Proton-Rocking-Chair-Type Redox Capacitors Based on Indium Tin Oxide Electrodes with Multilayer Films Containing Ru Complexes.
Proton-Rocking-Chair-Type Redox Capacitors Based on Indium Tin Oxide Electrodes with Multilayer Films Containing Ru Complexes.
复制标题
基于氧化铟锡电极和含钌配合物多层膜的质子摇椅型氧化还原电容器。
DOI：
10.1021/acsami.8b05907
复制
发表时间：
2018
影响因子：
9.5
通讯作者：
Masa
中科院分区：
文献类型：
--
作者：
Kai Yoshikawa;Daisuke Motoyama;Yusuke Hiruma;Hiroaki Ozawa;Shusaku Nagano;Masa
使用可扩展的逐层（LbL）组装薄膜制造了可充电质子摇椅型氧化还原电容器，该薄膜由两种双核Ru配合物组成，这些配合物表现出具有不同Ru（II/III）氧化还原电位的质子耦合电子转移（PCET）反应（RuNH-OH和RuCH-OH）。RuNH-OH和RuCH-OH含有不同的配位环境，其分别涉及在两端的两个膦酸酯接头配体和桥接的2，6，2 '，6'-四（苯并咪唑-2-基）-4，4 '-联吡啶或1，3，1'，3 '-四（苯并咪唑-2-基）-5，5'-联苯配体。通过膦酸酯基团与锆（IV）离子之间的络合作用将分子单元组装到氧化铟锡（ITO）电极上。这些多层膜的LbL生长过程中，通过电化学或紫外-可见光谱测量监测。由此获得的LbL膜上的ITO电极显示PCET反应在不同的电位，这取决于桥接配体。在RuCH-OH的桥连配体中引入环化的Ru-C键导致钌（III）氧化态的稳定，因此，RuCH-OH的桥连苯并咪唑基团中的亚氨基N-H质子与相应的RuNH-OH络合物相比表现出较低的p Ka值。使用pH指示剂探针证实了在ITO电极上的Ru多层膜中伴随氧化还原反应的质子运动。对于质子摇椅型氧化还原电容器的性能测试，在NaClO 4水溶液中检查了由ITO电极上的RuNH-OH和RuCH-OH多层膜组成的双电极系统。在恒电流条件下，发生稳定、可逆和可重复的充电/放电过程。电容随着LbL层数目的增加而增加。为了比较，一个类似的氧化还原电容器组成的两个RuNMe-OH和RuCMe-OH类似物，其中所有四个亚氨基N-H质子的苯并咪唑部分的N-Me基团的保护，构建和检查。在这些复合物中，与含有RuNH-OH和RuCH-OH的电池组成的PCET型电容器相比，电容降低了77%;这一结果强烈表明，质子运动对电荷存储起着比阴离子运动更重要的作用。在这样的LbL膜组成的Ru络合物，表现出PCET型氧化还原反应，电容大大提高与层数的增加，并使用质子作为电荷载体。
A rechargeable proton-rocking-chair-type redox capacitor was fabricated using scalable layer-by-layer-(LbL)-assembled films composed of two dinuclear Ru complexes that exhibit proton-coupled electron-transfer (PCET) reactions with different Ru(II/III) redox potentials (RuNH-OH and RuCH-OH). RuNH-OH and RuCH-OH contain different coordination environments that involve two phosphonate linker ligands at both ends and bridging 2,6,2',6'-tetrakis(benzimidazol-2-yl)-4,4'-bipyridine or 1,3,1',3'-tetrakis(benzimidazol-2-yl)-5,5'-biphenyl ligands, respectively. The molecular units were assembled onto indium tin oxide (ITO) electrodes by complexation between the phosphonate groups and zirconium(IV) ions. The LbL growing process of these multilayer films was monitored by electrochemical or UV-vis spectroscopic measurements. The thus obtained LbL films on the ITO electrodes showed PCET reactions at different potentials, depending on the bridging ligands. The introduction of cyclometalated Ru-C bonds in the bridging ligand of RuCH-OH led to the stabilization of the ruthenium(III) oxidation state, and therefore, RuCH-OH exhibited lower p Ka values for the imino N-H protons in the bridging benzimidazole groups compared to those of the corresponding RuNH-OH complex. The proton movements that accompany the redox reaction in the Ru multilayer films on the ITO electrode were confirmed using a pH indicator probe. For the performance test of a proton-rocking-chair-type redox capacitor, a two-electrode system composed of RuNH-OH and RuCH-OH multilayer films on ITO electrodes was examined in an aqueous solution of NaClO4. Under galvanostatic conditions, stable, reversible, and repeatable charging/discharging processes occurred. The capacitance increased with an increasing number of LbL layers. For comparison, a similar redox capacitor composed of two RuNMe-OH and RuCMe-OH analogues, in which all four imino N-H protons on the benzimidazole moieties are protected by N-Me groups, was constructed and examined. In these complexes, the capacitance decreased by 77% compared to the PCET-type capacitor composed of a cell containing RuNH-OH and RuCH-OH; this result strongly suggests that the proton movement plays a more important role for the charge storage than the anion movement. In such LbL films composed of Ru complexes that exhibit PCET-type redox reactions, the capacitance is drastically improved with an increasing number of layers and using protons as charge carriers.
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影响因子：
4.6
作者：
Tomai, Takaaki;Mitani, Satoshi;Komatsu, Daiki;Kawaguchi, Yuji;Honma, Itaru
通讯作者：
Honma, Itaru
影响因子：
4.6
作者：
Wen-Wen Yang-Wen;Yu‐Wu Zhong;S. Yoshikawa;Jiang‐Yang Shao;Shigeyuki Masaoka;K. Sakai;J. Yao;Masa-aki Haga
通讯作者：
Wen-Wen Yang-Wen;Yu‐Wu Zhong;S. Yoshikawa;Jiang‐Yang Shao;Shigeyuki Masaoka;K. Sakai;J. Yao;Masa-aki Haga
影响因子：
4.6
作者：
Masa-aki Haga;‡. H. Hong;Y. Shiozawa;Y. Kawata;H. Monjushiro;and Tsuyoshi Fukuo;R. Arakawa
通讯作者：
Masa-aki Haga;‡. H. Hong;Y. Shiozawa;Y. Kawata;H. Monjushiro;and Tsuyoshi Fukuo;R. Arakawa
archaerhodopsin-3从光驱动质子泵到光门控通道的功能转换
DOI：
--
发表时间：
2014
期刊：
影响因子：
--
作者：
井上圭一;下野和実;鈴木悠斗;谷ヶ崎仁;宮内正二;林重彦;神取秀樹;須藤雄気
通讯作者：
須藤雄気
影响因子：
2.8
作者：
Nagashima, Takumi;Nakabayashi, Takuya;Haga, Masa-aki
通讯作者：
Haga, Masa-aki