Mandal Tanmoy, Kumar Abhishek, Panda Jatin, Kumar Dutta Tapas, Choudhury Joyanta
Organometallics & Smart Materials Laboratory, Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal, 462066, Madhya Pradesh, India.
Functional Materials Laboratory, Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal, 462066, Madhya Pradesh, India.
Angew Chem Int Ed Engl. 2023 Dec 11;62(50):e202314451. doi: 10.1002/anie.202314451. Epub 2023 Nov 8.
In recent times, heterogenization of homogeneous molecular catalysts onto various porous solid support structures has attracted significant research focus as a method for combining the advantages of both homogeneous as well as heterogeneous catalysis. The design of highly efficient, structurally robust and reusable heterogenized single-site catalysts for the CO hydrogenation reaction is a critical challenge that needs to be accomplished to implement a sustainable and practical CO -looped renewable energy cycle. This study demonstrated a heterogenized catalyst [Ir-HCP-(B/TPM)] containing a molecular Ir-abnormal N-heterocyclic carbene (Ir-aNHC) catalyst self-supported by hierarchical porous hyper-crosslinked polymer (HCP), in catalytic hydrogenation of CO to inorganic formate (HCO ) salt that is a prospective candidate for direct formate fuel cells (DFFC). By employing this unique and first approach of utilizing a directly knitted HCP-based organometallic single-site catalyst for CO -to-HCO in aqueous medium, extremely high activity with a single-run turnover number (TON) up to 50816 was achieved which is the highest so far considering all the heterogeneous catalysts for this reaction in water. Additionally, the catalyst featured excellent reusability furnishing a cumulative TON of 285400 in 10 cycles with just 1.6 % loss in activity per cycle. Overall, the new catalyst displayed attributes that are important for developing tangible catalysts for practical applications.
近年来，将均相分子催化剂负载于各种多孔固体载体结构上的多相化方法，作为一种结合均相催化和多相催化优点的手段，已吸引了大量研究关注。设计用于CO加氢反应的高效、结构稳健且可重复使用的多相化单中心催化剂，是实现可持续且实用的CO循环可再生能源循环所需攻克的一项关键挑战。本研究展示了一种多相化催化剂[Ir-HCP-(B/TPM)]，其包含由分级多孔超交联聚合物（HCP）自负载的分子铱反常N-杂环卡宾（Ir-aNHC）催化剂，该催化剂用于将CO催化氢化为无机甲酸盐（HCO ），无机甲酸盐是直接甲酸燃料电池（DFFC）的一种潜在候选物。通过采用这种独特的、首次将基于HCP的直接编织有机金属单中心催化剂用于水相中CO转化为HCO 的方法，实现了极高的活性，单次运行的周转数（TON）高达50816，就水相中该反应的所有多相催化剂而言，这是目前为止最高的。此外，该催化剂具有出色的可重复使用性，在10个循环中累积TON达到285400，每个循环的活性损失仅为1.6%。总体而言，这种新型催化剂展现出了对于开发实际应用的实用催化剂而言很重要的特性。
