铂催化氧还原反应过程中磷酸的影响及抑制磷酸吸附策略

与低温(<100oC)质子交换膜燃料电池相比,磷酸掺杂PBI膜燃料电池可工作于100–200 oC,工作温度的提高有利于提高电极反应动力学速率、增加Pt催化剂对CO等毒物的耐受性,以及简化电池水管理等.然而,磷酸在Pt催化剂表面吸附较强,这将造成Pt一定程度的毒化.基于“第三体效应”,即在Pt表面预吸附某些小分子,可在一定程度上抑制磷酸吸附,然而预吸附分子同时也将占据Pt表面部分活性位点,因而Pt的催化性能最终由两个因素决定：磷酸抑制程度和预吸附分子在Pt表面的覆盖度.
　　本文系统考察了Pt表面预吸附分子覆盖度和预吸附分子链长对其催化氧还原反应(ORR)活性的影响.首先,通过控制预吸附了胺类分子的Pt电极的电位,得到表面具有不同覆盖度的Pt电极,考察了0.1 mol/L H3PO4电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律;为分离磷酸吸附和修饰分子吸附本身对Pt催化活性的影响,对比了0.1 mol/L HClO4电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律.进一步对比研究了不同链长胺分子——正丁胺(BA)、正辛胺(OA)及十二胺(DA)等作为修饰分子对Pt/C催化剂电催化ORR活性的影响.结果表明,随修饰分子在Pt表面覆盖度提高,在0.1 mol/L HClO4溶液中,由于预吸附分子占据Pt部分活性位,修饰后光滑Pt电极表面的本征活性单调下降;而在0.1 mol/L H3PO4中,修饰后光滑Pt电极表面的ORR活性呈现先升高后降低的趋势,当预吸附分子覆盖度约为20%时,其ORR活性最高,为未修饰的光滑Pt电极表面的1.67倍.这表明预吸附分子有效抑制了磷酸的吸附,且当预吸附分子覆盖度约为20%时,预吸附分子对Pt表面的占据与其抑制磷酸吸附的作用达到最佳平衡点.然而,当修饰分子BA, OA和DA在Pt表面覆盖度分别为38.6%,26.1%和26.1%时, Pt/C在0.1 mol/L H3PO4中的ORR催化活性接近,分别为未经修饰Pt/C电催化剂的1.7,1.8和2.0倍,这表明预吸附分子链长对ORR催化活性影响较小,表面预吸附分子抑制磷酸吸附的策略对Pt/C催化剂也同样适用.同时, Pt/C电极经BA, OA和DA修饰后,其在0.1 mol/L HClO4中的比表面活性分别为未经修饰Pt/C电催化剂的1.0,1.1和1.3倍,与修饰后光滑Pt电极表面本征ORR活性变化规律不一致.然而,与Pt在HClO4电解质中的ORR活性相比, ORR的半波电位仍有大约123 mV的差距,今后还需继续从催化剂的角度,如调控Pt表面的吸附特性,或从创新电解质的角度,如有机磷酸电解质等出发解决磷酸毒化的问题.     

