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硝酸活化三聚氰胺前驱体对g-C3N4结构和可见光催化性能的影响
叶仕雄, 舒庆
2020, 36(1): 1-10  doi: 10.11862/CJIC.2019.262
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摘要:
为缩短e-和h+的迁移途径而改善g-C3N4易发生光生载流子复合的缺陷,采用不同物质的量浓度的HNO3活化三聚氰胺前驱体,通过形成质子化氨基基团,制备了一系列x-HNO3-g-C3N4x=1,2,3,4,5 mol·L-1)光催化剂。采用N2物理吸附-脱附、X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)、荧光光谱(PL)、紫外-可见漫反射光谱(UV-Vis DRS)、瞬态光电流响应谱(TCS)和电化学阻抗图谱(EIS)等测试手段对上述光催化剂进行了表征分析,以考察催化剂的结构与其光催化性能之间的影响作用规律。以罗丹明B(RhB)为模拟染料污染物,分别以x-HNO3-g-C3N4和直接煅烧三聚氰胺得到的g-C3N4为光催化剂,进行了可见光催化降解活性差异性能测试研究。由实验结果可知:3 mol·L-1-HNO3-g-C3N4的光催化活性最高,相较于直接煅烧三聚氰胺得到的g-C3N4,在60 min内,其可将RhB的降解率从38%提高到99%。将3 mol·L-1-HNO3-g-C3N4催化剂循环使用4次后,催化效果仍为99%。这是因为三聚氰胺前驱体经HNO3活化后,可使经热聚合制备而成的g-C3N4产品具有较高的聚合度,从而得到具有大比表面积的多层g-C3N4;此外,PL结果证明其荧光强度明显降低,而使载流子寿命获得了显著提高;EIS结果表明其载流子传输能力有了明显的增强,从而提高了g-C3N4的光催化活性。
全固态Z-型CdS/Au/Bi2MoO6异质结的构筑及其光催化性能
郭莉, 赵强, 张越诚, 张媛媛, 韩宣宣, 张开来, 王丹军, 付峰
2020, 36(1): 11-20  doi: 10.11862/CJIC.2020.023
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摘要:
采用简单的化学还原沉积和二次水热的方法成功制备了CdS和Au共同修饰Z型CdS/Au/Bi2MoO6(CdS/Au/BMO)光催化剂。通过X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)等测试技术对其组成、形貌、光吸收特性和光电化学性能等进行系统表征。实验结果表明,CdS/Au/BMO-2复合材料在可见光照射下表现出最佳的降解效率,其降解RhB的速率常数约为BMO的8.8倍和CdS的20倍。Au NPs作为固态电子媒介,为光生电子的传输和转移提供了一个通道,同时Au NPs的表面等离子体共振(SPR)效应和CdS纳米粒子显著拓宽了催化体系对可见光的响应范围;通过对催化剂的组成、结构和光电性能表征,确定了CdS/Au/BMO的能带结构,进而探讨了CdS/Au/BMO活性增强机制。
热处理对富氮碳纳米纤维结构及储锂性能的影响
王靖靖, 张江, 王金月, 王璐, 李轩科
2020, 36(1): 31-39  doi: 10.11862/CJIC.2020.026
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以聚丙烯腈(PAN)为原料,经静电纺丝、稳定化和碳化,制备了碳纳米纤维(CNFs)。系统地研究了氮的种类及含量对锂离子电池(LIBs)中Li+的储存性能和负极容量的影响。碳化过程中纤维从无定形碳向石墨化碳结构转变,含氮官能团减少,结构的变化对Li+在CNFs电极中的存储位置有很大的影响。结果表明,Li+不仅可以存储在石墨化碳层之间,还可以存储在氮功能化引起的缺陷部位,后者主要是由于碳材料的氮掺杂而使LIBs的电化学性能改善。碳化温度为600℃时,可以产生足够高的氮含量,从而提高电极的容量。在电流密度为0.1 A·g-1时,循环200次之后比容量高达560 mAh·g-1,即使在1 A·g-1的高电流密度下,循环1 000次比电容量仍然保持在200 mAh·g-1
共沉淀法制备稀土Ce掺杂的纳米ZnO及其光催化降解染料的性能
钟伟, 夏颖帆, 翟杭玲, 高越, 李世慧, 吕春欣
2020, 36(1): 40-52  doi: 10.11862/CJIC.2020.006
