Monolayer Molecular Functionalization Enabled by Acid–Base Interaction for High-Performance Photochemical CO2 Reduction,ACS Energy Letters

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Monolayer Molecular Functionalization Enabled by Acid–Base Interaction for High-Performance Photochemical CO2 Reduction
ACS Energy Letters ( IF 19.3 ) Pub Date : 2022-06-08 , DOI: 10.1021/acsenergylett.2c01147
Bo Shang _{1,

2} , Fengyi Zhao ₃ , Chungseok Choi _{1,

2} , Xiaofan Jia ₁ , Magnus Pauly ₄ , Yueshen Wu _{1,

2} , Zixu Tao _{1,

2} , Yiren Zhong _{1,

2} , Nia Harmon _{1,

2} , Paul A. Maggard ₄ , Tianquan Lian ₃ , Nilay Hazari ₁ , Hailiang Wang _{1,

2}

Affiliation

We report the development of a hybrid catalyst consisting of carbon nitride (CN_x) and cobalt phthalocyanine tetracarboxylic acid (CoPc-COOH), which converts CO₂ to CO with high reaction rate (1067 μmol/g·h) and high selectivity (over 98%), under simulated solar irradiation. The carboxylic acid substituents on the phthalocyanine ligands play a critical role as they bind to the amine groups of CN_x to enable nearly ideal monolayer coverage of the molecular cocatalyst on the semiconductor surface and promote catalytic activity from the molecular complex. Specifically, the CN_x/CoPc-COOH hybrid material achieves a reaction rate 16 times higher than a CN_x material containing unsubstituted CoPc molecules. We further show that activation and deactivation of the CN_x/CoPc-COOH composite, which are associated with the reduction and decomposition of CoPc-COOH, respectively, both proceed at a nearly constant rate regardless of the CO₂ reduction reaction rate. The decoupling of charge carrier injection and CO₂ reduction catalysis has important mechanistic implications for future performance optimization and materials design of photocatalysts for CO₂ reduction.

中文翻译：

通过酸碱相互作用实现单层分子功能化，实现高性能光化学 CO2 还原

_{我们报告了由氮化碳 (CN x}_{) 和钴酞菁四羧酸(} CoPc-COOH)组成的混合催化剂的开发，该催化剂以高反应速率 (1067 μmol/g·h) 和高选择性 (超过98%），在模拟太阳辐射下。酞菁配体上的羧酸取代基起着关键作用，因为它们与 CN _x的胺基结合，使半导体表面上的分子助催化剂几乎达到理想的单层覆盖，并促进分子复合物的催化活性。具体来说，CN _{x /CoPc-COOH 杂化材料的反应速率是 CN}_x的 16 倍含有未取代的 CoPc 分子的材料。我们进一步表明，CN _x /CoPc-COOH 复合材料的活化和失活分别与 CoPc-COOH 的还原和分解相关，无论 CO ₂还原反应速率如何，都以几乎恒定的速率进行。电荷载流子注入和CO ₂还原催化的解耦对未来CO ₂还原光催化剂的性能优化和材料设计具有重要的机理意义。

更新日期：2022-06-08

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