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综述
高配位3d过渡金属单离子磁体磁各向异性研究
崔会会, 孙同明, 王淼, 陈磊, 汤艳峰
2021, 37(2): 193-205  doi: 10.11862/CJIC.2021.044
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摘要:
单离子磁体(SIMs)因其磁性双稳态和慢弛豫机制而在高密度信息存储、量子计算和分子自旋电子学等方面具有潜在的应用价值。其中3d过渡金属单离子磁体(3d-SIMs)磁构关系较为简单且易于分析,因此得到了众多研究者的关注。目前文献上报道的大多数3d-SIMs通常具有较低的配位数,而对于高配位(七配位和八配位)的3d-SIMs缺少深入而系统的研究。我们结合近年来的研究成果,从磁各向异性的基本性质、实验表征和理论计算3个方面出发,对高配位3d过渡金属单离子磁体的配位环境、磁各向异性和慢磁弛豫行为进行了综述,分析了配位构型和配位原子等配位环境对高配位3d过渡金属单离子磁体磁各向异性的影响,为高配位3d过渡金属单分子磁体的设计与调控提供思路。
论文
三维钴基MOF[KCo7(OH)3(ip)6(H2O)4]·12H2O作为超级电容器的高容量电极材料
戎红仁, 王先梅, 马艳伟, 高葛祥, 苏豪祺, 赖梨芳, 刘琦
2021, 37(2): 206-212  doi: 10.11862/CJIC.2021.042
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摘要:
为了开发较高能量密度的超级电容器,我们通过简单的溶剂热反应合成了一种三维的钴基金属有机框架(MOF)化合物([KCo7(OH)3(ip)6(H2O)4]·12H2O,Co-ip;ip=间苯二甲酸根),并考察了其作为超级电容器电极材料的性能。Co-ip电极显示出高比电容、良好的循环稳定性和优良的倍率性能。在1 mol·L-1 KOH溶液中,电流密度为1 A·g-1时,其最大比电容为1 660 F·g-1。在电流密度为2 A·g-1条件下,循环3 000次后,其比电容的保持率为82.7%。优异的超级电容性能可归因于Co-ip具有纳米尺寸颗粒和三维的多孔结构。
键长和电子效应共同调控的β-二酮Dy(Ⅲ)配合物的合成、结构与磁性
董艳萍, 李光明
2021, 37(2): 213-220  doi: 10.11862/CJIC.2021.041
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N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl21)、[Dy(EIFD)3(EDM)]·CH2Cl22)和[Dy(EIFD)3(TEG)](3)。X射线单晶衍射分析表明,3个配合物都是八配位的单核结构,配位构型分别为双帽三棱柱、正十二面体和双帽三棱柱,分别具有C2vD2dC2v对称性。磁学性质显示了配合物1~3具有慢弛豫现象,能垒分别为95.1 K(1)、40.5 K(2)、53.8和13.4 K(3),且配合物13有明显的蝴蝶状磁滞回线。进一步讨论了配合物中Dy—O键长和含氧辅助配体的电子效应对配合物有效翻转能垒的影响。
对十四烷氧基亚胺衍生物对CN-的高选择性“双响应”识别
籍向东, 刘彩云, 张书芳, 王文霞, 岳国仁, 曹成
2021, 37(2): 221-228  doi: 10.11862/CJIC.2021.036
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设计并合成了一种新型长链烷氧基亚胺衍生物R,系统研究了受体R对10种阴离子的紫外可见(UV-Vis)及裸眼识别性能。结果表明,该受体对F-、Ac-和CN-表现出良好的UV-Vis识别能力,且在H2O/DMSO(1:1,V/V)体系中可对CN-实现单一裸眼识别。受体R识别CN-的检出限可达7.02 μmol·L-1,并制备了受体R对阴离子的检测试纸。Job曲线表明受体与阴离子以1:2的比例结合。最后利用UV-Vis滴定、核磁滴定、质谱及理论计算推测了CN-离子的识别机理,在CN-离子核磁滴定中发现了“反应型”与“氢键型”双响应识别现象,而在F-的核磁滴定中发生去质子化过程。
Tb3+,Sm3+掺杂的YNbO4多色荧光材料的制备及发光性能
南赏瑞, 付振东, 张云霄, 刘桂霞
2021, 37(2): 229-234  doi: 10.11862/CJIC.2021.004
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采用溶胶-凝胶法合成了YNbO4:Tb3+,Sm3+系列荧光粉。光谱测试表明:体系中的NbO43-基团能够吸收紫外光并将能量传递给Tb3+和Sm3+,从而增强荧光粉的发光强度。在290 nm激发下,YNbO4:Tb3+,Sm3+荧光粉的发射光谱中既出现了Tb3+的绿光发射又出现了Sm3+的橙光发射。通过改变Sm3+的掺杂浓度,实现了荧光粉发射光的光色可调。
刚性二咪唑配体组装金属有机大环与金属有机凝胶的结构与性质
陈雨, 卫杨帆, 李嘉欣, 罗文琦, 金传明
2021, 37(2): 235-242  doi: 10.11862/CJIC.2021.035
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用配体2-(4-吡啶基)-咪唑(4-PIM)和2-(4-(1-咪唑基)-苯基)-咪唑(IPI)分别与AgClO4和ZnCl2反应得到了配合物[Ag(4-PIM)]ClO41)和[Zn(IPI)]Cl2·H2O(2)。晶体结构分析表明配合物12分别具有M4L4和M2L2金属有机大环结构,且金属有机大环分子结构中存在较强的分子间作用力、芳环之间π-π作用和氢键作用。刚性配体IPI分别与AgNO3和Zn(NO32在甲醇、乙醇、二甲基亚砜、乙二醇、四氢呋喃、乙腈等有机溶剂中均能形成超分子凝胶;在乙醇溶剂中IPI与AgNO3、AgClO4、AgBF4、AgPF6、Ag(OSO2CF3)、Zn(NO32、Zn(BF42、Zn(ClO42、Co(NO32分别作用也能形成金属有机凝胶。配体IPI分子中咪唑环的1号位的N原子连接H原子,能分别与水分子或者溶剂分子之间形成氢键,可能是“锁”住溶剂分子形成凝胶的关键因素。扫描电镜图片显示配体IPI与AgNO3等银盐和Zn(NO32等锌盐在不同溶剂中能分别形成蓬松棉花状结构和疏松似面包状结构的金属有机超分子凝胶。
