Capture and activation of CO₂ play a crucial role in its catalytic transformation into fuels and chemicals. Here a two-dimensional SiN₄C₄ monolayer material with dispersed SiN₄ sites was predicted to have high stability and unusual capability to tackle the inertia of CO₂ by extensive first-principles calculations and ab initio molecular dynamics simulations. The chemical adsorption of CO₂ on the SiN₄C₄ monolayer sheet is favorable thermodynamically and almost barrier free. Such an activation mechanism under mild conditions comes from the remarkable charge transfer interactions between CO₂ and the SiN₄ moiety, where an approximately planar tetracoordinate silicon behaves as a strong electron donor. Application of an external electric field may remarkably influence the adsorption and activation of CO₂, while it has no effect on CH₄, N₂, and H₂, which may open up an efficient and promising avenue for the separation and activation of CO₂. Furthermore, the metal-free SiN₄C₄ monolayer exhibits good activity toward CO₂ electroreduction to HCOOH, CH₃OH, and CH₄ with low limiting potentials of −0.46 V.

中文翻译：

---

解决CO ₂的惰性：无金属SiN ₄ C ₄单层薄板上的活化和电还原

CO _2的捕获和活化在其催化转化为燃料和化学品方面起着至关重要的作用。在这里，通过广泛的第一性原理计算和从头算分子动力学模拟，预测了具有分散的SiN ₄位点的二维SiN ₄ C ₄单层材料具有很高的稳定性和非凡的能力来应对CO ₂的惯性。在SiN ₄ C ₄单层片材上化学吸附CO ₂是热力学上有利的，并且几乎没有障碍。这种在温和条件下的激活机制来自CO ₂和SiN之间显着的电荷转移相互作用₄部分，其中近似平面的四配位硅表现为强电子给体。施加外部电场可能会显着影响CO ₂的吸附和活化，而对CH ₄，N ₂和H ₂没有影响，这可能为CO ₂的分离和活化开辟一条有效而有希望的途径。。此外，无金属的SiN ₄ C ₄单层对-CO ₂电还原为HCOOH，CH ₃ OH和CH ₄表现出良好的活性，且极限电位为-0.46V。