铂催化氧还原反应过程中磷酸的影响及抑制磷酸吸附策略（英文）

与低温(100 oC)质子交换膜燃料电池相比,磷酸掺杂PBI膜燃料电池可工作于100–200 oC,工作温度的提高有利于提高电极反应动力学速率、增加Pt催化剂对CO等毒物的耐受性,以及简化电池水管理等.然而,磷酸在Pt催化剂表面吸附较强,这将造成Pt一定程度的毒化.基于"第三体效应",即在Pt表面预吸附某些小分子,可在一定程度上抑制磷酸吸附,然而预吸附分子同时也将占据Pt表面部分活性位点,因而Pt的催化性能最终由两个因素决定:磷酸抑制程度和预吸附分子在Pt表面的覆盖度.本文系统考察了Pt表面预吸附分子覆盖度和预吸附分子链长对其催化氧还原反应(ORR)活性的影响.首先,通过控制预吸附了胺类分子的Pt电极的电位,得到表面具有不同覆盖度的Pt电极,考察了0.1 mol/L H_3PO_4电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律;为分离磷酸吸附和修饰分子吸附本身对Pt催化活性的影响,对比了0.1 mol/L HClO_4电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律.进一步对比研究了不同链长胺分子——正丁胺(BA)、正辛胺(OA)及十二胺(DA)等作为修饰分子对Pt/C催化剂电催化ORR活性的影响.结果表明,随修饰分子在Pt表面覆盖度提高,在0.1 mol/L HClO_4溶液中,由于预吸附分子占据Pt部分活性位,修饰后光滑Pt电极表面的本征活性单调下降;而在0.1 mol/L H_3PO_4中,修饰后光滑Pt电极表面的ORR活性呈现先升高后降低的趋势,当预吸附分子覆盖度约为20%时,其ORR活性最高,为未修饰的光滑Pt电极表面的1.67倍.这表明预吸附分子有效抑制了磷酸的吸附,且当预吸附分子覆盖度约为20%时,预吸附分子对Pt表面的占据与其抑制磷酸吸附的作用达到最佳平衡点.然而,当修饰分子BA,OA和DA在Pt表面覆盖度分别为38.6%,26.1%和26.1%时,Pt/C在0.1 mol/L H_3PO_4中的ORR催化活性接近,分别为未经修饰Pt/C电催化剂的1.7,1.8和2.0倍,这表明预吸附分子链长对ORR催化活性影响较小,表面预吸附分子抑制磷酸吸附的策略对Pt/C催化剂也同样适用.同时,Pt/C电极经BA,OA和DA修饰后,其在0.1 mol/L HClO_4中的比表面活性分别为未经修饰Pt/C电催化剂的1.0,1.1和1.3倍,与修饰后光滑Pt电极表面本征ORR活性变化规律不一致.然而,与Pt在HClO_4电解质中的ORR活性相比,ORR的半波电位仍有大约123 m V的差距,今后还需继续从催化剂的角度,如调控Pt表面的吸附特性,或从创新电解质的角度,如有机磷酸电解质等出发解决磷酸毒化的问题.     

一步热解核黄素制备高性能氧还原反应电催化剂

质子交换膜燃料电池具有零污染、能量密度高、操作温度低和超静低音等优点,因而广泛应用于新能源汽车动力电源.然而质子交换膜燃料电池阴极氧还原反应(ORR)过程缓慢且复杂,因此需要大量的高性能ORR电催化剂.商品铂基催化剂是目前最为广泛使用的ORR催化剂,然而其高昂的价格阻碍了燃料电池汽车的商业化进程.因此,近年来人们致力于研发高性能的非贵金属ORR催化剂,并成功获得了具有高ORR活性及优异稳定性的催化剂.然而开发贵金属替代催化剂还存在制备过程较为复杂、单体有毒等缺点.核黄素具有成本低廉、无毒、氮含量高等优点,本文将其直接作为碳源和氮源,以无水氯化铁为铁前驱体,通过简单的一步热解法制备了高性能的Fe-N-C催化剂.表征结果表明,合成的催化剂表面由于氮的掺杂导致石墨烯存在较多的缺陷,其比表面积为301 m2 g-1且孔径分布主要位于45 nm处;催化剂由很薄、卷曲的石墨烯片层和一些颗粒组成,其中的碳材料高度石墨化且存在Fe2O3晶体.结合X射线光电子能谱和催化剂的ORR活性,推导出石墨化氮为ORR的主要活性位,铁在ORR反应中也起着重要作用.在氧气饱和的0.1 mol L-1 KOH溶液中,Fe-N-C催化剂的ORR活性达到4.16 mA cm-2,与商品Pt/C催化剂相当(4.46 mA cm-2).采用计时电流法在0.66 V(相对于RHE电位)下运行3 h后,Fe-N-C催化剂电流仅下降了3%,而Pt/C催化剂下降了40%,表明Fe-N-C催化剂与Pt/C催化剂具有相近的ORR活性,但稳定性比Pt/C催化剂更出色.测试结果表明,Fe-N-C催化剂的抗甲醇毒化性能远优于Pt/C催化剂.在酸性介质中,Fe-N-C催化剂的ORR活性比Pt/C催化剂低,但稳定性更高.总之,该Fe-N-C催化剂在碱性介质中有较高的活性和稳定性,在酸性介质中有较高的稳定性.因此,我们采用廉价、无毒的核黄素作为碳氮源,通过简单的一步热解法制备出的Fe-N-C催化剂能较好地满足燃料电池ORR催化剂高性能和低成本的要求,具有很好的应用前景.     

