Tian Jiaqi, Hou Lei, Xia Weizhi, Wang Zi, Tu Yusong, Pei Wei, Zhou Si, Zhao Jijun
College of Physics Science and Technology, Yangzhou University, Yangzhou 225009, China.
School of Physics, South China Normal University, Guangzhou 510631, China.
Phys Chem Chem Phys. 2023 Oct 25;25(41):28533-28540. doi: 10.1039/d3cp03473a.
Artificial photosynthesis is a crucial reaction that addresses energy and environmental challenges by converting CO into fuels and value-added chemicals. However, efficient catalytic activity using earth-abundant materials can be challenging due to intrinsic limitations. Herein, we explore neutral (TiO) ( = 1-6) atomic clusters for CO hydrogenation comprehensive calculations combined with time-dependent functional theory. Our results show that these (TiO) clusters exhibit outstanding thermodynamic stabilities and decent surficial activities for CO activation and H dissociation, both of which possess kinetic barriers down to 0-0.74 eV. We establish a relationship between the binding strength of *CO species and electron characterization for these (TiO) clusters. These clusters, which have a wide energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccpied molecular orbital (LUMO) that allows them to harvest the solar light in the ultraviolet regime, enabling efficient catalysis for driving the catalysis of CO conversion. They provide exclusive reaction channels and high selectivity for yielding HCOOH products the carboxyl mechanism, involving the kinetic barrier of the limiting step of 0.74-1.25 eV. We also investigated the substrate effect on supported (TiO) clusters, with non-metallic substrates featuring inert surfaces serving as suitable options for anchoring (TiO) clusters while preserving their intrinsic activity and selectivity. These computational results have significant implications not only for meeting energy demands but also for mitigating carbon emissions by utilizing CO as an alternative feedstock rather than considering it solely as a greenhouse gas.
人工光合作用是一种关键反应，通过将一氧化碳转化为燃料和高附加值化学品来应对能源和环境挑战。然而，由于内在限制，使用储量丰富的材料实现高效催化活性可能具有挑战性。在此，我们结合含时密度泛函理论进行综合计算，探索用于一氧化碳加氢的中性（TiO）（n = 1 - 6）原子团簇。我们的结果表明，这些（TiO）团簇表现出出色的热力学稳定性以及对一氧化碳活化和氢解离的良好表面活性，这两者的动力学势垒低至0 - 0.74电子伏特。我们建立了这些（TiO）团簇的*CO物种结合强度与电子特性之间的关系。这些团簇在最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）之间具有较宽的能隙，这使它们能够在紫外区域捕获太阳光，从而实现驱动一氧化碳转化催化的高效催化。它们为生成甲酸产物提供了独特的反应通道和高选择性——通过羧基机理，其限速步骤的动力学势垒为0.74 - 1.25电子伏特。我们还研究了负载型（TiO）团簇的底物效应，具有惰性表面的非金属底物是锚定（TiO）团簇的合适选择，同时能保持其固有活性和选择性。这些计算结果不仅对满足能源需求具有重要意义，而且对于通过将一氧化碳用作替代原料而非仅仅将其视为温室气体来减少碳排放也具有重要意义。