有序介孔氮掺杂碳负载三氧化二铁的制备及其催化氧还原性能
肖周荣, 侯放, 张香文, 王莅, 李国柱
2021, 37(2): 243-250  doi: 10.11862/CJIC.2021.024
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摘要:
制备了有序介孔氮掺杂碳负载三氧化铁,有效降低了氧还原的过电势。通过扫描电子显微镜、透射电子显微镜、氮气吸附-脱附测试、粉末X射线衍射、X射线光电子能谱、拉曼光谱等技术表征了所制备的催化剂的物理化学性质。此外,用旋转圆盘电极测试了其在碱性条件下对氧还原反应的催化活性和选择性。实验结果表明:氮气热解后铁以三氧化二铁的形式负载于有序介孔氮掺杂碳中,其比表面积达到755 cm2·g-1。拉曼和X射线光电子能谱结果表明,加入铁前驱体后所制备的催化剂石墨化程度有所提升、阻抗降低、导电性增加。在碱性条件下,Fe2O3@NC催化剂呈现出4电子氧还原反应,其起始电位(-0.01 V vs Ag/AgCl)和半波电位(-0.13 V vs Ag/AgCl)与商用20% Pt/C相当。此外,该催化剂具有较好的抗甲醇性能且其恒电压稳定性优于商用Pt/C。Fe2O3@NC催化剂用于锌-空电池放电测试,其放电功率可以达到88 mW·cm-2,是商用Pt/C的1.29倍。
吡啶-2-甲醛酰腙镉配合物的合成、晶体结构与荧光性质
黄妙龄, 骆耿耿, 林金清
2021, 37(2): 251-258  doi: 10.11862/CJIC.2021.023
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合成了3个不同结构的吡啶-2-甲醛缩对氯苯氧乙酰腙(HL)与镉的配合物。通过X射线单晶衍射、红外光谱、紫外光谱、荧光光谱以及热重等分析,对其进行晶体结构和性质的研究。单晶衍射结构解析表明:配合物1属单斜晶系,C2/c空间群,是一个通过氯离子桥联的二聚体,分子式为[Cd(HL)Cl2]2;配合物2属单斜晶系,P21/c空间群,是一个含2个有机配体、蝴蝶状的单核分子,其分子式为[Cd(HL)2Br2];配合物3属三斜晶系,P1空间群,配合物中只含有一个有机配体,其分子式为[Cd(HL)I2]。固体荧光分析表明:配体和配合物均有很强的荧光性,且发绿光。
双溶剂法制备CuCl@MIL-101(Cr)配位型吸附剂及其脱硫性能
李玉霞, 李帅帅, 刘晓勤, 孙林兵
2021, 37(2): 259-266  doi: 10.11862/CJIC.2021.016
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分别以CuCl2和维生素C为Cu(Ⅱ)源和绿色还原剂,MIL-101(Cr)为多孔载体,采用双溶剂法直接将CuCl2引入MIL-101(Cr)孔道内并全部还原成CuCl,成功实现了在金属有机骨架材料上构筑Cu(Ⅰ)活性位。结果表明,双溶剂法不会影响载体MIL-101(Cr)的结构,引入的铜物种全部被选择性地还原成CuCl。当CuCl负载量为2.85 mmol·g-1时,吸附剂对噻吩的吸附性能达到最佳,饱和吸附量为0.175 mmol·g-1,明显高于载体MIL-101(Cr)的0.112 mmol·g-1。本策略实现了在温和条件下高效可控地制备Cu(Ⅰ)功能化吸附剂,其丰富的Cu(Ⅰ)位点和高孔隙率使得该吸附剂具有较好的吸附脱硫性能。
CoBx/Co3O4电催化剂的制备及其氧析出性能
刘国强
2021, 37(2): 267-275  doi: 10.11862/CJIC.2021.022
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采用NaBH4溶液处理经水热、热处理步骤制得Co3O4纳米棒,得到表面富含氧空位以及无定型CoBx的Co3O4(CoBx/Co3O4)氧析出(OER)电催化剂。利用X射线衍射(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)、X射线光电子能谱仪(XPS)等技术表征了催化剂的物相、微观形貌、元素组成以及表面化学键结构等。通过电化学工作站测试了电极材料的OER活性、稳定性、电化学阻抗等。结果表明,经NaBH4处理后,Co3O4表面高价态Co被还原至低价态Co,最终其表面有无定型CoBx的生成,并含有大量氧空位,有效提升了OER性能。在1.0 mol·L-1 KOH电解质溶液中,达到10 mA·cm-2的电流密度时,CoBx/Co3O4所需的过电位由Co3O4的346 mV降至298 mV。
B掺杂尖晶石型LiMn2O4正极材料的制备及长循环电化学性能
刘清, 郭俊明, 刘晓芳, 白红丽, 向明武, 白玮, 段开娇
2021, 37(2): 276-284  doi: 10.11862/CJIC.2021.046
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采用固相燃烧法制备了单晶多面体尖晶石型LiMn1.94B0.06O4正极材料,利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)以及充放电测试等手段,对其晶体结构和电化学性能等进行了表征。结果表明,B掺杂没有改变尖晶石型LiMn2O4的晶体结构,促进了(440)和(400)晶面的优先生长,形成了高暴露的(111)晶面及少部分(110)和(100)晶面的单晶多面体LiMn1.94B0.06O4晶粒,减少了Mn的溶解和提供了更多的锂离子扩散通道,其晶粒尺寸在160~350 nm之间。在10C、25℃的条件下,LiMn1.94B0.06O4电极的首次放电比容量可达到103.0 mAh·g-1,2 000次循环后,表现出较好的容量保持率(57.7%);在15C高倍率下,LiMn1.94B0.06O4仍然保持了67.1 mAh·g-1的首次放电比容量,1 500次循环后,仍能维持46.2%的容量保持率;在1C、55℃的条件下,其初始放电比容量高达125.2 mAh·g-1,表现出良好的高温性能。B掺杂能够有效提高尖晶石型LiMn2O4的高倍率性能和循环寿命,稳定晶体结构,抑制Jahn-Teller效应和缓解Mn的溶解。
烧绿石结构Y2-xMgxRu2O7-δ(x=0.05、0.1、0.15)的制备及其OER催化活性
韩天茹, 吴静静, 屈紫馨, 唐鑫
2021, 37(2): 285-294  doi: 10.11862/CJIC.2021.043