一步热解核黄素制备高性能氧还原反应电催化剂（英文）

质子交换膜燃料电池具有零污染、能量密度高、操作温度低和超静低音等优点,因而广泛应用于新能源汽车动力电源.然而质子交换膜燃料电池阴极氧还原反应(ORR)过程缓慢且复杂,因此需要大量的高性能ORR电催化剂.商品铂基催化剂是目前最为广泛使用的ORR催化剂,然而其高昂的价格阻碍了燃料电池汽车的商业化进程.因此,近年来人们致力于研发高性能的非贵金属ORR催化剂,并成功获得了具有高ORR活性及优异稳定性的催化剂.然而开发贵金属替代催化剂还存在制备过程较为复杂、单体有毒等缺点.核黄素具有成本低廉、无毒、氮含量高等优点,本文将其直接作为碳源和氮源,以无水氯化铁为铁前驱体,通过简单的一步热解法制备了高性能的Fe–N–C催化剂.表征结果表明,合成的催化剂表面由于氮的掺杂导致石墨烯存在较多的缺陷,其比表面积为301 m~2g~(–1)且孔径分布主要位于45 nm处;催化剂由很薄、卷曲的石墨烯片层和一些颗粒组成,其中的碳材料高度石墨化且存在Fe_2O_3晶体.结合X射线光电子能谱和催化剂的ORR活性,推导出石墨化氮为ORR的主要活性位,铁在ORR反应中也起着重要作用.在氧气饱和的0.1 mol L~(–1) KOH溶液中,Fe–N–C催化剂的ORR活性达到4.16 mA cm~(–2),与商品Pt/C催化剂相当(4.46 mA cm~(–2)).采用计时电流法在0.66 V(相对于RHE电位)下运行3 h后,Fe–N–C催化剂电流仅下降了3%,而Pt/C催化剂下降了40%,表明Fe–N–C催化剂与Pt/C催化剂具有相近的ORR活性,但稳定性比Pt/C催化剂更出色.测试结果表明,Fe–N–C催化剂的抗甲醇毒化性能远优于Pt/C催化剂.在酸性介质中,Fe–N–C催化剂的ORR活性比Pt/C催化剂低,但稳定性更高.总之,该Fe–N–C催化剂在碱性介质中有较高的活性和稳定性,在酸性介质中有较高的稳定性.因此,我们采用廉价、无毒的核黄素作为碳氮源,通过简单的一步热解法制备出的Fe–N–C催化剂能较好地满足燃料电池ORR催化剂高性能和低成本的要求,具有很好的应用前景.     

