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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(3): 425-439
doi: 10.11862/CJIC.20240201
摘要:
电催化二氧化碳还原技术能够有效地将CO2转化为有价值的化学品，从而减少CO2排放，为CO2的治理提供一举两得的解决方案，并能够助力我国实现“碳达峰”和“碳中和”的碳排放目标。目前，常用的单金属纳米催化剂具有催化位点单一以及产物与中间体的吸附能调控困难等缺点，导致其在催化剂选择性、活性及稳定性等方面表现不佳。而双金属纳米催化剂由于存在2种原子配位，能够调整催化剂的电子结构，实现对中间体结合能的精细调控，并带来丰富且灵活的活性位点，从而被广泛研究。本文综述了国内外最新的双金属纳米催化剂的研究进展，主要针对双金属纳米催化剂的精细调控手段，如掺杂调控、非均相结构调控、合金化调控和几何结构调控进行了总结，对其中所存在的协同效应、应力效应和电子效应等双金属纳米催化剂的催化机理进行了阐述。在此基础上，总结了目前双金属纳米催化剂研究的不足，并对未来的研究方向与发展前景进行了展望。
电催化二氧化碳还原技术能够有效地将CO2转化为有价值的化学品，从而减少CO2排放，为CO2的治理提供一举两得的解决方案，并能够助力我国实现“碳达峰”和“碳中和”的碳排放目标。目前，常用的单金属纳米催化剂具有催化位点单一以及产物与中间体的吸附能调控困难等缺点，导致其在催化剂选择性、活性及稳定性等方面表现不佳。而双金属纳米催化剂由于存在2种原子配位，能够调整催化剂的电子结构，实现对中间体结合能的精细调控，并带来丰富且灵活的活性位点，从而被广泛研究。本文综述了国内外最新的双金属纳米催化剂的研究进展，主要针对双金属纳米催化剂的精细调控手段，如掺杂调控、非均相结构调控、合金化调控和几何结构调控进行了总结，对其中所存在的协同效应、应力效应和电子效应等双金属纳米催化剂的催化机理进行了阐述。在此基础上，总结了目前双金属纳米催化剂研究的不足，并对未来的研究方向与发展前景进行了展望。
2025, 41(3): 440-452
doi: 10.11862/CJIC.20240371
摘要:
采用熔盐法制备出铝掺杂的钛酸锶(Al-SrTiO3)，并通过水热法及气相氮化法在Al-SrTiO3表面紧密负载了Ni3N助催化剂。通过对Ni3N/Al-SrTiO3体系载流子转移特性表征以及密度泛函理论计算分析发现，Al-SrTiO3上的光生电子在费米能级差的作用下可快速转移到Ni3N上，有效促进了Al-SrTiO3上光生载流子的分离，从而提高其分解水析氢性能。光催化析氢测试结果表明，当Ni3N助催化剂负载量(Ni与Al-SrTiO3的质量比)为7%时，Al-SrTiO3的析氢速率相对负载前提升了82倍。
采用熔盐法制备出铝掺杂的钛酸锶(Al-SrTiO3)，并通过水热法及气相氮化法在Al-SrTiO3表面紧密负载了Ni3N助催化剂。通过对Ni3N/Al-SrTiO3体系载流子转移特性表征以及密度泛函理论计算分析发现，Al-SrTiO3上的光生电子在费米能级差的作用下可快速转移到Ni3N上，有效促进了Al-SrTiO3上光生载流子的分离，从而提高其分解水析氢性能。光催化析氢测试结果表明，当Ni3N助催化剂负载量(Ni与Al-SrTiO3的质量比)为7%时，Al-SrTiO3的析氢速率相对负载前提升了82倍。
2025, 41(3): 453-460
doi: 10.11862/CJIC.20240326
摘要:
通过较为简单的水热法制备了V掺杂MnO2(VMO)，并研究了其作为水系锌离子电池(ZIB)正极材料的电化学性能。材料表征和电化学性能结果表明V被均匀地掺杂到MnO2中。V掺杂不仅扩大了MnO2的层间距，增加了比表面积，还提高了其内部离子电导率。组装成的ZIB在电流密度为0.1 A·g-1的条件下，初始放电容量可达362 mAh·g-1。V的掺杂使MnO2的晶格结构更加稳定，Jahn-Teller畸变效应减弱，电极材料的结构稳定性提高。当电流密度为1 A·g-1时，经过300圈的充放电循环后，其放电容量仍然能够达到初始容量的87%。
通过较为简单的水热法制备了V掺杂MnO2(VMO)，并研究了其作为水系锌离子电池(ZIB)正极材料的电化学性能。材料表征和电化学性能结果表明V被均匀地掺杂到MnO2中。V掺杂不仅扩大了MnO2的层间距，增加了比表面积，还提高了其内部离子电导率。组装成的ZIB在电流密度为0.1 A·g-1的条件下，初始放电容量可达362 mAh·g-1。V的掺杂使MnO2的晶格结构更加稳定，Jahn-Teller畸变效应减弱，电极材料的结构稳定性提高。当电流密度为1 A·g-1时，经过300圈的充放电循环后，其放电容量仍然能够达到初始容量的87%。
