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将双金属硼化物与含有氰胺缺陷的石墨相氮化碳相结合用于高效光催化固氮。

Integrating bimetallic borides with g-CN containing cyanamide defects for efficient photocatalytic nitrogen fixation.

作者信息

Li Di, Li Qin, Zhang Qiong, Yang Ran, Ye Qianjin, Tian Dan, Jiang Deli

机构信息

Institute for Energy Research, Jiangsu University, Zhenjiang 212013, China.

School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China.

出版信息

J Colloid Interface Sci. 2024 Oct 15;672:631-641. doi: 10.1016/j.jcis.2024.05.238. Epub 2024 Jun 1.

Abstract

The sustainable generation of ammonia by photocatalytic nitrogen fixation under mild conditions is fascinating compared to conventional industrial processes. Nevertheless, owing to the low charge transfer efficiency, the insufficient light absorption capacity and limited active sites of the photocatalyst cause the difficult adsorption and activation of N molecules, thereby resulting in a low photocatalytic conversion efficiency. Herein, a novel bimetallic CoMoB nanosheets (CoMoB) co-catalyst modified carbon nitride with dual moiety defects (CN-TH) Schottky junction photocatalyst is designed for photocatalytic nitrogen reduction reaction (NRR). The photocatalytic nitrogen reduction rate of the optimized CoMoB/CN-TH photocatalyst is 4.81 mM·g·h, which is 6.2 and 2.2 times higher than carbon nitride (CN) (0.78 mM·g·h) and CN-TH (2.21 mM·g·h), respectively. The excellent photocatalytic NRR performance is ascribed not only to the introduction of dual moiety defects (cyano and cyanamide groups) that extends the visible light absorption range and promotes exciton polarization dissociation, but also to the formation of interfacial electric field between CoMoB and CN-TH, which effectively facilitates the interfacial charge transfer. Thus, the synergistic interaction between CN-TH and CoMoB further increases the electron numble of CoMoB active sites, which effectively strengthens the adsorption and activation of N and weakens the NN triple bond, thereby enhancing the photocatalytic NRR activity. This work highlights the introduced dual moiety defects and bimetallic CoMoB co-catalyst to synergistically enhance the photocatalytic nitrogen reduction performance.

摘要

与传统工业过程相比,在温和条件下通过光催化固氮可持续生成氨具有吸引力。然而,由于电荷转移效率低,光催化剂的光吸收能力不足和活性位点有限,导致N分子的吸附和活化困难,从而导致光催化转化效率低。在此,设计了一种新型双金属CoMoB纳米片(CoMoB)共催化剂修饰的具有双部分缺陷(CN-TH)肖特基结光催化剂的氮化碳,用于光催化氮还原反应(NRR)。优化后的CoMoB/CN-TH光催化剂的光催化氮还原速率为4.81 mM·g·h,分别比氮化碳(CN)(0.78 mM·g·h)和CN-TH(2.21 mM·g·h)高6.2倍和2.2倍。优异的光催化NRR性能不仅归因于引入了双部分缺陷(氰基和氰胺基),其扩展了可见光吸收范围并促进了激子极化解离,还归因于CoMoB和CN-TH之间形成的界面电场,这有效地促进了界面电荷转移。因此,CN-TH和CoMoB之间的协同相互作用进一步增加了CoMoB活性位点的电子数量,有效地增强了N的吸附和活化并削弱了NN三键,从而提高了光催化NRR活性。这项工作突出了引入的双部分缺陷和双金属CoMoB共催化剂协同增强光催化氮还原性能。

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