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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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2025, 41(6): 1049-1057
doi: 10.11862/CJIC.20240456
摘要:
圆偏振发光(circularly polarized luminescence，CPL)材料因其独特的手性光学特性，在3D显示、生物成像、数据存储和自旋光电子器件等领域展现出广泛的应用潜力，近年来备受科研人员关注。然而，当前的研究主要集中在紫外/可见光区，具有近红外CPL特性的分子材料却非常稀少。相较于可见光波段，近红外光具有穿透能力强、背景散射小等优点，在生物成像、探测和加密通信等领域具有显著优势。作为靛蓝的异构体，β-异靛蓝具有丰富的结构修饰和配位模式，为开发近红外CPL分子材料提供了理想的骨架。本文系统阐述基于β-异靛蓝骨架的CPL分子材料的有趣发现过程，以及如何在此基础上简单高效地实现近红外CPL分子材料的制备。最后，展望基于β-异靛蓝骨架的近红外CPL分子材料的未来发展，预测该骨架将成为近红外CPL领域一类重要的明星骨架材料。
圆偏振发光(circularly polarized luminescence，CPL)材料因其独特的手性光学特性，在3D显示、生物成像、数据存储和自旋光电子器件等领域展现出广泛的应用潜力，近年来备受科研人员关注。然而，当前的研究主要集中在紫外/可见光区，具有近红外CPL特性的分子材料却非常稀少。相较于可见光波段，近红外光具有穿透能力强、背景散射小等优点，在生物成像、探测和加密通信等领域具有显著优势。作为靛蓝的异构体，β-异靛蓝具有丰富的结构修饰和配位模式，为开发近红外CPL分子材料提供了理想的骨架。本文系统阐述基于β-异靛蓝骨架的CPL分子材料的有趣发现过程，以及如何在此基础上简单高效地实现近红外CPL分子材料的制备。最后，展望基于β-异靛蓝骨架的近红外CPL分子材料的未来发展，预测该骨架将成为近红外CPL领域一类重要的明星骨架材料。
2025, 41(6): 1058-1067
doi: 10.11862/CJIC.20240418
摘要:
采用溶剂热法合成了一系列Cs2NaBiCl6: Mn2+与Cs2Na1-xKxBiCl6: Mn2+荧光粉，并通过理论计算与实验表征相结合的方式系统研究了其晶体结构和发光性能。结果表明，Cs2NaBiCl6: Mn2+体系表现出以[BiCl6]3-八面体为中心的局域激发吸收近紫外光，随着Mn2+掺杂浓度的增加，[BiCl6]3-向Mn2+发生能量转移，从而促进了Mn2+的d轨道之间的电子跃迁并产生橙黄色发光。进一步引入K+后，Cs2NaBiCl6: Mn2+发光强度和颜色纯度得到提升。实验证实K+的引入有效调谐了Cs2NaBiCl6: Mn2+的态密度组成，促进了[BiCl6]3-的 1S0→3P1, 2电子跃迁，增强了Cs2NaBiCl6: Mn2+的发光强度，并利用CIE软件计算得到其色纯度为93.58%。最终结果表明，Cs2Na1-xKxBiCl6: Mn2+具有较强的橙黄色发光特性。
采用溶剂热法合成了一系列Cs2NaBiCl6: Mn2+与Cs2Na1-xKxBiCl6: Mn2+荧光粉，并通过理论计算与实验表征相结合的方式系统研究了其晶体结构和发光性能。结果表明，Cs2NaBiCl6: Mn2+体系表现出以[BiCl6]3-八面体为中心的局域激发吸收近紫外光，随着Mn2+掺杂浓度的增加，[BiCl6]3-向Mn2+发生能量转移，从而促进了Mn2+的d轨道之间的电子跃迁并产生橙黄色发光。进一步引入K+后，Cs2NaBiCl6: Mn2+发光强度和颜色纯度得到提升。实验证实K+的引入有效调谐了Cs2NaBiCl6: Mn2+的态密度组成，促进了[BiCl6]3-的 1S0→3P1, 2电子跃迁，增强了Cs2NaBiCl6: Mn2+的发光强度，并利用CIE软件计算得到其色纯度为93.58%。最终结果表明，Cs2Na1-xKxBiCl6: Mn2+具有较强的橙黄色发光特性。
2025, 41(6): 1068-1082
doi: 10.11862/CJIC.20250048
摘要:
通过溶剂热-电沉积法成功制备了一种具有丰富活性位点的镍铜合金/氧化锌/泡沫镍(NiCu/ZnO/NF)异质界面结构复合催化剂，并对其形貌结构、物相构成、析氢反应(HER)性能、光热性能和全解水性能进行了测试和分析。研究表明：NiCu/ZnO/NF具有优异的HER催化性能，在10 mA·cm-2的电流密度下所需的过电位仅为25 mV。高效的催化活性可能是由于NiCu/ZnO异质界面结构的协同效应加快了电子转移速率和优化了HER过程。此外，NiCu/ZnO/NF还表现出了优异的光热转换性能，在光照条件下其HER过电位显著降低，在10 mA·cm-2的电流密度下过电位降低至8 mV。此外，将NiCu/ZnO/NF集成到自设计的电解槽-热电装置进行全解水反应，其在50 mA·cm-2电流密度时的槽电压低至0.88 V。
通过溶剂热-电沉积法成功制备了一种具有丰富活性位点的镍铜合金/氧化锌/泡沫镍(NiCu/ZnO/NF)异质界面结构复合催化剂，并对其形貌结构、物相构成、析氢反应(HER)性能、光热性能和全解水性能进行了测试和分析。研究表明：NiCu/ZnO/NF具有优异的HER催化性能，在10 mA·cm-2的电流密度下所需的过电位仅为25 mV。高效的催化活性可能是由于NiCu/ZnO异质界面结构的协同效应加快了电子转移速率和优化了HER过程。此外，NiCu/ZnO/NF还表现出了优异的光热转换性能，在光照条件下其HER过电位显著降低，在10 mA·cm-2的电流密度下过电位降低至8 mV。此外，将NiCu/ZnO/NF集成到自设计的电解槽-热电装置进行全解水反应，其在50 mA·cm-2电流密度时的槽电压低至0.88 V。
2025, 41(6): 1083-1093
doi: 10.11862/CJIC.20250008
摘要:
通过一步电沉积法在碳布(CC)表面构建了镍钴双金属磷化物(NiCoP)与聚吡咯(PPy)复合的NiCoP/PPy/CC材料，并探究了吡咯的添加量对材料形貌、结构以及性能的影响。当吡咯的浓度为3 mol·L-1时制备的NiCoP/PPy/CC-3电极的电化学性能最佳，其在三电极体系中表现出较好的电化学性能，在4.0 mA·cm-2的电流密度下，该电极的面积比电容为1 068.11 mF·cm-2，对应的质量比电容为508.62 F·g-1，并且在8.0 mA·cm-2的电流密度下进行6 000次循环后的电容保持率为90.1%。将该电极应用于柔性非对称超级电容器中，该柔性器件可实现180°的弯折，并且在8.0 mA·cm-2的电流密度下进行10 000次循环后，器件的初始比电容仍保持88.6%。此外，将2个非对称超级电容器串联可以有效地点亮发光二极管(LED)。
通过一步电沉积法在碳布(CC)表面构建了镍钴双金属磷化物(NiCoP)与聚吡咯(PPy)复合的NiCoP/PPy/CC材料，并探究了吡咯的添加量对材料形貌、结构以及性能的影响。当吡咯的浓度为3 mol·L-1时制备的NiCoP/PPy/CC-3电极的电化学性能最佳，其在三电极体系中表现出较好的电化学性能，在4.0 mA·cm-2的电流密度下，该电极的面积比电容为1 068.11 mF·cm-2，对应的质量比电容为508.62 F·g-1，并且在8.0 mA·cm-2的电流密度下进行6 000次循环后的电容保持率为90.1%。将该电极应用于柔性非对称超级电容器中，该柔性器件可实现180°的弯折，并且在8.0 mA·cm-2的电流密度下进行10 000次循环后，器件的初始比电容仍保持88.6%。此外，将2个非对称超级电容器串联可以有效地点亮发光二极管(LED)。
2025, 41(6): 1094-1100
doi: 10.11862/CJIC.20240464
摘要:
以2，5-二溴对苯二甲酸(H2BDC-Br2)为桥联配体，采用快速合成法，与HfCl4进行自组装，成功制备了一个与传统UiO-66结构相同的三维多孔铪基金属有机框架(UiO-66-Br2-Hf) (1)。首先通过热重分析(TGA)、粉末X射线衍射(PXRD)等表征手段证实了 1的卓越的结构稳定性。进而系统地考察了其在水分子辅助下的质子导电能力，发现其质子电导率与温度和相对湿度(RH)呈正相关关系，且在100 ℃和98% RH下，其质子电导率高达3.11×10-3 S·cm-1。最后，结合结构分析、氮气和水蒸气吸附测试以及活化能计算等，对其质子导电机制进行了探究。
以2，5-二溴对苯二甲酸(H2BDC-Br2)为桥联配体，采用快速合成法，与HfCl4进行自组装，成功制备了一个与传统UiO-66结构相同的三维多孔铪基金属有机框架(UiO-66-Br2-Hf) (1)。首先通过热重分析(TGA)、粉末X射线衍射(PXRD)等表征手段证实了 1的卓越的结构稳定性。进而系统地考察了其在水分子辅助下的质子导电能力，发现其质子电导率与温度和相对湿度(RH)呈正相关关系，且在100 ℃和98% RH下，其质子电导率高达3.11×10-3 S·cm-1。最后，结合结构分析、氮气和水蒸气吸附测试以及活化能计算等，对其质子导电机制进行了探究。
2025, 41(6): 1101-1111
doi: 10.11862/CJIC.20240441
摘要:
基于不同单金属氧化物对草酸锂(Li2C2O4，LCO)分解的促进效果，以CuO-Mn2O3混合物为前驱体，采用简便的固相烧结法合成了一系列Mn、Cu物质的量之比(x)不同的CuMnxO1+1.5x双金属氧化物催化剂。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、N2吸附-脱附等温线和扫描电子显微镜(SEM)等方法表征了材料的结构组成与微观形貌，并探究了其对LCO电化学活性的影响规律。结果表明，在0.05C和2.5~4.5 V下，以CuMn1.1O2.7为催化剂时LCO的充电比容量可达404.7 mAh·g-1，同时脱锂电位降低至4.44 V，首次库仑效率仅为1.3%，可作为正极补锂添加剂应用于磷酸铁锂(LFP)体系；此外，采用密度泛函理论(DFT)计算揭示了LCO分解的速率控制步骤和催化剂的作用机制。将一定量的LCO/CuMn1.1O2.7补锂剂添加至LFP浆料中制作成扣式半电池，并对其进行电化学性能测试，结果表明，在最佳补锂剂含量下，相应LFP电极的首次充电比容量为205.9 mAh·g-1，LCO的实际利用率可达74.1%，而且补锂剂的添加能改善LFP的循环性能。
基于不同单金属氧化物对草酸锂(Li2C2O4，LCO)分解的促进效果，以CuO-Mn2O3混合物为前驱体，采用简便的固相烧结法合成了一系列Mn、Cu物质的量之比(x)不同的CuMnxO1+1.5x双金属氧化物催化剂。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、N2吸附-脱附等温线和扫描电子显微镜(SEM)等方法表征了材料的结构组成与微观形貌，并探究了其对LCO电化学活性的影响规律。结果表明，在0.05C和2.5~4.5 V下，以CuMn1.1O2.7为催化剂时LCO的充电比容量可达404.7 mAh·g-1，同时脱锂电位降低至4.44 V，首次库仑效率仅为1.3%，可作为正极补锂添加剂应用于磷酸铁锂(LFP)体系；此外，采用密度泛函理论(DFT)计算揭示了LCO分解的速率控制步骤和催化剂的作用机制。将一定量的LCO/CuMn1.1O2.7补锂剂添加至LFP浆料中制作成扣式半电池，并对其进行电化学性能测试，结果表明，在最佳补锂剂含量下，相应LFP电极的首次充电比容量为205.9 mAh·g-1，LCO的实际利用率可达74.1%，而且补锂剂的添加能改善LFP的循环性能。
2025, 41(6): 1112-1122
doi: 10.11862/CJIC.20240423
摘要:
本研究开发了一例近红外荧光探针NSHD，该探针由商业原料经一步合成得到。NSHD以荧光-比色双模式快速响应过氧亚硝酸根阴离子(ONOO-)，不受生命体其他常见金属离子、活性物种和生理范围pH变化的干扰。在0~20 μmol·L-1范围内，探针荧光强度与ONOO-浓度间存在良好的线性关系。质谱测试数据表明ONOO-使探针发生氧化裂解，导致荧光发射和颜色变化。此外，该探针具有良好的生物相容性，在活HeLa细胞(人类宫颈癌细胞)中实现了对胞内ONOO-的成像。
