Jana Anupam, Saha Sinthia, Mondal Suvendu Sekhar, Kaur Navjot, Bhunia Asamanjoy
Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata, 700032, India.
Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, 14476, Potsdam, Germany.
Chem Asian J. 2025 Mar 17;20(6):e202401401. doi: 10.1002/asia.202401401. Epub 2025 Jan 8.
The development of robust, efficient, and cost-effective heterogeneous photocatalysts for visible light-driven CO reduction continues to be a significant challenge in the quest for sustainable energy solutions. As a result, increasing attention is being directed towards the exploration of high-performance photocatalysts capable of converting CO into valuable chemical feedstocks. In context to this, Imidazolate Frameworks Potsdam (IFPs), a class of metal-organic frameworks (MOFs), can be a promising candidate for CO photoreduction due to their ease of synthesis, use of low-cost, earth-abundant metals, and high chemical and thermal stability. In this study, we report the solvothermal synthesis of Zn(II)- and Co(II)-based IFPs, specifically IFP-1(Zn) and IFP-5(Co), for photocatalytic CO reduction. Moreover, we demonstrate the enhanced photocatalytic activity of redox-innocent Zn-based IFP-1 by partially substituting Zn(II) with redox-active Co(II) in IFP-1(Zn), resulting in the formation of a bimetallic photocatalyst, IFP-1(Zn/Co). The metal-exchanged IFP-1(Zn/Co) exhibited significantly improved CO evolution (637 μmol g in 1 hour), compared to the pristine IFP-1(Zn) (29 μmol g). Notably, among all the prepared photocatalysts, IFP-5(Co) outperformed both the systems, achieving a CO evolution of 1174 μmol g within 1 hour, due to the presence of catalytic cobalt sites. In addition, through the combination of photophysical and electrochemical studies, along with DFT calculations, we have proposed a plausible mechanism for the photocatalytic CO reduction.
开发坚固、高效且经济高效的用于可见光驱动CO还原的非均相光催化剂，在寻求可持续能源解决方案的过程中仍然是一项重大挑战。因此，越来越多的注意力正转向探索能够将CO转化为有价值化学原料的高性能光催化剂。在此背景下，咪唑盐框架波茨坦（IFPs），一类金属有机框架（MOFs），由于其易于合成、使用低成本且储量丰富的金属以及高化学和热稳定性，可能是CO光还原的有前途的候选者。在本研究中，我们报告了用于光催化CO还原的基于Zn(II)和Co(II)的IFPs，即IFP-1(Zn)和IFP-5(Co)的溶剂热合成。此外，我们通过在IFP-1(Zn)中用氧化还原活性的Co(II)部分替代Zn(II)，证明了氧化还原惰性的基于Zn的IFP-1的增强光催化活性，从而形成了双金属光催化剂IFP-1(Zn/Co)。与原始的IFP-1(Zn)（29 μmol g）相比，金属交换的IFP-1(Zn/Co)表现出显著改善的CO析出（1小时内637 μmol g）。值得注意的是，在所有制备的光催化剂中，IFP-5(Co)的性能优于这两个体系，由于存在催化钴位点，在1小时内实现了1174 μmol g的CO析出。此外，通过光物理和电化学研究以及DFT计算相结合，我们提出了一种合理的光催化CO还原机制。
