钙钛矿(结构)
卤化物
化学
密度泛函理论
离子键合
过电位
带隙
催化作用
吉布斯自由能
电子结构
物理化学
结晶学
计算化学
无机化学
离子
物理
热力学
凝聚态物理
生物化学
电极
电化学
有机化学
作者
Yuzhen Fang,Shuangxin Dou,Qianqian Shang,Dongting Wang,Junhai Liu,Xiangjin Kong
标识
DOI:10.1016/j.commatsci.2022.111576
摘要
The halide perovskites (CsPbBr3-xIx) with excellent photoelectric properties can be used as electrocatalysts for nitrogen reduction reaction (NRR). Their electronic structures and activation mechanism of the adsorbed species for N2-to-NH3 based on CsPbBr3-xIx (x = 0, 1, 2, 3) have been investigated using first principle calculations based on density functional theory (DFT). The calculated results reveal that CsPbBr3-xIx system can keep the stable perovskite structure as the tolerance factors (t) are 0.8621, 0.8583, 0.8546 and 0.8512 for x = 0, 1, 2 and 3, respectively. The stability, ionic property and energy gap values of CsPbBr3-xIx perovskite decrease with the increase of I doping amount. CsPbBr2I and CsPbBrI2 display the suitable d-band center (−1.792 eV and −1.8311 eV), the lower Gibbs free energy (1.16 eV and 1.13 eV), and the smaller overpotential (η = 1.00 eV and 0.97 eV) for the pronation of *N2 to produce *N2H species, which is the rate-determining step for the NRR. The DFT results indicate the order of NRR performance is CsPbBrI2 > CsPbBr2I > CsPbI3 > CsPbBr3. Compared the alternative, enzymatic and distal reaction paths based on the catalyst of CsPbBrI2 [1 0 0], the distal path has the lowest energy barrier, and it can be concluded that the distal path would be the feasible NRR reaction mechanism for CsPbBr3-xIx system.
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