本研究开发了一例近红外荧光探针NSHD，该探针由商业原料经一步合成得到。NSHD以荧光-比色双模式快速响应过氧亚硝酸根阴离子(ONOO-)，不受生命体其他常见金属离子、活性物种和生理范围pH变化的干扰。在0~20 μmol·L-1范围内，探针荧光强度与ONOO-浓度间存在良好的线性关系。质谱测试数据表明ONOO-使探针发生氧化裂解，导致荧光发射和颜色变化。此外，该探针具有良好的生物相容性，在活HeLa细胞(人类宫颈癌细胞)中实现了对胞内ONOO-的成像。
2025, 41(6): 1123-1130
doi: 10.11862/CJIC.20240440
摘要:
采用离子束辅助沉积(IBAD)技术制备氮掺杂CeO2薄膜并对其光催化性能进行了研究。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、紫外可见吸收光谱(UV-Vis)对制备的薄膜进行了表征。实验结果表明，通过IBAD技术制备氮掺杂CeO2薄膜的方法可以实现体相均匀氮掺杂，且掺氮量远高于传统氮掺杂方法。SEM结果表明，氮离子束轰击作用并没有改变CeO2的晶体结构，但是会改变CeO2的结晶度和晶格参数，同时，样品表面变得更光滑、粒径更小。另外，该方法使CeO2薄膜的可见光吸收边从370 nm红移到480 nm，增加了其可见光吸收性能。光催化降解亚甲蓝测试结果显示，在可见光下催化120 min时，溶液中的亚甲蓝降解率已经高于90%，并在6次循环稳定性测试后降解率保持在86%左右，显示出良好的光催化稳定性。
采用离子束辅助沉积(IBAD)技术制备氮掺杂CeO2薄膜并对其光催化性能进行了研究。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、紫外可见吸收光谱(UV-Vis)对制备的薄膜进行了表征。实验结果表明，通过IBAD技术制备氮掺杂CeO2薄膜的方法可以实现体相均匀氮掺杂，且掺氮量远高于传统氮掺杂方法。SEM结果表明，氮离子束轰击作用并没有改变CeO2的晶体结构，但是会改变CeO2的结晶度和晶格参数，同时，样品表面变得更光滑、粒径更小。另外，该方法使CeO2薄膜的可见光吸收边从370 nm红移到480 nm，增加了其可见光吸收性能。光催化降解亚甲蓝测试结果显示，在可见光下催化120 min时，溶液中的亚甲蓝降解率已经高于90%，并在6次循环稳定性测试后降解率保持在86%左右，显示出良好的光催化稳定性。
2025, 41(6): 1131-1140
doi: 10.11862/CJIC.20240419
摘要:
使用绿色溶剂水溶解CsBr，以达到提高CsBr溶解度、简化CsPbBr3钙钛矿太阳能电池(perovskite solar cells)制备工艺和提高薄膜质量的目的。结果表明，在停留时间为5 s、退火温度为250 ℃的条件下，旋涂1遍质量浓度为250 mg·mL-1的CsBr水溶液所制备的电池性能最优，实现了1.64 V的最高开路电压(open circuit voltage，VOC)，短路电流密度(short-circuit current，JSC)为7.55 mA·cm-2，填充因子(fill factor，FF)为85.46%，光电转换效率(photoelectric conversion efficiency，PCE)为10.51%。
使用绿色溶剂水溶解CsBr，以达到提高CsBr溶解度、简化CsPbBr3钙钛矿太阳能电池(perovskite solar cells)制备工艺和提高薄膜质量的目的。结果表明，在停留时间为5 s、退火温度为250 ℃的条件下，旋涂1遍质量浓度为250 mg·mL-1的CsBr水溶液所制备的电池性能最优，实现了1.64 V的最高开路电压(open circuit voltage，VOC)，短路电流密度(short-circuit current，JSC)为7.55 mA·cm-2，填充因子(fill factor，FF)为85.46%，光电转换效率(photoelectric conversion efficiency，PCE)为10.51%。
2025, 41(6): 1141-1150
doi: 10.11862/CJIC.20240258
摘要:
以双齿席夫碱5-[(4-ethylbenzylidene)amino]quinolin-8-ol(HL1)、5-{[(1，1′-biphenyl)-4-ylmethylene]amino}quinolin-8-ol(HL2)为配体，与Sm(acac)3·2H2O反应，通过溶剂热法，设计与构筑了2例结构新颖的Sm4配合物[Sm4(L1)6(acac)4(μ3-OH)2]·CH3CN (1)和[Sm4(L2)6(acac)4(μ3-OH)2]·CH3CN (2)，其中Hacac=乙酰丙酮。单晶X射线衍射分析表明：配合物1和2结构相似，其结构主要由4个Sm(Ⅲ)离子、4个acac-、6个L1-或L2-以及2个μ3-OH-组成。中心的4个Sm(Ⅲ)离子通过6个μ2-O和2个μ3-OH-相互连接，形成一个菱形的Sm4核心。采用紫外光谱法、循环伏安法和荧光光谱法研究了配合物 1和 2与小牛胸腺DNA(CTDNA)之间的相互作用。研究表明，配合物1和2与CTDNA的相互作用是插入结合。
以双齿席夫碱5-[(4-ethylbenzylidene)amino]quinolin-8-ol(HL1)、5-{[(1，1′-biphenyl)-4-ylmethylene]amino}quinolin-8-ol(HL2)为配体，与Sm(acac)3·2H2O反应，通过溶剂热法，设计与构筑了2例结构新颖的Sm4配合物[Sm4(L1)6(acac)4(μ3-OH)2]·CH3CN (1)和[Sm4(L2)6(acac)4(μ3-OH)2]·CH3CN (2)，其中Hacac=乙酰丙酮。单晶X射线衍射分析表明：配合物1和2结构相似，其结构主要由4个Sm(Ⅲ)离子、4个acac-、6个L1-或L2-以及2个μ3-OH-组成。中心的4个Sm(Ⅲ)离子通过6个μ2-O和2个μ3-OH-相互连接，形成一个菱形的Sm4核心。采用紫外光谱法、循环伏安法和荧光光谱法研究了配合物 1和 2与小牛胸腺DNA(CTDNA)之间的相互作用。研究表明，配合物1和2与CTDNA的相互作用是插入结合。
2025, 41(6): 1151-1161
doi: 10.11862/CJIC.20240202
摘要:
设计了一种绿色的再生废纸纤维素(RCewp)与氧化还原石墨烯(rGO)复合的薄膜(RCewp/rGO)并将其作为活性材料，其在7 000 s的循环中稳定输出的最大峰值电流为10 μA，且在100 Ω负载下的输出功率最高可达2.34 μW·cm-2。同时，研究表明金属集流体对湿气发电的影响显著，其中不锈钢集流体在70%的相对湿度(RH)条件下，产生的开路电压最大可达53 mV，因为集流体的氧化还原反应在湿气作用下增强了电流和电压的输出。此外，该湿气发电薄膜与镁空气电池结合时表现出优异的性能：在50%RH下，RCewp/rGO电极能够产生高达1.37 V的开路电压(Voc)和0.132 mA·cm-2的短路电流密度；当RH升高至90%时，开路电压进一步增大至1.57 V，短路电流密度达到64.2 mA·cm-2。而对于未与湿气发电薄膜相连的Mg-滤纸-Ni电极，其输出功率和短路电流密度仅为3.76×10-4 mW和0.306 μA·cm-2。
设计了一种绿色的再生废纸纤维素(RCewp)与氧化还原石墨烯(rGO)复合的薄膜(RCewp/rGO)并将其作为活性材料，其在7 000 s的循环中稳定输出的最大峰值电流为10 μA，且在100 Ω负载下的输出功率最高可达2.34 μW·cm-2。同时，研究表明金属集流体对湿气发电的影响显著，其中不锈钢集流体在70%的相对湿度(RH)条件下，产生的开路电压最大可达53 mV，因为集流体的氧化还原反应在湿气作用下增强了电流和电压的输出。此外，该湿气发电薄膜与镁空气电池结合时表现出优异的性能：在50%RH下，RCewp/rGO电极能够产生高达1.37 V的开路电压(Voc)和0.132 mA·cm-2的短路电流密度；当RH升高至90%时，开路电压进一步增大至1.57 V，短路电流密度达到64.2 mA·cm-2。而对于未与湿气发电薄膜相连的Mg-滤纸-Ni电极，其输出功率和短路电流密度仅为3.76×10-4 mW和0.306 μA·cm-2。
2025, 41(6): 1162-1172
doi: 10.11862/CJIC.20250081
摘要:
The abnormal metabolic activity of the tumor can increase the oxygen consumption in tumor cells, and the poor blood perfusion often happens in tumor regions as well, which are the main reasons that result in a hypoxic situation in the tumor. A fluorescence probe, AQD, with selective response toward hypoxia was designed for the detection of hypoxic tumor cells, which was obtained by the covalent connection of a large planar conjugated fluorophore with good fluorescence stability and a N, N-dimethylaniline moiety via the azo bond. The introduction of the azo bond in AQD caused significant fluorescence emission quenching, and the probe was reduced under hypoxic conditions to release the fluorophore via breaking the azo bond, resulting in the gradual recovery of fluorescence emission. Probe AQD exhibited a remarkable fluorescence response in hypoxic conditions, high selectivity, and good biocompatibility, which was successfully used for the imaging of hypoxic tumor cells and realized the detection of hypoxic A549 cells.
The abnormal metabolic activity of the tumor can increase the oxygen consumption in tumor cells, and the poor blood perfusion often happens in tumor regions as well, which are the main reasons that result in a hypoxic situation in the tumor. A fluorescence probe, AQD, with selective response toward hypoxia was designed for the detection of hypoxic tumor cells, which was obtained by the covalent connection of a large planar conjugated fluorophore with good fluorescence stability and a N, N-dimethylaniline moiety via the azo bond. The introduction of the azo bond in AQD caused significant fluorescence emission quenching, and the probe was reduced under hypoxic conditions to release the fluorophore via breaking the azo bond, resulting in the gradual recovery of fluorescence emission. Probe AQD exhibited a remarkable fluorescence response in hypoxic conditions, high selectivity, and good biocompatibility, which was successfully used for the imaging of hypoxic tumor cells and realized the detection of hypoxic A549 cells.
