内部连接体替代改善了金属氧-有机框架中的外部氧气演变反应
Jianwen Su1, Renyi Li2, Dingding Huang1
1State Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, No. 18 Fuxue Road, Changping District, Beijing 102249, China.
ACS applied materials & interfaces
|December 27, 2025
概括
研究人员通过替换连接物来设计金属氧化物-有机框架 (MHOFs),从而创建协调不足的位. 这种缺陷工程增强了用于可持续水电解的催化活性.
科学领域:
- 材料科学 材料科学 材料科学
- 电化学 电化学 电化学
- 催化剂是一种催化剂.
背景情况:
- 催化剂的工程协调缺陷对于提高活动,同时保持结构完整性至关重要.
- 金属氧化物有机框架 (MHOFs) 为催化剂开发提供了一个有前途的平台.
- 在缺陷引发的活动和结构稳定之间取得平衡仍然是一个重大挑战.
研究的目的:
- 开发MHOF中缺陷工程的新策略,同时提高催化活性和结构稳定性.
- 研究内部连接体替代对MHOF电子结构和催化性能的影响.
- 为设计水电解的高效和耐用电催化剂建立一个理论框架.
主要方法:
- 通过内部连接体替代合成Ni-{ABDA}{0.75}{BA}{0.25},用单碳酸酸 (BA) 替换25%的二碳酸链接体 (ABDA).
- 描述了材料的结构,通过 π-π 堆叠和低协调 Ni 位点的生成确认了通过 π-π 堆叠和低协调 Ni 位点的长距离秩序.
- 在0.1 M KOH中评估了电催化性能,在1 mA cm-2时测量了超电位.
- 利用结合的实验和理论分析 (例如,DFT) 来理解增强催化机制.
主要成果:
- 优化后的Ni-ABDA) 0.75 (BA) 0.25催化剂表现出显著降低的超电位 (326 mV在1 mA cm-2),表现优于原始的Ni-ABDA122 mV和商业的IrO2.
- 连接体缺陷诱导了电子密度的重新分配,降低了氧气演化反应中速度决定步骤的热力学障碍.
- 在协调不足的Ni位点的定制电子结构优化了*O和*OOH中间体的吸附,打破了缩放关系.
结论:
- 内部连接体替代是MHOF中缺陷工程的有效策略,增强了触媒活性,而不损害结构稳定性.
- 这项研究提供了一个机械的理解,如何低协调的金属站点和定制的电子结构提高电催化性能.
- 这项工作为设计高效和耐用的电催化剂,用于可持续的水电解奠定了基础.
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