The electronic structure of the active center of Co3Se4 electrocatalyst was adjusted by Te doping for efficient oxygen evolution.

In order to enhance the energy efficiency of water electrolysis, it is imperative to devise electrocatalysts for oxygen evolution reaction that are both non-precious metal-based and highly efficient. Efficient catalyst design is generally based on electronic structural engineering. Considering the electronegativity disparity between selenium (Se) and tellurium (Te), the tunable bandgaps, and the conductive metallic nature of Te. We designed a material wherein Te atoms are uniformly doped onto the surface of Cobalt tetra selenide (Co3Se4) nanorods, leading to the synthesis of a defect-rich material. Experimental results demonstrate that Te doping in Co3Se4 increases active sites and optimizes the electronic structure of Co cations, enhancing the design of multi-defect structures. This promotes the generation of the Co(oxy) hydroxide (CoOOH) active phase, enhancing catalytic activity by maximizing the binding strength between Co sites and oxygenated intermediates. Te-Co3Se4 nanorods exhibit good catalytic activity for oxygen evolution reactions, with an overpotential of 269 mV at a driving current density of 50 mA cm-2 and excellent stability in alkaline media (over 100 h). This discovery indicates the feasibility of strategically combining various imperfect structures, thereby unlocking the latent potential of diverse catalysts in electrocatalytic reactions.

Deciphering the Space Charge Effect of the p-n Junction between Copper Sulfides and Molybdenum Selenides for Efficient Water Electrolysis in a Wide pH Range.

Space charge transfer is crucial for an efficient electrocatalytic process, especially for narrow-band-gap metal sulfides/selenides. Herein, we designed and synthesized a core-shell structure which is an ultrathin MoSe2 nanosheet coated CuS hollow nanoboxes (CuS@MoSe2) to form an open p-n junction structure. The space charge effect in the p-n junction region will greatly improve electron mass transfer and conduction, and also have abundant active interfaces. It was used as a bifunctional electrocatalyst for water oxidation at a wide pH range. It exhibits a low overpotential of 49 mV for the HER and 236 mV for the OER at a current density of 10 mA·cm-2 in acidic pH, 72 mV for the HER and 219 mV at 10 mA·cm-2 for the OER in alkaline pH, and 62 mV for the HER and 230 mV at 10 mA·cm-2 for the OER under neutral conditions. The experimental results and density functional theory calculations testify that the p-n junction in CuS@MoSe2 designed and synthesized has a strong space charge region with a synergistic effect. The built-in field can boost the electron transport during the electrocatalytic process and can stabilize the charged active center of the p-n junction. This will be beneficial to improve the electrocatalytic performance. This work provides the understanding of semiconductor heterojunction applications and regulating the electronic structure of active sites.