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xLi2MnO3-(1-x) Li[Ni0.8Co0.15Al0.05]O2(0.5 ≤ x ≤ 0.8)的结构和电化学性能
陈培雷, 黄继春, 陈亦新, 季崇星, 朱德澄, 李德成
2019, 35(6): 937-946  doi: 10.11862/CJIC.2019.112
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摘要:
采用喷雾干燥法结合后续的热处理,成功地制备了一系列新型的基于富锂层状固溶体Li2MnO3和Li[Ni0.8Co0.15Al0.05]O2结合的xLi2MnO3-(1-x)Li[Ni0.8Co0.15Al0.05]O2(0.5 ≤ x ≤ 0.8)材料,并对其晶体结构、表面形貌、元素价态以及电化学性能进行了一系列的研究。实验结果表明,随着x值的增大,材料的晶体结构逐渐从层状的Li[Ni0.8Co0.15Al0.05]O2过渡到类Li2MnO3结构。对样品进行淬火处理对晶粒的微观晶体结构和元素价态产生复杂影响,这种变化使得淬火的样品表现出较好的电化学性能。其中x=0.6的样品淬火后表现出较好的电化学性能,100次循环后可逆容量可达209 mAh·g-1
相位可控的氟钪纳米晶的合成及其上转换发光性能
丁玉洁, 金星, 刘倩, 钱桂香, AbdullahM. Asiri, HadiM. Marwani
2019, 35(6): 947-954  doi: 10.11862/CJIC.2019.134
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控制反应条件如表面活性剂的组成、加入量或反应时间,可以制得不同形态、相结构且具有上转换发光(UCL)的氟钪纳米晶(NCs)。改变表面活性剂油酸(OA)/油胺(OM)的比例有利于晶体结构从立方相ScF3:Yb,Er转变为具有上转换发光性能增强的正交相KSc2F7:Yb,Er纳米晶,而纳米晶的形态会发生从小到大的转变。改变掺杂元素的种类及含量,在980 nm光激发下,KSc2F7纳米晶的上转换发光可以从蓝色变到白色,再到主要发射紫色光。
Ag3PO4/Ag2S/g-C3N4复合光催化剂的制备与性能
邓军阳, 汪杰, 朱思龙, 聂龙辉
2019, 35(6): 955-964  doi: 10.11862/CJIC.2019.127
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摘要:
通过沉积法和离子交换法成功地制备了Ag3PO4/Ag2S/g-C3N4复合型光催化剂。利用X射线多晶粉末衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、N2吸附-脱附等温线、紫外-可见漫反射光谱、荧光光谱等手段对样品进行了表征。通过降解罗丹明B考察其可见光催化活性及稳定性,研究了硫化钠与磷酸银物质的量的比值(nNa2S/nAg3PO4)、g-C3N4添加量对所制备复合光催化材料性能的影响,同时对光催化机理进行了探讨。结果表明,随着nNa2S/nAg3PO4的增加,所得复合催化材料活性先增加后降低;当nNa2S/nAg3PO4为1.5%、g-C3N4与Ag3PO4的质量比为3:7时制备的催化剂ASC1.5的光催化活性最好,在可见光照射下,40 min内可将罗丹明B完全降解,且5次循环使用后仍保持较高的催化活性。和Ag3PO4相比,Ag3PO4/Ag2S/g-C3N4复合型光催化材料的活性与稳定性都得到明显提高,这主要归因于复合催化剂比表面积和孔结构的增加,载流子分离效率的提高。光催化机理研究表明,空穴(h+)、超氧阴离子自由基(·O2-)和羟基自由基(·OH)都是光催化过程中的主要活性物种。三者作用大小依次为:h+ > ·O2- > ·OH。
5-氟尿嘧啶卟啉锰/锌配合物的合成、光电性质及抗癌活性
任丽磊, 彭晓霞, 王树军, 肖立伟, 李泽强
2019, 35(6): 965-970  doi: 10.11862/CJIC.2019.106
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合成了新型5-氟尿嘧啶修饰的自由卟啉5-(2-(5-氟尿嘧啶-3-基)乙氧基苯基)-10,15,20-三苯基卟啉(L)及其锰配合物(MnL)和锌配合物(ZnL)。通过紫外-可见光谱、红外光谱、核磁共振氢谱及高分辨质谱等手段进行了结构表征。研究了它们的荧光性质和电化学性质;应用标准磺酰罗丹明B法(SRB法)测试了目标化合物对人肺癌细胞株A549、人肝癌细胞株Bel-7402和人结肠癌细胞株HCT-8生长的抑制活性。结果表明:相同实验条件下,不同金属离子对配合物的荧光强度存在较大影响:锌配合物具有荧光猝灭的性质,而锰配合物未能观察到明显的荧光发射光谱;与自由卟啉和锌配合物相比,锰配合物除卟啉环发生氧化还原反应外,Mn2+自身也发生了氧化还原反应;抗癌活性测试显示锰配合物较其他2种化合物有较好的抗癌活性。
哑铃型磁金介孔硅复合微球的制备及磁/光热催化性能测定
许丽丽, 周妹婷, 杨阿龙, 王家幸, 周天夫, 张莹
2019, 35(6): 971-977  doi: 10.11862/CJIC.2019.132
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以金纳米粒为种子采取外延氧化生长氧化铁的方式,制备了哑铃型磁金纳米复合材料(Au-Fe3O4);以十六烷基三甲基溴化铵(CTAB)和F127为双模板剂通过溶胶凝胶法进一步包覆了介孔二氧化硅层(Au-Fe3O4@mSiO2)。所制备Au-Fe3O4纳米粒子呈哑铃型,单分散性较好,尺寸分布均一,粒径为12~15 nm。Au-Fe3O4@mSiO2复合物磁热性能与浓度和外加磁场强度成正比;浓度为25 mg·mL-1时,磁场电流从25.5 A增大到42.5 A,溶液升温速率从0.39℃·min-1增大到0.76℃·min-1。Au-Fe3O4@mSiO2复合物光热性能与浓度和激光照射功率密度成正比;复合物浓度为25 mg·mL-1时,功率密度从0.3 W·cm-2增大到1.2 W·cm-2,溶液升温速率从0.69℃·min-1增大到2℃·min-1。相同浓度的复合物溶液,光热性能明显优于磁热性能。浓度为25 mg·mL-1的Au-Fe3O4@mSiO2复合物催化S-亚硝基谷胱甘肽(GSNO)释放NO的反应在60 min时达到持续稳定释放,释放量最大为9.743 μmol·L-1
不同金属负载对Cr/Al2O3-TiO2催化剂结构及氧化NO性能的影响
魏炜, 牟一蒙, 梁红, 李树华, 乔智威, 彭峰
2019, 35(6): 978-986  doi: 10.11862/CJIC.2019.107
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采用溶胶-凝胶法和浸渍法制备Cr/Al2O3-TiO2催化剂,在考察不同Cr负载量的基础上,研究不同金属负载与焙烧温度对Cr/Al2O3-TiO2催化剂结构与性能影响。程序升温氧化(TPO)结果表明,当Cr负载量为10%(w/w)时具有较好的催化活性;不同金属负载Cr/Al2O3-TiO2时,负载Co及在焙烧温度为550℃时催化剂具有较好的活性。通过程序升温还原(H2-TPR)表征发现,Co的负载使催化剂的低温氧化还原能力逐渐提高,表明Co-Cr具有较好的协同催化作用。X射线光电子能谱(XPS)表征表明,Co增加了Cr6+和表面吸附氧(Oβ)含量,随着焙烧温度的升高(450~550℃),晶格氧不断向催化剂表面流动,表面化学吸附氧Oβ比例逐渐增加,导致催化活性不断升高,说明Cr6+和Oβ是催化氧化NO的重要活性物种。
核壳结构Ag@BaGdF5:Yb3+, Ho3+多功能纳米复合材料的制备及其性能
隋晶婷, 陈子禹, 刘桂霞, 宋超, 董相廷
2019, 35(6): 987-995  doi: 10.11862/CJIC.2019.119
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采用简单的液相法制备了核壳结构的Ag@BaGdF5:Yb3+,Ho3+纳米复合材料。XRD测试表明复合材料中含有立方相的Ag和立方相的BaGdF5。电镜照片表明复合粒子为球形,包覆后颗粒变大,包覆层BaGdF5:Yb3+,Ho3+的厚度约为14 nm。荧光光谱测试表明复合材料具有良好的上转换发光性能,以绿光发射最强,同时样品具有良好的顺磁性和光热转换性能。MTT测试表明复合材料具有良好的生物相容性,将其同HeLa细胞共同培养后用980 nm激光照射,具有明亮的绿色上转换荧光成像。将不同浓度的纳米复合材料和商用计算机断层扫描(CT)成像造影剂碘比醇进行比较,纳米复合材料具有更高的CT成像性能。在NIR照射下,纳米复合材料生成的热足以有效杀死HeLa细胞。
