Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study

Recently, metal-organic frameworks are one of the potential catalytic materials for electrocatalytic applications. The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory. Firstly, the catalytic activities of heterometallic clusters are investigated. Among all heterometallic clusters, Fe 2 Mn-Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction, and Fe 2 Co-Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction, respectively 100 and 50 mV lower than those of Pt(111) and RuO 2 (110) catalysts. The analysis of the potential gap of Fe 2 M clusters indicates that Fe 2 Mn, Fe 2 Co, and Fe 2 Ni clusters possess good bifunctional catalytic activity. Additionally, the catalytic activity of Fe 2 Mn and Fe 2 Co connected through 3,3′,5,5′-azobenzen-etetracarboxylate linker to form Fe 2 M-PCN-Fe 2 M is explored. Compared with Fe 2 Mn-PCN-Fe 2 Mn, Fe 2 Co-PCN-Fe 2 Co, and isolated Fe 2 M clusters, the mixed-metal Fe 2 Co-PCN-Fe 2 Mn possesses excellent bifunctional catalytic activity, and the values of potential gap on the Mn and Co sites of Fe 2 Co-PCN-Fe 2 Mn are 0.69 and 0.70 V, respectively. Furthermore, the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst. In conclusion, the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.