Preparation of carbon alloy catalysts for polymer electrolyte fuel cells from nitrogen-containing rigid-rod polymers

‘Carbon Alloy Catalysts’ (CAC), non-precious metal catalysts for the oxygen reduction reaction (ORR), were prepared from various kinds of nitrogen-containing rigid-rod aromatic polymers, polyimides, polyamides and azoles, by carbonization at 900 °C under nitrogen flow. The catalytic activity for ORR was evaluated by the onset potential, which was taken at a current density of −2 μA cm⁻². Carbonized polymers having high nitrogen content showed higher onset potential. In particular, CACs derived from azole (Az5) had an onset potential of 0.8 V, despite being was prepared without any metals.     

Hydrogen-rich gas from catalytic steam gasification of municipal solid waste (MSW): Influence of catalyst and temperature on yield and product composition

In the present study the catalytic steam gasification of MSW to produce hydrogen-rich gas or syngas (H₂ + CO) with calcined dolomite as a catalyst in a bench-scale downstream fixed bed reactor was investigated. The influence of the catalyst and reactor temperature on yield and product composition was studied at the temperature range of 750–950 °C, with a steam to MSW ratio of 0.77, for weight hourly space velocity of 1.29 h⁻¹. Over the ranges of experimental conditions examined, calcined dolomite revealed better catalytic performance, at the presence of steam, tar was completely decomposed as temperature increases from 850 to 950 °C. Higher temperature resulted in more H₂ and CO production, higher carbon conversion efficiency and dry gas yield. The highest H₂ content of 53.29 mol%, and the highest H₂ yield of 38.60 mol H₂/kg MSW were observed at the highest temperature level of 950 °C, while, the maximum H₂ yield potential reached 70.14 mol H₂/kg dry MSW at 900 °C. Syngas produced by catalytic steam gasification of MSW varied in the range of 36.35–70.21 mol%. The char had a highest ash content of 84.01% at 950 °C, and negligible hydrogen, nitrogen and sulphur contents.     

Performance improvement of direct carbon fuel cell by introducing catalytic gasification process

In this paper, the effects of catalytic gasification on the solid oxide electrolyte DCFC (direct carbon fuel cell) performance are experimentally investigated and analyzed using K, Ca, Ni as catalyst in carbon black and controlling the temperatures of cell and carbon black at 750 °C and 700-1000 °C, respectively. The average power densities are 976, 1473 and 1543 W m⁻² respectively for 900, 950 and 1000 °C pure carbon black gasification. Catalytic gasification improves the DCFC performance significantly. For the same performance of pure carbon black, the gasification temperatures decrease about 200, 130 and 150 °C with K, Ca and Ni additives, respectively. The catalytic effects for carbon black gasification with CO₂ are: K > Ni > Ca. For typical identical temperature DCFC operating at 750 °C, the power densities of 0.7 V discharging are 1477, 1034 and 1123 W m⁻² for the carbon black with K, Ca and Ni additives, respectively. It is possible to reduce the operation temperature of DCFC to the medium temperature range of solid oxide electrolyte (600-800 °C) by introducing catalytic gasification process.     

Syngas production from catalytic gasification of waste polyethylene: Influence of temperature on gas yield and composition

The catalytic steam gasification of waste polyethylene (PE) from municipal solid waste (MSW) to produce syngas (H₂ + CO) with NiO/γ-Al₂O₃ as catalyst in a bench-scale downstream fixed bed reactor was investigated. The influence of the reactor temperature on the gas yield, gas composition, steam decomposition, low heating value (LHV), cold gas efficiency and carbon conversion efficiency was investigated at the temperature range of 700–900 °C, with a steam to waste polyethylene ratio of 1.33. Over the ranges of experimental conditions examined, NiO/γ-Al₂O₃ catalyst revealed better catalytic performance as a view of increasing product gas yield and of decreasing char and liquid yields in the presence of steam. Higher temperature resulted in more H₂ and CO production, higher carbon conversion efficiency and product gas yield. The highest syngas (H₂ + CO) content of 64.35 mol%, the highest H₂ content of 36.98 mol%, and the highest CO content of 27.37 mol%, were achieved at the highest temperature level of 900 °C. Syngas produced with a H₂/CO molar ratio in the range of 0.83–1.35, was highly desirable as feedstock for Fischer–Tropsch synthesis for the production of transportation fuels.     

Activity of dealloyed PtCo3 and PtCu3 nanoparticle electrocatalyst for oxygen reduction reaction in polymer electrolyte membrane fuel cell

We report a comparative study of the alloy formation and electrochemical activity of dealloyed PtCo₃ and PtCu₃ nanoparticle electrocatalysts for the oxygen reduction reaction (ORR). For the Pt-Co system the maximum annealing temperatures were 650 °C, 800 °C and 900 °C for 7 h to drive the Pt-Co alloy formation and the particle growth. EDS and XRD were employed for the characterization of catalyst powders. The RDE and RRDE experiments were conducted in 0.1 M HClO₄ at room temperature.We demonstrate that the mass and surface area specific ORR activities of Pt-Co and Pt-Cu alloys after voltammetric activation exhibit a considerable improvement compared to those of pure Pt/C. The dealloyed PtCo₃ (800 °C/7 h) electrocatalyst performs 3 times higher in terms of Pt-based mass activity and 4-5 times higher in terms of ECSA-based specific activity than a 28.2 wt.% Pt/C. Dealloyed Pt-Co catalysts (800 °C/7 h) show the most favorable balance between mass and specific ORR activity with a particle size of 2.2 ± 0.1 nm. We hypothesize that geometric strain effects of the dealloyed Pt-Co nanoparticles, similar to those found in dealloyed PtCu₃ nanoparticles, are responsible for the improvement in ORR activity [1].     

Thermocatalytic decomposition of methane for hydrogen production using activated carbon catalyst: Regeneration and characterization studies

A series of experiments was conducted to study the deactivation and regeneration of activated carbon catalyst used for methane thermocatalytic decomposition to produce hydrogen. The catalyst becomes deactivated due to carbon deposition and six decomposition cycles of methane at temperatures of 850 and 950 °C, and five cycles of regeneration by using CO₂ at temperatures of 900, 950 and 1000 °C were carried out to evaluate the stability of the catalyst. The experiment was conducted by using a thermobalance by monitoring the mass gain during decomposition or the mass lost during the regeneration with time. The initial activity and the ultimate mass gain of the catalyst decreased after each regeneration cycle at both reaction temperatures of 850 and 950 °C, but the amount is smaller under the more severe regenerating conditions. For the reaction at 950 °C, comparison between the first and sixth reaction cycles shows that the initial activity decreased by 69, 51 and 42%, while the ultimate mass gain decreased by 62%, 36% and 16% when CO₂ gasification carried out at 900, 950 and 1000 °C respectively. Temperature -programmed oxidation profiles for the deactivated catalyst at reaction temperature of 950 °C and after several cycles showed two peaks which are attributed to different carbon characteristics, while one peak was obtained when the experiment was carried out at 850 °C. In conclusion, conducting methane decomposition at 950 °C and regeneration at 1000 °C showed the lowest decrease in the mass gain with reaction cycles.     

Hydrogen-rich gas from catalytic steam gasification of biomass in a fixed bed reactor: Influence of particle size on gasification performance

The catalytic steam gasification of biomass was carried out in a lab-scale fixed bed reactor in order to evaluate the effects of particle size at different bed temperatures on the gasification performance. The bed temperature was varied from 600 to 900 °C and the biomass was separated into five different size fractions (below 0.075 mm, 0.075–0.15 mm, 0.15–0.3 mm, 0.3–0.6 mm and 0.6–1.2 mm). The results show that with decreasing particle size, the dry gas yield, carbon conversion efficiency and H₂ yield increased, and the content of char and tar decreased. And the differences due to particle sizes in gasification performance practically disappear as the higher temperature bound is approached. Hydrogen and carbon monoxide contents in the produced gas increase with decreasing particle size at 900 °C, reaching to 51.2% and 22.4%, respectively.     

Electrocatalytic reduction of dioxygen on PdCu for polymer electrolyte membrane fuel cells

The present research is aimed to study the oxygen reduction reaction (ORR) on a PdCu electrocatalyst synthesized through reduction of PdCl₂ and CuCl with NaBH₄ in a THF solution. Characterization of PdCu electrocatalyst was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. Characterization results showed that the synthesis method produced spherical agglomerated nanocrystalline PdCu particles of about 10 nm size. The electrochemical activity was evaluated using cyclic voltammetry (CV), rotating disc electrode (RDE) and electrochemical impedance spectroscopy (EIS) in a 0.5 M H₂SO₄ electrolyte at 25 °C. The onset potential for ORR on PdCu is shifted by ca. 30 mV to more positive values and enhanced catalytic current densities were observed, compared to that of pure Pd catalyst. The synthesized PdCu electrocatalyst dispersed on a carbon black support was tested as cathode electrode in a membrane-electrode assembly (MEA) achieving a power density of 150 mW cm⁻² at 0.38 V and 80 °C.     