2025, 41(3): 461-468
doi: 10.11862/CJIC.20240316
摘要:
采用溶胶-凝胶法制备Eu3+离子掺杂Sc2W3O12红色荧光粉，并通过Gd3+掺杂降低Sc2W3O12基质晶体结构的对称性，增强荧光粉的发光强度。结果显示，Gd3+的掺入并没有改变Sc2W3O12的晶体结构；随着Gd3+掺杂浓度的递增，晶格畸变加剧，来源于Eu3+的 5D0→7F2(612 nm)发光强度显著增强，Gd3+最佳掺杂浓度为0.25，其发光强度为单掺Eu3+的1.95倍，色坐标为(0.613 4，0.350 3)，与标准红光色坐标(0.670，0.330)较为接近。此外，荧光粉具有一定的热稳定性，即当温度达到498 K时，Gd3+离子掺杂浓度为0.25时制备的样品荧光强度与未掺杂Gd3+离子的样品相比得到了提升，是室温下的53%，其激活能为0.104 1 eV。
采用溶胶-凝胶法制备Eu3+离子掺杂Sc2W3O12红色荧光粉，并通过Gd3+掺杂降低Sc2W3O12基质晶体结构的对称性，增强荧光粉的发光强度。结果显示，Gd3+的掺入并没有改变Sc2W3O12的晶体结构；随着Gd3+掺杂浓度的递增，晶格畸变加剧，来源于Eu3+的 5D0→7F2(612 nm)发光强度显著增强，Gd3+最佳掺杂浓度为0.25，其发光强度为单掺Eu3+的1.95倍，色坐标为(0.613 4，0.350 3)，与标准红光色坐标(0.670，0.330)较为接近。此外，荧光粉具有一定的热稳定性，即当温度达到498 K时，Gd3+离子掺杂浓度为0.25时制备的样品荧光强度与未掺杂Gd3+离子的样品相比得到了提升，是室温下的53%，其激活能为0.104 1 eV。
2025, 41(3): 469-479
doi: 10.11862/CJIC.20240309
摘要:
为了解决全无机CsPbBr3钙钛矿太阳能电池中严重的载流子非辐射复合现象限制其光电转换效率提升的问题，通过在TiO2电子传输层表面旋涂质量浓度为1.5 mg·mL-1的SnCl2溶液来有效改善钙钛矿薄膜的结晶性和表面形貌，从而降低光生载流子的非辐射复合，提高载流子的提取和传输能力。实验结果表明，通过对TiO2表面施加SnCl2进行修饰后，器件最高开路电压(open-circuit voltage，VOC)达到1.59 V，短路电流密度(short circuit current density，JSC)达到7.62 mA·cm-2，同时获得了81.35%的填充因子(fill factor，FF)，光电转换效率(photoelectric conversion efficiency，PCE)也从8.01%提高至9.92%。
为了解决全无机CsPbBr3钙钛矿太阳能电池中严重的载流子非辐射复合现象限制其光电转换效率提升的问题，通过在TiO2电子传输层表面旋涂质量浓度为1.5 mg·mL-1的SnCl2溶液来有效改善钙钛矿薄膜的结晶性和表面形貌，从而降低光生载流子的非辐射复合，提高载流子的提取和传输能力。实验结果表明，通过对TiO2表面施加SnCl2进行修饰后，器件最高开路电压(open-circuit voltage，VOC)达到1.59 V，短路电流密度(short circuit current density，JSC)达到7.62 mA·cm-2，同时获得了81.35%的填充因子(fill factor，FF)，光电转换效率(photoelectric conversion efficiency，PCE)也从8.01%提高至9.92%。
2025, 41(3): 480-490
doi: 10.11862/CJIC.20240259
摘要:
首先采用柠檬酸辅助溶胶-凝胶法制备钴酸镧(LaCoO3，LCO)，并利用水热法制备LaCoO3/g-C3N4(LCO/CN)p-n型异质结复合光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)和光致发光(PL)光谱对LCO/CN进行了表征，评价了其对盐酸四环素(TC)的光催化降解性能，同时使用自由基捕获剂验证了光催化反应中起作用的活性基团，并推测了反应机理。结果表明，LCO和CN的复合显著增强了CN的光催化活性，当二者质量比为10%时制备的10%LCO/CN呈现出最佳的光催化性能，在120 min内对10 mg·L-1 TC的降解率高达96.2%，反应速率常数达到0.018 93 min-1，分别是CN和LCO的3.04倍和1.93倍。3次循环回收实验结果显示，10%LCO/CN对TC的降解率下降得较少，表明该催化剂具有良好的稳定性和实用性。
