Electrochemical nitrate reduction to ammonia is a promising alternative strategy to the traditional Haber-Bosch process but suffers from a low Faradaic efficiency and limited ammonia yield due to the sluggish multi-electron/proton-involved steps. Herein, we report a typical hollow cobalt phosphide nanosphere electrocatalyst assembled on a self-supported carbon nanosheet array synthesized with a confinement strategy that exhibits an extremely high ammonia yield rate of 8.47 mmol h−1 cm−2 through nitrate reduction reaction, which is highly superior to previously reported values to our knowledge. In situ experiments and theoretical investigations reveal that the dynamic equilibrium between the generation of active hydrogen on cobalt phosphide and its timely consumption by nitrogen intermediates leads to a superior ammonia yield with a high Faradaic efficiency. This unique insight based on active hydrogen equilibrium provides new opportunities for large-scale ammonia production through electrochemical techniques and can be further used for carbon dioxide capture.
TiO 2 /graphene/NiFe-layered double hydroxide nanorod arrays were fabricated as highly efficient photoanodes for photoelectrochemical water splitting with simultaneously enhanced charge separation and water oxidation efficiency.
1 June 2019 in Applied Catalysis B: Environment and Energy
Electrochemical alcohols oxidation offers a promising approach to produce valuable chemicals and facilitate coupled H2 production. However, the corresponding current density is very low at moderate cell potential that substantially limits the overall productivity. Here we report the electrooxidation of benzyl alcohol coupled with H2 production at high current density (540 mA cm−2 at 1.5 V vs. RHE) over a cooperative catalyst of Au nanoparticles supported on cobalt oxyhydroxide nanosheets (Au/CoOOH). The absolute current can further reach 4.8 A at 2.0 V in a more realistic two-electrode membrane-free flow electrolyzer. Experimental combined with theoretical results indicate that the benzyl alcohol can be enriched at Au/CoOOH interface and oxidized by the electrophilic oxygen species (OH*) generated on CoOOH, leading to higher activity than pure Au. Based on the finding that the catalyst can be reversibly oxidized/reduced at anodic potential/open circuit, we design an intermittent potential (IP) strategy for long-term alcohol electrooxidation that achieves high current density (>250 mA cm−2) over 24 h with promoted productivity and decreased energy consumption.
A new electrochemical synthesis route was developed for the fabrication of Fe-containing layered double hydroxide (MFe-LDHs, M = Ni, Co and Li) hierarchical nanoarrays, which exhibit highly-efficient electrocatalytic performances for the oxidation reactions of several small molecules (water, hydrazine, methanol and ethanol). Ultrathin MFe-LDH nanoplatelets (200–300 nm in lateral length; 8–12 nm in thickness) perpendicular to the substrate surface are directly prepared within hundreds of seconds (<300 s) under cathodic potential. The as-obtained NiFe-LDH nanoplatelet arrays display promising behavior in the oxygen evolution reaction (OER), giving rise to a rather low overpotential (0.224 V) at 10.0 mA cm−2 with largely enhanced stability, much superior to previously reported electro-oxidation catalysts as well as the state-of-the-art Ir/C catalyst. Furthermore, the MFe-LDH nanoplatelet arrays can also efficiently catalyze several other fuel molecules’ oxidation (e.g., hydrazine, methanol and ethanol), delivering a satisfactory electrocatalytic activity and a high operation stability. In particular, this preparation method of Fe-containing LDHs is amenable to fast, effective and large-scale production, and shows promising applications in water splitting, fuel cells and other clean energy devices.