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以六水合硝酸锌和六水合硝酸铈(Ⅲ)为原料,通过共沉淀法制备了一系列稀土Ce掺杂的纳米ZnO,并采用X射线粉末衍射(XRD)、傅里叶红外光谱(IR)、扫描电镜(SEM)、X射线能谱分析(EDS)、紫外可见漫反射光谱对其进行了全面表征。部分样品还通过X射线光电子能谱(XPS)和光致荧光光谱(PL)进行了进一步分析。分别在日光和紫外光条件下,对这一系列Ce掺杂的ZnO进行了光催化降解亚甲基蓝的性能研究,得出当Ce的掺杂量为3%(n/n)时(ZnO-3% Ce),其光催化活性最佳,光催化降解亚甲基蓝的效率均超过98%。选取ZnO-3% Ce作为催化剂,分别进一步考察其在日光和紫外光下对罗丹明B和甲基橙的光催化降解性能。研究结果表明,ZnO-3% Ce在日光和紫外光下均表现出较好的光催化降解效果,体现出良好的光降解普适性。日光下光降解效率顺序为:亚甲基蓝>罗丹明B >甲基橙,而紫外光下降解效率顺序为:罗丹明B >亚甲基蓝>甲基橙。最后,我们研究了催化剂ZnO-3% Ce的循环利用及稳定性性能。实验结果表明:该催化剂循环使用3次之后,光催化效率仍然稳定在97%以上,并且其结构和组成保持不变,体现出优异的稳定性和应用前景。
Co3V2O8/石墨烯复合负极材料的合成及其储锂性能
郑浩, 金佳幸, 程劲松, 赵荣飞, 李琳
2020, 36(1): 62-68  doi: 10.11862/CJIC.2020.010
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以石墨烯为基底,CoCl2·2H2O和NH4VO3为原料,采用水热结合热处理方法合成了Co3V2O8/石墨烯复合电极材料;采用XRD、Raman、XPS、SEM、(HR-)TEM和恒电流充放电等对材料进行了结构表征与电化学性能测试。结果表明:Co3V2O8/rGO复合材料表现出优异的放电比容量、优秀的倍率性能和稳定的循环性能(当电流密度为200 mA·g-1,经过100次循环后,可逆放电比容量为1 208 mAh·g-1);Co3V2O8/rGO电极材料表现出优异的倍率和循环性能可以归因于:独特的石墨烯包覆结构可以有效地提高材料的导电性和增强结构的稳定性、缓解Co3V2O8粒子在循环过程中的聚结和膨胀现象;此外,Co3V2O8纳米颗粒均匀地嵌在石墨烯层间防止了石墨烯片层间的堆叠。
水热法合成AgInS2/ZnS核/壳结构量子点及其荧光性能
陈婷, 胡晓博, 徐彦乔, 王连军, 江莞, 江伟辉, 谢志翔
2020, 36(1): 69-78  doi: 10.11862/CJIC.2020.024
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以硫脲为硫源,采用谷胱甘肽(GSH)和柠檬酸钠(SC)为配体,通过水热法制备了水溶性AgInS2/ZnS(AIS/ZnS)核/壳结构量子点。系统研究了反应温度和配体用量对量子点的合成及其荧光性能的影响。采用X射线衍射(XRD)、透射电子显微镜(TEM)、紫外可见吸收光谱(UV-Vis)和光致发光光谱(PL)分别对量子点的物相、形貌和光学性能进行了表征,并考察了量子点的稳定性。实验结果表明,随着反应温度从70℃升高至90℃,促进了ZnS壳层的形成,有效地钝化了量子点的表面缺陷,获得的AIS/ZnS核/壳量子点的发光强度显著提高,发光峰位从600 nm蓝移至580 nm。配体的添加可以有效地平衡Zn2+的化学反应活性,减缓ZnS壳层的生长,抑制核壳界面缺陷的形成,还能消除量子点的表面态,当nGSH/nZn2+=2.0,nSC/nZn2+=2.5时,AIS/ZnS量子点的荧光性能最佳。此外,AIS/ZnS核/壳结构量子点还具有优异的光学稳定性。
长寿命高镍无钴锂离子正极材料的制备
班丽卿, 柏祥涛, 庄卫东, 李文进, 黄巍, 卢世刚
2020, 36(1): 79-86  doi: 10.11862/CJIC.2020.011
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通过调整不同配锂量、不同焙烧温度以及包覆改性对高镍无钴二元材料性能的影响因素进行了研究。对不同原样和其改性后的材料进行了X射线粉末衍射(XRD)分析和首次充放电性能和倍率性能、循环性能等电化学性能测试。其中过锂量(质量分数)为5%,焙烧温度为820℃的材料性能优异,其首次放电比容量为171.6 mAh·g-1,1C和3C的放电比容量分别为147.8、129.8 mAh·g-1。对材料进行锰化合物(质量分数1.0%)包覆处理后,材料的残碱量下降明显,加工性能优异,倍率性能得到明显改善,1C和3C的放电比容量分别提升为156.5、141.8 mAh·g-1。2Ah软包电池常温循环830周容量保持率为80%,高温循环345周容量保持率为80%。
