Electronic Modulation of Electrocatalytically Active Center of Cu₇S₄ Nanodisks by Cobalt-Doping for Highly Efficient Oxygen Evolution Reaction

Abstract

Cu-based electrocatalysts have seldom been studied for water oxidation because of their inferior activity and poor stability regardless of their low cost and environmentally benign nature. Therefore, exploring an efficient way to improve the activity of Cu-based electrocatalysts is very important for their practical application. Modifying electronic structure of the electrocatalytically active center of electrocatalysts by metal doping to favor the electron transfer between catalyst active sites and electrode is an important approach to optimize hydrogen and oxygen species adsorption energy, thus leading to the enhanced intrinsic electrocatalytic activity. Herein, Co-doped CuS nanodisks were synthesized and investigated as highly efficient electrocatalyst for oxygen evolution reaction (OER) due to the optimized electronic structure of the active center. Density-functional theory (DFT) calculations reveal that Co-engineered CuS could accelerate electron transfer between Co and Cu sites, thus decrease the energy barriers of intermediates and products during OER, which are crucial for enhanced catalytic properties. As expected, Co-engineered CuS nanodisks exhibit a low overpotential of 270 mV to achieve current density of 10 mA cm as well as decreased Tafel slope and enhanced turnover frequencies as compared to bare CuS. This discovery not only provides low-cost and efficient Cu-based electrocatalyst by Co doping, but also exhibits an in-depth insight into the mechanism of the enhanced OER properties.

Super‐Stretchable Zinc–Air Batteries Based on an Alkaline‐Tolerant Dual‐Network Hydrogel Electrolyte

“…[39,40] The high-performance electrocatalysts of FeNC on 2D porous carbon, that is reported in our previous work, [3] are attached on the CNT paper to enhance oxygen reduction reactions (ORR) and oxygen evolution reaction (OER) [41][42][43] ( Figure S9a, Supporting Information). To fabricate stretchable zinc-air battery, flexible CNT paper is employed as electrode owing to its high porosity for air diffusion and good contact with the hydrogel electrolyte.…”

Aluminum‐Tailored Energy Level and Morphology of Co3−xAlxO4 Porous Nanosheets toward Highly Efficient Electrocatalysts for Water Oxidation

“…For example, exposed higher density of active Co 3+ Oh sites in {112} facets of Co 3 O 4 nanocrystals exhibite superior bifunctional activity for oxygen reduction and evolution reactions, as well as enhanced metal‐air battery performance . The electronic modulation (energy level engineering) of the electrocatalytically active center to enhance the intrinsic activity of active sites is the other way to improve the electrocatalytic performance of catalysts . To this end, defect‐engineering has been explored to modulate the electronic structure of transition metal‐based oxides, thus optimizing the energy level to reduce the required activation energy during the electrocatalytic processes .…”

Peptide Nanotube‐Templated Biomineralization of Cu2−xS Nanoparticles for Combination Treatment of Metastatic Tumor

“…23–0958) (Figure D) . The high‐resolution X‐ray photoelectron spectroscopy (XPS) of Cu 2p revealed strong binding energy peaks at 933.78 and 953.97 eV, which could be assigned to Cu 2p 3/2 and Cu 2p 1/2 , respectively, implying the presence of Cu(I) and Cu(II) in the CuS–PNTs nanocomposites (Figure E) . Meanwhile, the S 2p XPS spectra of the CuS–PNTs showed binding energy peaks at 162.08, 163.30, and 164.20 eV, referring to the bridging S 2− and the peak at 169.03 eV assigned to the SO 4 2− species (Figure F).…”