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综述
多酸基光敏剂在染料敏化太阳能电池中的应用
谷易桐, 陈黎, 李建平, 刘丽, 陈维林, 刘丁, 王恩波
2019, 35(11): 1905-1920  doi: 10.11862/CJIC.2019.227
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染料敏化太阳能电池(dye-sensitized solar cells,简写为DSSCs)是由Michael Grätzel等开发的第三代光伏电池,它具有低成本、制作简单、光学性能可调、光电转换效率高等优势。其中光敏剂是DSSCs的重要组成部分,通过吸收可见光将电子传递到半导体导带,对整个电池的电子循环至关重要。广泛采用的光敏剂为N719等贵金属配合物,但其价格非常昂贵,很难实现大规模产业化。因此寻找低成本的非贵金属光敏剂是该领域的一项挑战。多金属氧酸盐(简称多酸,Polyoxometalates,简写为POMs)是一类具有纳米尺寸的分子基纳米材料,是分子型无机类半导体材料。多酸的富氧表面可以被活化和修饰,吸收光谱可以覆盖可见区甚至近红外区,具有合适的氧化还原电势,良好的热稳定性和溶解性。近年来,一系列研究表明多酸可以作为光敏剂应用在DSSCs中。本文中,我们以课题组多年来在POMs和太阳能电池领域的研究工作积累以及国内外同行专家的研究工作为基础,对多酸基光敏剂在DSSCs中的应用进行了详细综述。首先我们阐述了DSSCs的研究意义、多酸的简介、多酸的能级测量及调控。之后我们重点综述了多酸作为DSSCs中的光敏剂和共敏剂的研究。最后,我们对多酸基光敏剂在DSSCs领域的发展前景进行了总结和展望。本文有望引起多酸化学、材料化学及新兴交叉学科领域研究者的广泛研究兴趣,并为太阳能电池光敏剂的研究提供新的思路。
金属-有机框架衍生的中空碳材料及其在电化学能源存储与氧还原领域中的应用
刘虎, 杨东辉, 王许云, 韩宝航
2019, 35(11): 1921-1933  doi: 10.11862/CJIC.2019.237
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金属-有机框架材料(metal-organic frameworks,MOFs)是一类由金属离子或金属团簇与有机配体通过配位键连接形成的具有周期性网络结构的多孔配位聚合物。这类材料通常具有孔道规整、比表面积大、孔隙率高、结构可设计及孔壁易修饰等特点,诸多的优点使得MOFs的研究从配位化学跨越到多个学科领域,成为当前多学科交叉前沿热点之一。近来的研究发现,以MOFs为前驱体碳化后制得的碳材料可保留MOFs的大比表面积和多孔结构,同时可以实现均匀的杂原子(如N、P、S、B等)掺杂,而且通过选择合适的MOFs前驱体可调控产物的组成和形貌尺寸,这些显著的结构特征使其具备了成为高性能功能性材料的潜力。最近,以MOFs为模板或前驱体制备的中空碳材料引起了人们的广泛关注,这主要是因为中空结构可有效缓解材料在电化学过程中产生的体积变化及受到的冲击,而且中空结构可暴露出更多的活性位点,具有快速的传质过程,使得材料发挥出最优性能,故而此类材料可被用在二次电池、电容器、电催化等多种电化学器件和多个领域中。基于此,本文综述了MOFs衍生的中空碳材料在储能器件及电催化领域的研究进展,主要包括锂离子电池、锂硫/硒电池、钠离子电池、超级电容器、电催化氧还原等领域,并对这类材料当前面临的挑战及未来的发展趋势进行了阐述。
多酸基主客体框架材料POMs@MOFs(COFs)
李季坤, 赵帅恒, 胡长文
2019, 35(11): 1934-1956  doi: 10.11862/CJIC.2019.230
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多酸具有组成、结构和尺寸易于调控的优点以及良好的电子储存和氧化还原能力,在催化、光电、磁等领域具有广阔的应用前景。特别是在催化领域,更是受到化学家们的青睐。多酸在催化反应过程中易团聚而导致失活,且比表面积较低,而将其引入到结构明确、多孔的框架材料中则能较好地解决以上问题。因此,该类材料已成为多酸化学领域的研究热点之一。本文按照多酸基主客体框架材料的合成方法,即原位合成法、浸渍合成法和机械研磨合成法来进行分类,并分别讨论了其优缺点。并进一步总结了该类材料在催化、染料吸附降解、质子传导以及光电传感等领域的性能和应用,并对其未来发展趋势进行了展望。
仿生矿化增强材料
曹含, 潘海华, 唐睿康
2019, 35(11): 1957-1973  doi: 10.11862/CJIC.2019.250
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近年来,随着材料科学领域的发展,机械性能优异且具有特定功能的有机-无机复合材料成为了研究热点。而天然的生物矿化过程产生了在自然界中分布广泛、结构特征多样性、机械性能优异的天然生物矿物,比如牙齿、骨骼、珍珠、贝壳、海胆刺、海洋红虫颚等。这些天然复合增强材料中的矿化组织结构特点和矿化机理为仿生设计与合成具有特定结构、特定功能和优异机械性能的材料提供了理论依据。通过模拟天然过程的仿生矿化方法,利用有机基质调控无机矿物成核生长为固态矿物,最终能够定向组装具有特定有序结构和先进功能的有机-无机复合材料。本文主要综述了自然界中通过生物矿化过程得到的高强度、高韧性的天然复合增强材料,以及受生物矿化增强现象的启发,在化学与材料仿生矿化合成中出现的一些有机-无机复合的增强材料。
单分子磁环最新进展及研究展望
李晓磊
2019, 35(11): 1987-1998  doi: 10.11862/CJIC.2019.246
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与单分子磁体的定义(SMMs)相类似,单分子磁环(SMTs)定义为具有环形磁双稳态的一类分子。该类配合物的特征在于弱耦合磁矩的"涡旋"空间分布导致总磁矩为零,但是分子仍具有环形磁矩。单分子磁环为量子计算和信息存储提供了广阔的应用前景,也可以作为具有磁电耦合效应的多铁材料。自从在[Dy3]分子中首次观察到典型的单分子磁环行为以来,研究人员在合成单分子磁环方面做出了巨大的努力,致力于合成具有环形磁矩的分子以及设法将环形磁矩增强。本文将对近年报道的新兴单分子磁环配合物进行详细地分析讨论,旨在阐明影响环形磁矩排列的因素以及单分子磁环配合物的综合设计策略,指导探索合成具有增强环形磁矩的单分子磁环配合物。
水系锌离子二次电池锌负极的研究进展
王福慧, 刘辉彪
2019, 35(11): 1999-2012  doi: 10.11862/CJIC.2019.239
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锌离子二次电池具有优异的充放电性能、高功率密度和能量密度、低成本、高安全性和环境友好的特点,极具发展前景。金属锌,因优异的导电性、低的平衡电势、高的理论比容量和低成本等因素,是水系二次电池中理想的负极材料,然而也存在着枝晶生长、腐蚀和钝化等问题,限制了锌离子二次电池的可逆容量和循环寿命,通过优化调节锌负极的形貌与表面修饰等方法可以提高电池性能。本文综述了水系锌离子二次电池负极材料的研究进展,涵盖了金属锌负极、复合锌负极和锌合金,且展望了锌负极的发展前景。
单离子磁体及其磁弛豫动力学的研究进展
芶晓霜, 王梦梦, 孟茜茜, 程鹏
2019, 35(11): 2013-2030  doi: 10.11862/CJIC.2019.232
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单分子磁体因其在高密度信息存储、自旋电子学以及量子计算方面有潜在的应用价值而被广泛关注。单离子磁体是具有单个金属自旋中心的单分子磁体,其特点是结构简单、可设计性强和磁构关系更易研究。本文介绍了近年来典型的单离子磁体及其磁弛豫动力学的研究进展。
Reviews
pH-Sensitive Iridium, Ruthenium and Platinum Complexes for Tumor-Specific Fluorescence Imaging and Cancer Therapy
Si-Qi ZHANG, Li-Hua GAO, Hua ZHAO, Ke-Zhi WANG
2019, 35(11): 1974-1986  doi: 10.11862/CJIC.2019.231
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Acidic pH in tumor tissues provides a powerful platform for accurate tumor diagnosis and efficient therapy. The pH-sensitive iridium, ruthenium and platinum metal complexes have attracted increasing attention due to their high physicochemical stability, favorable spectral properties and tumor targetability. In this review, we summarize formation mechanisms of the acidic tumor microenvironment and recent advances on the acidic microenvironment-sensitive metal complexes of iridium, ruthenium and platinum for tumor imaging chemotherapy agents.
