Facile solvothermal synthesis of Pt-Cu nanocatalyst with improved electrocatalytic activity toward methanol oxidation (original) (raw)
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Applied Catalysis B: Environmental, 2013
A bimetallic Pt-Cu carbon-supported catalyst (Pt(Cu)/C) has been prepared by a room temperature twostep procedure involving the chemical reduction of Cu ions by sodium borohydride in the presence of Vulcan XC72R carbon powder, followed by the partial galvanic replacement of Cu particle layers by Pt, upon immersion in a chloroplatinate solution. The characterization of the Pt(Cu)/C catalyst by XRD has proven the formation of a Pt-Cu alloy while cyclic voltammetry in deaerated acid revealed similar characteristics to those of pure Pt. These two findings point to the existence of Pt-rich outer layers and a Pt-Cu core. The electrocatalytic activity of the bimetallic Pt(Cu)/C catalyst towards methanol oxidation is comparable to or better than that of a commercial 20% Pt Vulcan XC72R catalyst (when assessed by voltammetric or prolonged chronoamperometric experiments respectively). This is attributed to the effect of Cu on CO poison adsorption and removal from Pt. Moreover, related to the same effect but also to the reduced Pt loading of the mixed Pt-Cu particles, the specific mass activity of the prepared catalyst is superior to that of the commercial catalyst. (S. Sotiropoulos). et al. applied the technique to the partial replacement of Ti surface layers or Cu and Pb polylayers by Pt, resulting in the latter case in Pt shell-Cu (or Pb) core particles, denoted as Pt(Cu) or Pt(Pb). Sotiropoulos and co-workers expanded the method to the replacement of Pb, Cu, Fe, Co, Ni polylayers by Pt and Au .
Journal of Power Sources, 2006
The organic sol method for preparing ultrafine transition metal colloid particles reported for the first time by Bonnemann et al. [H. Bonnemann, W. Brijoux, R. Brinkmann, E. Dinjus, T. Jouen, B. Korall, Angew. Chem. Int. Ed. Engl., 30 (1991) 1312] has been improved in this paper. The improved organic sol method uses SnCl 2 as the reductant and methanol as the organic solvent. Thus, this method is very simple and inexpensive. It was found that the average size of the Pt particles in the Pt/C catalysts can be controlled by adjusting the evaporating temperature of the solvent. Therefore, the Pt/C catalysts prepared by the same method are suitable for evaluating the size effect of the Pt particles on electrocatalytic performance for methanol oxidation. The results of the X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that when the evaporating temperatures of the solvent are 65, 60, 50, 40, and 30 • C, the average sizes of the Pt particles in the Pt/C catalysts prepared are: 2.2, 3.2, 3.8, 4.3, and 4.8 nm, respectively. The X-ray photoelectron spectroscopic (XPS) results demonstrated that the small Pt particles are easily oxidized and the decomposition/adsorption of methanol cannot proceed on the surfaces of Pt oxides. Thus, the Pt/C catalyst with small Pt particles has a low electrocatalytic activity for methanol oxidation. The Pt/C catalyst with a large average size of the Pt particles also possesses a small electrochemically active surface area. Therefore, only the Pt/C catalyst with a middle average size of Pt particles, such as 3.8 nm exhibited optimal electrocatalytic performance for methanol oxidation. Because the Pt/C catalysts with the different particle sizes were prepared with the same method, the size effect on the electrocatalytic performance of the catalysts could be reliably investigated.
Nano PtCuO particles were deposited on Vulcan XC-72R carbon black using the impregnation and microwave irradiation methods. The prepared catalysts were characterized by XRD, TEM and EDX analyses. TEM images indicated that the microwave method provides homogeneously distributed catalyst particles in smaller size, compared to the one prepared by the impregnation method. The electrocatalytic activity of Pt‒CuO/C electrocatalysts was investigated to oxidize methanol in 0.5 M H2SO4 solution by applying cyclic voltammetry and chronoamperometry techniques. The oxidation current density of Pt‒CuO/C electrocatalyst, prepared by the microwave method, showed two folds increment with a potential shift in the negative direction by 69 and 36 mV at the first and second oxidation peaks, respectively, relative to those at the catalyst prepared by the impregnation method. The effect of varying methanol concentration on the resulting oxidation current density of Pt‒ CuO/C electrocatalysts was studied. Some kinetic information about the reaction order with respect to methanol and Tafel slope values was calculated. Slower current density decay was observed in the chronoamperogram of Pt‒CuO/C electrocatalyst, prepared by the microwave method, reflecting a lower degree of surface poisoning.