金属Sr、Fe掺杂对LaCoO3催化氧化碳烟及抗硫性能影响
魏炜, 吴艾纯, 乔智威, 李树华, 梁红, 彭峰
2020, 36(1): 87-96  doi: 10.11862/CJIC.2020.031
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利用柠檬酸-EDTA(乙二胺四乙酸)配位法制备了La1-xSrxCo1-yFeyO3催化剂,展现出较好的催化氧化碳烟(soot)活性和抗硫性能。通过X射线衍射(XRD)、傅利叶红外光谱(FT-IR)、扫描电镜(SEM)、H2-程序升温还原(H2-TPR)、X射线光电子能谱(XPS)和SO2程序升温脱附(SO2-TPD)等研究了Sr、Fe掺杂对催化剂物理化学性质及抗硫能力影响。当Sr掺杂LaCoO3时有利于形成较多的表面吸附氧(O2-、O-)和氧空位,且低温氧化还原性能亦有较大改善,提高了催化氧化碳烟活性,其Ti(起燃温度)和Tm(最大碳烟燃烧速率温度)分别为284和347℃。当催化剂同时掺杂Sr、Fe时,其低温氧化还原性能进一步改善,并形成较多Fe4+离子,有利于提高催化氧化碳烟活性。催化剂SO2中毒失活主要来源于Co2+/Co3+和表面吸附氧的硫酸化(SO32-、SO42-)。XPS和SO2-TPD结果表明,LaSrCoFeO3抗硫性主要来源于Fe3+与SO2结合形成的硫酸盐物种,降低了SO2对活性组分表面吸附氧和Fe4+毒化。TPO(程序升温氧化)结果表明,硫化后的LaSrCoFeO3-S仍具有较好的催化氧化碳烟活性,其Tm仅为361℃,表明Sr、Fe同时掺杂具有较好的低温催化氧化碳烟活性和良好的抗硫性能。
一种用于活体细胞Zn2+检测的高灵敏度比例计量荧光探针
张长丽, 徐鉴, 黄芳, 赵海荣, 陈昌云
2020, 36(1): 97-105  doi: 10.11862/CJIC.2020.009
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无论是在水溶液还是乙腈溶液中,2-PBI(2-(2'-吡啶基)苯并咪唑)的发射光谱都表现出一定的红移,但由于该分子对Zn2+低的结合能力以及多变的配位比例,2-PBI不能作为一个比例计量型的Zn2+荧光探针。本研究通过在2-PBI的5位引入推电子基团NN-二甲基,增加探针的配位原子数同时促进探针的ICT效应,设计合成比例计量型Zn2+荧光探针DBITA。实验结果表明,除了172 nm的大斯托克斯位移外,DBITA还表现出特定的Zn2+诱导的红移,发射波长从534 nm红移到609 nm,DBITA与Zn2+以1:1比例结合。此外,DBITA对Zn2+表现出极高的亲和力,配合物DBITA/Zn2+结合的Kd值为0.16 pmol·L-1。在HeLa细胞中,DBITA完成了细胞内的Zn2+的定量造影。
普鲁士蓝正极材料的离子交换法制备及电化学储钾性能
孙云坡, 谢健, 赵新兵, 庄大高, 张根林
2020, 36(1): 106-112  doi: 10.11862/CJIC.2020.008
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采用氯化钾(KCl)和钠基普鲁士蓝(NPB)材料Na2-xMn[Fe(CN)6]z·yH2O为原料,通过离子交换法制备了掺钠钾基普鲁士蓝(NKPB)材料K1.9Na0.1Mn[Fe(CN)6]·0.4H2O。电化学测试表明,与用传统共沉淀法制备的钾基普鲁士蓝(KPB)材料K1.85Mn[Fe(CN)6]0.980.02·0.7H2O(□代表[Fe(CN)6]空位)相比,采用离子交换法制备的NKPB具有更高的容量(0.1C首次放电容量达136.3 mAh·g-1)、较好的循环稳定性(0.5C经过100次循环,容量保持率为96.1%)和优异的倍率性能(5C和10C容量分别为87.6和68.4 mAh·g-1)。NKPB优异的电化学性能与其高的钾含量、完整的晶体结构、钠离子掺杂、纳米级的颗粒尺寸,以及独特的开放框架结构有关。
化学-微波法制备高膨胀率膨胀蛭石及对亚甲基蓝的吸附机理
解颜岩, 孙红娟, 彭同江, 罗利明, 田景斐, 秦亚婷
2020, 36(1): 113-122  doi: 10.11862/CJIC.2020.004
