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SAPO-18分子筛晶化机理及其甲醇制烯烃性能
郭云鸦, 梁光华, 张燕挺, 何祖光, 梁亚凝, 李宁, 李晓峰, 窦涛
2019, 35(2): 185-193  doi: 10.11862/CJIC.2019.044
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摘要:
分别以拟薄水铝石、硅溶胶、磷酸为铝源、硅源、磷源,NN-二异丙基乙胺为模板,采用水热法制备出不同晶化时间下的SAPO-18分子筛。采用X射线衍射(XRD)、电子扫描显微镜(SEM)、氨气程序升温脱附(NH3-TPD)、固体核磁共振(29Si MAS NMR,27Al MAS NMR)、傅里叶红外(FT-IR)等对不同晶化时间下的产物进行表征以及甲醇制烯烃(MTO)催化性能检测。表征结果结合MTO催化反应性能表明:水热体系下SAPO-18分子筛生长过程可分为3个阶段:晶化初期(≤ 2 h),快速生长期(6~12 h),生长稳定期(1~3 d)。其中,在晶化初期只有极少量的硅进入Al(PO)4类中间体;此后为快速生长期,硅原子进入Al(PO)4类中间体及SAPO-18晶体取代磷、铝原子,以SMⅡ机制为主,SMⅢ机制为辅;在生长稳定期2种取代机制主次发生了变化。
以[Eu(PBrBA)3phen]和[Eu(PCBA)3phen]为探针的温敏漆制备及其性能对比
毕冠, 孙晶, 周晨, 于文生, 王媛, 唐娟
2019, 35(2): 203-208  doi: 10.11862/CJIC.2019.029
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以氧化铕(Eu2O3)、对氯苯甲酸(PCBA)、对溴苯甲酸(PBrBA)和菲咯啉(phen)为原料制备了菲咯啉对氯苯甲酸铕[Eu(PCBA)3 phen]、菲咯啉对溴苯甲酸铕[Eu(PBrBA)3phen]两种探针分子,并将这2种探针分子掺杂在甲基丙烯酸甲酯(MMA)中,以过氧化苯甲酰(BPO)为引发剂,制得Eu(PCBA)3phen/PMMA和Eu(PBrBA)3phen/PMMA温敏漆样品。利用红外光谱仪、扫描电子显微镜、紫外-可见分度光度计和荧光光谱仪对探针分子的组成结构、发光性能、形貌和温敏漆的温度敏感性进行了测试分析,研究了不同配体对探针分子发光性能和温敏漆性能的影响。结果表明,Eu3+分别与对氯苯甲酸(PCBA)和对溴苯甲酸(PBrBA)2种主配体配位,并且第二配体菲咯啉(phen)均参与了配位,成功合成了2种配合物。2种配合物均发出Eu3+的特征荧光,其中以PBrBA为主配体的菲咯啉铕三元配合物具有更好的发光性能。此外,基于这2种探针分子制备的温敏漆在50~90℃范围内均具有温度猝灭性能,以Eu(PCBA)3phen为探针制成的温敏漆温度敏感性更强。
磷灰石结构荧光粉Ba10(PO4)6F2:Ce3+, Tb3+的合成、发光和能量传递
程少文, 张娜, 卓宁泽, 朱月华, 陈永浩, 蒋鹏, 杜文慧, 叶恩淦, 王海波
2019, 35(2): 209-216  doi: 10.11862/CJIC.2019.038
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采用高温固相法合成了系列Ce3+和Ce3+/Tb3+激活的具有磷灰石结构荧光粉Ba10(PO46F2。用X射线衍射(XRD)、扫描电镜(SEM)、激发和发射(PLE和PL)光谱对样品进行了表征分析。研究结果表明:所合成的荧光粉Ba10(PO46F2:Ce3+,Tb3+具有氟磷灰石结构,样品微观呈现不规则形貌。荧光粉Ba10-x(PO46F2xCe3+的相对发射强度随着x增加而增强,当x=0.09时,荧光强度达到最大。荧光粉Ba10(PO46F2:Ce3+,Tb3+的激发光谱为240~330 nm的宽带,发射光谱呈现出Ce3+的5d→4f跃迁紫外光(335和358 nm)发射和Tb3+的4f→4f跃迁绿光(542 nm)发射。光谱特性表明,发光过程中存在Ce3+→Tb3+能量传递,能量传递效率可以达到60%。计算Ce3+和Tb3+的临界距离为0.79 nm,能量传递机理是偶极-偶极交互作用。此外,详细论述了Ce3+和Tb3+之间的能量传递和发光的过程。通过调节Tb3+的掺杂浓度,对荧光粉发光色坐标与Tb3+的掺杂浓度之间的关系也进行了研究,随着Tb3+的掺杂量从0增加0.52,荧光粉Ba10(PO46F2:Ce3+,Tb3+的发射光谱色坐标可以从(0.149 4,0.045 1)蓝色区变化到(0.280 1,0.585 3)绿色区。
碳纳米管改性g-C3N4提升可见光催化降解性能
王鹏, 李昭, 周颖梅, 徐艳, 朱捷, 王士凡, 蔡可迎, 李靖, 堵锡华, 杨朋举
2019, 35(2): 217-224  doi: 10.11862/CJIC.2019.022
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以尿素为原料,引入少量的多壁碳纳米管(CNT)改性,采用简便方法制备CNT/g-C3N4催化剂。利用扫描电镜(SEM)、透射电镜(TEM)、傅里叶红外光谱仪(FT-IR)、X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见-近红外分光光度计(UV-Vis-NIR Spectrophotometer)、荧光光谱(PL)等手段对CNT/g-C3N4催化剂进行表征。结果表明,g-C3N4与CNT之间的协同作用,影响了g-C3N4的能带结构,增强了其对可见光的吸收,改善了光生载流子的分布,提高了电子-空穴对的分离效率。并以罗丹明B(RhB)水溶液模拟废水,在可见光下考察催化剂的光催化降解性能,发现当CNT掺杂量为0.1%(w/w)时效果最佳,降解速率常数是体相g-C3N4的3.1倍,且研究发现超氧自由基是该体系下的主要活性物种。
系列Ag-Ln配位聚合物的合成、结构及发光性能
王岩, 陈飞霏, 胡晓双, 赵然, 迟玉贤, 金晶
2019, 35(2): 225-235  doi: 10.11862/CJIC.2019.014
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采用水热合成法,以吡嗪-2-羧酸(2-Hpzc)、3,5-吡啶二羧酸(3,5-H2PDA)和草酸(H2ox)为配体,合成9种Ag-Ln配位聚合物:{[LnAg(2-pzc)2(ox)]·H2O}n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H2O)]n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)0.5(H2O)2]n(Ln=Sm(7),Dy(8),Ho(9))。配位聚合物1~4是同构的,由2-pzc-和ox2-连接,而配位聚合物5~9是以3,5-PDA2-和ox2-为桥联配体,均呈现3D网状结构。光物理性能研究表明配位聚合物均表现出Ln(Ⅲ)的特征发射,这可归因于Ag-配体部分(d-block)的敏化作用。另外,在晶体场和Ag(Ⅰ)离子4d轨道的共同作用下,Ln(Ⅲ)离子的4f轨道被调谐,使部分能级发生明显的位移,表现为相应NIR发射带的位移,在其UV-Vis-NIR吸收光谱中可以得到佐证。
凹凸棒石/g-C3N4-AgFeO2复合材料制备及其光催化性能
谢登裕, 蒋亿, 纪媛媛, 殷明慧, 盛振环, 赵伟, 殷竟洲, 李乔琦, 仲慧, 张莉莉
2019, 35(2): 236-244  doi: 10.11862/CJIC.2019.040
