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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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2023, 39(11): 2033-2041
doi: 10.11862/CJIC.2023.171
摘要:
以铪簇作为金属有机骨架的连接点、刚性双羧基配体2，2'-联吡啶-5，5'-二羧酸作为连接器、乙酸或三氟乙酸和水作为结构调节剂，通过溶剂热法合成得到八面体结构（Hf-MOFs-1）和片状结构（Hf-MOFs-2）的铪基纳米金属有机骨架（Hf-nMOFs），再经Fe3+修饰得到多功能金属有机骨架材料（Hf-Fe-MOFs-1和Hf-Fe-MOFs-2）。模拟肿瘤微环境体系中羟基自由基检测结果表明，X射线照射能显著促进Hf-Fe-MOFs-1和Hf-Fe-MOFs-2材料产生羟基自由基，且片状Hf-Fe-MOFs-2羟基自由基产生能力高于八面体Hf-Fe-MOFs-1。进一步地，在细胞层面证实了材料能够成功被细胞摄入并实现低剂量X射线促进的化学动力学协同治疗。
以铪簇作为金属有机骨架的连接点、刚性双羧基配体2，2'-联吡啶-5，5'-二羧酸作为连接器、乙酸或三氟乙酸和水作为结构调节剂，通过溶剂热法合成得到八面体结构（Hf-MOFs-1）和片状结构（Hf-MOFs-2）的铪基纳米金属有机骨架（Hf-nMOFs），再经Fe3+修饰得到多功能金属有机骨架材料（Hf-Fe-MOFs-1和Hf-Fe-MOFs-2）。模拟肿瘤微环境体系中羟基自由基检测结果表明，X射线照射能显著促进Hf-Fe-MOFs-1和Hf-Fe-MOFs-2材料产生羟基自由基，且片状Hf-Fe-MOFs-2羟基自由基产生能力高于八面体Hf-Fe-MOFs-1。进一步地，在细胞层面证实了材料能够成功被细胞摄入并实现低剂量X射线促进的化学动力学协同治疗。
2023, 39(11): 2042-2054
doi: 10.11862/CJIC.2023.183
摘要:
以氨水为矿化剂，通过添加NH4+离子水热合成了具有较低骨架硅铝比的ZSM-5分子筛。通过X射线衍射（XRD）、扫描电镜（SEM）、固体核磁共振（MAS-NMR）等表征手段，研究了硅源、铝源、矿化剂、阳离子等对ZSM-5分子筛的结晶度、形貌尺寸和骨架硅铝比等的影响，研究了ZSM-5分子筛的骨架硅铝比对正庚烷催化裂化反应的影响。研究表明，投料硅铝比越低，铝原子越难进入到分子筛骨架中；当氨水为矿化剂、正硅酸四乙酯为硅源时可以合成骨架硅铝比较低的氢型ZSM-5分子筛，添加NH4+离子可以增强骨架铝的嵌入，进一步降低分子筛的骨架硅铝比（24.2）。正庚烷裂化反应结果表明，降低分子筛的骨架硅铝比可以提高正庚烷裂化反应的活性，但会降低低碳烯烃的选择性。
以氨水为矿化剂，通过添加NH4+离子水热合成了具有较低骨架硅铝比的ZSM-5分子筛。通过X射线衍射（XRD）、扫描电镜（SEM）、固体核磁共振（MAS-NMR）等表征手段，研究了硅源、铝源、矿化剂、阳离子等对ZSM-5分子筛的结晶度、形貌尺寸和骨架硅铝比等的影响，研究了ZSM-5分子筛的骨架硅铝比对正庚烷催化裂化反应的影响。研究表明，投料硅铝比越低，铝原子越难进入到分子筛骨架中；当氨水为矿化剂、正硅酸四乙酯为硅源时可以合成骨架硅铝比较低的氢型ZSM-5分子筛，添加NH4+离子可以增强骨架铝的嵌入，进一步降低分子筛的骨架硅铝比（24.2）。正庚烷裂化反应结果表明，降低分子筛的骨架硅铝比可以提高正庚烷裂化反应的活性，但会降低低碳烯烃的选择性。
2023, 39(11): 2055-2064
doi: 10.11862/CJIC.2023.166
摘要:
以过硫酸钾（KPS）为引发剂，甲基丙烯酸缩水甘油酯（GMA）和苯乙烯（St）为单体，采用无皂乳液聚合法制备了表面官能团化的高分子微球。研究发现添加微量NaCl制备得到的高分子微球，经四氢呋喃（THF）溶胀处理后，能够得到单分散且表面完整的中空P（St-co-GMA）微球。随后使用有机溶胀的方式将Eu（Ⅲ）配合物染料负载于微球壳层中，实现了α1微球蛋白（α1-MG）和β2微球蛋白（β2-MG）的免疫层析检测。
以过硫酸钾（KPS）为引发剂，甲基丙烯酸缩水甘油酯（GMA）和苯乙烯（St）为单体，采用无皂乳液聚合法制备了表面官能团化的高分子微球。研究发现添加微量NaCl制备得到的高分子微球，经四氢呋喃（THF）溶胀处理后，能够得到单分散且表面完整的中空P（St-co-GMA）微球。随后使用有机溶胀的方式将Eu（Ⅲ）配合物染料负载于微球壳层中，实现了α1微球蛋白（α1-MG）和β2微球蛋白（β2-MG）的免疫层析检测。
2023, 39(11): 2065-2073
doi: 10.11862/CJIC.2023.180
摘要:
设计合成两亲性的单季铵盐分子作为助结构导向剂，两亲性分子具有晶体生长抑制剂或者致孔剂作用，最终导向合成多级孔/小晶粒SAPO-34分子筛。助结构导向剂减少Si进入AlPO4骨架，降低分子筛的强酸酸性。相较于传统的SAPO-34分子筛（CS），添加助结构导向剂合成的多级孔SAPO-34颗粒尺寸较小，介孔孔体积较高，强酸酸性较弱，其在甲醇制烯烃反应中的双烯（乙烯和丙烯）选择性提高约4%，催化剂的寿命延长一倍。
设计合成两亲性的单季铵盐分子作为助结构导向剂，两亲性分子具有晶体生长抑制剂或者致孔剂作用，最终导向合成多级孔/小晶粒SAPO-34分子筛。助结构导向剂减少Si进入AlPO4骨架，降低分子筛的强酸酸性。相较于传统的SAPO-34分子筛（CS），添加助结构导向剂合成的多级孔SAPO-34颗粒尺寸较小，介孔孔体积较高，强酸酸性较弱，其在甲醇制烯烃反应中的双烯（乙烯和丙烯）选择性提高约4%，催化剂的寿命延长一倍。
2023, 39(11): 2074-2082
doi: 10.11862/CJIC.2023.185
摘要:
我们通过热注入的方法制备了一种高CO耐性的金属间PtBi纳米片。所制备的金属间PtBi纳米片在甲醇氧化反应（MOR）中展现出优异的催化性能和良好的稳定性能，最大的质量活性高达4.09 A·mgPt-1，接近商业Pt/C的3.2倍。计时电流-时间（I-t）稳定性测试之后，活性仅仅衰减5.7%，远低于商业Pt/C。CO吸附-脱附（CO-Stripping）曲线和循环伏安演变（CV-Evolution）曲线证实了金属间PtBi纳米片高的CO耐受性。
我们通过热注入的方法制备了一种高CO耐性的金属间PtBi纳米片。所制备的金属间PtBi纳米片在甲醇氧化反应（MOR）中展现出优异的催化性能和良好的稳定性能，最大的质量活性高达4.09 A·mgPt-1，接近商业Pt/C的3.2倍。计时电流-时间（I-t）稳定性测试之后，活性仅仅衰减5.7%，远低于商业Pt/C。CO吸附-脱附（CO-Stripping）曲线和循环伏安演变（CV-Evolution）曲线证实了金属间PtBi纳米片高的CO耐受性。
2023, 39(11): 2083-2090
doi: 10.11862/CJIC.2023.182
摘要:
合成了2个苯甲羟肟酸有机锡配合物：[（o-Cl-C6H4CH2）2Sn（C6H5CONO）2]（1）和[（o-CH3-C6H4CH2）2Sn（C6H5CONO）（C6H5COO）]（2）。通过元素分析、红外光谱、核磁共振氢谱、热重分析、单晶X射线衍射等方法对配合物进行了结构表征，对其结构进行量子化学从头计算和体外抗癌活性研究。结果显示：配合物均为单锡核结构，配合物1为六配位的畸变八面体构型，配合物2为五配位的畸变三角双锥构型；配合物1对人宫颈癌细胞（HeLa）、肝癌细胞（HuH-7）和肺腺癌细胞（H1975）显示出比临床使用的顺铂强的抑制活性，而配合物2的抑制活性要弱得多。
合成了2个苯甲羟肟酸有机锡配合物：[（o-Cl-C6H4CH2）2Sn（C6H5CONO）2]（1）和[（o-CH3-C6H4CH2）2Sn（C6H5CONO）（C6H5COO）]（2）。通过元素分析、红外光谱、核磁共振氢谱、热重分析、单晶X射线衍射等方法对配合物进行了结构表征，对其结构进行量子化学从头计算和体外抗癌活性研究。结果显示：配合物均为单锡核结构，配合物1为六配位的畸变八面体构型，配合物2为五配位的畸变三角双锥构型；配合物1对人宫颈癌细胞（HeLa）、肝癌细胞（HuH-7）和肺腺癌细胞（H1975）显示出比临床使用的顺铂强的抑制活性，而配合物2的抑制活性要弱得多。
2023, 39(11): 2091-2102
doi: 10.11862/CJIC.2023.174
摘要:
采用一步热解法制备了一系列氮掺杂石墨烯包覆的Ru基催化剂（Ru@G-CS），并将该催化剂用于对苯二甲酸二甲酯（DMT）加氢制备1，4-环己烷二甲酸二甲酯（DMCD）的反应中。利用粉末X射线衍射、拉曼光谱、N2吸附-脱附、X射线光电子能谱、扫描电子显微镜和透射电子显微镜对催化剂的组成、结构和表面形貌进行了表征。实验发现：Ru@G-CS（1∶4）催化剂具有最高的活性和优异的稳定性，在160℃、2.5 MPa、mDMT/mRu=833的条件下，反应4 h后DMT的转化率可达100%，DMCD的选择性高于98.5%；且该催化剂的活性经10次循环使用后未见明显下降。表征结果表明，氮掺杂石墨烯骨架中的氮原子可以促进Ru的分散，而且与负载的Ru之间存在较强的相互作用，这种电子-结构的协同效应可能是Ru@G-CS（1∶4）催化剂表现出优异的活性和稳定性的主要原因。
采用一步热解法制备了一系列氮掺杂石墨烯包覆的Ru基催化剂（Ru@G-CS），并将该催化剂用于对苯二甲酸二甲酯（DMT）加氢制备1，4-环己烷二甲酸二甲酯（DMCD）的反应中。利用粉末X射线衍射、拉曼光谱、N2吸附-脱附、X射线光电子能谱、扫描电子显微镜和透射电子显微镜对催化剂的组成、结构和表面形貌进行了表征。实验发现：Ru@G-CS（1∶4）催化剂具有最高的活性和优异的稳定性，在160℃、2.5 MPa、mDMT/mRu=833的条件下，反应4 h后DMT的转化率可达100%，DMCD的选择性高于98.5%；且该催化剂的活性经10次循环使用后未见明显下降。表征结果表明，氮掺杂石墨烯骨架中的氮原子可以促进Ru的分散，而且与负载的Ru之间存在较强的相互作用，这种电子-结构的协同效应可能是Ru@G-CS（1∶4）催化剂表现出优异的活性和稳定性的主要原因。
2023, 39(11): 2103-2112
doi: 10.11862/CJIC.2023.172
摘要:
通过碱性水热-离子交换法制备了Cu、N共掺杂TiO2纳米管（Cu/N-TNT），对其光催化重整甘油制备合成气性能进行了研究。结果表明，Cu/N-TNT具有富含氧空位（OV）的管状结构，N以Ti-N形式取代部分O形成杂质能级，Cu以Cu2+形式掺杂在催化剂晶格间隙和表面，Cu、N共掺杂促进TiO2表面电荷有效分离，有利于其光催化重整甘油制备合成气活性和选择性的提高。紫外光照射8 h时，掺Cu量为0.15%的Cu/N-TNT催化剂上CO和H2产量分别为7.3和8.5 mmol·g-1，是原始TiO2的9.1和70.8倍，nH2/nCO从0.52提高为1.18，nCO/nCO2从0.21提高至0.42。Cu/N-TNT表面N和OV为醛类脱羰和甲酸脱水生成CO提供反应活性位点，Cu作为浅势阱提高光生电子-空穴分离效率。光生空穴（h+）是光催化重整甘油制备合成气过程中的主要活性物种，大量羟基自由基（·OH）和超氧自由基（·O2-）会导致甘油过度氧化，使CO选择性降低。