2025, 41(6): 1173-1182
doi: 10.11862/CJIC.20250112
摘要:
In this study, a self-calibrating near-infrared fluorescence probe was designed and synthesized based on the dual-fluorophore strategy utilizing methylene blue and coumarin. The probe utilized methylene blue (emission spectrum range: 640-740 nm) and coumarin fluorophore (emission spectrum range: 440-600 nm) as signal output units, thereby achieving effective spectral separation and highly selective detection of HClO. Under physiological pH conditions, HClO triggers an oxidation-cleavage reaction, releasing methylene blue and coumarin, which emit distinct red and green fluorescence, respectively. This dualemission feature enabled rapid HClO detection with two-channel detection limits of 25.13 nmol·L-1 (green channel) and 31.55 nmol·L-1 (red channel). Furthermore, in cell imaging experiments, this probe demonstrated excellent cell membrane permeability and low cytotoxicity, successfully enabling the monitoring of both endogenous and exogenous HClO in living cells. By incorporating a two-channel self-calibration system, the probe effectively mitigated signal variations caused by instrumental or environmental interference, substantially improving detection sensitivity and reliability.
In this study, a self-calibrating near-infrared fluorescence probe was designed and synthesized based on the dual-fluorophore strategy utilizing methylene blue and coumarin. The probe utilized methylene blue (emission spectrum range: 640-740 nm) and coumarin fluorophore (emission spectrum range: 440-600 nm) as signal output units, thereby achieving effective spectral separation and highly selective detection of HClO. Under physiological pH conditions, HClO triggers an oxidation-cleavage reaction, releasing methylene blue and coumarin, which emit distinct red and green fluorescence, respectively. This dualemission feature enabled rapid HClO detection with two-channel detection limits of 25.13 nmol·L-1 (green channel) and 31.55 nmol·L-1 (red channel). Furthermore, in cell imaging experiments, this probe demonstrated excellent cell membrane permeability and low cytotoxicity, successfully enabling the monitoring of both endogenous and exogenous HClO in living cells. By incorporating a two-channel self-calibration system, the probe effectively mitigated signal variations caused by instrumental or environmental interference, substantially improving detection sensitivity and reliability.
2025, 41(6): 1183-1195
doi: 10.11862/CJIC.20250034
摘要:
A low-cost 1D cobalt-based coordination polymer (CP) [Co(BGPD)(DMSO)2(H2O)2] (Co-BD; H2BGPD=N, N'-bis(glycinyl)pyromellitic diimide; DMSO=dimethyl sulfoxide) was synthesized by a simple method, and its crystal structure was characterized. In a three-electrode system, Co-BD, as the electrode material for supercapacitors, achieved a specific capacitance of 830 F·g-1 at 1 A·g-1, equivalent to a specific capacity of 116.4 mAh·g-1, and exhibited high-rate capability, reaching 212 F·g-1 at 20 A·g-1. Impressively, Co-BD||rGO (reduced graphene oxide), representing an asymmetrical supercapacitor, owns a higher energy density of 14.2 Wh·kg-1 at 0.80 kW·kg-1, and an excellent cycle performance (After 4 000 cycles at 1 A·g-1, the capacitance retention was up to 94%).
A low-cost 1D cobalt-based coordination polymer (CP) [Co(BGPD)(DMSO)2(H2O)2] (Co-BD; H2BGPD=N, N'-bis(glycinyl)pyromellitic diimide; DMSO=dimethyl sulfoxide) was synthesized by a simple method, and its crystal structure was characterized. In a three-electrode system, Co-BD, as the electrode material for supercapacitors, achieved a specific capacitance of 830 F·g-1 at 1 A·g-1, equivalent to a specific capacity of 116.4 mAh·g-1, and exhibited high-rate capability, reaching 212 F·g-1 at 20 A·g-1. Impressively, Co-BD||rGO (reduced graphene oxide), representing an asymmetrical supercapacitor, owns a higher energy density of 14.2 Wh·kg-1 at 0.80 kW·kg-1, and an excellent cycle performance (After 4 000 cycles at 1 A·g-1, the capacitance retention was up to 94%).
2025, 41(6): 1196-1206
doi: 10.11862/CJIC.20240445
摘要:
Iron (Fe) nanoparticles and graphite (Gr) with different masses of bismuth trisulfide (Bi2S3) were mixed by high-energy ball milling treatment to fabricate the corresponding composite iron anodes Bi2S3@Fe-Gr. The hydrogen evolution reaction and iron passivation process on these iron electrodes were investigated in alkaline and neutral solutions. The iron electrode Bi2S3-3@Fe-Gr (The additional amount of Bi2S3 was 3 mg) revealed the strongest ability to inhibit hydrogen evolution among the iron electrodes of the present investigation, while the Bi2S3-6@Fe-Gr electrode (The additional amount of Bi2S3 was 6 mg) delivered significant performance in inhibiting anodic passivation. This is because the high-energy ball milling process leads to the well-dispersion of Bi2S3 and the changes in the surface of Fe nanoparticles, thereby slowing down the passivation of the iron electrode surface.