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以凹凸棒石(简称凹土,ATP)为基体,通过原位化学法一步直接合成g-C3N4薄层材料,并将其有效固载于凹土表面(ATP/g-C3N4),再通过原位沉淀法引入不同比例AgFeO2纳米颗粒,构筑系列兼具磁分离特性和高效光催化活性的ATP/g-C3N4-AgFeO2-Y复合光催化剂(Y=wATP/g-C3N4/(wATP/g-C3N4+wAgFO2)×100%,表示ATP/g-C3N4在ATP/g-C3N4-AgFeO2复合材料中所占的质量百分数)。采用XRD、SEM、BET、UV-Vis、PL和ICP表征其结构和物化性能,以酸性红G(ARG)为目标降解物,研究其光催化性能。研究发现:通过形成Si-O-C键,g-C3N4薄层被均匀固定在凹土表面;AgFeO2纳米颗粒均匀沉积于ATP/g-C3N4表面并形成Z型异质结,ATP/g-C3N4-AgFeO2-Y具有比ATP/g-C3N4和AgFeO2更优异的可见光光催化性能,且随着ATP/g-C3N4含量的增大呈先升高而后下降的趋势;当Y=57%时复合材料的性能最佳,ATP/g-C3N4-AgFeO2-57%对20 mg·L-1酸性红G的降解率可达97.4%,循环4次使用后,降解率仍保持94.2%。通过自由基捕获实验研究了光催化反应机理,发现·O2-是光催化过程的主要活性物种。
Pr1-xSrCo0.5Ni0.5O4+δ阴极材料的合成及电化学性质
刘建伟, 孙丽萍, 赵辉, 霍丽华
2019, 35(2): 245-253  doi: 10.11862/CJIC.2019.030
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采用固相法合成中温固体氧化物燃料电池(IT-SOFC)阴极材料Pr1-xSrCo0.5Ni0.5O4+δ(P1-xSCN,x=0.00,0.05,0.10,0.15,0.20),并对材料的物相、热膨胀系数(TEC)、电导率、电极的微观形貌以及电化学性质进行表征。XRD结果表明,该材料形成单一的K2NiF4结构,空间群为I4/mmm,并与电解质材料Ce0.9Gd0.1O1.95(CGO)具有良好的高温化学相容性。碘量法分析表明随着Pr离子缺位浓度增加,P1-xSCN中Co/Ni离子平均化合价随着x的增加而升高,至x=0.10后逐渐降低,而氧空位含量逐渐升高。引入Pr离子缺位使材料的电导率明显提高,其中P0.90SCN在700℃空气中电导率值为309 S·cm-1。TEC测试结果显示,随着Pr缺位的增加,热膨胀系数逐渐增大,最大值为1.51×10-5 K-1。交流阻抗谱(EIS)测试结果表明,Pr缺位明显降低了电极的极化阻抗值,P0.90SCN阴极在700℃空气中的极化阻抗值为0.21 Ω·cm2。电解质支撑NiO-CGO/CGO/P0.90SCN单电池在700℃最大输出功率密度为197.8 mW·cm-2
g-C3N4/双钙钛矿复合材料的制备及氧催化性能
王成, 黄红霞, 肖阳, 梁大铭
2019, 35(2): 254-262  doi: 10.11862/CJIC.2019.033
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通过溶胶-凝胶法制备出不同Ni掺杂比例的双钙钛矿Sr2NixCo2-xO6x=0.2,0.4,0.6,0.8),通过热分解法制备出具有层状结构的纳米颗粒g-C3N4,并制备其复合物催化剂。将双钙钛矿和g-C3N4分别制备成双功能电极片,用于测试其对氧还原(ORR)和氧析出(OER)的催化活性,然后选取具有最佳氧催化活性的Ni掺杂比例x=0.4的双钙钛矿与一定重量比例的g-C3N4进行复合,测试复合催化剂的氧催化活性。结果表明,复合后的催化剂催化效果明显优于单一催化剂,当g-C3N4添加量占双钙钛矿的30%(w/w)时复合催化剂催化氧还原反应的最大电流密度为395.7 mA·cm-2(-0.6 V vs Hg/HgO),氧析出反应的最大电流密度为372.0 mA·cm-2(1 V vs Hg/HgO),这表明g-C3N4与Sr2Ni0.4Co1.6O6复合后协同催化能够提高双钙钛矿的氧催化活性。
Bi/BiVO4&Bi4V2O11复合催化剂的制备及其光催化性能
梁梦君, 邓楠, 向心怡, 梅英, 杨志远, 杨赟, 杨水金
2019, 35(2): 263-270  doi: 10.11862/CJIC.2019.028
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经由溶剂热反应、光辅助还原过程制备Bi/BiVO4&Bi4V2O11纳米复合光催化材料。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨率透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、N2吸附-脱附等温线和光致发光(PL)等手段对该复合物进行表征。实验结果表明当金属Bi与BiVO4&Bi4V2O11的质量比值为0.8,可见光照射30 min时,Bi/BiVO4&Bi4V2O11复合催化剂对罗丹明B(RhB)的降解率可达95.6%。此外,Bi/BiVO4&Bi4V2O11对四环素(TC)的降解也表现出增强的光催化性能。Bi/BiVO4&Bi4V2O11复合材料提升的光催化性能可能归因于金属Bi的表面等离子体共振(SPR)效应、拓宽的可见光吸收范围和增大的比表面积。此外,提出了复合光催化剂可能的光催化机理。
Bi5O7I/聚苯胺复合光催化剂的制备及光催化活性
王璐, 李曦, 唐子聪, 周楠, 俞峥松, 董永志, 李小争, 魏登贵, 董玉林, 李全华, 刘鹏
2019, 35(2): 271-276  doi: 10.11862/CJIC.2019.047
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首先采用化学氧化聚合法合成聚苯胺(PANI),再采用溶剂热法制备了Bi5O7I/PANI复合材料,并采用X射线衍射、傅里叶变换红外光谱、场发射扫描电镜、紫外-可见漫反射光谱和荧光光谱等对所制备材料进行了表征,考察了复合材料在可见光光照条件下降解罗丹明B(RhB)的催化性能。结果表明当负载PANI后,Bi5O7I/PANI的复合材料都表现出优异的光催化性能。当PANI负载量在5%(w/w)时,催化效率最佳。在60 min内,其降解RhB的速率常数为Bi5O7I的3.9倍。捕获实验表明超氧自由基和空穴是该过程的主要活性物种。Bi5O7I/PANI具有优异光催化性能的原因主要在于,负载的PANI扩展了可见光吸收范围并增强了可见光吸收强度,而且PANI和Bi5O7I匹配的能级结构抑制了光生电子-空穴的复合效率。
氰基合钴(Ⅲ)氢键型笼状超分子晶体的合成、结构及介电性质
郑晓媛, 刘洋, 秦刘磊, 俞非凡, 朱春立, 刘尊奇
2019, 35(2): 277-284  doi: 10.11862/CJIC.2019.036
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以2-氯苯胺(o-chloroaniline,o-CA)、18-冠醚-6(18-crown-6)和钴氰酸为原料,在甲醇和水的混合溶液内通过蒸发法合成氰基合钴配合物氢键笼状超分子晶体材料(H)0.5o-CAH)[Co(CN)6]0.5·(18-crown-6)0.5·H2O(1)。并通过单晶X射线衍射、红外光谱、粉末X射线衍射、元素分析、热重分析(TG)和介电常数测试等对超分子晶体进行了结构及电性能表征。测试结果表明,该晶体在低温下属于三斜晶系,空间群为P1,晶胞参数为a=0.869 22(1)nm,b=0.964 09(12)nm,c=1.129 93(14)nm,α=77.894 0(10)°,β=78.877 0(10)°,γ=88.684 0(10)°。结构显示氰基合钴配合物、超分子阳离子和水分子通过氢键相互作用在空间内形成三维笼状。笼状顶点的钴原子随着温度的变化其间距发生明显的伸缩,导致晶体在260 K附近观察到明显的介电异常现象。