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采用溶胶-凝胶法制备系列的镁掺杂Y2-xMgxRu2O7-δ(YMRO-xx=0.05、0.1、0.15)催化剂,通过X射线光电子能谱对其进行价态分析发现,采用小离子半径的Mg2+取代烧绿石结构中处于A位的部分Y3+,进一步增加了烧绿石结构中氧缺陷数量,也引发了部分Ru4+转变为Ru5+,释放电子到表面,促进了氧析出反应(OER)。其中YMRO-0.1催化剂的含氧缺陷浓度最高,其催化活性最高。在达到10 mA·cm-2电流密度时,相比于RuO2(358 mV)、Y2Ru2O7-δ(294 mV),YMRO-0.1仅需施加265 mV过电位并且其Tafel斜率相对于RuO2(88 mV·dec-1)和Y2Ru2O7-δ(64 mV·dec-1)仅为45 mV·dec-1。此外,由于氧空位增多,即活性位点增多,降低了自由基从金属位点脱附的吉布斯自由能,促进了OER催化性能。第一性原理表明,替位原子MgY与氧空位形成复合体,可以降低氧空位形成能,同时随着Mg2+引入,带隙变小,电荷迁移能也随之变小,进而可以得到更高的催化活性。
用于高性能超级电容器的“三明治”结构Co9S8/NiTe/Ni的设计与合成
陈鑫林, 朱志平, 吴宝鑫, 陈曙光, 周攀, 贺浩
2021, 37(2): 295-304  doi: 10.11862/CJIC.2021.031
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首先采用乙醇胺-氢氧化钾体系,实现了在泡沫镍表面原位生长NiTe活性物质层,随后以此为基体,通过复合Co9S8活性物质,构建出具有“三明治”结构、高容量、高循环稳定性的Co9S8/NiTe/Ni复合电极材料。该电极不仅在2 A·g-1电流密度下表现出1 890 F·g-1的比电容,而且在大电流密度下依然表现出优异的稳定性。
钼基吡啶类有机-无机杂化晶体材料的合成、可逆相变及介电性质
张子钰, 秦刘磊, 刘洋, 李辉, 胡宏志, 刘尊奇
2021, 37(2): 305-315  doi: 10.11862/CJIC.2021.034
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以钼酸铵、4-二甲氨基吡啶为原料,在乙醇、甲醇、HBr和水的混合溶液中通过溶剂挥发法成功合成有机-无机杂化晶体材料(C7H11N24[MoOBr4(H2O)]2Br21)。并通过变温红外光谱、单晶X射线衍射、粉末X射线衍射、热重、介电和差热分析等测试方法对晶体进行结构、热能及电性能表征分析。结构显示阴-阳离子在空间内形成π-π堆积一维链状和多维氢键网状结构。随着温度的改变以钼配离子[MoOBr4(H2O)]-为顶点的结构空穴变形引起四聚体[MoOBr4(H2O)]2Br2的氢键二面角发生明显折叠摆动,导致化合物1在238 K温度附近产生明显热能同结构相转移以及可逆性介电异常峰。
用于光降解罗丹明B及光解水制氢的直接Z型异质结CeO2@NiAl-LDHs:性能及机理
张连阳, 吴俊杰, 孟跃, 夏盛杰
2021, 37(2): 316-326  doi: 10.11862/CJIC.2021.053
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我们构建了一种具有核壳结构的直接型Z型异质结CeO2@NiAl-LDHs(LDHs=水滑石),其同时兼具高的氧化降解罗丹明B(36.91 mg·g-1·h-1)与还原制氢性能(14.08 mmol·g-1·h-1)。通过密度泛函理论(DFT)计算证实了该异质结中存在内建电场,促使电子从LDHs组分到CeO2组分之间的传递。通过表面光电压谱(SPV)和瞬态光电压(TPV)进一步证实了异质结内部的内建电场加速了电子和空穴的传递,抑制了电子和空穴的复合,从而使得更多的电子和空穴可参与氧化和还原,促使CeO2@NiAl-LDHs异质结光催化剂对罗丹明B的氧化降解和光解水制氢均表现出了较高的活性。
Articles
MoSe2/Ag3PO4 Composites: Preparation and Photocatalytic Properties for Degradation of Rhodamine B under Visible Light
Xin-Gang WANG, Kai LIU, Hui ZHU, Chong-Yu LI, Lei-Lei LIN, Feng GUO, Hong-Liang DAI
2021, 37(2): 327-339  doi: 10.11862/CJIC.2021.038
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摘要:
The as-prepared MoSe2/Ag3PO4 by in-situ deposition showed favorable photocatalytic activity and stability. Heterostructure of MoSe2/Ag3PO4 had efficient separation of photogenerated electron-hole pairs that led to the elevated photocatalytic activity. The transfer of photogenerated electrons from the surface of Ag3PO4 to MoSe2 reduced the possibility of Ag+ to metallic Ag. When the mass ratio of MoSe2 and Ag3PO4 was 1:5 (champion combination), the obtained MoSe2/Ag3PO4 could reach to 98% for RhB degradation under visible light irradiation within 30 min. In addition, MoSe2/Ag3PO4 still achieved 89% of the degradation under visible light irradiation after four regenerations. Eventually, the photocatalytic degradation of RhB by MoSe2/Ag3PO4 was revealed by liquid chromatography/mass spectrometry (LC/MS).
