...
首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
【24h】

Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO

机译:动力学和结构研究,选择性的起源,以及人工合成CO的界面电荷转移

获取原文
获取原文并翻译 | 示例
           

摘要

The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-visible (UV-vis) spectroscopy. X-ray crystallographic, density functional theory (DFT), and electrochemical kinetic studies of the Re(bipy-fBu)(CO)_3(L) catalyst for the reduction of CO_2 to CO. A remarkable selectivity for CO_2 over H~+ was observed by stopped-flow UV-vis spectroscopy of [Re(bipy-tBu)(CO)_3]~(-1). The reaction with CO_2 is about 25 times faster than the reaction with water or methanol at the same concentrations. X-ray crystallography and DFT studies of the doubly reduced anionic species suggest that the highest occupied molecular orbital (HOMO) has mixed metal-ligand character rather than being purely doubly occupied d_z~2, which is believed to determine selectivity by favoring CO_2 (σ + π) over H~+ (σ only) binding. Electrocatalytic studies performed with the addition of Bronsted acids reveal a primary H/D kinetic isotope effect indicating that transfer of protons to Re-CO_2 is involved in the rate limiting step. Lastly, the effects of electrode surface modification on interfacial electron transfer between a semiconductor and catalyst were investigated and found to affect the observed current densities for catalysis more than threefold, indicating that the properties of the electrode surface need to be addressed when developing a homogeneous artificial photosynthetic system.
机译:人工光合作用系统的有效设计需要优化几个重要的相互作用。在这里,我们报告停止流的紫外可见(UV-vis)光谱。 Re(bipy-fBu)(CO)_3(L)催化剂的X射线晶体学,密度泛函理论(DFT)和电化学动力学研究,用于将CO_2还原为CO。通过[Re(bipy-tBu)(CO)_3]〜(-1)的停止流紫外可见光谱观察。与CO_2的反应比在相同浓度下与水或甲醇的反应快约25倍。 X射线晶体学和DFT研究显示,双还原阴离子物种具有最高的占据分子轨道(HOMO)具有混合的金属-配体特征,而不是纯双占据的d_z〜2,这被认为是通过促进CO_2(σ +π)超过H〜+(仅σ)绑定。添加布朗斯台德酸进行的电催化研究显示出主要的H / D动力学同位素效应,表明质子向Re-CO_2的转移参与了限速步骤。最后,研究了电极表面改性对半导体与催化剂之间的界面电子转移的影响,发现其对所观察到的催化电流密度的影响超过三倍,这表明在开发均质人工晶体时需要解决电极表面的特性。光合系统。

著录项

  • 来源
  • 作者单位

    Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358;

    Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358;

    Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358;

    Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358;

    Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358;

    Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195-1700;

    Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195-1700;

    Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358;

  • 收录信息 美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    carbon dioxide reduction; electrochemistry; kinetics; electrocatalyst;

    机译:减少二氧化碳;电化学动力学;电催化剂;

相似文献

  • 外文文献
  • 中文文献
  • 专利
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