论文
一种螯合型Fe2+探针的构筑及性质
李泽冉, 朱健萍, 于涵洋, 陈韵聪, 何卫江, 郭子建
2019, 35(11): 2031-2037  doi: 10.11862/CJIC.2019.223
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铁是人体的必需过渡金属元素,体内铁离子平衡的紊乱与多种疾病相关。发展铁离子探针,实现细胞和生命体中铁离子时空分布的跟踪与成像,对铁离子生理功能的研究具有重要价值。我们将BODIPY荧光团与三联吡啶通过乙烯基偶联,构建了新型Fe2+螯合型探针BTPY,通过比色法与荧光法结合,实现了Fe2+的特异性检测。探针最大激发波长582 nm在可见光区,荧光发射波长678 nm在近红外区,满足活体近红外成像的初步要求。BTPY与Fe2+/Fe3+结合导致吸收波长由573 nm红移至607 nm,溶液颜色由红色到蓝色。其他金属离子的结合不发生明显吸收峰和颜色变化。同时,Fe2+引起BTPY荧光猝灭而Fe3+对BTPY荧光不造成明显影响,实现了Fe2+与Fe3+的区分。
基于三吡啶烯烃配体的一维配位聚合物:合成、结构及光电性质
陈慧娴, 刘春玉, 周璇, 陈敏敏, 倪春燕, 郎建平
2019, 35(11): 2038-2044  doi: 10.11862/CJIC.2019.228
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在室温下,用三吡啶烯烃配体dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine(ppvppa)与银盐溶液反应,分别得到3个具有类似的一维链结构的配位聚合物{[Ag(ppvppa)]BF4}n1)、{[Ag(ppvppa)]PF6}n2)和{[Ag(ppvppa)]NO3}n3)。在溶剂热条件下,用ppvppa与Ni(Ⅱ)反应,得到另一个以辅助羧酸配体桥联的一维配位聚合物{[Ni(ppvppa)(2,3-NDC)(H2O)]·2H2O}n4)。对配合物1~4分别进行了元素分析、红外、热重、粉末X射线衍射、单晶X射线衍射等结构表征。配合物1~3呈现出由ppvppa连接Ag(Ⅰ)形成的阳离子一维双股链结构。配合物4呈现出由2,3-NDC配体桥联2个相邻的[Ni2(ppvppa)2(H2O)2]单元形成的中性一维双股链结构。含有Ag(Ⅰ)的配合物1~3表现出良好的荧光性质,而含Ni(Ⅱ)的配合物4没有荧光响应。选取配合物14作为代表,研究了它们的光电流响应性质。配合物14均表现出灵敏的阳极光电流响应,且在多次循环后仍保持稳定且可重复,其光电流值分别为2和6 μA,明显强于空白ITO电极的光电流响应。
核壳结构MoOx/C微球的制备及储锂性能
白玉林, 王澄, 吴越, 刘于斯, 马超, 蔡志鹏, 王开学, 陈接胜
2019, 35(11): 2045-2050  doi: 10.11862/CJIC.2019.233
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采用水热法合成了MoO3/酚醛树脂前驱体,然后在空气中进行煅烧处理,成功制备了一种新型核壳MoOx/C微球。对材料的晶体结构、形貌和元素价态进行分析表明,该材料的主要成分是单斜相MoO2、正交晶系MoO3和碳。树脂在空气中的煅烧碳化将MoO3/酚醛树脂前驱体中的六方晶系的MoO3还原为单斜相MoO2。其中少量的MoO2会在空气中重新被氧化成正交晶系的MoO3,形成了MoO2/MoO3异质结构。在这一系列反应的综合作用下,形成这种表面有裂纹的核壳MoOx/C微球复合材料。将该材料用作锂离子电池负极材料,表现出了循环稳定性高、倍率性能好等优异的电化学性能。在100 mA·g-1的电流密度下充放电循环100次之后,可逆容量达640.6 mAh·g-1
SAPO-11的绿色制备及在棕榈油催化加氢制备生物航煤方面的应用
刘思阳, 白依凡, 李伟
2019, 35(11): 2051-2056  doi: 10.11862/CJIC.2019.242
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通过加入晶种的方法降低在合成SAPO-11分子筛过程中有机胺类模板剂的含量从而减少对环境的污染。通过调节晶种及模板剂的含量,得到加入4%晶种、模板剂与Al2O3物质的量比值(ntemplate/nAl2O3)为0.6的条件下得到的晶体的形貌、结晶度等最好。分子筛负载Ni-Mo金属合成催化剂,以棕榈油加氢脱氧产物(HDO)为原料,在623 K下测得对生物航煤的选择性为66.1%,转化率为79.8%。
污泥与醋糟共热解特性及碱金属迁移规律
李强强, 张阳倩, 郑颜, 张毅民
2019, 35(11): 2057-2065  doi: 10.11862/CJIC.2019.252
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分别采用热重分析仪、真空固定床反应器和原子吸收光谱研究了污泥与醋糟共热解过程中反应动力学、产物分布和碱金属迁移行为,探究了协同效应及碱金属迁移规律。结果表明,两者共热解过程中存在明显协同效应;与理论计算相比,混合物分解所需的活化能下降了35.38%~29.49%,脱挥发指数比计算低3.5×10-8。协同效应导致气体产率增加,生物炭、液体产率降低;醋糟的存在加速了污泥的脱挥发分析出,提高了气体产物中合成气含量,加大了生物炭中大芳香环的裂解反应,使生物油中酚类和酯类物质含量明显增加;热解终止时,碱金属元素析出量达到79.19%~86.73%。
双吡啶酰腙Schiff碱双核Fe(Ⅱ)配合物的合成与磁性
张男, 苑娟, 刘美姣, 金怡姝, 寇会忠
2019, 35(11): 2066-2072  doi: 10.11862/CJIC.2019.234
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基于己二酰肼双缩(溴代)吡啶甲醛Schiff碱配体HLxx=1,2),合成了2例双核Fe(Ⅱ)配合物,并通过红外光谱、X射线单晶衍射分析及磁化率测量等手段对配合物进行了表征。X射线单晶衍射分析结果表明,每个独立单元中均含有2个Fe(Ⅱ)离子、2个配体单元和4个高氯酸根阴离子,Fe(Ⅱ)离子呈N4O2八面体配位构型。分子间ππ堆积作用将配阳离子连成超分子一维链结构。磁性测试表明2个配合物都是高自旋态,同时配合物2呈现弱的分子间铁磁耦合作用。
纳米氧化铪的制备与热膨胀性
孙静, 李强, 林鲲, 刘占宁, 邢献然
2019, 35(11): 2073-2077  doi: 10.11862/CJIC.2019.249
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制备了尺寸为4 nm的HfO2纳米颗粒,并借助X射线原子对分布函数方法,研究了尺寸约4 nm和体相HfO2颗粒的晶格热膨胀。结果表明,在纳米尺度的HfO2中,晶格沿ac轴的热膨胀性增大,b轴热膨胀性稍微减小,体积热膨胀性增大。同时纳米HfO2晶格热膨胀的各向异性比体相大。该现象是由于尺寸效应导致结构畸变变大,尤其是次近邻Hf-O-Hf键角减小,随后升温过程中该畸变发生热弛豫趋向恢复至平衡位置导致的。
金属单原子模型催化剂热稳定性的反应力场(ReaxFF)分子动力学研究
杨文琦, 汪杰, 乔园园, 王贵昌
2019, 35(11): 2078-2082  doi: 10.11862/CJIC.2019.251
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金属催化剂的催化活性与其配位不饱和度密切相关,配位不饱和度越高,其催化活性一般也越高。单原子催化剂(SAC,或ad-atom)模型在金属表面上具有最小的配位数,因而往往表现为高的催化活性,但其热稳定性值得深入的研究。在本工作中,我们基于反应力场(ReaxFF),运用LAMMPS(large-scale atomic/molecular massively parallel simulator)软件包进行大尺度分子动力学模拟,研究单原子模型的热稳定性。模拟结果表明,只有Fe1/Fe(100)单原子催化模型可以在较高温度下稳定存在,而其他金属单原子表面分散结构则随温度升高而发生单原子聚集形成大的纳米颗粒或沉降的现象。同时我们也研究了在H2和O2气氛下Ni1/Ni(111)催化剂的动态行为,发现与真空环境相比,H2和O2气氛在一定程度上提高了催化剂的稳定性。
生物金属有机框架ZnBTCA对CO2的选择性吸附性能
才红, 吴光伟, 赖佳丽, 陈锦萍, 陈燕飞, 李丹
2019, 35(11): 2083-2088  doi: 10.11862/CJIC.2019.236
