在Fe-Porphyrin基金属有机框架中的活性位点调节通过联结轴协调:加速电催化和电荷传输动力学
Itamar Liberman1, Ran Shimoni1, Raya Ifraemov1
1Department of Chemistry and Ilse Katz Institute for Nanoscale Science and Technology , Ben-Gurion University of the Negev , Beer-Sheva 8410501 , Israel.
Journal of the American Chemical Society
|January 9, 2020
概括
研究人员为人工太阳能燃料生产量身定制的金属有机框架 (MOF). 用配体修改铁氨酸活性部位增强了氧降解反应 (ORR) 的电催化活性.
科学领域:
- 材料科学
- 电化学
- 催化剂
背景情况:
- 人工太阳能燃料发电需要将许多催化站点固定在电极上.
- 金属有机框架 (MOF) 提供高度的电化学活性催化剂用于能量转化.
- 之前的MOF电催化研究还没有探索固定活性位点的分子水平定制.
研究的目的:
- 通过连接剂修饰来研究MOF定电催化剂的分子级调节.
- 为了提高MOF安装的Fe-porphyrins在能量转换反应中的电催化性能.
主要方法:
- 合成的MOF与Fe-氨酸的活性部位.
- 通过轴协调向Fe-porphyrins引入电子捐赠配体.
- 进行电化学表征以评估氧化还原导电性和氧降解反应 (ORR) 速率.
主要成果:
- 基因对基因的轴性协调显著改变了电子特性.
- 观察到基于氧化还原的MOF导电率和ORR电催化率的提高.
- 电化学研究表明,氧化还原跳跃并不是MOF中质子合电子转移反应的唯一速度限制因素.
结论:
- 通过配体协调对MOF活性位点进行分子级定制是提高电催化性能的一种可行的策略.
- 电催化MOF的未来改进应该考虑除了氧化还原跳跃之外的因素,包括与质子相关的化学步骤和质量传输动力学.
- 优化基于MOF的电催化剂需要一个整体的方法来解决电子特性,化学动力学和质量传输.
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