通过碱性水热-离子交换法制备了Cu、N共掺杂TiO2纳米管（Cu/N-TNT），对其光催化重整甘油制备合成气性能进行了研究。结果表明，Cu/N-TNT具有富含氧空位（OV）的管状结构，N以Ti-N形式取代部分O形成杂质能级，Cu以Cu2+形式掺杂在催化剂晶格间隙和表面，Cu、N共掺杂促进TiO2表面电荷有效分离，有利于其光催化重整甘油制备合成气活性和选择性的提高。紫外光照射8 h时，掺Cu量为0.15%的Cu/N-TNT催化剂上CO和H2产量分别为7.3和8.5 mmol·g-1，是原始TiO2的9.1和70.8倍，nH2/nCO从0.52提高为1.18，nCO/nCO2从0.21提高至0.42。Cu/N-TNT表面N和OV为醛类脱羰和甲酸脱水生成CO提供反应活性位点，Cu作为浅势阱提高光生电子-空穴分离效率。光生空穴（h+）是光催化重整甘油制备合成气过程中的主要活性物种，大量羟基自由基（·OH）和超氧自由基（·O2-）会导致甘油过度氧化，使CO选择性降低。
2023, 39(11): 2113-2120
doi: 10.11862/CJIC.2023.168
摘要:
采用水热法合成了一例结构新颖且罕见的Keggin型多金属氧酸盐基金属有机骨架化合物，即[Cu4（3，5-datrz）4][PW9ⅥW3ⅤO39]·H2O（1），其中3，5-datrz=3，5-二氨基-1，2，4-三氮唑，并通过单晶X射线衍射、傅里叶变换红外光谱、热重分析、粉末X射线衍射和元素分析进行了表征。单晶X射线衍射分析表明：化合物1属于单斜晶系，空间群为C2/c，不对称结构包含2个Cu+、2个3，5-datrz配体、0.5个Keggin型磷钨酸阴离子和1个水分子，除结晶水外各组分之间通过共价键连接成Keggin型多金属氧酸盐基金属有机骨架化合物。以化合物1为非均相催化剂，在温度为55℃时催化H2O2氧化碘离子反应。结果表明，1催化下的碘单质生成速率为6.11×10-7 mol·L-1·s-1，且重复使用次数达到6次时转化率仍能高达99.6%。
采用水热法合成了一例结构新颖且罕见的Keggin型多金属氧酸盐基金属有机骨架化合物，即[Cu4（3，5-datrz）4][PW9ⅥW3ⅤO39]·H2O（1），其中3，5-datrz=3，5-二氨基-1，2，4-三氮唑，并通过单晶X射线衍射、傅里叶变换红外光谱、热重分析、粉末X射线衍射和元素分析进行了表征。单晶X射线衍射分析表明：化合物1属于单斜晶系，空间群为C2/c，不对称结构包含2个Cu+、2个3，5-datrz配体、0.5个Keggin型磷钨酸阴离子和1个水分子，除结晶水外各组分之间通过共价键连接成Keggin型多金属氧酸盐基金属有机骨架化合物。以化合物1为非均相催化剂，在温度为55℃时催化H2O2氧化碘离子反应。结果表明，1催化下的碘单质生成速率为6.11×10-7 mol·L-1·s-1，且重复使用次数达到6次时转化率仍能高达99.6%。
2023, 39(11): 2121-2130
doi: 10.11862/CJIC.2023.175
摘要:
通过焙烧-超声混合法成功地制备了BiOBr/g-C3N4 S型异质结复合光催化剂。采用多种表征手段对样品物理属性进行了表征，包括X射线多晶粉末衍射仪（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-VisDRS）。研究了所制备样品有/无Fe3+的光-自芬顿催化/光催化降解罗丹明B（RhB）性能。通过捕获实验确定了光催化反应中的主要活性物种，提出了光-自芬顿反应的降解机理。研究结果表明，BiOBr/g-C3N4 S型异质结能原位生成H2O2，添加Fe3+后，H2O2被原位活化成活性物种且光生电流和载流子分离效率获得显著提高。该光-自芬顿过程能高效降解RhB，其反应速率常数为0.208 min-1，约为无Fe3+光催化反应速率常数的5.3倍，在光-自芬顿循环使用过程中表现出良好的稳定性。Fe3+的加入促进了光生电荷的分离和H2O2的活化，超氧阴离子自由基（·O2-）、空穴和羟基是光-自芬顿催化过程中的主要活性物种，且·O2-作用更大。
通过焙烧-超声混合法成功地制备了BiOBr/g-C3N4 S型异质结复合光催化剂。采用多种表征手段对样品物理属性进行了表征，包括X射线多晶粉末衍射仪（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-VisDRS）。研究了所制备样品有/无Fe3+的光-自芬顿催化/光催化降解罗丹明B（RhB）性能。通过捕获实验确定了光催化反应中的主要活性物种，提出了光-自芬顿反应的降解机理。研究结果表明，BiOBr/g-C3N4 S型异质结能原位生成H2O2，添加Fe3+后，H2O2被原位活化成活性物种且光生电流和载流子分离效率获得显著提高。该光-自芬顿过程能高效降解RhB，其反应速率常数为0.208 min-1，约为无Fe3+光催化反应速率常数的5.3倍，在光-自芬顿循环使用过程中表现出良好的稳定性。Fe3+的加入促进了光生电荷的分离和H2O2的活化，超氧阴离子自由基（·O2-）、空穴和羟基是光-自芬顿催化过程中的主要活性物种，且·O2-作用更大。
2023, 39(11): 2131-2142
doi: 10.11862/CJIC.2023.170
摘要:
本研究采用PO43-掺杂和AlF3包覆的协同改性策略制备了P-LNCM@AlF3正极材料（P=PO43-，LNCM=Li1.2Ni0.13Co0.13Mn0.54O2），提高了LNCM的结构稳定性以及抑制了界面副反应。其中，大四面体的PO43-聚阴离子掺杂在晶格中抑制了过渡金属离子的迁移，降低体积变化，从而稳定了晶体结构，而且PO43-掺杂能够扩大锂层间距，促进Li+的扩散，从而提升材料的倍率性能。此外，AlF3包覆层能抑制材料与电解液的副反应从而提升界面稳定性。基于以上优势，P-LNCM@AlF3正极表现出了优异的电化学性能。在1C电流密度下表现出了179.2 mAh·g-1的放电比容量，循环200圈后仍有161.5 mAh·g-1的放电比容量，容量保持率可达90.12%。即使在5C的高电流密度下仍可提供128.8 mAh·g-1的放电比容量。
本研究采用PO43-掺杂和AlF3包覆的协同改性策略制备了P-LNCM@AlF3正极材料（P=PO43-，LNCM=Li1.2Ni0.13Co0.13Mn0.54O2），提高了LNCM的结构稳定性以及抑制了界面副反应。其中，大四面体的PO43-聚阴离子掺杂在晶格中抑制了过渡金属离子的迁移，降低体积变化，从而稳定了晶体结构，而且PO43-掺杂能够扩大锂层间距，促进Li+的扩散，从而提升材料的倍率性能。此外，AlF3包覆层能抑制材料与电解液的副反应从而提升界面稳定性。基于以上优势，P-LNCM@AlF3正极表现出了优异的电化学性能。在1C电流密度下表现出了179.2 mAh·g-1的放电比容量，循环200圈后仍有161.5 mAh·g-1的放电比容量，容量保持率可达90.12%。即使在5C的高电流密度下仍可提供128.8 mAh·g-1的放电比容量。
2023, 39(11): 2143-2150
doi: 10.11862/CJIC.2023.178
摘要:
采用简单的溶剂热法制备出具有孪晶结构的红细胞状硫化铜材料。研究不同前驱体比例和反应时间对硫化铜产物微观形貌的影响，并对孪晶结构红细胞状硫化铜可能的形成机理进行分析。在可见光照射下孪晶结构红细胞状硫化铜与H2O2组成的类芬顿系统表现出优异的降解性能，光照50 min后，亚甲蓝降解率可达95%。对比孪晶结构红细胞状硫化铜与合成的花球状硫化铜的催化性能，结果表明含有孪晶结构的红细胞状硫化铜对亚甲蓝的降解性能更好，说明孪晶的存在有利于加速光生电子-空穴的分离。
采用简单的溶剂热法制备出具有孪晶结构的红细胞状硫化铜材料。研究不同前驱体比例和反应时间对硫化铜产物微观形貌的影响，并对孪晶结构红细胞状硫化铜可能的形成机理进行分析。在可见光照射下孪晶结构红细胞状硫化铜与H2O2组成的类芬顿系统表现出优异的降解性能，光照50 min后，亚甲蓝降解率可达95%。对比孪晶结构红细胞状硫化铜与合成的花球状硫化铜的催化性能，结果表明含有孪晶结构的红细胞状硫化铜对亚甲蓝的降解性能更好，说明孪晶的存在有利于加速光生电子-空穴的分离。
2023, 39(11): 2151-2159
doi: 10.11862/CJIC.2023.177
摘要:
电催化CO2还原反应（eCO2RR）受到催化剂本征活性以及传质的限制，导致材料的催化活性低、反应起始电位高等问题。我们以类沸石锌盐咪唑骨架（ZIF-8）材料为研究对象，探究了不同粒径ZIF-8材料的eCO2RR性能。优选粒径为50 nm的ZIF-8材料，进一步引入碳纳米管（CNT）作为其导电基底材料，通过原位生长，构建了复合材料ZIF-8-50@CNT的多级孔结构和疏水界面。eCO2RR实验结果表明，CNT的引入提高了催化剂的导电性，优化后的复合材料有效地降低了反应的起始电位。在-1.1 V（相对可逆氢电极（RHE））电位下，CO部分电流密度为15.6 mA·cm-2，ZIF-8-50@CNT催化剂的比表面活性提升了3.5倍（相比ZIF-8-50），塔菲尔斜率降低到136 mV·dec-1。并且产物CO的选择性和稳定性得到了提高，在宽电势窗口-0.9~-1.2 V（vs RHE）内，CO的法拉第效率（FE）保持在80%以上。在10 h稳定性测试中，催化剂活性保持稳定，整体增强了复合材料eCO2RR的性能。
电催化CO2还原反应（eCO2RR）受到催化剂本征活性以及传质的限制，导致材料的催化活性低、反应起始电位高等问题。我们以类沸石锌盐咪唑骨架（ZIF-8）材料为研究对象，探究了不同粒径ZIF-8材料的eCO2RR性能。优选粒径为50 nm的ZIF-8材料，进一步引入碳纳米管（CNT）作为其导电基底材料，通过原位生长，构建了复合材料ZIF-8-50@CNT的多级孔结构和疏水界面。eCO2RR实验结果表明，CNT的引入提高了催化剂的导电性，优化后的复合材料有效地降低了反应的起始电位。在-1.1 V（相对可逆氢电极（RHE））电位下，CO部分电流密度为15.6 mA·cm-2，ZIF-8-50@CNT催化剂的比表面活性提升了3.5倍（相比ZIF-8-50），塔菲尔斜率降低到136 mV·dec-1。并且产物CO的选择性和稳定性得到了提高，在宽电势窗口-0.9~-1.2 V（vs RHE）内，CO的法拉第效率（FE）保持在80%以上。在10 h稳定性测试中，催化剂活性保持稳定，整体增强了复合材料eCO2RR的性能。
2023, 39(11): 2160-2168
doi: 10.11862/CJIC.2023.179
摘要:
Cu(ClO4)2·6H2O and (1-methyl-1H-benzimidazol-2-yl) methanol (HL) reacted in a mixed solution of methanol and acetonitrile to produce dark blue[Cu(HL)3](ClO4)2·H2O (1) and light blue[Cu(HL)3](ClO4)2 (2). Their structures were characterized by elemental analysis, IR, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. The test results showed that complexes 1 and 2 are both composed of[Cu(HL)3]2+ and the counter anion ClO4-, except for the addition of one free water molecule in 1. The Cu(Ⅱ) ions in 1 and 2 are coordinated with N and O atoms from the HL; the coordination number was six. The results of TGA showed that the structures of 1 and 2 could remain unchanged in a range of 30-245℃. However, complex 1 with a dark blue color had a wider absorption peak at 289 nm compared to 2 with a light blue color. The adsorption experiment showed that 1 exhibited better adsorption performance for Cr(Ⅵ) than 2 at pH=4-8. It can be seen that the free water molecule in 1 has a certain impact on light absorption and the adsorption of Cr(Ⅵ).
