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2026, 42(6): 1121-1130
doi: 10.11862/CJIC.20260115
Abstract:
采用溶剂热法，以双烯基化合物1，5-二[(E)-2-(吡啶-4-基)乙烯基]萘(1，5-bpvn)为主配体，分别引入轴向长度不同的对苯二甲酸(H2bdc)和联苯二甲酸(4，4′-H2bpdc)作为辅助配体，构筑了2例Cd基柱层式配位聚合物[Cd2(1，5-bpvn)2(bdc)2]n (CP1)和[Cd(1，5-bpvn)(4，4′-bpdc)]n (CP2)。单晶结构分析表明，辅助配体的轴向尺寸对框架拓扑结构和穿插模式具有显著调控作用。CP1呈现典型的二重穿插网络，而CP2则形成不多见的自穿插框架。此外，CP1中1，5-bpvn配体间存在in-phase和out-of-phase两种堆积方式，相邻烯烃基团的间距和取向满足固相[2+2]光化学环加成反应的要求。在自然光照射下，CP1发生单晶到单晶转化，生成含双环丁烷二聚体的光反应产物[Cd2(tpdnpp)(bdc)2]n (CP1-C，tpdnpp=四(4-吡啶基)-1，2，11，12-二乙桥-[2.2]萘并环番)。相比之下，CP2中1，5-bpvn配体构象明显扭曲，烯烃间距较大，不满足光环加成条件。研究了CP1和CP2的荧光性质以及CP1在环加成反应前后的荧光变化。
采用溶剂热法，以双烯基化合物1，5-二[(E)-2-(吡啶-4-基)乙烯基]萘(1，5-bpvn)为主配体，分别引入轴向长度不同的对苯二甲酸(H2bdc)和联苯二甲酸(4，4′-H2bpdc)作为辅助配体，构筑了2例Cd基柱层式配位聚合物[Cd2(1，5-bpvn)2(bdc)2]n (CP1)和[Cd(1，5-bpvn)(4，4′-bpdc)]n (CP2)。单晶结构分析表明，辅助配体的轴向尺寸对框架拓扑结构和穿插模式具有显著调控作用。CP1呈现典型的二重穿插网络，而CP2则形成不多见的自穿插框架。此外，CP1中1，5-bpvn配体间存在in-phase和out-of-phase两种堆积方式，相邻烯烃基团的间距和取向满足固相[2+2]光化学环加成反应的要求。在自然光照射下，CP1发生单晶到单晶转化，生成含双环丁烷二聚体的光反应产物[Cd2(tpdnpp)(bdc)2]n (CP1-C，tpdnpp=四(4-吡啶基)-1，2，11，12-二乙桥-[2.2]萘并环番)。相比之下，CP2中1，5-bpvn配体构象明显扭曲，烯烃间距较大，不满足光环加成条件。研究了CP1和CP2的荧光性质以及CP1在环加成反应前后的荧光变化。
2026, 42(6): 1131-1145
doi: 10.11862/CJIC.20260063
Abstract:
通过在多孔CaFe2O4上负载CaCO3，制备了一系列磁性多孔CaCO3/CaFe2O4复合材料(CCFO-x，x为合成时Ca(CH3COO)2·H2O与CaFe2O4的物质的量之比)。多孔CaFe2O4载体不仅使活性CaCO3有效分散，进而提供更多的可接触吸附位点，而且赋予了吸附剂一定的磁性，使其可以从溶液中快速分离。吸附实验结果表明，CCFO-x对磷酸盐的吸附量随着材料中Ca含量的增加而增加。其中，CCFO-5对磷酸盐的最大吸附量达到246 mg·g-1，远高于载体CaFe2O4(134 mg·g-1)。动力学拟合和吸附等温线结果揭示了CCFO-5对磷酸盐的吸附为单层化学吸附。并且，CCFO-5在酸性条件下仍能保持良好的磷酸盐吸附性能(pH=3.00~7.00，平衡吸附量Qe=174~144 mg·g-1)，且具有优异的抗离子干扰能力。机理分析表明，CCFO-5在吸附磷酸盐过程中存在表面质子化、静电作用、配体交换以及内层配位反应等化学过程，从而形成了稳定的Ca10(PO4)6(OH)2化合物。回收实验表明，当固液比为15 g·L-1时，1.0 mol·L-1的HCl洗脱剂对所吸附磷酸盐的富集率达到567.4%。
通过在多孔CaFe2O4上负载CaCO3，制备了一系列磁性多孔CaCO3/CaFe2O4复合材料(CCFO-x，x为合成时Ca(CH3COO)2·H2O与CaFe2O4的物质的量之比)。多孔CaFe2O4载体不仅使活性CaCO3有效分散，进而提供更多的可接触吸附位点，而且赋予了吸附剂一定的磁性，使其可以从溶液中快速分离。吸附实验结果表明，CCFO-x对磷酸盐的吸附量随着材料中Ca含量的增加而增加。其中，CCFO-5对磷酸盐的最大吸附量达到246 mg·g-1，远高于载体CaFe2O4(134 mg·g-1)。动力学拟合和吸附等温线结果揭示了CCFO-5对磷酸盐的吸附为单层化学吸附。并且，CCFO-5在酸性条件下仍能保持良好的磷酸盐吸附性能(pH=3.00~7.00，平衡吸附量Qe=174~144 mg·g-1)，且具有优异的抗离子干扰能力。机理分析表明，CCFO-5在吸附磷酸盐过程中存在表面质子化、静电作用、配体交换以及内层配位反应等化学过程，从而形成了稳定的Ca10(PO4)6(OH)2化合物。回收实验表明，当固液比为15 g·L-1时，1.0 mol·L-1的HCl洗脱剂对所吸附磷酸盐的富集率达到567.4%。
2026, 42(6): 1146-1154
doi: 10.11862/CJIC.20260053
Abstract:
硼中子俘获疗法(BNCT)利用硼携带剂在中子照射下释放高能粒子，实现细胞尺度精准杀伤，但临床硼携带剂硼苯丙氨酸(BPA)和巯基十二水合十二硼酸钠(BSH)存在含硼量不足及缺乏成像等缺陷。本研究选择二十面体碳硼烷作为硼源，金纳米簇作为荧光探针骨架，将葡萄糖基团引入金纳米簇表面，构建集靶向性、富硼性与荧光成像于一体的新型硼携带剂(AuGSCB-Glu)。该硼携带剂在乳腺癌MCF-7细胞中表现出高特异性成像和高的硼摄取量，并在细胞水平显示出BNCT治疗效果。
硼中子俘获疗法(BNCT)利用硼携带剂在中子照射下释放高能粒子，实现细胞尺度精准杀伤，但临床硼携带剂硼苯丙氨酸(BPA)和巯基十二水合十二硼酸钠(BSH)存在含硼量不足及缺乏成像等缺陷。本研究选择二十面体碳硼烷作为硼源，金纳米簇作为荧光探针骨架，将葡萄糖基团引入金纳米簇表面，构建集靶向性、富硼性与荧光成像于一体的新型硼携带剂(AuGSCB-Glu)。该硼携带剂在乳腺癌MCF-7细胞中表现出高特异性成像和高的硼摄取量，并在细胞水平显示出BNCT治疗效果。
2026, 42(6): 1155-1163
doi: 10.11862/CJIC.20260018
Abstract:
基于第一性原理计算对氮化物钙钛矿CeBN3(B=Ta、Nb)的电子结构、光学性质、本征点缺陷及缺陷钝化效果进行了系统分析。计算结果表明，CeTaN3和CeNbN3均为直接带隙半导体材料，带隙值分别为1.10和0.91 eV；CeTaN3存在N间隙(Ni)深能级缺陷，与之相比，CeNbN3未引入深能级缺陷，其能带附近电荷分布更局域，同时具有较低的载流子有效质量和较高的光吸收系数。此外，当碱金属(Li、Na、K、Rb、Cs)分别掺杂CeTaN3中的Ce时，Li、Na、K和Rb掺杂体系中Ni缺陷的跃迁能级均变浅，其中Rb掺杂钝化缺陷的效果最为显著，而Cs掺杂未能钝化Ni的跃迁能级。
基于第一性原理计算对氮化物钙钛矿CeBN3(B=Ta、Nb)的电子结构、光学性质、本征点缺陷及缺陷钝化效果进行了系统分析。计算结果表明，CeTaN3和CeNbN3均为直接带隙半导体材料，带隙值分别为1.10和0.91 eV；CeTaN3存在N间隙(Ni)深能级缺陷，与之相比，CeNbN3未引入深能级缺陷，其能带附近电荷分布更局域，同时具有较低的载流子有效质量和较高的光吸收系数。此外，当碱金属(Li、Na、K、Rb、Cs)分别掺杂CeTaN3中的Ce时，Li、Na、K和Rb掺杂体系中Ni缺陷的跃迁能级均变浅，其中Rb掺杂钝化缺陷的效果最为显著，而Cs掺杂未能钝化Ni的跃迁能级。
2026, 42(6): 1164-1174
doi: 10.11862/CJIC.20250378
Abstract:
面向农产品中有机磷农药残留的快速检测需求，我们基于酶抑制效应构建了一种金属团簇基电化学传感器NF/KbE-CS/Au25-xAgx@G/GCE，其中，NF、KbE、CS、Au25-xAgx、G、GCE分别代表Nafion、白芸豆酯酶、壳聚糖、Au25-xAgx(PET)18纳米团簇(PET=2-苯乙硫醇)、多层石墨烯、玻碳电极。该传感器中，Au25-xAgx@G复合材料不仅为生物酶的固定提供了理想基质，更凭借其优异导电性与双金属协同电催化效应，显著促进了界面电子传输，有效放大了检测信号。此外，通过Au25-xAgx@G与KbE-CS的协同作用，实现了对丙溴磷的高灵敏检测。测试条件优化后，该传感器对KbE活性的抑制率与丙溴磷质量浓度的对数在10~2 200 μg·L-1范围内呈良好的线性关系(R2=0.988 4)，检出限低至0.064 μg·L-1。所构建的传感器表现出良好的重现性、稳定性与抗干扰能力，并成功应用于实际样品中的农药检测。
面向农产品中有机磷农药残留的快速检测需求，我们基于酶抑制效应构建了一种金属团簇基电化学传感器NF/KbE-CS/Au25-xAgx@G/GCE，其中，NF、KbE、CS、Au25-xAgx、G、GCE分别代表Nafion、白芸豆酯酶、壳聚糖、Au25-xAgx(PET)18纳米团簇(PET=2-苯乙硫醇)、多层石墨烯、玻碳电极。该传感器中，Au25-xAgx@G复合材料不仅为生物酶的固定提供了理想基质，更凭借其优异导电性与双金属协同电催化效应，显著促进了界面电子传输，有效放大了检测信号。此外，通过Au25-xAgx@G与KbE-CS的协同作用，实现了对丙溴磷的高灵敏检测。测试条件优化后，该传感器对KbE活性的抑制率与丙溴磷质量浓度的对数在10~2 200 μg·L-1范围内呈良好的线性关系(R2=0.988 4)，检出限低至0.064 μg·L-1。所构建的传感器表现出良好的重现性、稳定性与抗干扰能力，并成功应用于实际样品中的农药检测。
2026, 42(6): 1175-1189
doi: 10.11862/CJIC.20250375
Abstract:
采用混配体策略，选取异烟酸(HINA)与刚性配体3，3′，5，5′-偶氮苯四羧酸(H4ABTC)与硝酸钴在水热条件下反应，成功协同组装成具有3D菱形孔道结构的金属有机框架(MOF)：[Co4(μ3-OH)2(ABTC)(INA)2(DMF)2]n (SXNU-6-Co，DMF=N，N-二甲基甲酰胺，SXNU=Shanxi Normal University)。其规整孔道内富含偶氮键和吡啶氮活性位点，结合四核金属氧簇中不同配位数Co原子的Co2+/Co3+可逆氧化还原对，协同调控了对4-氨基苯酚(4-AP)的吸附与电催化性能。基于此构建的SXNU-6-Co/GCE(GCE=玻碳电极)传感器在0.2~328 μmol·L-1范围内对4-AP展现出良好的线性响应，检出限低至10.47 nmol·L-1(S/N=3)。巨正则蒙特卡罗(GCMC)模拟结果表明，4-AP与框架中的氮原子之间存在π-π和氢键相互作用，显著增强了底物分子与框架间的相互作用。
