...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Catalysis science & technology >Hydrogen evolution by cobalt hangman porphyrins under operating conditions studied by vibrational spectro-electrochemistry
【24h】

Hydrogen evolution by cobalt hangman porphyrins under operating conditions studied by vibrational spectro-electrochemistry

机译：氢刽子手钴卟啉的进化在操作条件下研究了振动spectro-electrochemistry

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Cobalt hangman complexes are promising catalysts for dihydrogen production, yet their electrocatalytic performance in aqueous environment is still a topic of dispute. Surface-enhanced resonance Raman (SERR) spectro-electrochemistry has a great potential to give insight into the reaction mechanism of such molecular catalysts attached to electrodes under turnover conditions. However, the intrinsic catalytic activity of plasmonic supports and photoinduced side-reactions make the in situ analysis of their structures very challenging. In this work, the structure of hangman complexes attached to electrodes via dip-coating was investigated during catalytic turnover by electrochemistry and SERR spectroscopy. In order to explore the relevance of the hanging group for proton supply, complexes bearing a carboxylic acid and an ester hanging group were compared. For the former, SERR spectra recorded under turnover conditions indicate the reductive formation of a Co-III-H species, followed by laser-induced translocation of a proton to the carboxylic hanging group and the associated formation of the CoI state. Due to the lack of a proton accepting group, hangman complexes with an ester group could not be trapped in the Co-I intermediate state and as a consequence SERR spectra solely reflected the (photo-enriched) Co-II resting state under turnover conditions. These results represent the first Raman spectroscopic insights into intermediates of dihydrogen evolution catalysed by cobalt hangman complexes on electrodes and support the direct involvement of the hanging group as a proton shuttle.
机译：刽子手钴配合物是有前途的催化剂生产二氢,然而他们electrocatalytic性能水环境仍然是一个争议的话题。表面增强共振拉曼(SERR)spectro-electrochemistry有巨大的潜力洞察到的反应机理分子催化剂与电极营业额的条件。支持和催化活性的电浆光诱导的副反应使原位分析他们的结构非常具有挑战性。这项工作,刽子手复合体的结构连接到电极通过浸涂研究在催化营业额电化学和SERR光谱学。探索挂组的相关性质子供应,复合物轴承羧基酸和酯挂组比较。对于前者,SERR光谱记录下营业额显示还原条件组建一个Co-III-H物种,紧随其后激光质子的易位羧基挂组和相关的CoI状态的形成。质子接受集团与一个刽子手复合物酯组不能被困在共同SERR中间状态和结果光谱仅仅反映了(photo-enriched)Co-II营业额条件下静息状态。这些结果代表第一个拉曼光谱见解的中间体进化二氢催化了钴刽子手配合物在电极和直接的支持挂着集团的参与作为一个质子航天飞机。

著录项

相似文献

  • 中文文献
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号