通过单原子催化剂的 n-p 对偶工程调制光催化二氧化碳还原反应

Nanomaterials Pub Date : 2024-07-11 DOI:10.3390/nano14141183
Guowei Yin, Chunxiao Zhang, Yundan Liu, Yuping Sun, Xiang Qi
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引用次数: 0

摘要

过渡金属(TM)单原子催化剂(SAC)已广泛应用于光催化二氧化碳还原。本研究通过第一原理计算,引入了正负掺杂工程,以解释二维(2D)双铋氧卤化物基阴极上光催化还原 CO2 的调制。正负掺杂是通过带负电的 TM SAC 与掺杂剂-缺陷对中带正电的 Cl 空位(VCl)之间的库仑相互作用而建立的。根据带电缺陷的形成能,Fe、Co 和 Ni SAC 的中性掺杂剂-缺陷对(PTM0)以及基于 Cu SAC 的-1e 电荷态对(PCu-1)是稳定的。n-p 编码掺杂的静电吸引力通过中和带相反电荷的 VCl 缺陷和 TM 掺杂,增强了 TM SAC 的稳定性和可溶性。n-p 编码掺杂稳定了 TM SAC 周围的电子积累。积累的电子改变了 d 轨道的排列,并使 d 带中心向费米级移动,从而提高了基于 d 带理论的 TM SAC 的还原能力。除了 n-p codoping 的静电吸引外,PCu-1 还在 Cu SACs 周围积累了额外的电子,形成了半占位的 dx2-y2 态,从而进一步上移了 d 带中心,提高了光催化还原 CO2 的能力。Cl 多空位的逸散性限制了带有 Cl 多空位的 n 对的浓度(PTM@nCl(n > 1))。PTM@nCl (n > 1) 周围带正电的中心会屏蔽电荷转移到 CO2 分子,从而阻碍 CO2 还原。
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Modulation of Photocatalytic CO2 Reduction by n–p Codoping Engineering of Single-Atom Catalysts
Transition metal (TM) single-atom catalysts (SACs) have been widely applied in photocatalytic CO2 reduction. In this work, n–p codoping engineering is introduced to account for the modulation of photocatalytic CO2 reduction on a two-dimensional (2D) bismuth-oxyhalide-based cathode by using first-principles calculation. n–p codoping is established via the Coulomb interactions between the negatively charged TM SACs and the positively charged Cl vacancy (VCl) in the dopant–defect pairs. Based on the formation energy of charged defects, neutral dopant–defect pairs for the Fe, Co, and Ni SACs (PTM0) and the −1e charge state of the Cu SAC-based pair (PCu−1) are stable. The electrostatic attraction of the n–p codoping strengthens the stability and solubility of TM SACs by neutralizing the oppositely charged VCl defect and TM dopant. The n–p codoping stabilizes the electron accumulation around the TM SACs. Accumulated electrons modify the d-orbital alignment and shift the d-band center toward the Fermi level, enhancing the reducing capacity of TM SACs based on the d-band theory. Besides the electrostatic attraction of the n–p codoping, the PCu−1 also accumulates additional electrons surrounding Cu SACs and forms a half-occupied dx2−y2 state, which further upshifts the d-band center and improves photocatalytic CO2 reduction. The metastability of Cl multivacancies limits the concentration of the n–p pairs with Cl multivacancies (PTM@nCl (n > 1)). Positively charged centers around the PTM@nCl (n > 1) hinders the CO2 reduction by shielding the charge transfer to the CO2 molecule.
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