complex 2 belongs to the monoclinic system with space group P21/n. Additionally, the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bacterial strains (Candida albicans, Staphylococcus aureus, and Escherichia coli). The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria, and the complexes possessed stronger antibacterial activities against the same bacteria than the free ligand.
A novel compound (H2L)SCN (5-methyl-3-phenyl-2H-pyrazol-1-ium thiocyanate) has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol. Two zinc(Ⅱ) complexes [Zn(HL)2(NCS)(CH3COO)] (1) and [Zn2(L)2(HL)2(NCS)2]2·2CH3OH (2) have been synthesized by the coordination reactions of Zn(OAc)2·2H2O or ZnCl2 with (H2L)SCN under reflux conditions. Elemental analyses and single-crystal X-ray diffraction have confirmed the structures of the synthesized compounds. The (H2L)SCN ligand and complex 1 pertain to the triclinic system with space group P1, while complex 2 belongs to the monoclinic system with space group P21/n. Additionally, the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bacterial strains (Candida albicans, Staphylococcus aureus, and Escherichia coli). The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria, and the complexes possessed stronger antibacterial activities against the same bacteria than the free ligand.
2024, 40(10): 1995-2008
doi: 10.11862/CJIC.20240164
摘要:
This work adopts a multi-step etching-heat treatment strategy to prepare porous silicon microsphere composite with Sb-Sn surface modification and carbon coating (pSi/Sb-Sn@C), using industrial grade SiAl alloy micro-spheres as a precursor. pSi/Sb-Sn@C had a 3D structure with bimetallic (Sb-Sn) modified porous silicon micro-spheres (pSi/Sb-Sn) as the core and carbon coating as the shell. Carbon shells can improve the electronic conductivity and mechanical stability of porous silicon microspheres, which is beneficial for obtaining a stable solid electrolyte interface (SEI) film. The 3D porous core promotes the diffusion of lithium ions, increases the intercalation/delithiation active sites, and buffers the volume expansion during the intercalation process. The introduction of active metals (Sb-Sn) can improve the conductivity of the composite and contribute to a certain amount of lithium storage capacity. Due to its unique composition and microstructure, pSi/Sb-Sn@C showed a reversible capacity of 1 247.4 mAh·g-1 after 300 charge/discharge cycles at a current density of 1.0 A·g-1, demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.
This work adopts a multi-step etching-heat treatment strategy to prepare porous silicon microsphere composite with Sb-Sn surface modification and carbon coating (pSi/Sb-Sn@C), using industrial grade SiAl alloy micro-spheres as a precursor. pSi/Sb-Sn@C had a 3D structure with bimetallic (Sb-Sn) modified porous silicon micro-spheres (pSi/Sb-Sn) as the core and carbon coating as the shell. Carbon shells can improve the electronic conductivity and mechanical stability of porous silicon microspheres, which is beneficial for obtaining a stable solid electrolyte interface (SEI) film. The 3D porous core promotes the diffusion of lithium ions, increases the intercalation/delithiation active sites, and buffers the volume expansion during the intercalation process. The introduction of active metals (Sb-Sn) can improve the conductivity of the composite and contribute to a certain amount of lithium storage capacity. Due to its unique composition and microstructure, pSi/Sb-Sn@C showed a reversible capacity of 1 247.4 mAh·g-1 after 300 charge/discharge cycles at a current density of 1.0 A·g-1, demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.
2024, 40(10): 2009-2020
doi: 10.11862/CJIC.20240120
摘要:
In this work, p-phenylenediamine and L-cysteine were used as raw materials, and water-soluble N, S co-doped carbon dots (N, S-CDs) with excellent performance were prepared through a one-step solvothermal method. The morphology and structure of N, S-CDs were characterized by transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, and the basic photophysical properties were investigated via UV-Vis absorption spectra and fluorescence spectra. Meanwhile, the N, S-CDs have excellent luminescence stability with pH, ionic strength, radiation time, and storage time. Experimental results illustrated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1. The quenching mechanism is proved to be the inner filter effect. In addition, this sensor can also detect baicalein in biofluids (serum and urine) with good accuracy and reproducibility.
In this work, p-phenylenediamine and L-cysteine were used as raw materials, and water-soluble N, S co-doped carbon dots (N, S-CDs) with excellent performance were prepared through a one-step solvothermal method. The morphology and structure of N, S-CDs were characterized by transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, and the basic photophysical properties were investigated via UV-Vis absorption spectra and fluorescence spectra. Meanwhile, the N, S-CDs have excellent luminescence stability with pH, ionic strength, radiation time, and storage time. Experimental results illustrated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1. The quenching mechanism is proved to be the inner filter effect. In addition, this sensor can also detect baicalein in biofluids (serum and urine) with good accuracy and reproducibility.
Green synthesis of MIL-101/Au composite particles and their sensitivity to Raman detection of thiram
2024, 40(10): 2021-2030
doi: 10.11862/CJIC.20240059
摘要:
Metal-organic framework (MOF) MIL-101 and surface plasmon polariton (SPP) supported gold nanoparticles (Au NPs) hybrid systems were developed as a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) detection platform, in which a green electrostatic self-assembly technology was adopted to construct the substrate. In an aqueous solution, the electronegativity of the particles can be used to prepare the composite substrate without any surface modifier. Due to the enrichment capacity of MIL-101 and the electromagnetic enhancement from Au NPs, the well-designed MIL-101/Au composites possessed ultrahigh sensitivity with the detection limit of Rhodamine 6G (R6G) as low as 10-10 mol·L-1. Meanwhile, the substrate exhibits high stability, excellent reproducibility, and recyclability. Additionally, the novel substrate can be explored for direct capture, and sensitively detect pesticide residues such as thiram.
Metal-organic framework (MOF) MIL-101 and surface plasmon polariton (SPP) supported gold nanoparticles (Au NPs) hybrid systems were developed as a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) detection platform, in which a green electrostatic self-assembly technology was adopted to construct the substrate. In an aqueous solution, the electronegativity of the particles can be used to prepare the composite substrate without any surface modifier. Due to the enrichment capacity of MIL-101 and the electromagnetic enhancement from Au NPs, the well-designed MIL-101/Au composites possessed ultrahigh sensitivity with the detection limit of Rhodamine 6G (R6G) as low as 10-10 mol·L-1. Meanwhile, the substrate exhibits high stability, excellent reproducibility, and recyclability. Additionally, the novel substrate can be explored for direct capture, and sensitively detect pesticide residues such as thiram.
2024, 40(10): 2031-2039
doi: 10.11862/CJIC.20240109
摘要:
Two new coordination polymers, [Ni(Hpdc)(bib)(H2O)]n (1) and {[Ni(bib)3](ClO4)2}n (2), were prepared by mixing Ni2+, 3, 5-pyrazoledicarboxylic acid (H3pdc)/p-nitrobenzoic acid and 1, 4-bis(imidazol-1-ylmethyl) butane (bib) by a hydrothermal method, respectively. X-ray crystallography reveals a 2D network constructed by six-coordinated Ni (Ⅱ) centers, bib, and Hpdc2- ligands in complex 1, while a 2D network is built by Ni (Ⅱ) and bib ligands in 2. Furthermore, the quantum-chemical calculations have been performed on'molecular fragments'extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.
Two new coordination polymers, [Ni(Hpdc)(bib)(H2O)]n (1) and {[Ni(bib)3](ClO4)2}n (2), were prepared by mixing Ni2+, 3, 5-pyrazoledicarboxylic acid (H3pdc)/p-nitrobenzoic acid and 1, 4-bis(imidazol-1-ylmethyl) butane (bib) by a hydrothermal method, respectively. X-ray crystallography reveals a 2D network constructed by six-coordinated Ni (Ⅱ) centers, bib, and Hpdc2- ligands in complex 1, while a 2D network is built by Ni (Ⅱ) and bib ligands in 2. Furthermore, the quantum-chemical calculations have been performed on'molecular fragments'extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.