Two Complexes Based on Terpyridine/Benzotricarboxylic Acid Ligands: Synthesis, Structures and Properties
Xiao-Li CHEN, Lu SHANG, Meng-Ping HUANG, Yu-Qing TONG, Jia-nan ZHANG, Wan-Nian XUE
2021, 37(2): 340-350  doi: 10.11862/CJIC.2021.037
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A coordination polymer (CP) and a complex based on H3tbtd/H3bbta and bpy ligands, namely {[Co3(tbtd)2 (bpy)2(H2O)]·5H2O}n (1) and[Cd2(Hbbta)(bpy)3(C2O4)(H2O)] (2) (H3tbtd=4-(2, 4, 6-tricarboxylphenyl)-2, 2', 6', 2″-terpyridine, H3bbta=1-fluoro-2, 4, 6-phenyltriacid, bpy=2, 2'-dipyridine), have been hydrothermal synthesized and structurally characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction analyses. 1 shows 2D network structure, which is linked into 3D supramolecular network through intermolecular hydrogen bonding interactions. 2 is binuclear structure, which is linked by π…π stack interactions and hydrogen bonding interactions to form 2D supramolecular network. CP 1 exhibited photocatalytic activities for degradation of methyl orange (MO) under UV light irradiation and showed good stabilities toward UV-light photocatalysis. In addition, luminescence property of 2 and thermal stabilities of 1~2 were also studied.CCDC: 1986403, 1, 2004223, 2.
Trimethylamine Vapour Sensing Properties of MoO3-GQDs Prepared by Hydrothermal Method
Akhtar Ali, Peng DAI, Xiang-Feng CHU, Shi-Ming LIANG, Li-Fang HE
2021, 37(2): 351-360  doi: 10.11862/CJIC.2021.039
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A series of MoO3-GQDs nano-composites with different amounts of graphene quantum dots (GQDs) were prepared by the hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, Scanning electron microscope, Transmission electron microscope, FTIR and so on. The gas sensing properties of MoO3-GQDs were investigated. It was found that the amount of GQDs in the composites had a great influence on the gas response and gas sensing selectivity of the nano-composites. The sensor based on the MoO3-GQDs nano-composite (S-6, the amount of GQDs suspension was 6.0 mL) showed high response and good gas sensing selectivity to TMA at 230℃; the response of the sensor to 1 000 μL·L-1 TMA was 74.08; the response time and recovery time to 1 000 μL·L-1 TMA were 73 and 34 s, respectively; the sensor based on MoO3-GQDs (S-6) composite could detect 1 μL·L-1 TMA vapor at 230℃.
Syntheses, Crystal Structures, and Photocatalytic Properties of Cobalt(Ⅱ) and Manganese(Ⅱ) Coordination Polymers Assembled from 4-((Carboxymethyl)thio)benzoic Acid
Yu LI, Hui-Feng JIANG, Xiao-Ling CHEN, Wen-Da QIU
2021, 37(2): 361-367  doi: 10.11862/CJIC.2021.028
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Two 2D cobalt(Ⅱ) and manganese(Ⅱ) coordination polymers, namely {[Co(μ3-L)(4, 4'-bipy)]·H2O}n (1) and {[Mn(μ-L)(4, 4'-bipy)(H2O)2]·H2O}n (2), have been constructed hydrothermally using 4-((carboxymethyl)thio)benzoic acid (H2L), 4, 4'-bipyridine(4, 4'-bipy), and cobalt or manganese chlorides. Single-crystal X-ray diffraction analyses reveal that 1 and 2 crystallize in the triclinic and monoclinic systems, space groups P1 and P21/c, respectively. Complexes 1 and 2 show two different 2D sheets composed of dimer Co(Ⅱ) or 1D Mn(Ⅱ) chain units. The structural difference of 1 and 2 is driven by the metal (Ⅱ) nodes. The photocatalytic properties of two complex were investigated, showing that 2 is a promising photocatalyst for the UV-light-driven degradation of methylene blue as a model organic dye pollutant. CCDC: 1967233, 1; 1967234, 2.
Synthesis, Characterization, Antitumor Activity, and Theoretical Calculations of Co(Ⅱ) Complex Based on Pyridine-2, 6-dicarboxylic Acid
Li ZHANG, Chang JIANG, Lin-Feng GUO, Xiao-Ling ZHANG, Xiong-Qiang LIN, Jie KANG, Wei-Ming SUN
2021, 37(2): 368-374  doi: 10.11862/CJIC.2021.027
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A new cobalt complex, namely[Co(Hpdc)(bpy)Cl]·C2H5OH (bpy=2, 2'-bipyridine), was synthesized by using pyridine-2, 6-dicarboxylic acid (H2pdc) as ligand under hydrothermal condition, and followed by experimental characterization of infrared spectroscopy and X-ray single-crystal diffraction. To deeply reveal the electronic structure of this complex, density functional theory calculations were employed to investigate its charge distribution, electrostatic potential, frontier molecular orbitals, and relevant electronic properties under aqueous condition. Moreover, the antitumor activity of this complex was evaluated by thiazolyl blue tetrazolium bromide (MTT) assay in chronic myelocytic leukemia (K562) and esophageal carcinoma (OE-19) cancer cell lines, and the resulting IC50 values were estimated to be as low as (0.22±0.05) μg·mL-1 and (0.82±0.16) μg·mL-1 (i. e., (0.48±0.11) μmol·L-1 and (1.77±0.35) μmol·L-1) for K562 and OE-19, respectively, demonstrating its cytotoxic activity against these two cancer cell lines. CCDC: 1994088.
Synthesis, Structures, Luminescence and Photocatalytic Properties of Three Lanthanide Complexes Based on Ditoluoyl-Tartrate
Xiao-Li GAO, Mei-Rong HAN, Hui-Fang REN, Si-Si FENG
2021, 37(2): 375-384  doi: 10.11862/CJIC.2021.033
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摘要:
Three one-dimensional (1D) lanthanide complexes[Ln(HDTTA)3(CH3OH)3]n (Ln=Ce (1), Pr (2), Sm (3)) (D-H2DTTA=(+)-di(p-toluoyl)-D-tartaric acid) were synthesized at room temperature and normal pressure. They were fully structurally characterized by IR, elemental analysis, single-crystal and powder X-ray diffraction. The structure analysis shows that complexes 1~3 are isomorphic. They belong to chiral R3 space group of trigonal system and display infinite 1D chains structure along c axis. Photoluminescence measurements indicated that D-H2DTTA ligand can partly sensitize the f-f transition luminescence of Pr3+ and Sm3+ cations but Ce3+ at 609 nm, which is attributed to the mismatching between the excited state energy levels of metal cations and ligands. Additionally, Complex 1 exhibited photocatalytic property for the degradation of methylene blue under UV light irradiation in the solution. The photocatalytic performance was up to 76% within 160 min without any other reagents. CCDC: 2017862, 1; 2017863, 2; 2017864, 3.