采用混配体策略，选取异烟酸(HINA)与刚性配体3，3′，5，5′-偶氮苯四羧酸(H4ABTC)与硝酸钴在水热条件下反应，成功协同组装成具有3D菱形孔道结构的金属有机框架(MOF)：[Co4(μ3-OH)2(ABTC)(INA)2(DMF)2]n (SXNU-6-Co，DMF=N，N-二甲基甲酰胺，SXNU=Shanxi Normal University)。其规整孔道内富含偶氮键和吡啶氮活性位点，结合四核金属氧簇中不同配位数Co原子的Co2+/Co3+可逆氧化还原对，协同调控了对4-氨基苯酚(4-AP)的吸附与电催化性能。基于此构建的SXNU-6-Co/GCE(GCE=玻碳电极)传感器在0.2~328 μmol·L-1范围内对4-AP展现出良好的线性响应，检出限低至10.47 nmol·L-1(S/N=3)。巨正则蒙特卡罗(GCMC)模拟结果表明，4-AP与框架中的氮原子之间存在π-π和氢键相互作用，显著增强了底物分子与框架间的相互作用。
2026, 42(6): 1190-1202
doi: 10.11862/CJIC.20250365
Abstract:
以泡沫镍(NF)为基底，并将其作为镍源，结合钼酸铵(钼源)和硫脲(硫源)，通过水热法在NF骨架上原位生长出MoS2/Ni3S2@NF(MNS@NF)复合光热材料。通过X射线衍射仪、扫描电子显微镜(SEM)和X射线光电子能谱仪对复合材料的结构和形貌进行了表征，并对复合光热材料的光吸收性能和界面蒸发性能进行了研究。结果表明，在模拟太阳光照(光照强度为1 kW·m-2)下，水热反应温度为200 ℃、反应时间为24 h的条件下合成的样品MNS@NF-200-24的光吸收率达到91.7%，其在去离子水中的界面蒸发速率达到2.846 kg·m-2·h-1，界面蒸发效率达到95.6%。此外，还测试了MNS@NF-200-24在模拟海水中的界面蒸发速率，蒸发1 h后速率达到2.360 kg·m-2·h-1，界面蒸发连续12 h后稳定在2.000 kg·m-2·h-1，宏观表面无结晶盐析出。蒸发冷凝得到的水达到世界卫生组织(WHO)与美国环境保护署(EPA)饮用水标准。
以泡沫镍(NF)为基底，并将其作为镍源，结合钼酸铵(钼源)和硫脲(硫源)，通过水热法在NF骨架上原位生长出MoS2/Ni3S2@NF(MNS@NF)复合光热材料。通过X射线衍射仪、扫描电子显微镜(SEM)和X射线光电子能谱仪对复合材料的结构和形貌进行了表征，并对复合光热材料的光吸收性能和界面蒸发性能进行了研究。结果表明，在模拟太阳光照(光照强度为1 kW·m-2)下，水热反应温度为200 ℃、反应时间为24 h的条件下合成的样品MNS@NF-200-24的光吸收率达到91.7%，其在去离子水中的界面蒸发速率达到2.846 kg·m-2·h-1，界面蒸发效率达到95.6%。此外，还测试了MNS@NF-200-24在模拟海水中的界面蒸发速率，蒸发1 h后速率达到2.360 kg·m-2·h-1，界面蒸发连续12 h后稳定在2.000 kg·m-2·h-1，宏观表面无结晶盐析出。蒸发冷凝得到的水达到世界卫生组织(WHO)与美国环境保护署(EPA)饮用水标准。
2026, 42(6): 1203-1214
doi: 10.11862/CJIC.20250370
Abstract:
以杨絮(PC)为原料，采用乙醇溶剂热法对其进行预处理，再进行碳化，制备了高比表面积的杨絮衍生多孔碳(DPCC)，并研究了其对染料的吸附性能及动力学性能。通过单因素实验优化工艺参数，确定最佳预处理条件(液固比为17 mL·g-1、200 ℃处理2 h)，在此条件下制备的DPCC-10比表面积达到518 m2·g-1。结合傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、拉曼(Raman)光谱、扫描电镜(SEM)和N2吸附-脱附测试等表征手段，证实预处理过程能够有效去除木质素和半纤维素等，形成丰富的多级孔道结构。吸附实验表明，DPCC-10对亚甲蓝(MB)的最大吸附量达到385.71 mg·g-1，优于多数报道的生物质衍生吸附剂。DPCC-10对染料的吸附过程满足准二级动力学方程，表明该吸附以化学吸附为主。经过4次吸附-脱附循环后，DPCC-10对MB的吸附容量仍保持初始值的92.01%，表明材料具有优异的可再生性能。
以杨絮(PC)为原料，采用乙醇溶剂热法对其进行预处理，再进行碳化，制备了高比表面积的杨絮衍生多孔碳(DPCC)，并研究了其对染料的吸附性能及动力学性能。通过单因素实验优化工艺参数，确定最佳预处理条件(液固比为17 mL·g-1、200 ℃处理2 h)，在此条件下制备的DPCC-10比表面积达到518 m2·g-1。结合傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、拉曼(Raman)光谱、扫描电镜(SEM)和N2吸附-脱附测试等表征手段，证实预处理过程能够有效去除木质素和半纤维素等，形成丰富的多级孔道结构。吸附实验表明，DPCC-10对亚甲蓝(MB)的最大吸附量达到385.71 mg·g-1，优于多数报道的生物质衍生吸附剂。DPCC-10对染料的吸附过程满足准二级动力学方程，表明该吸附以化学吸附为主。经过4次吸附-脱附循环后，DPCC-10对MB的吸附容量仍保持初始值的92.01%，表明材料具有优异的可再生性能。