[摘要]  (466) [HTML全文] (466) [PDF 2598KB] (1)
摘要:
采用溶剂热法制备的生物金属有机框架ZnBTCA,在CO2的吸附过程中表现出有趣的主客体化学现象,通过计算发现随着CO2吸附量的增加,吸附焓逐渐增大。采用4种模型分别对其进行拟合,并通过理想吸附溶液理论模拟预测ZnBTCA对二元混合气体的选择性,试图找到ZnBTCA反常吸附行为的合理解释:ZnBTCA带有氨基和N-活性位点,且孔道内含有大量的客体离子。虽然ZnBTCA孔径较大,但由于其本身的阴离子框架,孔道中的(CH32NH2+抗衡离子并未完全去除而降低了可接触的微孔体积,在吸附过程中存在分子筛效应,在二元混合气体中对CO2具有很高的吸附选择性。
4-(2-羟基-3-氯)苯基-2, 2':6', 2"-三联吡啶Cu(Ⅱ)配合物的合成、结构表征及抗肿瘤活性
钟玉君, 陈振锋, 梁宏
2019, 35(11): 2089-2094  doi: 10.11862/CJIC.2019.253
[摘要]  (563) [HTML全文] (563) [PDF 3218KB] (0)
摘要:
以4-(2-羟基-3-氯)苯基-2,2':6',2"-三联吡啶(HL)为配体,合成了一种新的铜(Ⅱ)配合物[Cu2μ-L-κO,O)2Cl2](1),并通过红外光谱、电喷雾质谱、元素分析及单晶X射线衍射分析等方法对配合物1进行结构表征。配合物1为双核结构,中心铜(Ⅱ)离子为五配位扭曲四方锥几何构型,每个铜离子与1个Cl-以及来自配体(L-)的2个N原子和2个羟基O原子配位,2个铜(Ⅱ)离子通过羟基的桥联形成双核结构。MTT实验结果表明:配合物1对所选5种癌细胞株表现出不同的抑制活性,尤其是对MGC80-3细胞的抑制作用最明显,抑制率高达(84.30±1.28)%,其IC50值为(3.36±0.43)μmol·L-1。流式细胞术分析结果显示:配合物1能诱导MGC80-3细胞凋亡。在配合物1浓度为4.5 μmol·L-1时,MGC80-3的凋亡百分数为41.4%。此外,配合物1将MGC80-3细胞阻滞于G1期,从而抑制肿瘤细胞的生长。
CYCU-3孔内合成聚吡咯及其电导性能表征
周盈汐, 王会锋, 孙福兴
2019, 35(11): 2095-2100  doi: 10.11862/CJIC.2019.238
[摘要]  (467) [HTML全文] (467) [PDF 1532KB] (0)
摘要:
以具有一维介孔孔道的金属有机框架材料CYCU-3作为主体材料,采用碘氧化法在其孔道内进行了吡咯的聚合反应,从而得到了复合材料PPy@CYCU-3。利用粉末X射线衍射、扫描电镜、热重、红外、荧光光谱等对CYCU-3、吸附吡咯后的Py@CYCU-3以及孔内聚合后的复合材料PPy@CYCU-3进行了表征,证明了孔内聚合的成功进行,而且在聚合过程中,CYCU-3基本保持了结构的稳定,形貌也未发生改变。而且,PPy@CYCU-3复合材料是具有多孔性和电导性的多功能材料。氮气吸附表明该材料为典型的微孔材料,其BET比表面积为420 m2·g-1。电导测试表明该材料的电导率为10-7 S·cm-1,高于CYCU-3的电导率(σ≈10-13 S·cm-1)6个数量级,是一种半导体材料。
一例夹心型混合价锑钼酸盐的合成、结构及性质
杨宗斐, 牟秋水, 王亚平, 马鹏涛, 王敬平, 牛景杨
2019, 35(11): 2101-2107  doi: 10.11862/CJIC.2019.245
[摘要]  (644) [HTML全文] (644) [PDF 4257KB] (2)
摘要:
以(NH46Mo7O24·4H2O、Sb2O3和Sb2O5等为原料,利用常规水溶液法合成了一例结构新颖的含有混合价锑的杂多钼酸盐:[(CH34N]8Na41H17[(Sb3O3)(SbMo6O242]6·162H2O(1),并通过元素分析、红外光谱、热重分析和X射线单晶衍射等分析手段对化合物1进行了表征。化合物1含有夹心型的多酸阴离子簇[(Sb3O3)(SbMo6O242]11-,并进一步通过Na+连接形成二维结构。此外,我们还研究了该化合物的变色性质。当该化合物的粉末被加热或氙灯(300 W)照射时,其颜色由淡黄色变为青黄色或棕褐色。
Articles
Synthesis, Crystal Structures and Fluorescence Properties of Two Nanosized Zr-Based Molecular Capsules
Yan-Li TAO, Wei-Chao CHEN, Xin-Long WANG, Zhong-Min SU
2019, 35(11): 2108-2116  doi: 10.11862/CJIC.2019.224
[摘要]  (540) [HTML全文] (540) [PDF 3985KB] (1)
摘要:
Two nanosized zirconium-based molecular capsules (Zr-MCs), namely[Cp3Zr3(μ3-O)(μ2-OH)3]2(BPDC)3Cl2 ·H2O (Zr-MC-1) and[Cp3Zr3(μ3-O)(μ2-OH)3]2(NDC)3Cl2·3H2O (Zr-MC-2), have been synthesized by reacting zirconocenedichloride (Cp2ZrCl2) with 4, 4'-biphenyldicarboxylic acid (4, 4'-H2BPDC) and 2, 6-naphthalenedicar-boxylic acid (2, 6-H2NDC), respectively, which are constructed by two trinuclear zirconocene building blocks and three linear carboxylate ligands. They were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and N2 adsorption-desorption tests. In addition, the fluorescence spectra indicate that Zr-MC-1 and Zr-MC-2 are deep-blue and blue emitting materials with emission peaks at 404 and 456 nm, respectively.
Bi-functional Lanthanide Compounds: Synthesis, Structures, Magnetism and Fluorescence
Yong-Fang HAN, Li-Zhen CAI, Guo-Cong GUO
2019, 35(11): 2117-2124  doi: 10.11862/CJIC.2019.229
[摘要]  (475) [HTML全文] (475) [PDF 2748KB] (0)
摘要:
Two isostructural lanthanide (Ln) compounds with N-succinopyridine (HL) ligand, namely[Ln(HL)2(H2O)4]Cl3 (Ln=Pr (1), Eu (2)), have been synthesized and structurally characterized. Both 1 and 2 feature 1D chains with metal ions double-bridged by carboxyl ligands, which are further interconnected through hydrogen bonds to yield a 3D supramolecular architecture. Variable temperature magnetic susceptibility measurements revealed the presence of antiferromagnetic interaction between Pr(Ⅲ) ions for 1 but weak ferromagnetic interactions between Eu(Ⅲ) ions for 2. Solid-state luminescence measurement showed that 2 emitted intense red luminescence, but no characteristic peak of 1 was observed due to the large energy gap of the Pr(Ⅲ) ion.
