Boosting Lattice Oxygen Oxidation of Perovskite to Efficiently Catalyze Oxygen Evolution Reaction by FeOOH Decoration.

In the process of oxygen evolution reaction (OER) on perovskite, it is of great significance to accelerate the hindered lattice oxygen oxidation process to promote the slow kinetics of water oxidation. In this paper, a facile surface modification strategy of nanometer-scale iron oxyhydroxide (FeOOH) clusters depositing on the surface of LaNiO3 (LNO) perovskite is reported, and it can obviously promote hydroxyl adsorption and weaken Ni-O bond of LNO. The above relevant evidences are well demonstrated by the experimental results and DFT calculations. The excellent hydroxyl adsorption ability of FeOOH-LaNiO3 (Fe-LNO) can obviously optimize OH- filling barriers to promote lattice oxygen-participated OER (LOER), and the weakened Ni-O bond of LNO perovskite can obviously reduce the reaction barrier of the lattice oxygen participation mechanism (LOM). Based on the above synergistic catalysis effect, the Fe-LNO catalyst exhibits a maximum factor of 5 catalytic activity increases for OER relative to the pristine perovskite and demonstrates the fast reaction kinetics (low Tafel slope of 42 mV dec-1) and superior intrinsic activity (TOFs of ~40 O2 S-1 at 1.60 V vs. RHE).

Boosting the electrocatalytic performance of NiFe layered double hydroxides for the oxygen evolution reaction by exposing the highly active edge plane (012).

The intrinsic activity of NiFe layer double hydroxides (LDHs) for the oxygen evolution reaction (OER) suffers from its predominantly exposed (003) basal plane, which is thought to have poor activity. Herein, we construct a hierarchal structure of NiFe LDH nanosheet-arrays-on-microplates (NiFe NSAs-MPs) to elevate the electrocatalytic activity of NiFe LDHs for the OER by exposing a high-activity plane, such as the (012) edge plane. It is surprising that the NiFe NSAs-MPs show activity of 100 mA cm-2 at an overpotential (η) of 250 mV, which is five times higher than that of (003) plane-dominated NiFe LDH microsheet arrays (NiFe MSAs) at the same η, representing the excellent electrocatalytic activity for the OER in alkaline media. Besides, we analyzed the OER activities of the (003) basal plane and the (012) and (110) edge planes of NiFe LDHs by density functional theory with on-site Coulomb interactions (DFT+U), and the calculation results indicated that the (012) edge plane exhibits the best catalytic performance among the various crystal planes because of the oxygen coordination of the Fe site, which is responsible for the high catalytic activity of NiFe NSAs-MPs.

Porous Microrod Arrays Constructed by Carbon-Confined NiCo@NiCoO2 Core@Shell Nanoparticles as Efficient Electrocatalysts for Oxygen Evolution.

The study of cost-efficient and high-performance electrocatalysts for oxygen evolution reaction (OER) has attracted much attention. Here, porous microrod arrays constructed by carbon-confined NiCo@NiCoO2 core@shell nanoparticles (NiCo@NiCoO2 /C PMRAs) are fabricated by the reductive carbonization of bimetallic (Ni, Co) metal-organic framework microrod arrays (denoted as NiCo-MOF MRAs) and subsequent controlled oxidative calcination. They successfully combine the desired merits including large specific surface areas, high conductivity, and multiple electrocatalytic active sites for OER. In addition, the oxygen vacancies in NiCo@NiCoO2 /C PMRAs significantly improve the conductivity of NiCoO2 and accelerate the kinetics of OER. The above advantages obviously enhance the electrocatalytic performance of NiCo@NiCoO2 /C PMRAs. The experimental results demonstrate that the NiCo@NiCoO2 /C PMRAs as electrocatalysts exhibit high catalytic activity, low overpotential, and high stability for OER in alkaline media. The strategy reported will open up a new route for the fabrication of porous bimetallic composite electrocatalysts derived from MOFs with controllable morphology for electrochemical energy conversion devices.

Activating CoOOH Porous Nanosheet Arrays by Partial Iron Substitution for Efficient Oxygen Evolution Reaction.

Iron-substituted CoOOH porous nanosheet arrays grown on carbon fiber cloth (denoted as Fex Co1-x OOH PNSAs/CFC, 0≤x≤0.33) with 3D hierarchical structures are synthesized by in situ anodic oxidation of α-Co(OH)2 NSAs/CFC in solution of 0.01 m (NH4 )2 Fe(SO4 )2 . X-ray absorption fine spectra (XAFS) demonstrate that CoO6 octahedral structure in CoOOH can be partially substituted by FeO6 octahedrons during the transformation from α-Co(OH)2 to Fex Co1-x OOH, and this is confirmed for the first time in this study. The content of Fe in Fex Co1-x OOH, no more than 1/3 of Co, can be controlled by adjusting the in situ anodic oxidation time. Fe0.33 Co0.67 OOH PNSAs/CFC shows superior OER electrocatalytic performance, with a low overpotential of 266 mV at 10 mA cm-2 , small Tafel slope of 30 mV dec-1 , and high durability.