Iron (Fe) nanoparticles and graphite (Gr) with different masses of bismuth trisulfide (Bi2S3) were mixed by high-energy ball milling treatment to fabricate the corresponding composite iron anodes Bi2S3@Fe-Gr. The hydrogen evolution reaction and iron passivation process on these iron electrodes were investigated in alkaline and neutral solutions. The iron electrode Bi2S3-3@Fe-Gr (The additional amount of Bi2S3 was 3 mg) revealed the strongest ability to inhibit hydrogen evolution among the iron electrodes of the present investigation, while the Bi2S3-6@Fe-Gr electrode (The additional amount of Bi2S3 was 6 mg) delivered significant performance in inhibiting anodic passivation. This is because the high-energy ball milling process leads to the well-dispersion of Bi2S3 and the changes in the surface of Fe nanoparticles, thereby slowing down the passivation of the iron electrode surface.
2025, 41(6): 1207-1216
doi: 10.11862/CJIC.20250005
摘要:
Two new complexes, [Zn2(L1)(HL1)(NO3)]·CH3OH (1) and [Zn3(L2)(L3)3Cl]·CH3OH (2), were successfully synthesized by'one-pot'method based on cinnoline-3-ylhydrazine ligand and zinc with 2-hydroxy-4-methoxybenz-aldehyde and 2-hydroxy-3-methoxybenzaldehyde ligands, respectively, where H2L1=5-methoxy-2-(phthalazin-1-yl-hydrazonomethyl)-phenol, H2L2=2-methoxy-6-(phthalazin-1-yl-hydrazonomethyl)-phenol, HL3=2-(1, 8-dihydro-[1,2,4]triazolo[3,4-α]phthalazin-3-yl)-6-methoxy-phenol. Complexes 1 and 2 were characterized by infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction, etc. It is worth noting that the cinnolin-3-yl-hydrazine ligand and 2-hydroxy-3-methoxybenzaldehyde form two types of Schiff bases (H2L2 and HL3) when in situ reacting and coordinating with Zn(Ⅱ), and HL3 also has two coordination modes. In addition, the fluorescence performance showed that complex 1 can achieve selective and sensitive sensing of Al3+ in water with a detection limit of 6.37 μmol·L-1.
Two new complexes, [Zn2(L1)(HL1)(NO3)]·CH3OH (1) and [Zn3(L2)(L3)3Cl]·CH3OH (2), were successfully synthesized by'one-pot'method based on cinnoline-3-ylhydrazine ligand and zinc with 2-hydroxy-4-methoxybenz-aldehyde and 2-hydroxy-3-methoxybenzaldehyde ligands, respectively, where H2L1=5-methoxy-2-(phthalazin-1-yl-hydrazonomethyl)-phenol, H2L2=2-methoxy-6-(phthalazin-1-yl-hydrazonomethyl)-phenol, HL3=2-(1, 8-dihydro-[1,2,4]triazolo[3,4-α]phthalazin-3-yl)-6-methoxy-phenol. Complexes 1 and 2 were characterized by infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction, etc. It is worth noting that the cinnolin-3-yl-hydrazine ligand and 2-hydroxy-3-methoxybenzaldehyde form two types of Schiff bases (H2L2 and HL3) when in situ reacting and coordinating with Zn(Ⅱ), and HL3 also has two coordination modes. In addition, the fluorescence performance showed that complex 1 can achieve selective and sensitive sensing of Al3+ in water with a detection limit of 6.37 μmol·L-1.
2025, 41(6): 1217-1226
doi: 10.11862/CJIC.20240457
摘要:
A novel coordination polymer (CP) {[Cd2(L)(1,4-bimb)1.5(DMF)2]·DMF}n (1) (H4L=5, 5′-[1,1′-biphenyl-4,4′-diylbis(oxy)]diisophthalic acid, 1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene) has been designed and synthesized through solvothermal reaction. Structural analysis shows that Cd(Ⅱ) is connected by H4L and 1,4-bimb to form a 2D network, and 1,4-bimb further expands the 2D network into a 3D framework. CP 1 can be used as an excellent fluorescence sensor for Fe3+ and 4-nitrophenol (4-NP), with low detection limits and good anti-interference. The detection limits of Fe3+ and 4-NP were 0.034 and 0.031 μmol·L-1, respectively. In addition, the fluorescence quenching mechanism was studied. 1 was successfully applied to determine Fe3+ and 4-NP content in the Yanhe River water sample.
A novel coordination polymer (CP) {[Cd2(L)(1,4-bimb)1.5(DMF)2]·DMF}n (1) (H4L=5, 5′-[1,1′-biphenyl-4,4′-diylbis(oxy)]diisophthalic acid, 1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene) has been designed and synthesized through solvothermal reaction. Structural analysis shows that Cd(Ⅱ) is connected by H4L and 1,4-bimb to form a 2D network, and 1,4-bimb further expands the 2D network into a 3D framework. CP 1 can be used as an excellent fluorescence sensor for Fe3+ and 4-nitrophenol (4-NP), with low detection limits and good anti-interference. The detection limits of Fe3+ and 4-NP were 0.034 and 0.031 μmol·L-1, respectively. In addition, the fluorescence quenching mechanism was studied. 1 was successfully applied to determine Fe3+ and 4-NP content in the Yanhe River water sample.
2025, 41(6): 1227-1234
doi: 10.11862/CJIC.20240448
摘要:
The reaction of Mg2+ and 5-{1, 3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid (H2L) leads to two metal-organic frameworks, [Mg(L)(DMF)2(H2O)2]2·5DMF·2H2O (1) with a 1D structure and [Mg2(L)2(DMSO)3(H2O)] (2) with a 2D (4, 4)-net structure. Interestingly, the two compounds exhibit distinct luminescent responses to external mechanical stimuli. 1 exhibited exceptional resistance mechanical chromic luminescence (RMCL), which can be attributed to the predominant hydrogen bonds and the presence of high-boiling-point solvent molecules within its structure. 2 had a reversible MCL property, which can be attributed to the dominant π-π weak interactions, coupled with the reversible destruction/restoration of its crystallinity under grinding/fumigation.
The reaction of Mg2+ and 5-{1, 3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid (H2L) leads to two metal-organic frameworks, [Mg(L)(DMF)2(H2O)2]2·5DMF·2H2O (1) with a 1D structure and [Mg2(L)2(DMSO)3(H2O)] (2) with a 2D (4, 4)-net structure. Interestingly, the two compounds exhibit distinct luminescent responses to external mechanical stimuli. 1 exhibited exceptional resistance mechanical chromic luminescence (RMCL), which can be attributed to the predominant hydrogen bonds and the presence of high-boiling-point solvent molecules within its structure. 2 had a reversible MCL property, which can be attributed to the dominant π-π weak interactions, coupled with the reversible destruction/restoration of its crystallinity under grinding/fumigation.
2025, 41(6): 1235-1244
doi: 10.11862/CJIC.20240429
摘要:
We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ) complexes featuring a transition metal as their core atom to identify some appropriate organic light-emitting diode (OLED) materials. By utilizing electronic structure, frontier molecular orbitals, minimum single-line absorption, triplet excited states, and emission spectral data derived from the density functional theory, the usefulness of these Ir(Ⅲ) complexes, including (piq)2Ir(acac), (piq)2Ir(tmd), (piq)2Ir(tpip), (fpiq)2Ir(acac), (fpiq)2Ir(tmd), and (fpiq)2Ir(tpip), in OLEDs was examined, where piq=1-phenylisoquinoline, fpiq=1-(4-fluorophenyl) isoquinoline, acac=(3Z)-4-hydroxypent-3-en-2-one, tmd=(4Z)-5-hydroxy-2, 2, 6, 6-tetramethylhept-4-en-3-one, and tpip=tetraphenylimido-diphosphonate. These complexes all have low-efficiency roll-off properties, especially (fpiq)2Ir(tpip). Some researchers have successfully synthesized complexes extremely similar to (piq)2Ir(acac) through the Suzuki-Miyaura coupling reaction.
We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ) complexes featuring a transition metal as their core atom to identify some appropriate organic light-emitting diode (OLED) materials. By utilizing electronic structure, frontier molecular orbitals, minimum single-line absorption, triplet excited states, and emission spectral data derived from the density functional theory, the usefulness of these Ir(Ⅲ) complexes, including (piq)2Ir(acac), (piq)2Ir(tmd), (piq)2Ir(tpip), (fpiq)2Ir(acac), (fpiq)2Ir(tmd), and (fpiq)2Ir(tpip), in OLEDs was examined, where piq=1-phenylisoquinoline, fpiq=1-(4-fluorophenyl) isoquinoline, acac=(3Z)-4-hydroxypent-3-en-2-one, tmd=(4Z)-5-hydroxy-2, 2, 6, 6-tetramethylhept-4-en-3-one, and tpip=tetraphenylimido-diphosphonate. These complexes all have low-efficiency roll-off properties, especially (fpiq)2Ir(tpip). Some researchers have successfully synthesized complexes extremely similar to (piq)2Ir(acac) through the Suzuki-Miyaura coupling reaction.