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基于工业蛭石优异的热膨胀性及阳离子交换性,利用化学-微波法制备高膨胀率膨胀蛭石(HEV),采用对比分析法对亚甲基蓝(MB)的吸附性能进行了研究。结果表明,HEV膨胀率高(膨胀率K=60倍),比表面积大(80 m2·g-1),孔径主要分布在2~5 nm之间,仍保持蛭石、水金云母和金云母的物相结构,阳离子交换容量由原样的0.835 mmol·g-1增加到1.005 mmol·g-1。HEV对MB的吸附容量受MB初始浓度、吸附时间、溶液pH和吸附温度影响。当MB溶液初始浓度为300 mg·L-1、吸附时间为240 min、溶液pH值为9、吸附温度为298 K时,吸附量为419.87 mg·g-1,远高于蛭石原矿。吸附过程符合Langmuir模型与准二级动力学模型,为单分子层吸附和吸附势垒较低的自发无序吸热反应过程。HEV具有优异的阳离子交换性和吸附性,是一种具有开发价值的高效低成本吸附剂。
一种天线分子与卟啉染料自组装在染料敏化太阳能电池中的应用
贾海浪, 李珊珊, 龚炳泉, 顾磊, 关明云
2020, 36(1): 123-131  doi: 10.11862/CJIC.2020.014
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以卟啉分子H2-pTCPP作为基础染料,通过配位自组装的方法将天线分子S3修饰到染料结构中。结果表明经天线分子修饰后染料敏化太阳能电池器件的整体性能得到了极大的改善。天线效应有效地提高了器件的光子捕获能力,光电流得到了显著的提高,并且电荷复合行为也得到了明显的抑制。基于H2-pTCPP的电池器件显示了1.18%的转换效率,而经过天线分子修饰后的Mn-pTCPP+S3显示了2.64%的转换效率,性能提高了1.2倍。
不对称Salen配体的Ni(Ⅱ)/Cu(Ⅱ)/Mn(Ⅲ)配合物的合成及其晶体结构
张奇龙, 王家忠, 杨小生, 朱必学
2020, 36(1): 132-138  doi: 10.11862/CJIC.2020.030
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将(1R,2R)-环己二胺与2-羟基-1-萘甲醛和3,5-二叔丁基水杨醛反应,得到非对称Salen配体H2L,然后将配体H2L与Ni(OAc)2·4H2O、Cu(OAc)2·H2O、Mn(OAc)2·4H2O进行配位反应,得到3个单核配合物[Ni(L)]·CH2Cl21),[Cu(L)](2),[Mn(L)(Cl)]·CH2Cl23),分别采用1H NMR、FT-IR和元素分析对化合物进行了表征,并通过X射线单晶衍射技术测定了配体和3个配合物的晶体结构。配体H2L属于正交晶系,P212121空间群。配合物1属于单斜晶系,P21/c空间群,而配合物2和配合物1的结构相似。配合物3属于三斜晶系,P1空间群。
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Preparation and High Electrocatalytic Activity for the Oxidation of Ethanol of PdAu Alloy Foam Films
Jun LIU, Quan ZHOU, Jia-Qi XIE, Rong LI
2020, 36(1): 21-30  doi: 10.11862/CJIC.2019.195
[摘要]  (69) [HTML全文] (69) [PDF 4083KB] (1)
摘要:
Three-dimensional (3D) porous Au-doped PdAu alloy foam films were obtained by using a hydrogen bubble dynamic template electrodeposition method. The morphology and structure features of 3D porous Au-doped Pd alloy foam films were characterized by field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Due to the special porous structures and the electronic effects, the Au-doped PdAu alloy foam films showed high electrocatalytic activity toward the electrooxidation of ethanol in alkaline media as compared to pure porous Pd film.