Synthesis of Fluorescent Mesoporous Silica Nanoparticles and Application for Intracellular Drug Delivery
Min-Min CHEN, Hao-Ran GENG, Jin-Xia HU, Qiong ZHANG, Amfo Agyekum Godfred, Zhuo-Qi ZHANG, Xi-Chuan CAO
2019, 35(11): 2125-2135  doi: 10.11862/CJIC.2019.244
[摘要]  (485) [HTML全文] (485) [PDF 4688KB] (1)
摘要:
Here, we reported the synthesis and FITC-functionalized of mesoporous silica nanoparticles (MSNs) for tracing bioimaging and sustained drug release. Firstly, the MSNs-FITC were synthesized through one-pot method and characterized by SEM, TEM, FT-IR, XRD and the N2 adsorption-desorption isotherm respectively. Then a classic anticancer drug doxorubicin (DOX) was loaded into the MSNs-FITC. The DOX-loaded nanocarriers exhibited obviously pH dependent release behavior with accelerated release rate in acidic environment. Meanwhile, the in vitro cytotoxicity evaluation exhibited that the nude MSNs-FITC were highly biocompatible. Furthermore, the confocal laser scanning microscope (CLSM) images indicated that MSNs-FITC could penetrate into living cells effectively and dose-depended internalization of MSNs-FITC were further investigated by flow cytometry analysis (FCM).
Postsynthetic Modification of UiO-66 with Perfluoroalkyl for Adsorbing Organic Pollutants
Meng-Ying XU, Gan-Lin SONG, Bao-Hang HAN
2019, 35(11): 2136-2144  doi: 10.11862/CJIC.2019.247
[摘要]  (479) [HTML全文] (479) [PDF 4052KB] (0)
摘要:
Through postsynthetic modification (PSM) of metal-organic frameworks with perfluoroacetyl and perfluoropropionyl as functional groups, hydrophobic frameworks (UiO-66-F1 and UiO-66-F2) were obtained. Both frameworks exhibited lipophilicity, which indicates that they are potential absorbents for liposoluble solvent. The crystallinity, stability, and exceptional porosity of modified MOFs decreased slightly compared to those of UiO-66-NH2. Their Brunauer-Emmett-Teller (BET) specific surface areas were 810 and 610 m2·g-1 for UiO-66-F1 and UiO-66-F2, respectively. Suitable pore size and hydrophobic microenvironment made the frameworks easier to adsorb organic pollutants in water. Furthermore, they showed an obvious increase in adsorption capacity for a variety of organic solvents and endowed outstanding recycling performance without a significant reduction in adsorption capacity after recycle ten times.
Metal-Organic Frameworks with 2, 6-Di(1H-imidazol-1-yl)naphthalene and Dicarboxylate Ligands: Synthesis, Crystal Structure and Photoluminescence Sensing Property
Zhi-Qiang LIU, Shi-Hu CAO, Zhe ZHANG, Jun-Feng WU, Yue ZHAO, Wei-Yin SUN
2019, 35(11): 2145-2151  doi: 10.11862/CJIC.2019.225
[摘要]  (474) [HTML全文] (474) [PDF 3354KB] (0)
摘要:
Reactions of 2, 6-di(1H-imidazol-1-yl)naphthalene (L) and dicarboxylic acid ligands with corresponding metal salts under solvothermal conditions gave rise to three new metal-organic frameworks (MOFs)[Co(L)(AIP)]·2DMF (1), [Co(L)(AIP)]·DMF (2) and[Co(L)(IDC)(H2O)2]·0.5L·H2O (3) (H2AIP=5-aminoisophthalic acid, H2IDC=4, 4'-iminodibenzoic acid). The MOFs have been structurally characterized by single-crystal and powder X-ray diffraction analyses, elemental analyses, infrared spectra (IR) and thermogravimetric analysis (TGA). MOF 1 crystallizes in monoclinic space group C2/c, while 2 and 3 are triclinic space group P1. MOFs 1 and 3 have distinct infinite one-dimensional (1D) chain structures, and 2 is a two-dimensional (2D) network, which are further linked together by hydrogen bonding interactions to give the eventual three-dimensional (3D) supramolecular architectures. Furthermore, the thermal stability and photoluminescence property of the MOFs were investigated, and it was found that 3 can efficiently detect acetone molecules via fluorescent quenching.
Receptor Influence on Sensing Performance of Metal-Free Porphyrin Sensor
Cong GENG, Hui ZHENG, Yu-Ting CHEN, Jian-Zhuang JIANG
2019, 35(11): 2152-2158  doi: 10.11862/CJIC.2019.235
[摘要]  (494) [HTML全文] (494) [PDF 3299KB] (0)
摘要:
The optical properties of a metal-free tetra(aryl)porphyrin with two N, N-di(2-pyridylmethyl)amino groups (Porphyrin-2-DPA) upon respective addition of different metal ion were investigated. Systemic studies show that the rigid π-conjugated tetrapyrrole macrocyclic moiety of Porphyrin-2-DPA is employed not only as the sensitive signaling fluorophore but also as the primary receptor with excellent binding affinity and distinctive selectivity to metal ion, which together with the no-conjugated DPA auxiliary receptor endows Porphyrin-2-DPA the sensitive versatile sensor to Pb2+/Cu2+ on the basis of dual-optical signals.
Synthesis, Crystal Structure, Magnetic Properties and Catalytic Activity of Co(Ⅱ)/Ni(Ⅱ) Complexes with 3, 3'-(Pyridine-3, 5-diyl) Dibenzoic Acid
Xiao HAN, Zhichao SHAO, Bei ZHAO, Ning REN, Xiang-Ru MENG, Jie DING, Hong-Wei HOU
2019, 35(11): 2159-2167  doi: 10.11862/CJIC.2019.241
[摘要]  (474) [HTML全文] (474) [PDF 4586KB] (0)
摘要:
Two complexes 1~2 (1={[Co2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n and 2={[Ni2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n, H2pddb=3, 3'-(pyridine-3, 5-diyl) dibenzoic acid, DMA=N, N-dimethylacetamide) have been synth-esized and identified by Infrared spectroscopy (IR), elemental analysis, thermogravimetric analysis (TG) and single crystal X-ray diffraction. Structural analyses show that 1 and 2 are isostructural, and display a 3D (3, 6)-connected net with the point symbol (42·6)·(44·62·88·10). Besides, the UV-Vis absorption spectra in solid state, the magnetic properties and catalytic activity of 1~2 were investigated. Between the proximal Co(Ⅱ)/Ni(Ⅱ) ions, the variable-temperature (2~300 K) magnetic susceptibilities of 1~2 display antiferromagnetic coupling. Furthermore, 1 have been verified to be effectual catalysts for the oxidation of arylacycloalkanes in aqueous medium.
Anti-hemolysis of Human Erythrocytes by Two Daidzein Derivatives Containing Nitrogen
Hui-Qing LIU, Mei-Xuan YU, Jing-Lei SONG, Xi YAN, Ning XU, Hai-Jun HAO
2019, 35(11): 2168-2176  doi: 10.11862/CJIC.2019.240
[摘要]  (489) [HTML全文] (489) [PDF 1130KB] (0)
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Two new daidzein derivatives containing nitrogen, 4', 7-bis(((sodium glycinate)carbonyl)methoxy) isoflavone (L1) and 4', 7-bis((hydrazinocarbonyl) methoxy) isoflavone (L2), have been synthesized and characterized by elemental analysis, IR and 1H NMR. The antioxidant properties of the daidzein derivatives were studied by evaluating its ability to capture the hydroxyl free radical, the superoxide anion free radical, and to protect erythrocytes of human blood against oxidative damage induced from AAPH (2, 2'-azobis(2-amidinopropane) hydrochloride). Results of the experiments suggest that the daidzein derivatives show excellent antioxidant activity in physiological pH condition compared with vitamin C. Especially in the hydroxyl radical scavenging activity and suppressing the hemolysis of erythrocytes of human blood, the antioxidant capacity of the daidzein derivatives is more outstanding. The IC50 values of the daidzein derivatives were in the range of 0.1~1 μmol·L-1 on hydroxyl free radical scavenging activity, which was 104 times higher than that of vitamin C.