综述
铋基纳米材料在癌症成像诊断与治疗中的应用
刘应兵, 于文生, 王进贤, 董相廷, 付振东, 刘桂霞
2021, 37(1): 1-15  doi: 10.11862/CJIC.2021.013
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随着纳米医学的快速发展,纳米诊疗材料因其兼具诊断和治疗等多功能性而受到越来越多的关注。铋(Bi)基纳米材料具有优异的光学、电学和磁学性质,在肿瘤的诊疗一体化领域具有广阔的应用前景。我们总结了Bi基纳米材料常用的构建方法,重点介绍了其在计算机断层扫描(CT)成像、光声(PA)成像、放射疗法(RT)、光热疗法(PTT)及协同作用方面的应用研究进展,并对其未来发展进行了总结和展望。
论文
混合熔盐法低温合成Sm2Ti2S2O5及其光催化分解水产氢
晁明坤, 马贵军
2021, 37(1): 16-22  doi: 10.11862/CJIC.2021.006
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以TiO2、TiS2及Sm2O3为前驱体,分别加入LiCl-KCl与LiCl-CsCl的最低共熔混合物作为熔盐,在较低温度下成功合成了Sm2Ti2S2O5(STSO)颗粒。通过对比不同温度下所制备产物的X射线衍射图,首次表明STSO的热力学结晶温度在520℃左右,远低于之前报道的650℃的最低合成温度。扫描电子显微镜照片显示,采用2种混合熔盐制备的STSO都呈片状形貌;同一合成温度下,采用LiCl-CsCl熔盐制备的STSO的厚度小于LiCl-KCl所得产物。采用出射光波长大于420 nm的氙灯作为光源,在含有Na2S-Na2SO3空穴牺牲剂的溶液中,所制备的STSO颗粒表现出最高35 μmol·h-1的光催化分解水产氢活性以及20 h以上的产氢稳定性。
盐酸氯丙嗪对八肋游仆虫中心蛋白C端功能的抑制
董倩, 叶旭文, 杨静, 王文明, 赵亚琴, 杨斌盛
2021, 37(1): 23-32  doi: 10.11862/CJIC.2021.019
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通过荧光光谱分析、等温滴定量热(ITC)、圆二色谱(CD)、电泳等技术研究了盐酸氯丙嗪(CPZ)和八肋游仆虫中心蛋白C端(apoC-EoCen)的结合以及CPZ对蛋白功能的影响。结果表明,在室温下10 mmol·L-1 Hepes溶液(pH=7.4)中,CPZ与apoC-EoCen以物质的量之比为1:1结合,条件结合常数约为104L·mol-1。CPZ的结合导致蛋白质的二级结构发生改变,α螺旋含量减小;对金属离子诱导中心蛋白的聚集产生了抑制作用,Tb3+敏化荧光强度也降低;阻碍了中心蛋白与着色性病干皮病C组蛋白(XPC)的结合;且影响了apoC-EoCen类核酸酶活性,导致蛋白对pBR322 DNA的切割能力下降;抑制了蛋白质的磷酸化。综合实验结果表明盐酸氯丙嗪是中心蛋白的生物功能阻断剂,对中心蛋白的功能具有良好的调控作用。
以2-(2-吡啶基)苯并噻吩为主配体的两种蓝紫光二价铂配合物的合成与性质
王登强, 陈宇, 刘小庆, 卞健健, 尹新颖, 滕明瑜, 戎梅竹, 汪正良
2021, 37(1): 33-38  doi: 10.11862/CJIC.2021.012
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摘要:
以2-(2-吡啶基)苯并噻吩(2-(2-pyridyl)benzothiophene,btp)作为主配体,分别以邻二氮菲[1, 10]并咪唑联苯酚(2-(1H-imidazo[4,5-f][1, 10]phenanthrolin-2-yl)phenol,ipap)和3-甲基-6-苯基咪唑[2,1-b]噻唑(3-Methyl-6-phenylimidazo[2,1-b]thiazole,mpmt)作为辅助配体,成功合成了2个二价铂配合物[(btp)Pt(ipap)]Cl与(btp)Pt(mpmt)Cl,并得到了配合物(btp)Pt(mpmt)Cl的晶体结构。由金属-配体电荷转移引起的2种配合物发光,具有60%左右的内量子效率,发射峰在426 nm(蓝色)与381 nm(紫色)处。HOMO/LUMO轨道能级分别为-4.69 eV/-2.55 eV与-4.80 eV/-2.21 eV。单晶衍射结果表明,较低的共轭程度导致了该类配合物的短波长发射。
溶胶-凝胶法制备Fe掺杂MgF2催化剂及其催化1,1-二氟乙烷(R152a)脱HF反应的性能
张蕾, 李雨臻, 李利春, 韩文锋, 李瑛, 唐浩东
2021, 37(1): 39-46  doi: 10.11862/CJIC.2021.021
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通过助剂掺杂的方法解决MgF2催化剂高温失活的问题。采用溶胶-凝胶法制备了一系列Fe3+掺杂的高比表面MgF2催化剂,并通过N2吸附-脱附测试、X射线衍射(XRD)、能量色散X射线光谱(EDS)和NH3程序升温脱附技术(NH3-TPD)、电子自旋共振(ESR)、X射线光电子能谱(XPS)等对FeF3/MgF2催化剂的物化性质进行了表征。结果表明,一定量(物质的量分数小于20%)的Fe3+掺杂可以有效地减少MgF2晶粒度,且随着Fe3+掺杂量的增加,催化剂的比表面积、酸性及1,1-二氟乙烷(R152a,C2H4F2)脱HF反应的催化活性均呈现增加趋势,但当Fe3+掺杂量超过20%时,催化剂明显失活。
三维α-MnO2@Co3O4异质材料的制备、表征及其催化性能
刘恒发, 谢钰, 刘琪, 程高, 孙明, 余林
2021, 37(1): 47-54  doi: 10.11862/CJIC.2021.003
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α-MnO2纳米线为基底,原位生长ZIF-67,再经焙烧转化为三维α-MnO2@Co3O4异质材料,并用于甲苯的催化燃烧反应。结果表明:粒径大小约为12 nm的Co3O4纳米颗粒均匀生长在MnO2纳米线外表面,形成异质界面。该复合材料的低温可还原性能更佳,具有更多的表面活性氧物种。相比于α-MnO2纳米线,α-MnO2@Co3O4表现出更佳的甲苯催化燃烧性能:起燃温度(转化率10%)T10为202℃,完全燃烧温度(转化率90%)T90为235℃。
复合催化剂α-(Fe,Cu)OOH/RGO的制备、表征及其协同H2O2在可见光下去除环丙沙星性能
许俊鸽, 洪俊贤, 胡蝶
2021, 37(1): 55-64  doi: 10.11862/CJIC.2021.008
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采用一步回流法制备了α-(Fe,Cu)OOH/RGO复合催化剂,通过粉末X射线衍射、扫描电子显微镜和X射线光电子能谱等对催化剂进行了表征,并以30 mg·L-1的环丙沙星(CIP)为目标污染物,研究了不同制备条件下所得催化剂在可见光照射下协同H2O2对CIP的去除效果。结果表明,成功实现了α-(Fe,Cu)OOH纳米棒在石墨烯二维薄片上原位生长,α-(Fe,Cu)OOH/RGO复合材料的可见光吸收边发生红移,禁带宽度从2.02 eV变为1.76 eV。石墨烯复合不但增强了对污染物的吸附能力,而且加快了光生电子的分离、迁移速率,还提高了反应体系中电子的传导效率。当石墨烯复合比例(质量分数)为1%时,复合催化剂的催化性能最佳。当催化剂投加量为0.40 g·L-1,H2O2浓度为0.10 mol·L-1时,反应120 min,CIP被全部去除。α-(Fe,Cu)OOH/RGO循环使用5次,对CIP的去除率均在90%以上,表明催化剂具有较强的催化活性和较好的稳定性。
