Atomic emission spectroelectrochemistry applied to dealloying phenomena II. Selective dissolution of iron and chromium during active-passive cycles of an austenitic stainless steel

Atomic emission spectroelectrochemistry was used to investigate selective dissolution of a 304 austenitic stainless steel sample in 2 M H₂SO₄. The partial dissolution rates of Fe, Cr, Ni, Mn, Mo, and Cu were measured as function of time during a series of potentiostatic triggered activation/passivation cycles. When first exposed to sulfuric acid solution, the steel sample was in a passive state with a total steady state ionic dissolution rate expressed as an equivalent current density of 10 μA cm⁻². A transition into the active and passive state could be triggered by cathodic (−700 mV vs. Ag/AgCl) and anodic (+400 to +700 mV vs. Ag/AgCl) potentiostatic pulses respectively of variable time. Excess Cr dissolution was observed during the activation cycle as compared to Fe and a depletion of Cr dissolution was observed during the passivation cycle. These results are interpreted in terms of the dissolution of a Cr rich passive layer during activation and selective dissolution of Fe, Mn, Ni and other elements to form a Cr rich passive layer during passivation. Quantitative analysis of the excess Cr showed that the residual film contained approximately 0.38 μg Cr/cm². Fe does not appear to be incorporated into the film at this early stage of passive film growth. Residual films of metallic nickel and copper were formed on the surface during the active period that subsequently dissolved during passivation.     

Modulated Cr(III) oxidation in KOH solutions at a gold electrode: Competition between disproportionation and stepwise electron transfer

The electrochemical oxidation of aqueous Cr(III) was examined using cyclic voltammetry with a polycrystalline Au electrode in KOH solutions of varying pH and Cr(III) concentration. The mechanism and kinetics for the oxidation of Cr(III) is a quasi-reversible diffusion-controlled reaction and is largely dependent on the solution pH. The reaction mechanism is initiated by an irreversible electrochemical electron transfer to form Cr(IV) which is the rate-determining step (RDS). Following the RDS, subsequent oxidation of Cr to its hexavalent state occurs by the disproportionation of Cr(IV) at low KOH concentrations and electron transfer at high KOH concentrations due to the involvement of OH⁻ in the disproportionation reaction. As the solution pH increases, the Cr(III) oxidation peak potential shifts negatively owing to the involvement of OH⁻ in the RDS. The competitive adsorption of OH⁻ and CrO₂⁻ on the electrode surface also plays an important role in the oxidation behavior.     

Interactions of polyelectrolytes bearing carboxylate and/or sulfonate groups with Cu(II) and Ni(II)

The interactions between the water-soluble polyelectrolytes poly(acrylic acid) (PAA) and poly(vinyl sulfonic acid) (PVS), and Cu(II) and Ni(II) are studied by the liquid-phase polymer-based retention (LPR) technique. Assuming a Ni(II)-PVS interaction of electrostatic nature, the nature of the Ni(II)-PAA interaction is found to be electrostatic, while Cu(II)-PAA interactions imply the formation of coordinative bonds. The charge related formation constants for the systems Ni(II)-PAA, Ni(II)-PVS, and Cu(II)-PVS are found to be 57.57×10², 43.4×10², and 60.5×102 M⁻¹, respectively in a 0.010 M NaNO₃ aqueous solution at pH 5, and 1.4×10² for both systems containing Ni(II) and 1.3×10² M⁻¹ for the system Cu(II)-PVS in a 0.10 M NaNO₃ aqueous solution at pH 5.     

Environmental assessment of natural radionuclides and heavy metals in waters discharged from a lignite-fired power plant