Cu(ClO4)2·6H2O and (1-methyl-1H-benzimidazol-2-yl) methanol (HL) reacted in a mixed solution of methanol and acetonitrile to produce dark blue[Cu(HL)3](ClO4)2·H2O (1) and light blue[Cu(HL)3](ClO4)2 (2). Their structures were characterized by elemental analysis, IR, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. The test results showed that complexes 1 and 2 are both composed of[Cu(HL)3]2+ and the counter anion ClO4-, except for the addition of one free water molecule in 1. The Cu(Ⅱ) ions in 1 and 2 are coordinated with N and O atoms from the HL; the coordination number was six. The results of TGA showed that the structures of 1 and 2 could remain unchanged in a range of 30-245℃. However, complex 1 with a dark blue color had a wider absorption peak at 289 nm compared to 2 with a light blue color. The adsorption experiment showed that 1 exhibited better adsorption performance for Cr(Ⅵ) than 2 at pH=4-8. It can be seen that the free water molecule in 1 has a certain impact on light absorption and the adsorption of Cr(Ⅵ).
2023, 39(11): 2169-2180
doi: 10.11862/CJIC.2023.188
摘要:
Bi3OXy(WO6)1-y (X=Cl, Br, I) solid solution materials were successfully prepared by a simple two-step hydrothermal method, which enhanced the adsorption and photocatalytic properties while changing the morphology. The structures and properties of the three composites were characterized in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). Solid solutions were speculated in principle. Compared to the BW monomer, the formation of the BI solid solution in Bi3OXy((WO6)1-y resulted in a decreased band-gap, which led to an enhanced capacity for absorbing visible light. Furthermore, it helped to reduce the recombination rate of electron-hole pairs generated by light. Bi3OXy((WO6)1-y exhibited a strong adsorption capacity for rhodamine B (RhB) cationic dye. Adsorption kinetics of different materials were investigated through adsorption experiments conducted at high concentrations.
Bi3OXy(WO6)1-y (X=Cl, Br, I) solid solution materials were successfully prepared by a simple two-step hydrothermal method, which enhanced the adsorption and photocatalytic properties while changing the morphology. The structures and properties of the three composites were characterized in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). Solid solutions were speculated in principle. Compared to the BW monomer, the formation of the BI solid solution in Bi3OXy((WO6)1-y resulted in a decreased band-gap, which led to an enhanced capacity for absorbing visible light. Furthermore, it helped to reduce the recombination rate of electron-hole pairs generated by light. Bi3OXy((WO6)1-y exhibited a strong adsorption capacity for rhodamine B (RhB) cationic dye. Adsorption kinetics of different materials were investigated through adsorption experiments conducted at high concentrations.
2023, 39(11): 2181-2187
doi: 10.11862/CJIC.2023.187
摘要:
Four isomorphic rare earth complexes[M(Hcpna)(cpna)(H2O)3]n, where M=Dy (1), Ho (2), Er (3), Tm (4), have been synthesized by a solvothermal method based on 5-(4-carboxyphenoxy)nicotinic acid ligand (H2cpna) and rare earth metal ions Dy3+, Ho3+, Er3+, and Tm3+. Single crystal X-ray diffraction analyses reveal that complexes 1, 2, 3, and 4 are isostructural, and the structures are all 1D chain structures. The complexes were characterized by IR, elemental analysis, and powder X-ray diffraction, while the fluorescence and magnetic properties of the complexes were studied. The fluorescence test results show that the fluorescence intensity of complexes 1-4 were all lower than that of the H2cpna ligand. The magnetism of complexes 1-4 were studied in the 2-300 K range at 1 kOe dc field. The χmT values of complexes 1, 2, 3, and 4 were 14.04, 14.15, 11.08, and 6.83 cm3·mol-1·K respectively at room temperature.
Four isomorphic rare earth complexes[M(Hcpna)(cpna)(H2O)3]n, where M=Dy (1), Ho (2), Er (3), Tm (4), have been synthesized by a solvothermal method based on 5-(4-carboxyphenoxy)nicotinic acid ligand (H2cpna) and rare earth metal ions Dy3+, Ho3+, Er3+, and Tm3+. Single crystal X-ray diffraction analyses reveal that complexes 1, 2, 3, and 4 are isostructural, and the structures are all 1D chain structures. The complexes were characterized by IR, elemental analysis, and powder X-ray diffraction, while the fluorescence and magnetic properties of the complexes were studied. The fluorescence test results show that the fluorescence intensity of complexes 1-4 were all lower than that of the H2cpna ligand. The magnetism of complexes 1-4 were studied in the 2-300 K range at 1 kOe dc field. The χmT values of complexes 1, 2, 3, and 4 were 14.04, 14.15, 11.08, and 6.83 cm3·mol-1·K respectively at room temperature.