2025, 41(6): 1245-1255
doi: 10.11862/CJIC.20240389
摘要:
Bovine serum albumin (BSA) and glycine (Gly) dual-ligand-modified copper nanoclusters (BSA-Gly CuNCs) with high fluorescence intensity were synthesized by a one-pot strategy. Based on the competitive fluorescence quenching and dynamic quenching effects of ornidazole (ONZ) on BSA-Gly CuNCs, a simple and sensitive detection method for ONZ was successfully developed. The experimental results demonstrate that the addition of the small molecule Gly can more effectively protect CuNCs, and thus enhance its fluorescence intensity and stability. The proposed assay allowed for the detection of ONZ in a linear range of 0.28 to 52.60 μmol·L-1 and a detection limit of 0.069 μmol·L-1. Compared with the single-ligand-modified CuNCs, dual-ligand-modified BSA-Gly CuNCs had higher fluorescence intensity, stability, and sensing ability and were successfully applied to evaluate ONZ in actual ONZ tablets.
Bovine serum albumin (BSA) and glycine (Gly) dual-ligand-modified copper nanoclusters (BSA-Gly CuNCs) with high fluorescence intensity were synthesized by a one-pot strategy. Based on the competitive fluorescence quenching and dynamic quenching effects of ornidazole (ONZ) on BSA-Gly CuNCs, a simple and sensitive detection method for ONZ was successfully developed. The experimental results demonstrate that the addition of the small molecule Gly can more effectively protect CuNCs, and thus enhance its fluorescence intensity and stability. The proposed assay allowed for the detection of ONZ in a linear range of 0.28 to 52.60 μmol·L-1 and a detection limit of 0.069 μmol·L-1. Compared with the single-ligand-modified CuNCs, dual-ligand-modified BSA-Gly CuNCs had higher fluorescence intensity, stability, and sensing ability and were successfully applied to evaluate ONZ in actual ONZ tablets.
2025, 41(2): 225-234
doi: 10.11862/CJIC.20240224
摘要:
系统研究了中空纤维NaA分子膜在蒸汽渗透中结合真空抽吸和N2吹扫操作对乙醇深度脱水的过程。研究发现吹扫作用在乙醇深度脱水中占主导作用，与未加吹扫气的对照工况(操作温度100℃、原料液进料流量为30 mL·min-1)相比，N2吹扫(吹扫气流量为60 mL·min-1)可加倍提升脱水速率，快速得到超低含水量乙醇(水的质量分数约0.5%)，效率提升约43%；升高温度至120℃时，增大原料液进料流量为50 mL·min-1时乙醇产品中水的质量分数可进一步降至0.068‰，收率达99.86%。
系统研究了中空纤维NaA分子膜在蒸汽渗透中结合真空抽吸和N2吹扫操作对乙醇深度脱水的过程。研究发现吹扫作用在乙醇深度脱水中占主导作用，与未加吹扫气的对照工况(操作温度100℃、原料液进料流量为30 mL·min-1)相比，N2吹扫(吹扫气流量为60 mL·min-1)可加倍提升脱水速率，快速得到超低含水量乙醇(水的质量分数约0.5%)，效率提升约43%；升高温度至120℃时，增大原料液进料流量为50 mL·min-1时乙醇产品中水的质量分数可进一步降至0.068‰，收率达99.86%。
2025, 41(2): 235-244
doi: 10.11862/CJIC.20240311
摘要:
为研究取代基对铱磷光配合物光物理性质的影响，以2，4-二(2，4-二取代基苯基)吡啶[2，4-(2，4-2R-phenyl)2py，R=甲基(HL1)、甲氧基(HL2)、氟(HL3)、三氟甲基(HL4)]为主配体，即在主配体上2个苯基的2位和4位同时引入4个相同的甲基、甲氧基、氟或三氟甲基，同时以乙酰丙酮(Hacac)为辅助配体，合成出4个铱磷光配合物(Ln)2Ir (acac)[n=1(Ir1)、2(Ir2)、3(Ir3)、4(Ir4)]。通过元素分析、核磁共振谱(1H NMR和13C NMR)和单晶X射线衍射表征了铱磷光配合物的组成、空间结构和分子堆积。通过溶液和固态光致发光光谱、紫外可见吸收光谱、荧光寿命和理论计算对铱磷光配合物的光物理性能进行了深入和系统的研究。结果表明：4个铱磷光配合物均呈稍微扭曲的八面体构型，中心Ir(Ⅲ)分别与2个主配体的C和N原子配位形成五元螯合环，同时和辅助配体acac-的2个氧原子配位形成稳定的六元螯合环。配合物Ir1、Ir2、Ir3和Ir4在溶液状态下的发射波长分别为537、515、514和553 nm，溶液中量子产率分别为68%、83%、88%和81%，荧光寿命分别为26.75、163.93、64.50和330.39 ns。4个铱磷光配合物具有不同的电子云分布特征，取代基能够调控电子云在苯环上的分布，进一步实现发射波长、发光颜色，荧光寿命和分子堆积的调控。
为研究取代基对铱磷光配合物光物理性质的影响，以2，4-二(2，4-二取代基苯基)吡啶[2，4-(2，4-2R-phenyl)2py，R=甲基(HL1)、甲氧基(HL2)、氟(HL3)、三氟甲基(HL4)]为主配体，即在主配体上2个苯基的2位和4位同时引入4个相同的甲基、甲氧基、氟或三氟甲基，同时以乙酰丙酮(Hacac)为辅助配体，合成出4个铱磷光配合物(Ln)2Ir (acac)[n=1(Ir1)、2(Ir2)、3(Ir3)、4(Ir4)]。通过元素分析、核磁共振谱(1H NMR和13C NMR)和单晶X射线衍射表征了铱磷光配合物的组成、空间结构和分子堆积。通过溶液和固态光致发光光谱、紫外可见吸收光谱、荧光寿命和理论计算对铱磷光配合物的光物理性能进行了深入和系统的研究。结果表明：4个铱磷光配合物均呈稍微扭曲的八面体构型，中心Ir(Ⅲ)分别与2个主配体的C和N原子配位形成五元螯合环，同时和辅助配体acac-的2个氧原子配位形成稳定的六元螯合环。配合物Ir1、Ir2、Ir3和Ir4在溶液状态下的发射波长分别为537、515、514和553 nm，溶液中量子产率分别为68%、83%、88%和81%，荧光寿命分别为26.75、163.93、64.50和330.39 ns。4个铱磷光配合物具有不同的电子云分布特征，取代基能够调控电子云在苯环上的分布，进一步实现发射波长、发光颜色，荧光寿命和分子堆积的调控。
2025, 41(2): 245-253
doi: 10.11862/CJIC.20240307
摘要:
在溶剂热条件下通过2，5-双(2H-四唑-5-基)对苯二甲酸配体(H4dtztp)与稀土Eu3+自组装得到了一例二维铕金属有机骨架[Eu (dtztp)0.5(H2dtztp)0.5(DMF)3]·0.113H2O (Eu-MOF)，其中DMF为N，N-二甲基甲酰胺。利用X射线单晶衍射、粉末X射线衍射、热重分析和元素分析等技术确定了Eu-MOF的空间结构、相纯度和稳定性，同时，对Eu-MOF的固态荧光以及抗生素检测功能进行了探究。结果表明：Eu-MOF属于三斜晶系，\begin{document}$P \overline{1}$\end{document}
在溶剂热条件下通过2，5-双(2H-四唑-5-基)对苯二甲酸配体(H4dtztp)与稀土Eu3+自组装得到了一例二维铕金属有机骨架[Eu (dtztp)0.5(H2dtztp)0.5(DMF)3]·0.113H2O (Eu-MOF)，其中DMF为N，N-二甲基甲酰胺。利用X射线单晶衍射、粉末X射线衍射、热重分析和元素分析等技术确定了Eu-MOF的空间结构、相纯度和稳定性，同时，对Eu-MOF的固态荧光以及抗生素检测功能进行了探究。结果表明：Eu-MOF属于三斜晶系，
2025, 41(2): 254-266
doi: 10.11862/CJIC.20240260
摘要:
基于原子层沉积技术(ALD)制备TiO2和Al2O3纳米层并结合高温热处理优化工艺，研究了异质氧化物双层表面包覆和晶格内双阳离子梯度掺杂的2种表界面修饰法对NaNi1/3Fe1/3Mn1/3O2(NFM)正极材料电化学储钠性能和热稳定性的提升作用，以及其产气抑制效应。结果表明，在2.0~4.0 V (vs Na/Na+)工作电压和1C (120 mA·g-1)电流密度下，当容量达到第2次循环容量的60%时，经表面包覆的NFM@TiO2(10)@Al2O3(10)和表层晶格掺杂的NFM#Ti (35)#Al (10)正极材料(括号中数字对应ALD沉积的次数)分别能够循环319和358次，显著优于未修饰NFM材料(250次)，同时通过差示扫描量热法(DSC)测得的热失控温度分别提升了6.1和9.7℃。原位差分电化学质谱(DEMS)测试表明，表面包覆显著抑制了H2等主要气体成分的形成，而晶格掺杂避免了电解液的二次分解，这可能是由于电解液质子化和高电压下氧化分解等有害副反应的减少。