高分散Fe-N-C氧还原反应电催化剂及其在直接甲醇燃料电池中的应用

氧还原反应(ORR)是燃料电池和金属空气电池等洁净发电装置中阴极的主要反应,该反应动力学过程慢,电化学极化严重. Pt基电催化剂具有较好的ORR活性,然而Pt资源有限、价格昂贵,研制高活性、低成本的代Pt电催化剂意义重大.经过几十年的探索,研究者发现将含有C, N和Fe等元素的前体进行高温热处理得到的Fe-N-C电催化剂对ORR具有良好的活性,然而在高温热解过程中Fe容易发生聚集而形成大块颗粒,导致Fe的利用率不高,影响了电催化剂的ORR活性.
　　本文分别以聚吡咯和乙二胺四乙酸二钠(EDTA-2Na)为C和N的前驱体,利用高温热解形成的富含微孔的碳材料对铁前体的吸附及锚定作用,获得了一种Fe高度分散的Fe-N-C电催化剂.采用物理吸脱附技术、高分辨透射电镜(HRTEM)和扫描电镜对Fe-N-C及其制备过程中相关电催化剂的孔结构及表面形貌进行了表征.结果表明,在第一步热解过程中, EDTA-2Na的Na对碳材料起到了活化作用,形成富含微孔的N掺杂碳材料(N-C-1),其BET比表面积达到1227 m2/g,孔径约1.1 nm.在第二步热解过程中, N-C-1有效地抑制了Fe的聚集,产物Fe-N-C中的Fe元素均匀地分布在碳材料中,其比表面积高达1501 m2/g.
　　电化学测试结果表明,在碱性介质(0.1 mol/L NaOH)中, Fe-N-C电催化剂对ORR具有良好的催化活性, ORR起始电位(Eo)为1.08 V (vs. RHE),半波电位(E1/2)0.88 V,电子转移数n接近4, H2O2产率<3%,与商品20%Pt/C(Johnson Matthey)接近.电化学加速老化测试结果表明, Fe-N-C的E1/2未发生明显变化,而Pt的负移45 mV,表明Fe-N-C具有很好的稳定性;在酸性介质(0.1 mol/L HClO4)中, Fe-N-C的Eo为0.85 V, E1/2为0.75 V,其E1/2比Pt/C负移约0.15 V,表明在酸性介质中Fe-N-C对ORR的催化活性还有待提高.采用TEM、X射线衍射、X射线光电子能谱以及穆斯堡尔谱等方法研究了电催化剂构效关系.结果表明, Fe-N-C较好的ORR活性主要来自于高分散的Fe-N4结构,此外, N(吡啶N和石墨N)掺杂的C也对反应具有一定的催化活性.
　　与Pt/C相比, Fe-N-C电催化剂具有很好的耐甲醇性能.本文对比了Fe-N-C和Pt/C作为阴极催化剂的直接醇类燃料电池(DMFC)性能,采用质子交换膜的DMFC最大功率密度分别为47(Fe-N-C)和79 mW/cm2(Pt/C),而采用碱性电解质膜的则分别为33(Fe-N-C)和8 mW/cm2(Pt/C).结合半电池结果表明, Fe-N-C电催化剂在碱性介质中具有比Pt更为优秀的催化活性和稳定性,有望用作DMFC阴极代Pt催化剂.     

高分散Fe-N-C氧还原反应电催化剂及其在直接甲醇燃料电池中的应用（英文）

氧还原反应(ORR)是燃料电池和金属空气电池等洁净发电装置中阴极的主要反应,该反应动力学过程慢,电化学极化严重.Pt基电催化剂具有较好的ORR活性,然而Pt资源有限、价格昂贵,研制高活性、低成本的代Pt电催化剂意义重大.经过几十年的探索,研究者发现将含有C,N和Fe等元素的前体进行高温热处理得到的Fe-N-C电催化剂对ORR具有良好的活性,然而在高温热解过程中Fe容易发生聚集而形成大块颗粒,导致Fe的利用率不高,影响了电催化剂的ORR活性.本文分别以聚吡咯和乙二胺四乙酸二钠(EDTA-2Na)为C和N的前驱体,利用高温热解形成的富含微孔的碳材料对铁前体的吸附及锚定作用,获得了一种Fe高度分散的Fe-N-C电催化剂.采用物理吸脱附技术、高分辨透射电镜(HRTEM)和扫描电镜对Fe-N-C及其制备过程中相关电催化剂的孔结构及表面形貌进行了表征.结果表明,在第一步热解过程中,EDTA-2Na的Na对碳材料起到了活化作用,形成富含微孔的N掺杂碳材料(N-C-1),其BET比表面积达到1227 m~2/g,孔径约1.1 nm.在第二步热解过程中,N-C-1有效地抑制了Fe的聚集,产物Fe-N-C中的Fe元素均匀地分布在碳材料中,其比表面积高达1501 m~2/g.电化学测试结果表明,在碱性介质(0.1 mol/L NaOH)中,Fe-N-C电催化剂对ORR具有良好的催化活性,ORR起始电位(E_o)为1.08 V(vs.RHE),半波电位(E_(1/2))0.88 V,电子转移数n接近4,H_2O_2产率3%,与商品20%Pt/C(Johnson Matthey)接近.电化学加速老化测试结果表明,Fe-N-C的E_(1/2)未发生明显变化,而Pt的负移45 mV,表明Fe-N-C具有很好的稳定性;在酸性介质(0.1 mol/L HClO_4)中,Fe-N-C的E_o为0.85 V,E_(1/2)为0.75 V,其E_(1/2)比Pt/C负移约0.15 V,表明在酸性介质中Fe-N-C对ORR的催化活性还有待提高.采用TEM、X射线衍射、X射线光电子能谱以及穆斯堡尔谱等方法研究了电催化剂构效关系.结果表明,Fe-N-C较好的ORR活性主要来自于高分散的Fe-N_4结构,此外,N(吡啶N和石墨N)掺杂的C也对反应具有一定的催化活性.与Pt/C相比,Fe-N-C电催化剂具有很好的耐甲醇性能.本文对比了Fe-N-C和Pt/C作为阴极催化剂的直接醇类燃料电池(DMFC)性能,采用质子交换膜的DMFC最大功率密度分别为47(Fe-N-C)和79 mW/cm~2(Pt/C),而采用碱性电解质膜的则分别为33(Fe-N-C)和8 mW/cm~2(Pt/C).结合半电池结果表明,Fe-N-C电催化剂在碱性介质中具有比Pt更为优秀的催化活性和稳定性,有望用作DMFC阴极代Pt催化剂.     