原位制备的铁配合物催化烯烃选择性环氧化
宋虹瑾, 李璐, 张妮, 王斐, 吕婧, 孟祥光
2019, 35(2): 285-292  doi: 10.11862/CJIC.2019.046
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制备了配体2-(2-吡啶基)-噁唑啉。该含氮配体能够在乙腈溶液中与三氟甲磺酸亚铁和其它辅助配体原位形成具有催化活性的六配位金属亚铁配合物。量子化学计算表明配体上的氮原子而非氧原子与铁配位。研究表明,以H2O2为氧化剂,该金属配合物能够在乙腈溶液中高活性地催化末端芳香烯烃和脂肪烯烃的环氧化反应;该反应条件温和、迅速、选择性好并且适用底物范围宽泛。辅助配体、溶剂和氧化剂等因素对反应的活性和选择性影响很敏感,文中对这些影响进行了较详细的研究。
作为Be2+磷光探针的含9-冠-3的铱配合物
潘淼, 胡媛媛, 赵卓, 姚永林, 周会东, 童碧海, 张千峰
2019, 35(2): 293-299  doi: 10.11862/CJIC.2019.049
[摘要]  (42) [HTML全文] (42) [PDF 3014KB] (0)
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以4'-(2-苯并噻唑基)苯并-9-冠-3(BTZ9C3)为主配体,用2,2'-联吡啶(bpy)及3-三氟甲基-5-(2'-吡啶基)-1,2-二唑(Hfppz)辅助配体分别合成了离子型铱配合物[Ir(BTZ9C3)2(bpy)]PF61)和中性铱配合物[Ir(BTZ9C3)2(fppz)](2)。配合物的结构通过核磁、高分辨质谱进行了表征,并测定了配合物1的单晶结构。对它们光物理性能的研究表明,2种配合物掺杂在PMMA中的发光为黄绿光发射,配合物1的发光波长为535 nm,配合物2的发光波长为541 nm,发光量子效率分别为10.8%,45.0%,发光寿命分别为3.01和2.58 μs,为典型的磷光发射。通过循环伏安法测得配合物12的HOMO能级分别为-5.60和-5.35 eV。2种配合物对Be2+都有发光增强的选择性识别效果,化学计量比为1:2,最低检测限低至6.0 μmol·L-1。抗干扰能力方面,离子型配合物1的抗干扰能力较好,而中性配合物2受Al3+的干扰较大。
三乙醇胺改性Cu/Zn/Al类水滑石衍生氧化物催化合成气制备低碳醇
程淑艳, 郝艳红, 寇佳伟, 高阳艳
2019, 35(2): 300-306  doi: 10.11862/CJIC.2019.041
[摘要]  (32) [HTML全文] (32) [PDF 876KB] (2)
摘要:
采用共沉淀法制备Cu/Zn/Al类水滑石前驱体,并用配体三乙醇胺(TEA)对其进行改性。前驱体经焙烧后成功获得TEA改性的Cu/Zn/Al催化剂。借助XRD、FTIR、H2-TPR、CO-TPD及SEM等方法对催化剂进行表征,并将其应用于合成气制备异丁醇的活性评价反应中。结果表明,TEA的加入能够改变催化剂形貌,使催化剂表面呈松散絮状结构。TEA可使类水滑石前驱体的结构发生膨胀,其焙烧获得的催化剂中有明显的晶格扭曲和晶格缺陷。TEA对催化剂结构的改变有利于Cu/Zn/Al催化剂中CuO组分的氢还原和CO在催化剂表面的化学吸附,从而促进异丁醇的合成。当TEA的添加比例为nTEA/nZn=0.5时,TEA改性的Cu/Zn/Al催化剂的催化效果达到最佳。
具有聚集荧光增强性质的双(4-二乙氨基水杨醛)缩偶氮二甲酰肼二丁基锡的合成和晶体结构
冯泳兰, 邝代治, 张复兴, 庾江喜, 蒋伍玖, 朱小明
2019, 35(2): 307-313  doi: 10.11862/CJIC.2019.043
[摘要]  (51) [HTML全文] (51) [PDF 3776KB] (0)
摘要:
在甲醇溶液中,卡巴肼、(4-二乙氨基)水杨醛和二乙酸二丁基锡"一锅法"反应,合成了一个新颖的基于双(4-二乙氨基水杨醛)缩偶氮二甲酰肼(L)的七配位有机锡配合物[Sn(L)(n-butyl)2]nT)。经元素分析、IR、(1H,119Sn,13C)NMR和X射线衍射晶体结构表征,T的晶体属单斜晶系C2/c空间群,中心锡周围由双(4-二乙氨基水杨醛)缩偶氮二甲酰肼的O,N配位原子占据赤道位置和2个丁基占据顶端位置形成畸变五角双锥构型。通过烯醇式氧原子的桥联配位作用,T向一维带状无限扩展产生"竹筏状"超分子结构。配合物T在二甲基甲酰胺、四氢呋喃、乙醇、甲醇和甲苯有机溶剂及其有机溶剂-水混合物中具有强荧光发射峰,当含水量的体积分数在0~10%(V/V)时具有良好的聚集荧光增强效应,含水量大于10%(V/V)时发生荧光淬灭。
Articles
One-Pot Synthesis of Rose-like Ce-Doped SnS2 with Enhanced Visible-Light Photocatalytic Property for Reduction of Cr(Ⅵ)
Guo-Hui LI, Yuan-Yuan SUN, Hua-Long XING, Jian-Cong ZHENG, Chen-Chen LIN, Zhen-Fan SUN
2019, 35(2): 194-202  doi: 10.11862/CJIC.2019.006
[摘要]  (61) [HTML全文] (61) [PDF 5293KB] (0)
摘要:
The Ce-doped SnS2 samples were prepared successfully through a one-pot hydrothermal method under mild conditions. The as-prepared SnS2 samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with Energy dispersive X-ray Spectroscopy (EDS) which confirmed the doping of Ce. The results indicated the spiral growth mode and rose-like morphology of the samples. The effects of Ce doping on the photoabsorption, band gap, the potential of conduction band and the separation efficiency of photo-induced carriers were checked by diffuse reflectance spectrum (DRS) and electrochemical examinations. The reductive abilities of the samples were evaluated by the reduction of Cr(Ⅵ) chosen as a model pollutant. The results reveal that photocatalytic properties of Ce/SnS2 were strongly dependent on the proportion of Ce ions and the optimum doping amount of Ce is 5% (n/n).