基于原子层沉积技术(ALD)制备TiO2和Al2O3纳米层并结合高温热处理优化工艺，研究了异质氧化物双层表面包覆和晶格内双阳离子梯度掺杂的2种表界面修饰法对NaNi1/3Fe1/3Mn1/3O2(NFM)正极材料电化学储钠性能和热稳定性的提升作用，以及其产气抑制效应。结果表明，在2.0~4.0 V (vs Na/Na+)工作电压和1C (120 mA·g-1)电流密度下，当容量达到第2次循环容量的60%时，经表面包覆的NFM@TiO2(10)@Al2O3(10)和表层晶格掺杂的NFM#Ti (35)#Al (10)正极材料(括号中数字对应ALD沉积的次数)分别能够循环319和358次，显著优于未修饰NFM材料(250次)，同时通过差示扫描量热法(DSC)测得的热失控温度分别提升了6.1和9.7℃。原位差分电化学质谱(DEMS)测试表明，表面包覆显著抑制了H2等主要气体成分的形成，而晶格掺杂避免了电解液的二次分解，这可能是由于电解液质子化和高电压下氧化分解等有害副反应的减少。
2025, 41(2): 267-274
doi: 10.11862/CJIC.20240223
摘要:
通过将纳米Bi颗粒与三维多孔碳(3DPC)材料复合制备得到Bi/3DPC复合材料，有效提高了Bi的电化学性能。3DPC作为碳框架能缓冲充放电过程中Bi的体积膨胀以及提升材料导电性，且其微孔和介孔能够增加材料的比表面积，为吸附钠离子提供活性位点。Bi和3DPC发挥协同效应，在钠离子电池中展现出良好的倍率性能和长期循环稳定性。在5 A·g-1的电流密度下，Bi/3DPC在循环1 000圈后仍保持268.52 mAh·g-1的比容量。
通过将纳米Bi颗粒与三维多孔碳(3DPC)材料复合制备得到Bi/3DPC复合材料，有效提高了Bi的电化学性能。3DPC作为碳框架能缓冲充放电过程中Bi的体积膨胀以及提升材料导电性，且其微孔和介孔能够增加材料的比表面积，为吸附钠离子提供活性位点。Bi和3DPC发挥协同效应，在钠离子电池中展现出良好的倍率性能和长期循环稳定性。在5 A·g-1的电流密度下，Bi/3DPC在循环1 000圈后仍保持268.52 mAh·g-1的比容量。
2025, 41(2): 275-283
doi: 10.11862/CJIC.20240213
摘要:
通过引入—OH、—NH2和—SO3H极性官能团，设计了具有高比表面积、亚胺键连接的二维三聚茚酮基共价有机骨架(truxenone-based covalent organic frameworks，TRO-COFs)，并通过巨正则蒙特卡洛(giant canonical Monte Carlo，GCMC)模拟和密度泛函理论(density functional theory，DFT)探究了298 K和0~1.0×105 Pa条件下极性官能团对TRO-COFs的CO2捕获性能的影响。结合能和内聚能的分析表明官能团引入后结构仍保持较高的稳定性。极性官能团的引入显著增强了TRO-COFs的CO2吸附性能。CO2吸附量大小顺序为TRO-COF-SO3H>TRO-COF-NH2>TRO-COF-OH>TRO-COF-H。在298 K和1.0×105 Pa条件下，TRO-COF-SO3H表现出8.02 mmol·g-1的CO2吸附量及CO2优于N2和CH4的选择性(37和26)。同时，通过径向分布函数和气体吸附密度分布也进一步说明了不同极性官能团对CO2捕获与分离性能影响的差异。最后，从吸附热、范德瓦耳斯力和库仑相互作用等多个角度详细阐明了极性官能团的作用机制。
通过引入—OH、—NH2和—SO3H极性官能团，设计了具有高比表面积、亚胺键连接的二维三聚茚酮基共价有机骨架(truxenone-based covalent organic frameworks，TRO-COFs)，并通过巨正则蒙特卡洛(giant canonical Monte Carlo，GCMC)模拟和密度泛函理论(density functional theory，DFT)探究了298 K和0~1.0×105 Pa条件下极性官能团对TRO-COFs的CO2捕获性能的影响。结合能和内聚能的分析表明官能团引入后结构仍保持较高的稳定性。极性官能团的引入显著增强了TRO-COFs的CO2吸附性能。CO2吸附量大小顺序为TRO-COF-SO3H>TRO-COF-NH2>TRO-COF-OH>TRO-COF-H。在298 K和1.0×105 Pa条件下，TRO-COF-SO3H表现出8.02 mmol·g-1的CO2吸附量及CO2优于N2和CH4的选择性(37和26)。同时，通过径向分布函数和气体吸附密度分布也进一步说明了不同极性官能团对CO2捕获与分离性能影响的差异。最后，从吸附热、范德瓦耳斯力和库仑相互作用等多个角度详细阐明了极性官能团的作用机制。
2025, 41(2): 284-292
doi: 10.11862/CJIC.20240212
摘要:
采用两步水热法制备了BiSbO4/BiOBr复合材料，并对其微观形貌、物相结构、化学组成、光学性能、光催化性能进行测试。结果表明：由纳米棒组成的BiSbO4成功负载到片状BiOBr表面，二者产生的异质结结构不仅拓宽了催化剂的光响应范围还提升了光生电子-空穴对分离效率。其在模拟可见光下的光催化性能都优于单一的BiSbO4和BiOBr，当BiSbO4在复合材料中的质量分数为6%时，所制备的复合材料的光催化降解亚甲蓝(MB)性能最佳，其在模拟可见光下照射120 min后对MB的降解率达91.3%，经过4次循环后降解率仍有77.4%。
采用两步水热法制备了BiSbO4/BiOBr复合材料，并对其微观形貌、物相结构、化学组成、光学性能、光催化性能进行测试。结果表明：由纳米棒组成的BiSbO4成功负载到片状BiOBr表面，二者产生的异质结结构不仅拓宽了催化剂的光响应范围还提升了光生电子-空穴对分离效率。其在模拟可见光下的光催化性能都优于单一的BiSbO4和BiOBr，当BiSbO4在复合材料中的质量分数为6%时，所制备的复合材料的光催化降解亚甲蓝(MB)性能最佳，其在模拟可见光下照射120 min后对MB的降解率达91.3%，经过4次循环后降解率仍有77.4%。
2025, 41(2): 293-307
doi: 10.11862/CJIC.20240210
摘要:
以V2O5/TiO2催化剂为基体，制备了一系列Ce、Mn改性催化剂，并结合氮气吸附-脱附、X射线衍射、X射线光电子能谱、扫描电子显微镜分析了催化剂的结构及活性组成，探究了其反应活性。结果表明，制备的改性V2O5/TiO2催化剂分散性好，Ce-Mn双金属改性提高了催化剂的NH3转化率和N2选择性。Ce、Mn负载量(Ce或Mn与TiO2的质量比)分别为8%、6%时，310℃下改性材料的NH3转化率为100%，N2选择性为78%。原位漫反射傅里叶变换红外光谱表征显示催化剂表面羟基吸附的NH3会优先参与反应，温度升高后催化剂表面的Brønsted和Lewis酸位点上吸附的NH3开始参与反应，较高温度下Lewis酸位点是主要的NH3转化位点。
以V2O5/TiO2催化剂为基体，制备了一系列Ce、Mn改性催化剂，并结合氮气吸附-脱附、X射线衍射、X射线光电子能谱、扫描电子显微镜分析了催化剂的结构及活性组成，探究了其反应活性。结果表明，制备的改性V2O5/TiO2催化剂分散性好，Ce-Mn双金属改性提高了催化剂的NH3转化率和N2选择性。Ce、Mn负载量(Ce或Mn与TiO2的质量比)分别为8%、6%时，310℃下改性材料的NH3转化率为100%，N2选择性为78%。原位漫反射傅里叶变换红外光谱表征显示催化剂表面羟基吸附的NH3会优先参与反应，温度升高后催化剂表面的Brønsted和Lewis酸位点上吸附的NH3开始参与反应，较高温度下Lewis酸位点是主要的NH3转化位点。
2025, 41(2): 308-320
doi: 10.11862/CJIC.20240138
摘要:
研究了不同油酸(OA)、油胺(OLA)配体添加量在制备CdSe纳米晶体中对量子点荧光特性的影响，深入分析了OA和OLA配体在CdSe纳米晶体生长过程中的作用机理。在采用逐层生长法制备CdSe纳米晶体时，研究了OA和OLA配体对晶体尺寸及尺寸分布的影响，并制备了尺寸分布良好的较大尺寸CdSe纳米晶体。采用多种方法对CdSe纳米晶体的光学性能、晶体结构、微观形貌及尺寸分布进行表征分析。结果表明，OA配体的添加会使CdSe纳米晶体发射峰红移，且添加量与发射峰红移波长呈正相关，发射峰可调范围为548.5~604.0 nm；OLA配体添加量较少时会使CdSe纳米晶体发射峰蓝移，但随着OLA配体添加量的增加发射峰逐渐红移，发射峰可调范围为548.0~584.4 nm；在逐层生长法中引入OA和OLA配体可有效改善由于多次逐层生长而产生的发射峰双峰现象。最终通过调整制备工艺，制备了荧光发射可视化分离的4种CdSe纳米晶体，其尺寸分布良好，具有较高的光致发光量子产率(PLQY)，抗光漂白性能较好。
研究了不同油酸(OA)、油胺(OLA)配体添加量在制备CdSe纳米晶体中对量子点荧光特性的影响，深入分析了OA和OLA配体在CdSe纳米晶体生长过程中的作用机理。在采用逐层生长法制备CdSe纳米晶体时，研究了OA和OLA配体对晶体尺寸及尺寸分布的影响，并制备了尺寸分布良好的较大尺寸CdSe纳米晶体。采用多种方法对CdSe纳米晶体的光学性能、晶体结构、微观形貌及尺寸分布进行表征分析。结果表明，OA配体的添加会使CdSe纳米晶体发射峰红移，且添加量与发射峰红移波长呈正相关，发射峰可调范围为548.5~604.0 nm；OLA配体添加量较少时会使CdSe纳米晶体发射峰蓝移，但随着OLA配体添加量的增加发射峰逐渐红移，发射峰可调范围为548.0~584.4 nm；在逐层生长法中引入OA和OLA配体可有效改善由于多次逐层生长而产生的发射峰双峰现象。最终通过调整制备工艺，制备了荧光发射可视化分离的4种CdSe纳米晶体，其尺寸分布良好，具有较高的光致发光量子产率(PLQY)，抗光漂白性能较好。
2025, 41(2): 321-328
doi: 10.11862/CJIC.20240207
摘要:
通过配体取代反应合成了2个双膦配体桥联的四铁配合物[Fe4(CO)10(μ-SCH2CH (CH3) S)2(dppa)](1)和[Fe4(CO)10(μ-SCH2CH (CH3) S)2(trans-dppv)](2)，其中dppa=双(二苯基膦)乙炔，trans-dppv=trans-1，2-双(二苯基膦)乙烯。配合物的结构经过元素分析、红外光谱、核磁共振氢谱、磷谱以及单晶X射线衍射等方法的表征。用循环伏安法研究了新配合物的电化学性质，结果表明它们均可以在乙腈溶液中催化醋酸中的质子还原产生氢气。其中配合物2的催化效率要明显优于配合物1。
通过配体取代反应合成了2个双膦配体桥联的四铁配合物[Fe4(CO)10(μ-SCH2CH (CH3) S)2(dppa)](1)和[Fe4(CO)10(μ-SCH2CH (CH3) S)2(trans-dppv)](2)，其中dppa=双(二苯基膦)乙炔，trans-dppv=trans-1，2-双(二苯基膦)乙烯。配合物的结构经过元素分析、红外光谱、核磁共振氢谱、磷谱以及单晶X射线衍射等方法的表征。用循环伏安法研究了新配合物的电化学性质，结果表明它们均可以在乙腈溶液中催化醋酸中的质子还原产生氢气。其中配合物2的催化效率要明显优于配合物1。
2025, 41(2): 329-338
doi: 10.11862/CJIC.20240206
摘要:
采用传统固相法制备了La3+掺杂的0.28Pb (In1/2Nb1/2) O3-0.32Pb (Zn1/3Nb2/3) O3-0.3PbTiO3-0.1PbZrO3(PIN-PZN-PZT)四元压电陶瓷，研究了La3+掺杂量对PIN-PZN-PZT四元压电陶瓷微观结构和电学性能的影响。结果表明：引入La3+可以增强压电陶瓷局部结构异质性，进而提升介电弛豫特性并提高压电性能。当La2O3含量为1.5%时，获得了兼具高电致应变(0.23%)和高居里温度(206℃)的压电陶瓷材料。
采用传统固相法制备了La3+掺杂的0.28Pb (In1/2Nb1/2) O3-0.32Pb (Zn1/3Nb2/3) O3-0.3PbTiO3-0.1PbZrO3(PIN-PZN-PZT)四元压电陶瓷，研究了La3+掺杂量对PIN-PZN-PZT四元压电陶瓷微观结构和电学性能的影响。结果表明：引入La3+可以增强压电陶瓷局部结构异质性，进而提升介电弛豫特性并提高压电性能。当La2O3含量为1.5%时，获得了兼具高电致应变(0.23%)和高居里温度(206℃)的压电陶瓷材料。
2025, 41(2): 339-348
doi: 10.11862/CJIC.20240172
摘要:
合成了颗粒状、立方体状、纤维状和片状的BaTiO3粉体，并采用扫描电子显微镜、X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱对合成粉体的物相、形貌进行表征；比较不同形貌、催化条件下BaTiO3粉体的压电催化活性，并结合有限元分析解释了压电催化活性差异的原因。结果显示，片状形貌下的BaTiO3粉体具有压电催化活性优势，原因在于其产生了高压电势。且当催化剂固含量为2 g·L-1、超声频率为40 kHz、染料质量浓度为5 mg·L-1时具有较优的催化活性，并结合自由基捕获实验揭示了片状BaTiO3压电催化降解罗丹明B (RhB)染料的机制，即超氧自由基和羟基自由基作为主要反应物实现了污染物的降解。
合成了颗粒状、立方体状、纤维状和片状的BaTiO3粉体，并采用扫描电子显微镜、X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱对合成粉体的物相、形貌进行表征；比较不同形貌、催化条件下BaTiO3粉体的压电催化活性，并结合有限元分析解释了压电催化活性差异的原因。结果显示，片状形貌下的BaTiO3粉体具有压电催化活性优势，原因在于其产生了高压电势。且当催化剂固含量为2 g·L-1、超声频率为40 kHz、染料质量浓度为5 mg·L-1时具有较优的催化活性，并结合自由基捕获实验揭示了片状BaTiO3压电催化降解罗丹明B (RhB)染料的机制，即超氧自由基和羟基自由基作为主要反应物实现了污染物的降解。
2025, 41(2): 349-356
doi: 10.11862/CJIC.20240098
摘要:
利用水热法合成了一种宽带近红外Na3CrF6荧光粉，研究了其结构、微观形貌和光致发光性能。结果表明，在435 nm激发光的照射下，Na3CrF6荧光粉可发出650~850 nm宽带近红外光，其峰值位于738 nm处，半高宽为95 nm；通过分析光谱数据，发现Cr3+在Na3CrF6荧光粉中的晶体场强度为1.72，处于弱晶体场环境中；298~473 K温度范围内，随着加热温度的升高，Na3CrF6荧光粉的发光强度缓慢下降。
利用水热法合成了一种宽带近红外Na3CrF6荧光粉，研究了其结构、微观形貌和光致发光性能。结果表明，在435 nm激发光的照射下，Na3CrF6荧光粉可发出650~850 nm宽带近红外光，其峰值位于738 nm处，半高宽为95 nm；通过分析光谱数据，发现Cr3+在Na3CrF6荧光粉中的晶体场强度为1.72，处于弱晶体场环境中；298~473 K温度范围内，随着加热温度的升高，Na3CrF6荧光粉的发光强度缓慢下降。
2025, 41(2): 357-364
doi: 10.11862/CJIC.20240096
摘要:
采用高温固相法制备了Sr1-xZrSi2O7∶xDy3+荧光粉，并用X射线衍射仪、扫描电子显微镜和荧光光谱仪对其晶体结构、形貌、光致发光特性和热稳定性进行了研究。结果表明，该荧光粉可以在353 nm的近紫外光激发下获得蓝光(493 nm)和橙红光(581 nm)发射峰，这2个峰分别归属于Dy3+离子的4F9/2→6H15/2和4F9/2→6H13/2能级跃迁。在该荧光粉中，Dy3+的猝灭浓度为0.03，猝灭机制是偶极-偶极相互作用。当温度升高到150℃时，其发光强度仍可以保持室温的83%，具有良好的热稳定性。
采用高温固相法制备了Sr1-xZrSi2O7∶xDy3+荧光粉，并用X射线衍射仪、扫描电子显微镜和荧光光谱仪对其晶体结构、形貌、光致发光特性和热稳定性进行了研究。结果表明，该荧光粉可以在353 nm的近紫外光激发下获得蓝光(493 nm)和橙红光(581 nm)发射峰，这2个峰分别归属于Dy3+离子的4F9/2→6H15/2和4F9/2→6H13/2能级跃迁。在该荧光粉中，Dy3+的猝灭浓度为0.03，猝灭机制是偶极-偶极相互作用。当温度升高到150℃时，其发光强度仍可以保持室温的83%，具有良好的热稳定性。
2025, 41(2): 365-384
doi: 10.11862/CJIC.20240063
摘要:
本工作研究了镍钴双金属磷化物(Ni-Co-P)在水溶液中的稳定性。结果显示，Ni-Co-P能与H2O反应，发生自腐蚀生成Ni2+、Co2+和PO43-离子，同时产生H2。Ni-Co-P与H2O的自腐蚀反应速率受到镍钴比例影响，Ni-Co-P中的Co含量升高，其在水中的腐蚀速率降低。详细研究了镍、钴投料比(nNi/nCo)为1∶2制备的Ni-Co-P在水中的腐蚀行为，其在水中的腐蚀速率与溶液pH值、氧气含量、光照、温度等因素有关。为了抑制Ni-Co-P (nNi/nCo=1/2)在水溶液中的腐蚀，在其表面包裹一层惰性TiO2保护层，这层TiO2保护层能有效减缓Ni-Co-P在水中的腐蚀，增强其稳定性。
本工作研究了镍钴双金属磷化物(Ni-Co-P)在水溶液中的稳定性。结果显示，Ni-Co-P能与H2O反应，发生自腐蚀生成Ni2+、Co2+和PO43-离子，同时产生H2。Ni-Co-P与H2O的自腐蚀反应速率受到镍钴比例影响，Ni-Co-P中的Co含量升高，其在水中的腐蚀速率降低。详细研究了镍、钴投料比(nNi/nCo)为1∶2制备的Ni-Co-P在水中的腐蚀行为，其在水中的腐蚀速率与溶液pH值、氧气含量、光照、温度等因素有关。为了抑制Ni-Co-P (nNi/nCo=1/2)在水溶液中的腐蚀，在其表面包裹一层惰性TiO2保护层，这层TiO2保护层能有效减缓Ni-Co-P在水中的腐蚀，增强其稳定性。
2025, 41(2): 385-394
doi: 10.11862/CJIC.20240298
摘要:
Binary composites (ZIF-67/rGO) were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source, 2-methylimidazole as organic ligand, and reduced graphene oxide (rGO) as carbon carrier. Then Ru3+ was introduced for ion exchange, and the porous Ru-doped Co3O4/rGO (Ru-Co3O4/rGO) composite electrocatalyst was prepared by annealing. The phase structure, morphology, and valence state of the catalyst were analyzed by X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). In 1 mol·L-1 KOH, the oxygen evolution reaction (OER) performance of the catalyst was measured by linear sweep voltammetry, cyclic voltammetry, and chronoamperometry. The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer. At the same time, rGO as a carbon carrier can improve the electrical conductivity of Ru-Co3O4 particles, and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst. The results showed that the electrochemical performance of Ru-Co3O4/rGO was much better than that of Co3O4/rGO, and the overpotential of Ru-Co3O4/rGO was 363.5 mV at the current density of 50 mA·cm-2.
