Azofra Luis Miguel, MacFarlane Douglas R, Sun Chenghua
ARC Centre of Excellence for Electromaterials Science (ACES), School of Chemistry, Faculty of Science, Monash University, Clayton, VIC 3800, Australia.
Phys Chem Chem Phys. 2016 Jul 21;18(27):18507-14. doi: 10.1039/c6cp02453j. Epub 2016 Jun 24.
Graphene-like carbon nitride (g-C3N4), a metal-free 2D material that is of interest as a CO2 reduction catalyst, is stabilised by corrugation in order to minimise the electronic repulsions experienced by the N lone pairs located in their structural holes. This conformational change not only stabilises the Fermi level in comparison with the totally planar structure, but also increases the potential depth of the π-holes, representing the active sites where the catalytic CO2 conversion takes place. Finally, as a result of corrugation, our DFT-D3 calculations indicate that the reaction Gibbs free energy for the first H(+)/e(-) addition decreases by 0.49 eV with respect to the totally planar case, suggesting that corrugation not only involves the material's stabilisation but also enhances the catalytic performance for the selective production of CO/CH3OH.
类石墨烯氮化碳（g-C3N4）是一种无金属二维材料，作为二氧化碳还原催化剂备受关注，它通过波纹状结构实现稳定，以最小化位于其结构孔洞中的氮孤对电子所经历的电子排斥。这种构象变化不仅与完全平面结构相比稳定了费米能级，还增加了π-孔洞的势阱深度，而π-孔洞是催化二氧化碳转化发生的活性位点。最后，由于波纹状结构，我们的DFT-D3计算表明，相对于完全平面的情况，第一次H(+)/e(-)加成的反应吉布斯自由能降低了0.49 eV，这表明波纹状结构不仅涉及材料的稳定化，还提高了选择性生产CO/CH3OH的催化性能。
