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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]  (45) [HTML全文] (45) [PDF 4083KB] (0)
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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]  (21) [HTML全文] (21) [PDF 3213KB] (0)
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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]  (22) [HTML全文] (22) [PDF 3159KB] (0)
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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]  (67) [HTML全文] (67) [PDF 6355KB] (0)
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]  (23) [HTML全文] (23) [PDF 2180KB] (0)
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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]  (9) [HTML全文] (9) [PDF 4083KB] (0)
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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]  (45) [HTML全文] (45) [PDF 5876KB] (0)
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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]  (41) [HTML全文] (41) [PDF 3154KB] (0)
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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]  (19) [HTML全文] (19) [PDF 1826KB] (0)
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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.
综述
多酸基光敏剂在染料敏化太阳能电池中的应用
谷易桐, 陈黎, 李建平, 刘丽, 陈维林, 刘丁, 王恩波
2019, 35(11): 1905-1920  doi: 10.11862/CJIC.2019.227
[摘要]  (572) [HTML全文] (572) [PDF 10775KB] (572)
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染料敏化太阳能电池(dye-sensitized solar cells,简写为DSSCs)是由Michael Grätzel等开发的第三代光伏电池,它具有低成本、制作简单、光学性能可调、光电转换效率高等优势。其中光敏剂是DSSCs的重要组成部分,通过吸收可见光将电子传递到半导体导带,对整个电池的电子循环至关重要。广泛采用的光敏剂为N719等贵金属配合物,但其价格非常昂贵,很难实现大规模产业化。因此寻找低成本的非贵金属光敏剂是该领域的一项挑战。多金属氧酸盐(简称多酸,Polyoxometalates,简写为POMs)是一类具有纳米尺寸的分子基纳米材料,是分子型无机类半导体材料。多酸的富氧表面可以被活化和修饰,吸收光谱可以覆盖可见区甚至近红外区,具有合适的氧化还原电势,良好的热稳定性和溶解性。近年来,一系列研究表明多酸可以作为光敏剂应用在DSSCs中。本文中,我们以课题组多年来在POMs和太阳能电池领域的研究工作积累以及国内外同行专家的研究工作为基础,对多酸基光敏剂在DSSCs中的应用进行了详细综述。首先我们阐述了DSSCs的研究意义、多酸的简介、多酸的能级测量及调控。之后我们重点综述了多酸作为DSSCs中的光敏剂和共敏剂的研究。最后,我们对多酸基光敏剂在DSSCs领域的发展前景进行了总结和展望。本文有望引起多酸化学、材料化学及新兴交叉学科领域研究者的广泛研究兴趣,并为太阳能电池光敏剂的研究提供新的思路。
金属-有机框架衍生的中空碳材料及其在电化学能源存储与氧还原领域中的应用
刘虎, 杨东辉, 王许云, 韩宝航
2019, 35(11): 1921-1933  doi: 10.11862/CJIC.2019.237
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金属-有机框架材料(metal-organic frameworks,MOFs)是一类由金属离子或金属团簇与有机配体通过配位键连接形成的具有周期性网络结构的多孔配位聚合物。这类材料通常具有孔道规整、比表面积大、孔隙率高、结构可设计及孔壁易修饰等特点,诸多的优点使得MOFs的研究从配位化学跨越到多个学科领域,成为当前多学科交叉前沿热点之一。近来的研究发现,以MOFs为前驱体碳化后制得的碳材料可保留MOFs的大比表面积和多孔结构,同时可以实现均匀的杂原子(如N、P、S、B等)掺杂,而且通过选择合适的MOFs前驱体可调控产物的组成和形貌尺寸,这些显著的结构特征使其具备了成为高性能功能性材料的潜力。最近,以MOFs为模板或前驱体制备的中空碳材料引起了人们的广泛关注,这主要是因为中空结构可有效缓解材料在电化学过程中产生的体积变化及受到的冲击,而且中空结构可暴露出更多的活性位点,具有快速的传质过程,使得材料发挥出最优性能,故而此类材料可被用在二次电池、电容器、电催化等多种电化学器件和多个领域中。基于此,本文综述了MOFs衍生的中空碳材料在储能器件及电催化领域的研究进展,主要包括锂离子电池、锂硫/硒电池、钠离子电池、超级电容器、电催化氧还原等领域,并对这类材料当前面临的挑战及未来的发展趋势进行了阐述。
多酸基主客体框架材料POMs@MOFs(COFs)