Bi2WO6/UiO-66复合材料的制备及其光催化性能
何云鹏, 金雪阳, 李文卓, 杨水金, 吕宝兰
2019, 35(6): 996-1004  doi: 10.11862/CJIC.2019.135
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通过水热法制备了一种复合光催化剂Bi2WO6/UiO-66,探究了模板剂乙酸(CH3COOH)对UiO-66形貌的影响和2种中心元素Bi与Zr的不同物质的量之比对光催化性能的影响。通过XRD、SEM、N2吸附-脱附、UV-Vis DRS、XPS等对催化剂的物相、形貌、比表面积、光吸收性能、元素组成等进行表征。实验结果表明,当nBinZr=2:1时,Bi2WO6/UiO-66对罗丹明B(RhB)的光催化活性最高,可见光照射50 min后,RhB的相对浓度降低98.5%。经过5次循环利用实验,催化剂的光催化活性没有明显下降,说明复合光催化剂的稳定性高。根据自由基捕获实验证明了空穴(h+)为光催化中起决定性作用的活性物质,结合电化学测试以及UV-Vis DRS表征提出了可能的光催化降解机理。
氧掺杂氮化碳纳米片的制备及其光解水制氢性能
祝凯, 欧阳杰, 刘家满, 祝玉鑫, 曾黔, 崔言娟
2019, 35(6): 1005-1012  doi: 10.11862/CJIC.2019.114
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以草酸为氧源,二聚氰胺和尿素为原料,采用两步热聚合方式合成氧掺杂氮化碳纳米片催化剂(CNO)。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、X射线光电子能谱分析(XPS)、荧光光谱(PL)及电化学测试等技术对催化剂进行结构表征分析。在可见光照射下通过分解水制氢反应对CNO的光催化还原性能进行评价。结果表明,草酸中的O元素通过取代氮化碳三嗪环结构中N原子直接键合到sp2杂化碳上,形成O掺杂CNO。经O掺杂改性后的氮化碳具有良好的层状堆积结构,可见光吸收性明显提高,同时禁带宽度降低。O掺杂的引入加速了光生电子-空穴对的分离和传输,能大幅度提高氮化碳的光催化分解水制氢性能,在可见光照下达88.6 μmol·h-1,是未掺杂CN的3.91倍。
花状硫化铜的合成及其光电催化性能
钱尼胜, 方文娟, 嵇小荷, 张华
2019, 35(6): 1013-1019  doi: 10.11862/CJIC.2019.138
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通过硫化介孔Cu2O微球得到花状CuxS纳米催化材料,并采用丝网印刷法制备出CuxS/FTO对电极。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等表征手段对所得材料的结构和形貌进行了探究,同时系统考察了溶液浓度、硫化时间、催化剂印刷层数对CuxS/FTO电极的催化性能影响和所组装量子点敏化太阳电池的光电转换效率,其中基于Zn-Cu-In-Se量子点敏化的电池转换效率达8.80%,表现出花状CuxS优异的光电催化性能。
绿色磷光四配位氮杂环卡宾铜(Ⅰ)配合物的合成及发光性质
杨冰冰, 赵丰, 许胜先, 何海峰
2019, 35(6): 1020-1026  doi: 10.11862/CJIC.2019.129
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为了制备发光性能优良的新型四配位氮杂环卡宾铜(Ⅰ)配合物,以咪唑、苯并咪唑、2-溴-5-氟-6-甲基吡啶和溴化苄为初始原料,反应生成氮杂环卡宾配体(Ph-Im-flumePy)PF6和(Ph-BenIm-mePy)PF6,随后卡宾配体与Cu粉及配体双(2-二苯基膦)苯醚(POP)反应,制备出2个四配位类型的氮杂环卡宾铜(Ⅰ)配合物[Cu(Ph-Im-flumePy)(POP)]PF6P1)和[Cu(Ph-BenIm-flumePy)(POP)]PF6P2)。通过核磁、质谱技术对产物结构进行了表征。系统研究了配合物的紫外-可见吸收光谱、发射光谱以及发光寿命等光学特性。结果表明,配合物P1P2的最低吸收峰分别位于325和335 nm处。粉末状态下,配合物P1在514 nm处有较强的绿光发射,量子发光效率为82.6%,激发态寿命为56 μs;而配合物P2的波长在516 nm处,量子发光效率为49.2%,激发态寿命为50.6 μs。在PMMA(10%,w/w)膜片中,配合物P1的发射波长蓝移至505 nm处,激发态寿命为40.7 μs,量子发光效率为38.0%;而配合物P2的发射波长位于508 nm处,激发态寿命为61 μs,量子发光效率为44.2%。
中温固体氧化物燃料电池阴极Sr3Fe2-xNixO7-δ(x=0, 0.1, 0.2, 0.3)的制备与性能
赵忱, 张婷, 和永, 曲亮武, 周青军
2019, 35(6): 1027-1033  doi: 10.11862/CJIC.2019.113
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采用溶胶凝胶法(sol-gel)合成了Sr3Fe2-xNixO7-δx=0,0.1,0.2,0.3)系列阴极材料,通过X射线衍射、热膨胀系数测试、电导率测试、极化阻抗(Rp)测试、单电池性能测试等对材料的物相结构、热力学性能、电化学性能进行了表征。结果表明,所有样品均成功合成为具有类钙钛矿结构的单一纯相。热膨胀系数随着Ni元素掺杂含量的提高而不断下降。其高温电导率随着Ni元素掺杂含量的提高而升高,SFN30具有该系列最高的电导率101 S·cm-1。该系列样品的极化阻抗随着Ni元素掺杂含量的提高呈现先下降后上升的趋势,SFN10在800℃具有小的极化阻抗(Rp=0.078 8 Ω·cm2)。电解质支撑的单电池输出功率变化趋势与极化阻抗趋势一致,SFN10在800℃获得421.6 mW·cm-2的输出功率密度。
沉积Pt对Ag2CO3纳米晶的物理化学性质和光催化性能影响
陈范云, 张萌迪, 马小帅, 李家德, 余长林
2019, 35(6): 1034-1040  doi: 10.11862/CJIC.2019.115
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采用NaBH4还原法合成了系列Pt沉积的Ag2CO3复合光催化剂。通过在可见光照射下降解甲基橙研究沉积不同含量的Pt对Ag2CO3光催化性能的影响。应用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电镜(TEM)、光电子能谱(XPS)、傅立叶变换红外光谱(FT-IR)、光致发光光谱(PL)、紫外可见漫反射吸收光谱(DRS)、光电流(PC)和N2物理吸附等研究了沉积Pt纳米颗粒对Ag2CO3纳米晶的物理化学性质的影响。结果表明,沉积质量分数为0.1%~0.5%的Pt,可使Ag2CO3的活性提升3倍以上,同时光催化剂的稳定性得到极大改善。Pt/Ag2CO3光催化性能大幅提升的主要原因是,沉积少量的Pt可以增强Ag2CO3对可见光的吸收,同时增大Ag2CO3的比表面积和表面羟基的数量;另外,沉积在Ag2CO3表面的Pt粒子可以承担电子俘获中心的作用,使Ag2CO3中光激发产生的电子(e-)有效地转移到Pt上,加速光生电子-空穴对的分离速率,产生更多的光催化活性自由基,在提升光催化活性的同时,减少Ag2CO3中的Ag+被光生电子(e-)还原的几率,增强Ag2CO3的抗光腐蚀能力。
热处理温度对La-Y-Ni合金相结构和电化学性能的影响
郭淼, 苑慧萍, 刘彧儒, 蒋利军
2019, 35(6): 1041-1049  doi: 10.11862/CJIC.2019.123
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采用磁悬浮感应熔炼法制备了组分为LaY2Ni9.7Mn0.5Al0.3的合金,在不同温度(1 073~1 373 K)下对合金进行热处理,利用X射线衍射法(XRD)、电子探针(EPMA)和电化学性能测试等方法,系统地研究了热处理温度对合金相结构和电化学性能的影响。结果表明,热处理可以显著提高合金的相均匀度,随着热处理温度的升高合金中的主相Ce2Ni7相先增加后减少。电化学研究表明,合金电极的最大放电容量、倍率性能和循环稳定性随着热处理温度的升高均呈现先升高后降低的趋势,与Ce2Ni7相含量的变化一致。电化学压力-组成-温度(P-C-T)测试表明,合金具有2个放氢平台,且随着热处理温度的升高合金的放氢坪台压增加。当热处理温度为1 273 K时,合金的Ce2Ni7相含量最高为86.53%(w/w),电化学性能最佳,最大放电容量为386.80 mAh·g-1(60 mA·g-1),在电流密度为900 mA·g-1时的高倍率性能HRD900=89.45%,循环300周后的容量保持率S300=72.18%(300 mA·g-1)。