首先采用柠檬酸辅助溶胶-凝胶法制备钴酸镧(LaCoO3，LCO)，并利用水热法制备LaCoO3/g-C3N4(LCO/CN)p-n型异质结复合光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)和光致发光(PL)光谱对LCO/CN进行了表征，评价了其对盐酸四环素(TC)的光催化降解性能，同时使用自由基捕获剂验证了光催化反应中起作用的活性基团，并推测了反应机理。结果表明，LCO和CN的复合显著增强了CN的光催化活性，当二者质量比为10%时制备的10%LCO/CN呈现出最佳的光催化性能，在120 min内对10 mg·L-1 TC的降解率高达96.2%，反应速率常数达到0.018 93 min-1，分别是CN和LCO的3.04倍和1.93倍。3次循环回收实验结果显示，10%LCO/CN对TC的降解率下降得较少，表明该催化剂具有良好的稳定性和实用性。
2025, 41(3): 491-498
doi: 10.11862/CJIC.20240271
摘要:
为了探究配体对铈氧簇的形成、结构和性质的影响及铈氧簇的潜在应用，使用糠酸(HFA)作为配体，通过溶液法合成了首例由糠酸根稳定的六核铈氧簇，并利用单晶X射线衍射、粉末X射线衍射、X射线光电子能谱、元素分析、热重和光谱等技术表征了其晶体NH4[Ce6O4(OH)4(FA)12(NO3)(H2O)]·5CH3CN·12H2O (1)的结构、组分和光谱性质。结果发现Ce(Ⅳ)离子即使在酸性条件下也具有较强的水解能力，其自身的水解缩合反应及与HFA的配位反应共同促使了化合物1的形成。通过芬顿反应产生羟基自由基(·OH)并采用甲基紫作为指示剂，进一步研究了化合物1清除自由基的能力。结果表明，其能有效地清除·OH，且清除效率随化合物1溶液体积的增加而提升。
为了探究配体对铈氧簇的形成、结构和性质的影响及铈氧簇的潜在应用，使用糠酸(HFA)作为配体，通过溶液法合成了首例由糠酸根稳定的六核铈氧簇，并利用单晶X射线衍射、粉末X射线衍射、X射线光电子能谱、元素分析、热重和光谱等技术表征了其晶体NH4[Ce6O4(OH)4(FA)12(NO3)(H2O)]·5CH3CN·12H2O (1)的结构、组分和光谱性质。结果发现Ce(Ⅳ)离子即使在酸性条件下也具有较强的水解能力，其自身的水解缩合反应及与HFA的配位反应共同促使了化合物1的形成。通过芬顿反应产生羟基自由基(·OH)并采用甲基紫作为指示剂，进一步研究了化合物1清除自由基的能力。结果表明，其能有效地清除·OH，且清除效率随化合物1溶液体积的增加而提升。
2025, 41(3): 499-508
doi: 10.11862/CJIC.20240238
摘要:
通过相转化共带浇筑法制备了一种基于Li6.4La3Zr1.4Ta0.6O12(LLZTO)固态电解质和3D多孔结构的铜复合层的集流体。LLZTO的加入为锂离子提供了丰富的离子传输通道与成核位点，而且具有3D多孔结构的铜为复合材料提供了丰富的比表面积，并可容纳大量的死锂等其他负极反应的副产物，同时相转化共带浇筑法操作简便，适合大面积商业化运用。制备的Cu-LLZTO@Li对称电池在4 mA·cm-2的电流密度下实现了280 h的长循环寿命与25 mV的超低电压滞后，相较于铜箔和3D-Cu分别提升了4倍和3倍。得益于稳定的固态电解质(SEI)膜与无锂枝晶的生成，Cu-LLZTO@Li对称电池相较于Cu foil@Li和3D-Cu@Li对称电池表现出最低的欧姆电阻(2.749 Ω·cm-2)和界面电阻(0.544 Ω·cm-2)。Cu-LLZTO半电池在70圈循环中未产生软短路并保持了98.4%的库仑效率，循环中的充放电电压平台始终维持在0.15 V的较低水平。
通过相转化共带浇筑法制备了一种基于Li6.4La3Zr1.4Ta0.6O12(LLZTO)固态电解质和3D多孔结构的铜复合层的集流体。LLZTO的加入为锂离子提供了丰富的离子传输通道与成核位点，而且具有3D多孔结构的铜为复合材料提供了丰富的比表面积，并可容纳大量的死锂等其他负极反应的副产物，同时相转化共带浇筑法操作简便，适合大面积商业化运用。制备的Cu-LLZTO@Li对称电池在4 mA·cm-2的电流密度下实现了280 h的长循环寿命与25 mV的超低电压滞后，相较于铜箔和3D-Cu分别提升了4倍和3倍。得益于稳定的固态电解质(SEI)膜与无锂枝晶的生成，Cu-LLZTO@Li对称电池相较于Cu foil@Li和3D-Cu@Li对称电池表现出最低的欧姆电阻(2.749 Ω·cm-2)和界面电阻(0.544 Ω·cm-2)。Cu-LLZTO半电池在70圈循环中未产生软短路并保持了98.4%的库仑效率，循环中的充放电电压平台始终维持在0.15 V的较低水平。
