As a promising and practical way to decrease CO₂ emissions, the conversion of CO₂ to value-added chemicals has received significant recent attention. The activation of CO₂ on catalyst surfaces might proceed via a chemisorption state with a bent CO₂ configuration, in which substrate electrons are transferred into the antibonding orbital of the CO₂ adsorbate. Based on density functional theory calculations, we present an extensive survey of CO₂ chemisorption and dissociation on flat and stepped surfaces of several transition metals. The binding energy of the chemisorbed CO₂ is closely correlated with the extent of electron transfer from the metal to CO₂, as evidenced by a linear relationship found between the CO₂ adsorption energy and its Bader charge. Transition state scaling (TSS) correlations between binding energies of transition states and binding energies of either initial or final states are found to exist for the dissociation of the chemisorbed CO₂ on flat and stepped surfaces, which can be used to predict the efficacies of the catalysts. Our results show that defect sites at stepped surfaces have a strong influence on CO₂ chemical activation and dissociation.

作为减少CO ₂排放的一种有前途且实用的方法，将CO 2 转化为_增值化学品最近受到了极大的关注。_{CO 2}在催化剂表面的活化可能通过具有弯曲CO ₂构型的化学吸附状态进行，其中底物电子被转移到CO ₂吸附物的反键轨道中。基于密度泛函理论计算，我们对几种过渡金属的平面和阶梯表面上的 CO _{2化学吸附和解离进行了广泛调查。}化学吸附的 CO ₂的结合能与电子从金属转移到 CO 的程度密切相关_{如图2所示，CO 2}吸附能与其巴德电荷之间存在线性关系。发现过渡态结合能与初始或最终状态结合能之间存在过渡态标度 (TSS) 相关性，用于化学吸附 CO ₂在平坦和阶梯表面上的解离，可用于预测催化剂。我们的结果表明，阶梯表面的缺陷位点对CO ₂化学活化和解离有很大的影响。