三(三甲基硅烷)亚磷酸酯添加剂改善高镍三元正极材料的高电压循环性能
董庆雨, 毛亚云, 郭峰, 程振杰, 董厚才, 陈鹏, 康拓, 吴晓东, 沈炎宾, 陈立桅
2019, 35(6): 1050-1058  doi: 10.11862/CJIC.2019.117
[摘要]  (13) [HTML全文] (13) [PDF 6124KB] (2)
摘要:
研究了三(三甲基硅烷)亚磷酸酯(TMSP)添加剂对高镍三元正极材料LiNi0.83Mn0.05Co0.12O2(LNMC811)高电压循环性能的影响。结合电化学表征、理论计算、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)等方法研究发现,在高电位(4.5 Vvs Li/Li+)下,TMSP添加剂能够在LNMC811正极表面被氧化分解,生成一层富含导锂离子性能好的硅酸盐和电化学稳定的无机碳酸锂,且电解液主要分解产物(有机碳酸锂和氟化锂)含量较少的正极固体电解质界面(CEI)膜;分析表明覆盖在正极表面的薄而均匀的CEI膜,能够很好的降低充放电过程的极化电压,隔离电解液和正极的接触,减少电解液的分解,抑制金属离子的溶出,稳定正极晶体结构,使LNMC811材料能够在4.5 V(vs Li/Li+)高电压循环时仍然保持良好的循环性能和倍率性能。
Cr3+在不同基质Y3Ga5O12或Ga2O3中的荧光特性
洪薪超, 孙晶, 周晨, 唐娟, 毕冠
2019, 35(6): 1059-1064  doi: 10.11862/CJIC.2019.125
[摘要]  (13) [HTML全文] (13) [PDF 3207KB] (2)
摘要:
以Ga2O3、Y2O3、Cr(NO33·9H2O为原料,柠檬酸为配位剂,通过溶胶-凝胶高温固相合成法制备出Ga2-2xO3:2xCr3+(Ga2O3xCr)与Y3Ga5-5xO12:5xCr3+(YGG:xCr)2种多晶粉体(x=0.01,0.03,0.05,0.07)。并采用X射线衍射(XRD)、红外光谱(IR)、扫描电镜(SEM)、荧光光谱(PL)对样品的结构、组成、形貌和荧光性能进行测试分析。XRD和IR分析结果显示在900℃煅烧后Ga2O3xCr和YGG:xCr两种样品均成相。SEM照片显示Ga2O3xCr样品形貌为柱形多面体,YGG:xCr为短棒状。PL结果显示Cr3+在Ga2O3和YGG两种基质中的最强荧光发射峰分别位于742和740 nm,均属于Cr3+2E-4A2跃迁,对比发现Cr3+在YGG基质中的荧光发射强度更强,在远红光区的荧光性能更好,能满足温室照明中植物光合作用的需求。
Articles
Syntheses, Crystal Structures and Electrochemical Properties of Two Chiral Cu Complexes Based on D(-)/L(+)-4-Hydroxyphenylglycine
Man-Yu LIU, Ya-Jing SHI, Lan-Zhi WANG, Hui-Hua SONG
2019, 35(6): 1065-1075  doi: 10.11862/CJIC.2019.130
[摘要]  (44) [HTML全文] (44) [PDF 4830KB] (1)
摘要:
Two chiral coordination compounds based on D(-)/L(+)-4-hydroxyphenylglycine (D/L-Hhpg), {[Cu(D-hpg)(phen)(NO3)]·1.5H2O}n (1) and {[Cu(L-hpg)(phen)(NO3)]·2H2O}n (2) (phen=1, 10-phenanthroline) have been syn-thesized and characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, solid-state CD spectra and TG-DSC analysis. Compounds 1 and 2 are orthorhombic, P212121 chiral space groups. They are 1D chain structure, which is extended into a 3D supramolecular structure by the hydrogen bond. Interestingly, the compounds 1 and 2 exist left-handed or right-handed supramolecular helix chains along the b axis direction by the hydrogen bond respectively, which is extended by the hydrogen bond between coordinated nitrate anion and lattice water. Furthermore, based on the central metal ions of Cu(Ⅱ), further explored the compounds 1 and 2 of electrochemical properties, Analysis of cyclic voltammetry at varying scan rates (0.03 to 0.13 V·s-1) demonstrates a linear relationship between the anode peak current and the scan rate, indicating a surface-controlled electrochemical process.
Syntheses, Characterization and Crystal Structures of Five 1D Complexes Based on Semi-rigid Bis(thiazolylbenzimidazole) and Different Types of Carboxylic Acid Linkers
Lu LIU, Ping-Ning JIN, Ying LI, Hui-Hui LOU, Jian-Ji WANG, Yu-Ping ZHANG, Hong-Wei HOU, Jin-Ge DU
2019, 35(6): 1076-1084  doi: 10.11862/CJIC.2019.101
[摘要]  (12) [HTML全文] (12) [PDF 3357KB] (1)
摘要:
Five coordination complexes, formulated as {[Zn(btbb)0.5(m-phda)]·0.5H2O}n (1), {[Cd2(btbb)(adtda)2(H2O)]·H2O}n (2), [Mn2(btbb)(tbi)2]n (3), {[Cd(btbb)0.5(3-Nitro-o-bdc)(H2O)]·H2O}n (4) and[Cd2(btbb)(tbi)2]n (5) (btbb=1, 4-bis(2-(4-thiazolyl)benzimidazole-1-ylmethyl)benzene, m-H2phda=m-phenylenediacetic acid, H2adtda=1, 3-adaman-tanedicarboxylic acid, H2tbi=5-tert-butylisophthalic acid, 3-Nitro-o-H2bdc=3-Nitro-1, 2-benzenedicarboxylic acid), have been obtained by hydro(solv)thermal reactions and structurally characterized. Complex 1 exhibits a 1D chain structure containing 22-membered rings. Complex 2 features a 1D chain structure having an 8-membered rings and btbb serves only as an ornament here. Complex 3 is a 1D double chain structure. Complex 4 possesses a 1D chain structure containing 14-membered rings. Complex 5 shows a 1D double chain taking on stair-step. CCDC: 1883643,1;1883644,2;1883645,3;1883646,4;1883647,5.