2024, 40(10): 1850-1860
doi: 10.11862/CJIC.20240173
摘要:
采用溶剂热合成方法，合成了一种新型金属配位聚合物{[Zn2(L)(H2O)(DMA)]·DMA·2.3H2O}n (1)，其中L4-为完全脱去质子的N，N'-二(4-羧基苄基)-5-氨基间苯二甲酸，DMA为N，N-二甲基乙酰胺。单晶X射线衍射结果显示，该配合物属于三斜晶系，空间群为P1，a=0.989 6(5) nm，b=1.370 5(5) nm，c=1.382 1(5) nm，α=80.067(5)°，β=76.729(5)°，γ=76.611(5)°，结构是由二维金属有机层通过π…π相互作用而扩展成的三维超分子骨架。红外光谱验证了锌离子与L4-配体成功配位。粉末X射线衍射(PXRD)实验证实了配合物1具有较高的纯度。热重分析结果显示配合物1在室温至416.9 ℃区间内具有较好的热稳定性。在273 nm的激发光下，配合物1在437 nm处有较强的荧光发射，可以在30 s内快速检测乙醇溶液中的炭疽生物标志物——吡啶-2，6-二甲酸，具有选择性高、抗干扰能力强、检测限低(约为15 μmol·L-1)等特点。结合PXRD图和紫外可见吸收光谱揭示了其检测机理为晶体骨架坍塌而诱导的荧光猝灭。
采用溶剂热合成方法，合成了一种新型金属配位聚合物{[Zn2(L)(H2O)(DMA)]·DMA·2.3H2O}n (1)，其中L4-为完全脱去质子的N，N'-二(4-羧基苄基)-5-氨基间苯二甲酸，DMA为N，N-二甲基乙酰胺。单晶X射线衍射结果显示，该配合物属于三斜晶系，空间群为P1，a=0.989 6(5) nm，b=1.370 5(5) nm，c=1.382 1(5) nm，α=80.067(5)°，β=76.729(5)°，γ=76.611(5)°，结构是由二维金属有机层通过π…π相互作用而扩展成的三维超分子骨架。红外光谱验证了锌离子与L4-配体成功配位。粉末X射线衍射(PXRD)实验证实了配合物1具有较高的纯度。热重分析结果显示配合物1在室温至416.9 ℃区间内具有较好的热稳定性。在273 nm的激发光下，配合物1在437 nm处有较强的荧光发射，可以在30 s内快速检测乙醇溶液中的炭疽生物标志物——吡啶-2，6-二甲酸，具有选择性高、抗干扰能力强、检测限低(约为15 μmol·L-1)等特点。结合PXRD图和紫外可见吸收光谱揭示了其检测机理为晶体骨架坍塌而诱导的荧光猝灭。
2024, 40(10): 1861-1868
doi: 10.11862/CJIC.20240242
摘要:
采用高温固相法制备不同浓度Eu3+掺杂CaLaGaO4系列红色荧光粉。研究结果显示，该系列荧光粉能够被392 nm的近紫外光有效激发，在609 nm处有强烈的红光发射，其光强主要依赖于Eu3+的 5D0→7F2跃迁所发射的光，且在Eu3+浓度达到0.3时发光强度达到最大，其色坐标为(0.613，0.359)，与标准红光坐标(0.670，0.330)较为接近，色纯度高达96.3%。由于热猝灭效应，当样品温度升高至498 K时，发光强度仍保持室温下的75%，激活能为0.151 3 eV。
采用高温固相法制备不同浓度Eu3+掺杂CaLaGaO4系列红色荧光粉。研究结果显示，该系列荧光粉能够被392 nm的近紫外光有效激发，在609 nm处有强烈的红光发射，其光强主要依赖于Eu3+的 5D0→7F2跃迁所发射的光，且在Eu3+浓度达到0.3时发光强度达到最大，其色坐标为(0.613，0.359)，与标准红光坐标(0.670，0.330)较为接近，色纯度高达96.3%。由于热猝灭效应，当样品温度升高至498 K时，发光强度仍保持室温下的75%，激活能为0.151 3 eV。
2024, 40(10): 1869-1880
doi: 10.11862/CJIC.20240187
摘要:
通过水浴-逆共沉淀法制备磁性催化剂MnFe2O4@AC (MFA)，并对其结构和磁性进行了系统表征。结果显示，MnFe2O4纳米颗粒包覆在活性炭(AC)表面，构成了多级孔结构。MFA较AC基体材料的比表面积有所下降，但仍高达176 m2·g-1，平均孔径为8.49 nm。MFA的比磁化强度高达38.92 emu·g-1，可利用外磁场实现高效固液分离。以MFA为催化剂，在紫外光辅助下活化过硫酸氢钾(PMS)降解盐酸四环素(TC)。研究表明，在紫外光辐照下MFA/PMS体系对TC降解率能够达到97.70%，是无紫外光照射体系的1.2倍；共存阴离子、药剂制度、TC初始质量浓度等因素对系统的催化性能具有显著影响。循环5次之后，降解率仍可达到82.76%。自由基猝灭实验表明，超氧自由基(·O2-)和单线态氧(1O2)是紫外光辅助MFA/PMS高级氧化体系中的主要活性氧。机理分析表明，MFA的高吸附性为催化降解提供了良好的基础，紫外光辐照和MFA/PMS高级氧化体系的协同效应可显著提升活性基团的生成效率，从而促进了有机分子的降解。
通过水浴-逆共沉淀法制备磁性催化剂MnFe2O4@AC (MFA)，并对其结构和磁性进行了系统表征。结果显示，MnFe2O4纳米颗粒包覆在活性炭(AC)表面，构成了多级孔结构。MFA较AC基体材料的比表面积有所下降，但仍高达176 m2·g-1，平均孔径为8.49 nm。MFA的比磁化强度高达38.92 emu·g-1，可利用外磁场实现高效固液分离。以MFA为催化剂，在紫外光辅助下活化过硫酸氢钾(PMS)降解盐酸四环素(TC)。研究表明，在紫外光辐照下MFA/PMS体系对TC降解率能够达到97.70%，是无紫外光照射体系的1.2倍；共存阴离子、药剂制度、TC初始质量浓度等因素对系统的催化性能具有显著影响。循环5次之后，降解率仍可达到82.76%。自由基猝灭实验表明，超氧自由基(·O2-)和单线态氧(1O2)是紫外光辅助MFA/PMS高级氧化体系中的主要活性氧。机理分析表明，MFA的高吸附性为催化降解提供了良好的基础，紫外光辐照和MFA/PMS高级氧化体系的协同效应可显著提升活性基团的生成效率，从而促进了有机分子的降解。
2024, 40(10): 1881-1891
doi: 10.11862/CJIC.20240170
摘要:
采用简单的室温搅拌法和一步硫化法制备了MnO2纳米线支撑中空十二面体CoNi2S4 (MnO2/CoNi2S4)电极材料。超长MnO2纳米线为电子转移提供了直接路径，而且其较大的长径比有利于形成自支撑的三维导电网络结构；中空多孔的CoNi2S4提供了更丰富的活性位点，同时缓解了充放电过程中的体积变化。得益于以上优势，MnO2/CoNi2S4在1 A·g-1时具有1 531.1 F·g-1的比电容，在10 A·g-1时具有86.9%的电容保持率。利用MnO2/CoNi2S4作为正极、活性炭(AC)为负极组装的MnO2/CoNi2S4||AC器件实现了高能量密度(800 W·kg-1时40 Wh·kg-1)和优异的循环稳定性(5 000次循环后保持64.8%)。
采用简单的室温搅拌法和一步硫化法制备了MnO2纳米线支撑中空十二面体CoNi2S4 (MnO2/CoNi2S4)电极材料。超长MnO2纳米线为电子转移提供了直接路径，而且其较大的长径比有利于形成自支撑的三维导电网络结构；中空多孔的CoNi2S4提供了更丰富的活性位点，同时缓解了充放电过程中的体积变化。得益于以上优势，MnO2/CoNi2S4在1 A·g-1时具有1 531.1 F·g-1的比电容，在10 A·g-1时具有86.9%的电容保持率。利用MnO2/CoNi2S4作为正极、活性炭(AC)为负极组装的MnO2/CoNi2S4||AC器件实现了高能量密度(800 W·kg-1时40 Wh·kg-1)和优异的循环稳定性(5 000次循环后保持64.8%)。
2024, 40(10): 1892-1902
doi: 10.11862/CJIC.20240139
摘要:
以2，5-二氟苯甲酸(HDFBA)为第一配体，2，2'∶6'，2″-三联吡啶(terpy)、1, 10-菲咯啉(phen)为第二配体，成功合成4种稀土有机配合物闪烁体：[Tb(DFBA)3(terpy)(H2O)] (1)、[Eu(DFBA)3(terpy)(H2O)] (2)、[Tb(DFBA)3(phen)] (3)、[Eu(DFBA)3(phen)] (4)。这些稀土有机配合物闪烁体展现出优异的X射线剂量响应性、光稳定性以及高达(25 100±2 000) photons·MeV-1的稳态X射线激发的相对光产额。通过调节配合物中Eu3+和Tb3+的物质的量之比，实现了从绿色到红色的多色发光。将它们以一定的比例掺入聚乙烯醇(PVA)基质中获得均匀闪烁体薄膜，实现了高分辨(11.2 lp·mm-1) X射线成像。