2023, 39(11): 2188-2196
doi: 10.11862/CJIC.2023.181
摘要:
Based on the energetic ligand 4, 5-bis(tetrazol-5-yl)imidazole (H3BTI), a novel energetic coordination polymer[Co4(HBTI)4(H2O)8] (1) was prepared under hydrothermal conditions. The crystal structure measurement indicates that 1 exhibits a tetranuclear structure with the central ion Co (Ⅱ) adopting octahedral geometry. The non-isothermal kinetic parameters of 1 were determined using two different methods including Kissinger and Ozawa-Doyle. Through the density functional theory (DFT) calculation, its explosive performance was further conducted. Additionally, its friction sensitivity and impact sensitivity were larger than 360 N and 40 J, respectively. Further-more, during the combustion decomposition process, compound 1 could effectively advance the decomposition temperature of ammonium perchlorate (AP) and 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane (RDX) by 25 and 11℃, respectively.
Based on the energetic ligand 4, 5-bis(tetrazol-5-yl)imidazole (H3BTI), a novel energetic coordination polymer[Co4(HBTI)4(H2O)8] (1) was prepared under hydrothermal conditions. The crystal structure measurement indicates that 1 exhibits a tetranuclear structure with the central ion Co (Ⅱ) adopting octahedral geometry. The non-isothermal kinetic parameters of 1 were determined using two different methods including Kissinger and Ozawa-Doyle. Through the density functional theory (DFT) calculation, its explosive performance was further conducted. Additionally, its friction sensitivity and impact sensitivity were larger than 360 N and 40 J, respectively. Further-more, during the combustion decomposition process, compound 1 could effectively advance the decomposition temperature of ammonium perchlorate (AP) and 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane (RDX) by 25 and 11℃, respectively.
2023, 39(11): 2197-2208
doi: 10.11862/CJIC.2023.173
摘要:
A facile precipitation transformation method at room temperature was employed to efficiently prepare the FeTrz@PB heterostructural composites containing both[Fe(Htrz)2(trz)](BF4) (Htrz=1H-1, 2, 4-triazole) and Prussian blue KFeⅢ[FeⅡ(CN)6] with the coexistence of spin crossover (SCO) and long-range magnetic ordering (LRMO). The controllable growth process of these heterostructural composites was fully characterized by scanning electron micro-scope, transmission electron microscope, powder X-ray diffraction, FTIR, X-ray photoelectron spectroscopy, energy-dispersion X-ray analysis, thermogravimetric analysis, and magnetic studies. The size of the PB particles and the appearance of FeTrz@PB can be tuned by controlling the reaction time. Increasing the reaction time leads to the increased ratio of the PB phase in the FeTrz@PB composites. Remarkably, magnetic studies on FeTrz@PB revealed the coexistence of SCO above room temperature (362-392 K) and LRMO at low temperatures (ca. 5.6 K). The high spin (HS) fraction and ZFC/FC intensity gradually increased with the growth time, while the heights of the hysteresis loops decreased gradually.
A facile precipitation transformation method at room temperature was employed to efficiently prepare the FeTrz@PB heterostructural composites containing both[Fe(Htrz)2(trz)](BF4) (Htrz=1H-1, 2, 4-triazole) and Prussian blue KFeⅢ[FeⅡ(CN)6] with the coexistence of spin crossover (SCO) and long-range magnetic ordering (LRMO). The controllable growth process of these heterostructural composites was fully characterized by scanning electron micro-scope, transmission electron microscope, powder X-ray diffraction, FTIR, X-ray photoelectron spectroscopy, energy-dispersion X-ray analysis, thermogravimetric analysis, and magnetic studies. The size of the PB particles and the appearance of FeTrz@PB can be tuned by controlling the reaction time. Increasing the reaction time leads to the increased ratio of the PB phase in the FeTrz@PB composites. Remarkably, magnetic studies on FeTrz@PB revealed the coexistence of SCO above room temperature (362-392 K) and LRMO at low temperatures (ca. 5.6 K). The high spin (HS) fraction and ZFC/FC intensity gradually increased with the growth time, while the heights of the hysteresis loops decreased gradually.
2023, 39(11): 2209-2218
doi: 10.11862/CJIC.2023.176
摘要:
Two new 3D rare-earth molybdate frameworks, [Ln(H2O)3]3[LnMo12O42]·xH2O, where Ln=Eu (1), Tb (2); x=7 (1), 10.17 (2), have been synthesized by slow evaporation. Both of these rare earth molybdate frameworks have a new rare-earth-centered icosahedron[LnMo12O42] building unit, which is further connected to adjacent ones by {LnO9} polyhedra to form a 3D network. Photoluminescence tests reveal that 1 and 2 exhibited different emission properties, which are caused by the f-orbital energy levels of Eu3+ and Tb3+. 1 exhibited bright red emissions (CIE chromaticity coordinates: (0.66, 0.33)) corresponding to the transition from 5D0 to 7FJ (J=4, 3, 2, 1, 0), with high luminescent emission intensity and high quantum yield (about 60%). 2 exhibited light green emissions (CIE chromaticity coordinates: (0.34, 0.60)) corresponding to the transition from 5D4 to 7FJ (J=6, 5, 4, 3), with lower luminescent emission intensity and quantum yield (about 20%). Interestingly, the introduction of Tb and the presence of a large number of solvent molecules in compound 2, both lead to partial fluorescence quenching but have little effect on the fluorescence properties of 1.
Two new 3D rare-earth molybdate frameworks, [Ln(H2O)3]3[LnMo12O42]·xH2O, where Ln=Eu (1), Tb (2); x=7 (1), 10.17 (2), have been synthesized by slow evaporation. Both of these rare earth molybdate frameworks have a new rare-earth-centered icosahedron[LnMo12O42] building unit, which is further connected to adjacent ones by {LnO9} polyhedra to form a 3D network. Photoluminescence tests reveal that 1 and 2 exhibited different emission properties, which are caused by the f-orbital energy levels of Eu3+ and Tb3+. 1 exhibited bright red emissions (CIE chromaticity coordinates: (0.66, 0.33)) corresponding to the transition from 5D0 to 7FJ (J=4, 3, 2, 1, 0), with high luminescent emission intensity and high quantum yield (about 60%). 2 exhibited light green emissions (CIE chromaticity coordinates: (0.34, 0.60)) corresponding to the transition from 5D4 to 7FJ (J=6, 5, 4, 3), with lower luminescent emission intensity and quantum yield (about 20%). Interestingly, the introduction of Tb and the presence of a large number of solvent molecules in compound 2, both lead to partial fluorescence quenching but have little effect on the fluorescence properties of 1.
2023, 39(11): 2219-2230
doi: 10.11862/CJIC.2023.186
摘要:
Under solvothermal conditions, the reaction of 2-pyridinealdoxime (HL) with NiCl2·6H2O and Zn(OAc)2· 2H2O has led to a Ni2ⅡZn2Ⅱ cluster complex with composition[Ni2Zn2(L)4Cl2(CH3O)2] (1). This complex was characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, etc. The results show that 1 belongs to the orthorhombic system with the Pna21 space group. The structure of 1 contains two NiⅡ ions, two ZnⅡ ions, two Cl- ions, four L- ligands, and two CH3O- anions. The magnetic properties and photocatalytic activity toward the degradation of dyes were investigated. Magnetic susceptibility measurements at 2-300 K for the microcrystals of 1 revealed antiferromagnetic NiⅡ⋯NiⅡ interactions. 1 exhibited excellent photocatalytic capability in the degradation of methyl orange (MO) and rhodamine B (RhB) within 180 min under ultraviolet radiation. The degradation efficiencies reached 83.9% and 71.1% respectively. The mechanism of photocatalytic dye degradation was further discussed.
Under solvothermal conditions, the reaction of 2-pyridinealdoxime (HL) with NiCl2·6H2O and Zn(OAc)2· 2H2O has led to a Ni2ⅡZn2Ⅱ cluster complex with composition[Ni2Zn2(L)4Cl2(CH3O)2] (1). This complex was characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, etc. The results show that 1 belongs to the orthorhombic system with the Pna21 space group. The structure of 1 contains two NiⅡ ions, two ZnⅡ ions, two Cl- ions, four L- ligands, and two CH3O- anions. The magnetic properties and photocatalytic activity toward the degradation of dyes were investigated. Magnetic susceptibility measurements at 2-300 K for the microcrystals of 1 revealed antiferromagnetic NiⅡ⋯NiⅡ interactions. 1 exhibited excellent photocatalytic capability in the degradation of methyl orange (MO) and rhodamine B (RhB) within 180 min under ultraviolet radiation. The degradation efficiencies reached 83.9% and 71.1% respectively. The mechanism of photocatalytic dye degradation was further discussed.
2023, 39(11): 2231-2239
doi: 10.11862/CJIC.2023.184
摘要:
In this work, by the reaction of salicylaldoxime (H2Saox), isobutyric acid (HiBuac), and Ti(OiPr)4 the hexanuclear titanium oxo cluster (TOC) of[Ti6(μ3-O)4(Saox)2(iBuac)4(OiPr)8] (1) was solvothermally synthesized, and by the reaction of acetohydroxamic acid (H2Ahox), phenylphosphonic acid (PhPO3H2) and Ti(OiPr)4 the octa-nuclear TOC of[Ti8(μ3-O)2(Ahox)2(PhPO3)4(OiPr)16] (2) was prepared. Both of them were characterized by IR, elemental analyses, and single-crystal X-ray diffraction. Spectral experiments indicate that the two complexes have absorptions in the visible region. The band gaps of complexes 1 and 2 were 2.43 and 2.61 eV respectively. Complex 2 is the first H2Ahox-based TOCs that showed photocatalytic H2 evolution activity with the rate of 140.2 μmol·g-1·h-1.