A Unique Luminescence Behavior Based on Polyhedral Oligomeric Silsesquioxane Compounds
Qing-Rui ZHANG, Ming-Xing SONG, Rui-Ping DENG, Liang ZHOU, Hong-Jie ZHANG
2019, 35(11): 2177-2184  doi: 10.11862/CJIC.2019.248
[摘要]  (480) [HTML全文] (480) [PDF 3415KB] (0)
摘要:
In this study, an unusual luminescence behavior from two polyhedral oligomeric silsesquioxane (POSS) monomers, aminopropyl isobutyl POSS (AIPOSS) and octal isobutyl POSS (OIPOSS) was observed after heating and stirring in their tetrahydrofuran (THF) solution. The chemical structures of these POSS samples were characterized before and after the heat treatment in THF by means of 1H and 29Si nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The valence state of silicon in the POSS sample was determined by X-ray photoelectron spectroscopy (XPS) as well. The characterization results showed that there is no obvious change in their structures, except tiny difference of the 1H NMR spectra. Photoluminescence (PL) properties of the treated/untreated POSS were studied in detail. According to the PL and structure characterization results, it is speculated that this unusual luminescence from the treated POSS is most likely caused by the adsorption effect of the POSS cage, forming the POSS/solvent adducts, which lead to the change of the electronic structure of the POSS, and consequently the luminescence of the treated POSS.
Hydrothermal Synthesis of Hierarchically Structured Flower-like Bismuth Tungstate for Photocatalytic Tetracycline Degradation
Yu-Qing ZHANG, Xue-Yu ZENG, Kai YU, Gui-Fang LIU, Hai-Lei CAO, Jian LÜ, Rong CAO
2019, 35(11): 2185-2191  doi: 10.11862/CJIC.2019.243
[摘要]  (477) [HTML全文] (477) [PDF 2714KB] (1)
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Hierarchically structured flower-like Bi2WO6 was fabricated via a simple template-free hydrothermal method. The as-prepared Bi2WO6 was applied in the removal of tetracycline antibiotics presented in aqueous phases under visible irradiation. The photocatalyst were characterized by a series of physical characterizations including powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-Vis diffuse reflectance spectra, nitrogen adsorption desorption test etc. The Bi2WO6 photocatalysts showed excellent degradation capacity towards tetracycline antibiotics (tetracycline (TC) and oxytetracycline (OTC)). Moreover, the TC degradation rates were generally higher in relatively alkaline solutions. The Bi2WO6 photocatalysts exhibited excellent stability and could be recycled for reuse.

  

综述
二氧化钛基Z型异质结光催化剂
梅邱峰, 张飞燕, 王宁, 鲁闻生, 宿新泰, 王伟, 武荣兰
2019, 35(8): 1321-1339  doi: 10.11862/CJIC.2019.167
[摘要]  (515) [HTML全文] (515) [PDF 12300KB] (515)
摘要:
二氧化钛(TiO2)因廉价、无毒、化学性质稳定以及具有较强的光催化氧化还原能力,在光催化领域占据着重要的地位。然而,可见光利用率低以及光生电子-空穴对的快速复合是限制其应用的2个主要因素。二氧化钛基Z型异质结作为一种新型光催化剂,既改善了二氧化钛的2个缺陷,又表现出比TiO2更强的氧化或还原能力。本文概括了TiO2光催化剂、异质结光催化剂和TiO2基Z型光催化剂的能带排列和电子传递原则,探讨了Z型异质结和type-Ⅱ异质结的异同点以及区分方法,并归纳总结了TiO2基Z型异质结在光催化领域中的应用。
Articles
Benzoimidazole-Based Cyclometalated Ir(Ⅲ) Complexes: Syntheses, Structures and Luminescence Modulation/Switching
Kai RUI, Shi-Shan WU, Deng-Ke CAO
2019, 35(8): 1340-1348  doi: 10.11862/CJIC.2019.156
[摘要]  (486) [HTML全文] (486) [PDF 2725KB] (486)
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Two iridium complexes[Ir(ppy)(qbiH)]NO3 (1·NO3) and[Ir(ppy)(qbi)] (2) have been synthesized. Their crystal structures indicate that an[Ir(ppy)2]+ unit is chelated by a neutral benzoimidazole-based ligand qbiH in 1·NO3, while anion ligand qbi- in 2. The different deprotonation degrees of ligands qbiH and qbi- in the two complexes lead to their clear differences in luminescence both in solution and in solid state. Complexes 1·NO3 and 2 in CH2Cl2 show the emissions at 581 and 574 nm, respectively. In solid state, a red emission at 611 nm was observed for 1·NO3, while an orange emission at 598 nm for 2. It is interesting that both 1·NO3 and 2 in solid state exhibited luminescence switching between red emission and orange emission, upon meeting Et3N/TFA vapor. This is due to the acid/base-induced structural interconversion between ligand qbiH and ligand qbi- in complexes 1·NO3 and 2. Moreover, we discuss the relationship between structure and luminescence for 1·NO3 and 2.
Cyclic Regeneration of Potassium-Modified Activated Semi-coke by Impregnation Method for Flue Gas Desulfurization
Hai-Tao WU, Qi-Dong ZHUO, Zi YANG, Jian-Dong SHI, Hong-Jian CHEN, Wen-Yu YIN, Xiao-Yan TANG, Yun-Shen MA, Rong-Xin YUAN
2019, 35(8): 1427-1435  doi: 10.11862/CJIC.2019.175
[摘要]  (491) [HTML全文] (491) [PDF 3737KB] (491)
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The potassium modified Activated Semi-coke (K/ASC) for SO2 removal was prepared using potassium carbonate (K2CO3) by the impregnation method. The ASC modified by 10%(w/w) K2CO3 (K10) exhibited good SO2 removal efficiency at 120℃. From 400 to 700℃, the higher the regeneration temperature is, the better is the desulfurization activity of K10 after regeneration. Cyclic regeneration of K10 (K10-R-600-n) showed that the sample had the best desulfurization performance after four regeneration cycles (K10-R-600-4), and its sulfur capacity was 68.9 mg·g-1, 24.37% higher than that of K10 (55.4 mg·g-1). The desulfurization products are divided into physisorbed SO2, H2SO4 and sulfate. The deposition of sulfate, which does not decompose after regeneration, results in the decrease of the desulfurization activity. The sulfur capacity of the sample after ten regeneration cycles (K10-R-600-10) remained 70% that of the fresh K10.
Syntheses and Crystal Structures of Two Discrete Complexes Generated from 3, 6-Bis(2-(4-oxide-quinoxaline)-yl)-4, 5-diaza-3, 5-octadiene and Ag(Ⅰ) Salt
Xiu-Hui REN, Peng WANG, Jian SU, Jun-Yan CHENG
2019, 35(8): 1436-1444  doi: 10.11862/CJIC.2019.174
[摘要]  (479) [HTML全文] (479) [PDF 5617KB] (479)
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Two novel discrete complexes with Ag(Ⅰ) centers based on the double Schiff-base ligand, 3, 6-bis(2-(4-oxide-quinoxaline)-yl)-4, 5-diaza-3, 5-octadiene (L), have been synthesized. The obtained Ag(Ⅰ) complexes, [Ag8(L)8](BF4)8·CH2Cl2·3CH3OH (1) and[Ag4(L)4](PF6)4·CH2Cl2 (2), were fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Both complexes exist as dimers. Through hydrogen bonds, uncoordinated counter ions and discrete molecular complex building blocks formed one-dimensional (1D) or two-dimensional (2D) frameworks.