李季坤, 赵帅恒, 胡长文
2019, 35(11): 1934-1956  doi: 10.11862/CJIC.2019.230
[摘要]  (509) [HTML全文] (509) [PDF 14288KB] (509)
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多酸具有组成、结构和尺寸易于调控的优点以及良好的电子储存和氧化还原能力,在催化、光电、磁等领域具有广阔的应用前景。特别是在催化领域,更是受到化学家们的青睐。多酸在催化反应过程中易团聚而导致失活,且比表面积较低,而将其引入到结构明确、多孔的框架材料中则能较好地解决以上问题。因此,该类材料已成为多酸化学领域的研究热点之一。本文按照多酸基主客体框架材料的合成方法,即原位合成法、浸渍合成法和机械研磨合成法来进行分类,并分别讨论了其优缺点。并进一步总结了该类材料在催化、染料吸附降解、质子传导以及光电传感等领域的性能和应用,并对其未来发展趋势进行了展望。
仿生矿化增强材料
曹含, 潘海华, 唐睿康
2019, 35(11): 1957-1973  doi: 10.11862/CJIC.2019.250
[摘要]  (512) [HTML全文] (512) [PDF 8175KB] (512)
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近年来,随着材料科学领域的发展,机械性能优异且具有特定功能的有机-无机复合材料成为了研究热点。而天然的生物矿化过程产生了在自然界中分布广泛、结构特征多样性、机械性能优异的天然生物矿物,比如牙齿、骨骼、珍珠、贝壳、海胆刺、海洋红虫颚等。这些天然复合增强材料中的矿化组织结构特点和矿化机理为仿生设计与合成具有特定结构、特定功能和优异机械性能的材料提供了理论依据。通过模拟天然过程的仿生矿化方法,利用有机基质调控无机矿物成核生长为固态矿物,最终能够定向组装具有特定有序结构和先进功能的有机-无机复合材料。本文主要综述了自然界中通过生物矿化过程得到的高强度、高韧性的天然复合增强材料,以及受生物矿化增强现象的启发,在化学与材料仿生矿化合成中出现的一些有机-无机复合的增强材料。
单分子磁环最新进展及研究展望
李晓磊
2019, 35(11): 1987-1998  doi: 10.11862/CJIC.2019.246
[摘要]  (497) [HTML全文] (497) [PDF 9132KB] (497)
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与单分子磁体的定义(SMMs)相类似,单分子磁环(SMTs)定义为具有环形磁双稳态的一类分子。该类配合物的特征在于弱耦合磁矩的"涡旋"空间分布导致总磁矩为零,但是分子仍具有环形磁矩。单分子磁环为量子计算和信息存储提供了广阔的应用前景,也可以作为具有磁电耦合效应的多铁材料。自从在[Dy3]分子中首次观察到典型的单分子磁环行为以来,研究人员在合成单分子磁环方面做出了巨大的努力,致力于合成具有环形磁矩的分子以及设法将环形磁矩增强。本文将对近年报道的新兴单分子磁环配合物进行详细地分析讨论,旨在阐明影响环形磁矩排列的因素以及单分子磁环配合物的综合设计策略,指导探索合成具有增强环形磁矩的单分子磁环配合物。
水系锌离子二次电池锌负极的研究进展
王福慧, 刘辉彪
2019, 35(11): 1999-2012  doi: 10.11862/CJIC.2019.239
[摘要]  (527) [HTML全文] (527) [PDF 17455KB] (527)
摘要:
锌离子二次电池具有优异的充放电性能、高功率密度和能量密度、低成本、高安全性和环境友好的特点,极具发展前景。金属锌,因优异的导电性、低的平衡电势、高的理论比容量和低成本等因素,是水系二次电池中理想的负极材料,然而也存在着枝晶生长、腐蚀和钝化等问题,限制了锌离子二次电池的可逆容量和循环寿命,通过优化调节锌负极的形貌与表面修饰等方法可以提高电池性能。本文综述了水系锌离子二次电池负极材料的研究进展,涵盖了金属锌负极、复合锌负极和锌合金,且展望了锌负极的发展前景。
单离子磁体及其磁弛豫动力学的研究进展
芶晓霜, 王梦梦, 孟茜茜, 程鹏
2019, 35(11): 2013-2030  doi: 10.11862/CJIC.2019.232
[摘要]  (539) [HTML全文] (539) [PDF 9298KB] (539)
摘要:
单分子磁体因其在高密度信息存储、自旋电子学以及量子计算方面有潜在的应用价值而被广泛关注。单离子磁体是具有单个金属自旋中心的单分子磁体,其特点是结构简单、可设计性强和磁构关系更易研究。本文介绍了近年来典型的单离子磁体及其磁弛豫动力学的研究进展。
Reviews
pH-Sensitive Iridium, Ruthenium and Platinum Complexes for Tumor-Specific Fluorescence Imaging and Cancer Therapy
Si-Qi ZHANG, Li-Hua GAO, Hua ZHAO, Ke-Zhi WANG
2019, 35(11): 1974-1986  doi: 10.11862/CJIC.2019.231
[摘要]  (508) [HTML全文] (508) [PDF 5204KB] (508)
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Acidic pH in tumor tissues provides a powerful platform for accurate tumor diagnosis and efficient therapy. The pH-sensitive iridium, ruthenium and platinum metal complexes have attracted increasing attention due to their high physicochemical stability, favorable spectral properties and tumor targetability. In this review, we summarize formation mechanisms of the acidic tumor microenvironment and recent advances on the acidic microenvironment-sensitive metal complexes of iridium, ruthenium and platinum for tumor imaging chemotherapy agents.