巯基/羧基修饰硅藻土及其对Pb(Ⅱ)、Cd(Ⅱ)的吸附性能
杜玉成, 李生辉, 谷恒学, 李杨, 吴俊书, 靳翠鑫
2021, 37(1): 65-73  doi: 10.11862/CJIC.2021.025
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以3-巯基丙基三甲氧基硅烷(MPTS)、3-氨基丙基三乙氧基硅烷(APTES)、柠檬酸(CA)为原料,采用水浴法、水浴/低温水热法,分别制备了巯基(—SH)、氨基/羧基(—NH2/—COOH)表面修饰的硅藻土。采用傅里叶变换红外光谱、扫描电子显微镜、氮气吸附-脱附测试、热重/差示扫描量热法、X射线光电子能谱等技术对样品进行了表征,并探讨分析了样品制备机理。当重金属离子溶液pH=7,吸附时间为4 h时,以MPTS制备的巯基修饰硅藻土吸附剂对Pb(Ⅱ)、Cd(Ⅱ)的最大吸附容量分别为396、365 mg·g-1;以APTES、CA制备的氨基/羧基缩合修饰硅藻土吸附剂对Pb(Ⅱ)、Cd(Ⅱ)最大吸附容量分别为485、462 mg·g-1
三元混配铜(Ⅱ)配合物的晶体结构、DNA作用及其生物活性
蔡戴宏, 莫慧雯, 何良, 乐学义
2021, 37(1): 74-84  doi: 10.11862/CJIC.2021.026
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利用溶剂缓慢挥发法合成了以5-氯-2-(2'-吡啶基)苯并咪唑为主配体、L-苯丙氨酸根为辅助配体的三元混配铜(Ⅱ)配合物:[Cu(HPBC)(L-Phe)(H2O)]ClO4(简称为1,HPBC=5-氯-2-(2'-吡啶基)苯并咪唑,L-Phe=L-苯丙氨酸根)。采用元素分析、红外光谱、紫外可见光谱、摩尔电导率测定和电喷雾质谱等手段对配合物1进行了表征,利用X射线单晶衍射确定配合物具有五配位的变形四方锥构型,并通过电子吸收光谱、荧光光谱、粘度测定及分子对接等方法揭示了配合物主要以插入作用的方式与小牛胸腺DNA(CT-DNA)结合。配合物对被测微生物(李斯特菌、金黄色葡萄球菌和大肠杆菌)及癌细胞(SGC-7901、Bel-7402、HeLa和A549)显示出良好的抗菌和细胞毒活性(IC50=1.69~2.50 μmol·L-1)。最重要的是,通过确定细胞的形态变化(AO/EB双染法)及细胞周期测定分析,揭示了配合物1通过DNA结合的途径诱导SGC-7901细胞凋亡。
基于1D/0D有序复合SnO2纳米晶的钙钛矿太阳能电池
刘德政, 杨高元, 向文灏, 王松, 李望南, 钟杰, 黄福志, 陈美华, 梁桂杰
2021, 37(1): 85-94  doi: 10.11862/CJIC.2021.005
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通过水热前驱体中的功能添加剂调控一维(1D)纳米棒阵列疏密度,继而在纳米棒间隙沉积零维(0D)纳米颗粒,制备1D/0D有序的复合SnO2电子传输层(ETL),并组装高效、稳定的钙钛矿太阳能电池。系统研究前驱体中NaCl添加剂以及后续纳米颗粒的沉积对复合ETL的形貌结构、光谱性能及界面电荷过程的作用规律,探讨上述作用对电池光电性能的影响机制。前驱体中NaCl的加入使棒密度变小,从而使0D纳米颗粒顺利渗透到1D纳米棒间隙中,其对钙钛矿/ETL和钙钛矿/FTO界面复合的抑制作用是造成器件开路电压和填充因子增大的原因。在经2 mL饱和NaCl水溶液改性的1D电子传输层ETL-2Cl的基础上,继续沉积0D的纳米颗粒,制备得到新型1D/0D复合电子传输层ETL-2P,后者优良的电荷复合抑制作用(复合电阻是ETL-2Cl的2.9倍)和高效的电子抽提性能(抽提速率3.03×107 s-1,抽提效率91.6%)促成了电池较优的光电性能(光电效率12.15%)。
Mn、Mg共掺杂Ni(OH)2的电化学性能
姚寿广, 窦飞, 刘顿, 程杰
2021, 37(1): 95-102  doi: 10.11862/CJIC.2021.014
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摘要:
采用缓冲溶液法制备复合掺杂Mn、Mg的正极材料Ni0.82Mn0.18-xMgx(OH)2(x=0.06、0.09、0.12)。采用XRD、XPS和SEM等测试表征材料的晶体结构、锰价态和形貌,采用循环伏安和恒流充放电测试研究Mn、Mg不同掺杂比例对氢氧化镍电化学性能的影响。结果表明,Mn、Mg掺杂样品均为β相,晶粒细化;Ni0.82Mn0.09Mg0.09(OH)2样品具有优异的电极反应可逆性和充放电性能,100 mA·g-1电流密度下的放电比容量(290.6 mAh·g-1)优于商用β-Ni(OH)2(281.1 mAh·g-1);且500 mA·g-1电流密度下循环30圈后,Ni0.82Mn0.09Mg0.09(OH)2的放电比容量未见衰减,其循环稳定性优于商用β-Ni(OH)2
铬-对苯二甲酸MOF的框架异构:MIL-88B(Cr)和MIL-101(Cr)
赵田, 朱和鑫, 董茗, 赵熠
2021, 37(1): 103-109  doi: 10.11862/CJIC.2021.018
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摘要:
可以通过简单地控制乙酸浓度的方法,在相似的水热合成条件下合成2种同一家族的金属有机框架材料(MOFs):MIL-88B(Cr)和MIL-101(Cr)。在相对较低的乙酸浓度下,可以得到平均粒径为100 nm的MIL-101(Cr),并拥有很高的BET比表面积(3 543 m2·g-1)。而在相对较高的乙酸浓度下,则可得到另一种具有“呼吸”特性结构的MOF——MIL-88B(Cr)。利用粉末X射线衍射、扫描电镜、N2吸附-脱附分析、热重分析等对它们的结构、形貌、孔隙率等性质做了详细的分析。
高镍系正极材料LiNi0.88Co0.07Al0.05O2的制备及性能表征
罗京, 刘建雄, 黄玲, 肖方明, 李文超, 唐仁衡, 王英
2021, 37(1): 110-120  doi: 10.11862/CJIC.2021.010
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摘要:
以镍钴氢氧化物为原料,采用异丙醇铝水解法合成Ni0.88Co0.07Al0.05(OH)2,将前驱体与锂源充分混合,通过3种烧结条件制备出球形LiNi0.88Co0.07Al0.05O2正极材料,借助X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)以及电化学测试等表征手段对材料的晶体结构、微观形貌和电化学性能进行了较系统的研究。研究表明,在500℃下保温3 h、700℃下保温14 h的条件下合成的LiNi0.88Co0.07Al0.05O2具有良好的综合电化学性能,0.2C放电比容量达192.2 mAh·g-1,首次充放电效率为81.6%,1C放电比容量为190.7 mAh·g-1,100周后放电比容量为141.1 mAh·g-1,容量保持率达到73.4%。
Articles
Preparation, Structures and Thermal Stabilities of Four Transition Metal Complexes Constructed by 3, 7-Di(3-pyridyl)-1, 5-dioxa-3, 7-diazacyclooctane Bipyridine Ligand
Li LI
2021, 37(1): 121-130  doi: 10.11862/CJIC.2021.009