Gross alpha, gross beta and ²²⁶Ra activities as well as the concentration of trace metals (V, Cr, Mn, Ni, Cu, Zn, Mo and Pb) in the discharge waters of the major lignite-fired power plant in Greece were measured during the period October 2004 to May 2006. Gross alpha activity of particulate matter in the discharge waters was 0.75 ± 0.40 Bq g⁻¹ (0.3-1.2 Bq g⁻¹) while the beta activity was 1.54 ± 0.50 Bq g⁻¹ (1.2-1.7 Bq g⁻¹). The ranges of water gross alpha, beta and ²²⁶Ra activities were 0.062-0.268 Bq L⁻¹, 0.064-0.268 Bq L⁻¹ and 0.021-0.062 Bq L⁻¹, respectively. The mean concentration of ²²⁶Ra in the discharge waters was at least one order of magnitude higher than in natural water bodies. Soil samples were collected from fields irrigated with discharge waters and 29.2 ± 2.2 Bq kg⁻¹ of ²³⁸U, 1.2 ± 0.2 Bq kg⁻¹ of ²³⁵U, 26.8 ± 0.8 Bq kg⁻¹ of ²²⁶Ra, 36.8 ± 1.5 Bq kg⁻¹ of ²³²Th and 492.6 ± 25.8 Bq kg⁻¹ of ⁴⁰K were determined. The concentration values of dissolved metals in the discharge waters were higher than those usually observed in water streams near coal-fired power plants or rivers due to metal leaching from lignite or/and by-products. However, the leaching at high pH’s as those observed in the discharged waters does not raise the concentration of the studied metals to values higher than the criteria maximum concentrations and criterion continuous concentration (CCC) values of the US EPA water quality criteria. Statistical analysis was further applied to reveal the correlations between the different water components. Hierarchical cluster analysis revealed four different clusters: the first cluster was primarily composed of radioactivity and physicochemical parameters; the second cluster consisted of Cu, Ni and Zn, the third of Mn, Fe, Mo and Pb and the fourth of V and Cr. This clustering agrees with the associations suggested for elements in most coals or with the Goldschmidt classification.     

Prediction of unconfined compressive strength of cement paste with pure metal compound additions

Neural network analysis was used to construct models of unconfined compressive strength (UCS) as a function of mix composition using existing data from literature studies of pure compound additions to Portland cement paste. The models were able to represent the known nonlinear dependency of UCS on age and water content, and generalised from the literature data to find relationships between UCS and contaminant concentrations, resulting in the following ranking of the UCS values predicted for addition of the contaminants, on an equimolar basis: at 7 days, Cl≈Cr(III)>NO₃⁻≈Cd>control>Zn≥Ni>Pb>Cu?Ba; at 28 days, Cl>Cr(III)>NO₃⁻≈control≥Zn≥Cd>Ni>Pb>Cu?Ba. Application of the best neural network to other data suggested that Cs is a retarder and Cr(VI) has no effect. No trends could be discerned for Hg, K, Mn, Na and SO₄²⁻. The root-mean-square error for the best neural network seems to be an estimate of the interlaboratory error for UCS.     

Atomic emission spectroelectrochemistry applied to dealloying phenomena: I. The formation and dissolution of residual copper films on stainless steel

The rates of elemental dissolution were measured for a 304 stainless steel containing 0.19% Cu in real time during linear sweep voltammetry experiments using the atomic emission spectroelectrochemistry (AESEC) method. The results demonstrate that Fe, Cr, Ni, Mn, and Mo dissolve simultaneously leaving a residual copper film that inhibits the steel dissolution. The formation and dissolution of the copper film leads to the appearance of two peaks in the anodic dissolution transient, one due to inhibition of steel by residual copper and the other due to the formation of the passive film. The addition of NaCl to the electrolyte results in a marked increase in the intensity of the second dissolution peak, while hardly affecting the first peak. This is interpreted in terms of the lowering of copper dissolution potential by chloride ions due to the stabilization of CuCl₂⁻. A simple phenomenological kinetic model is used to simulate the variation of dissolution rate with potential.     

Removal, preconcentration and determination of trace heavy metal ions in water samples by AAS via chemically modified silica gel N-(1-carboxy-6-hydroxy) benzylidenepropylamine ion exchanger

The use of chemically modified silica gel N-(1-carboxy-6-hydroxy) benzylidenepropylamine (SiG-CHBPA), ion exchanger for removal and preconcentration of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in natural water samples collected from River Nile, Mediterranean Sea and other locations followed by their consecutive AAS determination was described. The effects on the percentage of recovered metal ions including mass change of ion exchanger, stirring time, pH of sample solutions and eluent concentration were studied. The distribution coefficient K_d, ml g^− 1 and the percentage concentration of the studied metal ions on the ion exchanger at equilibrium, C_M,_eqm ,% (Recovery, %) were studied as a function of experimental parameters. The logarithmic values of the distribution coefficients, log K_d are 3-6.3. The interfering effects of some foreign ions on the removal, preconcentration and determination of the investigated metal ions were described. The metal-chelates formed between the ion exchanger and the studied metal ions were characterized by IR (absorption and reflectance), UV spectrometry, potentiometric titration and thermal analysis (TG and DTG). The reliability of the present method was confirmed by the comparison with a standard solvent extraction method. The present method is simple and rapidly applicable for the determination of the studied metal ions, ng ml^− 1 in different natural water samples.     

