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综述
碳纳米管基非贵金属催化剂在电催化氧化还原中的应用研究进展
王启晨, 王璟, 雷永鹏, 陈志彦, 宋垚, 罗世彬
2018, 34(5): 807-822  doi: 10.11862/CJIC.2018.101
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摘要:
燃料电池和金属-空气电池是将化学能直接转化成电能的绿色电池,具有能量密度高、安全和环保等优点,相比传统能源具有独特优势。然而,目前阴极氧还原反应(oxygen reduction reaction,ORR)使用的贵金属铂(Pt)储量低,成本高,易中毒失活,严重限制了燃料电池的大规模应用。因此,开发廉价、高效、稳定的非贵金属催化剂成为研究热点。碳纳米管具有本征sp2杂化结构、优异的导电性、高比表面积、良好的化学稳定性等突出优点,受到广泛关注。本文综述了碳纳米管基非贵金属ORR催化剂的最新进展,主要包括非金属掺杂、过渡金属-氮-碳纳米管、负载过渡金属及其衍生物(氧化物、碳化物、氮化物、硫化物等)、负载单原子、与其他碳材料(石墨烯、多孔碳、碳纳米纤维)复合以及碳纳米管基自支撑电极。最后,对碳纳米管基非贵金属ORR催化剂的研究前景和下一步研究方向进行了展望。
Article
Influence of Crystallinity and Binder on the Energy Delivery Efficiency for Porous Magnesium Cobaltate Supercapacitor Electrodes
Xue-Fei LUO, Lei GUO, Qian-Qian WEI, Jiang-Yan XU, Kuai-Bing WANG, Bo LÜ
2018, 34(5): 823-833  doi: 10.11862/CJIC.2018.119
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The magnesium/cobalt ternary oxide, porous MgCo2O4 nanostructures were synthesized by thermal decomposition of crystalline bimetallic coordination polymer precursors. As a result, various hydrothermal reaction time results in isostructural precursors with different crystallinity. When the pyrolysis temperature and binder are chose to be 500℃ and PTFE respectively, the superior practical capacitance with good energy delivery efficiency (η) is obtained. The corresponding MgCo2O4 electrode with high surface area and moderate crystallinity achieves a largest specific capacitance of 348 F·g-1, maximum η value (92.9%) and 93.7% of capacitance retention after 1 000 continuous charge-discharge cycles.
论文
溶剂热法合成Fe-CeO2与N-Fe-CeO2纳米粉体及其光催化性能
黄建平, 陈芳, 折小梅, 王赫, 石惠民
2018, 34(5): 834-842  doi: 10.11862/CJIC.2018.092
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采用溶剂热法合成了不同Fe掺杂含量的Fe-CeO2纳米粉体及不同氮源掺杂的N-10% Fe-CeO2nFe/(nFe+nCe)=10%)纳米粉体。利用TEM、XRD、XPS、Raman和UV-Vis等技术对其微观结构与形貌进行了表征,并通过降解亚甲基蓝溶液对其光催化性能进行了研究。结果表明,Fe掺杂可以提高CeO2的光催化性能,以10% Fe-CeO2催化效率最高,对亚甲基蓝的降解率从纯CeO2的67%提高到95%。而N的掺杂可调节10% Fe-CeO2催化性能。以浓氨水为氮源的N-10% Fe-CeO2(NH3·H2O-N-10% Fe-CeO2)的降解率可进一步提高到97%,并且具有较好的稳定性,经5次循环使用,对亚甲基蓝的光催化降解率仍高达89%。CeO2催化活性的提高主要由于掺杂Fe和N改变了CeO2的晶体结构与能带结构,促进了光生电子与空穴的产生与催化反应。
基于双金属Y/Zr-UiO-67的介孔氧化钇-氧化锆固溶体制备及其离子电导
陈平, 刘树成, 徐娇, 邱俊杰, 戴恩高, 刘毅
2018, 34(5): 843-849  doi: 10.11862/CJIC.2018.121
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采用溶剂热法,将不同物质的量的Y3+离子掺入金属有机框架UiO-67的次级结构单元(SBUs),得到具有Zr(Ⅳ)-O及Y(Ⅲ)-O混合次级结构单元的双金属有机框架Y/Zr-UiO-67。以此金属有机框架结构作为模板通过两步煅烧法制备介孔钇掺杂氧化锆。结果表明,这种金属有机框架结构衍生的氧化钇-氧化锆固溶体有高的比表面积和氧离子电导率。
采用复合锂源制备的LiFePO4/C材料及其碳含量优化
吴关, 周盈科
2018, 34(5): 850-856  doi: 10.11862/CJIC.2018.118
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采用Li2CO3与LiOH·H2O为复合锂源制备LiFePO4/C材料,同时优化了材料中的碳含量。由于氢氧化锂的熔点低于碳酸锂,在同样的烧结温度下,采用复合锂源可以获得更佳的熔融状态,在高温合成过程中使锂离子具有更高的扩散性,能够更顺利地得到高纯度的LiFePO4晶相。通过优化碳包覆量达到提高导电性与控制晶粒尺寸的目的,使材料晶相结构完整,纯度高,表现出优秀的加工性能与电化学性能。所制得的LiFePO4/C材料放电克容量达到158.2 mAh·g-1,在全电池中经过100 d存储后容量保持率仍然高于94.0%,具有优异的长期可靠性。
Dy3+,Eu3+共掺的LiGd(MoO4)2单一相荧光粉的合成、发光及能量传递
于汀, 高明燕, 宋岩, 李丹, 刘桂霞, 董相廷, 王进贤
2018, 34(5): 857-863  doi: 10.11862/CJIC.2018.116
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采用溶胶-凝胶法制备了LiGd(MoO42:Dy3+,Eu3+系列荧光粉。用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)、荧光光谱仪等对所得样品的结构、形貌和发光性能进行了表征,并研究了其能量传递机理。结果表明:白钨矿结构的LiGd(MoO42:Dy3+,Eu3+荧光粉的形貌为不规则颗粒,其粒径为1.8 μm。在354 nm近紫外光激发下,该荧光粉显示出Dy3+的特征黄、蓝光发射和Eu3+的特征红光发射。计算Dy3+和Eu3+的临界距离为1.383 nm,Dy3+→Eu3+之间能量传递机理为偶极-四极相互作用。通过调节Dy3+、Eu3+的掺杂浓度,荧光粉可实现暖白光发射。此外,详细研究了稀土离子(Dy3+,Eu3+)的掺杂浓度与荧光粉的色温值之间的关系。
炔桥联不对称苯基取代双二茂铁衍生物的设计合成和电化学性质
张骁勇, 韩利民, 高媛媛, 贾慧劼, 索全伶
2018, 34(5): 864-873  doi: 10.11862/CJIC.2018.109
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以四苯基环戊二烯酮为起始原料,经过八步连续反应,成功地合成了3个炔桥联不对称五苯基取代双二茂铁衍生物Fc'-C≡C-Fc(1)、Fc'-C≡C-C≡C-Fc(2)和Fc'-C≡C-C≡C-Fc'(3)(Fc'=五苯基二茂铁基,Fc=二茂铁基)。在设计合成双二茂铁衍生物的过程中,首先经过4步反应,制备出已知化合物Fc'-H(4),再连续进行3步反应,分别得到3个中间化合物Fc'-COCH35),Fc'-CCl=CHCHO(6)和Fc'-C≡CH(7),最后利用偶联反应,得到目标化合物1~3。利用X射线单晶衍射和循环伏安法,测定了化合物125、7的晶体结构,研究了化合物1~7的电化学性质。研究结果表明,分子的C-H…π键相互作用和空间位阻是导致化合物12分子中Fc'和Fc基空间排布取向不同的主要原因。当二茂铁的一个环戊二烯环上引入5个苯取代基时,铁中心的氧化还原电位将升高(Epa(Fc'-H)=0.658 V,Epa(Fc-H)=0.511 V)。与已知化合物Fc-C≡C-Fc(ΔE=0.215 V)和Fc-C≡C-C≡C-Fc(ΔE=0.134 V)相比,化合物1~3的氧化电位差值(ΔE)均有不同程度地提高(ΔE1=0.236 V;ΔE2=0.170 V;ΔE3=0.146 V)。将1与Fc-C≡C-Fc,2与Fc-C≡C-C≡C-Fc和3进行比较发现,当炔桥两端连接不同的基团Fc'和Fc时,其氧化电位差值(ΔE)将明显提高。
