Electrocatalytic performance of different cobalt molybdate structures for water oxidation in alkaline media. Issue 37 (5th September 2018)

• Record Type: Journal Article
• Authors: Rodriguez, Mariandry; Stolzemburg, Matheus C. P.; Bruziquesi, Carlos G. O.; Silva, Adilson C.; Abreu, Cíntia G.; Siqueira, Kisla P. F.; Oliveira, Luiz C. A.; S. Pires, Maíra; Lacerda, Lívia C. T.; Ramalho, Teodorico C.; Dias, Anderson; Pereira, Márcio C.
• Is Part Of: CrystEngComm. Volume 20:Issue 37(2018)
• Page Start: 5592
• Page End: 5601
• Publication Date: 2018-09-05
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c8ce01073k
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : Among the CoMoO4 polymorphs, the α-phase exhibits the highest performance for the oxygen evolution reaction. Abstract : Cobalt molybdates with different crystalline structures, i.e., α, β, and hydrated (H)-CoMoO4, were synthesized, and their electrocatalytic activities were thoroughly examined for catalyzing the oxygen evolution reaction (OER) in alkaline media. The material characteristics were associated with the electrocatalytic properties by evaluating the CoMoO4 crystal structures (XRD and Raman), morphologies (TEM), and electrochemical features (electrochemically active surface area, roughness factor, electrochemical impedance, Tafel analysis, and controlled-current electrolysis). These combined findings revealed that the electrocatalytic performance is greatly influenced by the crystalline structures of CoMoO4, following the order α-CoMoO4 > H-CoMoO4 > β-CoMoO4 . The H-CoMoO4 catalysts crystallized in the triclinic space group, P 1̄ (#2), with Z = 4. On the other hand, the α- and β-CoMoO4 catalysts exhibited a monoclinic structure, C 2/ m (#12), with Z = 8. In the OER experiments, α-CoMoO4 showed an overpotential of 0.43 ± 0.05 V compared to the 0.51 ± 0.05 V and 0.56 ± 0.04 V exhibited by the H-CoMoO4 and β-CoMoO4 catalysts, respectively, to achieve 10 mA cm −2 . All CoMoO4 structures displayed stability for at least 6 h at a controlled current density of 10 mA cm −2 . Finally, computational simulations indicate that the coexistence of Co and Mo ions in edge-shared octahedral sites of α-CoMoO4 may favor the interaction between the O atom of the water molecule and the metal adsorption sites due to its surface being electronically less dense than β- and H-CoMoO4 surfaces, thus resulting in its higher performance for OER.