以2，5-二氟苯甲酸(HDFBA)为第一配体，2，2'∶6'，2″-三联吡啶(terpy)、1, 10-菲咯啉(phen)为第二配体，成功合成4种稀土有机配合物闪烁体：[Tb(DFBA)3(terpy)(H2O)] (1)、[Eu(DFBA)3(terpy)(H2O)] (2)、[Tb(DFBA)3(phen)] (3)、[Eu(DFBA)3(phen)] (4)。这些稀土有机配合物闪烁体展现出优异的X射线剂量响应性、光稳定性以及高达(25 100±2 000) photons·MeV-1的稳态X射线激发的相对光产额。通过调节配合物中Eu3+和Tb3+的物质的量之比，实现了从绿色到红色的多色发光。将它们以一定的比例掺入聚乙烯醇(PVA)基质中获得均匀闪烁体薄膜，实现了高分辨(11.2 lp·mm-1) X射线成像。
2024, 40(10): 1903-1910
doi: 10.11862/CJIC.20240155
摘要:
制备了空心硫化铜(H-Cu2-xS)纳米颗粒，并利用其空腔结构负载声敏剂原卟啉(PpIX)得到多功能复合纳米试剂(PpIX@H-Cu2-xS)。H-Cu2-xS在近红外光(NIR)照射条件下具有良好的光热转换效果，同时具有大的比表面积(68 m2·g-1)，可实现声敏剂PpIX的高效负载。在超声(US)激发条件下(10 min)，发现有46.1%的1，3-二苯基异苯并呋喃(DPBF)被PpIX@H-Cu2-xS产生的活性氧(ROS)氧化。在体外细胞实验中，PpIX@H-Cu2-xS显示出良好的生物安全性，在NIR/US激发条件下可以高效地杀死肿瘤细胞。
制备了空心硫化铜(H-Cu2-xS)纳米颗粒，并利用其空腔结构负载声敏剂原卟啉(PpIX)得到多功能复合纳米试剂(PpIX@H-Cu2-xS)。H-Cu2-xS在近红外光(NIR)照射条件下具有良好的光热转换效果，同时具有大的比表面积(68 m2·g-1)，可实现声敏剂PpIX的高效负载。在超声(US)激发条件下(10 min)，发现有46.1%的1，3-二苯基异苯并呋喃(DPBF)被PpIX@H-Cu2-xS产生的活性氧(ROS)氧化。在体外细胞实验中，PpIX@H-Cu2-xS显示出良好的生物安全性，在NIR/US激发条件下可以高效地杀死肿瘤细胞。
2024, 40(10): 1911-1918
doi: 10.11862/CJIC.20240105
摘要:
采用机械剥离法制备了2H相α-In2Se3[α-In2Se3(2H)]纳米片。通过X射线衍射(X-ray diffraction，XRD)、拉曼光谱、球差电镜和压电力显微镜对纳米片的结构和铁电性能进行详细表征，确定纳米片为具有特殊结构的α-In2Se3(2H)铁电材料。进一步在SiO2/Si基片上成功构造了基于α-In2Se3(2H)铁电的平面四端器件，详细研究其在各个方向的光响应。结果表明，具有本征结构的α-In2Se3(2H)在相互垂直方向均没有光响应。在器件两端分别施加电压后，α-In2Se3(2H)器件在相互垂直方向均出现了明显的光响应，尤其在接近于易极化轴方向施加电压后，α-In2Se3(2H)器件出现了各向异性光响应。
采用机械剥离法制备了2H相α-In2Se3[α-In2Se3(2H)]纳米片。通过X射线衍射(X-ray diffraction，XRD)、拉曼光谱、球差电镜和压电力显微镜对纳米片的结构和铁电性能进行详细表征，确定纳米片为具有特殊结构的α-In2Se3(2H)铁电材料。进一步在SiO2/Si基片上成功构造了基于α-In2Se3(2H)铁电的平面四端器件，详细研究其在各个方向的光响应。结果表明，具有本征结构的α-In2Se3(2H)在相互垂直方向均没有光响应。在器件两端分别施加电压后，α-In2Se3(2H)器件在相互垂直方向均出现了明显的光响应，尤其在接近于易极化轴方向施加电压后，α-In2Se3(2H)器件出现了各向异性光响应。
2024, 40(10): 1919-1931
doi: 10.11862/CJIC.20240094
摘要:
通过水热法制备了锰、铋共掺杂铌酸钠压电骨修复材料。通过扫描电镜、X射线衍射仪、X射线光电子能谱仪、压电力显微镜、电化学工作站、紫外可见近红外光谱仪、电子顺磁共振波谱仪等对该材料的微观形貌、组成结构、压电性能、声动力性能和类酶活性等进行表征。结果表明，该材料兼具压电性能和类酶活性，超声触发压电响应不仅促进细胞增殖，而且增强声动力和类酶活性，产生活性氧，协同杀死细菌/清除生物膜。
通过水热法制备了锰、铋共掺杂铌酸钠压电骨修复材料。通过扫描电镜、X射线衍射仪、X射线光电子能谱仪、压电力显微镜、电化学工作站、紫外可见近红外光谱仪、电子顺磁共振波谱仪等对该材料的微观形貌、组成结构、压电性能、声动力性能和类酶活性等进行表征。结果表明，该材料兼具压电性能和类酶活性，超声触发压电响应不仅促进细胞增殖，而且增强声动力和类酶活性，产生活性氧，协同杀死细菌/清除生物膜。
2024, 40(10): 1932-1942
doi: 10.11862/CJIC.20240065
摘要:
通过碳化技术和水热反应相结合成功制备了Co@C/MoS2复合吸波材料。结果表明，ZIF-67的碳化温度和Co@C/MoS2的微观结构对Co@C/MoS2复合材料的吸波性能具有重要影响。Co@C/MoS2的褶皱结构增强了入射波的反射与散射，进而优化了阻抗匹配，提高了材料的电磁波(EMW)吸收性能。当碳化温度为800 ℃，样品匹配厚度为1.7 mm时，Co@C/MoS2复合材料展现出最佳的吸波性能，最小反射损耗(RLmin)和有效吸收带宽(EAB)分别达到-101.84 dB和7.4 GHz。
通过碳化技术和水热反应相结合成功制备了Co@C/MoS2复合吸波材料。结果表明，ZIF-67的碳化温度和Co@C/MoS2的微观结构对Co@C/MoS2复合材料的吸波性能具有重要影响。Co@C/MoS2的褶皱结构增强了入射波的反射与散射，进而优化了阻抗匹配，提高了材料的电磁波(EMW)吸收性能。当碳化温度为800 ℃，样品匹配厚度为1.7 mm时，Co@C/MoS2复合材料展现出最佳的吸波性能，最小反射损耗(RLmin)和有效吸收带宽(EAB)分别达到-101.84 dB和7.4 GHz。
2024, 40(10): 1943-1952
doi: 10.11862/CJIC.20240079
摘要:
基于2-(3-吡啶基)-1H-吡唑-苯羧酸(Hppb)配体，成功合成3种溴离子参与配位的不同Cd(Ⅱ)配合物[Cd(Hppb)2Br2] (1)、[Cd2(ppb)2Br2] (2)和[Cd(Hppb)Br2]n (3)，并确定了其结构特征。在3种配合物中，Cd(Ⅱ)离子、配体、溴离子的比例分别为1∶2∶2、1∶1∶1、1∶1∶2，最终得到单核(0D)、双核(0D)、一维骨架的不同结构。配合物1中的Cd(Ⅱ)配位环境为轻微扭曲的八面体几何结构，而配合物2和3的中心离子则显示出扭曲的四方锥几何结构。3个配合物的ppb-或Hppb配体的连接模式存在明显差异。在配合物1中，2个Hppb配体为μ1-κN，N′配位模式。而在配合物2中，2个ppb-配体为μ2-κN，N′∶κO配位模式，并且作为2个μ1, 1桥连接2个Cd(Ⅱ)离子形成双核结构单元，2个Cd离子之间的距离为0.409 1(4) nm。在3中，中性Hppb配体为μ2-κN，N′∶κO配位模式，并通过μ1, 6桥连接Cd(Ⅱ)离子，沿b轴形成一维无限延长的链。利用Hirshfeld表面分析和二维指纹图对这3种配合物进行了研究。此外，配合物1~3的光致发光特性表明，配位阴离子Br-对Cd(Ⅱ)配合物的荧光发射有很大影响。
基于2-(3-吡啶基)-1H-吡唑-苯羧酸(Hppb)配体，成功合成3种溴离子参与配位的不同Cd(Ⅱ)配合物[Cd(Hppb)2Br2] (1)、[Cd2(ppb)2Br2] (2)和[Cd(Hppb)Br2]n (3)，并确定了其结构特征。在3种配合物中，Cd(Ⅱ)离子、配体、溴离子的比例分别为1∶2∶2、1∶1∶1、1∶1∶2，最终得到单核(0D)、双核(0D)、一维骨架的不同结构。配合物1中的Cd(Ⅱ)配位环境为轻微扭曲的八面体几何结构，而配合物2和3的中心离子则显示出扭曲的四方锥几何结构。3个配合物的ppb-或Hppb配体的连接模式存在明显差异。在配合物1中，2个Hppb配体为μ1-κN，N′配位模式。而在配合物2中，2个ppb-配体为μ2-κN，N′∶κO配位模式，并且作为2个μ1, 1桥连接2个Cd(Ⅱ)离子形成双核结构单元，2个Cd离子之间的距离为0.409 1(4) nm。在3中，中性Hppb配体为μ2-κN，N′∶κO配位模式，并通过μ1, 6桥连接Cd(Ⅱ)离子，沿b轴形成一维无限延长的链。利用Hirshfeld表面分析和二维指纹图对这3种配合物进行了研究。此外，配合物1~3的光致发光特性表明，配位阴离子Br-对Cd(Ⅱ)配合物的荧光发射有很大影响。
