Graphitic carbon nitride with the pyridinic N substituted by Al and Si as efficient photocatalysts for CO2 reduction

文献信息

发布日期 2023-11-27

DOI 10.1039/D3TA05398A

影响因子 12.732

作者

Min Zhang, Yaru Liu, Ya-nan Jiang, Yuchen Ma

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摘要

Efficient photocatalysts to reduce CO2 into fuels are still scarce. Graphitic carbon nitride (g-C3N4) is a promising metal-free photocatalyst, and replacing its lattice atoms by other elements is one common strategy to improve its activity in the CO2 reduction reaction (CO2RR). Using ten kinds of elements in groups IIIA to VIA as dopants to replace the pyridinic N in g-C3N4, our theoretical calculations uncover a strong correlation between electronegativity and Bader charges of the dopants and the reaction barrier in the initial step of the CO2RR, which reaches 1.72 eV on the pristine g-C3N4. We find that the barrier is inversely proportional to electronegativity for the elements possessing weak metallicity (B, O, P, S, As, and Se) whose reduction product is COOH*, and to Bader charge for those possessing strong metallicity (Al, Si, Ga, and Ge) whose reduction product is HCOO*. Si-doped g-C3N4 exhibits excellent activity and selectivity in producing HCOOH with a rate-determining barrier of just 0.57 eV, while Al-doped g-C3N4 is a promising catalyst to produce CH4 with all the barriers smaller than 0.81 eV except a 1.21 eV barrier in its rate-determining step. Activities of these two systems are comparable to that of g-C3N4 modified by noble metal atoms. Si and Al doping also significantly enhances visible light absorption. In contrast, g-C3N4 doped by the elements possessing weak metallicity is inefficient for the CO2RR due to the barrier being higher than 1.36 eV. This work may provide a strategy for the design of efficient CO2RR catalysts based on metal-free materials.

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来源期刊

Journal of Materials Chemistry A

CiteScore: 19.5

自引率: 4.7%

年发文量: 2211

Journal of Materials Chemistry A, B & C cover high quality studies across all fields of materials chemistry. The journals focus on those theoretical or experimental studies that report new understanding, applications, properties and synthesis of materials. The journals have a strong history of publishing quality reports of interest to interdisciplinary communities and providing an efficient and rigorous service through peer review and publication. The journals are led by an international team of Editors-in-Chief and Associate Editors who are all active researchers in their fields. Journal of Materials Chemistry A, B & C are separated by the intended application of the material studied. Broadly, applications in energy and sustainability are of interest to Journal of Materials Chemistry A, applications in biology and medicine are of interest to Journal of Materials Chemistry B, and applications in optical, magnetic and electronic devices are of interest to Journal of Materials Chemistry C. More than one Journal of Materials Chemistry journal may be suitable for certain fields and researchers are encouraged to submit their paper to the journal that they feel best fits for their particular article. Example topic areas within the scope of Journal of Materials Chemistry A are listed below. This list is neither exhaustive nor exclusive. Artificial photosynthesis Batteries Carbon dioxide conversion Catalysis Fuel cells Gas capture/separation/storage Green/sustainable materials Hydrogen generation Hydrogen storage Photocatalysis Photovoltaics Self-cleaning materials Self-healing materials Sensors Supercapacitors Thermoelectrics Water splitting Water treatment