Doped graphene/carbon black hybrid catalyst giving enhanced oxygen reduction reaction activity with high resistance to corrosion in proton exchange membrane fuel cells

Nitrogen doping of the carbon is an important method to improve the performance and durability of catalysts for proton exchange membrane fuel cells by platinum–nitrogen and carbon–nitrogen bonds. This study shows that p-phenyl groups and graphitic N acting bridges linking platinum and the graphene/carbon black(the ratio graphene/carbon black = 2/3) hybrid support materials achieved the average size of platinum nanoparticles with(4.88 ± 1.79) nm. It improved the performance of the lower-temperature hydrogen fuel cell up to 0.934 W cm^(-2) at 0.60 V, which is 1.55 times greater than that of commercial Pt/C. Doping also enhanced the interaction between Pt and the support materials, and the resistance to corrosion, thus improving the durability of the low-temperature hydrogen fuel cell with a much lower decay of 10 mV at 0.80 A cm^(-2) after 30 k cycles of an in-situ accelerated stress test of catalyst degradation than that of 92 mV in Pt/C, which achieves the target of Department of Energy(<30 mV). Meanwhile,Pt/Nr EGO_(2)-CB_(3) remains 78% of initial power density at 1.5 A cm^(-2) after 5 k cycles of in-situ accelerated stress test of carbon corrosion, which is more stable than the power density of commercial Pt/C, keeping only 54% after accelerated stress test.

Effect of HCO_3^- concentration on CO_2 corrosion in oil and gas fields

The effect of HCO3^- concentration on CO2 corrosion was investigated by polarization measurement of potentiodynamic scans and weight-loss method, Under the conditions of high pressure and high temperature, the corrosion rate of steel X65 decreased with the increase of HCO3^- concentration, while pH of solution increased. SEM, EDS, and XRD results of the corrosion scales indir cated that the typical FeCO3 crystallite was found at low HCO3^- concentration but Ca（Fe,Mg）（CO3）2 was found at high HCO3^- con- centration. Ca^2＋ and Mg^2＋ are precipitated preferential to Fe^2＋ at high pH value. Potentiodynamic polarization curves showed that the cathodic current density decreases with the increase of HCO3^- concentration at low HCO3^- concentration. When the HCO3^- concentration reaches 0.126 mol/L, increasing HCO3^- concentration promotes cathodic reactions. Anodic behavior is an active process at low HCO3^- concentration and the anodic current density decreases with the increase of HCO3^- concentration. An evident active-passive behavior is exhibited in anodic process at 0.126 mol/L HCO3^-.

Mechanism of protective film formation during CO_2 corrosion of X65 pipeline steel

Electrochemical techniques, X-ray diffraction （XRD）, and scanning electron microscopy （SEM） were applied to study the corrosion behaviors of X65 steel in static solution with carbon dioxide （CO2） at 65℃. The results show that iron carbonate （FeCO3） deposits on the steel surface as a corrosion product scale. This iron carbonate scale acts as a barrier to CO2 corrosion, and can reduce the general corrosion rate. The protection ability of the scale is closely related to the scale morphological characteristics.

Corrosion Inhibition of Carbon Steel in Hot Hydrochloric Acid Solutions

The dissolution of carbon steel in 5% HCl in the temperature range of 30~90℃ was inhibited by two organic compounds having the general formula: ClR NH2(CH2)n NH2 RCl where R is a benzyl group. The behaviour of these inhibitors in acidic medium were investigated using weight loss method, open circuit potential and linear polarization technique. These inhibitors provided satisfactory corrosion inhibition for carbon steel in hydrochloric acid solutions even at higher temperature and acid concentration (10%). The electrochemical results showed that the polarization resistance (Rp) values increased with increasing inhibitor concentration, also the corrosion current decreased and a higher inhibition efficiency was obtained. The protective properties of these two organic inhibitors were attributed to the chemisorption mechanism

Conductive and corrosion behaviors of silver-doped carbon-coated stainless steel as PEMFC bipolar plates