金红石TiO2纳米团簇与铀酰相互作用的相对论密度泛函理论计算
郑明, 张红星, 袁福龙, 潘清江
2018, 34(5): 874-882  doi: 10.11862/CJIC.2018.120
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采用全电子相对论密度泛函理论方法探索金红石型TiO2纳米团簇与铀酰的相互作用。考察金红石团簇模型(包括层数和表面积大小)变化对吸附铀形成复合物结构、吸附作用能等性质的影响,确定2层、表面积为1.1 nm×0.6 nm、包括63个原子的纳米团簇(标记为2L-Ti15)能够合理描述金红石纳米粒子性质的同时,还能节约计算资源。对2L-Ti15-[(UO2)(H2O)3]2+复合物计算表明,纳米团簇和铀酰存在共价键作用;优化得到U-Osurf键长0.233~0.238 nm,这一距离在已发现铀酰基配合物U-O距离范围内。在气相条件下,纳米团簇对铀酰吸附反应为放热过程(-3.02 eV);考虑溶剂介质环境的影响,反应则需要吸收少许能量(0.16 eV)。U-Osurf键的能量分解发现,纳米团簇和铀酰的化学键作用为轨道相互作用主导的(占94%),它的静电吸引略大于Pauli排斥。基于电子密度的QTAIM(quantum theory of atoms in molecule)分析揭示,U-Osurf作用是介于离子和共价之间的配位键,其强度高于复合物中的U-OH2键作用,但比U=O键弱。波函数分析表明,来自纳米团簇的O(2p)贡献HOMO轨道,并混有σ(U=O)成键性质,而LUMO轨道则为Ti(3d)修饰的U(5f)性质,复合物HOMO-LUMO带隙为2.40 eV,相对吸附前的纳米团簇半导体粒子的3.35 eV变窄。从吸收光谱角度而言,复合物体系可能在可见光区域具有更强的捕光性能。
水溶性膦酸双核金属钌催化t-BuOOH氧化醇性能
廖海深, 李辰, 易小艺
2018, 34(5): 883-888  doi: 10.11862/CJIC.2018.128
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双核金属钌膦酸配合物(NH43[Ru2(hedp)2]·2H2O(hedp=羟基亚乙基二膦酸)在常温水溶性体系中,无需相转移催化剂,可以高效催化t-BuOOH氧化各种醇类,包括一级醇、二级醇和长链醇。催化机理研究表明,双核金属钌膦酸配合物的[Ru-Ru]3-单元与t-BuOOH作用,可以形成含过氧键的Ru-Ru-OOtBu过渡态,然后再对底物醇进行氧化。该机理得到实验印证,如发现酸抑制而碱催进该反应,紫外可见光谱表明Ru-Ru-OOtBu的形成。
联合化疗与光动力治疗于一体的水溶性铜(Ⅱ)、镍(Ⅱ)酞菁的合成及体外抗癌活性
潘佳宝, 陈曦, 方文娟, 刘伟, 于光伟
2018, 34(5): 889-896  doi: 10.11862/CJIC.2018.127
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以邻苯二腈法合成了全水溶性铜酞菁(CuPc)6与镍酞菁(NiPc)7。对该类酞菁进行了光物理化学特性测试及体外细胞生物试验。结果表明:合成的铜酞菁6与镍酞菁7不仅水溶性好,而且对光热都十分稳定,并能有效产生单线态氧。体外细胞测试证实,铜酞菁6与镍酞菁7表现出了对癌细胞的避光下的抑制效应以及光照下的光动力治疗效应,显示了金属配合物化疗效应与光动力治疗的协同抗癌活性。
异喹啉酰肼构筑锌配合物的合成、晶体结构及其性质
巴聃, 吴文士, 黄妙龄, 石凤湘
2018, 34(5): 897-905  doi: 10.11862/CJIC.2018.129
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采用普通溶液法合成了配合物[Zn(eiqnthz)2]·DMF(1)和[Zn3(piqnthz)2Cl2]·2H2O(2)(Heiqnthz=N,N'-乙酰异喹啉甲酰肼,H2piqnthz=N,N'-丙酰异喹啉甲酰肼)。通过X射线单晶衍射分析、X射线粉末衍射分析、红外光谱分析、热重分析以及荧光光谱分析等分析方法对2个配合物进行结构测定和性质表征。结构分析表明配合物1是单核结构,单斜晶系,空间群为C2/c,锌离子周围有4个氮原子和2个氧原子与之配位,形成一个畸变的N4O2八面体构型。配合物2属于单斜晶系,C2/c空间群,三核结构。中心原子Zn(1)、Zn(2)、Zn(3)均为5配位,Zn(1)、Zn(3)位于分子两端并且是变形四角锥配位构型,Zn(2)位于中间形成三角双锥配位构型,整体呈V字型。荧光分析表明Heiqnthz、H2piqnthz与锌(Ⅱ)离子配位后其荧光都发生较大的红移。
不同调节剂制备MOF-Fe的性质及对Se(Ⅳ)的吸附性能
王锐, 龚勇, 许海娟, 魏世勇, 吴德勇
2018, 34(5): 906-916  doi: 10.11862/CJIC.2018.110
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以HF、HCl、H2O和NaAc溶液为调节剂合成了4种MOF-Fe样品,用X射线衍射(XRD)、透射电镜(TEM)、N2等温吸附-脱附、综合热分析(TG/DTG和DTA)和质子电位滴定研究了4种样品的结构与表面性质,以及对亚硒酸根(Se(Ⅳ))等温吸附特性。MOF-Fe(HF)、MOF-Fe(HCl)、MOF-Fe(H2O)和MOF-Fe(NaAc)四种样品均具有八面体MIL-100(Fe)的晶体结构,但它们的结晶度和晶面取向略有差异。4种样品的比表面积分别为1 683、1 517、1 641和1 734 m2·g-1,其总孔体积依次降低,微孔孔径分别为1.27、1.22、1.22和1.17 nm。MOF-Fe(HF)样品的脱羧基失重峰温度最高(415℃),苯环碳化失重峰温度最低(462℃);MOF-Fe(HCl)、MOF-Fe(H2O)和MOF-Fe(NaAc)样品出现了因氧化铁被碳还原所致的失重平台(566~716℃)。样品悬浮液从pH=6.0降到3.0时,消耗H+的量表现为MOF-Fe(H2O)> MOF-Fe(HCl)> MOF-Fe(HF)=MOF-Fe(NaAc),它们的电荷零点(pHZPC)依次为3.1、3.5、3.6和3.5。MOF-Fe(NaAc)、MOF-Fe(HCl)、MOF-Fe(H2O)和MOF-Fe(HF)对Se(Ⅳ)的吸附亲和力依次减小,它们对Se(Ⅳ)的吸附容量(Qm)分别为77.69、107.07、117.40和87.15 mg·g-1。显著性分析显示,MOF-Fe的羟基密度与样品吸附Se(Ⅳ)的Qm显著正相关。研究结果表明,MOF-Fe样品的结构热稳定性和羟基/配位水分子等活性位点密度受合成样品时加入的调节剂影响,用HF作为调节剂合成MOF-Fe样品有利于提高样品中羧基与苯环之间的C-C键合强度和热分解产物的稳定性,降低苯环碳化温度;HCl和H2O作为调节剂有利于提高样品的活性位点密度,可提高MOF-Fe样品对Se(Ⅳ)吸附容量。
镁掺杂纳米羟基磷灰石的制备及其在载药方面的应用
马晓雨, 刘永佳, 朱邦尚
2018, 34(5): 917-924  doi: 10.11862/CJIC.2018.106
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通过逐步沉淀反应一锅法制备了一系列不同含量的镁掺杂纳米羟基磷灰石。通过硝酸镁、硝酸钙不同的投料物质的量比调控纳米颗粒的形态和尺寸。通过透射电子显微镜(TEM)、X射线衍射(XRD)等分析手段对镁掺杂纳米羟基磷灰石进行物理化学性能表征,用MTT法评价其体外细胞毒性。研究结果表明:镁掺杂纳米羟基磷灰石呈现束状纳米纤维形态、比表面积大、细胞毒性较低;将其作为载体负载抗癌药物顺铂,具有很好的载药能力,载药量可达54%,该载药纳米颗粒还具备缓释特性(72 h释药量达到41.72%)和很好抑制癌细胞生长的效果。
软模板法制备三维花状MgAl-LDH及其吸附性能
黄云, 马若男, 曾宪哲, 相明雪, 崔锡俊, 章萍
2018, 34(5): 925-932  doi: 10.11862/CJIC.2018.132
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采用软模板法,以十二烷基硫酸钠(SDS)为模板剂,经水热合成制得三维花状双金属(MgAl)氢氧化物(3D-MgAl LDH)。通过XRD、FT-IR、SEM及TEM等表征手段,研究了原料Mg/Al物质的量之比、SDS浓度及反应时间对产物微观结构和表面形貌的影响规律,并初步探讨了3D-MgAl LDH的形成机理。结果表明,当nMg/nAl=2,SDS浓度为0.1 mol·L-1,水热反应时间为6 h时,可形成结晶度良好、花球形貌完整,纳米片厚度均一的三维花状LDH。在3D-MgAl LDH的形成过程中,SDS既以阴离子形态参与LDH形成,又因其类球状胶束特性附着在已形成的LDH表面或边缘诱导LDH纳米片交叉生长形成三维花状。吸附实验表明,3D-MgAl LDH对非离子型有机污染物具有良好的吸附作用,最大吸附量约为31 mg·g-1,去除率达到100%。
Pt-Al/MCM-41催化剂的制备及催化合成有机硅增效剂
