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增强CO2光还原的金属卟啉间隔金属邻苯二酚框架中的能带排列和氧化还原活性位点
作者:小柯机器人 发布时间:2021/10/21 13:44:03

中国科学院福建物质结构研究所林启普团队报道了用于增强CO2光还原的金属卟啉间隔金属邻苯二酚框架中的能带排列和氧化还原活性位点。相关研究成果发表在2021年10月15日出版的《德国应用化学》。

该文构建了两种新的化学稳定的金属卟啉桥连金属邻苯二酚框架,InTCP-Co和FeTCP-Co,在不添加牺牲剂和光敏剂的情况下实现人工光合作用。FeTCP-CO上的CO2光还原速率大大超过了InTCP-CO上的CO2光还原速率,并且每个邻苯二酚的不配位羟基的引入进一步极大地促进了光催化活性。其可以解释为铁氧配位链有助于能带排列并提供氧化还原活性位点,而未配位的羟基有助于可见光吸收率、电荷载流子转移和CO2-支架亲和力。

FeTCP-OH-Co的甲酸选择性为97.8%,反应速率分别是FeTCP-Co和InTCP-Co的4.3倍和15.7倍。以上发现也与光谱研究和DFT计算一致。

附:英文原文

Title: Energy Band Alignment and Redox-active Sites in Metalloporphyrin-Spaced Metal-Catechol Frameworks for Enhanced CO2 Photoreduction

Author: Er-Xia Chen, Mei Qiu, Yong-Fan Zhang, Liang He, Ya-Yong Sun, Hui-Li Zheng, Xin Wu, Jian Zhang, Qipu Lin

Issue&Volume: 2021-10-15

Abstract: Two new chemically-stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, are constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO  2  photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of an uncoordinated hydroxyl group per catechol into the network further greatly promotes the photocatalytic activity. It could be explained by the fact that the iron-oxo coordination chain helps the energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge carrier transfer, and CO  2  -scaffold affinity. With a formic acid selectivity of 97.8%, FeTCP-OH-Co affords CO  2  photoconversion with a reaction rate 4.3 and 15.7 times higher than those of FeTCP- Co and InTCP-Co, respectively. These findings are also consistent with the spectroscopic study and DFT calculation.

DOI: 10.1002/anie.202111622

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202111622

期刊信息

Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx