Coordination Tuning of Metal Porphyrins for Improved Oxygen Evolution Reaction

Author:

Lv Haoyuan1,Zhang Xue‐Peng1,Guo Kai1,Han Jinxiu1,Guo Hongbo1,Lei Haitao1,Li Xialiang1,Zhang Wei1,Apfel Ulf‐Peter23,Cao Rui1ORCID

Affiliation:

1. Key Laboratory of Applied Surface and Colloid Chemistry Ministry of Education School of Chemistry and Chemical Engineering Shaanxi Normal University 710119 Xi'an China

2. Ruhr-Universität Bochum Fakultät für Chemie und Biochemie Anorganische Chemie I Universitätsstrasse 150 44801 Bochum Germany

3. Fraunhofer UMSICHT Osterfelder Strasse 3 46047 Oberhausen Germany

Abstract

AbstractThe nucleophilic attack of water or hydroxide on metal‐oxo units forms an O−O bond in the oxygen evolution reaction (OER). Coordination tuning to improve this attack is intriguing but has been rarely realized. We herein report on improved OER catalysis by metal porphyrin 1‐M (M=Co, Fe) with a coordinatively unsaturated metal ion. We designed and synthesized 1‐M by sterically blocking one porphyrin side with a tethered tetraazacyclododecane unit. With this protection, the metal‐oxo species generated in OER can maintain an unoccupied trans axial site. Importantly, 1‐M displays a higher OER activity in alkaline solutions than analogues lacking such an axial protection by decreasing up to 150‐mV overpotential to achieve 10 mA/cm2 current density. Theoretical studies suggest that with an unoccupied trans axial site, the metal‐oxo unit becomes more positively charged and thus is more favoured for the hydroxide nucleophilic attack as compared to metal‐oxo units bearing trans axial ligands.

Funder

National Natural Science Foundation of China

Fundamental Research Funds for the Central Universities

Publisher

Wiley

Subject

General Chemistry,Catalysis

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3