陈秀莹, 谢慧琳, 胡文斌, 周新华, 周红军, 舒绪刚, 孙育青
2018, 34(5): 933-941  doi: 10.11862/CJIC.2018.114
[摘要]  (12) [HTML全文] (12) [PDF 6408KB] (12)
摘要:
以介孔硅MCM-41为载体,AlCl3为促进剂,制备了负载型Pt-Al/MCM-41催化剂。利用傅里叶红外光谱(FTIR)、N2吸附-脱附、X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、电感耦合等离子体发射光谱(ICP)对催化剂的结构、形貌以及金属间作用力进行了表征,着重探讨了不同Al加入量对催化剂结构和金属间作用力的影响,系统考察了Pt-Al/MCM-41用于催化聚乙二醇烯丙基醚和七甲基三硅氧烷合成有机硅增效剂。结果表明,Al的加入量对催化剂的结构和有序度有一定的影响,其比表面积、孔容和有序度随着Al用量的增加而逐步降低。此外,加入一定量的Al有利于提高Pt晶粒的分散度,减小其粒径。Pt1Al2/MCM-41催化剂具有良好的重复使用性,使用6次无明显失活,其转化率仍大于90%。合成有机硅增效剂的最佳工艺为:nPGAE/nMDHM=1.1,反应时间为4 h,反应温度为100℃,催化剂用量为0.5%,其转化率达94.1%。
Articles
Honeycomb-like Structured and Co-Mn Incorporated Carbon Materials Derived from Bombyx mori Cocoons Act as a Bifunctional Catalyst for Water Splitting
Ming ZHANG, Tao LI, Juan WANG, Yi PAN, Shi-Jie MA, Han ZHU, Ming-Liang DU
2018, 34(5): 942-950  doi: 10.11862/CJIC.2018.122
[摘要]  (11) [HTML全文] (11) [PDF 4327KB] (11)
摘要:
Porous and graphene-type honeycomb-like structured N-doped and Co-Mn incorporated carbon materials derived from Bombyx mori silk cocoons were synthesized via one-step thermal carbonization and graphitization process. Due to the high specific surface area of honeycomb-like structure, the exposed Co-Mn active sites and the pyridine-N and graphitic-N, the prepared 3% Co-Mn/silk cocoon carbon materials (3% Co-Mn/SCC) exhibits good hydrogen evolution reaction (HER) performance with a low onset potential of 121 mV, a low overpotential of 155 mV at 10 mA·cm-2 and a Tafel slope of 130 mV·dec-1 as well as a long-term stability in acidic electrolyte. Meanwhile, the 2% Co-Mn/SCC also shows great oxygen evolution reaction (OER) performance in 1 mol·L-1 KOH with the lowest onset potential 1.5 mV and a Tafel slope of 143 mV·dec-1. This result demonstrates that MCo-Mn/SCC (M is the mass fraction of Co and Mn) possess both HER and OER catalytic activity and can act as a bifunctional catalyst for water electrolysis.
Dinuclear Gd(Ⅲ)/Dy(Ⅲ) Complexes Based on Schiff base Ligands: Structures and Magnetic Properties
Ping-Ning JIN, Rui-Fang YAN, Peng HU, Yan-Ni WU, Yuan-Yuan GAO, Ling-Zhu HUANG, Yi-Xuan ZHU, Yan SU, Ying-Ling WANG
2018, 34(5): 951-956  doi: 10.11862/CJIC.2018.126
[摘要]  (14) [HTML全文] (14) [PDF 1417KB] (14)
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Two novel dinuclear Ln(Ⅲ) complexes[Gd2(L)4(HCOO)2(CH3OH)2] (1) and[Dy2(L)4(CH3COO)2(CH3OH)2] (2) (HL=2-hydroxy-3-methoxy-5-bromobenzaldehyde oxime) have been successfully synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy and elemental analyses. Single crystal X-ray crystallographic analyses reveal that these two complexes have similar structures, in which two symmetric nine-coordinate Ln(Ⅲ) ions are bridged by two phenoxide groups from two Schiff base ligands, two formate ions for 1 and two acetate ions for 2 respectively. Magnetic studies reveal that weak antiferromagnetic interaction between Gd(Ⅲ) ions existing in complex 1, while complex 2 shows slow relaxation of magnetization. CCDC: 1570377, 1; 1570378, 2.
Crystal Structures and Properties of Two Linear Trinuclear Complexes
Li-Wen WANG, Qi-Gao SHANG, Jing-Jing ZHOU, Hong ZHOU, Zhi-Quan PAN, Qing-Rong CHENG
2018, 34(5): 957-966  doi: 10.11862/CJIC.2018.105
[摘要]  (11) [HTML全文] (11) [PDF 1427KB] (11)
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Two new trinuclear complexes, [Co2CoL2(μ-OAc)4] (1) and[Ni3L2(μ-OAc)2(CH3OH)2]·2H2O (2), were obtained and fully characterized, where L was the condensation product between 2-hydroxy-1, 3-propane diamine and 5-fluorosalicylaldehyde. The interaction of complex 1 with DNA has been investigated by spectroscopy, viscosity measurements and electrochemical studies. Absorption spectroscopic investigation reveals intercalative binding of Co complex with DNA, with a binding constant of 2.43×105 L·mol-1. Fluorescence spectroscopy shows that complex 1 can displace ethidium bromide and bind to DNA, with a quenching constant of 4.92×103 L·mol-1. The variable-temperature magnetisms of complexes 1 and 2 show that there are antiferromagnetic couplings among the three metal centers in both complexes. CCDC: 1587441, 1; 1587442, 2.
