Nanoarchitectonics with redox active site modulation in bimetallic MIL-125(Ti, Mn) MOF for enhanced supercapacitor performance

Metal-organic frameworks (MOFs) with dual metal centres have received considerable attention as electrode materials for supercapacitor applications due to their redox-active sites and unique structural architecture. Herein, we present a simple one-step solvothermal approach to synthesize and optimize bimetallic MIL-125(Ti,Mn) MOF, where redox active site modulation enhances its electrochemical performance in asymmetric supercapacitors. The unique structure of MIL-125(Ti,Mn), featuring a spindle-like morphology anchored by flake-like sheets, facilitates interaction between active sites and electrolyte ions and modulates the redox active sites, leading to improved electrochemical performance. As such, the optimized MIL-125(Ti)-Mn-2 electrode demonstrates a high specific capacity of 137.2 mAhg −1 at 1 A g –1 and a capacity retention of more than 76.3 % after 5000 cycles. Furthermore, an asymmetric supercapacitor built with Mn-MIL-125(Ti)-2 and activated carbon achieved a high specific energy of 22.74 Wh kg –1 at a specific power of 996 W kg –1, while also demonstrating excellent stability with 71.2 % capacitance retention over 10,000 cycles at 10 Ag −1 . This one-pot incorporation strategy offers a novel route to modulate the structure of MIL-125(Ti) via Mn 2+ doping for enhanced supercapacitor performance. • Redox active sites of MIL-125(Ti) MOF were modulated by Mn 2+ incorporation for enhanced performance. • MIL-125(Ti)-Mn-2 delivered optimal performance owing to its intriguing physicochemical properties. • The optimal MIL-125(Ti)-Mn-2 electrode yields a C s of 137.2 mhAg −1 at 1 Ag −1 , and 76.3 % capacity retention after 5000 cycles. • The asymmetric device of MIL-125(Ti)-Mn-2//AC demonstrated a specific energy of 22.74 Wh kg −1 at 996 W kg −1 .