Co-deposition of Al-Cr-Ni alloys using constant potential and potential pulse techniques in AlCl3-NaCl-KCl molten salt

To improve the oxidation resistance of TiAl intermetallic compound under high temperature condition, cathodic co-deposition of Al-Cr and Al-Ni alloy was carried out by constant potential control or potential pulse control in AlCl₃-NaCl-KCl molten salt containing CrCl₂ and/or NiCl₂ at 423 K. Cathodic reduction of Ni and Cr starts at potential of 0.8 and 0.15 V versus Al/Al³⁺ in the molten salt, respectively. The co-deposition of Al, Cr, and Ni occurred at potentials more negative than −0.1 V to form a mixture of intermetallic compounds of Cr₂Al, Ni₃Al, and Al₃Ni. Concentration of Cr in the deposit was enhanced to 43 at% at −0.1 V; however, concentration of Ni in the deposit was 6 at% at the same potential. The concentration of Ni further decreased with more negative potential to 1 at% at −0.4 V. The potential pulse technique enhanced the Ni concentration in the deposit to about 30 at%, due to anodic dissolution of Al content from the deposit at the higher side of potential on the potential pulse electrolysis.     

Ni-Mo alloying of nickel surface by alternating pulsed electrolysis using molybdenum(VI) baths

Electrochemical Ni-Mo alloying of the surface of a nickel substrate was investigated using alternating pulsed electrolysis in an aqueous solution containing only molybdate ions (MoO₄²⁻) as a metal ion component. In this electrochemical process, the nickel substrate was slightly dissolved during the anodic pulses, providing nickel ions into the solution in the vicinity of the substrate, while Ni and Mo were both electrodeposited on the substrate surface during the subsequent cathodic pulses. Through the optimization of anodic and cathodic conditions independently based on a set of direct-current electrolysis data, amorphous Ni-Mo alloy layers were found to be formed at the surface of the nickel substrate by the alternating pulsed electrolysis using the MoO₄²⁻ solution of pH 3.0-5.0. The conditions for Ni-Mo alloy formation were discussed in terms of the dissolving regime of ionic species in the electrolytes determined by an equilibrium calculation.     

A comparative study of the physicochemical and electrochemical properties of Cr and Ni-W-P amorphous electrocoatings

A comparative study of the physicochemical and electrochemical properties of Cr and amorphous Ni-W-P electrocoatings is presented here. Amorphous Ni-W-P alloys were successfully produced by electrodeposition at 70 °C on copper substrate under galvanostatic control in the range of 50-400 mA cm⁻² and constant loads of 500 and 1600 C, using a solution containing 0.20 mol L⁻¹ Na₂WO₄.2H₂O; 0.02 mol L⁻¹ NiSO₄·6H₂O; 0.02 mol L⁻¹ NaPH₂O₂; 0.02 mol L⁻¹ H₃BO₃; 0.07 mol L⁻¹ (NH₄)₂SO₄; 0.20 mol L⁻¹ Na₃C₆H₅O₇·2H₂O; 0.0001 mol L⁻¹ CH₃(CH₂)₁₀·CH₂OSO₃Na. Cr electrocoatings were obtained from an industrial plating solution. The physicochemical characterization of the as-electrodeposited and as-annealed samples was carried out by scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive X-ray analysis (EDX) techniques. Corrosion tests were carried out at room temperature in 10⁻¹ mol L⁻¹ NaCl aqueous solutions, using potentiodynamic linear polarization (PLP). Among the various Ni-W-P electrocoatings studied here, the Ni₆₅W₂₀P₁₅ layer presented the best corrosion behavior and a slightly superior corrosion potential than the Cr electrocoating. Heat treatments gave rise to a cracked surface morphology in the Cr layers, while the surface morphology of the Ni₆₅W₂₀P₁₅ layers remained homogeneous and devoid of cracks. Heat treatments at 400 and 600 °C led to crystallization of the Ni-W-P layer, with precipitation of the Ni₃P, Ni and Ni-W phases and increasing hardness of the Ni-W-P layer as the heat treatment temperature rose. All the annealed Cr layers showed cracked surfaces and their hardness diminished as the annealing temperature increased. The presence of cracks impairs the mechanical and corrosion resistance properties of Cr layers. Ni₆₅W₂₀P₁₅ layer is a potential candidate to replace Cr in industrial applications, mainly at operational temperatures that exceed room temperature.     