直接甲醇燃料电池催化活性层的优化

本文考察了直接甲醇燃料电池 (DMFC)不同催化剂载量的膜电极性能 .对催化剂层中Nafion含量进行优化 ,研究了Nafion含量对电池的阻抗的影响 .实验发现 :DMFC适宜的阳极Pt_Ru/C载量为Pt 4mg/cm2 、Nafion质量百分含量为 2 1.4 % ;高电流密度下 ,阴极Pt/C载量为Pt4mg/cm2 、Nafion质量百分含量为 2 1.4 %时 ,有较好的放电性能 ,继续增加Nafion含量 ,阴极的欧姆极化和浓差极化增大 ,电池性能下降     

界面合金化的Pt^Ag催化剂对阴极氧还原反应的电催化特点

分别在酸性和碱性电解质中研究了界面合金化的纳米Ag承载Pt纳米结构催化剂Pt0.5^Ag-B/C(Pt/Ag原子比为0.5)对氧还原反应(ORR)的电催化特点.结果表明,该催化剂对ORR的半波电势(E1/2)与通常的Pt/C催化剂(E-TEK公司)相当,但前者的本征电催化活性是后者的近两倍.与未合金化的Pt0.5^Ag-A/C相比,在Pt0.5^Ag-B/C催化剂中形成的合金化的Pt/Ag界面不仅使ORR的E1/2正移,而且明显提高了贵金属Pt的分散度或利用率.     

Ru,Sn和Co促进的Pt/C催化剂电催化氧化甲醇的性能

 采用溶胶法制备了用于阴离子膜直接甲醇燃料电池的Pt-M/C(M=Ru, Sn和Co)阳极电催化剂,并用X射线衍射和X射线能谱技术对催化剂进行了表征. 结果表明,制备的Pt-M合金颗粒分布均匀,粒径为2～6 nm, 其组成与前驱体中相应金属的原子比基本吻合. 用循环伏安法测定了催化剂在不同碱性条件下的活性. 结果显示,随着碱性的增加,甲醇的起始氧化电位降低,峰电流和催化剂的活性增大; 相同碱强度下催化剂活性顺序为Pt50Ru50/C>Pt50Sn50/C>Pt75Co25/C, 添加Ru可明显提高Pt/C催化剂的活性. Pt50Ru50/C在1.0 mol/L NaOH+1.0 mol/L CH3OH溶液中的峰电流密度可达634.7 mA/mg.     