2024, 40(10): 1953-1964
doi: 10.11862/CJIC.20240028
摘要:
采用一步溶剂热法在泡沫镍(NF)基底上原位生长Cu/α-FeOOH纳米复合材料，制备了自支撑Cu/α-FeOOH/NF催化剂。相比于α-FeOOH/NF催化剂，Cu的引入为α-FeOOH的生长提供了更多的附着点，使得催化剂表面更加粗糙，并增大了催化剂与反应物的接触面积。Cu和无定形的α-FeOOH之间存在晶态和非晶态的异质界面，改变了催化剂的电子结构，促进电子从Ni、Fe向Cu转移，从而显著增强了催化剂对甲醇的吸附和氧化。电化学测试表明，Cu/α-FeOOH/NF催化剂具有优异的甲醇氧化反应(MOR)和析氢反应(HER)性能。在Cu/α-FeOOH/NF催化剂同时作为阴极、阳极的Cu/α-FeOOH/NF||Cu/α-FeOOH/NF HER-MOR耦合电解水系统中，达到10 mA·cm-2电流密度所需的电压比直接全水解系统降低了125 mV，且在较大电压(2.4 V)下能够稳定反应96 h。此外，阳极MOR产生了价值更高的甲酸盐，1.80 V下生成甲酸盐的法拉第效率高达97%。
采用一步溶剂热法在泡沫镍(NF)基底上原位生长Cu/α-FeOOH纳米复合材料，制备了自支撑Cu/α-FeOOH/NF催化剂。相比于α-FeOOH/NF催化剂，Cu的引入为α-FeOOH的生长提供了更多的附着点，使得催化剂表面更加粗糙，并增大了催化剂与反应物的接触面积。Cu和无定形的α-FeOOH之间存在晶态和非晶态的异质界面，改变了催化剂的电子结构，促进电子从Ni、Fe向Cu转移，从而显著增强了催化剂对甲醇的吸附和氧化。电化学测试表明，Cu/α-FeOOH/NF催化剂具有优异的甲醇氧化反应(MOR)和析氢反应(HER)性能。在Cu/α-FeOOH/NF催化剂同时作为阴极、阳极的Cu/α-FeOOH/NF||Cu/α-FeOOH/NF HER-MOR耦合电解水系统中，达到10 mA·cm-2电流密度所需的电压比直接全水解系统降低了125 mV，且在较大电压(2.4 V)下能够稳定反应96 h。此外，阳极MOR产生了价值更高的甲酸盐，1.80 V下生成甲酸盐的法拉第效率高达97%。
2024, 40(10): 1965-1974
doi: 10.11862/CJIC.20240014
摘要:
采用前驱体煅烧法制备具有吸附-光催化双功能的层状锌铝双金属氧化物(LDOs)。通过X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、紫外可见漫反射光谱(UV-Vis DRS)、扫描电子显微镜(SEM)等表征探究了双金属比例、煅烧温度对其吸附-光催化降解四环素(TC)性能的影响。结果表明，当Zn、Al物质的量之比为2∶1，煅烧温度为400 ℃时，可形成具有优异吸附-光催化活性的Zn2Al1@LDO400。吸附实验表明，Zn2Al1@LDO400对TC是化学吸附限制的非均相单分子层吸附，且高温利于吸附。利用自由基猝灭实验结合电子顺磁共振(EPR)测试证实光生空穴(h+)、羟基自由基(·OH)、超氧自由基(·O2-)作为活性物种参与TC的协同降解。
采用前驱体煅烧法制备具有吸附-光催化双功能的层状锌铝双金属氧化物(LDOs)。通过X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、紫外可见漫反射光谱(UV-Vis DRS)、扫描电子显微镜(SEM)等表征探究了双金属比例、煅烧温度对其吸附-光催化降解四环素(TC)性能的影响。结果表明，当Zn、Al物质的量之比为2∶1，煅烧温度为400 ℃时，可形成具有优异吸附-光催化活性的Zn2Al1@LDO400。吸附实验表明，Zn2Al1@LDO400对TC是化学吸附限制的非均相单分子层吸附，且高温利于吸附。利用自由基猝灭实验结合电子顺磁共振(EPR)测试证实光生空穴(h+)、羟基自由基(·OH)、超氧自由基(·O2-)作为活性物种参与TC的协同降解。
2024, 40(7): 1233-1242
doi: 10.11862/CJIC.20240057
摘要:
In this study, parallelogram-like macrocyclic supramolecular metallacycles [Pd6(bpy)6(L1)4](PF6)8 (1a) and [Pd6(bpy)6(L2)4](PF6)8 (2a), where HL1=1-(1H-pyrazole-4-yl)-4-(4-pyridyl)benzene, HL2=9-(1H-pyrazole-4-yl)-10-(4-pyridyl)anthracene, and bpy=2, 2'-bipyridine, are synthesized by reacting aryl pyrazole pyridine ligands with dipalla-dium corners in aqueous solutions via metal-directed hierarchical self-assembly. The structures of the supramolecular Pd parallelograms are confirmed through single-crystal X-ray diffraction. Notably, the two parallelogram metallacycles can be used as"turn-on"fluorescence sensors to detect HSO3- through a disassembly mechanism. In addition, the 1a-based sensor shows selective detection of HSO3- without interference from other anions. The detection limit was as low as 0.131 μmol·L-1. Furthermore, complex 1a presented the semiquantitative visual detection ability for HSO3- in the test trip mode via fluorescence changes.
In this study, parallelogram-like macrocyclic supramolecular metallacycles [Pd6(bpy)6(L1)4](PF6)8 (1a) and [Pd6(bpy)6(L2)4](PF6)8 (2a), where HL1=1-(1H-pyrazole-4-yl)-4-(4-pyridyl)benzene, HL2=9-(1H-pyrazole-4-yl)-10-(4-pyridyl)anthracene, and bpy=2, 2'-bipyridine, are synthesized by reacting aryl pyrazole pyridine ligands with dipalla-dium corners in aqueous solutions via metal-directed hierarchical self-assembly. The structures of the supramolecular Pd parallelograms are confirmed through single-crystal X-ray diffraction. Notably, the two parallelogram metallacycles can be used as"turn-on"fluorescence sensors to detect HSO3- through a disassembly mechanism. In addition, the 1a-based sensor shows selective detection of HSO3- without interference from other anions. The detection limit was as low as 0.131 μmol·L-1. Furthermore, complex 1a presented the semiquantitative visual detection ability for HSO3- in the test trip mode via fluorescence changes.