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摘要:
Four transition metal complexes, [Co(NO3) (H2O)2(L)2]NO3 (1), [Co2Cl4(L)2] ·CH2Cl2 (2), [Cd2(AcO)4(L)2] ·4CH3OH (3) and[Cd2(NO3)2(CH3OH)2(H2O)2(L)2](NO3)2·2H2O (4), were synthesized by employing a clamplike bipyridine ligand 3, 7-di(3-pyridyl)-1, 5-dioxa-3, 7-diazacyclooctane (L). Single-crystal X-ray analysis reveals that complex 1 is mononuclear structure; 2 is macrocyclic dimer; wheras 3 and 4 are rectangular dinuclear structures. The ligand molecules in these complexes has shown three types of coordination mode including mono-dentate, trans-bridge and cis-bridge. All of the complexes were also characterized by elemental analysis, IR, thermal stabilities and singlecrystal structure analysis.CCDC: 940778, 1; 915840, 2; 1446573, 3; 1446574, 4.
Reviews
Ni(OH)2 with Super-Small Nanoscale: Synthesis and Application in Li+ Adsorptions
Nan JING, An-Nan ZHOU, Guo-Hui WANG, Run-Wei WANG, Qing-Hong XU
2021, 37(1): 131-139  doi: 10.11862/CJIC.2021.015
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摘要:
α-Ni(OH)2 nanoparticles with 5 nm average diameter were prepared under the existence of glucose in water solution, and the size of α-Ni(OH)2 nanoparticles was found to be controlled by the concentration of glucose. A possible mechanism of the preparation process was proposed. When the synthesis was processed without existence of the glucose, β-Ni(OH)2 was obtained. The super-small α-Ni(OH)2 nanoparticles showed strong adsorption ability to Li+ ions when pH value of the solution was about 7.0 under room temperature. Maximum adsorption capacity of the super-small α-Ni(OH)2 nanoparticles to Li+ was about 214 mg·g-1; however, the β-Ni(OH)2 with diameter above 1.0 μm was low than 30 mg·g-1. Freundlich equation analysis and SEM images of the adsorption products indicate multilayers' adsorption process to Li+ of α-Ni(OH)2 nanoparticles.
Dynamic Formation of Pdδ+-Fe2+ Interface Promoting Reverse Water Gas Shift Reaction over Pd/FeOx Catalyst
Dian-Yu ZHANG, Fang LIU, Peng-Fei DU, Meng-Wei LI, Zhao-Xuan WU, Yi-Bing FENG, Yang ZHAO, Xiao-Yan XU, Xin-Xing ZHANG, Jun-Ling LU, Bing YANG
2021, 37(1): 140-150  doi: 10.11862/CJIC.2021.002
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We systematically investigated Pd/FeOx for the reverse water gas shift (RWGS) reaction using a combination of ex situ and in situ characterizations, including transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, temperature-programmed desorption/reduction/oxidation (TPD/TPR/TPO), and X-ray photoelectron spectroscopy (XPS). A highly dispersed Pd/FeOx catalyst was synthesized using Pd(acac)2 as the precursor. The catalyst exhibited high activity, with CO2 conversion of ~29% and CO selectivity ogreater than 98% at 400℃, which are among the highest values in the literature. Moreover, Pd/SiO2 and Pd-Fe/SiO2 were further studied to determine the significant role of the Pd-FeOx interface in promoting the RWGS reaction. Semi-in situ XPS revealed the dynamic formation of Pdδ+-Fe2+ species at the Pd-FeOx interface; the species acted as highly active sites for CO2 dissociation. Our results also showed the formation of the Pdδ+-Fe2+ interface during the RWGS reaction remarkably enhanced the activity and selectivity of the Pd-FeOx catalyst for the reaction, benefiting CO2 adsorption, C=O dissociation, and CO desorption.