2025, 41(3): 509-520
doi: 10.11862/CJIC.20240270
摘要:
利用水热反应制备了葡萄糖缩聚物包覆铁氰化钴晶体的复合前驱体，经过碳化、酸刻蚀和硫负载，最终获得一种双金属(Co、Fe)及氮掺杂的多孔碳/硫复合材料(e-CF@NPC/S，其中CF表示CoFe合金，NPC表示氮掺杂的多孔碳)。进而通过改变形成核壳的原料比例获得系列样品，研究其作为锂硫电池正极的电化学性能。结果表明：该材料的核壳结构提供了充足的空间应对电池反应过程中的活性物质负载及体积变化，碳外壳的空间位阻同时起到了抑制穿梭效应的积极作用和阻碍离子扩散的负面作用，而合金纳米粒子提供吸附和催化作用的效果取决于其表面活性位点的数量。在多种作用的协同下，e-CF@NPC-3/S表现出优异的综合电化学性能，在0.2C的电流密度下循环100次后能保持996.9 mAh·g-1的可逆比容量和92.35%的容量保持率。在1C的高电流密度下循环300次后，e-CF@NPC-3/S仍具有684.5 mAh·g-1的可逆比容量(循环衰减率为0.049%)。
利用水热反应制备了葡萄糖缩聚物包覆铁氰化钴晶体的复合前驱体，经过碳化、酸刻蚀和硫负载，最终获得一种双金属(Co、Fe)及氮掺杂的多孔碳/硫复合材料(e-CF@NPC/S，其中CF表示CoFe合金，NPC表示氮掺杂的多孔碳)。进而通过改变形成核壳的原料比例获得系列样品，研究其作为锂硫电池正极的电化学性能。结果表明：该材料的核壳结构提供了充足的空间应对电池反应过程中的活性物质负载及体积变化，碳外壳的空间位阻同时起到了抑制穿梭效应的积极作用和阻碍离子扩散的负面作用，而合金纳米粒子提供吸附和催化作用的效果取决于其表面活性位点的数量。在多种作用的协同下，e-CF@NPC-3/S表现出优异的综合电化学性能，在0.2C的电流密度下循环100次后能保持996.9 mAh·g-1的可逆比容量和92.35%的容量保持率。在1C的高电流密度下循环300次后，e-CF@NPC-3/S仍具有684.5 mAh·g-1的可逆比容量(循环衰减率为0.049%)。
2025, 41(3): 521-530
doi: 10.11862/CJIC.20240221
摘要:
将稻壳经低温炭化、KOH高温活化处理，得到无定形活性炭(AC)材料，再采用MgO原位负载的方法制备一系列炭负载MgO复合材料(MgO/AC)。采用X射线衍射(XRD)、激光共聚焦拉曼光谱、X射线光电子能谱(XPS)、扫描电子显微镜-X射线能谱(SEM-EDS)和氮气吸附-脱附测试研究了MgO/AC的表面形貌、元素组成，并详细分析了孔结构与电化学性能之间可能存在的关系。结果表明，对称超级电容器2.0MgO/AC||2.0MgO/AC在0.5 A·g-1电流密度下的比电容为211.9 F·g-1，当功率密度为0.41kW·kg-1时其具有18.30 Wh·kg-1的能量密度，且经过5 000次循环后的电容保持率为86.8%。
将稻壳经低温炭化、KOH高温活化处理，得到无定形活性炭(AC)材料，再采用MgO原位负载的方法制备一系列炭负载MgO复合材料(MgO/AC)。采用X射线衍射(XRD)、激光共聚焦拉曼光谱、X射线光电子能谱(XPS)、扫描电子显微镜-X射线能谱(SEM-EDS)和氮气吸附-脱附测试研究了MgO/AC的表面形貌、元素组成，并详细分析了孔结构与电化学性能之间可能存在的关系。结果表明，对称超级电容器2.0MgO/AC||2.0MgO/AC在0.5 A·g-1电流密度下的比电容为211.9 F·g-1，当功率密度为0.41kW·kg-1时其具有18.30 Wh·kg-1的能量密度，且经过5 000次循环后的电容保持率为86.8%。
2025, 41(3): 531-539
doi: 10.11862/CJIC.20240256
摘要:
采用剥离-重组法，以剥离的CoAl层状双金属氢氧化物(CoAl-LDH)纳米片为主体，β-Bi2O3纳米胶粒为客体, 成功制备了β-Bi2O3柱撑CoAl-LDH复合材料(β-Bi2O3/CoAl-LDH)。运用X射线衍射、透射电子显微镜、紫外可见吸收光谱和X射线光电子能谱等方法表征了材料的形貌、结构和光电化学特性。制备的β-Bi2O3/CoAl-LDH柱撑材料具有2.1 nm的层间通道、62 m2·g-1的比表面积和良好的可见光响应能力。在可见光辐照下，以四环素(TC)为模型污染物，考察材料光催化降解率。结果表明，β-Bi2O3/CoAl-LDH催化剂在90 min内可降解91.3%的TC，降解率远高于非柱撑的β-Bi2O3和CoAl-LDH。自由基捕获实验表明，超氧自由基(·O2-)和羟基自由基(·OH)是光催化体系主要的活性自由基。柱撑复合的β-Bi2O3与CoAl-LDH之间的电子耦合作用构建了Z型异质结，提高了光生电子与空穴对的分离率，赋予了材料良好的光催化性能。
