U.S.-Polish Collaborative Research on Electroanalytical Chemistry in the Absence of a Bulk Solution Phase

这个美国-波兰合作研究奖将研究“在没有散装溶液阶段的电分析化学”。主要研究人员是俄亥俄州迈阿密大学的James A. Cox博士和华沙大学的Pawel J. Kulesza博士。该计划的总体目标是描述某些离子导电固体在没有接触溶液相的情况下作为电化学研究介质的能力。特别感兴趣的是建立条件，在电极反应的速率和机制不受气相伴随物影响的条件下，使用这些电解质在电池中进行气相组分的电解。本研究中感兴趣的组分在传统的裸电极上通常是电化学沉默的，因此研究这些固体环境中的催化作用是本计划的必要部分。研究人员将研究两种一般材料作为固体电解质，由溶胶-凝胶工艺制备的玻璃状物质和多金属氧酸盐粉末。前者将是具有已知或预测离子电导率的干凝胶，如聚合钒、钌和铱氧化物。催化剂将以表面层的形式在电极上涂上干凝胶膜或这些膜的分散体。此外，将探索通过电化学生成金属中心的低氧化物，将选定的干凝胶转化为氧化还原介质。keggin型杂多矿-12-钨酸盐将包括所研究的原生多金属氧酸盐。测试系统将根据混合价系统的形成来选择。电子自交换动力学将与有效输运系数一起确定。一旦表征，多金属氧酸盐将被封装在干凝胶中。在这里，我们的目标是利用前者在一个环境中的催化活性，该环境允许所选的氧化还原反应在不受周围大气中其他成分（包括水）干扰的情况下进行。研究将使用传统的电化学仪器进行，包括伏安法和交流阻抗方法。这项研究的结果将指导用于空气中有害成分和具有有限蒸汽压力的目标固体或液体存在的安培传感器的发展。此外，这些电化学系统预计适用于净化小环境的大气。其他可能的应用包括设计能量存储设备和微型电子元件，如双层开关。这项化学研究实现了将美国和波兰的顶尖专家聚集在一起的计划目标，在平等、互惠和互利的基础上，在共同感兴趣和能力强的领域结合互补的努力和能力。

9529589 Cox This U.S.-Polish Cooperative Research award will study "Electroanalytical Chemistry in the Absence of a Bulk Solution Phase." The principal researchers are Dr. James A. Cox of Miami University, Ohio, and Dr. Pawel J. Kulesza of the University of Warsaw. The general goal of this program is to characterize certain ionically-conducting solids in terms of their ability to serve as media for electrochemical studies in the absence of a contacting solution phase. Of particular interest would be to establish conditions where electrolyses of gas-phase components can be performed at cells using these electrolytes under conditions where the rates and mechanisms of the electrode reaction are not influenced by concomitants in the gas phase. The components of interest in this study are generally electrochemically silent at conventional, bare electrodes, so the investigation of catalysis in the environment of these solids is a required part of this program. The researchers will investigate two general materials as solid electrolytes, glassy substances prepared by sol-gel processes and polyoxometallate powders. The former will be xerogels with known or predicted ionic conductivity such as polymeric vanadium, ruthenium, and iridium oxides. The catalysts will be in the form of surface layers on electrodes coated with films of the xerogels or dispersions with these films. In addition, conversion of selected xerogels into redox mediators by electrochemically generating lower oxides of the metal centers will be explored. Keggin-type heteropoly-12-tungstates will comprise the primary polyoxometallates investigated. The test systems will be selected on the basis of formation of mixed-valent systems. The kinetics of electron self-exchange will be determined along with the effective transport coefficient. Once characterized, the polyoxometallates will be encapsulated in xerogels. Here, the objective is to exploit the catalytic activity of the former in an envi ronment that permits the selected redox reaction to proceed without interference from other components, including water, of the surrounding atmosphere. The studies will be performed with conventional electrochemical instrumentation, including voltammetric and a.c. impedance methodology. The results of this investigation will guide the development of amperometric sensors for hazardous components in air and for the presence of targeted solids or liquids with finite vapor pressures. In addition, these electrochemical systems are projected to be suited to purifying the atmosphere of small environments. Other possible applications include the design of energy-storage devices and microscale electronic components such as bilayer switches. This research in chemistry fulfills the program objectives of bringing together leading experts in the U.S. and Poland to combine complementary efforts and capabilities in areas of strong mutual interest and competence on the basis of equality, reciprocity, and mutuality of benefit.