2026, 42(6): 1215-1228
doi: 10.11862/CJIC.20250368
Abstract:
采用高温热聚合结合原位溶剂热法构建了Z型g-C3N4/Bi2WO6异质结光催化材料。借助X射线衍射、傅里叶变换红外光谱、扫描电子显微镜、X射线光电子能谱、紫外可见近红外漫反射光谱对异质结材料的组成、结构和光学性质进行了详细表征。结果表明，氧空位缺陷通过局域表面等离激元共振效应提高了异质结对可见光和近红外光的吸收能力；Ⅱ型异质结向Z型异质结的转变提高了光生电子-空穴对的分离效率和氧化还原能力。g-C3N4/Bi2WO6异质结在可见光和近红外光照射下降解氧氟沙星的表观速率常数分别可以达到0.045 8和0.003 8 min-1，明显高于单组分g-C3N4和Bi2WO6。同时，该异质结具有良好的循环稳定性和可重复使用性。
采用高温热聚合结合原位溶剂热法构建了Z型g-C3N4/Bi2WO6异质结光催化材料。借助X射线衍射、傅里叶变换红外光谱、扫描电子显微镜、X射线光电子能谱、紫外可见近红外漫反射光谱对异质结材料的组成、结构和光学性质进行了详细表征。结果表明，氧空位缺陷通过局域表面等离激元共振效应提高了异质结对可见光和近红外光的吸收能力；Ⅱ型异质结向Z型异质结的转变提高了光生电子-空穴对的分离效率和氧化还原能力。g-C3N4/Bi2WO6异质结在可见光和近红外光照射下降解氧氟沙星的表观速率常数分别可以达到0.045 8和0.003 8 min-1，明显高于单组分g-C3N4和Bi2WO6。同时，该异质结具有良好的循环稳定性和可重复使用性。
2026, 42(6): 1229-1236
doi: 10.11862/CJIC.20250355
Abstract:
采用溶液扩散的方法分别合成了扩展式四硫富瓦烯衍生物C14H8(C3S2(S-R)2)2[R=苯基(T1)、噻吩-2-基(T2)、吡啶-2-基(T3)]与CuBr2的电荷转移复合物(T1)[Cu2Br6]·2THF、(T2)[Cu2Br6]·2THF和(T3)[Cu2Br6]。晶体结构研究表明，T12+、T22+和T32+呈现不同的分子构型，[Cu2Br6]2-呈平面构型和类八面体构型，3种复合物呈现不同的堆积结构。通过改变四硫富瓦烯衍生物的外围芳基，实现了对阴离子构型的有效调控，并且化合物T1~T3可根据阴离子构型调控自身构型。
采用溶液扩散的方法分别合成了扩展式四硫富瓦烯衍生物C14H8(C3S2(S-R)2)2[R=苯基(T1)、噻吩-2-基(T2)、吡啶-2-基(T3)]与CuBr2的电荷转移复合物(T1)[Cu2Br6]·2THF、(T2)[Cu2Br6]·2THF和(T3)[Cu2Br6]。晶体结构研究表明，T12+、T22+和T32+呈现不同的分子构型，[Cu2Br6]2-呈平面构型和类八面体构型，3种复合物呈现不同的堆积结构。通过改变四硫富瓦烯衍生物的外围芳基，实现了对阴离子构型的有效调控，并且化合物T1~T3可根据阴离子构型调控自身构型。
2026, 42(6): 1237-1246
doi: 10.11862/CJIC.20250322
Abstract:
采用Sm3+与Sb3+共掺杂的策略，实现了对Cs2NaGdCl6荧光粉发光颜色从蓝光到白光的有效调控。采用微波固相法合成了一系列Cs2NaGd0.985-xCl6∶0.015Sb3+，xSm3+(x=0~0.130)荧光粉。物相分析表明，所有样品均保持纯相双钙钛矿结构，Sm3+成功融入晶格。光谱分析发现，在336 nm激发下，材料同时产生源于自陷激子(STEs)的460 nm宽带蓝光发射和Sm3+的特征发射(568、604、653 nm)，并且该体系中存在STEs向Sm3+的有效能量传递，效率达13.34%(x=0.070)。当Sm3+掺杂浓度为0.070时，荧光粉表现出最优性能，光致发光量子产率(PLQY)为35.49%，且具备良好的热稳定性，423 K下发光强度保持为室温的68.6%，热活化能为163 meV。更重要的是，通过调控Sm3+浓度，实现了发光颜色从蓝光区到白光区的连续可控变化。
采用Sm3+与Sb3+共掺杂的策略，实现了对Cs2NaGdCl6荧光粉发光颜色从蓝光到白光的有效调控。采用微波固相法合成了一系列Cs2NaGd0.985-xCl6∶0.015Sb3+，xSm3+(x=0~0.130)荧光粉。物相分析表明，所有样品均保持纯相双钙钛矿结构，Sm3+成功融入晶格。光谱分析发现，在336 nm激发下，材料同时产生源于自陷激子(STEs)的460 nm宽带蓝光发射和Sm3+的特征发射(568、604、653 nm)，并且该体系中存在STEs向Sm3+的有效能量传递，效率达13.34%(x=0.070)。当Sm3+掺杂浓度为0.070时，荧光粉表现出最优性能，光致发光量子产率(PLQY)为35.49%，且具备良好的热稳定性，423 K下发光强度保持为室温的68.6%，热活化能为163 meV。更重要的是，通过调控Sm3+浓度，实现了发光颜色从蓝光区到白光区的连续可控变化。
2026, 42(6): 1247-1260
doi: 10.11862/CJIC.20250299
Abstract:
钯前驱体的化学结构及其与配体的协同作用，直接影响原位新生活性Pd(0)中心的构型，进而决定C—C偶联反应的效率，故本研究以[Pd(COD)X2](COD=1，5-环辛二烯，X=Cl、Br)为钯前驱体、有机膦(PR3)为调控配体，考察它们对C—C偶联反应催化性能的影响。通过元素分析、红外光谱、核磁共振及理论计算解析前驱体Pd(Ⅱ)中心的化学结构与溶剂稳定性，结合单晶X射线衍射分析反应后催化剂结构，研究前驱体结构在反应中的作用机制。结果表明，PR3调控的[Pd(COD)X2]/Pd(0)体系催化效率优于市售trans-[Pd(PPh3)2Cl2]，且呈现明确的配体依赖性(顺序为cis-[Pd(COD)X2]/Xantphos > cis-[Pd(COD)X2]/PPh3 > trans-[Pd(PPh3)2Cl2] > [Pd(COD)X2])及卤素依赖性([Pd(COD)Br2] > [Pd(COD)Cl2])。机理分析显示，PR3通过富电子膦与Pd(0)配位、大位阻效应抑制其团聚失活；PR3的构型调控与卤素键强协同影响Pd(0)生成：Xantphos的刚性骨架维持钯中心顺式配位，生成高活性cis-(Xantphos)-Pd(0)，暴露更多活性位点，而PPh3衍生的中间体易转化为顺反异构体混合物。此外，Pd-Br键能更低、更易断裂，促使[Pd(COD)Br2]更快生成Pd(0)，产物收率更高。
钯前驱体的化学结构及其与配体的协同作用，直接影响原位新生活性Pd(0)中心的构型，进而决定C—C偶联反应的效率，故本研究以[Pd(COD)X2](COD=1，5-环辛二烯，X=Cl、Br)为钯前驱体、有机膦(PR3)为调控配体，考察它们对C—C偶联反应催化性能的影响。通过元素分析、红外光谱、核磁共振及理论计算解析前驱体Pd(Ⅱ)中心的化学结构与溶剂稳定性，结合单晶X射线衍射分析反应后催化剂结构，研究前驱体结构在反应中的作用机制。结果表明，PR3调控的[Pd(COD)X2]/Pd(0)体系催化效率优于市售trans-[Pd(PPh3)2Cl2]，且呈现明确的配体依赖性(顺序为cis-[Pd(COD)X2]/Xantphos > cis-[Pd(COD)X2]/PPh3 > trans-[Pd(PPh3)2Cl2] > [Pd(COD)X2])及卤素依赖性([Pd(COD)Br2] > [Pd(COD)Cl2])。机理分析显示，PR3通过富电子膦与Pd(0)配位、大位阻效应抑制其团聚失活；PR3的构型调控与卤素键强协同影响Pd(0)生成：Xantphos的刚性骨架维持钯中心顺式配位，生成高活性cis-(Xantphos)-Pd(0)，暴露更多活性位点，而PPh3衍生的中间体易转化为顺反异构体混合物。此外，Pd-Br键能更低、更易断裂，促使[Pd(COD)Br2]更快生成Pd(0)，产物收率更高。
2026, 42(6): 1261-1275
doi: 10.11862/CJIC.20250329
Abstract:
采用高温固相法制备了Ca0.993-yScBO4∶0.007Bi3+，yEu3+(y=0~0.100)系列荧光粉。通过在CaScBO4基质中构建高效的Bi3+→Eu3+非辐射能量传递体系，成功实现了330 nm激发下发光颜色从蓝光区[CIE色坐标：(0.153，0.050)]到橙红光区[CIE色坐标：(0.530，0.270)]的连续调谐。该荧光粉的能量传递效率最高可达71.2%，机制为电偶极-电偶极相互作用，临界距离为1.36 nm。代表性橙红光样品Ca0.893ScBO4∶0.007Bi3+, 0.100Eu3+在423 K时仍保持室温积分强度的77.7%，热猝灭活化能为0.417 eV，表现出优异的热稳定性。相较于单掺的Ca0.993ScBO4∶0.007Bi3+蓝光荧光粉，该共掺体系在维持较高量子效率与优异热稳定性的同时，实现了蓝光至橙红光的宽范围颜色调谐。
采用高温固相法制备了Ca0.993-yScBO4∶0.007Bi3+，yEu3+(y=0~0.100)系列荧光粉。通过在CaScBO4基质中构建高效的Bi3+→Eu3+非辐射能量传递体系，成功实现了330 nm激发下发光颜色从蓝光区[CIE色坐标：(0.153，0.050)]到橙红光区[CIE色坐标：(0.530，0.270)]的连续调谐。该荧光粉的能量传递效率最高可达71.2%，机制为电偶极-电偶极相互作用，临界距离为1.36 nm。代表性橙红光样品Ca0.893ScBO4∶0.007Bi3+, 0.100Eu3+在423 K时仍保持室温积分强度的77.7%，热猝灭活化能为0.417 eV，表现出优异的热稳定性。相较于单掺的Ca0.993ScBO4∶0.007Bi3+蓝光荧光粉，该共掺体系在维持较高量子效率与优异热稳定性的同时，实现了蓝光至橙红光的宽范围颜色调谐。
2026, 42(6): 1276-1288
doi: 10.11862/CJIC.20260011
Abstract:
Using sodium phytate (PA) as a ligand precursor, boron-doped iron-cobalt phytate materials (B-FeCoPA) were synthesized via a one-step hydrothermal method. Boron incorporation into FeCoPA effectively modulates the local bonding environment and electronic structure through synergistic B-Fe-Co interactions, thereby facilitating electron transfer and enhancing the electrocatalytic activity for the oxygen evolution reaction (OER). The optimized B-FeCoPA exhibited an outstanding OER catalytic activity in alkaline electrolyte, achieving low overpotentials of 299 mV at 10 mA·cm-2 and 354 mV at 100 mA·cm-2, a small Tafel slope of 46 mV·dec-1, and a high Faradaic efficiency of 96%. Moreover, B-FeCoPA demonstrated good operational stability, maintaining a stable potential of approximately 1.52 V (vs RHE) at 10 mA·cm-2 over a 10-h continuous test in 1.0 mol·L-1 KOH.
Using sodium phytate (PA) as a ligand precursor, boron-doped iron-cobalt phytate materials (B-FeCoPA) were synthesized via a one-step hydrothermal method. Boron incorporation into FeCoPA effectively modulates the local bonding environment and electronic structure through synergistic B-Fe-Co interactions, thereby facilitating electron transfer and enhancing the electrocatalytic activity for the oxygen evolution reaction (OER). The optimized B-FeCoPA exhibited an outstanding OER catalytic activity in alkaline electrolyte, achieving low overpotentials of 299 mV at 10 mA·cm-2 and 354 mV at 100 mA·cm-2, a small Tafel slope of 46 mV·dec-1, and a high Faradaic efficiency of 96%. Moreover, B-FeCoPA demonstrated good operational stability, maintaining a stable potential of approximately 1.52 V (vs RHE) at 10 mA·cm-2 over a 10-h continuous test in 1.0 mol·L-1 KOH.
2026, 42(6): 1289-1298
doi: 10.11862/CJIC.20250369
Abstract:
A composite catalyst (Ni-NiO@CN) with nickel-nickel oxide (Ni-NiO) loaded on two-dimensional g-C3N4 (CN) was successfully constructed by hydrothermal coupled pyrolysis. The Ni-NiO nanostructure served as the methanol oxidation reaction (MOR) active center, and the N-rich CN matrix promoted electron transfer and effectively protected the active components from shedding through physical isolation. Ni-NiO@CN-500, obtained by calcination at 500 ℃, exhibited the highest activity with the current density of 164 mA·cm-2 at 1.67 V (vs RHE) in the alkaline medium. Furthermore, the current density of Ni-NiO@CN-500 could be maintained at 154.9 mA·cm-2 (94.5% of its initial value) in the CO-saturated alkaline methanol electrolyte, significantly outperforming commercial Pt/C catalysts.
