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通过Ru (II) 和Os (II) 八面体复合体将CO₂光催化转化为CO:一个DFT/TDDFT研究

Athanassios C Tsipis¹, Antonia A Sarantou¹

¹Laboratory of Inorganic Chemistry, Department of Chemistry, University of Ioannina, 45110, Greece. attsipis@uoi.gr.

Dalton transactions (Cambridge, England : 2003)

|March 27, 2024

概括

这项研究揭示了使用[(en) M(CO) 3Cl]复合体进行光催化二氧化碳减排的两个途径. 三甲胺 (TEOA) 作为电子捐赠体,通过DFT计算促进CO的产生.

科学领域:

光催化作用的光催化
有机金属化学有机金属化学
计算化学计算化学

背景情况:

减少二氧化碳 (CO2) 对可持续能源至关重要.
复合物 (M = Ru, Os) 是减少二氧化碳的潜在催化剂.
了解反应机制是优化催化效率的关键.

研究的目的:

阐明二氧化碳光催化降解的反应机制.
调查[MCO3Cl]复合物和三甲胺 (TEOA) 的作用.
用计算方法比较两个不同的催化路径.

主要方法:

密度函数理论 (DFT) 和时间依赖DFT (TDDFT) 的计算.
对几何和自由能反应概况的分析.
对光物理性质和激发状态的降低潜力的研究.

主要成果:

确定了两个反应途径,两者都由由TEOA通过减温火生成的17电子中间体启动.
路径1涉及TEOA离子结合和CO2插入,然后是质子和CO释放.
途径2涉及中介物直接捕获二氧化碳,然后进行质子化和减少,以产生二氧化碳.

结论:

这两种途径都有效地将二氧化碳转化为二氧化碳,TEOA充当牺牲电子捐赠者.
质子捐赠者的选择会影响反应概况,而溶剂的影响是最小的.
研究的复合物在紫外线区域吸收,并确定了特定的激发状态减少潜力.

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