Zheng Mei, Li Yi, Ding Kaining, Zhang Yongfan, Chen Wenkai, Lin Wei
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, P. R. China.
Phys Chem Chem Phys. 2020 Oct 7;22(38):21872-21880. doi: 10.1039/d0cp03824e.
On the basis of the electron "acceptance-donation" concept, a boron decorated melon-based carbon nitride (CN) is studied as a metal-free photocatalyst to efficiently reduce N2 to NH3 under visible light irradiation. The results revealed that a boron-interstitial (Bint)-decorated melon-based CN has an outstanding N2 reduction capacity through the enzymatic mechanism with a rather low overpotential (0.32 V). The excellent efficiency and selectivity of Bint-decorated melon-based CN in N2 reduction reaction (NRR) are attributed to the concentrated spin polarization on the B atom, the significant enhancement of visible and infrared light absorption, and the effective inhibition of the competitive hydrogen evolution reaction (HER). Importantly, B-doped melon-based CN has been successfully synthesized in the experiments, so obtaining Bint-decorated melon is promising, while proton transfer from the -NH2 group in CN to the B atom surely will affect the functionality of the catalyst through deactivation of the N2 adsorption site. Our study provides a novel single atom metal-free photocatalyst with high efficiency for NRR, which is conducive to the sustainable synthesis of ammonia.
基于电子“接受-捐赠”概念，研究了一种硼修饰的类石墨相氮化碳（CN）作为无金属光催化剂，在可见光照射下将N₂高效还原为NH₃。结果表明，硼间隙（Bint）修饰的类石墨相CN通过酶促机制具有出色的N₂还原能力，过电位相当低（0.32 V）。Bint修饰的类石墨相CN在N₂还原反应（NRR）中的优异效率和选择性归因于B原子上的集中自旋极化、可见光和红外光吸收的显著增强以及对竞争性析氢反应（HER）的有效抑制。重要的是，实验中已成功合成了B掺杂的类石墨相CN，因此获得Bint修饰的类石墨相是有前景的，而质子从CN中的-NH₂基团转移到B原子肯定会通过使N₂吸附位点失活来影响催化剂的功能。我们的研究提供了一种用于NRR的高效新型无金属单原子光催化剂，这有利于氨的可持续合成。
