Materials design of edge-modified polymeric carbon nitride nanoribbons for the photocatalytic CO2 reduction reaction.
Materials design of edge-modified polymeric carbon nitride nanoribbons for the photocatalytic CO2 reduction reaction.
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DOI：
10.1039/d2cp05027g
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发表时间：
2023-03
期刊：
影响因子：
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通讯作者：
Shaohua Liu;Yi Li;Yongfan Zhang;Wei-hui Lin
中科院分区：
文献类型：
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作者：
Shaohua Liu;Yi Li;Yongfan Zhang;Wei-hui Lin
纳米粒子的构建和功能基团的修饰是提高光催化剂性能的重要手段。在本文中，密度泛函理论（DFT）计算应用于评估光催化CO2还原反应（CO2 RR）中不同模型结构的电子吸收能力，即，瓜基氮化碳纳米带（MNR）和边缘改性的瓜基氮化碳纳米带（X-MNR，X = NO2、CF 3、CN、CHO、F、Cl、CH、OH、SH、CH 3和H）。发现X-MNR（X = NO_2、CN、CHO、CCH、OH和H）具有显著减小的带隙。同时，VBM和CBM在相同的光吸收波长范围内被有效分离，与实验观察一致。更重要的是，随着CO或HCOOH的形成，MNR、CHO-MNR、CN-MNR等中CO2 RR速率决定步骤的吉布斯自由能差大大降低。机理研究表明，通过边群改性的材料设计可以优化CO2 RR工艺。
Nanoribbon construction and modification with functional groups are important methods to improve the performance of photocatalysts. In this paper, density functional theory (DFT) calculations are applied to assess the electron absorption capacity of different model structures in the photocatalytic CO2 reduction reaction (CO2RR), i.e., melon-based carbon nitride nanoribbons (MNRs) and edge-modified melon-based carbon nitride nanoribbons (X-MNRs, X = NO2, CF3, CN, CHO, F, Cl, CCH, OH, SH, CH3, and H). It is found that X-MNRs (X = NO2, CN, CHO, CCH, OH, and H) have a significantly reduced band gap. Meanwhile, the VBM and CBM are effectively separated with the same optical absorption wavelength range, agreeing with the experimental observations. More importantly, the Gibbs free energy difference of the CO2RR rate-determining step is greatly reduced in MNRs, CHO-MNRs, CN-MNRs etc. with the formation of CO or HCOOH. The mechanism investigation indicates that the materials design via edge-group modification can optimize the CO2RR process.