简便方法制备氮掺杂的碳球用作高效非金属氧还原催化剂（英文）

随着人们环保意识的不断增强,社会对清洁能源的需求也日益增加.燃料电池具有效率高,燃料来源丰富,可直接将化学能转化成电能且污染小等优点,因而受到了广泛关注.然而,燃料电池的阴极氧还原反应(ORR)速率较慢,成为提高燃料电池整体效率的制约因素.因此,开发高性能的ORR催化剂,加快ORR反应速率具有非常重要的意义.目前,Pt基催化剂被认为是活性最好的商用ORR电催化剂.尽管此类催化剂具有较高的催化活性和良好的稳定性,但Pt的储量有限,价格高昂,抗燃料毒化性能差,限制了其大规模应用.近年来,为了减小Pt的用量,降低催化剂成本,人们除了致力于研究贵金属合金催化剂及非贵金属催化剂外,还把目光聚焦在了非金属催化剂,特别是碳及其复合材料的研究上.在众多碳材料中,碳球因具有良好的表面渗透性和较高的机械稳定性而被广泛应用于催化、吸附、药物输送和能量存储及转化等领域中.然而,碳球的表面化学惰性较强,比表面积较低,使其部分应用受到了限制.因此,人们采用了多种方法来调控碳球的物理化学性质.其中,向碳材料中掺入杂原子,尤其是氮原子的方法广受青睐.因为杂原子的掺入会显著增强作为主体的碳原子给电子的能力和表面吸附性质,从而对ORR表现出优异的催化活性和稳定性.本文以蔗糖作为碳源,三聚氰胺作为氮源,采用水热法及高温热解法制备了一系列氮掺杂的生物质碳球.并对氮掺杂量及热解温度进行了优化.结果表明,石墨化程度及石墨氮含量的提高,能有效地提高催化剂的活性.在优化了的条件下得到的催化剂N0.1C1.9S-900,表现出了比商业Pt/C催化剂更好的ORR催化性能.在0.1 mol/L KOH中,该催化剂催化ORR的起始电位和半波电位分别为–22.6和–133.6 mV(vs.Ag/AgCl),极限电流密度为4.6 mA/cm~2,分别比商业Pt/C高出7.2 mV,5.9 mV和0.2 mA/cm~2.同时,在经过30000 s的稳定性测试中,N0.1C1.9S-900催化剂的电流损失也远低于Pt/C,表明该催化剂具有良好的稳定性.此外,在抗甲醇毒化实验中,相比于商业Pt/C,N0.1C1.9S-900催化剂对甲醇有更好的耐受性.另外,该催化剂催化的ORR属于高效的4e~–途径.可见,该催化剂作为燃料电池的阴极氧还原反应催化剂具有广阔的前景.     

Synthesis,characterization and electrocatalytic properties of carbon nitride nanotubes for methanol electrooxidation

In this paper, carbon nitride nanotubes (CNNTs) have been synthesized with porous anodic aluminum oxide membrane as template by the thermal polymerization of sol–gel precursors for the first time. Field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis and X-ray photoelectron spectroscopy were applied to characterize the morphology and composition of the as-prepared nanotubes. The electrocatalytic activity and stability of CNNTs, towards methanol electrooxidation in 0.5 mol/dm³ H₂SO₄ solutions containing 1 mol/dm³ CH₃OH are presented at room temperature.     

Concurrent oxygen reduction and methanol oxidation in sulfuric acid solutions on platinized platinum electrodes

Steady-state polarization curves are compared in solutions of 0.5 M H₂SO₄ + O₂ (saturated), 0.5 M H₂SO₄ + (0.005–0.1) M CH₃OH, and 0.5 M H₂SO₄ + (0.005–0.1) M CH₃OH + O₂ (saturated) on a Pt/Pt electrode. A considerable difference is found between the currents in mixed solutions and those expected based on the principle of additivity of currents in CH₃OH and O₂ individual solutions. The surface coverages with the CH₃OH and O₂ adsorption products are determined in the potential range of 0.2–0.9 V (RHE). Open-circuit potentials are measured in mixed solutions. The obtained results suggest that the direct heterogeneous interaction between methanol and oxygen occurs alongside with faradaic reactions. This is assumed to lead to a decrease in methanol electrooxidation currents at E ≥ 0.8 V and their increase at E ≤ 0.65 V.     

