The prevalence of intermetallic charge transfer is a marvel for fine-tuning the electronic struct... more The prevalence of intermetallic charge transfer is a marvel for fine-tuning the electronic structure of the active centers in the electrocatalysts. Although, Pauling electronegativity is the primary deciding factor for the direction of charge transfer, we report an unorthodox intralattice 'inverse' charge transfer from Mo to Ni in two systems, Ni73Mo alloy electrodeposited on Cu nanowires and NiMo-hydroxide (Ni:Mo = 5:1) on Ni foam. The inverse charge transfer deciphered by X-ray absorption fine structure studies and X-ray photoelectron spectroscopy has been understood by the Bader charge and projected density of state analyses. The undercoordinated Mo-center pushes the Mo 4d-orbitals close to the Fermi energy in the valence band region while Ni 3d-orbitals lie in the conduction band. Since, electrons are donated from the electron-rich Mo-center to the electron-poor Ni-center, the inverse charge transfer effect navigates the Mo-center to become positively charged and vice versa. The reverse charge distribution in Ni73Mo accelerates the electrochemical hydrogen evolution reaction in alkaline and acidic media with 0.35 and 0.07 s-1 turnover frequency at-33 and-54 mV versus reversible hydrogen electrode, respectively. The mass activities are 12.5 and 67 A g-1 at 100 mV overpotential, respectively. Anodic potential oxidizes the Ni-center of NiMo-hydroxide for alkaline water oxidation with 0.43 O2 s-1 turnover frequency at 290 mV overpotential. This extremely durable homologous couple achieves water and urea splitting with cell voltages of 1.48 and 1.32 V, respectively at 10 mA cm-2 .
An unorthodox intra-lattice ‘inverse’ charge transfer occurs from the undercoordinated Mo-center ... more An unorthodox intra-lattice ‘inverse’ charge transfer occurs from the undercoordinated Mo-center to neighbouring Ni-centers in the Ni73Mo alloy (−) and NiMo-hydroxide (+). The self-supported couple splits alkaline water at 1.48 V at 10 mA cm−2.
The prevalence of intermetallic charge transfer is a marvel for fine-tuning the electronic struct... more The prevalence of intermetallic charge transfer is a marvel for fine-tuning the electronic structure of the active centers in the electrocatalysts. Although, Pauling electronegativity is the primary deciding factor for the direction of charge transfer, we report an unorthodox intralattice 'inverse' charge transfer from Mo to Ni in two systems, Ni73Mo alloy electrodeposited on Cu nanowires and NiMo-hydroxide (Ni:Mo = 5:1) on Ni foam. The inverse charge transfer deciphered by X-ray absorption fine structure studies and X-ray photoelectron spectroscopy has been understood by the Bader charge and projected density of state analyses. The undercoordinated Mo-center pushes the Mo 4d-orbitals close to the Fermi energy in the valence band region while Ni 3d-orbitals lie in the conduction band. Since, electrons are donated from the electron-rich Mo-center to the electron-poor Ni-center, the inverse charge transfer effect navigates the Mo-center to become positively charged and vice versa. The reverse charge distribution in Ni73Mo accelerates the electrochemical hydrogen evolution reaction in alkaline and acidic media with 0.35 and 0.07 s-1 turnover frequency at-33 and-54 mV versus reversible hydrogen electrode, respectively. The mass activities are 12.5 and 67 A g-1 at 100 mV overpotential, respectively. Anodic potential oxidizes the Ni-center of NiMo-hydroxide for alkaline water oxidation with 0.43 O2 s-1 turnover frequency at 290 mV overpotential. This extremely durable homologous couple achieves water and urea splitting with cell voltages of 1.48 and 1.32 V, respectively at 10 mA cm-2 .
An unorthodox intra-lattice ‘inverse’ charge transfer occurs from the undercoordinated Mo-center ... more An unorthodox intra-lattice ‘inverse’ charge transfer occurs from the undercoordinated Mo-center to neighbouring Ni-centers in the Ni73Mo alloy (−) and NiMo-hydroxide (+). The self-supported couple splits alkaline water at 1.48 V at 10 mA cm−2.
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