Ni–Cr enrichment on stainless steel SS316 L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thin continuous Ag-doped carbon film on a porous carbon-coated SS316 L substrate. The corrosion resistance of this film in 0.5 mol·L^（-1） H_2SO_4 solution containing 5 ppm F- at 80°C was investigated using polarization tests. The results showed that the surface treatment of the SS316 L strongly affected the adhesion of the carbon coating to the stainless steel. Compared to the bare SS316 L, the Ag-doped carbon-coated SS316 L bipolar plate was remarkably more stable in both the anode and cathode environments of proton exchange membrane fuel cell（PEMFC） and the interface contact resistance between the specimen and Toray 060 carbon paper was reduced from 333.0 m？·cm^2 to 21.6 m？·cm^2 at a compaction pressure of 1.2 MPa.

Synergic Mechanism of an Organic Corrosion Inhibitor for Preventing Carbon Steel Corrosion in Chloride Solution

The inhibition effect of dimethylethanolamine（DMEA） and its composite with carboxylic acid was studied with the electrochemical tests. The experimental results indicate that DMEA is not a good inhibitor but the composite of DMEA with caprylic acid exhibits excellent inhibiting efficiency. The synergic mechanism of the organic corrosion inhibitors（OCIs） was studied with quantum chemical calculations. It is found that the DMEA forms a quaternary ammonium salt with the proton in carboxylic acid, and a cyclic complex formed between the salt and Fe may be responsible for the enhancement of inhibiting efficiency. The possible hydrogen bond formed between DMEA and carboxylic acid is not enough for the inhibiting effect. This work is helpful to proposing theoretical interpretation as well as developing a functional organic inhibitor to improve the durability of reinforced concrete contaminated with chloride.

Influence of the C-S-H Amount on [Cl^-]/[OH^-]Ratio of Simulated Concrete SPS and the Corrosion Susceptibility of Steel

Two kinds of simulated concrete pore solutions（SPSs） were treated with different amounts of synthetic calcium silicate hydrate（C-S-H）. The variation of the [Cl^-]/[OH^-] ratio in SPS was measured and the corrosion susceptibility of carbon steel in the SPS was investigated with potentiodynamic polarization, EIS and weight lose tests. The experimental results showed that for the SPS at p H 12.5, as the amount of C-S-H increases, the [Cl^-]/[OH^-] ratio increases thereby causing an increase in the corrosion susceptibility of the steel. While for the SPS at p H 9.7, with increasing C-S-H amount, the drop amplitudes of both [Cl^-]/[OH^-] ratio and steel corrosion rate first decrease and then increase, and a 3% C-S-H addition shows the best inhibition effect. XPS results demonstrate that after C-S-H treating in p H 12.5 SPS the [Fe^（3＋）]/[Fe^（2＋）] ratio in the film on steel surface is reduced while in p H 9.7 SPS the [Fe^（3＋）]/[Fe^（2＋）] ratio is increased. The different effects of the C-S-H amount on the two SPSs and the steel corrosion behavior result from the influences of C-S-H on the SPS p H, which is related to the composition of the SPS.

Oxidation of Carbon Supports at Fuel Cell Cathodes： Differential Electrochemical Mass Spectrometric Study

The effects of O2 and the supported Pt nano-particles on the mechanisms and kinetics of the carbon support corrosion are investigated by monitoring the CO2 production using differential electrochemical mass spectrometry in a dual-thin layer flow cell. Carbon can be oxidized in different distinct potential regimes; O2 accelerates carbon oxidation, the rates of CO2 production from carbon oxidation in O2 saturated solution are two times of that in N2 saturated solution at the same potential; Pt can catalyze the carbon oxidation, with supported Pt nanoparticles, the overpotential for carbon oxidation is much smaller than that without loading in the carbon electrode. The mechanism for the enhanced carbon oxidation by Pt and O2 are discussed.