Migration,transformation and solidification/stabilization mechanisms of heavy metals in glass-ceramics made from MSWI fly ash and pickling sludge

In consideration of recycling solid waste to achieve high value-added products, glass-ceramics have been fabricated from municipal solid waste incineration (MSWI) fly ash, pickling sludge (PS), and waste glass (WG) by melting at 1450 °C firstly to achieve parent glass and then crystallizing at 850 °C. Results demonstrated that heavy metals have been well solidified in the prepared glass-ceramics, and relatively/extremely low leaching concentrations of heavy metals have been detected. The synthetic toxicity index of heavy metals has been greatly reduced from 7-18 to <3.2 after crystallization treatment, and the leaching concentrations of Cr, Ni, Zn, Cu, and Pb are 0.15, 0.05, 0.26, 0.12, 0.19 mg L^-1 respectively. Chemical morphology analysis, principal component analysis, TEM and EPMA were utilized to clarify the migration, transformation, and solidification mechanism of heavy metals from the as-received solid wastes. The major heavy metals, Cr and Ni which is responsible for the most toxicity, mainly exist in form of the oxidation state and residual state in parent glass, while the residual state in the glass-ceramics. The solidification performance was mostly positively correlated with the form of residue state, which the stability of heavy metals in glass-ceramics is improved. The solidification mechanism of heavy metals in glass-ceramics could be explained by the combination of chemical solidification/stabilization and physical coating. The TEM and EPMA confirmed that Cr and Ni mainly exist in the spinel crystalline (NiCr₂O₄, Fe_0.99Ni_0.01Fe_1.97Cr_0.03O₄) by solid solution or chemical substitution, and a small amount of Cr in the diopside phase. Pb, Cu, and Zn are homogenously dispersed in the glass-ceramics, which is considered as physical coating solidification.     

In situ radiotracer and voltammetric study of the formation of surface adlayers in the course of Cr(VI) reduction on polycrystalline and (1 1 1) oriented platinum

This paper is focused on the in situ radiotracer and voltammetric studies of the induced HSO₄⁻/SO₄²⁻ adsorption at Pt(poly) and Pt(1 1 1) surfaces in 0.1 mol dm⁻³ HClO₄ solution in the course of Cr(VI) electroreduction. Besides this, the sorption behavior of HSO₄⁻/SO₄²⁻ ions on bare Pt(poly) and Pt(1 1 1) electrodes is compared and discussed. From the experimental results it can be stated that: (i) although the extent of bisulfate/sulfate adsorption is strongly dependent upon the crystallographic orientation of Pt surfaces, the maximum coverage on the Pt(1 1 1) does not exceed 0.2 monolayer; (ii) the Cr(VI) electroreduction on both poly- and (1 1 1) oriented platinum proceeds via a ce (chemical-electron-transfer) mechanism to yield Pt surfaces covered with intermediate surface adlayers containing Cr(VI) particles (and reduced Cr-containing adspecies) and ‘strongly bonded’ HSO₄⁻/SO₄²⁻ ions; (iii) while the coverage of platinum surfaces by the intermediate complexes formed in the course of Cr(VI) electroreduction at E > 0.20 V is basically independent of the crystallographic orientation of the Pt electrode, the onset for rapid Cr(VI) reduction is highly affected by the nature and crystallographic orientation of the electrode.     

Electrodeposition of Co-Ni and Co-Ni-Cu systems in sulphate-citrate medium

Electrodeposition of Co-Ni and Co-Ni-Cu alloys was performed in a sulphate-citrate medium. Experimental electrodeposition parameters (pH, cobalt(II), nickel(II) and citrate concentrations) were varied in order to analyse their influence on the deposition. Anomalous Co-Ni codeposition occured in the citrate medium. High [Ni(II)]/[Co(II)] ratios (above 5) were suitable for the preparation of homogeneous magnetic Co-rich Co-Ni deposits of hexagonal close-packed (hcp) structure or face centred cubic (fcc) structure as a function of the deposition potential.The presence of very low copper(II) concentrations (<10⁻² mol dm⁻³) in the nickel-cobalt bath makes it possible to incorporate copper in the deposits in amounts ranging from 5 to 60% Cu, although uniform deposits are obtained only for low copper percentages. These ternary deposits are solid solutions with fcc structure and magnetic behaviour both dependent on the deposition potential.     

