通过调整金属位置提高光催化CO2还原成甲酸盐的选择性

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-02-05 DOI:10.1021/acscatal.4c06456

Honggang Zhang, Shaozhi Liu, Xiaolu Zhou, Zhaoke Zheng, Peng Wang, Hefeng Cheng, Zeyan Wang, Ying Dai, Yuanyuan Liu, Baibiao Huang

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引用次数: 0

摘要

光催化还原CO2为液体燃料HCOOH是解决环境和能源问题的理想策略，但设计具有高HCOOH选择性的光催化剂仍然是一个挑战。在本文中，铁基mof （Fe-BDC）中的配位O原子被N原子部分取代，以提供一个特殊的FeO4N2金属位。综合实验和计算结果表明，N原子的引入增加了Fe位点电子分布的不对称性，使得Fe位点电子密度增大，从而影响了关键*HCOOH中间体的形成和解吸，从而优化了co2 -生成甲酸酯的反应途径。结果表明，合成的Fe-PYC具有较高的甲酸选择性（93%），生成速率为238 μmol g-1 h-1， Fe-BDC为54%，生成速率为175 μmol g-1 h-1。这项工作提供了更深入地了解金属位的配位几何形状与CO2光还原选择性之间的相互作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Enhanced Selectivity of Photocatalytic CO2 Reduction to Formate via Tailoring the Metal Site

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Enhanced Selectivity of Photocatalytic CO2 Reduction to Formate via Tailoring the Metal Site

Photocatalytic reduction of CO₂ to liquid fuel HCOOH is an ideal strategy for addressing environmental and energy problems, but it still remains a challenge to design photocatalysts with high HCOOH selectivity. Herein, the coordinated O atom in iron-based MOFs (Fe-BDC) was partially replaced by the N atom to afford a special FeO₄N₂ metal site. Comprehensive experimental and calculation results suggest that the introduction of a N atom increases the asymmetry of electron distribution with a higher electron density in the Fe site, which affects the formation and desorption of the key *HCOOH intermediate and consequently optimizes the CO₂-to-formate reaction pathway. As a result, the synthesized Fe-PYC presents a higher formate selectivity (93%) with a formation rate of 238 μmol g^–1 h^–1 compared to that of Fe-BDC (54%, 175 μmol g^–1 h^–1). This work provides deeper insight into the interplay between the coordination geometry of metal sites and the selectivity of CO₂ photoreduction.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.