Regulating the selectivity of CO₂ photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the selectivity of CO₂ photoreduction. Prototypical ZnCo₂O₄ atomic layers with/without Ni-doping were first synthesized. Density functional theory calculations reveal that introducing Ni atoms creates several new energy levels and increases the density-of-states at the conduction band minimum. Synchrotron radiation photoemission spectroscopy demonstrates that the band structures are suitable for CO₂ photoreduction, while the surface photovoltage spectra demonstrate that Ni doping increases the carrier separation efficiency. In situ diffuse reflectance Fourier transform infrared spectra disclose that the CO₂^·− radical is the main intermediate, while temperature-programed desorption curves reveal that the ZnCo₂O₄ atomic layers with/without Ni doping favor the respective CO and CH₄ desorption. The Ni-doped ZnCo₂O₄ atomic layers exhibit a 3.5-time higher CO selectivity than the ZnCo₂O₄ atomic layers. This work establishes a clear correlation between elemental doping and selectivity regulation for CO₂ photoreduction, opening new possibilities for tailoring solar-driven photocatalytic behaviors.

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调节CO _2光还原的选择性特别具有挑战性。在这里，我们提出了有/无元素掺杂的原子层的理想模型，以研究掺杂工程对调整CO _2光还原选择性的影响。首先合成了具有/不具有Ni掺杂的典型ZnCo ₂ O ₄原子层。密度泛函理论计算表明，引入Ni原子会创建几个新的能级，并在导带最小值处增加状态密度。同步辐射光发射光谱表明该能带结构适用于CO ₂表面光电压光谱表明，Ni掺杂可提高载流子分离效率。原位漫反射傅里叶变换红外光谱中公开了该CO ₂ ^{· -}自由基是主要的中间，而温度设定为，脱附曲线揭示，碳酸锌₂ ö ₄与/原子层没有添加Ni的掺杂有利于各自CO和CH ₄解吸。Ni掺杂的ZnCo ₂ O ₄原子层的CO选择性是ZnCo ₂ O ₄的3.5倍原子层。这项工作建立了元素掺杂与CO _2光还原选择性调节之间的明确联系，为定制太阳能驱动的光催化行为开辟了新的可能性。

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