Ni- and Fe-based catalysts for hydrogen and carbon nanofilament production by catalytic decomposition of methane in a rotary bed reactor

Four catalysts, consisting of Ni, Ni:Cu, Fe or Fe:Mo as the active phase and Al₂O₃ or MgO as a textural promoter, were tested for the catalytic decomposition of methane in a rotary bed reactor, obtaining both CO₂-free hydrogen and carbon nanostructures in a single step. Hydrogen yields of up to 14.4 Ndm³ H₂·(h·g_cat)^− 1 were obtained using the Ni-based catalysts, and methane conversions above 80% were observed with the Fe-based catalysts. In addition to hydrogen production, the Ni-based catalysts allowed the large-scale production of fishbone-like carbon nanofibres, whereas the use of the Fe-based catalysts promoted the production of carbonaceous filaments having a high degree of structural order, consisting of both chain-like carbon nanofibres and carbon nanotubes.     

Heavy metals contribution of non-aqueous fluids used in offshore oil drilling

A monitoring program was performed to investigate heavy metal content alteration due to exploratory drilling for oil using non-aqueous fluids (NAFs) in Brazilian offshore, 900 m deep. Fourteen elements were monitored in 54 sites and it was verified that after drilling activities the average Ba concentration was remarkably increased with respect to background level, even 1 year after the activity. A minor increase in Mn and a moderate increase in Al concentrations were verified. The Cd, Cr, Ni, As, Co, Cu, Pb, V, and Zn concentrations were at the background levels, ca. 1 year after the NAFs drilling materials deposition on the seafloor. The Al, Ba, Cd, Cr, Cu, Ni and Zn mean concentrations were significantly different (P<0.05) between the three sampling operations (cruises) performed, while As, Cd, Fe and Pb presented different mean values according to the distance of the oil well, independent of the sampling operation. Interaction between sampling operation and distance was observed for Mn. In all sediment samples the Hg concentration was below the detection limit (0.07 μg g⁻¹).     

Methane reforming reaction with carbon dioxide over SBA-15 supported Ni-Mo bimetallic catalysts

A series of mesoporous molecular sieves SBA-15 supported Ni-Mo bimetallic catalysts (xMo1Ni, Ni = 12 wt.%, Mo/Ni atomic ratio = x, x = 0, 0.3, 0.5, 0.7) were prepared using co-impregnation method for carbon dioxide reforming of methane. The catalytic performance of these catalysts was investigated at 800 °C, atmospheric pressure, GHSV of 4000 ml·g_cat^− 1·h^− 1 and a V(CH₄)/(CO₂) ratio of 1 without dilute gas. The result indicated that the Ni-Mo bimetallic catalysts had a little lower initial activity compared with Ni monometallic catalyst, but it kept very stable performance under the reaction conditions. In addition, the Ni-Mo bimetallic catalyst with Mo/Ni atomic ratio of 0.5 showed high activity, superior stability and the lowest carbon deposition rate (0.00073g_c·g_cat^− 1·h^− 1) in 600-h time on stream. The catalysts were characterized by power X-ray diffraction, N₂-physisorption, H₂-TPR, CO₂-TPD, TG and TEM. The results indicate that the Ni-Mo bimetallic catalysts have smaller metal particle, higher metal dispersion, stronger basicity, metal-support interaction and Mo₂C species. It is concluded that Mo species in the Ni-Mo bimetallic catalysts play important roles in reducing effectively the amount of carbon deposition, especially the amount of shell-like carbon deposition.     

Selection of an oxidant for copper chemical mechanical polishing: Copper-iodate system

Diagnostic criteria were developed to elucidate the reduction mechanism of an oxidant on a copper (Cu) surface at the corrosion potential. The corrosion potential of Cu tu was measured for various pH and iodate (IO₃^–) concentrations using the rotating disk electrode technique. According to the measured corrosion potentials, IO₃^– was an effective CMP oxidant only below pH Application of the diagnostic criteria on the Cu – IO₃^– system showed that the reduction of IO₃^– on Cu was under the mixed kinetic and diffusion control at the corrosion potentia l below pH 3. Above pH 3, however, the anodic process dominated over the cathodic process.     