论文
一种螯合型Fe2+探针的构筑及性质
李泽冉, 朱健萍, 于涵洋, 陈韵聪, 何卫江, 郭子建
2019, 35(11): 2031-2037  doi: 10.11862/CJIC.2019.223
[摘要]  (639) [HTML全文] (639) [PDF 3973KB] (639)
摘要:
铁是人体的必需过渡金属元素,体内铁离子平衡的紊乱与多种疾病相关。发展铁离子探针,实现细胞和生命体中铁离子时空分布的跟踪与成像,对铁离子生理功能的研究具有重要价值。我们将BODIPY荧光团与三联吡啶通过乙烯基偶联,构建了新型Fe2+螯合型探针BTPY,通过比色法与荧光法结合,实现了Fe2+的特异性检测。探针最大激发波长582 nm在可见光区,荧光发射波长678 nm在近红外区,满足活体近红外成像的初步要求。BTPY与Fe2+/Fe3+结合导致吸收波长由573 nm红移至607 nm,溶液颜色由红色到蓝色。其他金属离子的结合不发生明显吸收峰和颜色变化。同时,Fe2+引起BTPY荧光猝灭而Fe3+对BTPY荧光不造成明显影响,实现了Fe2+与Fe3+的区分。
基于三吡啶烯烃配体的一维配位聚合物:合成、结构及光电性质
陈慧娴, 刘春玉, 周璇, 陈敏敏, 倪春燕, 郎建平
2019, 35(11): 2038-2044  doi: 10.11862/CJIC.2019.228
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摘要:
在室温下,用三吡啶烯烃配体dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine(ppvppa)与银盐溶液反应,分别得到3个具有类似的一维链结构的配位聚合物{[Ag(ppvppa)]BF4}n1)、{[Ag(ppvppa)]PF6}n2)和{[Ag(ppvppa)]NO3}n3)。在溶剂热条件下,用ppvppa与Ni(Ⅱ)反应,得到另一个以辅助羧酸配体桥联的一维配位聚合物{[Ni(ppvppa)(2,3-NDC)(H2O)]·2H2O}n4)。对配合物1~4分别进行了元素分析、红外、热重、粉末X射线衍射、单晶X射线衍射等结构表征。配合物1~3呈现出由ppvppa连接Ag(Ⅰ)形成的阳离子一维双股链结构。配合物4呈现出由2,3-NDC配体桥联2个相邻的[Ni2(ppvppa)2(H2O)2]单元形成的中性一维双股链结构。含有Ag(Ⅰ)的配合物1~3表现出良好的荧光性质,而含Ni(Ⅱ)的配合物4没有荧光响应。选取配合物14作为代表,研究了它们的光电流响应性质。配合物14均表现出灵敏的阳极光电流响应,且在多次循环后仍保持稳定且可重复,其光电流值分别为2和6 μA,明显强于空白ITO电极的光电流响应。
核壳结构MoOx/C微球的制备及储锂性能
白玉林, 王澄, 吴越, 刘于斯, 马超, 蔡志鹏, 王开学, 陈接胜
2019, 35(11): 2045-2050  doi: 10.11862/CJIC.2019.233
[摘要]  (506) [HTML全文] (506) [PDF 3615KB] (506)
摘要:
采用水热法合成了MoO3/酚醛树脂前驱体,然后在空气中进行煅烧处理,成功制备了一种新型核壳MoOx/C微球。对材料的晶体结构、形貌和元素价态进行分析表明,该材料的主要成分是单斜相MoO2、正交晶系MoO3和碳。树脂在空气中的煅烧碳化将MoO3/酚醛树脂前驱体中的六方晶系的MoO3还原为单斜相MoO2。其中少量的MoO2会在空气中重新被氧化成正交晶系的MoO3,形成了MoO2/MoO3异质结构。在这一系列反应的综合作用下,形成这种表面有裂纹的核壳MoOx/C微球复合材料。将该材料用作锂离子电池负极材料,表现出了循环稳定性高、倍率性能好等优异的电化学性能。在100 mA·g-1的电流密度下充放电循环100次之后,可逆容量达640.6 mAh·g-1
SAPO-11的绿色制备及在棕榈油催化加氢制备生物航煤方面的应用
刘思阳, 白依凡, 李伟
2019, 35(11): 2051-2056  doi: 10.11862/CJIC.2019.242
[摘要]  (504) [HTML全文] (504) [PDF 1903KB] (504)
摘要:
通过加入晶种的方法降低在合成SAPO-11分子筛过程中有机胺类模板剂的含量从而减少对环境的污染。通过调节晶种及模板剂的含量,得到加入4%晶种、模板剂与Al2O3物质的量比值(ntemplate/nAl2O3)为0.6的条件下得到的晶体的形貌、结晶度等最好。分子筛负载Ni-Mo金属合成催化剂,以棕榈油加氢脱氧产物(HDO)为原料,在623 K下测得对生物航煤的选择性为66.1%,转化率为79.8%。
污泥与醋糟共热解特性及碱金属迁移规律
李强强, 张阳倩, 郑颜, 张毅民
2019, 35(11): 2057-2065  doi: 10.11862/CJIC.2019.252
[摘要]  (511) [HTML全文] (511) [PDF 4615KB] (511)
摘要:
分别采用热重分析仪、真空固定床反应器和原子吸收光谱研究了污泥与醋糟共热解过程中反应动力学、产物分布和碱金属迁移行为,探究了协同效应及碱金属迁移规律。结果表明,两者共热解过程中存在明显协同效应;与理论计算相比,混合物分解所需的活化能下降了35.38%~29.49%,脱挥发指数比计算低3.5×10-8。协同效应导致气体产率增加,生物炭、液体产率降低;醋糟的存在加速了污泥的脱挥发分析出,提高了气体产物中合成气含量,加大了生物炭中大芳香环的裂解反应,使生物油中酚类和酯类物质含量明显增加;热解终止时,碱金属元素析出量达到79.19%~86.73%。
双吡啶酰腙Schiff碱双核Fe(Ⅱ)配合物的合成与磁性
张男, 苑娟, 刘美姣, 金怡姝, 寇会忠
2019, 35(11): 2066-2072  doi: 10.11862/CJIC.2019.234
[摘要]  (1676) [HTML全文] (1676) [PDF 2313KB] (1676)
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基于己二酰肼双缩(溴代)吡啶甲醛Schiff碱配体HLxx=1,2),合成了2例双核Fe(Ⅱ)配合物,并通过红外光谱、X射线单晶衍射分析及磁化率测量等手段对配合物进行了表征。X射线单晶衍射分析结果表明,每个独立单元中均含有2个Fe(Ⅱ)离子、2个配体单元和4个高氯酸根阴离子,Fe(Ⅱ)离子呈N4O2八面体配位构型。分子间ππ堆积作用将配阳离子连成超分子一维链结构。磁性测试表明2个配合物都是高自旋态,同时配合物2呈现弱的分子间铁磁耦合作用。
纳米氧化铪的制备与热膨胀性
孙静, 李强, 林鲲, 刘占宁, 邢献然
2019, 35(11): 2073-2077  doi: 10.11862/CJIC.2019.249
[摘要]  (502) [HTML全文] (502) [PDF 3202KB] (502)
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制备了尺寸为4 nm的HfO2纳米颗粒,并借助X射线原子对分布函数方法,研究了尺寸约4 nm和体相HfO2颗粒的晶格热膨胀。结果表明,在纳米尺度的HfO2中,晶格沿ac轴的热膨胀性增大,b轴热膨胀性稍微减小,体积热膨胀性增大。同时纳米HfO2晶格热膨胀的各向异性比体相大。该现象是由于尺寸效应导致结构畸变变大,尤其是次近邻Hf-O-Hf键角减小,随后升温过程中该畸变发生热弛豫趋向恢复至平衡位置导致的。
金属单原子模型催化剂热稳定性的反应力场(ReaxFF)分子动力学研究
杨文琦, 汪杰, 乔园园, 王贵昌
2019, 35(11): 2078-2082  doi: 10.11862/CJIC.2019.251
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摘要:
金属催化剂的催化活性与其配位不饱和度密切相关,配位不饱和度越高,其催化活性一般也越高。单原子催化剂(SAC,或ad-atom)模型在金属表面上具有最小的配位数,因而往往表现为高的催化活性,但其热稳定性值得深入的研究。在本工作中,我们基于反应力场(ReaxFF),运用LAMMPS(large-scale atomic/molecular massively parallel simulator)软件包进行大尺度分子动力学模拟,研究单原子模型的热稳定性。模拟结果表明,只有Fe1/Fe(100)单原子催化模型可以在较高温度下稳定存在,而其他金属单原子表面分散结构则随温度升高而发生单原子聚集形成大的纳米颗粒或沉降的现象。同时我们也研究了在H2和O2气氛下Ni1/Ni(111)催化剂的动态行为,发现与真空环境相比,H2和O2气氛在一定程度上提高了催化剂的稳定性。
生物金属有机框架ZnBTCA对CO2的选择性吸附性能
才红, 吴光伟, 赖佳丽, 陈锦萍, 陈燕飞, 李丹
2019, 35(11): 2083-2088  doi: 10.11862/CJIC.2019.236
[摘要]  (498) [HTML全文] (498) [PDF 2598KB] (498)
摘要:
采用溶剂热法制备的生物金属有机框架ZnBTCA,在CO2的吸附过程中表现出有趣的主客体化学现象,通过计算发现随着CO2吸附量的增加,吸附焓逐渐增大。采用4种模型分别对其进行拟合,并通过理想吸附溶液理论模拟预测ZnBTCA对二元混合气体的选择性,试图找到ZnBTCA反常吸附行为的合理解释:ZnBTCA带有氨基和N-活性位点,且孔道内含有大量的客体离子。虽然ZnBTCA孔径较大,但由于其本身的阴离子框架,孔道中的(CH32NH2+抗衡离子并未完全去除而降低了可接触的微孔体积,在吸附过程中存在分子筛效应,在二元混合气体中对CO2具有很高的吸附选择性。
4-(2-羟基-3-氯)苯基-2, 2':6', 2"-三联吡啶Cu(Ⅱ)配合物的合成、结构表征及抗肿瘤活性
钟玉君, 陈振锋, 梁宏
2019, 35(11): 2089-2094  doi: 10.11862/CJIC.2019.253
[摘要]  (595) [HTML全文] (595) [PDF 3218KB] (595)
摘要:
以4-(2-羟基-3-氯)苯基-2,2':6',2"-三联吡啶(HL)为配体,合成了一种新的铜(Ⅱ)配合物[Cu2μ-L-κO,O)2Cl2](1),并通过红外光谱、电喷雾质谱、元素分析及单晶X射线衍射分析等方法对配合物1进行结构表征。配合物1为双核结构,中心铜(Ⅱ)离子为五配位扭曲四方锥几何构型,每个铜离子与1个Cl-以及来自配体(L-)的2个N原子和2个羟基O原子配位,2个铜(Ⅱ)离子通过羟基的桥联形成双核结构。MTT实验结果表明:配合物1对所选5种癌细胞株表现出不同的抑制活性,尤其是对MGC80-3细胞的抑制作用最明显,抑制率高达(84.30±1.28)%,其IC50值为(3.36±0.43)μmol·L-1。流式细胞术分析结果显示:配合物1能诱导MGC80-3细胞凋亡。在配合物1浓度为4.5 μmol·L-1时,MGC80-3的凋亡百分数为41.4%。此外,配合物1将MGC80-3细胞阻滞于G1期,从而抑制肿瘤细胞的生长。
CYCU-3孔内合成聚吡咯及其电导性能表征
周盈汐, 王会锋, 孙福兴
2019, 35(11): 2095-2100  doi: 10.11862/CJIC.2019.238
[摘要]  (495) [HTML全文] (495) [PDF 1532KB] (495)
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以具有一维介孔孔道的金属有机框架材料CYCU-3作为主体材料,采用碘氧化法在其孔道内进行了吡咯的聚合反应,从而得到了复合材料PPy@CYCU-3。利用粉末X射线衍射、扫描电镜、热重、红外、荧光光谱等对CYCU-3、吸附吡咯后的Py@CYCU-3以及孔内聚合后的复合材料PPy@CYCU-3进行了表征,证明了孔内聚合的成功进行,而且在聚合过程中,CYCU-3基本保持了结构的稳定,形貌也未发生改变。而且,PPy@CYCU-3复合材料是具有多孔性和电导性的多功能材料。氮气吸附表明该材料为典型的微孔材料,其BET比表面积为420 m2·g-1。电导测试表明该材料的电导率为10-7 S·cm-1,高于CYCU-3的电导率(σ≈10-13 S·cm-1)6个数量级,是一种半导体材料。
一例夹心型混合价锑钼酸盐的合成、结构及性质
杨宗斐, 牟秋水, 王亚平, 马鹏涛, 王敬平, 牛景杨
2019, 35(11): 2101-2107  doi: 10.11862/CJIC.2019.245
[摘要]  (679) [HTML全文] (679) [PDF 4257KB] (679)
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以(NH46Mo7O24·4H2O、Sb2O3和Sb2O5等为原料,利用常规水溶液法合成了一例结构新颖的含有混合价锑的杂多钼酸盐:[(CH34N]8Na41H17[(Sb3O3)(SbMo6O242]6·162H2O(1),并通过元素分析、红外光谱、热重分析和X射线单晶衍射等分析手段对化合物1进行了表征。化合物1含有夹心型的多酸阴离子簇[(Sb3O3)(SbMo6O242]11-,并进一步通过Na+连接形成二维结构。此外,我们还研究了该化合物的变色性质。当该化合物的粉末被加热或氙灯(300 W)照射时,其颜色由淡黄色变为青黄色或棕褐色。
Articles
Synthesis, Crystal Structures and Fluorescence Properties of Two Nanosized Zr-Based Molecular Capsules
Yan-Li TAO, Wei-Chao CHEN, Xin-Long WANG, Zhong-Min SU
2019, 35(11): 2108-2116  doi: 10.11862/CJIC.2019.224
[摘要]  (573) [HTML全文] (573) [PDF 3985KB] (573)
摘要:
Two nanosized zirconium-based molecular capsules (Zr-MCs), namely[Cp3Zr3(μ3-O)(μ2-OH)3]2(BPDC)3Cl2 ·H2O (Zr-MC-1) and[Cp3Zr3(μ3-O)(μ2-OH)3]2(NDC)3Cl2·3H2O (Zr-MC-2), have been synthesized by reacting zirconocenedichloride (Cp2ZrCl2) with 4, 4'-biphenyldicarboxylic acid (4, 4'-H2BPDC) and 2, 6-naphthalenedicar-boxylic acid (2, 6-H2NDC), respectively, which are constructed by two trinuclear zirconocene building blocks and three linear carboxylate ligands. They were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and N2 adsorption-desorption tests. In addition, the fluorescence spectra indicate that Zr-MC-1 and Zr-MC-2 are deep-blue and blue emitting materials with emission peaks at 404 and 456 nm, respectively.
