一種新型態的漸進性超分子-以鎘作為中心金屬之配位超分子籠 (Cadmium coordination cage, CCC) 其獨特的立方八面體多孔結構由48個鎘離子作為配位節點和多價互補的三聯吡啶配體自組裝構成。金屬奈米粒子，尤其是小尺寸，是最有前景的催化材料之一，對於穩定性的調控，最理想的選擇是使用受限的多孔配位超分子籠來獲得分散性好且暴露出多個活性位點之金屬奈米表面。我們提出雙溶劑法(Double solvent methods)來製備超小粒徑且高孔洞性之4.2 nm Cu/CuOx@CCC 的奈米材料，並將其包覆到CCC超分子籠中。透過原位電化學X光吸收近邊結構 (XANES)之表徵，發現在不同電位下，具有CCC超分子籠保護的Cu/CuOx@CCC奈米粒子能夠維持氧化銅和銅的價態比例之恆定，這意味著CCC超分子籠的保護能夠提高催化穩定性。對於硝酸根還原反應(NO3RR)的電化學應用，電催化NO3RR在－0.9 V vs. RHE 下能夠獲得最高的氨產率 (218.72 mmol h−1 mg-1) 和 FE (~ 93.13%)，並抑制析氫反應的競爭。在100小時的穩定性測試中，由於CCC超分子籠的保護，Cu/CuOx@CCC保持穩定的電流密度且具有較小的波動干擾。;A novel-progressive supramolecule, Cadmium coordination cage (CCC), cuboctahedron porous structure, built up with 48 Cadmium-coordinated nodes and multivalent and complementary terpyridine-based ligands, surrounded by counterions of 96 PF6-. As one of the most promising species, metallic nanoparticles (MNPs), particularly small MNPs, have intense interest thanks to their great potential in catalysis. The most desirable choice is to use confined porous coordination cages to obtain well-dispersed MNPs with clean surfaces to control stability. We presented the Double-solvent method (DSM) for affording small Cu/CuOx NPs, which are encapsulated into cadmium coordination cages (Cu/CuOx@CCC). Given an ultrasmall particle size (4.2 nm) and high pore volume in CCC. Through in situ electrochemical X-ray absorption near-edge structure (XANES) characterization, it was found that under different potentials, the Cu/CuOx@CCC nanoparticles with CCC protection can maintain a fixed valence ratio of cuprous oxide and copper, which means that the CCC supramolecular cage protection can improve the stability of catalysis. Regarding the electrochemical application of nitrate reduction reaction (NO3RR), Electrocatalytic NO3RR performances perform that Cu/CuOx@CCC could deliver the highest NH3 yield (218.72 mmol h−1 mg-1) and FE (~ 93.13%) 2 at − 0.9 V vs. RHE, and suppress the HER competition. In the durability test, Cu/CuOx@CCC remains the stable current density with a small fluctuation due to the CCC cage protection.