35CrMo和00Cr13Ni5Mo硫化氢环境应力腐蚀开裂

用慢应变速率拉伸实验和U形试样浸泡实验、电化学极化技术并结合微观分析手段,在湿硫化氢介质中研究了35CrMo和00Cr13Ni5Mo两种钢的应力腐蚀开裂行为规律。结果表明,35CrMo和00Cr13Ni5Mo钢在实验条件下均具有一定应力腐蚀开裂（SCC）敏感性,其敏感性随着溶液pH的降低和H₂ S浓度的增大而增大;00Cr13Ni5Mo 在实验条件下抗SCC的能力均高于同条件下的35CrMo,在pH3.0的溶液中,二者性能比较接近,在pH4.5的溶液中,00Cr13Ni5Mo 耐H₂S环境SCC的性能明显提高,高于35CrMo,这主要是因为00Cr13Ni5Mo中的耐蚀合金元素增强了其钝化膜的稳定性、降低了氢脆作用所致。     

A three-step metal fractionation scheme for fly ashes collected in an Argentine thermal power plant

A new three-step fractionation scheme was applied to study the distribution of Al, As, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, S, Sb, Ti, V and Zn in fly ashes collected in the electrostatic precipitator of a thermal power plant in the city of San Nicolás (Argentina). Seven samples were collected during one week of operation in 2005. For the fractionation, the scheme applied consisted of extracting the elements in three fractions: (i) soluble and exchangeable elements, (ii) carbonates, oxides and reducible elements and (iii) residual elements. Metals and metalloids at μg g⁻¹ level were determined in each fraction by plasma based techniques namely, inductively coupled plasma optical emission spectrometry (ICP OES) and inductively coupled plasma mass spectrometry (ICP-MS). For validation, a certified reference materials NIST SRM 2711 (Montana soil) was subject to the same chemical sequential extraction procedure. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the major minerals present in the matrix. The predominant phases found in the total samples were mullite, quartz, iron oxides and lime. Total analyte concentration varied (in μg g⁻¹) from 1.54 for Cd to 30 600 for Al. The leachability of the 15 elements under study proved to be different. All the elements (except Cd and Pb) were detected in the soluble fraction in the order: Cu (0.10%) ∼ Mn (0.13%) < Ni (0.17%) ∼ Ti (0.19%) ∼ Fe (0.20%) ∼ As (0.21%) < Zn (0.86%) < Al (1.3%) < Cr (2.9%) < V (3.9%) < Sb (6.9%) < Mo (45.1%) < S (58.0%). Percentages higher than 20% of S (24.1%) < V (27.5%) < Mn (29.0%) were detected in the second fraction. Al, As, Cr, Cd, Cu, Fe, Ni, Pb, Sb and Zn were mostly associated to the residual fraction. Recoveries of the overall procedure varied between 106% (Mo) and 72% (Cr).     

Effect of reduction conditions on electrocatalytic activity of a ternary PtNiCr/C catalyst for methanol electro-oxidation

The effect of reduction conditions on a Pt₂₈Ni₃₆Cr₃₆/C catalyst was investigated by using two different reduction methods: hydrogen reduction and NaBH₄ reduction. In hydrogen reduced catalysts, dissolution of metallic Ni and Cr was observed during cyclic voltammetry (CV) tests, and a larger amount of Ni and Cr was dissolved when reduced at higher temperatures. For methanol electro-oxidation, the highest specific current density of 1.70 A m⁻² at 600 s of the chronoamperometry tests was observed in the catalyst reduced at 300 °C, which was ∼24 times that of a Pt/C catalyst (0.0685 A m⁻²). In NaBH₄ reduced catalysts, formation of an amorphous phase and a more Pt-rich surface was observed in X-ray diffraction and CV results, respectively, with increasing amounts of NaBH₄. When reduced by 50 times of the stoichiometric amount of NaBH₄, the PtNiCr/C catalyst (PtNiCr-50t) showed a current density of 34.1 A g_{noble metal}⁻¹, which was 81% higher than the 18.8 A g_{noble metal}⁻¹ value of a PtRu/C catalyst at 600 s of the chronoamperometry tests. After 13 h of chronoamperometry testing, the activity of the PtNiCr-50t (15.0 A g_{noble metal}⁻¹) was 110% higher than the PtRu/C catalyst (7.15 A g_{noble metal}⁻¹). The PtNiCr/C catalyst shows promise as a Ru-free methanol oxidation catalyst.