Binary composites (ZIF-67/rGO) were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source, 2-methylimidazole as organic ligand, and reduced graphene oxide (rGO) as carbon carrier. Then Ru3+ was introduced for ion exchange, and the porous Ru-doped Co3O4/rGO (Ru-Co3O4/rGO) composite electrocatalyst was prepared by annealing. The phase structure, morphology, and valence state of the catalyst were analyzed by X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). In 1 mol·L-1 KOH, the oxygen evolution reaction (OER) performance of the catalyst was measured by linear sweep voltammetry, cyclic voltammetry, and chronoamperometry. The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer. At the same time, rGO as a carbon carrier can improve the electrical conductivity of Ru-Co3O4 particles, and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst. The results showed that the electrochemical performance of Ru-Co3O4/rGO was much better than that of Co3O4/rGO, and the overpotential of Ru-Co3O4/rGO was 363.5 mV at the current density of 50 mA·cm-2.
2025, 41(2): 395-406
doi: 10.11862/CJIC.20240226
摘要:
Five cadmium naphthalene-diphosphonates, formulated as [Cd1.5(1,4-ndpaH2)2(4,4′-bpyH)(4,4′-bpy)0.5(H2O)2]2 (1), [Cd(1,4-ndpaH2)(1,4-bib)0.5(H2O)] (2), [Cd(1,4-ndpaH3)2(1,2-dpe)(H2O)]·(1,2-dpe)·7H2O (3), (1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH2)2(H2O)2] (4), and [Cd(1,4-ndpaH2)(H2O)]·H2O (5), have been synthesized from the self-assembly reactions of 1,4-naphthalenediphosphonic acid (1,4-ndpaH4) with Cd(NO3)2·4H2O by introducing auxiliary ligands with variation of rigidity, such as 4,4′-bipyridine (4,4′-bpy), 1,4-bis(1-imidazolyl)benzene (1,4-bib), 1,2-di(4-pyridyl)ethylene (1,2-dpe), 1,3-di(4-pyridyl)propane (1,3-dpp), and bis(imidazol-1-ylmethyl)benzene (1,2-bix), respectively. Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework, in which the {Cd3(PO2)2} trimers made up of corner-sharing two {CdO4N2} and one {CdO6} octahedra are connected by phosphonate groups, forming a ribbon, which are cross-linked by 4,4′-bipy ligands, forming a 2D layer. Compound 2 shows a 3D open-framework structure, where chains of corner-sharing {CdO4N} trigonal bipyramids and {PO3C} tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups. A 1D ladder-like chain structure is found in compound 3, where the ladder-like chains made up of corner-sharing {CdO5N} octahedra and {PO3C} tetrahedra are connected by 1,4-ndpaH22-. Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure, which is formed by ligand crosslinking double metal chains. Interestingly, In 4, flexible 1,2-bix was singly protonated, as guest molecules, filled between layer and layer, while flexible ligand 1,3-dpp is absent in 5. Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.
Five cadmium naphthalene-diphosphonates, formulated as [Cd1.5(1,4-ndpaH2)2(4,4′-bpyH)(4,4′-bpy)0.5(H2O)2]2 (1), [Cd(1,4-ndpaH2)(1,4-bib)0.5(H2O)] (2), [Cd(1,4-ndpaH3)2(1,2-dpe)(H2O)]·(1,2-dpe)·7H2O (3), (1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH2)2(H2O)2] (4), and [Cd(1,4-ndpaH2)(H2O)]·H2O (5), have been synthesized from the self-assembly reactions of 1,4-naphthalenediphosphonic acid (1,4-ndpaH4) with Cd(NO3)2·4H2O by introducing auxiliary ligands with variation of rigidity, such as 4,4′-bipyridine (4,4′-bpy), 1,4-bis(1-imidazolyl)benzene (1,4-bib), 1,2-di(4-pyridyl)ethylene (1,2-dpe), 1,3-di(4-pyridyl)propane (1,3-dpp), and bis(imidazol-1-ylmethyl)benzene (1,2-bix), respectively. Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework, in which the {Cd3(PO2)2} trimers made up of corner-sharing two {CdO4N2} and one {CdO6} octahedra are connected by phosphonate groups, forming a ribbon, which are cross-linked by 4,4′-bipy ligands, forming a 2D layer. Compound 2 shows a 3D open-framework structure, where chains of corner-sharing {CdO4N} trigonal bipyramids and {PO3C} tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups. A 1D ladder-like chain structure is found in compound 3, where the ladder-like chains made up of corner-sharing {CdO5N} octahedra and {PO3C} tetrahedra are connected by 1,4-ndpaH22-. Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure, which is formed by ligand crosslinking double metal chains. Interestingly, In 4, flexible 1,2-bix was singly protonated, as guest molecules, filled between layer and layer, while flexible ligand 1,3-dpp is absent in 5. Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.
2025, 41(2): 407-412
doi: 10.11862/CJIC.20240214
摘要:
A new cobalt(Ⅱ)-radical complex: [Co(im4-py)2(PNB)2] (im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl, HPNB=p-nitrobenzoic acid) has been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, and magnetic properties. X-ray diffraction analysis shows that the complex exists as mononuclear molecules and Co(Ⅱ)ion is four-coordinated with two radicals and two PNB- ligands. The magnetic susceptibility study indicates the complex exhibits weak ferromagnetic interactions between cobalt(Ⅱ) and im4-py radical. The magnetic property is explained by the magnetic and structure exchange mechanism.
A new cobalt(Ⅱ)-radical complex: [Co(im4-py)2(PNB)2] (im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl, HPNB=p-nitrobenzoic acid) has been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, and magnetic properties. X-ray diffraction analysis shows that the complex exists as mononuclear molecules and Co(Ⅱ)ion is four-coordinated with two radicals and two PNB- ligands. The magnetic susceptibility study indicates the complex exhibits weak ferromagnetic interactions between cobalt(Ⅱ) and im4-py radical. The magnetic property is explained by the magnetic and structure exchange mechanism.
2025, 41(2): 413-424
doi: 10.11862/CJIC.20240205
摘要:
Porous spherical MnCo2S4 was synthesized by a simple solvothermal method. Thanks to the well-designed bimetallic composition and the unique porous spherical structure, the MnCo2S4 electrode exhibited an exceptional specific capacitance of 190.8 mAh·g-1 at 1 A·g-1, greatly higher than the corresponding monometallic sulfides MnS (31.7 mAh·g-1) and Co3S4 (86.7 mAh·g-1). Impressively, the as assembled MnCo2S4||porous carbon (PC) hybrid supercapacitor (HSC), showed an outstanding energy density of 76.88 Wh·kg-1 at a power density of 374.5 W·kg-1, remarkable cyclic performance with a capacity retention of 86.8% after 10 000 charge-discharge cycles at 5 A·g-1, and excellent Coulombic efficiency of 99.7%.
Porous spherical MnCo2S4 was synthesized by a simple solvothermal method. Thanks to the well-designed bimetallic composition and the unique porous spherical structure, the MnCo2S4 electrode exhibited an exceptional specific capacitance of 190.8 mAh·g-1 at 1 A·g-1, greatly higher than the corresponding monometallic sulfides MnS (31.7 mAh·g-1) and Co3S4 (86.7 mAh·g-1). Impressively, the as assembled MnCo2S4||porous carbon (PC) hybrid supercapacitor (HSC), showed an outstanding energy density of 76.88 Wh·kg-1 at a power density of 374.5 W·kg-1, remarkable cyclic performance with a capacity retention of 86.8% after 10 000 charge-discharge cycles at 5 A·g-1, and excellent Coulombic efficiency of 99.7%.