Synthesis, Crystal Structure and luminescent Properties of Sr0.955Al2-xBxSi2O8: 0.025Eu2+ Phosphors
Fei WANG, Yi-Guang TIAN, Qiao ZHANG
2019, 35(6): 1085-1092  doi: 10.11862/CJIC.2019.126
[摘要]  (25) [HTML全文] (25) [PDF 4340KB] (1)
摘要:
A series of luminescence phosphors Sr0.955Al2-xBxSi2O8:0.025Eu2+ (x=0~0.9) were prepared via solid-state reaction in a weak reductive atmosphere. The lattice positions and the luminescent mechanism of Eu2+ in the host were discussed, the effects of B(Ⅲ)-substitution on the host lattices and spectral properties were also investigated. It was found that the complete solid solutions were formed in the whole range of x=0~0.9, as B(Ⅲ) substituted for Al(Ⅲ) entered to SrAl2Si2O8. The lattice parameters (a, b, c) and unit cell volume (V) of phosphors Sr0.955Al2-xBxSi2O8:0.025Eu2+ (x=0~0.9) decreased linearly and lattice parameter (β) increased linearly as the increase of substitution amount of B(Ⅲ). A broad excitation spectrum consisted of four excitation bands, which was in a range of 225~400 nm, and an apparent peak at 350 nm. Full width at half maximum (FWHM) increased from 90 to 102 nm as increase of the substitution amount of B(Ⅲ). The emission spectrum was a broad-band in a range of 370~600 nm, which could be fitted two peaks of 409 and 447 nm, and its apparent peak was at 409 nm. Two fitted peaks were blue shifted and the intensity ratio of the fitted peaks decreased linearly as the increase of the substitution amount of B(Ⅲ)). The coordination number of Sr2+ was 9 in SrAl2Si2O8:Eu2+, which has been confirmed by the experimental results and empirical formula of Van Uitert. The distance between the luminescent center Eu and the ligand O increased due to the Al(Ⅲ) replaced by B(Ⅲ), so that the crystal field strength of Eu2+ decreased, and the 5d energy level split of the luminescent center Eu2+ decreased, the center of gravity of the lowest emission level of Eu2+ was shifted upward, and the two fitted peaks were linearly blue-shifted.
A Tetradecanuclear Polyoxofluorovanadate Cluster Compound with 1-Methylimidazole Possessing Ring-like[V10O20] Ladder Core and Unusual Electronic Configuration: Synthesis, Structure and Theoretical Calculation
Yi-Ping TONG, Xiao-Dan ZHENG, Jia-Jia LI, Yan-Wen LIN, Guo-Tian LUO
2019, 35(6): 1093-1100  doi: 10.11862/CJIC.2019.121
[摘要]  (16) [HTML全文] (16) [PDF 1669KB] (1)
摘要:
A rare tetradecanuclear polyoxofluorovanadate cluster with 1-methylimidazole (L), containing mixed-valence[V14O36F2L2]6- anion, was synthesized and characterized crystallographically. The anion is composed of a special 0D cluster-like skeleton frame, i.e. the ring-shaped[V10O20] ladder, two grafted VO5F and VO3L fragments around the ladder. The density functional theory (DFT) and bond valence sum calculations indicate that the V ion in two grafted VO5F fragments are +4 oxidation state, while other V ions are +5 oxidation state. The frontier orbital analysis shows that the[V14O36F2L2]6- anion, should be chemically active in d orbital of grafted VO5F fragments, while its 2e oxidation species, the[V14O36F2L2]4- anion should be chemically active in the terminal V=O (d-p) π orbital of grafted VO3L fragments. The 2e introduction from[V14O36F2L2]4- to[V14O36F2L2]6- anion leads to the increasing structural stability of the[V10O20] ladder, and at the same time the increasing chemical activity of the grafted VO5F and VO3L fragments, together with a great decrease of energy gap from 1.59 to 0.53 eV.
Syntheses and Magnetic Properties of Spinel-Type MFe2O4 (M=Ca, Mg, Cu, Zn) Nanocrystalline Powders
Peng CHEN, Lin-Wen JIANG, Jin-Jun LIU, Shan-Shan YANG, Jiang-Tao LI, Hong-Bing CHEN, Jun HE, Yu WANG
2019, 35(6): 1101-1108  doi: 10.11862/CJIC.2019.133
[摘要]  (12) [HTML全文] (12) [PDF 5411KB] (1)
摘要:
Magnetic spinel-type MFe2O4 (M=Ca, Mg, Cu and Zn) nanocrystalline powders were successfully prepared by auto-combustion method using a novel amino-based gel. The phase identification, morphology and magnetic properties of as-synthesized powders were studied in detail. The high purity of synthesized MFe2O4 powders was comfirmed by energy dispersive X-ray spectroscopy. Magnetic properties of as-synthesized MFe2O4 nanocrystalline powders were investigated systematically. All the samples presented a rather narrow hysteresis loop, suggesting the soft magnetic features. The saturated magnetization (Ms) of the four ferrites were 2.1, 29.3, 24.1, and 4.2 emu·g-1, respectively, and the residual magnetization (Mr) were 0.2, 2.3, 11.4, and 0.2 emu·g-1, respectively. Mr/Ms values of four ferrite samples were all less than 0.5. Zero-field-cooled and field-cooled magnetic properties of CaFe2O4 and MgFe2O4 samples as two typical ferrites were investigated in detail. The magnetization of CaFe2O4 sample presented an inconsistent variation tendency below 75 K due to the occurrence of magnetic phase transition.
Syntheses, Structures and Hirshfeld Analyses of Trinuclear Ni(Ⅱ) Salamo-Type Complexes
Meng YU, Hao-Ran MU, Ling-Zhi LIU, Na LI, Yang BAI, Xiu-Yan DONG
2019, 35(6): 1109-1120  doi: 10.11862/CJIC.2019.128
[摘要]  (17) [HTML全文] (17) [PDF 4903KB] (1)
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Two newly designed complexes, {[Ni(L1)(n-propanol)]2(OAc)2Ni}·2(n-propanol) (1) and {[Ni(L2)(n-butanol)]2(OAc)2Ni}·2(n-butanol) (2) derived from tetradentate Salamo-type chelating ligands (H2L1=5-methoxy-2, 2'-(ethylenedioxybis(azomethine))diphenol and H2L2=4, 4'-dinitro-2, 2'-(ethylenediyldioxybis(nitrilomethylidyne))diphenol) have been synthesized and characterized by elemental analyses, IR and UV-Vis spectra, Hirshfeld surfaces analyses and single crystal X-ray crystallography. X-ray crystallographic analyses showed that complexes 1 and 2 are all symmetric trinuclear Ni(Ⅱ) complexes. Nickel(Ⅱ) in both 1 and 2 is hexa-coordinated, forming a twisted octahedral geometry. Both crystal structure and Hirshfeld surface analysis indicate that 1 and 2 form stable one-dimensional chain and two-dimensional supramolecular structures, respectively, by intermolecular hydrogen bonding.
