Efficient oxygen evolution reaction (OER) electrocatalysts are highly desired in the field of water electrolysis and rechargeable metal-air batteries. In this study, a chelate polymer, composed of copper (II) and dithiooxamide, was used to derive an efficient catalytic system for OER. Upon potential sweep in 1 M KOH, copper (II) centers of the chelate polymer were transformed to CuO and Cu(OH)2. The carbon-dispersed CuO nanostructures formed a nanocomposite which exhibits an enhanced catalytic activity for OER in alkaline media. The nanocomposite catalyst has an overpotential of 280 mV (at 1 mA/cm2) and a Tafel slope of 81 mV/dec in 1M KOH solution. It has a seven-fold higher current than an IrO2/C electrode, per metal loading. A catalytic cycle is proposed, in which CuO undergoes electrooxidation to Cu2O3 that further decomposes to CuO with the release of oxygen. This work reveals a new method to produce an active nanocomposite catalyst for OER in alkaline media using a non-noble metal chelate polymer and a porous carbon. This method can be applied to the synthesis of transition metal oxide nanoparticles used in the preparation of composite electrodes for water electrolyzers and can be used to derive cathode materials for aqueous-type metal-air batteries.
25 September 2018 in ACS Sustainable Chemistry & Engineering
Fully fluorinated coordination complexes show two types of guest recognition events: 1 : 1 selective recognition of CO2 and metal ion-selective adsorption of N2, O2, H2, NO, and CH4.
Nickel oxyhydroxides (NiOOHs) are well-known for their superior activity toward oxygen evolution reaction (OER) in alkaline solutions. However, their activity toward oxygen reduction reaction (ORR) has been largely unexplored. There exist three NiOOH polymorphs: α-, β-, and γ-NiOOH, characterized by different interlayer spacing. Although still debated, γ-NiOOH with a large layer spacing has been indicated as the active phase for OER. Here, a highly crystalline γ-NiOOH was prepared in a carbon matrix by the in situ electrochemical transformation of nickel dithiooxamide Ni(dto) in 1 M KOH solution. The catalyst prepared in this way showed low overpotential not only for OER, but also for ORR in alkaline solutions. The onset potential for ORR is ~0.81 V vs. RHE, and the reaction proceeds via the 2e− transfer pathway. The high OER catalytic activity and relatively low ORR overpotential make this nanocomposite catalyst a good candidate for bifunctional OER/ORR catalyst, stable in alkaline solutions.
The main objective of this work was to evaluate an impact of a support on the efficiency of nickel catalysts in the high-temperature conversion of lignocellulosic biomass to hydrogen-rich gas. The most important parameters influencing catalytic performance of the catalysts were identified. The properties of three materials (ZSM-5, ZrO2, and MCF (mesostructured cellular foam)) used as a support differing in surface acidity, surface area, pore structure, ability to interact with an active phase, and resistance to coking, have been studied. The results revealed that Ni/MCF, characterized by large pore size and pore volume, low acidity, small NiO crystallites size, and moderate interaction with the active phase, is the most efficient among studied catalysts, while an application of Ni on ZSM-5 support with high-acidity was not beneficial. The results suggest that structure of the support, in particular larger pore size and a better contact between an active phase and reaction intermediates, play an important role in the formation of gaseous products during thermal decomposition of lignocellulosic feedstock. On the other hand, high acidity of the support did not increase the formation of large amounts of hydrogen-rich gaseous products.