2024, 40(7): 1368-1376
doi: 10.11862/CJIC.20240066
摘要:
Two new viologen-polyoxometalate hybrid crystalline materials: (MV)2[HPW2ⅤW10ⅥO40] ·2H2O (1) and (EV)2[Mo8O26] (2) have been synthesized by using the cations of 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (methyl viologen, MV) and 1, 1'-diethyl-4, 4'-bipyridinium dibromide (ethyl viologen, EV) as the electron acceptors, and the electron-rich polyoxometalate anions as the electron donors. The structures of compounds 1 and 2 have been determined by single-crystal X-ray crystallography. Hydrogen bond interactions exist between the cations and the anions in 1 and 2. Interestingly, 2 has a photochromic performance with a light response time within 1 min. The photochromic mechanism of compound 2 has been investigated by solid-state diffuse reflection, electron paramagnetic resonance and theoretical calculation. 1 and 2 show good catalytic performance in the photocatalytic degradation of several organic dyes (methylene blue, pararosaniline hydrochloride and rhodamine 6G).
Two new viologen-polyoxometalate hybrid crystalline materials: (MV)2[HPW2ⅤW10ⅥO40] ·2H2O (1) and (EV)2[Mo8O26] (2) have been synthesized by using the cations of 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (methyl viologen, MV) and 1, 1'-diethyl-4, 4'-bipyridinium dibromide (ethyl viologen, EV) as the electron acceptors, and the electron-rich polyoxometalate anions as the electron donors. The structures of compounds 1 and 2 have been determined by single-crystal X-ray crystallography. Hydrogen bond interactions exist between the cations and the anions in 1 and 2. Interestingly, 2 has a photochromic performance with a light response time within 1 min. The photochromic mechanism of compound 2 has been investigated by solid-state diffuse reflection, electron paramagnetic resonance and theoretical calculation. 1 and 2 show good catalytic performance in the photocatalytic degradation of several organic dyes (methylene blue, pararosaniline hydrochloride and rhodamine 6G).
2024, 40(7): 1377-1386
doi: 10.11862/CJIC.20230415
摘要:
Two metal-organic frameworks (MOFs) containing rigid bis(triazole) ligand, namely {[Zn2(L)(TP)2(H2O)·H2O]}n (1) and [Zn(L)(HTMA)]n (2), where L=4, 4'-(3, 3'-dimethyl-(1, 1'-biphenyl)-4, 4'-diyl)bis(4H-1, 2, 4-triazole), H2TP=terephthalic acid, H3TMA=1, 3, 5-benzenetricarboxylic acid, were synthesized by using acid-base mixed ligands strategy and structurally characterized by X-ray single-crystal diffraction. Structural analysis reveals that MOF 1 displays a 3, 6-connected 2D structure with a new topological point symbol of (42·6)2(48·66·8), while MOF 2 presents a 2D sql topology structure. The catalytic studies reveal that 2 exhibits excellent catalytic activity for the cycloaddition reaction of CO2 with epoxides under mild conditions. Furthermore, 2 can be reused at least three times while maintaining its catalytic ability.
Two metal-organic frameworks (MOFs) containing rigid bis(triazole) ligand, namely {[Zn2(L)(TP)2(H2O)·H2O]}n (1) and [Zn(L)(HTMA)]n (2), where L=4, 4'-(3, 3'-dimethyl-(1, 1'-biphenyl)-4, 4'-diyl)bis(4H-1, 2, 4-triazole), H2TP=terephthalic acid, H3TMA=1, 3, 5-benzenetricarboxylic acid, were synthesized by using acid-base mixed ligands strategy and structurally characterized by X-ray single-crystal diffraction. Structural analysis reveals that MOF 1 displays a 3, 6-connected 2D structure with a new topological point symbol of (42·6)2(48·66·8), while MOF 2 presents a 2D sql topology structure. The catalytic studies reveal that 2 exhibits excellent catalytic activity for the cycloaddition reaction of CO2 with epoxides under mild conditions. Furthermore, 2 can be reused at least three times while maintaining its catalytic ability.
2024, 40(7): 1387-1396
doi: 10.11862/CJIC.20240045
摘要:
Two alkali-metal sulfamates nonlinear optical (NLO) crystals, Li(NH2SO3) and Na(NH2SO3), have been obtained through the facile evaporation method. Li(NH2SO3) crystallizes in the polar space group Pca21 (No.29). The structure of Li(NH2SO3) can be described as a 3D network formed by [LiO4]7- polyhedral connecting with NH2SO3- tetrahedra through corner-sharing. Na(NH2SO3) crystallizes in the polar space group P212121 (No.19). The structure of Na(NH2SO3) can be described as a 3D network formed by distorted [NaO6]11- octahedral connecting with NH2SO3- tetrahedra through corner-sharing. The UV-Vis-near-infrared spectra demonstrate that Li(NH2SO3) and Na(NH2SO3) possessed large optical band gaps of 5.25 and 4.81 eV, respectively. Powder second-harmonic generation (SHG) measurements demonstrate that the SHG intensity of Li(NH2SO3) and Na(NH2SO3) were 0.32 times and 0.31 times that of KH2PO4, respectively. First-principles calculations confirm the nonlinear optical performance mainly derived from the synergistic effect of amino sulfonate anions and alkali metal oxide anionic polyhedra.
Two alkali-metal sulfamates nonlinear optical (NLO) crystals, Li(NH2SO3) and Na(NH2SO3), have been obtained through the facile evaporation method. Li(NH2SO3) crystallizes in the polar space group Pca21 (No.29). The structure of Li(NH2SO3) can be described as a 3D network formed by [LiO4]7- polyhedral connecting with NH2SO3- tetrahedra through corner-sharing. Na(NH2SO3) crystallizes in the polar space group P212121 (No.19). The structure of Na(NH2SO3) can be described as a 3D network formed by distorted [NaO6]11- octahedral connecting with NH2SO3- tetrahedra through corner-sharing. The UV-Vis-near-infrared spectra demonstrate that Li(NH2SO3) and Na(NH2SO3) possessed large optical band gaps of 5.25 and 4.81 eV, respectively. Powder second-harmonic generation (SHG) measurements demonstrate that the SHG intensity of Li(NH2SO3) and Na(NH2SO3) were 0.32 times and 0.31 times that of KH2PO4, respectively. First-principles calculations confirm the nonlinear optical performance mainly derived from the synergistic effect of amino sulfonate anions and alkali metal oxide anionic polyhedra.
2024, 40(7): 1397-1408
doi: 10.11862/CJIC.20240009
摘要:
5-(dimethylamino) isophthalic acid (H2dia) and 1H-imidazole (mdz) were used as ligands to react with Zn(Ⅱ) or Cu(Ⅱ) metal salts to generate three new transition metal complexes [Zn(dia)(mdz)2]·2H2O (1), [Cu(dia)(mdz)2 (DMF)] (2) and [Cu(dia)(mdz)2]·H2O (3). Their structures were characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analyses, and Hirshfeld surface analyses. The results revealed that complexes 1 and 2 possess 1D linear chains, each four-coordinated Zn(Ⅱ) of 1 is located in the geometric center of the distorted tetrahedron, but the Cu(Ⅱ) metal center of 2 is five-coordinated and holds a triangular bipyramidal geometry. The zigzag 1D chain of complex 3 was obtained by changing the solvent in the synthesis, and the four-coordinated Cu(Ⅱ) ion is in the centre of the square planar. Results indicate that the geometries of metal centers and synthetic solvents have important effects on the structures of complexes. Abundant intermolecular hydrogen bonding plays an important role in the stability of their 3D supramolecular structures. Thermogravimetric analyses revealed that the complexes have good thermal stabilities. Solid fluorescence analyses showed that complex 1 had excellent fluorescence, but the fluorescence intensities of complexes 2 and 3 were much lower than those of ligands.
5-(dimethylamino) isophthalic acid (H2dia) and 1H-imidazole (mdz) were used as ligands to react with Zn(Ⅱ) or Cu(Ⅱ) metal salts to generate three new transition metal complexes [Zn(dia)(mdz)2]·2H2O (1), [Cu(dia)(mdz)2 (DMF)] (2) and [Cu(dia)(mdz)2]·H2O (3). Their structures were characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analyses, and Hirshfeld surface analyses. The results revealed that complexes 1 and 2 possess 1D linear chains, each four-coordinated Zn(Ⅱ) of 1 is located in the geometric center of the distorted tetrahedron, but the Cu(Ⅱ) metal center of 2 is five-coordinated and holds a triangular bipyramidal geometry. The zigzag 1D chain of complex 3 was obtained by changing the solvent in the synthesis, and the four-coordinated Cu(Ⅱ) ion is in the centre of the square planar. Results indicate that the geometries of metal centers and synthetic solvents have important effects on the structures of complexes. Abundant intermolecular hydrogen bonding plays an important role in the stability of their 3D supramolecular structures. Thermogravimetric analyses revealed that the complexes have good thermal stabilities. Solid fluorescence analyses showed that complex 1 had excellent fluorescence, but the fluorescence intensities of complexes 2 and 3 were much lower than those of ligands.