Bi-functional Lanthanide Compounds: Synthesis, Structures, Magnetism and Fluorescence
Yong-Fang HAN, Li-Zhen CAI, Guo-Cong GUO
2019, 35(11): 2117-2124  doi: 10.11862/CJIC.2019.229
[摘要]  (502) [HTML全文] (502) [PDF 2748KB] (502)
摘要:
Two isostructural lanthanide (Ln) compounds with N-succinopyridine (HL) ligand, namely[Ln(HL)2(H2O)4]Cl3 (Ln=Pr (1), Eu (2)), have been synthesized and structurally characterized. Both 1 and 2 feature 1D chains with metal ions double-bridged by carboxyl ligands, which are further interconnected through hydrogen bonds to yield a 3D supramolecular architecture. Variable temperature magnetic susceptibility measurements revealed the presence of antiferromagnetic interaction between Pr(Ⅲ) ions for 1 but weak ferromagnetic interactions between Eu(Ⅲ) ions for 2. Solid-state luminescence measurement showed that 2 emitted intense red luminescence, but no characteristic peak of 1 was observed due to the large energy gap of the Pr(Ⅲ) ion.
Synthesis of Fluorescent Mesoporous Silica Nanoparticles and Application for Intracellular Drug Delivery
Min-Min CHEN, Hao-Ran GENG, Jin-Xia HU, Qiong ZHANG, Amfo Agyekum Godfred, Zhuo-Qi ZHANG, Xi-Chuan CAO
2019, 35(11): 2125-2135  doi: 10.11862/CJIC.2019.244
[摘要]  (516) [HTML全文] (516) [PDF 4688KB] (516)
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Here, we reported the synthesis and FITC-functionalized of mesoporous silica nanoparticles (MSNs) for tracing bioimaging and sustained drug release. Firstly, the MSNs-FITC were synthesized through one-pot method and characterized by SEM, TEM, FT-IR, XRD and the N2 adsorption-desorption isotherm respectively. Then a classic anticancer drug doxorubicin (DOX) was loaded into the MSNs-FITC. The DOX-loaded nanocarriers exhibited obviously pH dependent release behavior with accelerated release rate in acidic environment. Meanwhile, the in vitro cytotoxicity evaluation exhibited that the nude MSNs-FITC were highly biocompatible. Furthermore, the confocal laser scanning microscope (CLSM) images indicated that MSNs-FITC could penetrate into living cells effectively and dose-depended internalization of MSNs-FITC were further investigated by flow cytometry analysis (FCM).