A composite catalyst (Ni-NiO@CN) with nickel-nickel oxide (Ni-NiO) loaded on two-dimensional g-C3N4 (CN) was successfully constructed by hydrothermal coupled pyrolysis. The Ni-NiO nanostructure served as the methanol oxidation reaction (MOR) active center, and the N-rich CN matrix promoted electron transfer and effectively protected the active components from shedding through physical isolation. Ni-NiO@CN-500, obtained by calcination at 500 ℃, exhibited the highest activity with the current density of 164 mA·cm-2 at 1.67 V (vs RHE) in the alkaline medium. Furthermore, the current density of Ni-NiO@CN-500 could be maintained at 154.9 mA·cm-2 (94.5% of its initial value) in the CO-saturated alkaline methanol electrolyte, significantly outperforming commercial Pt/C catalysts.
2026, 42(6): 1299-1311
doi: 10.11862/CJIC.20260362
Abstract:
A highly sensitive surface-enhanced Raman scattering (SERS) substrate was constructed, which was a Cu2O-GO-AuNSts sandwich heterostructure assembled on a filter membrane, with ultrathin graphene oxide (GO) precisely embedded between the thorn-like Cu2O microcrystals and gold nanostars (AuNSts). This heterostructure achieved strong electromagnetic enhancement and rapid photogenerated charge transfer by synergistically coupling broadband light absorption, efficient molecular enrichment, and abundant plasma "hotspots". Using rhodamine 6G (R6G) as probe molecules, the substrate achieved an ultra-low detection limit of 10-13 mol·L-1, demonstrating superior SERS sensitivity. More importantly, the heterostructure concurrently exhibited significant photocatalytic performance, thereby endowing the substrate with self-cleaning functionality. Even for the highly stable and recalcitrant persistent organic pollutant (POP), 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47), the characteristic SERS fingerprint could be clearly identified at a concentration as low as 10-7 mol·L-1. UV-Vis spectroscopy analysis revealed a degradation efficiency of approximately 66% after 20 h of light irradiation. The excellent SERS property of the sandwich structure originates from the synergistic effect of local surface plasmon resonance (LSPR) effect attributed to AuNSts and the molecular enrichment effect of GO lamellae and filter membrane, while the photocatalytic activity originates from the photo-induced charge transfer mechanism within the structure.
A highly sensitive surface-enhanced Raman scattering (SERS) substrate was constructed, which was a Cu2O-GO-AuNSts sandwich heterostructure assembled on a filter membrane, with ultrathin graphene oxide (GO) precisely embedded between the thorn-like Cu2O microcrystals and gold nanostars (AuNSts). This heterostructure achieved strong electromagnetic enhancement and rapid photogenerated charge transfer by synergistically coupling broadband light absorption, efficient molecular enrichment, and abundant plasma "hotspots". Using rhodamine 6G (R6G) as probe molecules, the substrate achieved an ultra-low detection limit of 10-13 mol·L-1, demonstrating superior SERS sensitivity. More importantly, the heterostructure concurrently exhibited significant photocatalytic performance, thereby endowing the substrate with self-cleaning functionality. Even for the highly stable and recalcitrant persistent organic pollutant (POP), 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47), the characteristic SERS fingerprint could be clearly identified at a concentration as low as 10-7 mol·L-1. UV-Vis spectroscopy analysis revealed a degradation efficiency of approximately 66% after 20 h of light irradiation. The excellent SERS property of the sandwich structure originates from the synergistic effect of local surface plasmon resonance (LSPR) effect attributed to AuNSts and the molecular enrichment effect of GO lamellae and filter membrane, while the photocatalytic activity originates from the photo-induced charge transfer mechanism within the structure.
2026, 42(6): 1312-1320
doi: 10.11862/CJIC.20250354
Abstract:
Two isostructural coordination polymers [Zn(L)(HCOO)]n (Zn-LFor) and [Zn(L)Cl]n (Zn-LCl) were synthesized by a hydrothermal method based on HL·NaX (HL=2-{[(pyridin-4-yl)methyl]amino}-3, 3-dimethylbutanoic acid, X-=HCOO-, Cl-). Zn-LFor and Zn-LCl belong to the orthorhombic system with space group P212121, which exhibit distorted square pyramidal structures. Interestingly, the values of the trigonality factor (τ5) are distinctively different. Zn-LCl has a τ5 value of 0.144, while the value of τ5 for Zn-LFor is only 0.089. Zn-LFor displayed an excellent fluorescence property, which can be used as a fluorescence probe to detect Cr2O72- in H2O solution with high selectivity and sensitivity, with a quenching constant (KSV) of 2.23×104 L·mol-1. The detection limit of Cr2O72- was calculated from the experimental data, and the value was 1.03 μmol·L-1.