Highly Sensitive Luminescent Sensor for Cr(Ⅲ) Based on a Water Dispersed Nano-sized Amorphous Methyl Salicylate Terbium Complex
Xiao-Jun LIU, Li-Ting SUN, Shu ZHANG, Chen ZHOU, Yan-Zhu LIU, Xue-Zhen ZHOU, Yong-Xiu LI
2019, 35(8): 1445-1454  doi: 10.11862/CJIC.2019.166
[摘要]  (489) [HTML全文] (489) [PDF 5335KB] (489)
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To expand the application fields of rare earth fluorescence complexes, and meet the requirements of high sensitivity and selectivity for the detection of trace chromium in aqueous solution, we prepared a sensitive luminescence sensor for Cr3+ ion based on a water dispersed nano-sized amorphous luminescence terbium complex with methyl salicylate (A-MS-Tb). It was found that the synthesized A-MS-Tb is an amorphous precipitation with particle size ranging from 50 to 100 nm and similar composition to the reported crystalline MS-Tb(C-MS-Tb). A-MS-Tb showed strong green luminescence at 494, 549, 591, 625 nm, which belongs to the energy level transition of 5D47FJ (J=6, 5, 4, 3) of Tb3+, respectively. The difference between A-MS-Tb and the reported C-MS-Tb lies in the stability and dispersion performance towards water which is very important for expanding its application as materials and sensors. In particularly, with the addition of Cr3+ into the water suspension of A-MS-Tb, the coordination between the ligand and Tb3+ is weakened, causing its green fluorescence to be quenched. Therefore, a highly sensitive sensor for detecting Cr3+ was established, and the sensitivity, selectivity and anti-interference ability was evaluated.
Preparation of Metal-Organic Framework-Derived Nano-Scale Nickel Phosphide Catalysts
Dan XU, Liang-Kui ZHU, Dan ZHOU, Yu-Rong FU, Xiao-Wen FU, Rong CHEN, Hai-Xia LI
2019, 35(8): 1455-1462  doi: 10.11862/CJIC.2019.148
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摘要:
Herein, nickel phosphides nanoparticles with different phases were successfully prepared by multi-step calcination and phosphidation process at low temperature using Ni based MOF (Ni-MOF) as the precursor. The resulting materials were applied to the hydrogen evolution reaction (HER) catalyst, Ni1P1-500 obtained at a mass ratio of Ni@C to red phosphorus of 1:1 and a pyrolysis temperature of 500℃ exhibited a remarkably enhanced electrocatalytic performance with a current density of 10 mA·cm-2 at an overpotential of 178 mV and a superior durability for the HER in acid media. A small Tafel slope of 62 mV·dec-1 revealed a Desorption-Heyrovsky mechanism during the HER. The excellent electrocatalytic performance might be ascribed to the presence of the proton acceptor (P site) and hydride-acceptor (Ni site) centers on the surface of nickel phosphide.
Three Cu(Ⅱ) Complexes with 1-(3-Ethylpyrazin-2-yl)ethylidene)-4-methylthiosemicarbazide: Crystal Structures and DNA-Binding Properties
Mu-Xuan LÜ, Lin-Yan BIAN, Meng-Ru LI, Yi YANG, Wei-Na WU, Yuan WANG, Zhong CHEN
2019, 35(8): 1463-1469  doi: 10.11862/CJIC.2019.169
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摘要:
Three Cu(Ⅱ) complexes, [Cu(L)Br]·DMF (1), [Cu(L)Cl]·2H2O (2), and [Cu2(L)2(SO4)]·H2O·CH3OH (3) (HL=1-(3-ethylpyrazin-2-yl)ethylidene)-4-methylthiosemicarbazide) have been synthesized and structurally determined by single-crystal X-ray diffraction. The results show that the Cu(Ⅱ) ion in 1 and 2 is surrounded by one anionic thiosemicarbazone ligand with N2S donor set and one halide ion (bromide for 1 and chloride for 2), thus giving a distorted planar square coordination geometry. However, in the dimeric complex 3, two Cu(Ⅱ) ions were doubly bridged by two S atoms of two TSC ligands to form a Cu2S2 core with Cu…Cu distance of 0.318 0 nm. Each of the Cu(Ⅱ) ions is also coordinated by two nitrogen atoms from one TSC ligand and one oxygen atom from the η2-SO42- at the outer axial site, with a distorted square pyramid coordination geometry. Moreover, the fluorescence spectra indicate that the interactions of the complexes with DNA are stronger than that of the thiosemicarbazone ligand.
Preparation of Coral-like Rutile Titania with Enhanced Photocatalytic Activity under UV and Visible Light
Jie ZHU, Feng-Juan GE, Yan CHEN, Yan XU, Xue-Yang ZHANG, Wei-Xin ZOU, Lin DONG
2019, 35(8): 1470-1476  doi: 10.11862/CJIC.2019.162
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摘要:
Coral-like rutile titania (Rut-dg) was synthesized by solvothermal method in diethylene glycol solution. Scanning electron microscope (SEM) and X-ray diffraction (XRD) indicated the spherical particles were homogeneously dispersed with the diameter about 1 μm, consisting regular arranged branches on the surface with diameter less than 10 nm. The BET surface area was as large as 228 m2·g-1, more than 7 times of commercial rutile titania sample. Given its unique morphology, the Rut-dg showed superior photocatalytic activity with hydrogen evolution 25 000 μmol·g-1·h-1 under ultraviolet irradiation, 50% higher than P25 and 13 times of commercial rutile sample. The hydrogen production under visible light was 270 μmol·g-1·h-1, while P25 and commercial rutile had no obvious activity. Further investigation demonstrated that no organics could be detected on the surface of Rut-dg, indicating the coral-like structures played the key role for the photocatalytic activity. After calcined at 300℃, the coral-like structures were sintered obviously and the surface area decreased by 50%. Meanwhile, the hydrogen production decreased by 15%~25%, also implying that the coral-like structures facilitated the hydrogen production dramatically.
Syntheses, Crystal Structures, Hirshfeld Surface Analysis of Two Salen-Type Halogenated Schiff-Base Ni(Ⅱ) Complexes
Qiong WU, Ya-Fang TANG, Qiao-Li ZI
2019, 35(8): 1477-1484  doi: 10.11862/CJIC.2019.189
[摘要]  (488) [HTML全文] (488) [PDF 4058KB] (488)
摘要:
The reaction between nickel nitrate and halogenated salen-type Schiff-base ligand in methanol solution led to the isolation of two new salen nickel(Ⅱ) complexes[Ni(3, 5-Cl-salcy)] (1) and[Ni(3-Cl-salcy)] (2), where 3, 5-Cl-salcyH2=N, N'-(±)-bis(3, 5-dichlorosalicylidene)cyclohexane-1, 2-diamine and 3-Cl-salcyH2=N, N'-(±)-bis(3-chloro-salicylidene)cyclohexane-1, 2-diamine. The crystal structures of complexes 1 and 2 were structurally characterized by single-crystal X-ray diffraction. Structural analysis reveals that the basic units of both complexes all consist of one nickel(Ⅱ) ion in[N2O2] coordination sphere, forming similar square planar geometries. PLATON software analysis indicates that there is not any hydrogen bond exists in the crystal structure of 1, and only unclassical hydrogen bonds exist in 2. However, Hirshfeld surface analysis shows that, although the strength of halogen atoms formed hydrogen bonds are weak, the C-H…X bonds play an important role in stabilization of three-dimensional networks of both complexes. Moreover, by comparison of the two complexes, we found that the difference in the number of halogen atoms in the ligand can have a very important influence on the proportion of weak exchange in the crystal.
Layered Co3O4/Ti Nanosheet Flexible Electrode with Low Transfer Resistance for Supercapacitor
Dan-Dan HAN, Yuan ZHAO, Ye SHEN, Yuan-Sheng DING, Zhen-Yu CHENG, Xiao-Yan JING, Xue-Yi ZHANG
2019, 35(8): 1485-1492  doi: 10.11862/CJIC.2019.165
[摘要]  (495) [HTML全文] (495) [PDF 3433KB] (495)
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The layered Co3O4 nanosheets with porous nature on Ti mesh were adopted to optimize the transfer resistance by a facile hydrothermal method. The synthesized materials were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical techniques. The results showed that the materials consisted of well-arranged micrometer length rectangular 2D flakes with uniform pore distribution. This unique microstructure obtained the electrode lower transfer resistance, higher structure stability, and better electrochemical performance for supercapacitor. The 2D porous layered Co3O4 nanosheet could achieve a relatively good capacitance retention of 91.8% at a current density of 100 mA·g-1 after 1 000 cycles and a low transfer resistance (Rct) of 0.29 Ω. These remarkable supercapacitive performances are attributed to the rationally 2D layered structure on flexible Ti mesh substrate, high utilization ratio of active materials of the flexible Co3O4/Ti electrode.
