Self-supported ultrathin NiCo layered double hydroxides nanosheets electrode for efficient electrosynthesis of formate

Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.

Intermetallic CuAu nanoalloy for stable electrochemical CO_(2) reduction

Copper is one of the most efficient catalysts widely investigated in electrochemical CO_(2) reduction, however, the further development of copper-based catalysts is constrained by severe stability problems. In this work, we developed a method for the synthesis of highly ordered Cu Au intermetallic nanoalloys(o-CuAu) under mild conditions(< 250℃), which can convert carbon dioxide to carbon monoxide with high selectivity and can operate stably for 160 h without current decay. The improved stability is believed to be due to the increased mixing enthalpy and stronger atomic interactions between Cu and Au atoms in the intermetallic nanoalloy. In addition, XPS results, Tafel slope and in situ IR spectroscopy demonstrate that high valence gold atoms on o-CuAu surface promote the reduction of CO_(2). In contrast, the disordered CuAu nanoalloy(d-CuAu) underwent atomic rearrangement to form a Cu-rich structure on the surface, leading to reduced stability. These findings may provide insight into the rational design of stable CO_(2) RR electrocatalysts through proper structural engineering.

Study of pyrolyzed hemin/C as non-platinum cathodic catalyst for direct methanol fuel cells

Biological reduction of O2 to H2O justifies a serious look at heme as a potential O2 reduction reaction(ORR) catalyst for low temperature fuel cells.In this study,a novel non-platinum electrocatalyst for ORR was prepared through hemin,which is hydrochloride of heme,supported on Black Pearls 2000 carbon black(Hm-BP) pyrolyzed at 700-900℃ in Ar atmosphere.The physical and electrocatalytic properties of as-prepared catalysts were characterized by TGA,XRD,XPS,TEM,rotating disk electrode(RDE) and rotating ring disk electrode(RRDE).It has found that the catalyst treated at 750℃(Hm-BP-750) exhibits the best property among the Hm-BP catalysts prepared.The onset potential of ORR on the Hm-BP-750 at 30℃ was measured ca.0.90 V(vs.RHE) in 0.1 M H2SO4,and mass current density was reached 15.3 mA mg-1 at 0.75 V.It has revealed that O2 could be reduced directly to water in a 4e process between 0.9 and 0.83V,and the yield of H2O2 was 0-18% in the potential range of 0.83-0.63 V.This methanol-tolerant catalyst also presents excellent stability in medium-term test of direct methanol fuel cell at 80℃.