Synthesis, Growth Mechanism and Application in Anticancer of CuS Hollow Spheres
Qing-Li HUANG, Li-Li WANG, Ting LI, Yong-Ping WU
2019, 35(2): 314-322  doi: 10.11862/CJIC.2019.032
[摘要]  (31) [HTML全文] (31) [PDF 3007KB] (0)
摘要:
Cage-like hollow morphologies of copper sulfide nanostructures have been selectively synthesized using cupric nitrate trihydrate (Cu(NO3)2·3H2O), oxalic acid (H2C2O4) and sodium sulphide nonahydrate (Na2S·9H2O) as starting materials in water solution by a self sacrificing templates hydrothermal method. X-ray diffraction (XRD), field scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products. The possible formation mechanism of CuS hollow spheres was proposed. The photo-thermal conversion experiments were also done. The results showed that hollow CuS exhibited high photo-thermal efficiency and high anticancer activity under NIR irradiation.
Syntheses, Structures and Magnetic Properties of Two Binuclear Lanthanide Complexes Bridged by Nitronyl Nitroxide Radical Ligands
Xue-Lan MEI, Min-Jie DU, Peng HU, Zong-Qun LI
2019, 35(2): 323-328  doi: 10.11862/CJIC.2019.034
[摘要]  (44) [HTML全文] (44) [PDF 792KB] (0)
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The reaction of Ln(acac)3·3H2O with NIT-PhOH radical yielded two new Ln-radical complexes[Ln2(acac)4(NIT-PhO)2] (Ln=Tb (1), Y (2); acac=acetylacetonato, NIT-PhOH=2-(2'-hydroxyphenyl)-4, 4, 5, 5-tetramethylimidazo-line-1-oxyl-3-oxide). Two complexes are isostructural and have binuclear structure in which two lanthanide ions are bridged by two radical ligands through their phenoxo-O atoms. DC magnetic susceptibility studies indicated that there exists weak antiferromagnetic interaction in complex 2.
Syntheses, Crystal Structures, and Luminescent Properties of Three Cobalt(Ⅱ), Lead(Ⅱ) and Zinc(Ⅱ) Complexes Constructed from Mixed Biphenyl Tricarboxylic Acid and N-Donor Ligands
Yu LI, Xun-Zhong ZOU, Wen-Da QIU, Wen-Liu ZHUANG, Na ZHAO, Xiao-Ling CHENG
2019, 35(2): 329-336  doi: 10.11862/CJIC.2019.002
[摘要]  (29) [HTML全文] (29) [PDF 2326KB] (2)
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Zero-dimensional mononuclear cobalt(Ⅱ) complex, 1D lead(Ⅱ) and 1D zinc(Ⅱ) coordination polymers, namely[Co(Hbtc)(phen)2(H2O)]·3H2O (1), [Pb(μ3-Hbtc)(2, 2'-bipy)]n (2) and {[Zn3(μ2-btc)2(μ2-H2O)(2, 2'-bipy)3(H2O)5]·8H2O}n (3), have been constructed hydrothermally using H3btc (H3btc=biphenyl-2, 4, 4'-tricarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and cobalt, lead or zinc chlorides. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the orthorhombic or triclinic systems, space groups Pna21 or P1. Complex 1 has a discrete monomeric structure, which is assembled to a 3D supramolecular framework through O-H…O hydrogen bond. Complexes 2 and 3 show a 1D chain based on binuclear units. Luminescent properties of all complexes have been studied.
Influences of cis-, trans-1, 2-Cyclohexanediamine Configurations on Iodoantimonate Organic-Inorganic Hybrid Isomers
Zhi-Wen LIANG, Xiao-Rou CHEN, Hui YU, Zhen-Hong WEI, Xiu-Xiu ZHANG, Hu CAI
2019, 35(2): 337-343  doi: 10.11862/CJIC.2019.027
[摘要]  (58) [HTML全文] (58) [PDF 2535KB] (1)
摘要:
Reactions of cis-and trans-1, 2-cyclohexanediamine (DAC) with antimony iodide in concentrated HI aqueous solution afforded two organic-inorganic hybrid isomers (cis-1, 2-DACH2)[SbI5]·H2O (1) and {(trans-1, 2-DACH2)[SbI5]·H2O}n (2), respectively. The single-crystal X-ray diffraction revealed that the inorganic component in compound 1 is a dimer[Sb2I10] built up from two[SbI6] octahedra by sharing I-I edge, and that in compound 2 is a zigzag chain constructed with corner-sharing octahedral[SbI6] units. In addition, both compounds have been investigated and compared by UV-Vis, fluorescent spectra, and DFT calculation.
X-ray Crystallography, Spectral Characterization and Computational Studies of Mercury(Ⅱ) Complex with 1-(p-Tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one
Pourmirza Mahsa, Ebrahimnezhad Shahla, Ramazani Ali, Bahrami Aidin, Alaei Sholeh., Reza Dadrass Ali.
2019, 35(2): 344-350  doi: 10.11862/CJIC.2019.031
[摘要]  (42) [HTML全文] (42) [PDF 1308KB] (1)
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The α-phosphorus ligand 1-(p-tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one(L) was prepared by the reaction of 2-bromo-1-(p-tolyl)ethan-1-one with tri(p-tolyl) phosphine. The reactions of L with cadmium chloride and mercury bromide resulted in[Cd(L)Cl2]2 (C1) and[Hg(L)(μ2-Br)Br]2 (C2), respectively. The complexes were characterized by IR and NMR (1H, 13C, 31P). The structure of C2 was detected by single crystal X-ray diffraction and its DFT computational studies at B3LYP/6-31G* level were also performed to reveal the interaction between the reaction site of complex C2 and nucleophilic groups such as Schiff base.
A Layered Cd(Ⅱ)-Organic Coordination Polymer Exhibiting Dual-Responsive Sensing Towards 2, 4, 6-Trinitrophenol and Fe3+
Jing-Jing SHI, Shan XU, Na LI, Xiu-Guang WANG, Xiao-Jun ZHAO, En-Cui YANG
2019, 35(2): 351-360  doi: 10.11862/CJIC.2019.045
[摘要]  (193) [HTML全文] (193) [PDF 4607KB] (0)
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A layered coordination polymer[Cd(QDA)]n (1) with distorted Cd2+ octahedron extended by three-connected 2, 3-quinoline dicarboxylate linkers was hydrothermally synthesized, exhibiting intense blue fluorescence and highly thermal and chemical stability. More interestingly, the complex dispersed in ethanol can quickly probe the trace amounts of 2, 4, 6-trinitrophenol (Ksv=6.61×104 L·mol-1, LOD=0.83 μmol·L-1) and Fe3+ (Ksv=1.74×104 L·mol-1, LOD=2.70 μmol·L-1) through fluorescence quenching with high quenching constants (Ksv) and low limits of detection (LOD).