Biomass Derived Highly-Ordered Carbon Tube as Cathode Material for High Performance Lithium-Sulfur Batteries
Meng-Yuan ZHANG, Xiao-Long YOU, Li-Jun LIU, Dessie Walle Maru, Ya-Juan LI, You-Nian LIU
2019, 35(8): 1493-1499  doi: 10.11862/CJIC.2019.178
[摘要]  (487) [HTML全文] (487) [PDF 3754KB] (487)
摘要:
A novel highly ordered carbon tube (OCT) arrays derived from palm tree fiber by carbonization and activation with KOH was prepared and used as hosts for lithium sulfur battery. The OCT possessed large specific area and pore volume, which could effectively store sulfur. The method was clean, facile and low cost. Moreover, the S@OCT composite exhibited admirable electrochemical performances. The S@OCT with 65%(w/w) sulfur delivered an initial discharge capacity of 1 255.2 mAh·g-1 (1.8 mAh·cm-2) and retained 756.9 mAh·g-1 (1.09 mAh·cm-2) at the current rate of 0.2C after 100 cycles with a high coulomb efficiency. What's more, when tested at 5C, its initial capacity was up to 649.1 mAh·g-1 (0.93 mA h·cm-2) and retained 504.2 mAh·g1 (0.72 mAh·cm-2) after 100 cycles.
DNA Targeting Rigid Dinuclear Ruthenium-Arene Complexes
Ji LI, Yuan-Yuan HAO, Yong QIAN, Xu-Lin XUE, Zhi SU, Hong-Ke LIU
2019, 35(8): 1500-1508  doi: 10.11862/CJIC.2019.184
[摘要]  (484) [HTML全文] (484) [PDF 2001KB] (484)
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Three dinuclear Ru(Ⅱ)-arene complexes[Ru2(η6-p-bip)2(1, 3-bib)2XY]X2 (X=Y=Cl- (1), X=Y=Br- (2), X=I- and Y=Cl- (3); 1, 3-bib=1, 3-di(1H-imidazol-1-yl)benzene, p-bip=biphenyl) were synthesized and fully characterized by 1H NMR and ESI-MS. Single crystal X-ray diffractions studies showed that complex 1 owns a rigid M2L2 bowl-like structure, where one Cl- is trapped inside the cavity to balance the charge. Complex 3 showed the best anticancer activities among complexes 1~3. The IC50 value of 3 towards to human lung cancer cells (A549) reached to 13.9 μmol·L-1, which is comparable to that of cisplatin (IC50=15.2 μmol·L-1). Complexes 1~3 have shown strong interactions with DNA and could induce the unwinding of the DNA superhelix structure.
Hydrogen Production from Formic Acid Decomposition Using AuPd and AgPd Dendritic Nanocatalysts
Jun LIU, Jia-Qi XIE, Xin-Hua WU, Rong LI, Li-Xin LAN
2019, 35(8): 1509-1519  doi: 10.11862/CJIC.2019.172
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Three-dimensional (3D) porous thin films of AuPd and AgPd foams comprised of nanodendrites possess superior catalytic activity for the production of high-quality H2 from formic acid decomposition at room temperature. The high catalytic activity was attributed to the presence of abundant active sites like steps, corners, kinks and edges in the nanodendrites, and to the electronic effect. Besides the high activity, there were some more advantages for the nanodendrtic alloy foam films. For example, the foam films could be quickly electrodeposited in 5 min on a Ti substrate utilizing the template of hydrogen bubbles without needing organic additives, and it could be used directly for the hydrogen production without post-treatments. The hydrogen production was easily controllable, and we could get hydrogen and stop hydrogen production just by immersing the electrodeposited foam film into and pulling it out of the solution of HCOOH+HCOONa. The foam films could also be easily reactivated either by drying after water cleaning or by potential cycling in H2SO4 solution.
论文
磺酸基功能化有机聚苯乙烯/无机磷酸氢锆催化环氧大豆油
邹晓川, 黄林玉, 全纹萱, 王存, 王跃, 赵欣, 谭脂文
2019, 35(8): 1349-1356  doi: 10.11862/CJIC.2019.173
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摘要:
首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化剂催化合成环氧化大豆油的催化性能。结果表明:以叔丁基过氧化氢(TBHP)为氧化剂,固体催化剂对大豆油的环氧反应具有良好的催化性能,相比于催化剂1(磺酸化低聚苯乙烯基膦酸-磷酸氢锆),在相同的条件下,催化剂2(磺酸化聚(苯乙烯-苯乙烯膦酸)-磷酸氢锆)表现出更高的催化活性(产率:58.6% vs 53.3%),这主要归因于催化剂2拥有更大的比表面积、孔容以及孔径,为底物和催化剂的接触提供足够的催化场所。催化剂2重复使用7次后,催化活性未见明显降低。第8次反应结束后,将其置于2 mol·L-1稀盐酸中静置过夜后,在进行第9和10次循环时,催化活性又得以恢复。
Li2O-Na2O-B2O3-SiO2烧结助剂对BaAl2Si2O8陶瓷结构与介电性能的影响
严欣堪, 丁士华, 张晓云, 黄龙, 张云
2019, 35(8): 1357-1362  doi: 10.11862/CJIC.2019.152
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采用传统固相反应工艺,按化学计量比合成BaO-Al2O3-SiO2(BAS)-x%(w/w)Li2O-Na2O-B2O3-SiO2(LNBS)(x=0,1,2,3,4)陶瓷。研究不同LNBS烧结助剂添加量对BAS系微波介质陶瓷的结构和介电性能的影响。通过Clausius-Mossotti公式计算讨论了BAS理论与实验介电常数(εr)的差异。研究结果表明:LNBS烧结助剂中Li+进入钡长石Al3+位或单四元环(S4R)间隙,并产生了O2-空位或Ba2+空位,从而促进BAS六方相向单斜相的转变。添加适量的LNBS烧结助剂后,BAS陶瓷的烧结温度从1 400℃降低到1 325℃,同时BAS陶瓷样品密度、品质因数(Qf)值以及频率温度系数(τf)得到改善。当x=1,烧结温度为1 325℃时,可获得综合性能相对较好的BAS陶瓷,其介电性能:Qf=35 199 GHz,εr=6.37,τf=-1.613×10-5-1
