Meihua Lu

Development of Cobalt Hydroxide as a Bifunctional Catalyst for Oxygen Electrocatalysis in Alkaline Solution

Co(OH)2 in the form of hexagonal nanoplates synthesized by a simple hydrothermal reaction has shown even greater activity than cobalt oxides (CoO and Co3O4) in oxygen reduction and oxygen evolution reactions (ORR and OER) under alkaline conditions. The bifunctionality for oxygen electrocatalysis as shown by the OER-ORR potential difference (ΔE) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts, when the Co(OH)2 nanoplates were compounded with nitrogen-doped reduced graphene oxide (N-rGO). The good performance was attributed to the nanosizing of Co(OH)2 and the synergistic interaction between Co(OH)2 and N-rGO. A zinc-air cell assembled with a Co(OH)2-air electrode also showed a performance comparable to that of the state-of-the-art zinc-air cells. The combination of bifunctional activity and operational stability establishes Co(OH)2 as an effective low-cost alternative to the platinum group metal catalysts.

Mn and Co co-substituted Fe3O4 nanoparticles on nitrogen-doped reduced graphene oxide for oxygen electrocatalysis in alkaline solution

A dispersion of Mn and Co co-substituted Fe3O4 (MCF, Mn : Co : Fe = 1 : 1: 1) nanoparticles on nitrogen-doped reduced graphene oxide (N-rGO) nanosheets was prepared by a hydrothermal method. This catalyst exhibited 80% of the oxygen reduction reaction (ORR) activity of a Sigma 20 wt% Pt/C catalyst; and 61% of the oxygen evolution reaction (OER) activity of a 20 wt% RuO2/C catalyst in alkaline solution. Extensive material characterizations by field-emission transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analysis, and inductively coupled plasma mass spectrometry (ICP-MS) were undertaken to suggest some possible reasons for the good electrochemical performance. The catalyst also delivered good performance in full zinc–air cell tests where it was used in the air electrode. The MCF catalyst has effectively combined the ORR activity of manganese oxide, the OER activity of cobalt oxide; and the electronic conductivity of bulk Fe3O4 into an integrated bifunctional catalytic system; and its good contact with the N-rGO nanosheets also reduces the external transport resistance in oxygen electrocatalysis.

Activity of Transition‐Metal (Manganese, Iron, Cobalt, and Nickel) Phosphates for Oxygen Electrocatalysis in Alkaline Solution

Although transition‐metal oxides are common non‐platinum group metal catalysts for the industrially important oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), the performance gap between transition‐metal oxides and platinum group metal catalysts is still substantial and there is a continuing need to search for alternatives. In this study, transition‐metal (Mn, Fe, Co, and Ni) phosphates prepared by a solution chemistry method under ambient conditions are found to display interesting electrocatalytic properties for the ORR and OER in alkaline solution. Among them, manganese phosphate is more active than most state‐of‐the‐art manganese oxides for the ORR, and nickel phosphate is as active as the best Ni‐based catalysts for the OER. Hence these phosphates can be used as tandem catalysts for rechargeable metal–air batteries in which both the ORR and OER take place. The good performance may be attributed to the stabilization of the catalytic centers by the phosphate framework. This study establishes phosphates as yet another class of highly active low‐cost non‐platinum group metal alternatives for oxygen electrocatalysis in alkaline solution.

A bifunctional oxygen electrocatalyst from monodisperse MnCo2O4 nanoparticles on nitrogen enriched carbon nanofibers

Monodisperse MnCo2O4 nanoparticles supported on nitrogen enriched carbon nanofibers (NCF) exhibited synergetic component interactions that resulted in higher ORR and OER activities than commercial Pt/C catalysts.

Exploring Metal Nanoclusters for Lithium–Oxygen Batteries

α-MnO2 nanowires modified with dispersed poly(3,4-ethylenedioxythiophene)-protected Au and Ag nanoclusters (Au-MnO2 and Ag-MnO2) were used for the first time as hybrid oxygen electrocatalysts for nonaqueous lithium-oxygen batteries. The Au-MnO2 and Ag-MnO2 hybrid catalysts surpassed the performance of pristine α-MnO2 nanowires in full-cell tests in the following order: Au-MnO2 > Ag-MnO2 > pristine α-MnO2. Specifically, cells with the Au-MnO2 catalyst could reduce the discharge/charge overpotentials at 100 mA g(-1) to 0.23/1.02 V and deliver discharge/charge capacities of 5784/5020 mAh g(-1). They could also be cycled for at least 60 times at the depth of discharge of 1000 mAh g(-1). The good full cell performance demonstrated the effectiveness of Au/Ag nanoclusters in promoting oxygen electrocatalysis on α-MnO2; forming discharge products with more reactive morphologies. It is therefore worthwhile to explore the use of Au and Ag nanoclusters in other catalyst systems for oxygen electrocatalysis in nonaqueous solutions.

Electronic Coupling of Cobalt Nanoparticles to Nitrogen‐Doped Graphene for Oxygen Reduction and Evolution Reactions

The rational design of nonprecious-metal electrocatalysts with activities comparable to or greater than that of platinum is extremely valuable to the development of high energy density metal-air batteries. Herein, the two-step preparation of a highly active oxygen electrocatalyst based on ultrasmall cobalt nanoparticles stabilized in a nitrogen-doped graphene matrix is reported. The catalyst performs as well as the commercial Pt/C catalyst in the oxygen reduction reaction, and better than the Pt/C catalyst in the oxygen evolution reaction. This particular electrocatalyst could significantly lower the overpotentials of oxygen electrochemical reactions in aqueous lithium-air batteries to attain a round-trip efficiency of about 79.0 % at a current density of 0.1 mA cm-2 , thereby surpassing the performance of the commercial Pt/C catalyst. The good performance may be attributed to strong metal-support interactions, maximized by a high dispersion of ultrasmall cobalt nanocrystals in a nitrogen-doped graphene matrix, which yields electrocatalytic properties greater than the sum of its parts.

Improving the Performance of Perovskite in Nonaqueous Oxygen Electrocatalysis

Nanoparticle (NP) aggregates of lanthanum cobalt oxide perovskite (LCO) were compounded with reduced graphene oxide (rGO) nanosheets and used as the cathode catalyst for nonaqueous lithium-oxygen batteries (LOBs). The LCO NP aggregates were completely surrounded by rGO nanosheets in the composite with 10.5 wt % of rGO (LCO-rGO-10.5) but were partially exposed in the composite with 7.5 wt % of rGO (LCO-rGO-7.5). Both composites performed better than pristine LCO NPs and rGO nanosheets in nonaqueous oxygen electrocatalysis. The LCO-rGO-7.5 composite excelled at capacity and rate performance, while the LCO-rGO-10.5 composite was better at cycle stability. The good performance of the LCO-rGO composites was due to the synergy of functions of LCO and rGO.