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论文
SAPO-18分子筛晶化机理及其甲醇制烯烃性能
郭云鸦, 梁光华, 张燕挺, 何祖光, 梁亚凝, 李宁, 李晓峰, 窦涛
2019, 35(2): 185-193  doi: 10.11862/CJIC.2019.044
[摘要]  (190) [HTML全文] (190) [PDF 6444KB] (190)
摘要:
分别以拟薄水铝石、硅溶胶、磷酸为铝源、硅源、磷源,NN-二异丙基乙胺为模板,采用水热法制备出不同晶化时间下的SAPO-18分子筛。采用X射线衍射(XRD)、电子扫描显微镜(SEM)、氨气程序升温脱附(NH3-TPD)、固体核磁共振(29Si MAS NMR,27Al MAS NMR)、傅里叶红外(FT-IR)等对不同晶化时间下的产物进行表征以及甲醇制烯烃(MTO)催化性能检测。表征结果结合MTO催化反应性能表明:水热体系下SAPO-18分子筛生长过程可分为3个阶段:晶化初期(≤ 2 h),快速生长期(6~12 h),生长稳定期(1~3 d)。其中,在晶化初期只有极少量的硅进入Al(PO)4类中间体;此后为快速生长期,硅原子进入Al(PO)4类中间体及SAPO-18晶体取代磷、铝原子,以SMⅡ机制为主,SMⅢ机制为辅;在生长稳定期2种取代机制主次发生了变化。
以[Eu(PBrBA)3phen]和[Eu(PCBA)3phen]为探针的温敏漆制备及其性能对比
毕冠, 孙晶, 周晨, 于文生, 王媛, 唐娟
2019, 35(2): 203-208  doi: 10.11862/CJIC.2019.029
[摘要]  (143) [HTML全文] (143) [PDF 2498KB] (143)
摘要:
以氧化铕(Eu2O3)、对氯苯甲酸(PCBA)、对溴苯甲酸(PBrBA)和菲咯啉(phen)为原料制备了菲咯啉对氯苯甲酸铕[Eu(PCBA)3 phen]、菲咯啉对溴苯甲酸铕[Eu(PBrBA)3phen]两种探针分子,并将这2种探针分子掺杂在甲基丙烯酸甲酯(MMA)中,以过氧化苯甲酰(BPO)为引发剂,制得Eu(PCBA)3phen/PMMA和Eu(PBrBA)3phen/PMMA温敏漆样品。利用红外光谱仪、扫描电子显微镜、紫外-可见分度光度计和荧光光谱仪对探针分子的组成结构、发光性能、形貌和温敏漆的温度敏感性进行了测试分析,研究了不同配体对探针分子发光性能和温敏漆性能的影响。结果表明,Eu3+分别与对氯苯甲酸(PCBA)和对溴苯甲酸(PBrBA)2种主配体配位,并且第二配体菲咯啉(phen)均参与了配位,成功合成了2种配合物。2种配合物均发出Eu3+的特征荧光,其中以PBrBA为主配体的菲咯啉铕三元配合物具有更好的发光性能。此外,基于这2种探针分子制备的温敏漆在50~90℃范围内均具有温度猝灭性能,以Eu(PCBA)3phen为探针制成的温敏漆温度敏感性更强。
磷灰石结构荧光粉Ba10(PO4)6F2:Ce3+, Tb3+的合成、发光和能量传递
程少文, 张娜, 卓宁泽, 朱月华, 陈永浩, 蒋鹏, 杜文慧, 叶恩淦, 王海波
2019, 35(2): 209-216  doi: 10.11862/CJIC.2019.038
[摘要]  (157) [HTML全文] (157) [PDF 4371KB] (157)
摘要:
采用高温固相法合成了系列Ce3+和Ce3+/Tb3+激活的具有磷灰石结构荧光粉Ba10(PO46F2。用X射线衍射(XRD)、扫描电镜(SEM)、激发和发射(PLE和PL)光谱对样品进行了表征分析。研究结果表明:所合成的荧光粉Ba10(PO46F2:Ce3+,Tb3+具有氟磷灰石结构,样品微观呈现不规则形貌。荧光粉Ba10-x(PO46F2xCe3+的相对发射强度随着x增加而增强,当x=0.09时,荧光强度达到最大。荧光粉Ba10(PO46F2:Ce3+,Tb3+的激发光谱为240~330 nm的宽带,发射光谱呈现出Ce3+的5d→4f跃迁紫外光(335和358 nm)发射和Tb3+的4f→4f跃迁绿光(542 nm)发射。光谱特性表明,发光过程中存在Ce3+→Tb3+能量传递,能量传递效率可以达到60%。计算Ce3+和Tb3+的临界距离为0.79 nm,能量传递机理是偶极-偶极交互作用。此外,详细论述了Ce3+和Tb3+之间的能量传递和发光的过程。通过调节Tb3+的掺杂浓度,对荧光粉发光色坐标与Tb3+的掺杂浓度之间的关系也进行了研究,随着Tb3+的掺杂量从0增加0.52,荧光粉Ba10(PO46F2:Ce3+,Tb3+的发射光谱色坐标可以从(0.149 4,0.045 1)蓝色区变化到(0.280 1,0.585 3)绿色区。
碳纳米管改性g-C3N4提升可见光催化降解性能
王鹏, 李昭, 周颖梅, 徐艳, 朱捷, 王士凡, 蔡可迎, 李靖, 堵锡华, 杨朋举
2019, 35(2): 217-224  doi: 10.11862/CJIC.2019.022
[摘要]  (154) [HTML全文] (154) [PDF 5404KB] (154)
摘要:
以尿素为原料,引入少量的多壁碳纳米管(CNT)改性,采用简便方法制备CNT/g-C3N4催化剂。利用扫描电镜(SEM)、透射电镜(TEM)、傅里叶红外光谱仪(FT-IR)、X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见-近红外分光光度计(UV-Vis-NIR Spectrophotometer)、荧光光谱(PL)等手段对CNT/g-C3N4催化剂进行表征。结果表明,g-C3N4与CNT之间的协同作用,影响了g-C3N4的能带结构,增强了其对可见光的吸收,改善了光生载流子的分布,提高了电子-空穴对的分离效率。并以罗丹明B(RhB)水溶液模拟废水,在可见光下考察催化剂的光催化降解性能,发现当CNT掺杂量为0.1%(w/w)时效果最佳,降解速率常数是体相g-C3N4的3.1倍,且研究发现超氧自由基是该体系下的主要活性物种。
系列Ag-Ln配位聚合物的合成、结构及发光性能
王岩, 陈飞霏, 胡晓双, 赵然, 迟玉贤, 金晶
2019, 35(2): 225-235  doi: 10.11862/CJIC.2019.014
[摘要]  (139) [HTML全文] (139) [PDF 5076KB] (139)
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采用水热合成法,以吡嗪-2-羧酸(2-Hpzc)、3,5-吡啶二羧酸(3,5-H2PDA)和草酸(H2ox)为配体,合成9种Ag-Ln配位聚合物:{[LnAg(2-pzc)2(ox)]·H2O}n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H2O)]n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)0.5(H2O)2]n(Ln=Sm(7),Dy(8),Ho(9))。配位聚合物1~4是同构的,由2-pzc-和ox2-连接,而配位聚合物5~9是以3,5-PDA2-和ox2-为桥联配体,均呈现3D网状结构。光物理性能研究表明配位聚合物均表现出Ln(Ⅲ)的特征发射,这可归因于Ag-配体部分(d-block)的敏化作用。另外,在晶体场和Ag(Ⅰ)离子4d轨道的共同作用下,Ln(Ⅲ)离子的4f轨道被调谐,使部分能级发生明显的位移,表现为相应NIR发射带的位移,在其UV-Vis-NIR吸收光谱中可以得到佐证。
凹凸棒石/g-C3N4-AgFeO2复合材料制备及其光催化性能
谢登裕, 蒋亿, 纪媛媛, 殷明慧, 盛振环, 赵伟, 殷竟洲, 李乔琦, 仲慧, 张莉莉
2019, 35(2): 236-244  doi: 10.11862/CJIC.2019.040
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摘要:
以凹凸棒石(简称凹土,ATP)为基体,通过原位化学法一步直接合成g-C3N4薄层材料,并将其有效固载于凹土表面(ATP/g-C3N4),再通过原位沉淀法引入不同比例AgFeO2纳米颗粒,构筑系列兼具磁分离特性和高效光催化活性的ATP/g-C3N4-AgFeO2-Y复合光催化剂(Y=wATP/g-C3N4/(wATP/g-C3N4+wAgFO2)×100%,表示ATP/g-C3N4在ATP/g-C3N4-AgFeO2复合材料中所占的质量百分数)。采用XRD、SEM、BET、UV-Vis、PL和ICP表征其结构和物化性能,以酸性红G(ARG)为目标降解物,研究其光催化性能。研究发现:通过形成Si-O-C键,g-C3N4薄层被均匀固定在凹土表面;AgFeO2纳米颗粒均匀沉积于ATP/g-C3N4表面并形成Z型异质结,ATP/g-C3N4-AgFeO2-Y具有比ATP/g-C3N4和AgFeO2更优异的可见光光催化性能,且随着ATP/g-C3N4含量的增大呈先升高而后下降的趋势;当Y=57%时复合材料的性能最佳,ATP/g-C3N4-AgFeO2-57%对20 mg·L-1酸性红G的降解率可达97.4%,循环4次使用后,降解率仍保持94.2%。通过自由基捕获实验研究了光催化反应机理,发现·O2-是光催化过程的主要活性物种。
Pr1-xSrCo0.5Ni0.5O4+δ阴极材料的合成及电化学性质
刘建伟, 孙丽萍, 赵辉, 霍丽华
2019, 35(2): 245-253  doi: 10.11862/CJIC.2019.030
[摘要]  (180) [HTML全文] (180) [PDF 4338KB] (180)
摘要:
采用固相法合成中温固体氧化物燃料电池(IT-SOFC)阴极材料Pr1-xSrCo0.5Ni0.5O4+δ(P1-xSCN,x=0.00,0.05,0.10,0.15,0.20),并对材料的物相、热膨胀系数(TEC)、电导率、电极的微观形貌以及电化学性质进行表征。XRD结果表明,该材料形成单一的K2NiF4结构,空间群为I4/mmm,并与电解质材料Ce0.9Gd0.1O1.95(CGO)具有良好的高温化学相容性。碘量法分析表明随着Pr离子缺位浓度增加,P1-xSCN中Co/Ni离子平均化合价随着x的增加而升高,至x=0.10后逐渐降低,而氧空位含量逐渐升高。引入Pr离子缺位使材料的电导率明显提高,其中P0.90SCN在700℃空气中电导率值为309 S·cm-1。TEC测试结果显示,随着Pr缺位的增加,热膨胀系数逐渐增大,最大值为1.51×10-5 K-1。交流阻抗谱(EIS)测试结果表明,Pr缺位明显降低了电极的极化阻抗值,P0.90SCN阴极在700℃空气中的极化阻抗值为0.21 Ω·cm2。电解质支撑NiO-CGO/CGO/P0.90SCN单电池在700℃最大输出功率密度为197.8 mW·cm-2
g-C3N4/双钙钛矿复合材料的制备及氧催化性能
王成, 黄红霞, 肖阳, 梁大铭
2019, 35(2): 254-262  doi: 10.11862/CJIC.2019.033
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摘要:
通过溶胶-凝胶法制备出不同Ni掺杂比例的双钙钛矿Sr2NixCo2-xO6x=0.2,0.4,0.6,0.8),通过热分解法制备出具有层状结构的纳米颗粒g-C3N4,并制备其复合物催化剂。将双钙钛矿和g-C3N4分别制备成双功能电极片,用于测试其对氧还原(ORR)和氧析出(OER)的催化活性,然后选取具有最佳氧催化活性的Ni掺杂比例x=0.4的双钙钛矿与一定重量比例的g-C3N4进行复合,测试复合催化剂的氧催化活性。结果表明,复合后的催化剂催化效果明显优于单一催化剂,当g-C3N4添加量占双钙钛矿的30%(w/w)时复合催化剂催化氧还原反应的最大电流密度为395.7 mA·cm-2(-0.6 V vs Hg/HgO),氧析出反应的最大电流密度为372.0 mA·cm-2(1 V vs Hg/HgO),这表明g-C3N4与Sr2Ni0.4Co1.6O6复合后协同催化能够提高双钙钛矿的氧催化活性。
Bi/BiVO4&Bi4V2O11复合催化剂的制备及其光催化性能
梁梦君, 邓楠, 向心怡, 梅英, 杨志远, 杨赟, 杨水金
2019, 35(2): 263-270  doi: 10.11862/CJIC.2019.028
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摘要:
经由溶剂热反应、光辅助还原过程制备Bi/BiVO4&Bi4V2O11纳米复合光催化材料。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨率透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、N2吸附-脱附等温线和光致发光(PL)等手段对该复合物进行表征。实验结果表明当金属Bi与BiVO4&Bi4V2O11的质量比值为0.8,可见光照射30 min时,Bi/BiVO4&Bi4V2O11复合催化剂对罗丹明B(RhB)的降解率可达95.6%。此外,Bi/BiVO4&Bi4V2O11对四环素(TC)的降解也表现出增强的光催化性能。Bi/BiVO4&Bi4V2O11复合材料提升的光催化性能可能归因于金属Bi的表面等离子体共振(SPR)效应、拓宽的可见光吸收范围和增大的比表面积。此外,提出了复合光催化剂可能的光催化机理。
Bi5O7I/聚苯胺复合光催化剂的制备及光催化活性
王璐, 李曦, 唐子聪, 周楠, 俞峥松, 董永志, 李小争, 魏登贵, 董玉林, 李全华, 刘鹏
2019, 35(2): 271-276  doi: 10.11862/CJIC.2019.047
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摘要:
首先采用化学氧化聚合法合成聚苯胺(PANI),再采用溶剂热法制备了Bi5O7I/PANI复合材料,并采用X射线衍射、傅里叶变换红外光谱、场发射扫描电镜、紫外-可见漫反射光谱和荧光光谱等对所制备材料进行了表征,考察了复合材料在可见光光照条件下降解罗丹明B(RhB)的催化性能。结果表明当负载PANI后,Bi5O7I/PANI的复合材料都表现出优异的光催化性能。当PANI负载量在5%(w/w)时,催化效率最佳。在60 min内,其降解RhB的速率常数为Bi5O7I的3.9倍。捕获实验表明超氧自由基和空穴是该过程的主要活性物种。Bi5O7I/PANI具有优异光催化性能的原因主要在于,负载的PANI扩展了可见光吸收范围并增强了可见光吸收强度,而且PANI和Bi5O7I匹配的能级结构抑制了光生电子-空穴的复合效率。
氰基合钴(Ⅲ)氢键型笼状超分子晶体的合成、结构及介电性质
郑晓媛, 刘洋, 秦刘磊, 俞非凡, 朱春立, 刘尊奇
2019, 35(2): 277-284  doi: 10.11862/CJIC.2019.036
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摘要:
以2-氯苯胺(o-chloroaniline,o-CA)、18-冠醚-6(18-crown-6)和钴氰酸为原料,在甲醇和水的混合溶液内通过蒸发法合成氰基合钴配合物氢键笼状超分子晶体材料(H)0.5o-CAH)[Co(CN)6]0.5·(18-crown-6)0.5·H2O(1)。并通过单晶X射线衍射、红外光谱、粉末X射线衍射、元素分析、热重分析(TG)和介电常数测试等对超分子晶体进行了结构及电性能表征。测试结果表明,该晶体在低温下属于三斜晶系,空间群为P1,晶胞参数为a=0.869 22(1)nm,b=0.964 09(12)nm,c=1.129 93(14)nm,α=77.894 0(10)°,β=78.877 0(10)°,γ=88.684 0(10)°。结构显示氰基合钴配合物、超分子阳离子和水分子通过氢键相互作用在空间内形成三维笼状。笼状顶点的钴原子随着温度的变化其间距发生明显的伸缩,导致晶体在260 K附近观察到明显的介电异常现象。
原位制备的铁配合物催化烯烃选择性环氧化
宋虹瑾, 李璐, 张妮, 王斐, 吕婧, 孟祥光
2019, 35(2): 285-292  doi: 10.11862/CJIC.2019.046
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摘要:
制备了配体2-(2-吡啶基)-噁唑啉。该含氮配体能够在乙腈溶液中与三氟甲磺酸亚铁和其它辅助配体原位形成具有催化活性的六配位金属亚铁配合物。量子化学计算表明配体上的氮原子而非氧原子与铁配位。研究表明,以H2O2为氧化剂,该金属配合物能够在乙腈溶液中高活性地催化末端芳香烯烃和脂肪烯烃的环氧化反应;该反应条件温和、迅速、选择性好并且适用底物范围宽泛。辅助配体、溶剂和氧化剂等因素对反应的活性和选择性影响很敏感,文中对这些影响进行了较详细的研究。
作为Be2+磷光探针的含9-冠-3的铱配合物
潘淼, 胡媛媛, 赵卓, 姚永林, 周会东, 童碧海, 张千峰
2019, 35(2): 293-299  doi: 10.11862/CJIC.2019.049