Synthesis, Crystal Structure and Magnetism of a[Dy2Co8] Core Complex with Diethanolamine Ligand
You-Zhu YU, Yu-Hua GUO, Yan-Hong SHEN, Li-Guo YANG, Yong-Sheng NIU, Xiao-Ming ZHENG, Hai-Hui ZHANG, Fang WANG
2018, 34(5): 967-972  doi: 10.11862/CJIC.2018.115
[摘要]  (16) [HTML全文] (16) [PDF 1548KB] (16)
摘要:
A new[Dy2Co8] core Complex[Dy2Co8(L)4(HL)4(HCOO)4(OH)2Cl2(CH3OH)2]Cl2·4CH3OH·2H2O (1) (H2L=diethanolamine) was prepared and characterized by single crystal X-ray diffraction, FTIR spectra, elemental and magnetic analysis. It crystallizes in the triclinic system, space group P1. X-ray diffraction analysis reveals that each Dy(Ⅲ) was nine-coordinated and each Co(Ⅱ) ion displays distorted octahedral coordination environment. CCDC: 1576526.
Syntheses, Crystal Structures and DNA-Binding of Two Zinc(Ⅱ) Complexes Constructed by 4-Methyl-1, 2, 3-thiadiazol-5-carboxylic Acid
Da-Ling WU, Min-Zhi ZHANG, Xiao-Yong WU, Guo-Liang ZHAO
2018, 34(5): 973-980  doi: 10.11862/CJIC.2018.107
[摘要]  (24) [HTML全文] (24) [PDF 2907KB] (24)
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Two new zinc complexes[Zn(MTC)2(bpp)]n (1) and[Zn(MTC)(phen)(H2O)2](MTC) (2) (HMTC=4-methyl-1, 2, 3-thiadiazol-5-carboxylic, C4H4N2O2S; bpp=1, 3-bis(4-pyridyl) propane; phen=1-10-phenanthroline) have been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR spectra, PXRD and TG. The single crystal X-ray diffraction reveals that the complex 1 is two-dimensional network structure and crystallized in monoclinic with space group P21/c. Central Zn2+ is four-coordinated forming a distorted tetrahedron coordina-tion geometry. The complex 2 is two-dimensional layered structure and crystallized in triclinic with space group P1. Central Zn2+ is five-coordinated forming a distorted trigonal bipyramid coordination geometry. In addition, the interaction of complexes and ligand with EB-DNA were also studied by EtBr fluorescence probe. The interaction of complexes with DNA is stronger than ligand.
Syntheses, Crystal Structures, and Magnetic Properties of 0D Tetranuclear Nickel(Ⅱ) Coordination Compound and 1D Manganese(Ⅱ) Coordination Polymer Constructed from Biphenyl Tricarboxylic Acid
Yu LI, Bing-Song WEN, Xun-Zhong ZOU, Bin HUANG, Wen-Da QIU, Ze-Min ZHANG, Ao YOU, Xiao-Ling CHENG
2018, 34(5): 981-988  doi: 10.11862/CJIC.2018.131
[摘要]  (14) [HTML全文] (14) [PDF 2705KB] (14)
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A 0D tetranuclear nickel(Ⅱ) coordination compound and a 1D manganese(Ⅱ) coordination polymer, namely[Ni2(μ3-Hbptc) (Hbptc)(phen)3(H2O)]2·4H2O (1) and {[Mn3(μ4-cptc)2(2, 2'-bipy)2(H2O)4]·2H2O}n (2), have been constr-ucted hydrothermally using H3bptc (H3bptc=biphenyl-2, 5, 3'-tricarboxylate acid), H3cptc (H3cptc=2-(4-carboxypyri-din-3-yl)terephalic acid), phen (phen=1, 10-phenanthroline) or 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and nickel or manganese chlorides. Single-crystal X-ray diffraction analyses revealed that both compounds crystallize in the triclinic system, space group P1. In compound 1, two μ3-Hbptc2- ligands bridge alternately neighboring Ni(Ⅱ) ions to form a discrete tetranuclear nickel(Ⅱ) structure. These Ni4 units are assembled to a 3D supramolecular framework through O-H…O hydrogen bond. In compound 2, three neighboring Mn(Ⅱ) ions are bridged by four different μ4-cptc3- ligands, giving rise to a centrosymmetric trinuclear Mn(Ⅱ) subunit. The adjacent Mn3 subunits are further linked by the cptc3- blocks into a 1D chain. Magnetic studies for compounds 1 and 2 demonstrate an antiferro-magnetic coupling between the adjacent metal centers.
Synthesis of Hierarchical ZSM-5 Zeolites via Two Stage Varying Temperature Crystallization with Enhanced Catalytic Cracking Performance
You-He WANG, Hong-Man SUN, Peng PENG, Peng BAI, Zi-Feng YAN, Fazle Subhan, Sheng-Fu JI
2018, 34(5): 989-996  doi: 10.11862/CJIC.2018.124
[摘要]  (13) [HTML全文] (13) [PDF 2052KB] (13)
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Hierarchical ZSM-5 zeolites with regular spherical structure were successfully synthesized via a facile two stage varying temperature crystallization using tetrapropylammonium hydroxide (TPAOH) as the single template. The fabricated samples were characterized by means of XRD, FT-IR, NH3-TPD, SEM, TEM and N2 adsorption-desorption isotherms. The results indicate that the spherical ZSM-5 zeolite particles with around 2 μm in diameter possess intercrystalline meso-and macropores generated from the aggregation of bar-shape ZSM-5 nanocrystals, which exhibit large specific surface area and mesopore volume. Compared to the ZSM-5 zeolite synthesized by constant temperature hydrothermal method, the hierarchical ZSM-5 zeolites have higher Brønsted acid to Lewis acid ratio (CBP/CLP) and strong acid to weak acid ratio (Cs/Cw), as well as the enhanced accessibility of the active sites, which were very important to the catalytic reaction. Catalytic tests reveal that hierarchical ZSM-5-contained catalytic cracking catalyst exhibit an outstanding performance in improving the propylene yield and conversion due to the enhancement of accessibility.
Heterobimetallic Cu(Ⅱ)-Nd(Ⅲ) and Zn(Ⅱ)-Ce(Ⅲ) Salamo-Type Complexes: Syntheses, Crystal Structures and Fluorescence Properties
Yu-Hua YANG, Yu ZHANG, Meng YU, Shan-Shan ZHENG, Wen-Kui DONG
2018, 34(5): 997-1006  doi: 10.11862/CJIC.2018.125
[摘要]  (18) [HTML全文] (18) [PDF 2695KB] (18)
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Heterobinuclear 3d-4f complexes having chemical formulae[Cu(L)Nd(NO3)3(C2H5OH)] (1) and[Zn(L)(OAc)Ce(NO3)2(CH3OH)] (2) with a Salamo-type ligand O, O'-(ethane-1, 2-diyl)bis(1-(3-ethoxy-2-hydroxyphenyl)-3-ethoxy-2-hydroxybenzaldehyde oxime) (H2L)were synthesized, and characterized by elemental analyses, IR, UV-Vis, fluorescence spectra and X-ray crystallography. Complex 1 is an asymmetrical dinuclear complex, the pentacoordinate Cu(Ⅱ) ion has a slightly distorted square pyramidal geometry, and deca-coordinated Nd(Ⅲ) ion possesses a distorted bicapped twelve surface geometry. Complex 2 is also an asymmetrical dinuclear complex, the penta-coordinate Zn(Ⅱ) ion bears a distorted square pyramidal geometry too, and deca-coordinated Ce(Ⅲ) ion adopts a distorted bicapped twelve surface geometry. Compared with the ligand H2L, complex 1 showed fluorescence quenching, while complex 2 exhibited the fluorescence enhancement when the excitation wavelength is 318 nm.