In this work, by the reaction of salicylaldoxime (H2Saox), isobutyric acid (HiBuac), and Ti(OiPr)4 the hexanuclear titanium oxo cluster (TOC) of[Ti6(μ3-O)4(Saox)2(iBuac)4(OiPr)8] (1) was solvothermally synthesized, and by the reaction of acetohydroxamic acid (H2Ahox), phenylphosphonic acid (PhPO3H2) and Ti(OiPr)4 the octa-nuclear TOC of[Ti8(μ3-O)2(Ahox)2(PhPO3)4(OiPr)16] (2) was prepared. Both of them were characterized by IR, elemental analyses, and single-crystal X-ray diffraction. Spectral experiments indicate that the two complexes have absorptions in the visible region. The band gaps of complexes 1 and 2 were 2.43 and 2.61 eV respectively. Complex 2 is the first H2Ahox-based TOCs that showed photocatalytic H2 evolution activity with the rate of 140.2 μmol·g-1·h-1.
2023, 39(1): 1-12
doi: 10.11862/CJIC.2022.268
摘要:
以多齿席夫碱配体H2L (H2L=(E)-N'-(3-乙氧基-2-羟基亚苄基)-3-羟基吡啶甲酰肼)为配体，与Ln (acac)3·2H2O (Ln=Tb、Ho、Er；acac-=乙酰丙酮根)反应，通过溶剂热法，成功得到了3例新的双核稀土配合物[Ln2(acac)2(L)2(C2H5OH)2](Ln=Tb (1)、Ho (2)、Er (3))。单晶X射线衍射分析表明：配合物1~3的结构主要由2个LnⅢ离子、2个乙酰丙酮根(acac-)、2个L2-及2个C2H5OH组成，中心LnⅢ离子通过2个μ2-O原子相互连接，形成一个平行四边形的Ln2O2核心。固体荧光实验测试结果表明：配合物1在室温下表现出TbⅢ离子的荧光特征发射峰。此外，生物活性研究表明，与配体H2L和稀土离子相比较，配合物1~3具有更强的抗菌活性。采用紫外光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了配合物1~3与小牛胸腺DNA之间的相互作用，结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。
以多齿席夫碱配体H2L (H2L=(E)-N'-(3-乙氧基-2-羟基亚苄基)-3-羟基吡啶甲酰肼)为配体，与Ln (acac)3·2H2O (Ln=Tb、Ho、Er；acac-=乙酰丙酮根)反应，通过溶剂热法，成功得到了3例新的双核稀土配合物[Ln2(acac)2(L)2(C2H5OH)2](Ln=Tb (1)、Ho (2)、Er (3))。单晶X射线衍射分析表明：配合物1~3的结构主要由2个LnⅢ离子、2个乙酰丙酮根(acac-)、2个L2-及2个C2H5OH组成，中心LnⅢ离子通过2个μ2-O原子相互连接，形成一个平行四边形的Ln2O2核心。固体荧光实验测试结果表明：配合物1在室温下表现出TbⅢ离子的荧光特征发射峰。此外，生物活性研究表明，与配体H2L和稀土离子相比较，配合物1~3具有更强的抗菌活性。采用紫外光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了配合物1~3与小牛胸腺DNA之间的相互作用，结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。
2023, 39(1): 13-22
doi: 10.11862/CJIC.2022.259
摘要:
前期采用环境友好方法制备的改性碳化硅颗粒，经较长时间放置，发现其由亲水性转变为超疏水性，接触角为156°。为解释这一新的现象，采用扫描电子显微镜、能谱、(高分辨)透射电子显微镜、X射线光电子能谱(XPS)对原粉碳化硅、改性后碳化硅及久置碳化硅进行了测试与分析。结果显示：改性后碳化硅经较长时间放置，表面胞状颗粒增大并出现凸起物，粗糙度增加，存在类似于荷叶的微纳米结构。改性后颗粒的主要成分为Ni、Si、O，其中凸起处Ni、O元素的含量明显高于凹陷处。Ni颗粒表面出现清晰的膜层，膜层厚度为2~3 nm，但结晶度偏低。XPS测试结果显示金属镍的特征峰正向移动近4 eV，与镍的氧化态特征峰相一致，从而解释了颗粒表面形态发生细小改变，自发形成超疏水膜层的机理。
前期采用环境友好方法制备的改性碳化硅颗粒，经较长时间放置，发现其由亲水性转变为超疏水性，接触角为156°。为解释这一新的现象，采用扫描电子显微镜、能谱、(高分辨)透射电子显微镜、X射线光电子能谱(XPS)对原粉碳化硅、改性后碳化硅及久置碳化硅进行了测试与分析。结果显示：改性后碳化硅经较长时间放置，表面胞状颗粒增大并出现凸起物，粗糙度增加，存在类似于荷叶的微纳米结构。改性后颗粒的主要成分为Ni、Si、O，其中凸起处Ni、O元素的含量明显高于凹陷处。Ni颗粒表面出现清晰的膜层，膜层厚度为2~3 nm，但结晶度偏低。XPS测试结果显示金属镍的特征峰正向移动近4 eV，与镍的氧化态特征峰相一致，从而解释了颗粒表面形态发生细小改变，自发形成超疏水膜层的机理。
2023, 39(1): 23-31
doi: 10.11862/CJIC.2022.257
摘要:
光生电子-空穴对的复合被认为是限制BiVO4材料光电催化转换效率的重要原因之一。基于此，通过简单的水热-煅烧方法构筑了BiVO4/ZnFe2O4同型异质结光阳极，BiVO4/ZnFe2O4复合光阳极在1.23 V (vs RHE)下的光电流密度为3.33 mA·cm-2，较纯BiVO4提升了2倍(1.20 mA·cm-2)。相关的结构及性能测试表明，BiVO4和ZnFe2O4形成了带隙错开的n-n异质结，使得光生载流子得到有效分离，更有效地参与水氧化过程，进而提高了BiVO4的光电催化水分解性能。
光生电子-空穴对的复合被认为是限制BiVO4材料光电催化转换效率的重要原因之一。基于此，通过简单的水热-煅烧方法构筑了BiVO4/ZnFe2O4同型异质结光阳极，BiVO4/ZnFe2O4复合光阳极在1.23 V (vs RHE)下的光电流密度为3.33 mA·cm-2，较纯BiVO4提升了2倍(1.20 mA·cm-2)。相关的结构及性能测试表明，BiVO4和ZnFe2O4形成了带隙错开的n-n异质结，使得光生载流子得到有效分离，更有效地参与水氧化过程，进而提高了BiVO4的光电催化水分解性能。
2023, 39(1): 32-44
doi: 10.11862/CJIC.2022.264
摘要:
通过静电自组装制备有机复合半导体N缺陷g-C3N5(NVs)修饰S掺杂苝酰亚胺(S-PDI)。NVs具有丰富的活性位点，而具有氨基基团的酰胺增强了S-PDI与NVs的分子间作用力。NVs质量分数30%的30% NVs/S-PDI对Cr(Ⅵ)的还原率为79.96%，对苯酚的降解率为74.40%；30% NVs/S-PDI协同氧化苯酚与还原Cr(Ⅵ)过程中，Cr(Ⅵ)的还原率为92.83%，苯酚的降解率为93.89%，即苯酚的氧化降解促进了Cr(Ⅵ)的还原，Cr(Ⅵ)的还原增强了苯酚的氧化降解。NVs/S-PDI充分利用导带的还原性能和价带的氧化性能，实现电子空穴的空间分离，协同强化光催化过程中的氧化半反应和还原半反应，同步提升光催化氧化还原性能。同时，光照产生的电子、H2O2与Cr(Ⅵ)形成一个光自芬顿反应过程，进一步促进了苯酚的氧化降解与Cr(Ⅵ)的还原去除。
通过静电自组装制备有机复合半导体N缺陷g-C3N5(NVs)修饰S掺杂苝酰亚胺(S-PDI)。NVs具有丰富的活性位点，而具有氨基基团的酰胺增强了S-PDI与NVs的分子间作用力。NVs质量分数30%的30% NVs/S-PDI对Cr(Ⅵ)的还原率为79.96%，对苯酚的降解率为74.40%；30% NVs/S-PDI协同氧化苯酚与还原Cr(Ⅵ)过程中，Cr(Ⅵ)的还原率为92.83%，苯酚的降解率为93.89%，即苯酚的氧化降解促进了Cr(Ⅵ)的还原，Cr(Ⅵ)的还原增强了苯酚的氧化降解。NVs/S-PDI充分利用导带的还原性能和价带的氧化性能，实现电子空穴的空间分离，协同强化光催化过程中的氧化半反应和还原半反应，同步提升光催化氧化还原性能。同时，光照产生的电子、H2O2与Cr(Ⅵ)形成一个光自芬顿反应过程，进一步促进了苯酚的氧化降解与Cr(Ⅵ)的还原去除。
2023, 39(1): 45-54
doi: 10.11862/CJIC.2022.263
摘要:
选取溴代噻唑和三乙炔基苯为单体，利用聚合反应自下而上构建含噻唑共轭微孔聚合物(NSCMP)，通过热解和KOH活化热解NSCMP制备了氮、硫杂原子硬炭(NSHC)和活化NSHC (KNSHC)。利用扫描电子显微镜、能量色散谱、氮气吸附-脱附和恒流充放电等表征2个样品的结构与电化学性能。研究表明KNSHC中N和S的质量分数分别为10.42%和2.23%，KNSHC比表面积高达2 140 m2·g-1。在0.2 A·g-1电流密度下循环500次后KNSHC和NSHC的可逆比容量分别为946.2和493.7 mAh·g-1。KNSHC的优异电化学性能归因于其独特的孔结构和氮、硫杂原子的协同作用。
选取溴代噻唑和三乙炔基苯为单体，利用聚合反应自下而上构建含噻唑共轭微孔聚合物(NSCMP)，通过热解和KOH活化热解NSCMP制备了氮、硫杂原子硬炭(NSHC)和活化NSHC (KNSHC)。利用扫描电子显微镜、能量色散谱、氮气吸附-脱附和恒流充放电等表征2个样品的结构与电化学性能。研究表明KNSHC中N和S的质量分数分别为10.42%和2.23%，KNSHC比表面积高达2 140 m2·g-1。在0.2 A·g-1电流密度下循环500次后KNSHC和NSHC的可逆比容量分别为946.2和493.7 mAh·g-1。KNSHC的优异电化学性能归因于其独特的孔结构和氮、硫杂原子的协同作用。
2023, 39(1): 55-62
doi: 10.11862/CJIC.2022.258
摘要:
为考察不同锰源对所制备尖晶石LiMn2O4(LMO)电化学性能的影响(特别是高温性能)，采用沉淀法制备前驱体，通过不同煅烧温度制备得到最常用的锰氧化物(MnO2、Mn2O3和Mn3O4)为锰源，经相同条件制备得到LMO正极材料，通过考察所得LMO形貌及电化学性能来研究锰源与LMO电化学性能的关系。研究结果表明，相同的前驱体在不同煅烧温度下可以得到不同的锰氧化物，且各自具有不同的形貌结构。由这些锰氧化物都可以得到高纯度的LMO，但产物形貌结构以及材料中的八面体晶体含量和尺寸不同。由Mn2O3制备得到的LMO材料中的八面体晶体含量最多，且尺寸最均匀，在3种LMO中容量性能、倍率性能和循环性能最好：0.2C (1C=148 mA·g-1)下首次放电比容量为131.8 mAh·g-1；3C下还有100.4 mAh·g-1的放电比容量。其对应半电池在0.5C下循环100次后，放电比容量还有116.0 mAh·g-1，容量保持率为93.9%，电化学储能性能远远优于其他2种LMO。即使是在高温55℃下，由Mn2O3得到的LMO也表现出明显优于其他2种材料的高倍率性能和抗衰减性能。
为考察不同锰源对所制备尖晶石LiMn2O4(LMO)电化学性能的影响(特别是高温性能)，采用沉淀法制备前驱体，通过不同煅烧温度制备得到最常用的锰氧化物(MnO2、Mn2O3和Mn3O4)为锰源，经相同条件制备得到LMO正极材料，通过考察所得LMO形貌及电化学性能来研究锰源与LMO电化学性能的关系。研究结果表明，相同的前驱体在不同煅烧温度下可以得到不同的锰氧化物，且各自具有不同的形貌结构。由这些锰氧化物都可以得到高纯度的LMO，但产物形貌结构以及材料中的八面体晶体含量和尺寸不同。由Mn2O3制备得到的LMO材料中的八面体晶体含量最多，且尺寸最均匀，在3种LMO中容量性能、倍率性能和循环性能最好：0.2C (1C=148 mA·g-1)下首次放电比容量为131.8 mAh·g-1；3C下还有100.4 mAh·g-1的放电比容量。其对应半电池在0.5C下循环100次后，放电比容量还有116.0 mAh·g-1，容量保持率为93.9%，电化学储能性能远远优于其他2种LMO。即使是在高温55℃下，由Mn2O3得到的LMO也表现出明显优于其他2种材料的高倍率性能和抗衰减性能。
2023, 39(1): 63-70
doi: 10.11862/CJIC.2022.271
摘要:
采用高温固相法合成了一系列Eu2+掺杂的MgY2Al3Si2O11N (MYASON)青光荧光粉。详细探讨了不同制备方法对荧光粉的物相结构和发光强度的影响，利用X射线衍射精修和X射线光电子能谱实验证明Si4+-N3-离子对成功掺入石榴石晶格中。通过荧光光谱、寿命衰减曲线和变温光谱研究了发光性能，研究结果表明，用365 nm紫外光激发MYASON∶Eu2+荧光粉时，在青光区域呈现不对称宽带发射，峰值为490 nm，可以为紫外芯片激发的白光发光二极管有效提供青光成分。
采用高温固相法合成了一系列Eu2+掺杂的MgY2Al3Si2O11N (MYASON)青光荧光粉。详细探讨了不同制备方法对荧光粉的物相结构和发光强度的影响，利用X射线衍射精修和X射线光电子能谱实验证明Si4+-N3-离子对成功掺入石榴石晶格中。通过荧光光谱、寿命衰减曲线和变温光谱研究了发光性能，研究结果表明，用365 nm紫外光激发MYASON∶Eu2+荧光粉时，在青光区域呈现不对称宽带发射，峰值为490 nm，可以为紫外芯片激发的白光发光二极管有效提供青光成分。
2023, 39(1): 71-79
doi: 10.11862/CJIC.2022.265
摘要:
稀土发光传感器可用于有害的有机小分子胺的检测，然而稀土离子较大的离子半径和不稳定的配位构型，使其在固态下对有机小分子胺实现高灵敏性的发光检测具有一定的挑战。通过在单β-二酮配体上引入胺醇识别基团，使其与稀土铕离子通过配位成功构筑了具有可调控配体内电荷转移(ILCT)性质的单核稀土配合物[Eu(L)3(H2O)2](HL=(2Z)-1-(4-(双(2-羟基乙基)氨基)苯基)-4，4，4-三氟-3-羟基丁-2-烯-1-酮)。配合物的传感研究表明，[Eu(L)3(H2O)2]在弱的亲核作用下对三丙胺等有机小分子胺表现出明显的发光增强响应。
稀土发光传感器可用于有害的有机小分子胺的检测，然而稀土离子较大的离子半径和不稳定的配位构型，使其在固态下对有机小分子胺实现高灵敏性的发光检测具有一定的挑战。通过在单β-二酮配体上引入胺醇识别基团，使其与稀土铕离子通过配位成功构筑了具有可调控配体内电荷转移(ILCT)性质的单核稀土配合物[Eu(L)3(H2O)2](HL=(2Z)-1-(4-(双(2-羟基乙基)氨基)苯基)-4，4，4-三氟-3-羟基丁-2-烯-1-酮)。配合物的传感研究表明，[Eu(L)3(H2O)2]在弱的亲核作用下对三丙胺等有机小分子胺表现出明显的发光增强响应。
2023, 39(1): 80-90
doi: 10.11862/CJIC.2022.255
摘要:
以多巴胺、钼酸铵、碳酸氢铵为原料，通过一步煅烧法合成一种MoO2@氮掺杂碳复合物(MoO2@CN)，并利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、拉曼光谱(Raman)等对其进行表征。以卡马西平(CBZ)为目标污染物，以过一硫酸氢钾(PMS)为氧化剂，在温度为25℃、pH为6.5的条件下，MoO2@CN/PMS在12 min内对CBZ的去除率达99.2%，与商用MoO2相比，其表观速率常数kobs(0.393 min-1)是商用MoO2(0.016 4 min-1)的24.0倍，这主要是由于制备的MoO2@CN比商用MoO2具有更好的电子传输能力以及更大的比表面积。MoO2@CN在pH为2.5~10.5时均能有效降解CBZ，而且对大多数染料、酚类化合物、抗生素等多种污染物均具有良好的降解性能。此外，MoO2@CN/PMS在60 min内对CBZ的总有机碳(TOC)去除率高达74.0%。电子顺磁共振波谱(EPR)和自由基猝灭实验显示MoO2@CN/PMS体系中主要起作用是硫酸根自由基(SO4·-)和羟基自由基(·OH)。更有意思的是，在Fe2+/PMS体系加入MoO2@CN后，其催化降解CBZ的性能显著增强，kobs(1.25 min-1)是单独Fe2+/PMS体系(0.079 7 min-1)的15.7倍，这主要归因于MoO2@CN的引入加快了Fe3+到Fe2+的转变，导致更多·OH的生成。
以多巴胺、钼酸铵、碳酸氢铵为原料，通过一步煅烧法合成一种MoO2@氮掺杂碳复合物(MoO2@CN)，并利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、拉曼光谱(Raman)等对其进行表征。以卡马西平(CBZ)为目标污染物，以过一硫酸氢钾(PMS)为氧化剂，在温度为25℃、pH为6.5的条件下，MoO2@CN/PMS在12 min内对CBZ的去除率达99.2%，与商用MoO2相比，其表观速率常数kobs(0.393 min-1)是商用MoO2(0.016 4 min-1)的24.0倍，这主要是由于制备的MoO2@CN比商用MoO2具有更好的电子传输能力以及更大的比表面积。MoO2@CN在pH为2.5~10.5时均能有效降解CBZ，而且对大多数染料、酚类化合物、抗生素等多种污染物均具有良好的降解性能。此外，MoO2@CN/PMS在60 min内对CBZ的总有机碳(TOC)去除率高达74.0%。电子顺磁共振波谱(EPR)和自由基猝灭实验显示MoO2@CN/PMS体系中主要起作用是硫酸根自由基(SO4·-)和羟基自由基(·OH)。更有意思的是，在Fe2+/PMS体系加入MoO2@CN后，其催化降解CBZ的性能显著增强，kobs(1.25 min-1)是单独Fe2+/PMS体系(0.079 7 min-1)的15.7倍，这主要归因于MoO2@CN的引入加快了Fe3+到Fe2+的转变，导致更多·OH的生成。
2023, 39(1): 91-97
doi: 10.11862/CJIC.2022.270
摘要:
在水热晶种法基础上采用两步变温晶化以高水硅比(nH2O/nSiO2)稀溶液配方为合成液，研制用于渗透汽化(PV)乙酸脱水的丝光沸石膜(MOR膜)，考察了变温晶化各段时间、水硅比与氟离子对MOR膜的形貌与分离性能的影响规律。结果表明：高温段晶化时间、水硅比与氟离子对MOR膜的形貌、结晶度和膜层厚度产生显著影响，并影响MOR膜渗透气化分离性能；在高温段(150℃)和低温段(120℃)的晶化时间分别为18和6 h，在水硅比为60且含氟离子体系中所制备的MOR膜的性能最佳，其对质量分数50%的乙酸水溶液的渗透通量和分离系数分别为1.45 kg·m-2·h-1和1 008。
在水热晶种法基础上采用两步变温晶化以高水硅比(nH2O/nSiO2)稀溶液配方为合成液，研制用于渗透汽化(PV)乙酸脱水的丝光沸石膜(MOR膜)，考察了变温晶化各段时间、水硅比与氟离子对MOR膜的形貌与分离性能的影响规律。结果表明：高温段晶化时间、水硅比与氟离子对MOR膜的形貌、结晶度和膜层厚度产生显著影响，并影响MOR膜渗透气化分离性能；在高温段(150℃)和低温段(120℃)的晶化时间分别为18和6 h，在水硅比为60且含氟离子体系中所制备的MOR膜的性能最佳，其对质量分数50%的乙酸水溶液的渗透通量和分离系数分别为1.45 kg·m-2·h-1和1 008。
2023, 39(1): 98-108
doi: 10.11862/CJIC.2022.281
摘要:
构建氧空位以及附着金属单质Bi (Bi0)是增强半导体材料光吸收性能、促进半导体光生载流子分离的有效方法。通过简单的共沉淀法及氢气热还原成功制备了PO43-掺杂Bi2O2CO3附着Bi0(Bi-P-BOC)的可见光催化剂，并对其在可见光下催化降解氧氟沙星(OFX)的性能及机理进行了研究。材料表征结果表明BOC随着PO43-的均匀掺杂，可见光吸收能力增强，表面缺陷增多，比表面积增大。而随着氢气热还原，BOC表面形成Bi0的同时也原位构建了大量的氧空位。可见光催化性能测试表明，Bi-P-BOC可以在180 min内降解约85%的OFX，降解速率为0.013 0 min-1，是BOC降解速率的8倍。Bi-P-BOC光催化降解机理表明其具有更好的可见光吸收能力，Bi0以及氧空位的存在促进了光生载流子的分离，h+是其光催化降解过程中的主要的活性氧物种(ROS)，此外，1O2和·O2-也对降解有一定贡献。
构建氧空位以及附着金属单质Bi (Bi0)是增强半导体材料光吸收性能、促进半导体光生载流子分离的有效方法。通过简单的共沉淀法及氢气热还原成功制备了PO43-掺杂Bi2O2CO3附着Bi0(Bi-P-BOC)的可见光催化剂，并对其在可见光下催化降解氧氟沙星(OFX)的性能及机理进行了研究。材料表征结果表明BOC随着PO43-的均匀掺杂，可见光吸收能力增强，表面缺陷增多，比表面积增大。而随着氢气热还原，BOC表面形成Bi0的同时也原位构建了大量的氧空位。可见光催化性能测试表明，Bi-P-BOC可以在180 min内降解约85%的OFX，降解速率为0.013 0 min-1，是BOC降解速率的8倍。Bi-P-BOC光催化降解机理表明其具有更好的可见光吸收能力，Bi0以及氧空位的存在促进了光生载流子的分离，h+是其光催化降解过程中的主要的活性氧物种(ROS)，此外，1O2和·O2-也对降解有一定贡献。