[摘要]  (165) [HTML全文] (165) [PDF 3014KB] (165)
摘要:
以4'-(2-苯并噻唑基)苯并-9-冠-3(BTZ9C3)为主配体,用2,2'-联吡啶(bpy)及3-三氟甲基-5-(2'-吡啶基)-1,2-二唑(Hfppz)辅助配体分别合成了离子型铱配合物[Ir(BTZ9C3)2(bpy)]PF61)和中性铱配合物[Ir(BTZ9C3)2(fppz)](2)。配合物的结构通过核磁、高分辨质谱进行了表征,并测定了配合物1的单晶结构。对它们光物理性能的研究表明,2种配合物掺杂在PMMA中的发光为黄绿光发射,配合物1的发光波长为535 nm,配合物2的发光波长为541 nm,发光量子效率分别为10.8%,45.0%,发光寿命分别为3.01和2.58 μs,为典型的磷光发射。通过循环伏安法测得配合物12的HOMO能级分别为-5.60和-5.35 eV。2种配合物对Be2+都有发光增强的选择性识别效果,化学计量比为1:2,最低检测限低至6.0 μmol·L-1。抗干扰能力方面,离子型配合物1的抗干扰能力较好,而中性配合物2受Al3+的干扰较大。
三乙醇胺改性Cu/Zn/Al类水滑石衍生氧化物催化合成气制备低碳醇
程淑艳, 郝艳红, 寇佳伟, 高阳艳
2019, 35(2): 300-306  doi: 10.11862/CJIC.2019.041
[摘要]  (137) [HTML全文] (137) [PDF 876KB] (137)
摘要:
采用共沉淀法制备Cu/Zn/Al类水滑石前驱体,并用配体三乙醇胺(TEA)对其进行改性。前驱体经焙烧后成功获得TEA改性的Cu/Zn/Al催化剂。借助XRD、FTIR、H2-TPR、CO-TPD及SEM等方法对催化剂进行表征,并将其应用于合成气制备异丁醇的活性评价反应中。结果表明,TEA的加入能够改变催化剂形貌,使催化剂表面呈松散絮状结构。TEA可使类水滑石前驱体的结构发生膨胀,其焙烧获得的催化剂中有明显的晶格扭曲和晶格缺陷。TEA对催化剂结构的改变有利于Cu/Zn/Al催化剂中CuO组分的氢还原和CO在催化剂表面的化学吸附,从而促进异丁醇的合成。当TEA的添加比例为nTEA/nZn=0.5时,TEA改性的Cu/Zn/Al催化剂的催化效果达到最佳。
具有聚集荧光增强性质的双(4-二乙氨基水杨醛)缩偶氮二甲酰肼二丁基锡的合成和晶体结构
冯泳兰, 邝代治, 张复兴, 庾江喜, 蒋伍玖, 朱小明
2019, 35(2): 307-313  doi: 10.11862/CJIC.2019.043
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在甲醇溶液中,卡巴肼、(4-二乙氨基)水杨醛和二乙酸二丁基锡"一锅法"反应,合成了一个新颖的基于双(4-二乙氨基水杨醛)缩偶氮二甲酰肼(L)的七配位有机锡配合物[Sn(L)(n-butyl)2]nT)。经元素分析、IR、(1H,119Sn,13C)NMR和X射线衍射晶体结构表征,T的晶体属单斜晶系C2/c空间群,中心锡周围由双(4-二乙氨基水杨醛)缩偶氮二甲酰肼的O,N配位原子占据赤道位置和2个丁基占据顶端位置形成畸变五角双锥构型。通过烯醇式氧原子的桥联配位作用,T向一维带状无限扩展产生"竹筏状"超分子结构。配合物T在二甲基甲酰胺、四氢呋喃、乙醇、甲醇和甲苯有机溶剂及其有机溶剂-水混合物中具有强荧光发射峰,当含水量的体积分数在0~10%(V/V)时具有良好的聚集荧光增强效应,含水量大于10%(V/V)时发生荧光淬灭。
Articles
One-Pot Synthesis of Rose-like Ce-Doped SnS2 with Enhanced Visible-Light Photocatalytic Property for Reduction of Cr(Ⅵ)
Guo-Hui LI, Yuan-Yuan SUN, Hua-Long XING, Jian-Cong ZHENG, Chen-Chen LIN, Zhen-Fan SUN
2019, 35(2): 194-202  doi: 10.11862/CJIC.2019.006
[摘要]  (208) [HTML全文] (208) [PDF 5293KB] (208)
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The Ce-doped SnS2 samples were prepared successfully through a one-pot hydrothermal method under mild conditions. The as-prepared SnS2 samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with Energy dispersive X-ray Spectroscopy (EDS) which confirmed the doping of Ce. The results indicated the spiral growth mode and rose-like morphology of the samples. The effects of Ce doping on the photoabsorption, band gap, the potential of conduction band and the separation efficiency of photo-induced carriers were checked by diffuse reflectance spectrum (DRS) and electrochemical examinations. The reductive abilities of the samples were evaluated by the reduction of Cr(Ⅵ) chosen as a model pollutant. The results reveal that photocatalytic properties of Ce/SnS2 were strongly dependent on the proportion of Ce ions and the optimum doping amount of Ce is 5% (n/n).
Synthesis, Growth Mechanism and Application in Anticancer of CuS Hollow Spheres
Qing-Li HUANG, Li-Li WANG, Ting LI, Yong-Ping WU
2019, 35(2): 314-322  doi: 10.11862/CJIC.2019.032
[摘要]  (115) [HTML全文] (115) [PDF 3007KB] (115)
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Cage-like hollow morphologies of copper sulfide nanostructures have been selectively synthesized using cupric nitrate trihydrate (Cu(NO3)2·3H2O), oxalic acid (H2C2O4) and sodium sulphide nonahydrate (Na2S·9H2O) as starting materials in water solution by a self sacrificing templates hydrothermal method. X-ray diffraction (XRD), field scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products. The possible formation mechanism of CuS hollow spheres was proposed. The photo-thermal conversion experiments were also done. The results showed that hollow CuS exhibited high photo-thermal efficiency and high anticancer activity under NIR irradiation.
