Yang Tianfu, Hu Hongyin, Wang Yan, Chen Xinqi, Fan Jianxian, Li Donghua, Liu Shuangbin, Li Jinmei, He Tianwei, Lu Shuanglong, Qiu Li
Yunnan Key Laboratory for Micro/Nano Materials and Technology, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan University, Kunming, 650091, P. R. China.
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, P. R. China.
Adv Mater. 2025 Mar;37(10):e2419547. doi: 10.1002/adma.202419547. Epub 2025 Jan 29.
Growing global concerns over energy security and climate change have intensified efforts to develop sustainable strategies for electrochemical CO reduction (eCORR). Covalent Organic Frameworks (COFs) have emerged as promising electrocatalysts for eCORR due to their tunable structures, high surface areas, and abundance of active sites. However, the performance of 2D COFs is often limited by layer stacking, which restricts active site exposure and reduces selectivity. To overcome these challenges, a new class of COFs known as pillar-layered COFs (PL-COFs) is developed featuring adjustable interlayer spacing and a 3D architecture. Characterization using PXRD, TEM, XPS, and EIS confirmed the successful integration of pillar molecules, which leads to increased interlayer spacing, crystallinity, and porosity. These structural advancements result in significantly improved electrochemical activity and selectivity for CO-to-CO conversion. Density functional theory simulations revealed that enhanced CO adsorption and CO desorption contribute to the outstanding performance of PL-COF-1, which boasts the largest interlayer spacing. This material achieved an impressive Faradaic efficiency of 91.3% and demonstrated a significant current density, outperforming both the original COF-366-Co and PL-COF-2. These findings highlight the effectiveness of the pillaring strategy in optimizing COF-based electrocatalysts, paving the way for next-generation materials for CO reduction and sustainable energy conversion.
全球对能源安全和气候变化的担忧日益加剧，这促使人们加大力度开发用于电化学CO还原（eCORR）的可持续策略。共价有机框架（COF）因其可调节的结构、高比表面积和丰富的活性位点，已成为eCORR有前景的电催化剂。然而，二维COF的性能往往受到层堆积的限制，这限制了活性位点的暴露并降低了选择性。为了克服这些挑战，开发了一类新型的COF，即柱撑层状COF（PL-COF），其具有可调节的层间距和三维结构。使用PXRD、TEM、XPS和EIS进行的表征证实了柱撑分子的成功整合，这导致层间距、结晶度和孔隙率增加。这些结构上的进步显著提高了电化学活性和CO到CO转化的选择性。密度泛函理论模拟表明，增强的CO吸附和CO解吸有助于PL-COF-1的优异性能，PL-COF-1具有最大的层间距。这种材料实现了91.3%的令人印象深刻的法拉第效率，并表现出显著的电流密度，优于原始的COF-366-Co和PL-COF-2。这些发现突出了柱撑策略在优化基于COF的电催化剂方面的有效性，为下一代CO还原和可持续能量转换材料铺平了道路。