Mesoporous SBA-15 Rods Supported Pd3Cl Catalysts for Sonogashira C-C Coupling
Rong HE, Ya-Pei YUN, Li-Li SUN, Hong-Ting SHENG, Yuan-Xin DU, Dong XIANG, Peng LI, Xiao-You YUAN, Man-Zhou ZHU, Xun HONG, Yu-En WU
2020, 36(1): 53-61  doi: 10.11862/CJIC.2020.022
[摘要]  (38) [HTML全文] (38) [PDF 3213KB] (1)
摘要:
In this work, atomically precise[Pd3Cl(PPh2)2(PPh3)3]+ (denoted as Pd3Cl) nanoclusters with high monodispersity were supported on the rod-like mesoporous SBA-15 by electrostatic attraction strategy. The well-defined Pd3Cl/SBA-15 catalysts exhibited good catalytic performance and recyclability for Sonogashira C-C coupling reaction under mild condition with environment-friendly water as solvent. Importantly, we investigated the relationship between structures and properties of Pd3Cl, which demonstrated that the synergistic effect between Pdδ+ (0 < δ < 2) and the ligand was the key to the catalytic reaction.
Simultaneous Detection of Dopamine and Uric Acid Based on Chiral MOF and Acetylene Black Modified Electrode
Zhi-Li FANG, Ping WANG, Sheng-Dong LIU, Xin WANG, Qi-Xiang NIE, Shao-Ming YANG, Wen-Yuan XU, Mei-Hua ZHOU
2020, 36(1): 139-147  doi: 10.11862/CJIC.2019.273
[摘要]  (39) [HTML全文] (39) [PDF 3159KB] (1)
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The chiral metal-organic framework, HMOF-Zn, with a large one-dimensional chiral channel and acetylene black (AB) were chosen as electrode materials to modify glassy carbon electrode (GCE) via a simple electrochemical method, denoted as HMOF-Zn@AB-Nafion-GCE. The HMOF-Zn@AB-Nafion-GCE sensor was used for simultaneous detection of dopamine (DA) and uric acid (UA). The experimental results showed that the HMOF-Zn@AB-Nafion-GCE sensor had high sensitivity and selectivity for UA and DA. And it was found that it exhibited higher sensitivity for DA than for UA on HMOF-Zn@AB-Nafion-GCE sensor. The high sensitivity and good selectivity of HMOF-Zn@AB-Nafion-GCE sensor for DA and UA are attributed to the synergistic effect of the large surface of HMOF-Zn, the bonding interaction between the analytes (DA or UA) and HMOF-Zn as well as the high conductivity of AB. At the same time, the proposed sensor exhibited excellent linear responses to DA and UA under optimized conditions. The detection ranges were 0.15~2.5 μmol·L-1 for DA and 0.2~4 μmol·L-1 for UA, with the detection limits of 0.003 and 0.02 μmol·L-1, respectively. Moreover, the high reproducibility of the sensor was obtained in all the experiments. The sensor was also successfully applied to the determination of DA in dopamine hydrochloride injection and UA in human urine sample.