2024, 40(7): 1409-1422
doi: 10.11862/CJIC.20240007
摘要:
Three new copper(Ⅱ) complexes 1-3 of Schiff base ligands HL1 (2-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone), HL2 (4-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) and L3 (2-methoxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) were synthesized from methanolic medium. The complexes were characterized by elemental analyses, spectroscopic methods, magnetic susceptibility measurements, and density functional theory (DFT) studies. The synthesized ligands were characterized structurally by single-crystal X-ray diffraction studies. The optimized structure of the complexes was ascertained by DFT studies. The DNA binding ability of the complexes with calf thymus DNA (CT-DNA) was studied by UV-Vis absorption and fluorescence emission spectral studies. Absorption spectral studies revealed a hyperchromic effect and suggested the possible mode of interaction with CT-DNA. The competitive binding studies using ethidium bromide (EB) show that the complexes can replace DNA from DNA-EB adduct and suggests that the complexes probably bind to CT-DNA in intercalative mode. In vitro antibacterial activity of the complexes against Gram-negative bacteria Klebsiella pneumoniae (K. pneumoniae), Escherichia coli(E. coli), and Shigella boydii (S. boydii), and gram-positive bacteria Staphylococcus aureus (S. aureus) exhibited an appreciable antibacterial activity of complex 2 against K. pneumoniae and S. boydii, but complexes 1 and 3 did not show any significant antibacterial activity.
Three new copper(Ⅱ) complexes 1-3 of Schiff base ligands HL1 (2-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone), HL2 (4-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) and L3 (2-methoxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) were synthesized from methanolic medium. The complexes were characterized by elemental analyses, spectroscopic methods, magnetic susceptibility measurements, and density functional theory (DFT) studies. The synthesized ligands were characterized structurally by single-crystal X-ray diffraction studies. The optimized structure of the complexes was ascertained by DFT studies. The DNA binding ability of the complexes with calf thymus DNA (CT-DNA) was studied by UV-Vis absorption and fluorescence emission spectral studies. Absorption spectral studies revealed a hyperchromic effect and suggested the possible mode of interaction with CT-DNA. The competitive binding studies using ethidium bromide (EB) show that the complexes can replace DNA from DNA-EB adduct and suggests that the complexes probably bind to CT-DNA in intercalative mode. In vitro antibacterial activity of the complexes against Gram-negative bacteria Klebsiella pneumoniae (K. pneumoniae), Escherichia coli(E. coli), and Shigella boydii (S. boydii), and gram-positive bacteria Staphylococcus aureus (S. aureus) exhibited an appreciable antibacterial activity of complex 2 against K. pneumoniae and S. boydii, but complexes 1 and 3 did not show any significant antibacterial activity.
2024, 40(7): 1243-1253
doi: 10.11862/CJIC.20240110
摘要:
通过在N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与CuI之间的置换反应，在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触，减少锌电极-电解液界面的析氢和腐蚀等副反应。同时，铜金属保护层还具有较好的亲锌性，更小的界面电阻，更低的成核能垒，有利于锌离子均匀沉积，从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过1 700 h(1 mA·cm-2)和1 330 h(3 mA·cm-2)的循环寿命。采用商用MnO2与之匹配得到的Cu@Zn||MnO2全电池不仅在1 A·g-1下具有168.5 mAh·g-1的可逆比容量，还可稳定循环2 000次以上
通过在N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与CuI之间的置换反应，在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触，减少锌电极-电解液界面的析氢和腐蚀等副反应。同时，铜金属保护层还具有较好的亲锌性，更小的界面电阻，更低的成核能垒，有利于锌离子均匀沉积，从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过1 700 h(1 mA·cm-2)和1 330 h(3 mA·cm-2)的循环寿命。采用商用MnO2与之匹配得到的Cu@Zn||MnO2全电池不仅在1 A·g-1下具有168.5 mAh·g-1的可逆比容量，还可稳定循环2 000次以上
2024, 40(7): 1254-1260
doi: 10.11862/CJIC.20240047
摘要:
通过一锅还原法成功制备了合金纳米团簇Au11-xCux(dppf)4Cl2(x=1、2；dppf=1，1'-双(二苯基膦)二茂铁)。晶体结构解析表明，合金团簇具有与Au11(dppf)4Cl2类似的几何结构，如含有缺陷二十面体金属内核，不同之处在于Cu原子取代了与Cl配位的Au原子。因此，Au11-xCux(dppf)4Cl2可视为Cu对Au11(dppf)4Cl2模板团簇的掺杂。Cu原子的引入并未改变模板团簇Au11(dppf)4Cl2的框架结构，但有效调控了电子结构，进而使其光吸收发生红移。