Syntheses, Spectroscopic Properties and THz Time Domain Spectroscopy of Two Copper(Ⅰ) Complexes Based on N-Donor and P-Donor Ligands
Xun PAN, Xiao-Nan KUANG, Ning ZHU, Zhi-Gang REN, Yu-Ping YANG, Xiu-Lan XIN, Zhong-Feng LI, Hong-Liang HAN, Qiong-Hua JIN
2019, 35(2): 361-368  doi: 10.11862/CJIC.2019.026
[摘要]  (65) [HTML全文] (65) [PDF 838KB] (0)
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Two novel copper(Ⅰ) complexes[Cu(bdppmapy)(2, 2'-bipy)]BF4 (1) and[Cu(bdppmapy)(2, 2'-bipy)]I (2) (2, 2'-bipy=2, 2'-bipyridine, bdppmapy=N, N-bis((diphenylphosphino)methyl)-2-pyridinamine) have been synthesized in mixed solvents of CH3OH and CH2Cl2 (1:1, V/V) and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H NMR and 31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1, a mononuclear complex, was generated by the reaction of[Cu(CH3CN)4]BF4 and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In complex 1, the central Cu(Ⅰ) forms a distorted tetrahedral geometry by coordinating with the diphosphine ligand (bdppmapy) and chelating N-donor ligand (2, 2'-bipy). Like 1, 2 was obtained by the reaction of CuI and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In the asymmetric unit of 2, the bdppmapy and 2, 2'-bipy ligands chelate central Cu(Ⅰ), respectively. The luminescent spectra show that the emission mechanism is metal-to-ligand charge transfer (MLCT). The application of terahertz time-domain spectroscopy also provides useful information for the research of complexes.
综述
仿生无机纳米材料改造生物体的研究进展
熊威, 唐睿康, 马为民, 邹志刚
2019, 35(1): 1-24  doi: 10.11862/CJIC.2019.008
[摘要]  (55) [HTML全文] (55) [PDF 13745KB] (55)
摘要:
在进化的过程中,生物体学会了利用材料来改造自身以适应环境的变化。自然界中的一些生物体可以通过生物矿化合成无机纳米材料为自己提供保护或其他特殊功能。但是自然界中还有部分生物体不具备生物矿化功能,受到自然界生物体利用纳米材料的启发,科学家们开始尝试通过人工赋予生物体纳米材料来对其进行改造。本文就基于生物-材料界面复合技术的纳米材料对生物体的改造,依次从调控机制、改造方法、功能应用等方面做了系统的阐述,重点介绍了通过仿生矿化对生物体进行纳米改造的研究进展,对仿生无机纳米材料改造生物体的领域现状做了分析和总结,并且对该领域的发展前景进行了展望。
论文
单一基质白光荧光粉Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+的晶胞参数变化和光谱特性
王飞, 田一光, 张乔
2019, 35(1): 25-33  doi: 10.11862/CJIC.2019.003
[摘要]  (94) [HTML全文] (94) [PDF 2959KB] (94)
摘要:
利用高温固相反应制备了Ca0.955-xAl2Si2O8:0.045Eu2+xMn2+x=0,0.05,0.10,0.15,0.20,0.25,0.30,0.325,0.35,0.375,0.40,0.425)一系列试样,系统研究了Mn2+取代基质中Ca2+进入晶格中对其晶胞参数和光谱特性影响。Mn2+以类质同相替代Ca2+进入晶体晶格中,形成了连续固溶体,试样均为三斜晶系,P1空间群。随着Mn2+掺杂量增加,晶胞参数(abcγ)和晶胞体积V均呈线性递减,且a轴减幅最大,b轴最小,晶面夹角(αβ)呈线性递增。在357 nm激发下,获得的Ca0.955-xAl2Si2O8:0.045Eu2+xMn2+发射光谱均有Eu2+的4f→5d跃迁产生的433 nm和Mn2+4T14G)→6A16S)跃迁产生的567 nm两个宽带谱组成。在荧光粉Ca0.955-xAl2Si2O8:0.045Eu2+xMn2+中,Eu2+与Mn2+间存在能量传递,Eu2+→Mn2+间能量传递的临界距离REu-Mn=0.947 1 nm,Eu2+→Mn2+能量传递过程为电四极-电四极的多极矩相互作用。通过改变Mn2+掺杂量,在紫外芯片的有效激发下,荧光粉的发射光颜色可从蓝光区(0.158 2,0.086 0)逐渐移至近白光区(0.295 3,0.298 9),可获得一种紫外激发适用于白光LED的单一组分白色荧光粉。
CoMoSx/γ-Al2O3催化剂在还原脱硫中的吸附性能和催化活性
刘哲男, 耿云峰, 石泉, 黎汉生, 史大昕, 吴芹, 赵芸, 冯彩虹, 矫庆泽
2019, 35(1): 34-42  doi: 10.11862/CJIC.2019.004
[摘要]  (53) [HTML全文] (53) [PDF 6509KB] (53)
摘要:
以等体积浸渍法与原位还原硫化法相结合制备了CoMoSx/γ-Al2O3催化剂。采用X射线衍射(XRD)、扫面电子显微镜/能谱(SEM/EDS)、X射线光电子能谱(XPS)、程序升温脱附/程序升温还原/程序升温表面反应-质谱分析(TPD/TPR/TPSR-MS)对催化剂进行了表征,系统地研究了CoMoSx/γ-Al2O3催化剂的结构、表面CO和SO2的吸附-脱附行为及其表面反应特性。采用微型固定床反应器评价了CoMoSx/γ-Al2O3催化剂的催化特性。研究表明,CoMoSx/γ-Al2O3催化剂由γ-Al2O3和高分散的Co-Mo-S组成,预硫化过程中不会出现CoS2和Co9S8等硫化物。γ-Al2O3几乎不会吸附CO,CoMoSx对CO具有强吸附作用;而γ-Al2O3和CoMoSx都可以吸附SO2,但γ-Al2O3的吸附作用较弱,CoMoSx的吸附作用较强。在γ-Al2O3上会吸附微量的COS,而CoMoSx不会吸附COS。在SO2与CO的表面反应中,吸附在CoMoSx上的SO2会与CO发生反应,而吸附在γ-Al2O3上的SO2不会发生反应。在400℃时,SO2的转化率和硫单质的选择性都接近100%。
两个基于多金属氧簇和咪唑类化合物的有机-无机杂化物的合成及性质
周欣, 叶晶, 王志花, 靳素荣
2019, 35(1): 43-49  doi: 10.11862/CJIC.2019.023
[摘要]  (64) [HTML全文] (64) [PDF 2981KB] (64)