A Design Strategy for Single‐Stranded Helicates using Pyridine‐Hydrazone Ligands and PbII

The reactions of py‐hz ligands ( L1–L5 ) with Pb(CF₃SO₃)₂?H₂O resulted in some rare examples of discrete single‐stranded helical Pb^II complexes. L1 and L2 formed non‐helical mononuclear complexes [Pb L1 (CF₃SO₃)₂]?CHCl₃ and Pb L2 (CF₃SO₃)₂][Pb L2 CF₃SO₃]CF₃SO₃?CH₃CN, which reflected the high coordination number and effective saturation of Pb^II by the ligands. The reaction of L3 with Pb^II resulted in a dinuclear meso‐helicate [Pb₂ L3 (CF₃SO₃)₂Br]CF₃SO₃?CH₃CN with a stereochemically‐active lone pair on Pb^II. L4 directed single‐stranded helicates with Pb^II, including [Pb₂ L4 (CF₃SO₃)₃]CF₃SO₃?CH₃CN and [Pb₂ L4 CF₃SO₃(CH₃OH)₂](CF₃SO₃)₃?2 CH₃OH?2 H₂O. The acryloyl‐modified py‐hz ligand L5 formed helical and non‐helical complexes with Pb^II, including a trinuclear Pb^II complex [Pb₃ L5 (CF₃SO₃)₅]CF₃SO₃?3CH₃CN?Et₂O. The high denticity of the long‐stranded py‐hz ligands L4 and L5 was essential to the formation of single‐stranded helicates with Pb^II.     

Dark Fermentative Hydrogen Production from Neutralized Acid Hydrolysates of Conifer Pulp

Concentrated acid hydrolysis of cellulosic material results in high dissolution yields. In this study, the neutralization step of concentrated acid hydrolysate of conifer pulp was optimized. Dry conifer pulp hydrolysis with 55?% H₂SO₄ at 45?°C for 2?h resulted in total sugar yields of 22.3?C26.2?g/L. The neutralization step was optimized for solid Ca(OH)₂, liquid Ca(OH)₂ or solid CaO, mixing time, and water supplementation. The highest hydrogen yield of 1.75?mol?H₂/mol glucose was obtained with liquid Ca(OH)₂, while the use of solid Ca(OH)₂ or CaO inhibited hydrogen fermentation. Liquid Ca(OH)₂ removed sulfate to below 30?mg SO₄ ^2?/L. Further optimization of the neutralization conditions resulted in the yield of 2.26?mol?H₂/mol glucose.     

Properties of new inorganic membranes prepared by metal alkoxide methods Part II: New inorganic-organic anion-exchange membranes prepared by the modified metal alkoxide methods with silane coupling agents

Four types of inorganic-organic anion exchangeable membranes were prepared on a microporous alumina substrate by dipcoating with solution containing Si(OC₂H₅)₄, C₂H₅OH, H₂O, CH₃COOH, two silane coupling agents in molar ratio 1:6.8:2:0.03:0.02, and on a silica membrane by liquid-phase coupling method with two solutions containing C₆H₅CH₃, H₂O, 2-(trimethoxysilyl)ethyl-2-pyridine in molar ratio 11:0.06:0.04 or C₂H₅OH, H₂O, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride in molar ratio 21:0.06:0.06. The alumina substrate and silica membrane showed cation exchangeability, but membranes dip-coated and liquid-phase coupled showed anion exchangeability and their ion-exchange capacity per unit area of membrane surface were in the range 4–9 × 10⁻³ meq. cm⁻². The static transport number for liquid-phase coupled membranes was in the range of 0.6–0.9, but for dip-coated membranes it was 0.5.     

Lattice Effects on the Spin‐Crossover Profile of a Mononuclear Manganese(III) Cation

