Crystalline Copper Selenide as a Reliable Non‐Noble Electro(pre)catalyst for Overall Water Splitting

• Published in: ChemSusChem 2020-06, Vol.13 (12), p.3222-3229
• Main Authors: Chakraborty, Biswarup, Beltrán‐Suito, Rodrigo, Hlukhyy, Viktor, Schmidt, Johannes, Menezes, Prashanth W., Driess, Matthias
• Format: Article
• Language: English
• Subjects: Catalysts; Chemical evolution; Copper; copper selenide; Copper selenides; Crystal structure; Crystallinity; Current density; electrocatalysis; Electrodes; Electrophoretic deposition; Hydrogen evolution reactions; klockmannite; Metal foams; Noble metals; non-noble metal catalyst; overall water splitting; Photosynthesis; Stability analysis; Water splitting
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.202000445

Electrochemical water splitting remains a frontier research topic in the quest to develop artificial photosynthetic systems by using noble metal‐free and sustainable catalysts. Herein, a highly crystalline CuSe has been employed as active electrodes for overall water splitting (OWS) in alkaline media. The pure‐phase klockmannite CuSe deposited on highly conducting nickel foam (NF) electrodes by electrophoretic deposition (EPD) displayed an overpotential of merely 297 mV for the reaction of oxygen evolution (OER) at a current density of 10 mA cm−2 whereas an overpotential of 162 mV was attained for the hydrogen evolution reaction (HER) at the same current density, superseding the Cu‐based as well as the state‐of‐the‐art RuO2 and IrO2 catalysts. The bifunctional behavior of the catalyst has successfully been utilized to fabricate an overall water‐splitting device, which exhibits a low cell voltage (1.68 V) with long‐term stability. Post‐catalytic analyses of the catalyst by ex‐situ microscopic, spectroscopic, and analytical methods confirm that under both OER and HER conditions, the crystalline and conductive CuSe behaves as an electro(pre)catalyst forming a highly reactive in situ crystalline Cu(OH)2 overlayer (electro(post)catalyst), which facilitates oxygen (O2) evolution, and an amorphous Cu(OH)2/CuOx active surface for hydrogen (H2) evolution. The present study demonstrates a distinct approach to produce highly active copper‐based catalysts starting from copper chalcogenides and could be used as a basis to enhance the performance in durable bifunctional overall water splitting. Transform to perform: A highly crystalline klockmannite CuSe has been used as an efficient bifunctional electro(pre)catalyst for the reaction of alkaline water splitting and, subsequently, its active structure at the anode and cathode has been uncovered.