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Articles
Effect of Crystallinity and Grain Size of Film on Mobility of C60 Thin Film Transistors
Yi LI, Xiao HAN, Zhi-Peng SUN, Yan-Wen MA
2018, 34(3): 415-420  doi: 10.11862/CJIC.2018.076
[摘要]  (21) [HTML全文] (21) [PDF 2562KB] (21)
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Fullerene (C60) thin films have been prepared on SiO2 substrates by vacuum deposition under different substrate temperature ranging from 30 to 190℃ and deposition pressure of 1×10-4 and 1×10-1 Pa. The effect of crystallinity and grain size on the mobility of the deposited C60 thin films are investigated. X-ray diffraction and atomic force microscopy observation indicates that both the crystallinity and the grain size of the C60 films increase with increasing substrate temperature. And the grain size of the films increase and the crystallinity keep almost unchanged with increasing deposition pressure. Field-effect measurements indicate that the mobilities of the C60 thin films are closely correlated with their crystallinities, and the increased crystallinity of the films gives the improved mobility. Different from the films of planar organic semiconducrors molecules, for the spherical C60 molecules films, the larger grain size could lead to the lower mobility.
Penta-nuclear Mixed-Valence Co(Ⅱ/Ⅲ) and 1D Chain Cu(Ⅱ) Complexes Incorporating Schiff Base Ligand with End-On Azido Bridging: Syntheses, Structures and Magnetic Properties
Ju-Mei TIAN, Jing-Ping ZHANG
2018, 34(3): 436-444  doi: 10.11862/CJIC.2018.053
[摘要]  (21) [HTML全文] (21) [PDF 3269KB] (21)
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Two novel complexes, [CoCo4(salhn)4(N3)6(CH3OH)2(H2O)2]·4CH3OH·2H2O (1) and[Cu2(salhn)(N3)2]n (2) (H2salhn=N, N'-bis(salicylidene)hydrazine), were synthesized and structurally characterized by X-ray single-crystal diffraction. Complex 1 is a zigzag-like penta-nuclear[CoCo4] cobalt cluster, while complex 2 consists of a 1D chain containing subunit[Cu2(salhn)(N3)2]. Both complexes possess bridged azide with the end-on (EO, μ-1, 1) coordination fashion. The magnetic measurements indicate that 1 and 2 both show antiferromagnetic behaviors.
Syntheses, Crystal Structures and Theoretical Calculation of Three-Dimensional Supramolecular Zinc/Manganese Complex
Zhi-Tao WANG, Valtchev Valentin, Qian-Rong FANG, Xiu-Mei LI, Ya-Ru PAN
2018, 34(3): 515-524  doi: 10.11862/CJIC.2018.038
[摘要]  (28) [HTML全文] (28) [PDF 3254KB] (28)
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Two new three-dimensional supramolecular complexes {[Zn2(pzdc)(L)2(H2O)]·H2O}n (1) and[Mn(μ2-O)(H2O)2(HL)]·NIPH (2) (H2pzdc=pyrazine-2, 3-dicarboxylic acid, H2NIPH=5-nitroisophthalic acid, HL=3-(2-pyridyl)pyrazole) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, UV spectrum, TG, fluorescence spectrum, single-crystal and powder X-ray diffraction. Complex 1 shows two-dimensional (2D) network, and complex 2 is zero-dimensional structure. They are further extended into a three-dimensional supramolecular network structure through hydrogen bonds and π-π interactions. Moreover, natural bond orbital (NBO) was analyzed by using the PBE0/LANL2DZ method built in Gaussian 09 program. The calculation results indicate the distinct covalent interaction between the coordinated atoms and Zn(Ⅱ), Mn(Ⅱ) ion, respectively.
Two Trinuclear Cobalt(Ⅱ) Salamo-Type Complexes: Syntheses, Crystal Structures, Solvent Effect and Fluorescent Properties
Li WANG, Quan-Peng KANG, Jing HAO, Yang ZHANG, Yang BAI, Wen-Kui DONG
2018, 34(3): 525-533  doi: 10.11862/CJIC.2018.035
[摘要]  (21) [HTML全文] (21) [PDF 2301KB] (21)
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Two trinuclear Co(Ⅱ) complexes, [Co3L(OAc)2(CH3CH2OH)2]·2CH3CH2OH·2CHCl3 (1) and[Co3L(OAc)2(C3H7OH)2] (2) were synthesized by the reaction of a new Salamo-type bisoxime chelating ligand of 4, 4'-dinitro-2, 2'-(1, 2-ethylenedioxybis(nitrilomethylidyne))diphenol (H2L) with cobalt(Ⅱ) acetate tetrahydrate in different solvents. Complexes 1 and 2 were characterized by elemental analyses, IR and UV-Vis spectra, and single crystal X-ray diffraction methods. In complexes 1 and 2, there are two ligand L2- moieties (which provide N2O2 donors), two acetate ions, two coordinated ethanol or n-propanol molecules, respectively. Although the two complexes were synthesized in different solvents, it is worthwhile that the Co(Ⅱ) ions in the structures of the two complexes adopt slightly distorted hexa-coordinated geometries. As a result, solvent effect was assumed to have played a crucial role in their coordination environment. In addition, when excited at 450 nm, the complexes 1 and 2 show an intense photoluminescence with maximum emission at ca. 568 and 566 nm, respectively.
Li(Ⅰ)/Na(Ⅰ) Complexes and Perchlorate Salt of 2-(5-Chloroquinolin-8-yloxy)-1-(pyrrolidin-1-yl)ethanone: Syntheses, Crystal Structures and Fluorescence Properties
Pan-Dong MAO, Wei-Na WU, Miao YANG, Qing-Wen YANG, Yuan WANG
2018, 34(3): 534-538  doi: 10.11862/CJIC.2018.087
[摘要]  (36) [HTML全文] (36) [PDF 1420KB] (36)
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Two complexes, [Li(L)2]ClO4 (1) and[Na(L)2]ClO4 (2) based on L (L=2-(5-chloroquinolin-8-yloxy)-1-(pyrrolidin-1-yl)ethanone) were synthesized and characterized by the X-ray diffraction analyses. The results show that complex 1 was isostructural with 2. The metal ion in each complex with a distorted octahedron geometry is surrounded by two acetamide ligands with N2O4 donor set. In addition, the structure of the perchlorate salt of L, namely (HL)ClO4·H2O was demonstrated. The fluorescence properties of all compounds have been investigated in detail.
Two Lead(Ⅱ)-Organic Coordination Polymers Based on N-Acetic-5-oxygen-nicotinic Acid: Syntheses, Structures and Fluorescence Properties
Yun-Xia LI, Yan XIA, Ling-Zhi LÜ, Yun-Long FENG
2018, 34(3): 539-544  doi: 10.11862/CJIC.2018.058
[摘要]  (44) [HTML全文] (44) [PDF 1764KB] (44)
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Two new lead coordination polymers, namely, [Pb4(μ3-O)2L2]n (1), [Pb3(μ4-O)2L]n (2) (H2L=N-acetic-5-oxygen-nicotinic acid) have been prepared by the reaction of Pb(NO3)2 with H2L and characterized by elemental analysis, IR and single crystal X-ray diffraction. Polymer 1 crystallizes in the monoclinic C2/c space group, and features[Pb4(μ3-O)2]n rigid inorganic chains, which are further linked by L2- ligands to form a 3D framework. Polymer 2 crystallizes in the orthorhombic P212121 space group, and displays a 3D framework with[Pb3(μ4-O)2]n inorganic chains. The thermodynamic stability and fluorescence properties of 2 were investigated.
