Sputtered Cu-doped NiO thin films as an efficient electrocatalyst for methanol oxidation

The efficient electrocatalysts for direct methanol oxidation play an essential role in the electrochemical energy conversion systems for their application in a wide range of portable applications. Consequently, Cu-doped NiO thin films on fluorine-doped tin oxide (FTO) were successfully prepared by the co-sputtering deposition technique, using various deposition times (300, 600, 900, and 1200 seconds), and producing films of different thicknesses (30, 55, 90, and 120 nm, respectively). X-ray diffraction (XRD) revealed the ideal crystallinity of the structure of the prepared films and was used to observe the effect of the thickness of the films on the crystal size. Energy-dispersive X-ray spectroscopy (EDS) confirmed the purity of the deposited film without any contamination. Field emission scanning electron microscopy (FESEM) images confirmed the film thickness increase with increasing deposition time. The surface roughness value of the Cu–NiO 1200 film was found to be 3.2 nm based on the atomic force microscopy (AFM) measurements. The deposited thin films of different thicknesses have been used as electrocatalysts for methanol oxidation at various concentrations of methanol (0, 0.5, 1, and 2 M), and displayed the highest electrocatalytic performance in 1 M methanol. Cu-doped NiO thin films have the advantage as electrocatalysts where they can be used directly without adding any binder or conducting agents, this is because Cu-doped NiO is deposited with high adhesion and strong electrical contact to the FTO substrate. A clear impact on the catalytic activity with increasing film thickness and a correlation between the film thickness and its catalytic activity was observed. The current density increased by about 60% for the Cu–NiO 1200 sample compared to Cu–NiO 300 sample, with the lowest onset potential of 0.4 V vs. Ag/AgCl. All deposited thin films of different thicknesses exhibited high stability at 0.6 V in 1 M methanol. This will open the window toward using physical deposition techniques for optimizing the electrocatalytic activity of different catalysts for electrocatalytic applications.

[1]  S. El-dek,et al.  Performance of Ni-doped BaTiO3 Hollow Porous Spheres supported reduced graphene oxide as an Efficient Bifunctional Electrocatalyst for Oxygen Evolution Reaction and Oxygen Reduction Reaction , 2023, Applied Surface Science.

[2]  N. B,et al.  Facile synthesis of boron doped NiCu2O4 for efficient methanol oxidation: Selective towards value-added formate formation , 2022, Ceramics International.

[3]  Pankaj Kumar,et al.  Recent advancements in the synthesis and electrocatalytic activity of two-dimensional metal–organic framework with bimetallic nodes for energy-related applications , 2022, Coordination Chemistry Reviews.

[4]  Mahmoud A. Hefnawy,et al.  Synergistic effect of Cu-doped NiO for enhancing urea electrooxidation: comparative electrochemical and DFT studies , 2021, Journal of Alloys and Compounds.

[5]  N. Dzade,et al.  Highly active methanol oxidation electrocatalyst based on 2D NiO porous nanosheets:a combined computational and experimental study , 2021 .

[6]  Zhigang Geng,et al.  Doping regulation in transition metal compounds for electrocatalysis. , 2021, Chemical Society reviews.

[7]  N. Barakat,et al.  Tungsten incorporation in nickel doped carbon nanofibers as efficient electrocatalyst for ethanol oxidation , 2020 .

[8]  W. E. El Rouby,et al.  3D NiCr-layered double hydroxide/reduced graphene oxide sand rose-like structure as bifunctional electrocatalyst for methanol oxidation , 2020 .

[9]  J. Michler,et al.  Electrodeposition of Mesoporous Ni-Rich Ni-Pt Films for Highly Efficient Methanol Oxidation , 2020, Nanomaterials.

[10]  Jeng-Yu Lin,et al.  Highly-porous hierarchically microstructure of graphene-decorated nickel foam supported two-dimensional quadrilateral shapes of cobalt sulfide nanosheets as efficient electrode for methanol oxidation , 2020 .

[11]  Yadong Li,et al.  Promoting electrocatalytic methanol oxidation of platinum nanoparticles by cerium modification , 2020 .

[12]  Chengyi Song,et al.  Effect of supporting materials on the electrocatalytic activity, stability and selectivity of noble metal-based catalysts for oxygen reduction and hydrogen evolution reactions , 2020 .

[13]  V. Komanicky,et al.  Enhancing catalytic activity of rhodium towards methanol electro-oxidation in both acidic and alkaline media by alloying with iron , 2020 .

[14]  A. Sahu,et al.  Pt-rare earth metal alloy/metal oxide catalysts for oxygen reduction and alcohol oxidation reactions: an overview , 2019, Sustainable Energy & Fuels.