Postsynthetic Modification of UiO-66 with Perfluoroalkyl for Adsorbing Organic Pollutants
Meng-Ying XU, Gan-Lin SONG, Bao-Hang HAN
2019, 35(11): 2136-2144  doi: 10.11862/CJIC.2019.247
[摘要]  (507) [HTML全文] (507) [PDF 4052KB] (507)
摘要:
Through postsynthetic modification (PSM) of metal-organic frameworks with perfluoroacetyl and perfluoropropionyl as functional groups, hydrophobic frameworks (UiO-66-F1 and UiO-66-F2) were obtained. Both frameworks exhibited lipophilicity, which indicates that they are potential absorbents for liposoluble solvent. The crystallinity, stability, and exceptional porosity of modified MOFs decreased slightly compared to those of UiO-66-NH2. Their Brunauer-Emmett-Teller (BET) specific surface areas were 810 and 610 m2·g-1 for UiO-66-F1 and UiO-66-F2, respectively. Suitable pore size and hydrophobic microenvironment made the frameworks easier to adsorb organic pollutants in water. Furthermore, they showed an obvious increase in adsorption capacity for a variety of organic solvents and endowed outstanding recycling performance without a significant reduction in adsorption capacity after recycle ten times.
Metal-Organic Frameworks with 2, 6-Di(1H-imidazol-1-yl)naphthalene and Dicarboxylate Ligands: Synthesis, Crystal Structure and Photoluminescence Sensing Property
Zhi-Qiang LIU, Shi-Hu CAO, Zhe ZHANG, Jun-Feng WU, Yue ZHAO, Wei-Yin SUN
2019, 35(11): 2145-2151  doi: 10.11862/CJIC.2019.225
[摘要]  (502) [HTML全文] (502) [PDF 3354KB] (502)
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Reactions of 2, 6-di(1H-imidazol-1-yl)naphthalene (L) and dicarboxylic acid ligands with corresponding metal salts under solvothermal conditions gave rise to three new metal-organic frameworks (MOFs)[Co(L)(AIP)]·2DMF (1), [Co(L)(AIP)]·DMF (2) and[Co(L)(IDC)(H2O)2]·0.5L·H2O (3) (H2AIP=5-aminoisophthalic acid, H2IDC=4, 4'-iminodibenzoic acid). The MOFs have been structurally characterized by single-crystal and powder X-ray diffraction analyses, elemental analyses, infrared spectra (IR) and thermogravimetric analysis (TGA). MOF 1 crystallizes in monoclinic space group C2/c, while 2 and 3 are triclinic space group P1. MOFs 1 and 3 have distinct infinite one-dimensional (1D) chain structures, and 2 is a two-dimensional (2D) network, which are further linked together by hydrogen bonding interactions to give the eventual three-dimensional (3D) supramolecular architectures. Furthermore, the thermal stability and photoluminescence property of the MOFs were investigated, and it was found that 3 can efficiently detect acetone molecules via fluorescent quenching.
Receptor Influence on Sensing Performance of Metal-Free Porphyrin Sensor
Cong GENG, Hui ZHENG, Yu-Ting CHEN, Jian-Zhuang JIANG
2019, 35(11): 2152-2158  doi: 10.11862/CJIC.2019.235
[摘要]  (519) [HTML全文] (519) [PDF 3299KB] (519)
摘要:
The optical properties of a metal-free tetra(aryl)porphyrin with two N, N-di(2-pyridylmethyl)amino groups (Porphyrin-2-DPA) upon respective addition of different metal ion were investigated. Systemic studies show that the rigid π-conjugated tetrapyrrole macrocyclic moiety of Porphyrin-2-DPA is employed not only as the sensitive signaling fluorophore but also as the primary receptor with excellent binding affinity and distinctive selectivity to metal ion, which together with the no-conjugated DPA auxiliary receptor endows Porphyrin-2-DPA the sensitive versatile sensor to Pb2+/Cu2+ on the basis of dual-optical signals.