2023, 39(1): 109-116
doi: 10.11862/CJIC.2022.261
摘要:
以二氰二胺、硒粉和钨酸钠为前驱体，采用一锅法成功制备出Se掺杂WO3·0.5H2O/g-C3N4(Se/WCN)催化剂。并采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)和X射线光电子能谱(XPS)对样品的物相结构、形貌及化学组成进行表征。与原始的WO3和g-C3N4相比，Se/WCN催化剂的起始电位降到了-0.75 V (vs RHE)，电流密度高达70 mA·cm-2，表现出更高的电催化活性。而光照后，Se/WCN的催化性能进一步提升，起始电位从-0.75 V (vs RHE)降至-0.65 V (vs RHE)，电荷转移电阻由371.4 Ω减小到310.0 Ω。
以二氰二胺、硒粉和钨酸钠为前驱体，采用一锅法成功制备出Se掺杂WO3·0.5H2O/g-C3N4(Se/WCN)催化剂。并采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)和X射线光电子能谱(XPS)对样品的物相结构、形貌及化学组成进行表征。与原始的WO3和g-C3N4相比，Se/WCN催化剂的起始电位降到了-0.75 V (vs RHE)，电流密度高达70 mA·cm-2，表现出更高的电催化活性。而光照后，Se/WCN的催化性能进一步提升，起始电位从-0.75 V (vs RHE)降至-0.65 V (vs RHE)，电荷转移电阻由371.4 Ω减小到310.0 Ω。
2023, 39(1): 117-126
doi: 10.11862/CJIC.2022.282
摘要:
设计、合成了2种配合物：[Ca (Phen)(Nap)2]n(1)和[Mn2(Phen)2(Nap)4(H2O)](2)(Phen=菲咯啉，HNap=1-萘甲酸)。通过红外光谱、元素分析、X射线单晶衍射和热重对其进行了结构表征。测定了配合物的激发光谱、发射光谱，以及配合物对人肺癌细胞(NCI-H460)、人乳腺癌细胞(MCF-7)、人肝癌细胞(HepG2)的体外抑制活性；利用紫外吸收光谱、荧光分光光度法研究了配合物与小牛胸腺DNA的相互作用。结果表明：配合物1、2的激发光谱和发射光谱具有很好的镜像关系，且配合物2的斯托克斯位移大于配合物1；配合物对3种癌细胞都有较好的抑制作用，但是2更优于1；配合物1和2与小牛胸腺DNA以静电作用发生沟面结合，结合常数分别为5.83×103和6.46×103 L·mol-1。
设计、合成了2种配合物：[Ca (Phen)(Nap)2]n(1)和[Mn2(Phen)2(Nap)4(H2O)](2)(Phen=菲咯啉，HNap=1-萘甲酸)。通过红外光谱、元素分析、X射线单晶衍射和热重对其进行了结构表征。测定了配合物的激发光谱、发射光谱，以及配合物对人肺癌细胞(NCI-H460)、人乳腺癌细胞(MCF-7)、人肝癌细胞(HepG2)的体外抑制活性；利用紫外吸收光谱、荧光分光光度法研究了配合物与小牛胸腺DNA的相互作用。结果表明：配合物1、2的激发光谱和发射光谱具有很好的镜像关系，且配合物2的斯托克斯位移大于配合物1；配合物对3种癌细胞都有较好的抑制作用，但是2更优于1；配合物1和2与小牛胸腺DNA以静电作用发生沟面结合，结合常数分别为5.83×103和6.46×103 L·mol-1。
2023, 39(1): 127-134
doi: 10.11862/CJIC.2022.260
摘要:
二水合氧化钨(WO3·2H2O)因其独特的层状结构且富含层间结构水，与无水WO3相比显示出更加优异的电致变色性能。我们采用简单、无模板的阴极电化学沉积方法，成功在氧化铟锡(ITO)导电玻璃基底上制备了WO3·2H2O薄膜。通过改变电沉积液中过氧化氢(H2O2)的加入量优化沉积液的成分，获得了具有纳米多孔结构的薄膜。由此制备的WO3·2H2O薄膜显示出大的光学对比度(633 nm处的光学对比度大于90%)、快速的响应速度(着色、褪色时间均小于10 s)，以及良好的循环稳定性(经10 000次循环后，光学对比度仍保持在90%左右)。
二水合氧化钨(WO3·2H2O)因其独特的层状结构且富含层间结构水，与无水WO3相比显示出更加优异的电致变色性能。我们采用简单、无模板的阴极电化学沉积方法，成功在氧化铟锡(ITO)导电玻璃基底上制备了WO3·2H2O薄膜。通过改变电沉积液中过氧化氢(H2O2)的加入量优化沉积液的成分，获得了具有纳米多孔结构的薄膜。由此制备的WO3·2H2O薄膜显示出大的光学对比度(633 nm处的光学对比度大于90%)、快速的响应速度(着色、褪色时间均小于10 s)，以及良好的循环稳定性(经10 000次循环后，光学对比度仍保持在90%左右)。
2023, 39(1): 135-140
doi: 10.11862/CJIC.2022.276
摘要:
Two ternary lanthanide complexes, [Eu(L)3(Phen)]2·2H2O (1) and [Tb(L)3(Phen)]2·2H2O (2), based on 3-((4, 6-dimethyl-2-pyrimidinyl)thio)-propanoic acid (HL) and 1, 10-phenanthroline (Phen) were prepared and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isostructural. Two lanthanide ions (Ln) are bridged by four carboxylate ligands. The rest two carboxylate ligands and Phen coordinate with Ln with bidentate chelating mode, forming the dimeric arrangement. The coordination number of Ln is nine with a distorted mono-capped square antiprismatic coordination polyhedron. The solid-state photoluminescent measurements suggest that both complexes showcase the characteristic emission bands of the metal center.
Two ternary lanthanide complexes, [Eu(L)3(Phen)]2·2H2O (1) and [Tb(L)3(Phen)]2·2H2O (2), based on 3-((4, 6-dimethyl-2-pyrimidinyl)thio)-propanoic acid (HL) and 1, 10-phenanthroline (Phen) were prepared and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isostructural. Two lanthanide ions (Ln) are bridged by four carboxylate ligands. The rest two carboxylate ligands and Phen coordinate with Ln with bidentate chelating mode, forming the dimeric arrangement. The coordination number of Ln is nine with a distorted mono-capped square antiprismatic coordination polyhedron. The solid-state photoluminescent measurements suggest that both complexes showcase the characteristic emission bands of the metal center.
2023, 39(1): 141-149
doi: 10.11862/CJIC.2022.272
摘要:
A binuclear monofunctional platinum(Ⅱ) complex, [Pt2(BPA-TPA)Cl2]Cl2 (Pt2-BPA-TPA), containing polypyridyl ligand 2, 6-bis((bis(pyridin-2-ylmethyl)amino)methyl)pyridine was synthesized and characterized by nuclear magnetic resonance and high-resolution mass spectroscopy. In addition, the structure of Pt2-BPA-TPA was determined by X-ray single-crystal diffraction. Agarose gel electrophoresis experiments were used to demonstrate the efficient pBR322 DNA-cleaving activity of Pt2-BPA-TPA at a low concentration of 10 μmol·L-1. In CCK-8 (cell counting kit-8) cytotoxicity studies using the A549 human lung cancer cell line, Pt2-BPA-TPA demonstrated enhanced anticancer activity compared with cisplatin. Mechanistic studies provided evidence that Pt2-BPA-TPA induces apoptosis via triggering DNA damage and upregulating downstream cellular signaling cascades of p21 and cleaved-caspase-3.