采用剥离-重组法，以剥离的CoAl层状双金属氢氧化物(CoAl-LDH)纳米片为主体，β-Bi2O3纳米胶粒为客体, 成功制备了β-Bi2O3柱撑CoAl-LDH复合材料(β-Bi2O3/CoAl-LDH)。运用X射线衍射、透射电子显微镜、紫外可见吸收光谱和X射线光电子能谱等方法表征了材料的形貌、结构和光电化学特性。制备的β-Bi2O3/CoAl-LDH柱撑材料具有2.1 nm的层间通道、62 m2·g-1的比表面积和良好的可见光响应能力。在可见光辐照下，以四环素(TC)为模型污染物，考察材料光催化降解率。结果表明，β-Bi2O3/CoAl-LDH催化剂在90 min内可降解91.3%的TC，降解率远高于非柱撑的β-Bi2O3和CoAl-LDH。自由基捕获实验表明，超氧自由基(·O2-)和羟基自由基(·OH)是光催化体系主要的活性自由基。柱撑复合的β-Bi2O3与CoAl-LDH之间的电子耦合作用构建了Z型异质结，提高了光生电子与空穴对的分离率，赋予了材料良好的光催化性能。
2025, 41(3): 540-548
doi: 10.11862/CJIC.20240405
摘要:
Using 2-dicyanomethylene-3-cyano-4, 5, 5-trimethyl-2, 5-dihydrofuran (TCF) as a near-infrared fluorescent chromophore, we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2, 4-dinitrophenyl ether as the recognized site for H2S. The probe TCF-NS displayed a rapid-response fluorescent against H2S with high sensitivity and selection but had no significant fluorescence response to other biothiols. Furthermore, TCF-NS was applied to sense H2S in living cells successfully with minimized cytotoxicity and a large Stokes shift.
Using 2-dicyanomethylene-3-cyano-4, 5, 5-trimethyl-2, 5-dihydrofuran (TCF) as a near-infrared fluorescent chromophore, we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2, 4-dinitrophenyl ether as the recognized site for H2S. The probe TCF-NS displayed a rapid-response fluorescent against H2S with high sensitivity and selection but had no significant fluorescence response to other biothiols. Furthermore, TCF-NS was applied to sense H2S in living cells successfully with minimized cytotoxicity and a large Stokes shift.
2025, 41(3): 549-560
doi: 10.11862/CJIC.20240348
摘要:
(2E, 6E)-4-methyl-2, 6-bis(pyridin-3-ylmethylene)cyclohexan-1-one (L1) and 4-methyl-2, 6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one (L2) were synthesized and combined with isophthalic acid (H2IP), then under solvothermal conditions, to react with transition metals achieving four novel metal organic frameworks (MOFs): [Zn(IP)(L1)]n (1), {[Cd(IP)(L1)]·H2O}n (2), {[Co(IP)(L1)]·H2O}n (3), and [Zn(IP)(L2)(H2O)]n (4). MOFs 1-4 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry, and elemental analysis. Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P21/n, and MOFs 2-4 belong to the triclinic system with the P1 space group. 1-3 are 2D sheet structures, 2 and 3 have similar structural characters, whereas 4 is a 1D chain structure. Furthermore, 1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B (RhB) and pararosaniline hydrochloride (PH). 4 could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile. 4 could promote the reaction to achieve corresponding products in moderate yields within 3 h. Moreover, the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity. A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.
(2E, 6E)-4-methyl-2, 6-bis(pyridin-3-ylmethylene)cyclohexan-1-one (L1) and 4-methyl-2, 6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one (L2) were synthesized and combined with isophthalic acid (H2IP), then under solvothermal conditions, to react with transition metals achieving four novel metal organic frameworks (MOFs): [Zn(IP)(L1)]n (1), {[Cd(IP)(L1)]·H2O}n (2), {[Co(IP)(L1)]·H2O}n (3), and [Zn(IP)(L2)(H2O)]n (4). MOFs 1-4 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry, and elemental analysis. Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P21/n, and MOFs 2-4 belong to the triclinic system with the P1 space group. 1-3 are 2D sheet structures, 2 and 3 have similar structural characters, whereas 4 is a 1D chain structure. Furthermore, 1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B (RhB) and pararosaniline hydrochloride (PH). 4 could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile. 4 could promote the reaction to achieve corresponding products in moderate yields within 3 h. Moreover, the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity. A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.