Six solvated salts of a mononuclear manganese(III) complex with a chelating hexadentate Schiff base ligand are reported. One member of the series, [MnL]PF₆^.0.5 CH₃OH ( 1 ), shows a rare low‐spin (LS) electronic configuration between 10–300 K. The remaining five salts, [MnL]NO₃? C₂H₅OH ( 2 ), [MnL]BF₄?C₂H₅OH ( 3 ), [MnL]CF₃SO₃?C₂H₅OH ( 4 ), [MnL]ClO₄?C₂H₅OH ( 5 ) and [MnL]ClO₄?0.5 CH₃CN ( 6 ), all show gradual incomplete spin‐crossover (SCO) behaviour. The structures of all were determined at 100 K, and also at 293 K in the case of 3 – 6 . The LS salt [MnL]PF₆^.0.5 CH₃OH is the only member of the series that does not exhibit strong hydrogen bonding. At 100 K two of the four SCO complexes ( 2 and 4 ) assemble into 1D hydrogen‐bonded chains, which weaken or rupture on warming. The remaining SCO complexes 3 , 5 and 6 do not form 1D hydrogen‐bonded chains, but instead exhibit discrete hydrogen bonding between cation/counterion, cation/solvent or counterion/solvent and show no significant change on warming.     

Three copper(II) complexes constructed from 4-(2-pyridyl)-<Emphasis Type="Italic">1H</Emphasis>-1,2,3-triazole ligands: syntheses,structures, optical,and electrochemical properties

Three Cu(II) complexes constructed from 4-(2-pyridyl)-1H-1,2,3-triazole (L), namely, [CuL₂Cl₂]·H₂O, [CuL₂(CH₃OH)(NO₃)]NO₃ and [CuL₂(H₂O)]SO₄, have been synthesized and characterized. X-ray crystal structure analyses revealed that [CuL₂Cl₂]·H₂O and [CuL₂(CH₃OH)(NO₃)]NO₃ have octahedral geometries, whilst [CuL₂(H₂O)]SO₄ adopts a square-pyramidal coordination geometry. In all three complexes, the Cu(II) atoms are chelated by two L ligands in the basal plane, whilst the apical positions are occupied by Cl^?, NO₃^?, CH₃OH or H₂O. The bandgaps between the HOMO and LUMO were estimated by cyclic voltammetry (CV) and diffuse reflectance spectroscopy (DRS) to be 3.43, 3.12, and 3.74 eV, respectively. Theoretical calculations on each structure gave similar results to the experiments. Frontier molecular orbital analyses showed that the higher electron density on the apical ligand, the lower the bandgap.     

Electroreduction of carbon monoxide on palladium electrodeposits in solutions containing copper ions

It is shown that the electroreduction of CO proceeds on electrolytic deposits of palladium (edPd) in 0.5 M H₂SO₄ + (1–5) mM CuSO₄ + CO(sat) solutions at the potentials more positive than the Cu²⁺/Cu equilibrium potential. Among the CO reduction products, methanol and formaldehyde are identified. The current efficiency with respect to CH₃OH exceeds 75% on edPd formed in 1% PdCl₂+0.5 M H₂SO₄ solutions. In addition, Cu⁺ ions, which probably form complexes with CO, are detected in the solution and are assumed to play the role of intermediate species in the mediator catalysis along with copper adatoms.     

Efficient synthesis of 1-R1-2-R-4,5-di(furan-2-yl)-1H-imidazoles and their luminescence properties

In this study, a series of 1-R₁-2-R-4,5-di(furan-2-yl)-1H-imidazole derivatives were synthesized in better yield 59.0%∼89.8% by the treatment of purified imidazole compounds with benzyl chloride or allyl chloride in the presence of sodium hydride, and were characterized by FT–IR, HRMS, ¹H NMR and ¹³C NMR spectroscopy. Furthermore, the luminescence properties of the synthesized products were investigated. It was found that N-substituted groups of imidazole have little influence on the absorption bands in a 0.1 N H₂SO₄ aqueous solution containing 0.5 mL of dissolved CH₃OH. However, the emission of some compounds in solution was sensitive to the polarity of the solvents.     

Cationic oligomerization of isoprene and structure of its oligomers

The results obtained in a study of isoprene cationic oligomerization in the presence of some oxyacids (H₂SO₄, CH₃SO₃H, Nafion^® H) are reported. Oligomers up to pentamers are obtained which were examined through gas chromatography/mass spectrometry analysis either of the reaction products or of the hydrogenated products. The structure of the dimer fraction was investigated and revealed the prevalent presence of α-pinene and p-cymene together with different cyclic unsaturated hydrocarbons. Only small quantities of linear dimers were found. Possible reaction mechanisms are presented.