鑭系金屬錯合物催化 CO2 羧化之反應機制探討

Abstract

隨著全球工業化進程的加速，人類活動大量釋放二氧化碳（CO₂）進入大氣層，導致全球暖化和極端氣候等一系列嚴重的環境問題。因此，需要尋找有效的技術和方法來減少大氣中的二氧化碳濃度，緩解其對環境的負面影響。參考自然界中，植物透過葉綠體行光合作用將大氣中的二氧化碳轉化為葡萄糖儲存的反應，葉綠體內的二磷酸核酮糖羧化酶（RuBisCo）在卡爾文循環中通過催化二氧化碳CO₂與核酮糖-1,5-雙磷酸（RuBP）的反應生成3-磷酸甘油酸（3-PGA），展示了自然界中二氧化碳固定的高效性和專一性，提供了一個理想的生物模板，用於設計和開發有效的二氧化碳反應催化劑。最近的研究表明，一種新型的雙(酰胺)稀土金屬胺基化合物{LRE[N(SiMe3)2]·THF}2 顯示出在常壓下高效催化末端炔烴與CO₂進行直接羧化反應的能力。特別是，基於Nd的化合物表現出最優的反應活性，其在溫和條件下可合成各種丙炔酸。這種稀土金屬胺基化合物與RuBisCo在卡爾文循環中的催化機制相似，因此，我們透過計算化學和分子模擬技術，進一部探討催化二氧化碳與末端炔烴羧化的反應機制和反應路徑。以便於未來優化催化劑的性能，最大限度地提高其對CO₂的選擇性和反應效率。研究基於RuBisCo和卡爾文循環機理的二氧化碳反應催化劑，不僅為應對全球暖化和環境污染提供了新的技術途徑，也在推動能源轉型和可持續發展方面展現出巨大的應用潛力。With the acceleration of global industrialization, human activities have released vast amounts of carbon dioxide (CO₂) into the atmosphere, leading to global warming and a series of severe environmental issues such as extreme weather. Therefore, it is essential to explore effective technologies and methods to reduce atmospheric CO₂ concentrations and mitigate its negative impact on the environment. Inspired by nature, plants convert atmospheric CO₂ into glucose through photosynthesis in chloroplasts. Within chloroplasts, the enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCo) catalyzes the reaction between CO₂ and ribulose-1,5-bisphosphate (RuBP) in the Calvin cycle to produce 3-phosphoglycerate (3-PGA), demonstrating the high efficiency and specificity of CO₂ fixation. This provides an ideal biological model for designing and developing effective CO₂ reactive catalysts.Recent studies have shown that a novel type of bis(amido) rare-earth metal amine complex, {LRE[N(SiMe₃)₂]·THF}₂, exhibits the ability to efficiently catalyze the direct carboxylation of terminal alkynes with CO₂ under atmospheric pressure. In particular, the Nd-based complex shows the highest catalytic activity, enabling the synthesis of various propiolic acids under mild conditions. This rare-earth metal amine complex exhibits a catalytic mechanism similar to that of RuBisCo in the Calvin cycle. Therefore, we utilize computational chemistry and molecular simulation techniques to further investigate the reaction mechanism and pathway of CO₂ carboxylation with terminal alkynes. This will facilitate future optimization of the catalyst’s performance to maximize its selectivity and efficiency toward CO₂.Developing CO₂ reaction catalysts inspired by RuBisCo and the Calvin cycle not only offers a new technological approach to addressing global warming and environmental pollution but also demonstrates significant potential in promoting energy transition and sustainable development.