2025, 41(3): 561-573
doi: 10.11862/CJIC.20240294
摘要:
We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen (N) co-doped biomass carbon dots (Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method. Compared with single N doped BCDs (N BCDs) and Prdoped BCDs (PrBCDs), Pr/N BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%. More importantly, under certain conditions, Pr/N-BCDs and 2, 4-dinitrophenylhydrazide (2, 4-DNPH) had significant fluorescence internal filtration effect (IFE) and dynamic quenching effect, and in the concentration range of 0.50-20 μmol·L-1, the concentration of 2, 4-DNPH had a good linear relationship with the fluorescence quenching signal, and the detection limit was as low as 2.1 nmol·L-1.
We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen (N) co-doped biomass carbon dots (Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method. Compared with single N doped BCDs (N BCDs) and Prdoped BCDs (PrBCDs), Pr/N BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%. More importantly, under certain conditions, Pr/N-BCDs and 2, 4-dinitrophenylhydrazide (2, 4-DNPH) had significant fluorescence internal filtration effect (IFE) and dynamic quenching effect, and in the concentration range of 0.50-20 μmol·L-1, the concentration of 2, 4-DNPH had a good linear relationship with the fluorescence quenching signal, and the detection limit was as low as 2.1 nmol·L-1.
2025, 41(3): 574-586
doi: 10.11862/CJIC.20240287
摘要:
A coordination polymer {[Cd(H2dpa)(bpy)]·3H2O}n (Cd-CP) was designed and hydrothermal synthesized based on 4-(2, 4-dicarboxyphenoxy) phthalic acid (H4dpa), 2, 2′-bipyridine (bpy) and Cd(NO3)2·4H2O. The structure was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, and infrared spectroscopy. Cd-CP belongs to the monoclinic crystal system with the P21/c space group and performs in a 1D double-chain structure. The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding. Thermogravimetric analysis shows that Cd-CP has good thermal stability. Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions (Fe3+ and Zn2+), 2, 4, 6-trinitrophenylhydrazine (TRI), and pyrimethanil (Pth). Interestingly, when Cd-CP was used for fluorescence detection of metal ions, it was found to have a fluorescence quenching effect on Fe3+ but had an obvious enhancement effect on Zn2+. Therefore, we designed an "on-off-on" logic gate. In addition, the mechanism of fluorescence sensing has been deeply explored.
A coordination polymer {[Cd(H2dpa)(bpy)]·3H2O}n (Cd-CP) was designed and hydrothermal synthesized based on 4-(2, 4-dicarboxyphenoxy) phthalic acid (H4dpa), 2, 2′-bipyridine (bpy) and Cd(NO3)2·4H2O. The structure was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, and infrared spectroscopy. Cd-CP belongs to the monoclinic crystal system with the P21/c space group and performs in a 1D double-chain structure. The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding. Thermogravimetric analysis shows that Cd-CP has good thermal stability. Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions (Fe3+ and Zn2+), 2, 4, 6-trinitrophenylhydrazine (TRI), and pyrimethanil (Pth). Interestingly, when Cd-CP was used for fluorescence detection of metal ions, it was found to have a fluorescence quenching effect on Fe3+ but had an obvious enhancement effect on Zn2+. Therefore, we designed an "on-off-on" logic gate. In addition, the mechanism of fluorescence sensing has been deeply explored.
2025, 41(3): 587-596
doi: 10.11862/CJIC.20240269
摘要:
Two new Mn(Ⅱ) coordination polymers, namely {[Mn2(HL)(phen)3(H2O)2]·7.5H2O}n (1) and [Mn4(HL)2(1, 4-bib)3(H2O)2]n (2), were synthesized under hydrothermal conditions by using Mn(Ⅱ) ions and 6-(3′, 4′-dicarboxylphenoxy)-1, 2, 4-benzenetricarboxylic acid (H5L) in the presence of N-auxiliary ligands 1, 10-phenanthroline (phen) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib). The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and powder X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ) units, while 2 features a (3, 8)-connected 3D network structure based on tetranuclear Mn(Ⅱ) units. Magnetic studies show that 1 and 2 exhibit antiferromagnetic interactions between manganese ions. 2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.
