RESUMO
Electrochemical water oxidation is believed to be an effective pathway to produce clean, carbon-free, and environmentally sustainable green energy. In this work, we report a simple, easy-to-construct, facile, low-cost, and single-step galvanic technique to synthesize a Pd-supported temperature-assisted MoOx thin film nanocomposite for effective water oxidation. The most suitable nanocomposite exhibits very low overpotential at 10 mA/cm2 with smaller Tafel slope values for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) processes in an alkaline medium. The formation of a metal oxide-metal junction accelerates the growth of more active sites, promoting induced electronic synergism at the MoOx-Pd interface. This endows higher electrical conductivity and faster electron transfer kinetics, thus accelerating the faster water dissociation reaction following the Tafel-Volmer mechanism to boost the HER process in an alkaline medium. The excellent electrochemical HER and OER performances of our electrocatalyst even supersede the accomplishments of the benchmark catalysts Pt/C and RuO2. Moreover, neither of these two catalysts demonstrates both catalytic reactions, i.e., HER and OER at the same time, which have been observed for our synthesized catalyst. Our findings illustrate the potential of a thin-film MoOx-Pd nanocomposite to be an exceedingly effective electrocatalyst developed by interface engineering strategies. This also provides insight into designing several other semiconductor composite catalysts using simple synthesis techniques for highly efficient HER/OER processes that could be alternatives to benchmark electrocatalysts for water electrolysis.
RESUMO
A huge variety of silver based ternary sulfide semiconductors (SCs) have been considered for the sustainable advancement of renewable energy sources. Herein, we have synthesized two important classes of newly emerging semiconductor nanocrystals (NCs) Ag3SbS3 (SAS), i.e. hexagonal and monoclinic by simply tuning the solvent polarity, of which the second one has been synthesized in a phase pure NC for the first time by the thermal decomposition of silver and antimony based dithiocarbamate (â¼N-CS2-M) complexes. Interestingly, these two systems exhibit two different semiconducting (SC) properties and band gaps; hexagonal SAS has a p type (Eg â¼ 1.65 eV) whereas monoclinic SAS has an n type (Eg â¼ 2.1 eV) character. For the first time ever we have designed a reducing working electrode (i.e. cathode) by modifying the rotating disc electrode (RDE) with hexagonal SAS that exhibits excellent electrochemical oxygen reduction reaction (ORR) activity (Eonset = 1.09 V vs. RHE and average number of electron transfer: 3.89) comparable to that of the highly expensive Pt/C (Eonset = 0.88 V vs. RHE and average number of electron transfer: 3.92). Density functional theory (DFT) investigation confirms the corroborations of experimental data with theoretical implications. In addition, the electrode fabricated from monoclinic SAS acts as an efficient photoanode which exhibits higher photoelectrochemical (PEC) methanol oxidation reaction (MOR) activity under illumination in alkaline medium compared to that of standard TiO2 grown on an indium tin oxide (ITO) coated glass slide. On illumination, the relative photocurrent density at the onset potential has been obtained to be 845 which is a very significant experimental output with respect to any other TiO2 or Pt@TiO2 based photocatalysts for this application. The physicochemical stability and reusability of both materials were supported by 50 hours of extended electrochemical chronoamperometric measurements and powder XRD and the TEM analyses after electrocatalysis. This study explores a possible pathway for designing simple and less expensive but catalytically efficient silver based ternary sulfide NC systems for developing an SC material to reduce the energy crisis in the near future.