CFx-Ru Composite Cathode for Lithium Primary Battery with Significantly Improved Electrochemical Performance
Ling-Xiao ZHANG, Li-Juan ZHANG, De-Ge XILI, Fan LI
2020, 36(1): 148-158  doi: 10.11862/CJIC.2020.005
[摘要]  (81) [HTML全文] (81) [PDF 6355KB] (1)
摘要:
CFx-Ru cathode materials for lithium primary batteries were synthesized by a simple in-situ chemical modification for the first time. Compared with pristine commercial CFx, CFx-Ru exhibited an improved capacity of 605 mAh·g-1 and a maximum power density of 8 727 W·kg-1 with a plateau of 2 V at 5C, which shows a promising application in the market. The structure, chemical environment and morphology were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. It is found that the ratio of F to C (nF/nC) and the peak area ratio of the C-F2 bond to the C-F covalent bond in CFx-Ru were both lowered, which is supposed to come from the reaction of RuO2 with CF2 inert group of CFx materials in situ synthesis. This in-situ chemical reaction consumed inactive CF2, produced conductive elemental ruthenium, and increased specific surface area due to gas phase product evolution. These features contribute to the excellent electrochemical performance of the modified material. The improved conductivity and larger specific surface area were further comfirmed by the results of electrochemical impedance spectroscopy and N2 adorption-desorption measurements.
Two Metal-Organic Frameworks Constructed by 1, 3-Di(1H-imidazol-4-yl) Ligand: Synthesis, Crystal Structure and Photoluminescence Property
Zhi-Qiang LIU, Jun-Feng WU, Jun CHEN, Xia WU, Yan WANG
2020, 36(1): 159-164  doi: 10.11862/CJIC.2020.003
[摘要]  (42) [HTML全文] (42) [PDF 2180KB] (2)
摘要:
Reactions of ligands 1, 3-di(1H-imidazol-4-yl)benzene (L) and with corresponding metal salts under hydrothermal conditions gave rise to two new metal-organic frameworks (MOFs), namely[Cd(L)(SO4)]n (1) and {[Ni(L)(SO4)]·H2O}n (2). All of MOFs have been structurally characterized by single-crystal X-ray diffraction analyses and characterized by elemental analysis, infrared spectra (IR), powder X-ray diffraction (PXRD) and thermo-gravimetric analysis (TGA). 1 belongs to orthorhombic system, space group Pnma, with a=0.707 28(5) nm, b=1.343 81(9) nm, c=1.407 31(9) nm, V=1.337 58(16) nm3, Dc=2.079 g·cm-3, Z=4, F(000)=824, GOF=1.072, R1=0.019 0, wR2=0.050 6. 2 belongs to triclinic system, space group P1, with a=0.986 65(18) nm, b=1.145 7(2) nm, c=1.302 5(2) nm, α=65.029(3)°, β=83.497(3)°, γ=86.423(4)°, V=1.326 0(4) nm3, Dc=1.441 g·cm-3, Z=2, F(000)=592, GOF=1.016, R1=0.043 4, wR2=0.077 1. All the MOFs have two-dimensional (2D) layer structures. Furthermore, the thermal stability and photoluminescence property of the MOFs were investigated.
Two 3D Pillar-Layered Homochiral Coordination Complexes: Syntheses, Structures and Properties
Zhong-Xuan XU, Xue-Lei BAI, Qin MENG
2020, 36(1): 165-172  doi: 10.11862/CJIC.2020.029
[摘要]  (27) [HTML全文] (27) [PDF 4083KB] (1)
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Two homochiral coordination polymers[Cd3((R)-CIA)2(bipy)2.5(H2O)2xGuest (1) and[Zn3((R)-CIA)(bmib)2(H2O)2Cl]·H2xGuest (2) ((R)-H3CIA=(R)-5-(1-carboxyethoxy) isophthalic acid, bipy=4, 4'-bipyridine, bmib=1, 4-bis(2-methyl-1H-imidazol-1-yl)benzene) were obtained under solvothermal reaction conditions. X-ray single crystal structure analysis reveals that complexes 1 and 2 are all 3D pillar-layered frameworks. From the viewpoint of structural topology, complex 1 possesses a (3, 3, 3, 6, 6)-connected net with a point symbol of (4.52)2(4.82)2(42.68.83. 102)(42.68.83.92)(5.8.9)2, while complex 2 is a (3, 4, 4)-connected net with a point symbol of (6·72)2(6·75)2(62·74). Moreover, thermal stabilities, CD spectra and luminescent properties of these new complexes have been studied.