Synthesis, Crystal Structure, Magnetic Properties and Catalytic Activity of Co(Ⅱ)/Ni(Ⅱ) Complexes with 3, 3'-(Pyridine-3, 5-diyl) Dibenzoic Acid
Xiao HAN, Zhichao SHAO, Bei ZHAO, Ning REN, Xiang-Ru MENG, Jie DING, Hong-Wei HOU
2019, 35(11): 2159-2167  doi: 10.11862/CJIC.2019.241
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摘要:
Two complexes 1~2 (1={[Co2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n and 2={[Ni2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n, H2pddb=3, 3'-(pyridine-3, 5-diyl) dibenzoic acid, DMA=N, N-dimethylacetamide) have been synth-esized and identified by Infrared spectroscopy (IR), elemental analysis, thermogravimetric analysis (TG) and single crystal X-ray diffraction. Structural analyses show that 1 and 2 are isostructural, and display a 3D (3, 6)-connected net with the point symbol (42·6)·(44·62·88·10). Besides, the UV-Vis absorption spectra in solid state, the magnetic properties and catalytic activity of 1~2 were investigated. Between the proximal Co(Ⅱ)/Ni(Ⅱ) ions, the variable-temperature (2~300 K) magnetic susceptibilities of 1~2 display antiferromagnetic coupling. Furthermore, 1 have been verified to be effectual catalysts for the oxidation of arylacycloalkanes in aqueous medium.
Anti-hemolysis of Human Erythrocytes by Two Daidzein Derivatives Containing Nitrogen
Hui-Qing LIU, Mei-Xuan YU, Jing-Lei SONG, Xi YAN, Ning XU, Hai-Jun HAO
2019, 35(11): 2168-2176  doi: 10.11862/CJIC.2019.240
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摘要:
Two new daidzein derivatives containing nitrogen, 4', 7-bis(((sodium glycinate)carbonyl)methoxy) isoflavone (L1) and 4', 7-bis((hydrazinocarbonyl) methoxy) isoflavone (L2), have been synthesized and characterized by elemental analysis, IR and 1H NMR. The antioxidant properties of the daidzein derivatives were studied by evaluating its ability to capture the hydroxyl free radical, the superoxide anion free radical, and to protect erythrocytes of human blood against oxidative damage induced from AAPH (2, 2'-azobis(2-amidinopropane) hydrochloride). Results of the experiments suggest that the daidzein derivatives show excellent antioxidant activity in physiological pH condition compared with vitamin C. Especially in the hydroxyl radical scavenging activity and suppressing the hemolysis of erythrocytes of human blood, the antioxidant capacity of the daidzein derivatives is more outstanding. The IC50 values of the daidzein derivatives were in the range of 0.1~1 μmol·L-1 on hydroxyl free radical scavenging activity, which was 104 times higher than that of vitamin C.
A Unique Luminescence Behavior Based on Polyhedral Oligomeric Silsesquioxane Compounds
Qing-Rui ZHANG, Ming-Xing SONG, Rui-Ping DENG, Liang ZHOU, Hong-Jie ZHANG
2019, 35(11): 2177-2184  doi: 10.11862/CJIC.2019.248
[摘要]  (504) [HTML全文] (504) [PDF 3415KB] (504)
摘要:
In this study, an unusual luminescence behavior from two polyhedral oligomeric silsesquioxane (POSS) monomers, aminopropyl isobutyl POSS (AIPOSS) and octal isobutyl POSS (OIPOSS) was observed after heating and stirring in their tetrahydrofuran (THF) solution. The chemical structures of these POSS samples were characterized before and after the heat treatment in THF by means of 1H and 29Si nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The valence state of silicon in the POSS sample was determined by X-ray photoelectron spectroscopy (XPS) as well. The characterization results showed that there is no obvious change in their structures, except tiny difference of the 1H NMR spectra. Photoluminescence (PL) properties of the treated/untreated POSS were studied in detail. According to the PL and structure characterization results, it is speculated that this unusual luminescence from the treated POSS is most likely caused by the adsorption effect of the POSS cage, forming the POSS/solvent adducts, which lead to the change of the electronic structure of the POSS, and consequently the luminescence of the treated POSS.
Hydrothermal Synthesis of Hierarchically Structured Flower-like Bismuth Tungstate for Photocatalytic Tetracycline Degradation
Yu-Qing ZHANG, Xue-Yu ZENG, Kai YU, Gui-Fang LIU, Hai-Lei CAO, Jian LÜ, Rong CAO
2019, 35(11): 2185-2191  doi: 10.11862/CJIC.2019.243
[摘要]  (505) [HTML全文] (505) [PDF 2714KB] (505)
摘要:
Hierarchically structured flower-like Bi2WO6 was fabricated via a simple template-free hydrothermal method. The as-prepared Bi2WO6 was applied in the removal of tetracycline antibiotics presented in aqueous phases under visible irradiation. The photocatalyst were characterized by a series of physical characterizations including powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-Vis diffuse reflectance spectra, nitrogen adsorption desorption test etc. The Bi2WO6 photocatalysts showed excellent degradation capacity towards tetracycline antibiotics (tetracycline (TC) and oxytetracycline (OTC)). Moreover, the TC degradation rates were generally higher in relatively alkaline solutions. The Bi2WO6 photocatalysts exhibited excellent stability and could be recycled for reuse.