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内置电场介导的酞菁钴/MIL-68(In)-NH异质结中的S型电荷迁移及Co-N4(II)位点用于促进光催化一氧化氮氧化

Built-in electric field mediated S-scheme charge migration and Co-N4(II) sites in cobalt phthalocyanine/MIL-68(In)-NH heterojunction for boosting photocatalytic nitric oxide oxidation.

作者信息

Li Guojun, Lian Zheng, Lyu Qiuqiu, Zhu Chenyu, Liu Zhinian, Zhang Shule, Zhong Qin

机构信息

School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, China.

State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210023, China.

出版信息

J Colloid Interface Sci. 2024 Dec;675:549-559. doi: 10.1016/j.jcis.2024.07.031. Epub 2024 Jul 6.

DOI:10.1016/j.jcis.2024.07.031
PMID:38986328
Abstract

The efficiency of photocatalytic Nitric Oxide(NO) oxidation is limited by the lack of oxygen(O) active sites and poor charge carrier separation. To address this challenge, we developed a molecular Cobalt Phthalocyanine modified MIL-68(In)-NH photocatalyst with a robust Built-in electric field(BIEF). In the 2 % CoPc-MIN sample, the BIEF strength is increased by 3.54 times and 5.83 times compared to pristine CoPc and MIL-68(In)-NH, respectively. This BIEF facilitates the efficient S-scheme charge transfer, thereby enhancing photogenerated carrier separation. Additionally, the Co-N4(II) sites in CoPc can effectively trap the separated photoexcited electrons in the S-scheme system. In addition, the Co-N4(II) sites can also serve as active sites for O adsorption and activation, promoting the generation of superoxide radical (O), thereby driving the direct conversion of NO to nitrate(NO). Consequently, the 2 % CoPc-MIN sample exhibits a remarkable photocatalytic NO removal efficiency of 79.37 % while effectively suppressing the formation of harmful by-product nitrogen dioxide(NO) to below 3.5 ppb. This study provides a feasible strategy for designing high-efficiency O activation photocatalysts for NO oxidation.

摘要

光催化氧化一氧化氮(NO)的效率受到氧(O)活性位点缺乏和电荷载流子分离不良的限制。为应对这一挑战,我们开发了一种具有强大内建电场(BIEF)的分子钴酞菁修饰的MIL-68(In)-NH光催化剂。在2% CoPc-MIN样品中,BIEF强度分别比原始CoPc和MIL-68(In)-NH提高了3.54倍和5.83倍。这种BIEF促进了高效的S型电荷转移,从而增强了光生载流子的分离。此外,CoPc中的Co-N4(II)位点可以有效地捕获S型系统中分离的光激发电子。此外,Co-N4(II)位点还可以作为O吸附和活化的活性位点,促进超氧自由基(O)的生成,从而推动NO直接转化为硝酸盐(NO)。因此,2% CoPc-MIN样品表现出79.37%的显著光催化NO去除效率,同时有效地将有害副产物二氧化氮(NO)的形成抑制到3.5 ppb以下。本研究为设计用于NO氧化的高效O活化光催化剂提供了一种可行的策略。

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