[15]  Li Gao,et al.  Nickel phosphate materials regulated by doping cobalt for urea and methanol electro-oxidation , 2019, International Journal of Hydrogen Energy.

[16]  Xiliang Luo,et al.  Oxygen vacancies confined in ultrathin nickel oxide nanosheets for enhanced electrocatalytic methanol oxidation , 2019, Applied Catalysis B: Environmental.

[17]  R. Zbořil,et al.  Electrocatalytic methanol oxidation over Cu, Ni and bimetallic Cu-Ni nanoparticles supported on graphitic carbon nitride , 2019, Applied Catalysis B: Environmental.

[18]  Qichun Zhang,et al.  Ultrafine Pt Nanoparticles and Amorphous Nickel Supported on 3D Mesoporous Carbon Derived from Cu-Metal-Organic Framework for Efficient Methanol Oxidation and Nitrophenol Reduction. , 2018, ACS applied materials & interfaces.

[19]  Zhou Li,et al.  Unique Cu@CuPt Core-Shell Concave Octahedron with Enhanced Methanol Oxidation Activity. , 2017, ACS applied materials & interfaces.

[20]  Fenglin Yang,et al.  NiFe Layered Double Hydroxide-Derived NiO-NiFe2O4/Reduced Graphene Oxide Architectures for Enhanced Electrocatalysis of Alkaline Water Splitting , 2016 .

[21]  A. Gross,et al.  The Importance of the Electrochemical Environment in the Electro-Oxidation of Methanol on Pt(111) , 2016 .

[22]  Wei D. Lu,et al.  Nanoscale electrochemistry using dielectric thin films as solid electrolytes. , 2016, Nanoscale.

[23]  Amani E. Fetohi,et al.  Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium , 2015 .

[24]  Paul N. Duchesne,et al.  Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum–nickel hydroxide–graphene , 2015, Nature Communications.

[25]  A. Fekry,et al.  Electrocatalytic oxidation of methanol on ordered binary catalyst of manganese and nickel oxide nanoparticles , 2015 .

[26]  M. Sandhyarani,et al.  Estimation of Crystallite Size, Lattice Strain and Dislocation Density of Nanocrystalline Carbonate Substituted Hydroxyapatite by X-ray Peak Variance Analysis☆ , 2014 .

[27]  M. V. Martínez-Huerta,et al.  TiC, TiCN, and TiN Supported Pt Electrocatalysts for CO and Methanol Oxidation in Acidic and Alkaline Media , 2013 .

[28]  R. Srivastava,et al.  Synthesis of NiCo2O4 and its application in the electrocatalytic oxidation of methanol , 2013 .

[29]  R. Sathyamoorthy,et al.  Physical properties of nanocrystalline CuO thin films prepared by the SILAR method , 2013 .

[30]  Yawen Tang,et al.  Platinum–Cobalt alloy networks for methanol oxidation electrocatalysis , 2012 .

[31]  Xiaoping Shen,et al.  Reduced graphene oxide supported FePt alloy nanoparticles with high electrocatalytic performance for methanol oxidation , 2012 .

[32]  M. M. Abbas,et al.  Effect of Deposition Time on the Optical Characteristics of Chemically Deposited Nanostructure PbS Thin Films , 2011 .

[33]  M. Yıldırım,et al.  Influence of films thickness and structure on the photo-response of ZnO films , 2010 .

[34]  S. A. Ghani,et al.  The Nanocrystalline Nickel with Catalytic Properties on Methanol Oxidation in Alkaline Medium , 2009 .

[35]  T. Maiyalagan,et al.  Electrochemical oxidation of methanol on Pt/V2O5–C composite catalysts , 2009 .

[36]  Ermete Antolini,et al.  The methanol oxidation reaction on platinum alloys with the first row transition metals The case of Pt-Co and -Ni alloy electrocatalysts for DMFCs: A short review , 2006 .

[37]  C. Vijayan,et al.  Effect of the organic solvent on the formation and stabilization of CdS and PbS nanoclusters. , 2005, Talanta.

[38]  R. M. A. Hameed,et al.  Nickel as a catalyst for the electro-oxidation of methanol in alkaline medium , 2004 .

[39]  L. Bulhões,et al.  Electrochemical oxidation of methanol on Pt nanoparticles dispersed on RuO2 , 2004 .

[40]  Xin Wang,et al.  Electrochemical Impedance Studies of Methanol Electro-oxidation on Pt/C Thin Film Electrode , 2002 .

[41]  W. Visscher,et al.  On the role of Ru and Sn as promotors of methanol electro-oxidation over Pt , 1995 .