Li Haoyang, Lu Qichen, Zhang Fenghua, Liu Qingda, Zhuang Jing, Li Zhong, Wang Xun
Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing, China.
Huaneng Clean Energy Research Institute, Beijing, China.
Nat Commun. 2025 Jul 1;16(1):5778. doi: 10.1038/s41467-025-60879-y.
Two-dimensional (2D) materials with intrinsic pores have attracted attention for catalytic and electronic applications. However, a significant gap exists between all-inorganic 2D networks with inorganic connectors and those with organic connectors due to the greater complexity of functionalizing inorganic molecules. Addressing this gap, we present a new class of 2D all-inorganic porous networks: single-layer cluster ionic-chain networks (CINs), constructed by using PWM (M = Mn, Co) polyoxometalate (POM) clusters as nodes and end-capping agents for ionic chains. The integration of POM clusters into these networks significantly alters the electronic and band structures. Notably, the Mn-based CIN exhibits extremely high catalytic activity, achieving a toluene oxidation conversion rate of over 1.45 mmol g h. Calculations suggest that POM clusters act as an 'electron buffer', stabilizing electron density at Mn sites and lowering the activation energy for toluene oxidation. This development showcases POM clusters as 'superatom' capping agents, establishing a pathway for all-inorganic 2D networks that could advance new catalytic materials with unique electronic properties.
具有固有孔隙的二维（2D）材料在催化和电子应用方面引起了关注。然而，由于无机分子功能化的复杂性更高，具有无机连接体的全无机二维网络与具有有机连接体的二维网络之间存在显著差距。为了弥补这一差距，我们提出了一类新型的二维全无机多孔网络：单层簇离子链网络（CINs），它是通过使用PWM（M = Mn、Co）多金属氧酸盐（POM）簇作为离子链的节点和封端剂构建而成。将POM簇整合到这些网络中会显著改变电子和能带结构。值得注意的是，基于锰的CIN表现出极高的催化活性，甲苯氧化转化率超过1.45 mmol g⁻¹ h⁻¹。计算表明，POM簇充当“电子缓冲剂”，稳定锰位点的电子密度并降低甲苯氧化的活化能。这一进展展示了POM簇作为“超原子”封端剂的作用，为全无机二维网络开辟了一条途径，有望推动具有独特电子性质的新型催化材料的发展。