Two Mono- and Binuclear Zn(Ⅱ) Coordination Complexes Containing 4-Pyridyl-NH-1, 2, 3-triazole Ligand: Syntheses, Structures and Photoluminescence Properties
Xue LEI, Yun-Zhou CHEN, Yuan-Xiang LI, Li-Hui JIA, Yun-Feng CHEN
2018, 34(3): 545-550  doi: 10.11862/CJIC.2018.060
[摘要]  (20) [HTML全文] (20) [PDF 1394KB] (20)
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Two Zn(Ⅱ) coordination complexes, [Zn2(L)2Cl4] (1) and[Zn(L)2Cl2]·2H2O (2) (L=4-pyridiyl-NH-1, 2, 3-triazole) are synthesized by reaction of ZnCl2·2H2O with rigid ligand L. Single crystal diffraction reveals that 1 and 2 crystallizes in space groups, P1 and P21/n, respectively. In the structures of 1 and 2, supramolecular interactions play important role in forming 3D structures. Photoluminescent properties of 1 and 2 in solid state and dilute methanolic solutions have been investigated in detail.
Synthesis of CuNPs@Cu(Ⅱ)-AMTD Metal-Organic Gel Composites with High Catalytic Activities
Yong CHENG, Fei-Fei SUN, Qi-Chun FENG, Ying-Hua ZHOU
2018, 34(3): 551-559  doi: 10.11862/CJIC.2018.059
[摘要]  (22) [HTML全文] (22) [PDF 4438KB] (22)
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The CuNPs@Cu(Ⅱ)-AMTD metal-organic gel composites was prepared by in situ growth of copper nanoparticles within gel matrix. The resulting material has been characterized by IR, SPR, SEM, TEM, EDX and XPS. It was found that CuNPs@Cu(Ⅱ)-AMTD composites exhibit excellent catalytic activities on the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) and other nitroarenes by NaBH4 in aqueous solution. The mechanism of the catalytic reaction has also been discussed.
Structural Differences of Two MOFs Adjusted by Central Metal Ions Inducing Different Photodegradation Efficiencies
Hui-Jun LI, Ya-Ling HE, Ning ZHANG, Qing-Qing LI, Zhou-Qing XU, Yuan WANG
2018, 34(3): 560-568  doi: 10.11862/CJIC.2018.078
[摘要]  (25) [HTML全文] (25) [PDF 4549KB] (25)
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By Reactions of Cu(Ⅱ), Co(Ⅱ) with H2PPCA ligand (H2PPCA=5-pyrazin-2-yl-1H-pyrazole-3-carboxylic acid) in the same hydrothermal conditions resulted in two distinct structural metal-organic frameworks (MOFs), namely, [Cu(PPCA)(H2O)]·H2O (HPU-7) and {[Co(PPCA)(H2O)]·H2O}n (HPU-8). HPU-7 that obtained from CuCl2·2H2O at 160℃ is a dinuclear cluster based on Cu(Ⅱ) ions and PPCA2- ligands. HPU-8 synthesized by Co(NO3)2·6H2O at 160℃ exhibits a 4, 4-connected 2D layer connected by dinuclear Co(Ⅱ) clusters and the skeletons of the PPCA2- ligands. The structural differences are dependent on the coordination geometries of central metal ions. And due to the structural differences, the two complexes display different photodegradation efficiencies toward methylene blue (MB).
Upconversion Emission and Temperature Sensing Behavior of LuF3: Yb3+, Er3+ Microcrystals Prepared by One-Step Hydrothermal Synthesis
Qi WANG, Jin-Sheng LIAO, Jiang-Fei GUO, Hai-Ping HUANG, He-Rui WEN
2018, 34(3): 579-588  doi: 10.11862/CJIC.2018.067
[摘要]  (23) [HTML全文] (23) [PDF 4570KB] (23)
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LuF3:Yb3+, Er3+ microcrystals codoped with Yb3+ nYB3+/nLu3+=5%~15%) and Er3+ ions (nEr3+/nLu3+=1%~5%) were synthesized by a facile hydrothermal process at different pH values. It is found that the pH value has a crucial effect on synthesis of the orthorhombic phase LuF3:Yb3+, Er3+. Under 980 nm excitation, LuF3:Yb3+, Er3+ phosphors exhibit strong green upconversion (UC) emission bands centered at 523 (2H11/24I15/2) and 539 nm (4S3/24I15/2) and weak red emissions near 660 nm (4F9/24I15/2). The optimum doping concentrations of Er3+ and Yb3+ for the highest emission intensity were determined by using X-ray diffraction (XRD) and photoluminescence (PL) analyses. Concentration dependent studies reveal that the optimal composition is 10% Yb3+ and 2% Er3+ co-doping concen-tration with a strong green emission. A possible UC mechanism for LuF3:Yb3+, Er3+ depends on the pump power is discussed. The temperature dependence of the fluorescence intensity ratios (FIR) for the two green UC emission bands peaked at 523 and 539 nm was studied in the range of 293~573 K under excitation by a 980 nm diode laser and the maximum sensitivity was approximately 15.3×10-4 K-1 at 490 K. This indicates that LuF3:Yb3+, Er3+ phosphors are potential candidates for optical temperature sensors with high sensitivity.
Construction of Two Coordination Polymers Based on 5-Methoxyisophthalic Acid Ligand: Structures, Luminescence and Catalytic Properties
Yang ZHANG, Jian WANG
2018, 34(3): 589-596  doi: 10.11862/CJIC.2018.073
[摘要]  (28) [HTML全文] (28) [PDF 2669KB] (28)
摘要:
Two new 1D cadmium/cobalt-based coordination polymers, {[Cd2(CH3O-ip)2(ethanol)2(H2O)4]·3H2O}n (1) and {[Co2(CH3O-ip)2(dmbpy)(H2O)4]·H2O·C2H3N}n (2) (CH3O-H2ip=5-methoxyisophthalic acid, dmbpy=2, 2'-dimethyl -4, 4'-bipyridine, C2H3N=acetonitrile), were synthesized in mixed solvent and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Both complexes are synthesized using dual linkers (CH3O-H2ip and dmbpy). Complex 1 is a wave-like chain and further connected into 2D network through O-H…O hydrogen bonds, whereas 2 shows a ladder chain and further linked into 3D supramolecular framework by O-H…O, O-H…N and C-H…O hydrogen bonds. Furthermore, the luminescence property of 1 and the catalytic degradation of methyl orange in a Fenton-like process of 1~2 are also investigated.
3D Silver Dendritic Thin Film: Controllable Growth and Application in Surface Enhanced Raman Spectroscopy
Hui-Juan ZHANG, Dong-Jie ZHANG, Cong-Yun ZHANG, Ya-Qing LIU
2018, 34(3): 597-604  doi: 10.11862/CJIC.2018.085
[摘要]  (51) [HTML全文] (51) [PDF 5638KB] (51)
摘要:
A novel surface enhanced Raman spectroscopy (SERS) substrate was fabricated via a simple galvanic displacement reaction, where large scale of silver dendritic were uniformly and symmetrically formed on anodic aluminum oxide (AAO) membrane. The morphology, distribution and density of these silver dendritic films could be tuned easily just by controlling the reaction time as well as the concentration of AgNO3. Such active SERS substrate exhibits extremely high sensitivity, excellent reproducibility and good stability. Raman signal sensitivity for rhodamine 6G (R6G) was tested as low as 1×10-11 mol·L-1. Additionally, the as-synthesized robust substrate displays good stability under an ambient condition for several months. This 3D eco-friendly AAO membrane based substrate provides not only high density of SERS hot spots, but also a very large area for capturing target analytes. It has potential applications for the detection of trace organic contaminants in the environment.