Journal of Nanomaterials, 2019
A facile method to prepare Pt-Cu nanowires (NWs) was introduced. Structural characterization such as high-resolution transmission electron microscope (HR-TEM), selected-area electron diffraction (SAED), EDS element mapping, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and inductively coupled plasma mass spectrometry (ICP-MS) showed the formation of Pt-Cu alloy, with a width of 4.5 nm on average. The formation process of Pt-Cu NWs was studied; it was found that bromine ion, who has preferential adsorption on Pt (100) face, served as a growth-directing agent; Brij58 not only served as a protector but also played an important role in forming Pt-Cu NWs; the mechanism was proposed. Their electrocatalytic activity towards methanol oxidation was investigated; we found that the current density of Pt-Cu NWs was 295 mA·mg-1 when the ratio of Pt/Cu is 1 : 1, which is 11.5 and 2.35 times higher than that of pure Pt (26 mA·mg-1) and commercial Pt/C (126 mA·mg-1). The high ele...
Bimetallic Cu–Pt/nanoporous carbon composite as an efficient catalyst for methanol oxidation
Journal of the Iranian Chemical Society, 2018
A novel bimetallic Cu-Pt nanoparticle supported onto Cu/indirectly carbonized nanoporous carbon composite (Cu-Pt/ICN-PCC) was prepared through a two-step process: first, carbonization of furfuryl alcohol-infiltrated MOF-199 [metal-organic framework Cu 3 (BTC) 2 (BTC = 1,3,5-benzene tricarboxylate)], without removing the Cu metal with HF aqueous solution; second, the partial galvanic replacement reaction (GRR) of Cu nanoparticles by Pt IV upon immersion in a platinum(IV) chloride solution. The synthesized materials characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDS), and electrochemical methods. The EDS result revealed that part of Cu nanoparticles have been substituted by Pt nanoparticles after GRR. The methanol oxidation at the surface of Cu-Pt/ICNPCC was investigated by cyclic voltammetry method in 0.5 M H 2 SO 4 and indicated good electro-catalytic activity towards methanol oxidation (E p = 0.85 V vs. NHE and j f = 1.00 mA cm −2). It is suggested that this improvement is attributed to the effect of proper Cu/ICNPCC for fine dispersion, efficient adhesion, and prevention of Pt coalescing.
iranian journal of catalysis, 2017
The impregnation method was used to synthesize Pt and Pt3Co supported on MWCNTs applying NaBH4 as the reducing agent. The structure, morphology, and chemical composition of the electrocatalysts were characterized through SEM, XRD, and EDX. X-ray diffraction showed a good crystallinity of the supported Pt nanoparticles on the composites and showed the formation of Pt3Co alloy. The SEM images revealed that the particles of Pt3Co were deposited uniformly on the surface of MWCNT with a diameter of 10 nm. EDX analysis confirmed the surface segregation of Co and Pt occurred (1:3 surface atomic ratio Pt-Co) for the Pt3Co/MWCNT nanocomposite. The Pt3Co/MWCNTs and Pt/MWCNTs electrocatalysts’ electrochemical performance was assessed against the methanol oxidation reaction (MOR) in 0.5 M H2SO4 solution using the chronoamperometry (CA) and the cyclic voltammetry (CV) methods. The minimum onset potential and the largest oxidation current density were obtained at Pt3Co/MWCNTs electrocatalyst. The...
Nanomaterials, 2021
Controlled deposition of metals is essential for the creation of bimetallic catalysts having predictable composition and character. Continuous co-electroless deposition (co-ED) permits the creation of bimetallic catalysts with predictive control over composition. This method was applied to create a suite of Cu–Pt mixed-metal shell catalysts for use in methanol electrooxidation in direct methanol fuel cell applications (DMFCs). Enhanced performance of Cu–Pt compositions over Pt alone was predicted by existing computational studies in the literature. Experimental evidence from this study supports the bifunctional catalyst explanation for enhanced activity and confirms the optimum Cu:Pt ratio as Cu3Pt for this methanol electrooxidation. This ability to control the composition of a bimetallic shell can be extended to other systems where the ratio of two metals is critical for catalytic performance.