Activity and selectivity of N2 fixation on B doped g-C9N10: a density functional theory study
Activity and selectivity of N2 fixation on B doped g-C9N10: a density functional theory study
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B 掺杂 g-C9N10 上 N2 固定的活性和选择性：密度泛函理论研究
DOI：
10.1039/d2tc02041f
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发表时间：
2022
影响因子：
6.4
通讯作者：
Morikawa Yoshitada
中科院分区：
文献类型：
--
作者：
Wang Yuelin;Pham Thanh Ngoc;Yan Likai;Morikawa Yoshitada
在温和的条件下，电催化或电催化驱动的N2固定制氨是一种很有前途的方法，可以取代工业上的Haber-Bosch工艺。最近的研究表明，硼原子由于其路易斯酸特性可以有效地活化N2，受此启发，本文研究了N2在B掺杂的g-C9 N10（具有三种不同掺杂构型的新型氮化碳材料）上的吸附和固定机制，即B在C（BC 1）和N（BN 1）位点的取代和B锚定的g-C9 N10（BA）。我们发现，由于N2的化学吸附能力，氮还原反应（N2 RR）只能在BN 1和BA上进行。BN 1和BA掺杂的g-C9 N10的最佳N2 RR机制是混合I机制，混合I低限制电位分别为−0.62 V和−0.44 V。然而，在BA掺杂的g-C9 N10中，由于H吸附比N2吸附更强的H中毒效应将抑制N2 RR选择性。相比之下，由于较弱的H吸附能力，BN 1掺杂的g-C9 N10的H中毒可以被有效地抑制，从而提高对N2 RR的选择性。电子结构分析表明，H-B相互作用是由B 2 py和H 1 s轨道的杂化引起的，而在BN 1中，由于2 py轨道的占据较少，这种杂化作用被抑制.我们的工作为更多的实验工作提供了有益的指导，以探索更多的B掺杂的氮化碳材料的N2固定领域。
N2 fixation driven by photocatalysis or electrocatalysis to produce ammonia under mild conditions is a promising method to replace the industrial Haber–Bosch process. Inspired by recent studies, which showed that the boron atom can effectively activate N2 due to its Lewis-acid characteristics, we herein investigate the mechanism of N2 adsorption and fixation on B doped g-C9N10, a new carbon nitride material, with three different doping configurations, namely substitutions of B at C (BC1) and N (BN1) sites and B anchored g-C9N10 (BA) by density functional theory calculations. We found that the nitrogen reduction reaction (N2RR) can only proceed on BN1 and BA due to N2 chemisorption ability. The optimal N2RR mechanism of the BN1 and BA doped g-C9N10 is the mix I mechanism with mix I low limiting potential of −0.62 V and −0.44 V, respectively. However, the H poisoning effect at BA doped g-C9N10 due to stronger H adsorption than N2 adsorption will suppress N2RR selectivity. In contrast, H poisoning at BN1 doped g-C9N10 can be effectively inhibited due to weaker H adsorption ability, thereby improving the selectivity for the N2RR. The electronic structure analysis indicates that the H–B interaction arises from hybridization between B 2py and H 1s orbitals, which is suppressed in the case of BN1 because the 2py orbital of is less populated BN1. Our work provides useful guidance for more experimental works to explore more B doped carbon nitride materials for the N2 fixation field.