Phase Modulating of Cu–Ni Nanowires Enables Active and Stable Electrocatalysts for the Methanol Oxidation Reaction

Abstract

The design and development of non‐noble metal alternatives with superior performance and promising long‐term stability that is comparable or even better than those of noble‐metal‐based catalysts is a significant challenge. Here, we report the thermal‐induced phase engineering of non‐noble‐metal‐based nanowires with superior electrochemical activity and stability for the methanol oxidation reaction (MOR) under alkaline conditions. The optimized Cu–Ni nanowires deliver an unprecedented mass activity of 425 mA mg−1, which is 4.3 times higher than that of the untreated one. Detailed catalytic investigations show that the enhanced performance is due to the large active area, the increased number of active sites (NiOOH), and fast methanol electrooxidation kinetics. In addition, the generated hollow feature in the nanowires provides a unique void space to release the volume expansion, where the activity can be maintained for 5 h without a distinct activity decay. The present work emphasizes the importance of precisely phase modulating of nanomaterials for the design of non‐noble metal electrocatalysts towards the MOR, which opens up a new pathway for the design of cost‐effective electrocatalysts with promising activity and long‐term stability.

Low‐Dimensional Metallic Nanomaterials for Advanced Electrocatalysis

“…[107] Copyright 2019, American Chemical Society Reproduced with permission. [108] Copyright 2019, Wiley-VCH.…”

“…reported a facile phase‐engineering strategy for the fabrication of 1D porous Cu–Ni nanowires by employing core–shell Cu–Ni nanowires as precursors, followed by phase transform through annealing at different temperatures (Figure 12d–h). [ 108 ] The structural synergistic, and fast methanol oxidation kinetics ensure the optimal Cu 1 Ni 1 nanowires (400 °C‐A/200 °C‐H) for outstanding electrocatalytic activity with an unprecedented mass activity of 425 mA mg −1 (Figure 12j). Moreover, the generated hollow features provide a unique void space in which to release the volume expansion, thus contributing to the large promotion in durability.…”

Robust copper nanocrystal/nitrogen-doped carbon monoliths as carbon monoxide-resistant electrodes for methanol oxidation reaction

“…Thus, it is crucial to seek highly active, stable and low-cost electrocatalysts for MOR. In recent years, non-noble metal based electrocatalysts, including Co [8,9], Ni [10,11], Cu [12,13], have attracted much attention as active catalysts for MOR. Among these transition metals, copper is a promising ingredient for MOR electrocatalysts, because of its high activity, high abundance, good stability and low price [14].…”

Unusual Effect of Trace Water on the Structure and Activity of NixCo1−x Electrocatalysts for the Methanol Oxidation Reaction

“…Ni‐based catalysts are considered to be the most promising candidates owing to their high poisoning tolerance and low cost. To date, two main ways have been employed to design and tune the Ni‐based catalysts: 1) using catalyst supports such as carbon materials (carbon nanofibers and graphene) and 2) controlling the catalyst morphology, which is related to the active surface of the catalyst …”

“…To date, two main ways have been employed to design and tune the Ni-based catalysts:1 )using catalyst supports such as carbon materials (carbon nanofibers and graphene) [9][10][11] and 2) controlling the catalystm orphology, which is related to the active surface of the catalyst. [12][13][14] Various synthetic methods have been proposed, such as the microemulsion method, [15,16] microwaver adiation synthesis, [17,18] polyol reduction, [19,20] and electrodeposition, [21][22][23] which are effective for the preparation of nickel-based catalysts with variousm orphologies and anisotropy,f or example, Ni-Co nanoflowers, [19,24] nanoneedles, [15] self-assembled Ni-Co nanoparticles, [25] dendrite-like Ni-Cu alloy, [26] and Ni-Co-Sn alloy nanoparticles. [27] Cu/NiCu nanowires synthesized by the microemulsion methods howed much highera ctivities than nickel nanoparticles in oxidizing methanol.…”