MoS2-rGO hybrid architecture as durable support for cathode catalyst in proton exchange membrane fuel cells

Carbon black is utilized as a conventional electrocatalyst support material for proton exchange membrane fuel cells. However, this support is prone to corrosion under oxidative and harsh environments, thus limiting the durability of the fuel cells. Meanwhile, carbon corrosion would also weaken the linkage between Pt and the support material, which causes Pt agglomeration, and consequently, deterioration of the cell performance. To overcome the drawbacks of a Pt/C electrocatalyst, a hybrid support material comprising molybdenum disulfide and reduced graphene oxide is proposed and synthesized in this study to exploit the graphitic nature of graphene and the availability of the exposed edges of MoS2. TEM results show the uniform dispersion of Pt nanoparticles over the MoS2-rGO surface. Electrochemical measurements indicate higher ECSA retention and better ORR activity after 10000 potential cycles for Pt/MoS2-rGO as compared to Pt/C, demonstrating the improved durability for this hybrid support material.

Effect of the duty cycle of pulsed current on nanocomposite layers formed by pulsed electrodeposition

Nickel-tungsten/carbon nanotube nanocomposite layers with high content and uniform dispersion of carbon nanotubes were fabricated using pulsed electrodeposition technique.Nanocomposite layers were analyzed by scanning electron microscopy, atomic force microscopy, microhardness, and Tafel polarization tests.The effect of the duty cycle of pulsed current or concentration of carbon nanotubes in the metallic matrix on electrochemical and mechanical properties of obtained layers has been investigated.It has been shown that both the electrochemical and mechanical properties of nanocomposite layers that formed by pulsed current were improved significantly with respect to un-composed Ni-W layer.The results were not only concerned by the concentration of carbon nanotubes in the layer but also influenced by the distribution of nanoparticulates in the metallic matrix.

Study on durability of Pt supported on graphitized carbon under simulated start-up/shut-down conditions for polymer electrolyte membrane fuel cells

The primary issue for the commercialization of proton exchange membrane fuel cell（PEMFC） is the carbon corrosion of support under start-up/shut-down conditions. In this study, we employ the nanostructured graphitized carbon induced by heat-treatment. The degree of graphitization starts to increase between 900 and 1300 ℃ as evidenced by the change of specific surface area, interlayer spacing, and ID/IG value. Pt nanoparticles are deposited on fresh carbon black（Pt/CB） and carbon heat-treated at 1700 ℃（Pt/HCB17） with similar particle size and distribution. Electrochemical characterization demonstrates that the Pt/HCB17 shows higher activity than the Pt/CB due to the inefficient microporous structure of amorphous carbon for the oxygen reduction reaction. An accelerating potential cycle between 1.0 and 1.5 V for the carbon corrosion is applied to examine durability at a single cell under the practical start-up/shutdown conditions. The Pt/HCB17 catalyst shows remarkable durability after 3000 potential cycles. The Pt/HCB17 catalyst exhibits a peak power density gain of 3%, while the Pt/CB catalyst shows 65% loss of the initial peak power density. As well, electrochemical surface area and mass activity of Pt/HCB17 catalyst are even more stable than those of the Pt/CB catalyst. Consequently, the high degree of graphitization is essential for the durability of fuel cells in practical start-up/shut-down conditions due to enhancing the strong interaction of Pt and π-bonds in graphitized carbon.

Segmented tomographic evaluation of structural degradation of carbon support in proton exchange membrane fuel cells

The variation of the three-dimensional(3D)structure of the membrane electrode of a fuel cell during proton exchange cycling involves the corrosion/compaction of the carbon support.The increasing degradation of the carbon structure continuously reduces the electrocatalytic performance of proton exchange membrane fuel cells(PEM-FCs).This phenomenon can be explained by performing 3D tomographic analysis at the nanoscale.However,conventional tomographic approaches which present limited experimental feasibility,cannot perform such evaluation and have not provided sufficient structural information with statistical significance thus far.Therefore,a reliable methodology is required for the 3D geometrical evaluation of the carbon structure.Here,we propose a segmented tomographic approach which employs pore network analysis that enables the visualization of the geometrical parameters corresponding to the porous carbon structure at a high resolution.This approach can be utilized to evaluate the 3D structural degradation of the porous carbon structure after cycling in terms of local surface area,pore size distribution,and their 3D networking.These geometrical parameters of the carbon body were demonstrated to be substantially reduced owing to the cycling-induced degradation.This information enables a deeper understanding of the degradation phenomenon of carbon supports and can contribute to the development of stable PEM-FC electrodes.