Two isostructural coordination polymers [Zn(L)(HCOO)]n (Zn-LFor) and [Zn(L)Cl]n (Zn-LCl) were synthesized by a hydrothermal method based on HL·NaX (HL=2-{[(pyridin-4-yl)methyl]amino}-3, 3-dimethylbutanoic acid, X-=HCOO-, Cl-). Zn-LFor and Zn-LCl belong to the orthorhombic system with space group P212121, which exhibit distorted square pyramidal structures. Interestingly, the values of the trigonality factor (τ5) are distinctively different. Zn-LCl has a τ5 value of 0.144, while the value of τ5 for Zn-LFor is only 0.089. Zn-LFor displayed an excellent fluorescence property, which can be used as a fluorescence probe to detect Cr2O72- in H2O solution with high selectivity and sensitivity, with a quenching constant (KSV) of 2.23×104 L·mol-1. The detection limit of Cr2O72- was calculated from the experimental data, and the value was 1.03 μmol·L-1.
2026, 42(6): 1321-1336
doi: 10.11862/CJIC.20250333
Abstract:
Two density functional theory methods were employed to evaluate the H2 storage capabilities of metallo-borospherenes TM8B6 (TM=Ni, Pd). Consequently, the superatoms Ni8B6 and Pd8B6, which accommodate 40 and 32 H2 molecules, respectively, exhibit gravimetric H2 uptake capacities of 13.134% and 6.562%, respectively. The average binding energies of Ni8B6(H2)40 and Pd8B6(H2)32 fall within the optimal range for reversible H2 storage applications. The interactions between H2 molecules and the parent structures were characterized using various wave function analysis methods. Polarization effects, alongside the Kubas mechanism, are pivotal to the adsorption of H2 on TM8B6. Moreover, the investigations examine the effect of temperature on the H2 storage capacity of TM8B6 at atmospheric pressure. Atom-centered density-matrix propagation molecular dynamics simulations confirm the reversibility of H2 adsorption and desorption cycles. The thermodynamic analyses of the desorption behavior of H2 molecules were conducted via a three-dimensional graph, plotted based on the relationship between the number of adsorbed H2 molecules and temperature as well as pressure, revealing that the majority of adsorbed H2 molecules can be released at 0.5 MPa and 358 K. Compared to the respective monomeric counterparts, the H2 storage densities of (TM8B6)2 dimers exhibit a slight reduction.
Two density functional theory methods were employed to evaluate the H2 storage capabilities of metallo-borospherenes TM8B6 (TM=Ni, Pd). Consequently, the superatoms Ni8B6 and Pd8B6, which accommodate 40 and 32 H2 molecules, respectively, exhibit gravimetric H2 uptake capacities of 13.134% and 6.562%, respectively. The average binding energies of Ni8B6(H2)40 and Pd8B6(H2)32 fall within the optimal range for reversible H2 storage applications. The interactions between H2 molecules and the parent structures were characterized using various wave function analysis methods. Polarization effects, alongside the Kubas mechanism, are pivotal to the adsorption of H2 on TM8B6. Moreover, the investigations examine the effect of temperature on the H2 storage capacity of TM8B6 at atmospheric pressure. Atom-centered density-matrix propagation molecular dynamics simulations confirm the reversibility of H2 adsorption and desorption cycles. The thermodynamic analyses of the desorption behavior of H2 molecules were conducted via a three-dimensional graph, plotted based on the relationship between the number of adsorbed H2 molecules and temperature as well as pressure, revealing that the majority of adsorbed H2 molecules can be released at 0.5 MPa and 358 K. Compared to the respective monomeric counterparts, the H2 storage densities of (TM8B6)2 dimers exhibit a slight reduction.
2026, 42(6): 1337-1344
doi: 10.11862/CJIC.20250325
Abstract:
A novel viologen-based photochromic coordination polymer, namely [Zn(CV)0.5(BDC)(H2O)]·2H2O (1), has been successfully constructed via solvothermal self-assembly of Zn2+ ions with the 1, 1′-bis(2-carboxyethyl)-4, 4′-bipyridinium ((H2CV)2+) as a photo-responsive functional unit and terephthalic acid (H2BDC) as an auxiliary bridging ligand. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 1D chain-like framework. Upon light irradiation, complex 1 exhibited a distinct photo-responsive color-changing behavior, transforming from colorless to blue. The blue-colored sample gradually faded and reverted to its original colorless state upon being placed in a dark environment at room temperature, demonstrating excellent reversible photochromic properties. On the basis of its photochromic performance, the application of this complex in ink-free printing has been explored. Furthermore, complex 1 emitted blue light under UV irradiation in a dark environment, revealing favorable photoluminescent characteristics. In addition, complex 1 possessed multiple photoswitchable properties.
A novel viologen-based photochromic coordination polymer, namely [Zn(CV)0.5(BDC)(H2O)]·2H2O (1), has been successfully constructed via solvothermal self-assembly of Zn2+ ions with the 1, 1′-bis(2-carboxyethyl)-4, 4′-bipyridinium ((H2CV)2+) as a photo-responsive functional unit and terephthalic acid (H2BDC) as an auxiliary bridging ligand. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 1D chain-like framework. Upon light irradiation, complex 1 exhibited a distinct photo-responsive color-changing behavior, transforming from colorless to blue. The blue-colored sample gradually faded and reverted to its original colorless state upon being placed in a dark environment at room temperature, demonstrating excellent reversible photochromic properties. On the basis of its photochromic performance, the application of this complex in ink-free printing has been explored. Furthermore, complex 1 emitted blue light under UV irradiation in a dark environment, revealing favorable photoluminescent characteristics. In addition, complex 1 possessed multiple photoswitchable properties.