Two new Mn(Ⅱ) coordination polymers, namely {[Mn2(HL)(phen)3(H2O)2]·7.5H2O}n (1) and [Mn4(HL)2(1, 4-bib)3(H2O)2]n (2), were synthesized under hydrothermal conditions by using Mn(Ⅱ) ions and 6-(3′, 4′-dicarboxylphenoxy)-1, 2, 4-benzenetricarboxylic acid (H5L) in the presence of N-auxiliary ligands 1, 10-phenanthroline (phen) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib). The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and powder X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ) units, while 2 features a (3, 8)-connected 3D network structure based on tetranuclear Mn(Ⅱ) units. Magnetic studies show that 1 and 2 exhibit antiferromagnetic interactions between manganese ions. 2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.
2025, 41(3): 597-604
doi: 10.11862/CJIC.20240268
摘要:
A trinuclear copper complex [Cu3(L2)2(SO4)2(H2O)7)]·8H2O (1) (HL2=1-hydroxy-3-(pyrazin-2-yl)-N- (pyrazin-2-ylmethyl)imidazo[1, 5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1, 5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H2L1 (N, N′-bis(pyrazin-2-ylmethyl)pyrazine-2, 3-dicarboxamide) with CuSO4·5H2O in aqueous solution at room temperature. Complex 1 was characterized by IR, single-crystal X-ray analysis, and magnetic susceptibility measurements. Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions, two in situ transformed L2- ligands, two coordinated sulfates, seven coordinated water molecules, and eight uncoordinated water molecules. Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.
A trinuclear copper complex [Cu3(L2)2(SO4)2(H2O)7)]·8H2O (1) (HL2=1-hydroxy-3-(pyrazin-2-yl)-N- (pyrazin-2-ylmethyl)imidazo[1, 5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1, 5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H2L1 (N, N′-bis(pyrazin-2-ylmethyl)pyrazine-2, 3-dicarboxamide) with CuSO4·5H2O in aqueous solution at room temperature. Complex 1 was characterized by IR, single-crystal X-ray analysis, and magnetic susceptibility measurements. Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions, two in situ transformed L2- ligands, two coordinated sulfates, seven coordinated water molecules, and eight uncoordinated water molecules. Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.
2025, 41(3): 605-612
doi: 10.11862/CJIC.20240251
摘要:
A tetranuclear Ln(Ⅲ)-based complex: [Dy4(dbm)4(L)6(μ3-OH)2]·CH3CN (1) (HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol, Hdbm=dibenzoylmethane) was manufactured and its structure was characterized in detail. X-ray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P21/n, which contains a rhombic Dy4 core. Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet (SMM) behavior. Its energy barrier Ueff/kB was 116.7 K, and the pre-exponential coefficient τ0=1.05×10-8 s.
A tetranuclear Ln(Ⅲ)-based complex: [Dy4(dbm)4(L)6(μ3-OH)2]·CH3CN (1) (HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol, Hdbm=dibenzoylmethane) was manufactured and its structure was characterized in detail. X-ray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P21/n, which contains a rhombic Dy4 core. Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet (SMM) behavior. Its energy barrier Ueff/kB was 116.7 K, and the pre-exponential coefficient τ0=1.05×10-8 s.
2025, 41(3): 613-623
doi: 10.11862/CJIC.20240273
摘要:
Two new transition-metal coordination polymers, {[Cd(oba)(L)2]·H2O}n (1) and [Cd(4-nph)(L)2]n (2) (H2oba=4, 4′-oxydibenzoic acid, 4-H2nph=4-nitrophthalic acid, L=2, 2′-biimidazole), were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy, elemental analyses, single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis. The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. Meanwhile, complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. In addition, both 1 and 2 exhibited luminescent properties in the solid state. Furthermore, quantum chemical calculations were carried out on the "molecular fragments" extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian16 program. The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ) ions.
Two new transition-metal coordination polymers, {[Cd(oba)(L)2]·H2O}n (1) and [Cd(4-nph)(L)2]n (2) (H2oba=4, 4′-oxydibenzoic acid, 4-H2nph=4-nitrophthalic acid, L=2, 2′-biimidazole), were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy, elemental analyses, single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis. The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. Meanwhile, complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. In addition, both 1 and 2 exhibited luminescent properties in the solid state. Furthermore, quantum chemical calculations were carried out on the "molecular fragments" extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian16 program. The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ) ions.
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%.