Spatial variability of soil resistivity and rational sampling for corrosion assessment of carbon steel in Daqing area

Soil resistivity is one of the key indicators of the corrosive classification assessment on metal materials in soil environment. This paper presents variance characters of various quantity of soil resistivity samples data based on the semi-variance function methods of Geo-statistical Analysis by analyzing the regional soil resistivity sampling data in Daqing area. Furthermore, the variance of the soil resistivity as well as entire soil circumstance due to different sampling amounts are also analyzed and compared by means of using the characteristic parameters of the semi-variance function. In addition, this work also studied the rational sampling quantities according to various measurement errors required and evaluated the local soil corrosivity on carbon steel based on the actual measuring data in this area.

Improved field emission properties of carbon nanotube cathodes by nickel electroplating and corrosion

Carbon nanotube（CNT） cathodes prepared by electrophoretic deposition were treated by a combination of nickel electroplating and cathode corrosion technologies.The characteristics of the samples were measured by scanning electron microscopy,energy dispersive X-ray spectroscopy,J-E and F-N plots.After the treatment,the CNT cathodes showed improved field emission properties such as turn-on field,threshold electric field,current density,stability and luminescence uniformity.Concretely,the turn-on field decreased from 0.95 to 0.45 V/μm at an emission current density of 1 mA/cm^2,and the threshold electric field decreased from 0.99 to 0.46 V/μm at a current density of 3 mA/cm^2.The maximum current density was up to 7 mA/cm2 at a field of 0.48 V/μm.In addition,the current density of the CNT cathodes fluctuated at around 0.7 mA/cm^2 for 20 h,with an initial current density 0.75 mA/cm^2.The improvement in field emission properties was found to be due to the exposure of more CNT tips,the wider gaps among the CNTs and the infiltration of nickel particles.

Failure mode investigation of fuel cell for vehicle application

The durability of proton exchange membrane fuel cells （PEMFCs） has been posing a key technical challenge to commercial spread of fuel cell vehicles （FCVs）. To improve the durability, it is necessary to optimize the fuel cell system （FCS） design against failure modes. The fuel cell durability research method at FCS scale was exhibited, and the failure modes of fuel cell were experimentally investigated in this paper. It is found that the fuel cell dry operation, start/stop cycle and gas diffusion layer （GDL） flooding are typical failure modes of fuel cells. After the modifications against the failure modes, the durability of FCSs is improved to over 3000 h step by step.

Electrochemical Characteristics in Seawater for Cold Thermal Spray-Coated Al-Mg Alloy Layer

For corrosion protection of carbon steel in a marine environment,cold arc thermal spray coating was applied to the surface with Al and Al-Mg alloy wires.The surface hardness of Al and Al-Mg thermal spray coatings increased with Mg content.And the various electrochemical experiments were carried out to evaluate corrosion damage characteristics of the thermal spray coating layers.The Al and Al-Mg thermal spray coating layers presented negative potentials compared to carbon steel in corrosion potential measurements.And an anodic polarization experiment revealed a tendency of activation polarization with no passivation.Furthermore,the corrosion damage of the thermal spray coating layer in galvanostatic experiment was observed mainly at the defect area,and the Al-3Mg thermal spray coating layer presented less surface damages than others.In addition,the Al-3Mg thermal spray coating layer showed the lowest corrosion rate while having a sufficient driving voltage for cathodic corrosion protection.Therefore,it is an optimal thermal spray material for sacrificial anode.