Syntheses, Crystal Structures and Photoluminescent Properties of Two Cadmium(II) Coordination Polymers Constructed from Tris(4-imidazolylphenyl)amine
Jian LI, Min YU, Guang-Xiang LIU
2018, 34(3): 605-613  doi: 10.11862/CJIC.2018.069
[摘要]  (19) [HTML全文] (19) [PDF 3507KB] (19)
摘要:
Two cadmium(Ⅱ) coordination polymers, [CdI(TIPA)(CDC)0.5]n (1) and {[Cd(TIPA)(MPDA)]·H2O}n (2), (TIPA=tris(4-imidazolylphenyl)amine, H2CDC=1, 4-cyclohexanedicarboxylic acid, H2MPDA=5-methylisophthalic acid), have been synthesized and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. Structural analyses reveal that complex 1 features a rare 2D→2D polyrotaxane network with (3, 4)-connected (4.52)(4.53.72) topology, which is further interlinked into a higher-dimensional supramolecular framework by intermolecular weak interactions, whereas complex 2 has a two-dimensional (3, 5)-connected novel network with (42.67.8)(42.6) topology and shows a 2D→3D parallel-parallel polycatenation framework. The results show that the carboxylates exert obvious influence on the resulting architectures. Meanwhile, the solid-state photoluminescence of two complexes at room temperature was also investigated.
论文
三维多枝雪花状银粉的制备及催化性能
郭帅龙, 巢云秀, 杨宏伟, 杨宇雯, 李郁秀, 方卫
2018, 34(3): 421-426  doi: 10.11862/CJIC.2018.040
[摘要]  (43) [HTML全文] (43) [PDF 2463KB] (43)
摘要:
室温下,以聚乙烯醇为保护剂,采用抗坏血酸还原硝酸银,于水相中一步合成出三维多枝雪花状银粉。结合X射线粉末衍射(XRD)、扫描电子显微镜(SEM)等结构表征手段,对三维多枝雪花状银粉的微观结构进行详细分析,在此基础上提出其可能的形成机理。此外,三维多枝雪花状银粉在4-硝基苯酚催化加氢反应中还表现出优异的催化活性。
一硼化铪的晶体结构预测与构效关系基因
魏晓婷, 曾庆丰, 张琪, 冯钦颢
2018, 34(3): 427-435  doi: 10.11862/CJIC.2018.080
[摘要]  (105) [HTML全文] (105) [PDF 3387KB] (105)
摘要:
利用基于进化算法的晶体结构预测软件USPEX,并结合第一性原理方法对HfB的稳定晶体结构进行全局搜索。在基态条件下,新发现2个HfB晶体结构(空间群:P6m2和R3m)。其中,P6m2结构比已报道的HfB晶体结构(空间群:PnmaCmcmI41/amdFm3m)具有最低的基态能量。这些结构中,B原子分别以二维类石墨烯(P6m2和R3m结构),zig-zag链(PnmaCmcm和41/amd结构)和孤立原子(Fm3m结构)3种形式存在,从而导致它们具有显著的化学键合特征、高温稳定性和强韧特性差异。
一种规整单壁碳纳米笼的合成与改性及其对水体结晶紫分子的吸附性能
朱鸿宇, 杨汉培, 孙慧华, 高照, 毛静涛, 吴俊明
2018, 34(3): 445-453  doi: 10.11862/CJIC.2018.047
[摘要]  (40) [HTML全文] (40) [PDF 4091KB] (40)
摘要:
运用催化气相沉积法及继之的纯化处理,获得了具有规整外型、中空及密集阵列的单壁三维结构碳纳米笼(carbon nanocages,CNCs)。尝试将其用于水体阳离子染料结晶紫(crystal violet,CV)的吸附去除,实验条件下其上CV的饱和吸附容量可达542.6 mg·g-1。进一步以十二烷基苯磺酸钠(sodium dodecyl benzene sulfonate,SDBS)对制得的CNCs表面进行亲水性改性,观察到了改性CNCs对CV吸附性能的明显提升,相同条件下其上CV的饱和吸附容量显著提升至748.5 mg·g-1。运用多种表征及测定,探明改性前后CNCs的组成和结构,并尝试与其吸附性能关联,在此基础上探明改性及促进机制,为进一步研发具有实用意义的污水处理技术提供有益参考。
反应介质对溶剂热法合成CuS晶体的影响
赵巍, 荣嘉诚, 刘念奇, 王子豪
2018, 34(3): 454-460  doi: 10.11862/CJIC.2018.052
[摘要]  (46) [HTML全文] (46) [PDF 3148KB] (46)
摘要:
以氯化铜、硫脲为反应物,通过溶剂热法合成了具有不同形貌的微纳米分级结构CuS晶体,研究了不同反应介质对材料的形貌、晶体结构以及反应产量等的影响。结果表明,以N,N-二甲基甲酰胺(DMF)为溶剂,可以得到微米级六角花状CuS晶体;以乙二醇或者水/DMF混合物为溶剂,得到的CuS晶体为微米球花状。CuS晶体的产量随着溶剂中水所占比例的增大,呈现先上升后下降的结果,当VDMF:VH2O=1:1时得到CuS的最大产量,为理论产量的64.5%。当VDMF:VH2O=2:1时得到的CuS晶体具有良好的光催化活性,能够在氙灯模拟的自然光照射2.5 h以内使罗丹明B污染物溶液的脱色率达到96.7%。
晶种导向下干胶法合成ZSM-5分子筛
陈艳红, 崔红霞, 韩东敏, 张强, 李春义
2018, 34(3): 461-466  doi: 10.11862/CJIC.2018.049
[摘要]  (49) [HTML全文] (49) [PDF 2738KB] (49)
摘要:
以廉价水玻璃为硅源,在晶种替代有机模板剂的条件下采用干胶法合成了ZSM-5分子筛。利用XRD、SEM、TEM、FTIR、N2吸附-脱附和NH3-TPD等分析方法对合成样品进行了表征和测试,考察了合成条件对ZSM-5分子筛晶化过程的影响。结果表明,在硅铝比(n/n)为30~70,钠硅比(n/n)为0.12~0.20时都可以得到结晶度良好的ZSM-5分子筛。研究发现,干胶法合成ZSM-5,在不引入外加水的情况下也可以得到ZSM-5样品,外加水的引入能够有效地提高晶化速率;与水热法合成ZSM-5分子筛相比,干胶法可以显著地缩短晶化时间,同时,合成样品的晶体尺寸也有所减小。
多孔纳米片状石墨相氮化碳的制备及其可见光催化
侯建华, 蔡瑞, 沈明, 蒋坤
2018, 34(3): 467-474  doi: 10.11862/CJIC.2018.064