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在室温条件下合成了2个多金属氧簇化合物(Hbidp)3(PMo12O40)·bidp(1)和(Hbid)3(PMo12O40)·bid(2)(bidp=苯并咪唑基苯酚,bid=苯并咪唑)。通过红外、元素分析和X射线单晶衍射分析对2个化合物进行了表征。化合物中多酸阴离子与有机组分通过氢键、静电引力及π-π堆积作用形成一维链状多金属氧簇化合物晶体。电化学性质研究表明化合物12均具有优良的氧化还原性质。光催化研究结果显示化合物1和化合物2对罗丹明B和亚甲基蓝具有良好的光催化降解作用。
二维配位聚合物衍生的氮掺杂碳/氧化锌纳米复合材料作为高性能的锂离子电池负极材料
温豪, 侍昌东, 胡瑶, 戎红仁, 沙彦勇, 刘洪江, 张汉平, 刘琦
2019, 35(1): 50-58  doi: 10.11862/CJIC.2019.015
[摘要]  (58) [HTML全文] (58) [PDF 3300KB] (58)
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通过一步煅烧二维锌基配位聚合物[Zn(tfbdc)(4,4'-bpy)(H2O)2](H2tfbdc=四氟对苯二甲酸;4,4'-bpy=4,4'-联吡啶),制备了氮掺杂碳/氧化锌复合纳米粒子(ZnO-N-C)。作为锂离子电池的负极材料,ZnO-N-C电极具有高的可逆容量,优异的循环稳定性和较好的倍率性能。在50 mA·g-1的电流密度下,50次循环后ZnO-N-C电极仍有611 mAh·g-1的可逆容量。
共沉淀法制备的CuGa2O4及其气敏性能
高翠苹, 汪艳, 储向峰, 梁士明, 高奇, 李学
2019, 35(1): 59-64  doi: 10.11862/CJIC.2019.005
[摘要]  (47) [HTML全文] (47) [PDF 3834KB] (47)
摘要:
采用共沉淀法制备了CuGa2O4粉体,采用X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)等对CuGa2O4粉体进行了表征。研究了热处理温度和pH对CuGa2O4粉体气敏性能的影响,实验结果表明热处理温度为800℃,pH=6.00(热处理4 h)条件下制备出的CuGa2O4粉体,在室温下(18±2)℃对三甲胺(TMA)具有较好的气敏选择性和较高灵敏度,对1 000 μL·L-1的TMA的灵敏度达到310.1,响应和恢复时间分别约为590和80 s,对1 μL·L-1的TMA的灵敏度可达到1.3。
氨基功能化KIT-6两步后嫁接制备及其吸附Pb2+性能
耿琳琳, 林志峰, 梅德均, 陈斯琪, 魏建文, 廖雷
2019, 35(1): 65-72  doi: 10.11862/CJIC.2019.001
[摘要]  (43) [HTML全文] (43) [PDF 3092KB] (43)
摘要:
以正硅酸乙酯作为硅源,三嵌段共聚物P123作为模板剂制备介孔材料KIT-6。再采用后嫁接法,先将3-氯丙基三甲氧基硅烷嫁接到KIT-6上,再用聚乙烯亚胺(PEI)进一步嫁接,合成出PEI功能化的PEI/KIT-6。用傅立叶变换红外光谱分析(FTIR)、X射线衍射(XRD)、热重分析(TGA)、元素分析、N2吸附-脱附、扫描电镜等手段进行结构的表征。用电感耦合等离子体光谱(ICP)测定材料的Pb2+吸附性能。结果表明氨基的表面平均负载量为0.374 mmol·g-1,并且改性后KIT-6仍具有高度有序性,并未出现孔道堵塞的现象。PEI/KIT-6在投加量为1 g·L-1,室温条件下,吸附100 mg·L-1 Pb2+的最佳pH值为6.0;吸附容量伴随温度的提高先增加后减小,最佳反应温度为35℃;材料在120 min内可以达到吸附平衡,吸附过程符合拟二级动力学方程;Langmuir和Freundlich模型均能较好地描述该吸附过程。吸附倾向于发生单分子层的化学吸附。
RGO/g-C3N4/MoS2复合材料的制备及其光催化性能
钟梓俊, 许若鹏, 黄浪欢, 谭绍早, 罗梓蓉
2019, 35(1): 73-81  doi: 10.11862/CJIC.2019.024
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摘要:
通过热解-水热两步法制备了石墨烯/石墨相氮化碳/二硫化钼(RGO/g-C3N4/MoS2)复合材料并使用多种分析表征手段对RGO/g-C3N4/MoS2的结构、形貌及光催化性能进行分析。结果表明,具有异质结构的g-C3N4/MoS2与RGO复合后,通过良好的界面接触和电荷的快速转移,增强了其光生电子-空穴的分离。经可见光照射120 min后,RGO/g-C3N4/MoS2复合材料可降解97%亚甲基蓝。此外,循环实验表明RGO/g-C3N4/MoS2复合材料具有良好的稳定性,经5次循环仍能保持93.2%的光催化活性。
Gd-N共掺杂SrTiO3/TiO2复合纳米纤维制备及光催化性能
李跃军, 曹铁平, 梅泽民, 李晓萍, 孙大伟, 杨殿凯
2019, 35(1): 82-88  doi: 10.11862/CJIC.2019.011
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摘要:
以静电纺丝技术制备的TiO2纳米纤维为基质和反应物,结合一步水热法制得Gd-N共掺杂SrTiO3/TiO2复合纳米纤维光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射(UV-Vis DRS)和荧光光谱(PL)等方法对其微观结构、形貌和光学性能进行表征。结果表明:SrTiO3和TiO2形成异质结能够使光生电子和空穴得到很好的分离,而Gd-N共掺杂产生新带隙,可以拓宽光谱响应范围至可见光区,并引起晶格缺陷,成为光生电子-空穴对的浅势捕获阱。Gd-N共掺杂与异质结的协同作用有效提高了SrTiO3/TiO2复合纳米纤维的可见光催化活性。
以开孔的二维MFI纳米片为构筑单元制备沸石片膜
吴云琴, 郑璐康, 陈琦, 俞梦婷, 王金桂, 张富民, 肖强, 朱伟东
2019, 35(1): 89-94  doi: 10.11862/CJIC.2019.012
[摘要]  (53) [HTML全文] (53) [PDF 2668KB] (53)
摘要:
以食人鱼溶液(体积比为3:1的95%~98%(w/w)H2SO4和30%(w/w)H2O2混合液)处理多层MFI(ML-MFI)除去有机结构导向剂(OSDA),经超声剥离和沉降纯化后得到了开孔的MFI沸石纳米片。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、N2吸附-脱附、傅立叶变换红外光谱(FT-IR)和热重分析(TGA)等手段对得到的MFI沸石纳米片进行表征,发现食人鱼溶液处理可移除ML-MFI中的OSDA,再经超声剥离得到可分散、开孔的MFI沸石纳米片。将MFI沸石纳米片用简单抽滤的方式沉积到自制Al2O3载体上,不经二次生长得到了连续的沸石纳米片膜。单组分气体渗透性能测试结果表明,制备的MFI沸石纳米片膜对正/异丁烷的理想选择性为4.1~5.8,正丁烷的渗透速率为2.2×10-7~4.1×10-7 mol·m-2·s-1·Pa-1
Ho3+-Yb3+掺杂磷酸盐玻璃陶瓷的制备与发光性能
赵梦洁, 邹翔宇, 夏宇行, 贾文韬, 张洪波, 邵晶, 苏春辉
2019, 35(1): 95-100  doi: 10.11862/CJIC.2019.007
[摘要]  (47) [HTML全文] (47) [PDF 2568KB] (47)
摘要:
采用传统熔融法制备了Na2O-Y2O3-P2O5-SiO2前驱体玻璃,并对前驱体玻璃样品进行热处理,成功合成透明磷酸盐玻璃陶瓷。对玻璃陶瓷样品进行XRD分析确定玻璃基质中有Na3.6Y1.8(PO43晶体析出。讨论了热处理时间对玻璃陶瓷结晶度和晶粒尺寸的影响,确定热处理温度为655℃,热处理时间为2 h。比较Ho3+单掺和Ho3+-Yb3+共掺玻璃陶瓷上转换发光强度,确定Ho3+与Yb3+的最佳掺杂物质的量之比为1:2。同时讨论了Ho3+-Yb3+之间的能量转移。使用积分球测得样品的上转换发光量子效率。
固溶体MAX相(Ti0.5V0.5)3AlC2的制备及其对MgH2储氢性能的催化影响
张欣, 沈正阳, 简旎, 姚建华, 高明霞, 潘洪革, 刘永锋
2019, 35(1): 101-108  doi: 10.11862/CJIC.2019.025
[摘要]  (52) [HTML全文] (52) [PDF 5120KB] (52)
摘要:
通过无压烧结法制备了固溶体MAX相(Ti0.5V0.53AlC2,研究了其添加对MgH2储氢性能的影响。结果发现,固溶体MAX相(Ti0.5V0.53AlC2中的Ti和V元素通过协同作用,呈现出更高的催化活性。添加质量分数10%(Ti0.5V0.53AlC2的MgH2样品的起始放氢温度为230℃,较原始MgH2降低了60℃。在275℃下等温放氢,(Ti0.5V0.53AlC2添加样品的放氢速率可达0.35%·min-1,是原始MgH2样品的4倍左右。此外,完全放氢后的MgH2-10%(Ti0.5V0.53AlC2样品在150℃、5 MPa氢压下,可在60 s内吸收4.7%的氢。计算显示,MgH2-10%(Ti0.5V0.53AlC2样品的表观活化能为79.6 kJ·mol-1,较原始MgH2(153.8 kJ·mol-1)降低了48%,这是MgH2放氢性能得到改善的主要原因。
基于阴离子调控策略的Co(Ⅱ)配位聚合物的合成、晶体结构及荧光性质
李响, 赵怀安, 苏剑, 程军妍, 王鹏
2019, 35(1): 109-115  doi: 10.11862/CJIC.2019.020
[摘要]  (55) [HTML全文] (55) [PDF 4126KB] (55)
摘要:
以三键桥联吡啶类配体2,6-二(3'-吡啶乙炔基)-4-甲基苯胺(L)为配体,在常温混合溶剂(二氯甲烷-甲醇)中分别与CoCl2、Co(SCN)2通过自组装反应,获得了一维及二维配位聚合物[Co(L Cl2]n1)及[Co(L)2(SCN)2]n2),通过红外、元素分析、X射线单晶衍射等检测手段对所合成的配合物进行了结构表征。对比12的单晶结构可以发现,配体L在配位聚合物12中的配位取向及结构相似,不同的是Co(Ⅱ)离子的配位数受配位阴离子的影响而不同:配位聚合物1中四配位的Co(Ⅱ)通过2个配体的相互连接呈现一维的弯曲链状结构,而配位聚合物2中六配位的Co(Ⅱ)则通过4个配体的相互连接得到二维的平面结构。2个配合物中均存在氢键及π-π相互作用。通过粉末衍射证明了配位聚合物12为单一晶相,其固态下的荧光测试显示,二者的荧光均减弱,并相对于配体L有红移(1)及蓝移(2)。
Articles
Preparation and CO2 Adsorption Property of Flake-like Nano-Structure CeO2 Crystals
Bo-Sheng ZHAO, Hui-Hu SHI, Liang MA, Hong DU, Jian-Bin ZHANG
2019, 35(1): 116-124  doi: 10.11862/CJIC.2019.019
[摘要]  (55) [HTML全文] (55) [PDF 5575KB] (55)
摘要:
Nano-structure flake-like CeO2 crystals with an average size of 4.94 μm×0.92 μm (length and width) and the thickness of 0.04~0.08 μm were prepared by simply calcining cerium carbonate precursors (CCPs) at 500℃ for 4 h, in which the flake-like CCPs were firstly prepared by stirring CeCl3 aqueous solution with CO2-storage material (CO2SM) for 0.5 h at room temperature. Interesting, the CO2SM could provide CO32- and act as dispersant and structure-directing agent for the preparation of flake-like CCPs. In the process, the effect of three factors, including CO2SM dosage, Ce3+ concentration and stirring time, on the morphology and size of CCPs were systemically studied, and the optimum preparation conditions of flake-like CCPs were confirmed at 0.1 g CO2SM with 50 mL 0.03 mol·L-1 Ce3+ aqueous solution at 1 000 r·min-1 for 0.5 h at room temperature. After calcining CCPs, the as-prepared flake-like CeO2 crystals presented the CO2 adsorption amount of 0.554 mmol·g-1 at room temperature.
Synthesis, Crystal Structure and DNA Binding of Copper(Ⅱ) Complex of Penciclovir
Rui-Xue LIU, De-Lin LAI, Qian-Jun DENG, Feng-Jie CHENG, Lan-Qiong FAN, Yan-Cheng LIU
2019, 35(1): 125-132  doi: 10.11862/CJIC.2019.013
[摘要]  (58) [HTML全文] (58) [PDF 1399KB] (58)
摘要:
The first metal complex of the clinical antivirus agent, penciclovir (PCV), was synthesized and structurally characterized by IR, elemental analysis and X-ray single crystal diffraction analysis. In this complex, copper(Ⅱ) was selected as the bioactive metal center, which was coordinated by two PCV molecules to form a new copper(Ⅱ) complex of PCV, [Cu(PCV)2(H2O)3]SO4 (1). The in vitro antitumor activity of complex 1 towards a variety of typical human tumor cell lines has been explored. The results indicated that complex 1 showed enhanced antitumor activity comparing with PCV alone towards all the tested cell lines, in which the human hepatoma cell line BEL-7404 was the most sensitive one to complex 1 (Inhibition ratio (55.83±16.41)%). The inhibitory activity of complex 1 is more than 3 times that of PCV (Inhibition ratio (17.38±5.53)%). Furthermore, the DNA binding mechanism of complex 1 was also studied and discussed by means of UV-Vis absorption and fluorescence emission spectral analyses, as well as the DNA viscosity experiment. The results suggested that DNA, as the primary antitumor target, should be an important binding target of complex 1. And the classic intercalative binding mode might exist between complex 1 and CT-DNA.