通过一锅还原法成功制备了合金纳米团簇Au11-xCux(dppf)4Cl2(x=1、2；dppf=1，1'-双(二苯基膦)二茂铁)。晶体结构解析表明，合金团簇具有与Au11(dppf)4Cl2类似的几何结构，如含有缺陷二十面体金属内核，不同之处在于Cu原子取代了与Cl配位的Au原子。因此，Au11-xCux(dppf)4Cl2可视为Cu对Au11(dppf)4Cl2模板团簇的掺杂。Cu原子的引入并未改变模板团簇Au11(dppf)4Cl2的框架结构，但有效调控了电子结构，进而使其光吸收发生红移。
2024, 40(7): 1270-1278
doi: 10.11862/CJIC.20240037
摘要:
以乙二醇为溶剂，聚乙烯吡咯烷酮为表面活性剂，通过一步溶剂热法合成了分级中空结构的BiOBr-Pt催化剂。合成的分级中空结构BiOBr-2h催化剂的比表面积为28 m2·g-1，是对比样品BiOBr-1h的2倍，这种结构为催化反应提供更多的反应活性位点。此外，在催化剂中引入Pt增强了BiOBr的载流子传导速率，而且Pt可以作为电子陷阱捕获周围大量电子，有效抑制光生载流子的复合，从而提高CO2还原的催化活性。光催化CO2还原实验结果表明，BiOBr-Pt的主要产物为CO，产物选择性为99%，其CO产率达到了20.8 μmol·h-1·g-1，为原始BiOBr的2.1倍。这一结果说明，这种Pt负载且具有分级中空结构的催化剂可以有效地将CO2转化为增值化学品。
以乙二醇为溶剂，聚乙烯吡咯烷酮为表面活性剂，通过一步溶剂热法合成了分级中空结构的BiOBr-Pt催化剂。合成的分级中空结构BiOBr-2h催化剂的比表面积为28 m2·g-1，是对比样品BiOBr-1h的2倍，这种结构为催化反应提供更多的反应活性位点。此外，在催化剂中引入Pt增强了BiOBr的载流子传导速率，而且Pt可以作为电子陷阱捕获周围大量电子，有效抑制光生载流子的复合，从而提高CO2还原的催化活性。光催化CO2还原实验结果表明，BiOBr-Pt的主要产物为CO，产物选择性为99%，其CO产率达到了20.8 μmol·h-1·g-1，为原始BiOBr的2.1倍。这一结果说明，这种Pt负载且具有分级中空结构的催化剂可以有效地将CO2转化为增值化学品。
2024, 40(7): 1279-1289
doi: 10.11862/CJIC.20240026
摘要:
通过碱处理结合铬改性策略实现了对高硅ZSM-5沸石孔道和酸性的协同调控，制备出了一种具有适宜酸性的高硅多级孔沸石催化剂。在碱处理的过程中，通过精细调节合成凝胶组成，在沸石晶体中引入的丰富共生界面，诱导了介孔的形成，从而打破了沸石硅铝比对常规碱处理法的限制。在铬改性的过程中，独特的多级孔结构促进了铬在催化剂中的分散，从而实现了对酸性的深度改性。在甲醇制丙烯催化反应中，制备的催化剂表现出了极佳的催化稳定性以及很高的丙烯和总低碳烯烃选择性。
通过碱处理结合铬改性策略实现了对高硅ZSM-5沸石孔道和酸性的协同调控，制备出了一种具有适宜酸性的高硅多级孔沸石催化剂。在碱处理的过程中，通过精细调节合成凝胶组成，在沸石晶体中引入的丰富共生界面，诱导了介孔的形成，从而打破了沸石硅铝比对常规碱处理法的限制。在铬改性的过程中，独特的多级孔结构促进了铬在催化剂中的分散，从而实现了对酸性的深度改性。在甲醇制丙烯催化反应中，制备的催化剂表现出了极佳的催化稳定性以及很高的丙烯和总低碳烯烃选择性。
2024, 40(7): 1290-1300
doi: 10.11862/CJIC.20240021
摘要:
通过在CsPbBr3薄膜上旋涂一次I2的异丙醇溶液以修饰CsPbBr3吸光层，钝化CsPbBr3层表面缺陷，改善CsPbBr3薄膜形貌。同时通过利用环境友好的绿色溶剂水溶解CsBr，显著提高了其溶解度，减少了旋涂次数，简化了电池制备流程。实验结果表明，在CsPbBr3钙钛矿太阳能电池(perovskite solar cells，PSCs)中，使用5 mg·mL-1 I2的异丙醇溶液界面修饰的器件具有最佳光伏性能，其最高开路电压(open-circuit voltage，VOC)为1.55 V，短路电流密度(short circuit current density，JSC)为7.45 mA·cm-2，填充因子(fill factor，FF)为85.54%，光电转换效率(photoelectric conversion efficiency，PCE)达到了9.88%。
通过在CsPbBr3薄膜上旋涂一次I2的异丙醇溶液以修饰CsPbBr3吸光层，钝化CsPbBr3层表面缺陷，改善CsPbBr3薄膜形貌。同时通过利用环境友好的绿色溶剂水溶解CsBr，显著提高了其溶解度，减少了旋涂次数，简化了电池制备流程。实验结果表明，在CsPbBr3钙钛矿太阳能电池(perovskite solar cells，PSCs)中，使用5 mg·mL-1 I2的异丙醇溶液界面修饰的器件具有最佳光伏性能，其最高开路电压(open-circuit voltage，VOC)为1.55 V，短路电流密度(short circuit current density，JSC)为7.45 mA·cm-2，填充因子(fill factor，FF)为85.54%，光电转换效率(photoelectric conversion efficiency，PCE)达到了9.88%。
2024, 40(7): 1301-1308
doi: 10.11862/CJIC.20240003
摘要:
合成了2个丁二酮肟有机锡化合物：双(三(2-甲基-2-苯基丙基)锡)丁二酮肟配合物(C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3)=NO)Sn(CH2C(CH3)2C6H5)3 (1)和二苄基锡氧氯丁二酮肟多核配合物[μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2(2)。通过元素分析、红外光谱、核磁共振(1H、13C、119Sn)、差热分析和单晶X射线衍射对配合物进行了结构表征，对其结构进行量子化学从头计算，并进行了体外抗癌活性研究。结果显示：配合物1为通过配体丁二酮肟桥联的双锡核中心对称分子，锡原子均为四配位的畸变四面体构型；配合物2为通过氧原子和丁二酮肟配体桥联的四锡核中心对称多环聚合结构，锡原子分别为五配位的畸变三角双锥构型和六配位的畸变八面体构型。配合物对人肝癌细胞(HUH7)、人肺癌细胞(A549)、人表皮癌细胞(A431)、人结肠癌细胞(HCT-116)和人乳腺癌细胞(MDA-MB-231)均有较强的抑制活性。
合成了2个丁二酮肟有机锡化合物：双(三(2-甲基-2-苯基丙基)锡)丁二酮肟配合物(C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3)=NO)Sn(CH2C(CH3)2C6H5)3 (1)和二苄基锡氧氯丁二酮肟多核配合物[μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2(2)。通过元素分析、红外光谱、核磁共振(1H、13C、119Sn)、差热分析和单晶X射线衍射对配合物进行了结构表征，对其结构进行量子化学从头计算，并进行了体外抗癌活性研究。结果显示：配合物1为通过配体丁二酮肟桥联的双锡核中心对称分子，锡原子均为四配位的畸变四面体构型；配合物2为通过氧原子和丁二酮肟配体桥联的四锡核中心对称多环聚合结构，锡原子分别为五配位的畸变三角双锥构型和六配位的畸变八面体构型。配合物对人肝癌细胞(HUH7)、人肺癌细胞(A549)、人表皮癌细胞(A431)、人结肠癌细胞(HCT-116)和人乳腺癌细胞(MDA-MB-231)均有较强的抑制活性。
2024, 40(7): 1309-1319
doi: 10.11862/CJIC.20240001
摘要:
结合Cu(Ⅱ)离子浸渍吸附方法及直流电弧等离子体喷射化学气相沉积技术制备了一种电化学/电生理双模Cu2O/Cu-垂直石墨烯微电极，并研究了电化学方法检测尿酸以及记录脑电信号的双响应性能。使用扫描电子显微镜、透射电子显微镜、X射线衍射仪表征了形貌、微结构及晶体成分，并测试了电化学及脑电记录能力。结果表明，该微电极直径仅为200 μm，大量镶嵌Cu2O/Cu纳米粒子的石墨烯纳米片垂直生长在基片上，排列成了一种三维的多孔结构，使其具有了高的电化学催化活性、短程离子扩散路径、以及长程导电网络。由此，以10 μL的饱和NaCl溶液为介质记录脑电信号时，该微电极的皮肤接触电阻低至约7.05 kΩ，生理电采集性能接近涂导电膏的商用湿电极。此外，该微电极还灵敏响应尿酸的氧化电流，检测浓度范围在0.5~500μmol·L-1，检测限低至0.024 μmol·L-1，且具有良好的抗干扰能力及长期稳定性。
结合Cu(Ⅱ)离子浸渍吸附方法及直流电弧等离子体喷射化学气相沉积技术制备了一种电化学/电生理双模Cu2O/Cu-垂直石墨烯微电极，并研究了电化学方法检测尿酸以及记录脑电信号的双响应性能。使用扫描电子显微镜、透射电子显微镜、X射线衍射仪表征了形貌、微结构及晶体成分，并测试了电化学及脑电记录能力。结果表明，该微电极直径仅为200 μm，大量镶嵌Cu2O/Cu纳米粒子的石墨烯纳米片垂直生长在基片上，排列成了一种三维的多孔结构，使其具有了高的电化学催化活性、短程离子扩散路径、以及长程导电网络。由此，以10 μL的饱和NaCl溶液为介质记录脑电信号时，该微电极的皮肤接触电阻低至约7.05 kΩ，生理电采集性能接近涂导电膏的商用湿电极。此外，该微电极还灵敏响应尿酸的氧化电流，检测浓度范围在0.5~500μmol·L-1，检测限低至0.024 μmol·L-1，且具有良好的抗干扰能力及长期稳定性。
2024, 40(7): 1320-1328
doi: 10.11862/CJIC.20230480
摘要:
在镍钴铝酸锂正极材料Li[Ni0.8Co0.15Al0.05]O2(NCA)制备过程中表面遗留的碱性物质会严重影响其循环稳定性能，针对这一难题，提出使用Y(PO3)3对其进行表面包覆改性，利用Y(PO3)3与表面残留的LiOH反应消除表面残碱，并探讨包覆改性对NCA整体性能的影响机制。测试分析结果表明，在低温煅烧过程中前驱体表面会形成均匀致密的Y(PO3)3和LiPO3包覆层，LiPO3有较高的离子电导率，双包覆层能够防止活性物质在电化学循环过程中与电解液相互接触时发生有害副反应，提高电极材料的循环稳定性。其中Y(PO3)3包覆量(质量分数)为1%的样品在0.1C下的首次库仑效率从未改性样品的78.65%提高到88.50%，在1C下循环150圈后容量保持率从59.38%提高到85.33%，相比于未改性样品具有更高的首次库仑效率和更优异的循环性能。
在镍钴铝酸锂正极材料Li[Ni0.8Co0.15Al0.05]O2(NCA)制备过程中表面遗留的碱性物质会严重影响其循环稳定性能，针对这一难题，提出使用Y(PO3)3对其进行表面包覆改性，利用Y(PO3)3与表面残留的LiOH反应消除表面残碱，并探讨包覆改性对NCA整体性能的影响机制。测试分析结果表明，在低温煅烧过程中前驱体表面会形成均匀致密的Y(PO3)3和LiPO3包覆层，LiPO3有较高的离子电导率，双包覆层能够防止活性物质在电化学循环过程中与电解液相互接触时发生有害副反应，提高电极材料的循环稳定性。其中Y(PO3)3包覆量(质量分数)为1%的样品在0.1C下的首次库仑效率从未改性样品的78.65%提高到88.50%，在1C下循环150圈后容量保持率从59.38%提高到85.33%，相比于未改性样品具有更高的首次库仑效率和更优异的循环性能。
2024, 40(7): 1329-1336
doi: 10.11862/CJIC.20230447
摘要:
以氧化石墨烯(GO)、乙酸锌(Zn(CH3COO)2)和硫脲为原料，采用水热法成功制备了还原氧化石墨烯/ZnS(rGO/ZnS)复合材料，并将该材料用作锂离子电池负极。高导电性的rGO可以为锂离子和电子的传输提供有效的路径，ZnS可以提供较高的理论比容量。rGO/ZnS复合材料在rGO与纳米级高度分散的类球形ZnS颗粒协同作用下展现了较好的嵌锂容量和循环性能。当GO质量浓度为2 mg·mL-1时制备的rGO/ZnS复合材料的倍率性能最好，循环稳定性最佳。
以氧化石墨烯(GO)、乙酸锌(Zn(CH3COO)2)和硫脲为原料，采用水热法成功制备了还原氧化石墨烯/ZnS(rGO/ZnS)复合材料，并将该材料用作锂离子电池负极。高导电性的rGO可以为锂离子和电子的传输提供有效的路径，ZnS可以提供较高的理论比容量。rGO/ZnS复合材料在rGO与纳米级高度分散的类球形ZnS颗粒协同作用下展现了较好的嵌锂容量和循环性能。当GO质量浓度为2 mg·mL-1时制备的rGO/ZnS复合材料的倍率性能最好，循环稳定性最佳。
2024, 40(7): 1337-1346
doi: 10.11862/CJIC.20230414
摘要:
为设计高稳定性且高灵敏度的纯金属有机骨架(MOF)电化学传感器以检测多巴胺(DA)，我们选用铟基MOF [In(2-NH3-BDC)(2-NH2-BDC)]·1.5H2O(RSMOF-1，RSMOF=resistance switchable metal-organic framework，2-NH2-H2BDC=2-氨基对苯二甲酸)修饰玻碳电极(RSMOF-1/GCE)。制备的电极RSMOF-1/GCE的DPV测试结果显示其线性范围为0.990~663 μmol·L-1、检出限为0.770 μmol·L-1。在多种干扰物质如尿酸、尿素、葡萄糖和对乙酰氨基酚存在的条件下，RSMOF-1/GCE对DA仍具有高的选择性。理论模拟结果显示，在RSMOF-1孔道内壁的—NH2可通过氢键增强与DA分子的相互作用，使RSMOF-1/GCE具有灵敏的电化学传感DA的性能。
为设计高稳定性且高灵敏度的纯金属有机骨架(MOF)电化学传感器以检测多巴胺(DA)，我们选用铟基MOF [In(2-NH3-BDC)(2-NH2-BDC)]·1.5H2O(RSMOF-1，RSMOF=resistance switchable metal-organic framework，2-NH2-H2BDC=2-氨基对苯二甲酸)修饰玻碳电极(RSMOF-1/GCE)。制备的电极RSMOF-1/GCE的DPV测试结果显示其线性范围为0.990~663 μmol·L-1、检出限为0.770 μmol·L-1。在多种干扰物质如尿酸、尿素、葡萄糖和对乙酰氨基酚存在的条件下，RSMOF-1/GCE对DA仍具有高的选择性。理论模拟结果显示，在RSMOF-1孔道内壁的—NH2可通过氢键增强与DA分子的相互作用，使RSMOF-1/GCE具有灵敏的电化学传感DA的性能。
2024, 40(7): 1347-1356
doi: 10.11862/CJIC.20230357
摘要:
使用多齿希夫碱配体H4L(H4L=N'，N″-((1E，1'E)-(1，10-菲咯啉-2，9-二酰基)双(亚甲基)双(2-羟基苯甲酰肼))与Tb(acac)3·2H2O反应(acac-=乙酰丙酮根)，通过溶剂热法，设计并合成了一例结构新颖的双核铽配合物[Tb2(L)(H2L)]·2CH3OH·CH3CN (1)，并研究了该配合物的结构、荧光性质及生物活性。单晶X射线衍射分析表明该配合物主要含有2个TbⅢ离子和2个失去不同质子的配体离子(L4-和H2L2-)。中心Tb1和Tb2离子都是九配位的，其几何构型呈现扭曲的呼啦圈形。固体荧光实验测试结果表明：该配合物在室温下表现出TbⅢ离子的荧光特征发射峰。生物活性研究表明，与配体H4L和稀土离子相比较，配合物具有更强的抗菌活性。采用紫外可见光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了该配合物与小牛胸腺DNA之间的相互作用，结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。
使用多齿希夫碱配体H4L(H4L=N'，N″-((1E，1'E)-(1，10-菲咯啉-2，9-二酰基)双(亚甲基)双(2-羟基苯甲酰肼))与Tb(acac)3·2H2O反应(acac-=乙酰丙酮根)，通过溶剂热法，设计并合成了一例结构新颖的双核铽配合物[Tb2(L)(H2L)]·2CH3OH·CH3CN (1)，并研究了该配合物的结构、荧光性质及生物活性。单晶X射线衍射分析表明该配合物主要含有2个TbⅢ离子和2个失去不同质子的配体离子(L4-和H2L2-)。中心Tb1和Tb2离子都是九配位的，其几何构型呈现扭曲的呼啦圈形。固体荧光实验测试结果表明：该配合物在室温下表现出TbⅢ离子的荧光特征发射峰。生物活性研究表明，与配体H4L和稀土离子相比较，配合物具有更强的抗菌活性。采用紫外可见光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了该配合物与小牛胸腺DNA之间的相互作用，结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。
2024, 40(7): 1357-1367
doi: 10.11862/CJIC.20230350
摘要:
将三聚氰胺、RuCl3及炭黑以一定的比例分散于乙醇中，采用旋转蒸干及高温热处理合成了一种氮掺杂碳(NC)负载Ru的Ru/NC催化剂。采用硼氢化钠液相化学还原法合成了不同Pt、Ru负载量的PtRu/NC催化剂，并用于电催化甲醇氧化反应(MOR)及电催化分解水析氢反应(HER)。结果表明，合成的催化剂中Pt1Ru/NC(Pt、Ru的实际负载量分别为1.14%、0.54%)表现出最优的MOR性能，质量活性达4.96 A·mgPtRu-1，且经10 000 s稳定性测试后质量活性保持在测试前的91.1%。同时，当电流密度为100mA·cm-2时，Pt1Ru/NC在HER中表现出最低的过电位(103 mV)和最小的Tafel斜率(15.29 mV·dec-1)。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、电感耦合等离子体发射光谱(ICP-OES)、STEM-能谱(STEM-EDS)技术表征了PtRu/NC双金属催化剂，其具有优异催化性能的原因如下：(1) PtRu双金属纳米颗粒高度分散于NC上；(2) Pt以纳米团簇或单原子形式负载于Ru上，后负载于NC，形成了Pt-Ru相分离结构；(3) Pt、Ru与N之间存在协同效应。
将三聚氰胺、RuCl3及炭黑以一定的比例分散于乙醇中，采用旋转蒸干及高温热处理合成了一种氮掺杂碳(NC)负载Ru的Ru/NC催化剂。采用硼氢化钠液相化学还原法合成了不同Pt、Ru负载量的PtRu/NC催化剂，并用于电催化甲醇氧化反应(MOR)及电催化分解水析氢反应(HER)。结果表明，合成的催化剂中Pt1Ru/NC(Pt、Ru的实际负载量分别为1.14%、0.54%)表现出最优的MOR性能，质量活性达4.96 A·mgPtRu-1，且经10 000 s稳定性测试后质量活性保持在测试前的91.1%。同时，当电流密度为100mA·cm-2时，Pt1Ru/NC在HER中表现出最低的过电位(103 mV)和最小的Tafel斜率(15.29 mV·dec-1)。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、电感耦合等离子体发射光谱(ICP-OES)、STEM-能谱(STEM-EDS)技术表征了PtRu/NC双金属催化剂，其具有优异催化性能的原因如下：(1) PtRu双金属纳米颗粒高度分散于NC上；(2) Pt以纳米团簇或单原子形式负载于Ru上，后负载于NC，形成了Pt-Ru相分离结构；(3) Pt、Ru与N之间存在协同效应。