[摘要]  (55) [HTML全文] (55) [PDF 5938KB] (55)
摘要:
以三聚氰胺和硫脲为前驱体,通过简易的氧气刻蚀制备了多孔纳米片状氮化碳。相比于三聚氰胺制备的薄片状氮化碳(MCNS),以硫脲制备的多孔纳米片状的g-C3N4(TCNS)片层更薄,其单片厚度约为30 nm,且TCNS的层状结构明显,能带隙约为3.03 eV,高于石墨相氮化碳(2.77 eV),更宽的禁带赋予载流子更强的氧化还原能力。较大的比表面积(114 m2·g-1)可以提供更多的活性位点,同时纳米片状结构可以促进电子与空穴的有效分离和转移,且能有效地降低光生载流子的复合率,因而TCNS具有更高的光催化活性。
La1-xSrxCoO3(x=0, 0.2, 0.4, 0.6, 0.8)钙钛矿型氧化物的催化性能及改性
于文婉, 黄红霞, 王成
2018, 34(3): 475-482  doi: 10.11862/CJIC.2018.063
[摘要]  (42) [HTML全文] (42) [PDF 3448KB] (42)
摘要:
通过溶胶-凝胶法制备出A位Sr掺杂的钙钛矿型氧化物La1-xSrxCoO3x=0,0.2,0.4,0.6,0.8),并将其作为催化剂应用于双功能氧电极中。测试结果表明,A位Sr的掺杂的La1-xSrxCoO3比LaCoO3具有更高的电催化活性,并且La0.6Sr0.4CoO3在氧还原和氧析出反应中均表现出最优的催化性能,最大电流密度分别达到0.244 A·cm-2(-0.6 V vs Hg/HgO)和0.303 A·cm-2(1 V vs Hg/HgO)。为进一步提高催化剂的催化活性,将水热法制备的α-MnO2纳米管与La0.6Sr0.4CoO3复合作为双功能催化剂。当α-MnO2的质量分数为40%时,比起单一的α-MnO2或钙钛矿氧化物,α-MnO2/La0.6Sr0.4CoO3复合材料表现出协同效应,有更好的双功能电催化活性,使双效氧电极具有更好的电化学性能及稳定性。
Y沸石和多级孔Y沸石封装CuPhen配合物催化性能的比较
王红燕, 赵彦鹏, 吕文苗, 路宁悦, 史秀锋, 范彬彬, 李瑞丰
2018, 34(3): 483-489  doi: 10.11862/CJIC.2018.061
[摘要]  (36) [HTML全文] (36) [PDF 770KB] (36)
摘要:
选用常规Y沸石和经后处理法制备的多级孔Y沸石为主体,采用自由配体法将铜菲咯啉(CuPhen)配合物封装在不同Y沸石中,制备了CuPhen/Y复合催化材料。采用X射线衍射、TEM、紫外-可见光谱、N2吸附-脱附、ICP和TG等手段对所制备复合催化材料的物化性质进行了较为详细的表征,并对封装在不同Y沸石主体中的铜配合物在不同尺寸大小反应底物中的催化氧化性能进行了比较研究。结果表明,在以双氧水为氧化剂的反应体系中,封装于多级孔Y沸石中的铜配合物在不同环烷烃氧化反应中的催化活性均高于封装在常规Y沸石中的催化活性,体现出多级孔Y沸石更为优越的主体性能。此外,同封装于常规Y沸石中的铜配合物一样,封装在多级孔Y沸石主体中的金属配合物催化剂也具有良好的稳定性。
丝素纤维/硫酸钙抗感染骨材料的制备及性能
刘世超, 连小洁, 徐睿, 史振东, 杜苗苗, 张斯若, 何志敏, 魏延, 黄棣, 王秀梅, 崔福斋
2018, 34(3): 490-498  doi: 10.11862/CJIC.2018.065
[摘要]  (34) [HTML全文] (34) [PDF 4492KB] (34)
摘要:
通过控制丝素蛋白自组装过程制备了溶液状态下的丝素纳米纤维(silk fibroin nanofibers,SFFs),与硫酸钙、万古霉素(vancomycin,VCM)复合,制备了VCM/CS/SFFs抗菌骨材料。通过SEM、XRD、紫外分光光度计、万能力学试验机、抑菌圈、MTT等手段分别研究了复合材料的微观形貌与结构、药物释放、力学、抑菌及细胞相容性等性能。结果显示,与水作为固化液相比,随着SFFs溶液(0.017 5~2.1 mg·mL-1)的加入,复合材料凝固时间可控,降解率逐渐降低,抗水性增强,韧性提高;同时随丝素纳米纤维含量的增加骨材料抗压强度表现为先增加后减小的趋势,一周内药物释放速率降低;材料同时具有抑菌作用;MTT实验结果显示,加入丝素纳米纤维后与纯的硫酸钙相比MC3T3细胞增殖明显。
Cu、Ni共掺杂ZnO光催化性能及机理
姜建辉, 梁鹏举, 刘速, 赵俭波, 徒康楠
2018, 34(3): 499-506  doi: 10.11862/CJIC.2018.072
[摘要]  (49) [HTML全文] (49) [PDF 6318KB] (49)
摘要:
以自制的Gemini表面活性剂为软模版,硝酸锌为锌源、硫酸铜为铜源、硝酸镍为镍源,采用水热法制备Cu、Ni共掺杂ZnO。用XRD、SEM-EDX、UV-Vis DRS和PL对样品进行表征。以罗丹明B为模拟污染物,研究了水热时间,水热温度,煅烧时间,煅烧温度,Cu、Ni掺杂量对光催化性能的影响。结果表明:Cu和Ni均掺入到了ZnO晶格中,光催化实验表明,当水热时间8 h、水热温度130℃、煅烧温度500℃、煅烧时间3 h,0.8 mg·L-1的1.0% Cu-3.0% Ni/ZnO在250 W高压汞灯灯光照射90 min后对10 mg·L-1罗丹明B溶液的降解率达到96.9%。
介孔碳/石墨烯复合材料的制备及其醌类改性电容性能
高秀丽, 李硕, 邢伟, 阎子峰
2018, 34(3): 507-514  doi: 10.11862/CJIC.2018.075
[摘要]  (24) [HTML全文] (24) [PDF 3786KB] (24)
摘要:
首先利用硬模板法制备出介孔碳/石墨烯复合材料,然后向复合材料中引入具有赝电容活性的醌类分子进一步增大材料的电容性能。研究结果表明,负载30%(w/w)叔丁基氢醌的介孔碳/石墨烯复合材料具有最佳的电容性能,在电流密度为0.5 A·g-1时,比电容值为355 F·g-1;当电流密度高达30 A·g-1时,其比电容值高达226 F·g-1,比电容保持率为64%,表现出良好的速率特性。
由5-取代基间苯二甲酸和二咪唑衍生物构筑的两个二维钴(Ⅱ)的配合物的合成、结构及性质
杨明星, 刘宇晴, 岑福艳, 陈丽娟, 林深
2018, 34(3): 569-578  doi: 10.11862/CJIC.2018.071
[摘要]  (47) [HTML全文] (47) [PDF 5594KB] (47)
摘要:
通过溶剂热法合成了2个二维钴配位聚合物[Co2(1,4-bib)2(5-hipa)2]n1)(5-H2hipa=5-hydroxyisophthalic acid,1,4-bib=1,4-bis(1-imidazolyl)benzene),[Co(Hbpt)(4,4'-bidpe)]n2)(H3bpt=biphenyl-4,4',5-tricarboxylic acid,4,4'-bidpe=4,4'-bis(imidazol-1-yl)diphenyl ether)。X射线单晶衍射实验测定和结构解析结果表明,配合物12中5-hipa2-、Hbpt2-配体的2个相间羧基将相邻的Co2+连接形成含有Co2O4C2八元环和Co2O4C10十六元环的一维链状结构。一维链之间通过1,4-bib,4,4'-bidpe配体上的咪唑基N原子与相邻Co(Ⅱ)离子配位连结形成二维层状结构。配合物1层与层之间通过相邻层中的5-hipa2-配体的羟基与羧基的分子间氢键连结形成三维超分子网络结构。配合物2中,Hbpt配体的羧基氢与层内的相邻链上参与弱配位羧基氧形成层内氢键。电化学性能测试结果表明,配合物1对氧还原反应具有电催化活性。