Syntheses, Crystal Structures and Photoluminescent Properties of Two Zinc(Ⅱ) Coordination Polymers Derived from 4, 4'-((1H-Imidazol-1-yl) methylene) dibenzoic Acid
Min YU, Fang XUAN, Guang-Xiang LIU
2019, 35(1): 133-140  doi: 10.11862/CJIC.2019.018
[摘要]  (42) [HTML全文] (42) [PDF 3001KB] (42)
摘要:
Two zinc(Ⅱ) coordination polymers, [Zn(HIMB)2]n (1) and {[Zn(IMB)]·1.5H2O}n (2), (H2IMB=4, 4'-((1H-imidazol-1-yl) methylene) dibenzoic acid), have been synthesized and characterized by IR spectroscopy, elemental analyses, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Complex 1 crystallizes in orthorhombic, space group C2221 with a=0.935 2(3) nm, b=2.583 3(8) nm, c=1.396 4(4) nm, V=3.373 6(18) nm3, Mr=707.98, Dc=1.394 g·cm-3, F(000)=1 456, μ=0.786 mm-1 and Z=4. The final R1=0.048 6 and wR2=0.120 1 for 2 794 observed reflections when I>2σ(I). Complex 2 belongs to tetragonal, space group I41/acd with a=1.853 5(2) nm, b=1.853 5(2) nm, c=4.309 7(5) nm, V=14.806 (4) nm3, Mr=412.69, Dc=1.481 g·cm-3, F(000)=6 752, μ=0.136 0 mm-1 and Z=32. The final R1=0.043 7 and wR2=0.117 1 for 3 615 observed reflections when I>2σ(I). Structural analyses reveal that complex 1 shows a 2D→2D polycatenane of 2-fold interpenetrated sql layer, whereas complex 2 possesses a 3D 2-fold interpenetrated (3, 6)-connected net with the point symbol of (611.84)(63)2. The results show that the solvent plays a significant role in the structure of the final products.
ARTICLES
In-Situ Formed Amorphous Co Nanoparticles for Efficiently Catalytic Hydrogen Production from the Methanolysis of Ammonia Borane
Hao CHEN, Zhe-Jian YU, Dan-Dan XU, Yang LI, Ming-Ming WANG, Liang-Min XIA, Shu-Ping LUO
2019, 35(1): 141-148  doi: 10.11862/CJIC.2019.017
[摘要]  (48) [HTML全文] (48) [PDF 3336KB] (48)
摘要:
Amorphous Co nanoparticles formed in-situ displayed high catalytic activity for hydrogen generation from the methanolysis reaction of ammonia borane, among many homogeneous catalysts and heterogeneous catalysts of cobalt. Its turnover number (TON) was up to 6 000 for ten cycles and its turnover frequency (TOF) was up to 515 molH2·molmetal-1·h-1. Moreover, the easily preparation and the great recycling performance made it have good application in future. After the kinetics studies, its catalytic activation energy (Ea) for the methanolysis reaction was measured as 20.00 kJ·mol-1, which was lower than most of the reported values for other nano-sized catalysts. Through the 11B NMR, trimethylborate was the only product. Furthermore, the catalytic reaction mechanism was preliminarily explained and discussed.
Syntheses, Crystal Structures and Luminescent Properties of Two Zinc(Ⅱ) Coordination Polymers Constructed from Ether-Bridged Tricarboxylic Acid
Yu LI, Xun-Zhong ZOU, Wen-Liu ZHUANG, Wen-Da QIU, Jin-Zhong GU
2019, 35(1): 149-154  doi: 10.11862/CJIC.2019.009
[摘要]  (62) [HTML全文] (62) [PDF 1413KB] (62)
摘要:
Two 1D zinc(Ⅱ) coordination polymers, namely[Zn(μ-Hcpta)(4, 4'-bipy)(H2O)]n (1) and {[Zn3(μ3-dbba)2(phen)3]·6H2O}n (2), have been constructed hydrothermally using two ether-bridged tricarboxylic acids:2-(4-carbo-xylphenoxy) terephthalic acid (H3cpta) and 2-(3, 5-dicarboxylatobenzyloxy) benzoic acid(H3dbba), 4, 4'-bipyridine (4, 4'-bipy), 1, 10-phenanthroline (phen) and zinc chloride. Single-crystal X-ray diffraction analyses revealed that two complexes crystallize in the monoclinic system, space groups P21 or I2. Complexes 1 and 2 show two different 1D chain structures.
Syntheses, Crystal Structures and Properties of Cu(Ⅱ), Ni(Ⅱ) and Cd(Ⅱ) Complexes Based on 4-Methyl-3-phenyl-5-(2-pyridyl)-1, 2, 4-triazole
Wei-Wei HE, Si-Yang Feng, Zhi-Rong QU, Hui TANG, Zuo-Xiang WANG
2019, 35(1): 155-164  doi: 10.11862/CJIC.2019.010
[摘要]  (54) [HTML全文] (54) [PDF 7534KB] (54)
摘要:
Complexes of[CuL2Cl]Cl·H2O (1), [NiL2(H2O)2](NO3)2 (2), [CuL2(H2O)2](ClO4)2 (3) and[CdL2(NO3)2]·CH3CN (4) were synthesized by the reactions of 4-methyl-3-phenyl-5-(2-pyridyl)-1, 2, 4-triazole (L) with CuCl2·2H2O, Ni(NO3)2·6H2O, Cu(ClO4)2·6H2O and Cd(NO3)2·4H2O, respectively. Their structures were determined by single crystal X-ray diffraction, and characterized by IR, UV-Vis, fluorescence and TGA. Complex 1 belongs to orthorhombic system with space group Fddd, and the central Cu1(Ⅱ) ion has a distorted tetragonal pyramid geometry[CuN4Cl]. The complexes of 2, 3 and 4 all belong to monoclinic system with space groups P21/n, P21/n and P21/c, respectively. All the central metal ions of 2, 3 and 4 have distorted octahedral configuration[NiN4O2], [CuN4O2], [CdN4O2].
Two Cd(Ⅱ)-Based Metal-Organic Frameworks for Luminescence Sensing of Metal Ions and Organic Molecules
Chun-Li ZHANG
2019, 35(1): 165-173  doi: 10.11862/CJIC.2019.021
[摘要]  (48) [HTML全文] (48) [PDF 3766KB] (48)
摘要:
Two cadmium metal-organic frameworks, {[Cd(L)(fma)]·0.5H2O}n (1) and {[Cd(L)0.5(sdb)]·DMF}n (2) (L=E, E-2, 5-dihexyloxy-1, 4-bis-(2-pyridin-vinyl) benzene, H2fma=fumaric acid, H2sdb=4, 4'-sulfonyldibenzoic acid), have been hydrothermally synthesized. Their applications in luminescence sensing of metal anions and organic molecules were explored. The results show that Fe3+ has a significant quenching influence on the luminescence intensity of MOFs 1 and 2. In addition, MOFs 1 and 2 also show some luminescence quenching ability on salicylaldehyde.
Decoration of Graphene Oxide Sheets with Luminescent Heteronuclear Rare-Earth Complexes
Yun-Tao LI, Shuo QIU, Teng DU, Wei WEI, Zhen-Bing HAN, Fang-Yi RUAN, Li-Hui CAO
2019, 35(1): 174-182  doi: 10.11862/CJIC.2019.016
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摘要:
A novel high luminescent performance of graphene oxide-rare earth hybrid material was prepared using a noncovalent approach. Herein, a heteronuclear rare earth complex were revealed in which the benzoic acid (BA) and 1, 10-phenanthroline hydrate (Phen) coordinated with Sm3+ and Gd3+, which was used to functionalize graphene oxide sheets (GOSs). The as-prepared products were characterized via Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, fluorescence spectrometer, decay lifetime and thermogravimetric analysis. The hybrid materials exhibited strong luminescence intensity, long lifetime and good thermal stability. Besides, Gd3+ ions had a strong sensitizing effect on materials and played a significant role in improving the luminescence intensity. The presence of GOSs did not quench the fluorescence performance of hybrid materials. Moreover, their fluorescence properties of Sm3+ and Gd3+ with different molar ratios were also studied.