ZIF67衍生硫化钴/多孔碳复合催化剂的制备及其电催化性能
李京修, 赵媛, 薛建军, 何娉婷, 王玲
2019, 35(8): 1363-1370  doi: 10.11862/CJIC.2019.163
[摘要]  (994) [HTML全文] (994) [PDF 5413KB] (994)
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采用离子交换法与热处理相结合的方法,以ZIF67为前驱体,硫代乙酰胺为硫源,制备出硫化钴/多孔碳(CoS/C)复合催化材料,并探讨了硫化时间对复合催化剂的形貌、结构及其氧还原(ORR)性能的影响。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)、N2吸附-脱附测定仪、X射线光电子能谱分析(XPS)、拉曼光谱仪(Raman)和旋转圆盘电极(RDE)技术表征催化剂的物理特征和电催化性能。研究结果显示,在碱性条件下该复合催化剂具有与20%(w/w)的商业Pt/C催化剂相媲美的ORR活性,其半波电位仅比Pt/C催化剂低31 mV。随着硫化时间的增加,硫化钴颗粒逐渐增大,催化剂中碳材料的无序程度出现先减小后增大的趋势。在硫化时间为10 min时,复合催化剂在0.1 mol·L-1 KOH中表现出良好的电催化活性,且在ORR过程中复合催化剂的平均转移电子数可达到3.72,接近于4,说明氧气在该催化剂表面发生的是四电子转移过程。
Bi@Bi2Sn2O7/TiO2等离子体复合纤维的制备及增强的光催化产氢活性
李跃军, 曹铁平, 赵艳辉, 孙大伟, 王霞
2019, 35(8): 1371-1378  doi: 10.11862/CJIC.2019.187
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以电纺TiO2纳米纤维为基质,采用一步水热法合成了Bi@Bi2Sn2O7/TiO2等离子体复合纤维光催化剂。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)、紫外-可见漫反射(UV-Vis DRS)和光致发光光谱(PL)等分析测试手段对样品的物相、形貌和光电性能等进行表征。以三乙醇胺为电子给体,研究了Bi@Bi2Sn2O7/TiO2复合纤维光催化裂解水制氢的反应过程。结果表明:在水热过程中,Bi2Sn2O7构筑在TiO2纳米纤维表面形成p-n结的同时,部分Bi3+被葡萄糖还原成金属Bi沉积在Bi2Sn2O7上。金属Bi的等离子体共振效应与p-n结的协同作用,有效提高了样品的光催化活性,产氢速率达到7.26 mmol·h-1·g-1
磺化酞菁铝修饰氨基功能化磁性材料及其光敏化降解双酚A
郭冬菁, 胡美琴, 沈昊宇, 张建, 孙洁, 许宜铭
2019, 35(8): 1379-1386  doi: 10.11862/CJIC.2019.168
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采用溶剂热法制备氨基功能化Fe3O4磁性材料(NH2@nFe3O4),通过浸渍法将磺化酞菁铝(AlPcS)负载于NH2@nFe3O4。材料的傅立叶红外、漫反射、X射线衍射、扫描电镜、透射电镜、振动磁强计等表征表明:AlPcS主要通过静电作用与NH2@nFe3O4结合,AlPcS-NH2@nFe3O4平均粒径为127 nm,饱和磁化强度为75.3 emu·g-1。在可见光和空气作用下,该功能化磁性材料对降解弱碱性水溶液中环境内分泌干扰物双酚A(BPA)具有较高的光敏化活性。随着AlPcS负载量的增加活性呈先升高后下降的趋势,负载量为3.4%(质量分数)的复合材料性能最佳,反应60 min后,20.0 mg·L-1 BPA降解率为96%;循环使用10次,BPA降解率仍保持93%以上。通过NaN3猝灭实验探讨了反应机理,证实1O2是光敏化过程中的主要活性物种。
施主掺杂对BaTiO3钙钛矿半导体纳米晶光催化性能的影响
孟国祥, 田晓霞, 张家瑞, 张翔, 韩丰庆, 屈绍波
2019, 35(8): 1387-1395  doi: 10.11862/CJIC.2019.183
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以沉淀法制备的Cu2O为牺牲模板剂,采用水热法制备La施主掺杂的BaTiO3钙钛矿半导体纳米晶,借助X射线衍射(XRD)、透射电子显微镜(TEM)、高分辨透射电镜(HRTEM)、X射线光电子能谱((XPS)、扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)表征La掺杂的BaTiO3晶的物相、微观形貌及光催化性能。结果表明,La掺杂BaTiO3构建了晶体缺陷,有效提高了BaTiO3的光催化性能。当掺杂量为4%(w/w)时,样品的光催化性能最好,在可见光照射360 min后,对4-硝基苯酚溶液的降解率可达到93.2%。该催化剂5次循环后的活性仍然大于86.7%,表明La施主掺杂的BaTiO3是一种有效的可见光催化剂。
烷基膦酸促进负载磷钨酸催化异丁烷/丁烯烷基化反应
许孟霞, 王怡博, 邓长顺, 丁丽平, 许逸达, 薛念华, 郭学锋, 彭路明, 丁维平
2019, 35(8): 1396-1402  doi: 10.11862/CJIC.2019.145
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异丁烷/丁烯烷基化是生产高辛烷值汽油的重要反应,目前主要采用液体强酸为催化剂,而固体催化剂用于该反应的性能均不理想。我们设计合成出十六烷基膦酸(HDPA)修饰的氧化硅负载型磷钨酸纳米多级结构催化剂(HDPA-HPW/SiO2),其结构与悬铃木果实相似。通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、透射电子显微镜镜(TEM)、氮气吸附-脱附、异丁烷吸附-脱附等对该催化剂进行了表征,并使用固定床微型反应器评价了其对异丁烷/丁烯烷基化反应的催化性能。结果表明,HDPA的外围修饰增强了催化剂对烃类反应物的吸附,减少了烯烃聚合副反应和催化剂表面积碳的产生,提高了高辛烷值产物的选择性,延长了催化剂的寿命。
锌镍单液流电池正极Ni1-xMnx(OH)2倍率性能分析
姚寿广, 窦飞, 邢如月, 程杰, 肖民
2019, 35(8): 1403-1410  doi: 10.11862/CJIC.2019.177
[摘要]  (507) [HTML全文] (507) [PDF 1689KB] (507)
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采用缓冲溶液法制备Mn掺杂Ni1-xMnx(OH)2x=0.1,0.2,0.3,0.4)。X射线衍射(XRD)测试表明x=0.1和0.2的样品主要是由β相组成;扫描电子显微镜(SEM)和氮气吸附-脱附测试表明掺杂Mn样品比不掺Mn的商用β-Ni(OH)2的颗粒更细小、多孔;恒流充放电测试表明,这种电极具有优良的高倍率性能,当x=0.2,电流密度800 mA·g-1时放电比容量为288.8 mAh·g-1,同等条件测试的商用β-Ni(OH)2放电比容量为198.7 mAh·g-1,循环580圈后仍有276 mAh·g-1的放电比容量,其衰减率为4.1%,而同等测试条件下的其它4种样品衰减率分别为46.1%(商用β-Ni(OH)2)、13.0%(x=0.1)、25.6%(x=0.3)、34.1%(x=0.4),可见这种Mn掺杂电极材料适合大电流密度充放电,能够改善镍电极的循环稳定性,降低镍电极成本。
“自上而下”方法制备少层石墨用作高容量铝离子电池正极
刘东海, 王俊明, 范卫超, 房金刚, 朱晓军, 孟垂舟
2019, 35(8): 1411-1418  doi: 10.11862/CJIC.2019.171
[摘要]  (507) [HTML全文] (507) [PDF 5609KB] (507)
摘要:
采用“自上而下”方法制备了具有少片层、小尺寸特征且晶型结构完美的石墨材料,通过增加离子嵌入位点的方式,突破传统石墨作为正极材料的固有容量限制,提升铝离子电池的电化学储能性能。扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等测试结果表明,该方法可以在不破坏石墨材料本身结构的前提下,有效实现对石墨片层的剥离,并且可以通过调节球磨时间的方式实现对石墨片层厚度和尺寸的调控。电化学测试结果表明,在3C的大电流密度下,以剥离的石墨材料为正极的铝离子电池放电容量可以达到93 mAh·g-1,在10C的高倍率下,放电容量仍保持在68 mAh·g-1,并显示出优异的循环性能。另外,该方法制备工艺简单、成本低廉,为促进高容量、长寿命铝离子电池的商业化应用打下了良好的基础。
NiCo2S4@碳纳米管构筑柔性薄膜电极的制备及其电化学性能
周阅微, 季昀辉, 谭徜彬, 宋伟杰, 许亮亮, 唐少春
2019, 35(8): 1419-1426  doi: 10.11862/CJIC.2019.185
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摘要:
以浮动催化化学气相沉积致密超薄碳纳米管薄膜(CNTF)为基体,通过两步酸处理使薄膜内制备的碳纳米管(CNT)分开并赋予其活性官能团,CNTF由超疏水转变为超亲水性,然后在CNT表面生长均匀的前驱体包覆层,离子进入超亲水薄膜内部确保了高负载量,最后进行液相硫化制得NiCo2S4@碳纳米管构筑柔性薄膜(NiCo2S4@CNTF)电极。利用扫描电子显微镜、X射线衍射等对产物进行了表征,证明优化产物为NiCo2S4均匀包覆多壁CNT构筑而成的三维网状柔性复合薄膜,单根CNT的表面是NiCo2S4纳米粒子构成、厚度约70 nm的粗糙包覆层。该复合薄膜比电容达到270.3 mF·cm-2,即使在高电流密度2.5 mA·cm-2下充放电循环10 000次后仍保持很好的可逆性,电容保持率达93%,库伦效率持续稳定在92%附近;重复大变形(弯曲、折叠、卷曲)后能保持结构完整性和性能稳定性。同时,探讨了电化学性能与结构间的关系,并揭示了性能增强的内在机理。