Two Coordination Polymers Constructed by Aromatic Tetracarboxylic Acid: Luminescent and Magnetic Properties
Li-Jun ZHAI, Jie ZHANG, Ling-Ling GAO, Ting GAO, Jiao-Jiao JIA, Yu-Lan NIU, Tuo-Ping HU
2020, 36(1): 173-182  doi: 10.11862/CJIC.2019.257
[摘要]  (63) [HTML全文] (63) [PDF 5876KB] (1)
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Two new coordination polymers (CPs) based on H4tptc, namely, {[Zn2(tptc)(1, 4-bimb)2]·H2O}n (1) and {[Ni(tptc)0.5(1, 2-bimb)(H2O)]·H2O}n (2) (H4tptc=p-terphenyl-3, 3", 5, 5"-tetracarboxylic acid, 1, 4-bimb=1, 4-bis (imid-azol-1-ylmethyl) benzene, 1, 2-bimb=1, 2-bis (imidazol-1-ylmethyl) benzene), have been synthesized under solvo-thermal conditions. The structural analyses reveal that complex 1 shows a 3D structure with the symbol of (86), while complex 2 presents a 2D layer network, which is further expanded into a 3D supramolecular structure through H-bonding interactions. Furthermore, the luminescence sensing of 1 for cations, anions as well as magnetic property of 2 have also been studied.
Syntheses, Structures and Terahertz Time-Domain Spectroscopy of Two Diimine-Copper(Ⅰ)-Phosphine Complexes
Ning ZHU, Xun PAN, Sen LIN, Yu-Ping YANG, Xiu-Lan XIN, Zhong-Feng LI, Fan ZHANG, Qiong-Hua JIN
2020, 36(1): 183-191  doi: 10.11862/CJIC.2020.015
[摘要]  (58) [HTML全文] (58) [PDF 3154KB] (1)
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Herein, two novel copper(Ⅰ) complexes, [Cu(PPh3)2(dppz)]Ⅰ (1) and[Cu2(dppm)2(dppz)2]Cl2 (2) (PPh3=triphenylphosphine, dppz=dipyrido[3, 2-a:2', 3'-c]phenazine, dppm=bis(diphenylphosphino) methane) have been synthesized, and the characterization of the complexes was carried out through single-crystal X-ray diffraction, elemental analysis, IR, 1H/31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). The results show that 1 is a mononuclear complex. The central Cu(Ⅰ) builds a distorted tetrahedral geometry by coordinating with two phosphine ligands (PPh3) and one chelating N-donor ligand (dppz). Different from 1, 2 exhibits a dinuclear structure which was obtained by the reaction of CuCl and dppm with dppz in 1:1:1 molar ratio, where the diphosphine ligand (dppm) was utilized as a bridging ligand coordinating to two copper(Ⅰ) atoms. The luminescent spectra show that the emission mechanism belongs to metal-to-ligand charge transfer (MLCT). At the same time, the terahertz (THz) time-domain spectroscopy was used to represent these two complexes as well as the corresponding ligands.
Syntheses, Crystal Structures, Luminescent and Magnetic Properties of Two 1D Cadmium(Ⅱ) and Nickel(Ⅱ) Coordination Polymers
Yu LI, Yong-Xuan CHEN, Na ZHAO, An-Sheng FENG, Xun-Zhong ZOU
2020, 36(1): 192-206  doi: 10.11862/CJIC.2020.017
[摘要]  (41) [HTML全文] (41) [PDF 1826KB] (3)
摘要:
Two 1D cadmium(Ⅱ) and nickel(Ⅱ) coordination polymers, namely {[M2(μ3-L)(phen)3]·5H2O}n (M=Cd (1), Ni (2)), were constructed hydrothermally using H4L (H4L=3-(2, 4-dicarboxyphenyl)-2, 6-pyridinedicarboxylic acid), phen (phen=1, 10-phenanthroline), and cadmium or nickel chlorides. Single-crystal X-ray diffraction analyses reveal that both compounds are isostructural and crystallize in the orthorhombic system, space group Pbca. Compound 1 or 2 feature a 1D metal-organic chain, which is assembled to a 2D supramolecular network through O-H…O hydrogen bond. The luminescent and magnetic properties for two compounds were also investigated.