The authors thank EPSRC for funding (Grant No. EP/G01244X/1 and EP/L017008/1). One of the authors (Xu) gratefully acknowledges the China Scholarship Council (CSC) for financial support.Electrochemical remediation of ammonia-containing wastewater at low cell voltage is an energy-effective technology which can simultaneously recover energy via hydrogen evolution reaction. One of the main challenges is to identify a robust, highly active and inexpensive anode for ammonia electrooxidation. Here we present an alternative anode, prepared by electrochemical co-deposition of Ni and Cu onto carbon paper. This NiCu bimetallic catalyst is characterised by scanning electron microscope, scanning transmission electron microscope, X-ray diffraction, x-ray photoelelectron spectroscopy, cyclic voltammetry, linear sweep voltammetry and chronoamperometry techniques. The stability and activity of NiCu bimetallic catalyst are largely improved in comparison with Ni or Cu catalyst. Moreover this noble-metal-free NiCu catalyst even performs better than Pt/C catalyst, as NiCu is not poisoned by ammonia. An ammonia electrolysis cell is fabricated with NiCu/carbon paper as anode for ammonia electrolysis. The influences of pH value, applied cell voltages and initial ammonia concentration on cell current density, ammonia removal and energy efficiency are tested. An ammonia removal efficiency of ∼80% and coulombic efficiency up to ∼92% have been achieved. Ni-Cu bimetal on carbon paper is a stable non-noble anode for efficient electrooxidation of ammonia.Publisher PDFPeer reviewe

Two dimensional (2D) semiconductor materials, such as molybdenum disulfide (MoS₂) have attracted considerable interest in a range of chemical and electrochemical applications, for example, as an abundant and low-cost alternative electrocatalyst to platinum for the hydrogen evolution reaction (HER). While it has been proposed that the edge plane of MoS₂ possesses high catalytic activity for the HER relative to the “catalytically inert” basal plane, this conclusion has been drawn mainly from macroscale electrochemical (voltammetric) measurements, which reflect the “average” electrocatalytic behavior of complex electrode ensembles. In this work, we report the first spatially-resolved measurements of HER activity on natural crystals of molybdenite, achieved using voltammetric scanning electrochemical cell microscopy (SECCM), whereby pixel-resolved linear-sweep voltammogram (LSV) measurements have allowed the HER to be visualized at multiple different potentials to construct electrochemical flux movies with nanoscale resolution. Key features of the SECCM technique are that characteristic surface sites can be targeted and analyzed in detail and, further, that the electrocatalyst area is known with good precision (in contrast to many macroscale measurements on supported catalysts). Through correlation of the local voltammetric response with information from scanning electron microscopy (SEM) and atomic force microscopy (AFM) in a multi-microscopy approach, it is demonstrated unequivocally that while the basal plane of bulk MoS₂ (2H crystal phase) possesses significant activity, the HER is greatly facilitated at the edge plane (e.g., surface defects such as steps, edges or crevices). Semi-quantitative treatment of the voltammetric data reveals that the HER at the basal plane of MoS₂ has a Tafel slope and exchange current density (J₀) of ∼120 mV per decade and 2.5 × 10⁻⁶ A cm⁻² (comparable to polycrystalline Co, Ni, Cu and Au), respectively, while the edge plane has a comparable Tafel slope and a J₀ that is estimated to be more than an order-of-magnitude larger (∼1 × 10⁻⁴ A cm⁻²). Finally, by tracking the temporal evolution of water contact angle (WCA) after cleavage, it is shown that cathodic polarization has a ‘self-cleaning’ effect on the surface of MoS₂, consistent with the time-independent (i.e., time after cleavage) HER voltammetric response.