TY - JOUR
T1 - Electrocatalytic H2O2 production through di-nuclear copper(II) hydroxo bridged complexes with pyrrolidine and piperidine-based ligands
AU - Pattanaik, Koyal
AU - Singh, Varsha
AU - Bhattacharya, Suman
AU - Ganesan, Vellaichamy
AU - Sabiah, Shahulhameed
N1 - Publisher Copyright:
© 2025
PY - 2025/9
Y1 - 2025/9
N2 - Hydrogen peroxide (H2O2) is one of the most significant molecules with a steadily increasing demand in medicine, chemical synthesis, and environmental protection. The current industrial production of H2O2 relies heavily on the anthraquinone process, a complex procedure that involves careful distillation generates hazardous waste, and results in the decomposition of large quantities of H2O2 due to its heat instability. The electrochemical process of oxygen reduction provides a highly efficient and ecologically benign method for generating H2O2. Two biphenyl anchored di-nuclear copper(II) hydroxo bridged complexes [Cu2(L1)2(µ-OH)2(H2O)2](ClO4)2, (1) and [Cu2(L2)2(µ-OH)2(H2O)2](ClO4)2, (2), where L1, 6-(2-(pyrrolidin-1-yl)ethyl)-6,7-dihydro-5H-dibenzo[c,e]azepine and L2, 6(2-(piperidin-1-yl) ethyl)-6,7-dihydro-5H-dibenzo[c,e]azepine, have been synthesized. Various analytical techniques including elemental analysis, UV–Vis, FT-IR, ESI-MS, and thermogravimetry analysis were used to characterize both complexes. X-ray diffraction of complex 1 revealed that the complex is centrosymmetric and di-nuclear with µ-OH bridges. Both units have copper(II) in a distorted square pyramid geometry. The synthesized complexes were immobilized on graphene to obtain Cu-L1 and Cu-L2 composites. These composites were characterized by Powder-XRD, FE-SEM and elemental mapping to ascertain their structural and morphological properties. They show a highly stable two-electron oxygen reduction process with onset potentials of 0.86 and 0.85 V vs RHE (Reversible Hydrogen Electrode). They showed greater electrochemical stability over 2000 CV cycles as analyzed by LSV responses. Further, the XRD patterns recorded before and after catalysis showed no significant changes, indicating that the composite materials remain stable during the ORR process. Additionally, FE-SEM images and the corresponding energy-dispersive X-ray spectroscopy (EDS) obtained before and after catalysis confirm the presence of C, O, N, and Cu.
AB - Hydrogen peroxide (H2O2) is one of the most significant molecules with a steadily increasing demand in medicine, chemical synthesis, and environmental protection. The current industrial production of H2O2 relies heavily on the anthraquinone process, a complex procedure that involves careful distillation generates hazardous waste, and results in the decomposition of large quantities of H2O2 due to its heat instability. The electrochemical process of oxygen reduction provides a highly efficient and ecologically benign method for generating H2O2. Two biphenyl anchored di-nuclear copper(II) hydroxo bridged complexes [Cu2(L1)2(µ-OH)2(H2O)2](ClO4)2, (1) and [Cu2(L2)2(µ-OH)2(H2O)2](ClO4)2, (2), where L1, 6-(2-(pyrrolidin-1-yl)ethyl)-6,7-dihydro-5H-dibenzo[c,e]azepine and L2, 6(2-(piperidin-1-yl) ethyl)-6,7-dihydro-5H-dibenzo[c,e]azepine, have been synthesized. Various analytical techniques including elemental analysis, UV–Vis, FT-IR, ESI-MS, and thermogravimetry analysis were used to characterize both complexes. X-ray diffraction of complex 1 revealed that the complex is centrosymmetric and di-nuclear with µ-OH bridges. Both units have copper(II) in a distorted square pyramid geometry. The synthesized complexes were immobilized on graphene to obtain Cu-L1 and Cu-L2 composites. These composites were characterized by Powder-XRD, FE-SEM and elemental mapping to ascertain their structural and morphological properties. They show a highly stable two-electron oxygen reduction process with onset potentials of 0.86 and 0.85 V vs RHE (Reversible Hydrogen Electrode). They showed greater electrochemical stability over 2000 CV cycles as analyzed by LSV responses. Further, the XRD patterns recorded before and after catalysis showed no significant changes, indicating that the composite materials remain stable during the ORR process. Additionally, FE-SEM images and the corresponding energy-dispersive X-ray spectroscopy (EDS) obtained before and after catalysis confirm the presence of C, O, N, and Cu.
KW - Copper(II) hydroxo bridged complexes
KW - Electrocatalysis
KW - Hydrogen peroxide
KW - Oxygen reduction
UR - https://www.scopus.com/pages/publications/105007733893
U2 - 10.1016/j.inoche.2025.114854
DO - 10.1016/j.inoche.2025.114854
M3 - Article
AN - SCOPUS:105007733893
SN - 1387-7003
VL - 179
JO - Inorganic Chemistry Communications
JF - Inorganic Chemistry Communications
M1 - 114854
ER -
