Mohanta Manish Kumar, Jena Puru
Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA.
Nanoscale. 2025 Apr 3;17(14):8505-8514. doi: 10.1039/d4nr03795b.
The conversion of CO into valuable chemical products has garnered significant interest due to the pressing need for sustainable solutions. Central to achieving this goal is the development of efficient and cost-effective catalysts. Although Cu is one of the most promising materials for CO reduction, it lacks selectivity. In this study, we explore the effect of doping on the binding affinity and activation of CO by focusing on XCu clusters, where X represents 3d and 4d transition metal atoms. By employing a multi-scale theoretical approach that integrates the artificial bee colony algorithm, an extended tight binding model, and density functional theory (DFT), the lowest energy geometries of XCu clusters were determined, revealing that the dopant X-atoms favour endohedral positions, preserving a cage-like structure and maximizing their coordination with the outer Cu-atoms. A thorough analysis of the structural, electronic, and magnetic properties elucidates the varying capabilities of these clusters for the electrochemical reduction of CO to CO. Doping of transition metal atoms is found to significantly modify the electronic and magnetic properties of the clusters, enhancing their reactivity towards CO. A significant reduction of about 20% in overpotential for CO reduction is observed in doped clusters compared to the pure Cu cluster. An empirical formula is proposed by fitting the DFT data using ordinary least squares (OLS) regression. This comprehensive study provides fundamental insights into the potential of bimetallic copper clusters for CO activation and reduction, emphasizing their role in advancing catalytic processes for sustainable chemical production.
由于对可持续解决方案的迫切需求，将一氧化碳转化为有价值的化学产品已引起了广泛关注。实现这一目标的核心是开发高效且具有成本效益的催化剂。尽管铜是用于一氧化碳还原最有前景的材料之一，但它缺乏选择性。在本研究中，我们通过关注XCu团簇（其中X代表3d和4d过渡金属原子）来探索掺杂对一氧化碳结合亲和力和活化的影响。通过采用一种多尺度理论方法，该方法整合了人工蜂群算法、扩展紧束缚模型和密度泛函理论（DFT），确定了XCu团簇的最低能量几何结构，结果表明掺杂剂X原子倾向于占据内包位置，保持笼状结构并使其与外部铜原子的配位最大化。对这些团簇的结构、电子和磁性性质进行的全面分析阐明了它们将一氧化碳电化学还原为一氧化碳的不同能力。发现过渡金属原子的掺杂会显著改变团簇的电子和磁性性质，增强它们对一氧化碳的反应性。与纯铜团簇相比，掺杂团簇中一氧化碳还原的过电位显著降低了约20%。通过使用普通最小二乘法（OLS）回归拟合DFT数据，提出了一个经验公式。这项全面的研究为双金属铜团簇在一氧化碳活化和还原方面的潜力提供了基本见解，强调了它们在推进可持续化学生产催化过程中的作用。