Syntheses, Structures and Magnetic Properties of Two Binuclear Lanthanide Complexes Bridged by Nitronyl Nitroxide Radical Ligands
Xue-Lan MEI, Min-Jie DU, Peng HU, Zong-Qun LI
2019, 35(2): 323-328  doi: 10.11862/CJIC.2019.034
[摘要]  (142) [HTML全文] (142) [PDF 792KB] (142)
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The reaction of Ln(acac)3·3H2O with NIT-PhOH radical yielded two new Ln-radical complexes[Ln2(acac)4(NIT-PhO)2] (Ln=Tb (1), Y (2); acac=acetylacetonato, NIT-PhOH=2-(2'-hydroxyphenyl)-4, 4, 5, 5-tetramethylimidazo-line-1-oxyl-3-oxide). Two complexes are isostructural and have binuclear structure in which two lanthanide ions are bridged by two radical ligands through their phenoxo-O atoms. DC magnetic susceptibility studies indicated that there exists weak antiferromagnetic interaction in complex 2.
Syntheses, Crystal Structures, and Luminescent Properties of Three Cobalt(Ⅱ), Lead(Ⅱ) and Zinc(Ⅱ) Complexes Constructed from Mixed Biphenyl Tricarboxylic Acid and N-Donor Ligands
Yu LI, Xun-Zhong ZOU, Wen-Da QIU, Wen-Liu ZHUANG, Na ZHAO, Xiao-Ling CHENG
2019, 35(2): 329-336  doi: 10.11862/CJIC.2019.002
[摘要]  (101) [HTML全文] (101) [PDF 2326KB] (101)
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Zero-dimensional mononuclear cobalt(Ⅱ) complex, 1D lead(Ⅱ) and 1D zinc(Ⅱ) coordination polymers, namely[Co(Hbtc)(phen)2(H2O)]·3H2O (1), [Pb(μ3-Hbtc)(2, 2'-bipy)]n (2) and {[Zn3(μ2-btc)2(μ2-H2O)(2, 2'-bipy)3(H2O)5]·8H2O}n (3), have been constructed hydrothermally using H3btc (H3btc=biphenyl-2, 4, 4'-tricarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and cobalt, lead or zinc chlorides. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the orthorhombic or triclinic systems, space groups Pna21 or P1. Complex 1 has a discrete monomeric structure, which is assembled to a 3D supramolecular framework through O-H…O hydrogen bond. Complexes 2 and 3 show a 1D chain based on binuclear units. Luminescent properties of all complexes have been studied.
Influences of cis-, trans-1, 2-Cyclohexanediamine Configurations on Iodoantimonate Organic-Inorganic Hybrid Isomers
Zhi-Wen LIANG, Xiao-Rou CHEN, Hui YU, Zhen-Hong WEI, Xiu-Xiu ZHANG, Hu CAI
2019, 35(2): 337-343  doi: 10.11862/CJIC.2019.027
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Reactions of cis-and trans-1, 2-cyclohexanediamine (DAC) with antimony iodide in concentrated HI aqueous solution afforded two organic-inorganic hybrid isomers (cis-1, 2-DACH2)[SbI5]·H2O (1) and {(trans-1, 2-DACH2)[SbI5]·H2O}n (2), respectively. The single-crystal X-ray diffraction revealed that the inorganic component in compound 1 is a dimer[Sb2I10] built up from two[SbI6] octahedra by sharing I-I edge, and that in compound 2 is a zigzag chain constructed with corner-sharing octahedral[SbI6] units. In addition, both compounds have been investigated and compared by UV-Vis, fluorescent spectra, and DFT calculation.
X-ray Crystallography, Spectral Characterization and Computational Studies of Mercury(Ⅱ) Complex with 1-(p-Tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one
Pourmirza Mahsa, Ebrahimnezhad Shahla, Ramazani Ali, Bahrami Aidin, Alaei Sholeh., Reza Dadrass Ali.
2019, 35(2): 344-350  doi: 10.11862/CJIC.2019.031
[摘要]  (126) [HTML全文] (126) [PDF 1308KB] (126)
摘要:
The α-phosphorus ligand 1-(p-tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one(L) was prepared by the reaction of 2-bromo-1-(p-tolyl)ethan-1-one with tri(p-tolyl) phosphine. The reactions of L with cadmium chloride and mercury bromide resulted in[Cd(L)Cl2]2 (C1) and[Hg(L)(μ2-Br)Br]2 (C2), respectively. The complexes were characterized by IR and NMR (1H, 13C, 31P). The structure of C2 was detected by single crystal X-ray diffraction and its DFT computational studies at B3LYP/6-31G* level were also performed to reveal the interaction between the reaction site of complex C2 and nucleophilic groups such as Schiff base.
A Layered Cd(Ⅱ)-Organic Coordination Polymer Exhibiting Dual-Responsive Sensing Towards 2, 4, 6-Trinitrophenol and Fe3+
Jing-Jing SHI, Shan XU, Na LI, Xiu-Guang WANG, Xiao-Jun ZHAO, En-Cui YANG
2019, 35(2): 351-360  doi: 10.11862/CJIC.2019.045
[摘要]  (310) [HTML全文] (310) [PDF 4607KB] (310)
摘要:
A layered coordination polymer[Cd(QDA)]n (1) with distorted Cd2+ octahedron extended by three-connected 2, 3-quinoline dicarboxylate linkers was hydrothermally synthesized, exhibiting intense blue fluorescence and highly thermal and chemical stability. More interestingly, the complex dispersed in ethanol can quickly probe the trace amounts of 2, 4, 6-trinitrophenol (Ksv=6.61×104 L·mol-1, LOD=0.83 μmol·L-1) and Fe3+ (Ksv=1.74×104 L·mol-1, LOD=2.70 μmol·L-1) through fluorescence quenching with high quenching constants (Ksv) and low limits of detection (LOD).
Syntheses, Spectroscopic Properties and THz Time Domain Spectroscopy of Two Copper(Ⅰ) Complexes Based on N-Donor and P-Donor Ligands
Xun PAN, Xiao-Nan KUANG, Ning ZHU, Zhi-Gang REN, Yu-Ping YANG, Xiu-Lan XIN, Zhong-Feng LI, Hong-Liang HAN, Qiong-Hua JIN
2019, 35(2): 361-368  doi: 10.11862/CJIC.2019.026
[摘要]  (147) [HTML全文] (147) [PDF 838KB] (147)
摘要:
Two novel copper(Ⅰ) complexes[Cu(bdppmapy)(2, 2'-bipy)]BF4 (1) and[Cu(bdppmapy)(2, 2'-bipy)]I (2) (2, 2'-bipy=2, 2'-bipyridine, bdppmapy=N, N-bis((diphenylphosphino)methyl)-2-pyridinamine) have been synthesized in mixed solvents of CH3OH and CH2Cl2 (1:1, V/V) and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H NMR and 31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1, a mononuclear complex, was generated by the reaction of[Cu(CH3CN)4]BF4 and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In complex 1, the central Cu(Ⅰ) forms a distorted tetrahedral geometry by coordinating with the diphosphine ligand (bdppmapy) and chelating N-donor ligand (2, 2'-bipy). Like 1, 2 was obtained by the reaction of CuI and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In the asymmetric unit of 2, the bdppmapy and 2, 2'-bipy ligands chelate central Cu(Ⅰ), respectively. The luminescent spectra show that the emission mechanism is metal-to-ligand charge transfer (MLCT). The application of terahertz time-domain spectroscopy also provides useful information for the research of complexes.