Aluminum Amine Compound Protected by β-Diketiminate Ligand: Preparation and Enhanced Performance as Catalyst for Ring-Opening Polymerization of ε-Caprolactone
Wen-Ling LI, Ben YAN, Chen-Guang SUN, Qiu-Miao SHEN, Wen-Qing LIU, Xiao-Li MA, Zhi YANG
2021, 37(1): 151-156  doi: 10.11862/CJIC.2021.007
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摘要:
An aluminum amine compound (L)AlH(NMe2) (L=HC(C(Me)NAr)2, Ar=2, 6-iPr2C6H3) (1) protected by steric β-diketiminate ligand L has been synthesized successfully. A two-step synthesis method was employed to prepare the aluminum amine (L)AlH(NMe2) compound. The aluminum amine compound (L)AlH(NMe2) was identified via NMR spectroscopy, elemental analysis, infrared diffuse reflectance spectroscopy and X-ray single crystal diffraction analysis. The aluminum amine compound containing both Al-NMe2 and Al-H substitutes showed excellent catalytic performance on the ring-opening polymerization of ε-caprolactone. The molecular weight and molecular weight distribution of the resultant polycaprolactone were determined by high performance gel penetration chromatography.
Easy Preparation of N-Doped Graphene-like Nanosheets as Excellent Metal-Free Cathodic Electrocatalysts of Zn-Air Battery
Xiao-Kun YANG, A-Ling CHEN, Qing-Feng YI
2021, 37(1): 157-170  doi: 10.11862/CJIC.2021.001
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Carbon-based materials have been paid much attention due to their own good electroactivity and resources availability. Herein, we reported a simple and versatile synthesis strategy for the preparation of nitrogen-doped and metal-free carbon catalysts with excellent oxygen reduction reaction (ORR) electroactivity. Using dicyandiamide (DCD) as nitrogen source and sucrose, β-cyclodextrin and chitosan as different carbon sources, N-doped graphene-like nanosheet samples CN-nanosh(suc), CN-nanosh(cyc) and CN-nanosh(ch) were prepared by an easy pyrolysis of their mixture. The samples exhibited outstanding ORR electroactivity in alkaline media with a comparable performance to the benchmark Pt/C. Alkaline Zn-air battery with the prepared sample CN-nanosh(suc) as the cathodic catalyst displayed the maximum power density of 201.33 mW·cm-2, and its discharge time can last for more than 50 h at a constant current density of 100 mA·cm-2, which is close to the optimum values of the similar Zn-air battery with the metal-free cathodic electrocatalysts reported so far.
Electrodeposition of NiS on CoNi2S4 for Flexible Solid-State Asymmetric Supercapacitors
Ye-Zeng HE, Hou-Qiang ZHAO, Peng LIU, Yan-Wei SUI, Fu-Xiang WEI, Ji-Qiu QI, Qing-Kun MENG, Yao-Jian REN, Dong-Dong ZHUANG
2021, 37(1): 171-179  doi: 10.11862/CJIC.2021.011
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An effective approach of depositing NiS on CoNi2S4 was adopted to improve the performance of bimetallic cobalt/nickel-sulfide. The as-obtained CoNi2S4@NiS had an excellent specific capacitance of 1 433 F·g-1 at 1 A·g-1 and shows a superior rate performance of 69.6% at 10 A·g-1. A flexible solid-state asymmetric supercapacitor assembled with CoNi2S4@NiS and the reduced graphene oxide showed a high energy density of 36.6 Wh·kg-1 at a power density of 800 W·kg-1 and had a fantastic cycle performance of 78.7% retention after 10 000 cycles, indicating that the CoNi2S4@NiS nanocomposite is a promising electrode material for energy storage devices.
Preparation and in Vitro Experiment of Attapulgite-based Microgels with Magnetic/Temperature Dual Sensitivities
Tian-Le LI, Hui ZHONG, Xiao-Rong LI, Jing ZHOU, Yi-Xin LIU, Wei-Cheng HU, Zhi-Peng CHENG, Cheng YAO
2021, 37(1): 180-188  doi: 10.11862/CJIC.2021.017
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摘要:
The folic acid (FA)-grafted magnetic FA-Fe3O4/ATP-P(NIPAM-AAM) composite microgels (attapulgite=ATP, N-isopropyl acrylamide=NIPAM, acrylamide=AAM) were prepared via a method of emulsion copolymerization. The as-prepared microgels were characterized by X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermogravimetric analysis (TG), infrared spectroscopy (IR), UV-visible spectroscopy (UV), scanning electron microscope (SEM) and transmission electron microscope (TEM). The dynamic light scattering (DLS) results show that the low critical solution temperature (LCST) of microgel was about 38.5℃. The drug delivery ability of the as-prepared microgels was evaluated by using doxorubicin hydrochloride (DOX) as the model drug. Based on the drug loading and releasing results, the presence of ATP increased the amount of drug loading and releasing. Compared with free DOX, the in vitro cytotoxicity of DOX loaded FA-Fe3O4/ATP-P(NIPAM-AAM) was decreased and the biocompatibility was improved. Those results indicate that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) can be used in potential as a slow-release drug system. The in vitro cellular uptake test revealed that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) at the assigned site were significantly richer than that of other sites. This result indicates that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) composite are targeting and expectable in the application of targeted drug releasing.
Errata
Correction to "Direct Observation of Magnetic Transitions in a Nickel(Ⅱ) Complex with Large Anisotropy"
N. Widener Chelsea, N. Bone Alexandria, Ozerov Mykhaylo, Richardson Rachael, Zheng-Guang LU, Thirunavukkuarasu Komalavalli, Smirnov Dmitry, Xue-Tai CHEN, Zi-Ling XUE
2021, 37(1): 189-189  doi: 10.11862/CJIC.2021.040
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