A binuclear monofunctional platinum(Ⅱ) complex, [Pt2(BPA-TPA)Cl2]Cl2 (Pt2-BPA-TPA), containing polypyridyl ligand 2, 6-bis((bis(pyridin-2-ylmethyl)amino)methyl)pyridine was synthesized and characterized by nuclear magnetic resonance and high-resolution mass spectroscopy. In addition, the structure of Pt2-BPA-TPA was determined by X-ray single-crystal diffraction. Agarose gel electrophoresis experiments were used to demonstrate the efficient pBR322 DNA-cleaving activity of Pt2-BPA-TPA at a low concentration of 10 μmol·L-1. In CCK-8 (cell counting kit-8) cytotoxicity studies using the A549 human lung cancer cell line, Pt2-BPA-TPA demonstrated enhanced anticancer activity compared with cisplatin. Mechanistic studies provided evidence that Pt2-BPA-TPA induces apoptosis via triggering DNA damage and upregulating downstream cellular signaling cascades of p21 and cleaved-caspase-3.
2023, 39(1): 150-158
doi: 10.11862/CJIC.2022.280
摘要:
To explore the potential applications of AlN in optoelectronic devices, the electronic structure and optical properties of AlN with different Lu doping concentrations (denoted as Al1-xLuxN, where x is the atomic fraction of Lu) were calculated by first-principles. The results show that the supercell volume of Al1-xLuxN increases with the increase of Lu doping concentration, while the bandgap does the opposite. The static dielectric constant of Al1-xLuxN increases in the low-energy region with the increase of Lu doping concentration. As Lu doping concentration increases, the peak intensity of reflectivity, refractive index, and absorption coefficient decrease, and the peaks shift to lower energy. The energy-loss spectra of Al1-xLuxN exhibit obvious plasma oscillation features, and the peaks are lower than that of the intrinsic AlN. The photoconductivity of Al1-xLuxN increases sharply in the low-energy region with the increase of energy.
To explore the potential applications of AlN in optoelectronic devices, the electronic structure and optical properties of AlN with different Lu doping concentrations (denoted as Al1-xLuxN, where x is the atomic fraction of Lu) were calculated by first-principles. The results show that the supercell volume of Al1-xLuxN increases with the increase of Lu doping concentration, while the bandgap does the opposite. The static dielectric constant of Al1-xLuxN increases in the low-energy region with the increase of Lu doping concentration. As Lu doping concentration increases, the peak intensity of reflectivity, refractive index, and absorption coefficient decrease, and the peaks shift to lower energy. The energy-loss spectra of Al1-xLuxN exhibit obvious plasma oscillation features, and the peaks are lower than that of the intrinsic AlN. The photoconductivity of Al1-xLuxN increases sharply in the low-energy region with the increase of energy.
2023, 39(1): 159-167
doi: 10.11862/CJIC.2022.277
摘要:
The organic substance 2,5-dibromoterephthalic acid (H2L1) was used as the primary ligand and 2,2'-bipyridine (L2) and 1,10-phenanthroline (L3) as the secondary ligands, respectively, and reacted with manganese sulphate monohydrate and cobalt nitrate hexahydrate by the solvothermal method to give complexes [Mn2(L1)2(L2)2 (H2O)2]n (1) and [Co2(L1)2(L3)2(H2O)2]n (2). The two complexes were investigated analytically by such as single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, etc. The results show that complex 1 is composed of Mn2+ coordination linking L12- and L2 to form an infinitely extended 2D network-like structure, with the layers forming a 3D network-like structure under intermolecular hydrogen bonding and π-π stacking. Complex 2 consists of Co2+ ligated to L12- and L3 to form an infinitely extended 2D network, with the layers stacked in a 3D network by intermolecular hydrogen bonding and π -π stacking. Both complexes had good fluorescence property and thermal stability, and the maximum emission wavelengths of complexes 1 and 2 were 355 and 365 nm, respectively.
The organic substance 2,5-dibromoterephthalic acid (H2L1) was used as the primary ligand and 2,2'-bipyridine (L2) and 1,10-phenanthroline (L3) as the secondary ligands, respectively, and reacted with manganese sulphate monohydrate and cobalt nitrate hexahydrate by the solvothermal method to give complexes [Mn2(L1)2(L2)2 (H2O)2]n (1) and [Co2(L1)2(L3)2(H2O)2]n (2). The two complexes were investigated analytically by such as single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, etc. The results show that complex 1 is composed of Mn2+ coordination linking L12- and L2 to form an infinitely extended 2D network-like structure, with the layers forming a 3D network-like structure under intermolecular hydrogen bonding and π-π stacking. Complex 2 consists of Co2+ ligated to L12- and L3 to form an infinitely extended 2D network, with the layers stacked in a 3D network by intermolecular hydrogen bonding and π -π stacking. Both complexes had good fluorescence property and thermal stability, and the maximum emission wavelengths of complexes 1 and 2 were 355 and 365 nm, respectively.
2023, 39(1): 168-180
doi: 10.11862/CJIC.2022.273
摘要:
Two cadmium-based coordination polymers [Cd(Htatb) (1,4-bimb)] ·H2O (1) and [Cd(Htatb) (1,4-bib) (H2O)]·DMF (2) (H3tatb=4, 4', 4″-s-triazine-2,4,6-tribenzoic acid, 1,4-bimb=1,4-bis(imidazole-1-ylmethyl) benzene, 1,4-bib=1,4-bis(1-imidazoly) benzene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy, elemental analysis, etc. 1 displays a 2D layer structure, further these layers are joined by O—H⋯O hydrogen bonding to generate a four-fold interpenetrating 3D architecture. 2 shows a 2D layer structure, further joined through O—H⋯O hydrogen bonding to produce a two-fold interpenetrating 3D architecture. Complexes 1 and 2 had fluorescent properties. 1 was highly selective and sensitive towards nitrobenzene and Fe3+ ion through different detection mechanisms, while CP 2 was highly selective and sensitive towards 2,4,6-trinitrophenol and CrO42- ion.
Two cadmium-based coordination polymers [Cd(Htatb) (1,4-bimb)] ·H2O (1) and [Cd(Htatb) (1,4-bib) (H2O)]·DMF (2) (H3tatb=4, 4', 4″-s-triazine-2,4,6-tribenzoic acid, 1,4-bimb=1,4-bis(imidazole-1-ylmethyl) benzene, 1,4-bib=1,4-bis(1-imidazoly) benzene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy, elemental analysis, etc. 1 displays a 2D layer structure, further these layers are joined by O—H⋯O hydrogen bonding to generate a four-fold interpenetrating 3D architecture. 2 shows a 2D layer structure, further joined through O—H⋯O hydrogen bonding to produce a two-fold interpenetrating 3D architecture. Complexes 1 and 2 had fluorescent properties. 1 was highly selective and sensitive towards nitrobenzene and Fe3+ ion through different detection mechanisms, while CP 2 was highly selective and sensitive towards 2,4,6-trinitrophenol and CrO42- ion.
2023, 39(1): 181-190
doi: 10.11862/CJIC.2022.278
摘要:
Two Mg-based metal-organic frameworks (MOFs) were prepared using a coordination competition strategy. Under acidic conditions, the reaction of Mg(Ⅱ) ions with formic acid generated from the thermal decomposition of N, N-dimethylformamide (DMF) formed a 3D formate Mg-MOF: [Mg3(HCO2)6]·DMF (1). However, under the same conditions but with a competing ligand 1,1'∶3',1″-terphenyl-3,3″,5, 5″-tetracarboxylic acid (H4L), formic acid was no longer involved in the coordination, resulting in a new 3D Mg-MOF: [Mg2(L) (H2O)3]·2H2O·2CH3CN·DMF (2). Single-crystal X-ray analysis revealed that 1 possesses [Mg4@Mg2] tetrahedral building units that form a dia topological network with a 1D channel size of 0.44 nm. In contrast, 2 has a unique [Mg2] binuclear cluster to build a sra topology network after bridging the 4-connected L4- linker. Interestingly, a dumbbell-shaped pore with a length of 1.42 nm is observed along the a-axis in 2. Gas adsorption studies reveal that 1 had a significantly accessible inner surface with a surface area of 342 m2·g-1. However, after solvent removal, 2 could not retain the original porous character. Featuring good water stability, 1 exhibited a type-Ⅰ CO2 adsorption isotherm with quick uptake at low pressure, and up to 14.5% of the sample weight at 298 K and 2 000 kPa. Ideal adsorption solution theory (IAST) and adsorption heat calculations show that 1 has a good ability for selective CO2 capture from CH4 contained mixture.
Two Mg-based metal-organic frameworks (MOFs) were prepared using a coordination competition strategy. Under acidic conditions, the reaction of Mg(Ⅱ) ions with formic acid generated from the thermal decomposition of N, N-dimethylformamide (DMF) formed a 3D formate Mg-MOF: [Mg3(HCO2)6]·DMF (1). However, under the same conditions but with a competing ligand 1,1'∶3',1″-terphenyl-3,3″,5, 5″-tetracarboxylic acid (H4L), formic acid was no longer involved in the coordination, resulting in a new 3D Mg-MOF: [Mg2(L) (H2O)3]·2H2O·2CH3CN·DMF (2). Single-crystal X-ray analysis revealed that 1 possesses [Mg4@Mg2] tetrahedral building units that form a dia topological network with a 1D channel size of 0.44 nm. In contrast, 2 has a unique [Mg2] binuclear cluster to build a sra topology network after bridging the 4-connected L4- linker. Interestingly, a dumbbell-shaped pore with a length of 1.42 nm is observed along the a-axis in 2. Gas adsorption studies reveal that 1 had a significantly accessible inner surface with a surface area of 342 m2·g-1. However, after solvent removal, 2 could not retain the original porous character. Featuring good water stability, 1 exhibited a type-Ⅰ CO2 adsorption isotherm with quick uptake at low pressure, and up to 14.5% of the sample weight at 298 K and 2 000 kPa. Ideal adsorption solution theory (IAST) and adsorption heat calculations show that 1 has a good ability for selective CO2 capture from CH4 contained mixture.