Effect of calcination temperature of mesoporous alumina xerogel (AX) supports on hydrogen production by steam reforming of liquefied natural gas (LNG) over Ni/AX catalysts

Mesoporous alumina xerogel (AX) supports prepared by a sol–gel method were calcined at various temperatures. Ni/mesoporous alumina xerogel (Ni/AX) catalysts were then prepared by an impregnation method, and were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of calcination temperature of AX supports on the catalytic performance of Ni/AX catalysts in the steam reforming of LNG was investigated. Physical and chemical properties of AX supports and Ni/AX catalysts were strongly influenced by the calcination temperature of AX supports. Crystalline structure of AX supports was transformed in the sequence of γ-alumina → (γ + θ)-alumina → θ-alumina → (θ + α)-alumina with increasing calcination temperature from 700 to 1000 °C. Nickel species were strongly bonded to the divalent vacancy of γ-alumina, (γ + θ)-alumina, and θ-alumina through the formation of nickel aluminate phase. In the steam reforming of LNG, both LNG conversion and hydrogen composition in dry gas showed volcano-shaped curves with respect to calcination temperature of AX supports. Among the catalysts tested, Ni/AX-900 (nickel catalyst supported on AX that had been calcined at 900 °C) showed the best catalytic performance. The smallest nickel crystalline size and the strongest nickel–alumina interaction were responsible for high catalytic performance of Ni/AX-900 catalyst in the steam reforming of LNG.     

Platinum/tin oxide/carbon cathode catalyst for high temperature PEM fuel cell

The performance of high temperature polymer electrolyte fuel cell (HT-PEMFC) using platinum supported over tin oxide and Vulcan carbon (Pt/SnOx/C) as cathode catalyst was evaluated at 160-200 °C and compared with Pt/C. This paper reports first time the Pt/SnOx/C preparation, fuel cell performance, and durability test up to 200 h. Pt/SnOx/C of varying SnO compositions were characterized using XRD, SEM, TEM, EDX and EIS. The face-centered cubic structure of nanosized Pt becomes evident from XRD data. TEM and EDX measurements established that the average size of the Pt nanoparticles were ∼6 nm. Low ionic resistances were derived from EIS, which ranged from 0.5 to 5 Ω-cm² for cathode and 0.05 to 0.1 Ω-cm² for phosphoric acid, doped PBI membrane. The addition of the SnOx to Pt/C significantly promoted the catalytic activity for the oxygen reduction reaction (ORR). The 7 wt.% SnO in Pt/SnO₂/C catalyst showed the highest electro-oxidation activity for ORR. High temperature PEMFC measurements performed at 180 °C under dry gases (H₂ and O₂) showed 0.58 V at a current density of 200 mA cm⁻², while only 0.40 V was obtained in the case of Pt/C catalyst. When the catalyst contained higher concentrations of tin oxide, the performance decreased as a result of mass transport limitations within the electrode. Durability tests showed that Pt/SnOx/C catalysts prepared in this work were stable under fuel cell working conditions, during 200 h at 180 °C demonstrate as potential cathode catalyst for HT-PEMFCs.     

Silver (Ag) as anode and cathode current collectors in high temperature planar solid oxide fuel cells

Planar electrolyte supported solid oxide fuel cells were operated at 900 °C with humidified H₂ for 200 h using silver mesh and paste for cathode current collection. Continuous potentiostatic tests at 0.7 V appeared to induce migration of Ag towards electrode-electrolyte interphase, while continuous OCV tests caused no mass transport. Similar SOFCs fueled by coal syngas at 850 °C using Ag for both anode and cathode current collection indicated little, if any, Ag migration; providing the possibility of employing Ag for 100 h laboratory scale tests using coal-derived syngas. Use of high temperature steam, carbon dioxide and carbon monoxide did not result in the formation of silver carbonates.     

Carbon supported Pt-Y electrocatalysts for the oxygen reduction reaction

Carbon supported Pt₃Y (Pt₃Y/C) and PtY (PtY/C) were investigated as oxygen reduction reaction (ORR) catalysts. After synthesis via reduction by NaBH₄, the alloy catalysts exhibited 10-20% higher mass activity (mA mg_Pt⁻¹) than comparably synthesized Pt/C catalyst. The specific activity (μA cm_Pt⁻²) was 23 and 65% higher for the Pt₃Y/C and PtY/C catalysts, respectively, compared to Pt/C. After annealing at 900 °C under a reducing atmosphere, Pt₃Y/C-900 and PtY/C-900 catalysts showed improved ORR activity; the Pt/C and Pt/C-900 (Pt/C catalyst annealed at 900 °C) catalysts exhibited specific activities of 334 and 393 μA cm_Pt⁻², respectively, while those of the Pt₃Y/C-900 and PtY/C-900 catalysts were 492 and 1050 μA cm_Pt⁻², respectively. X-ray diffraction results revealed that both the Pt₃Y/C and PtY/C catalysts have a fcc Pt structure with slight Y doping. After annealing, XRD showed that more Y was incorporated into the Pt structure in the Pt₃Y/C-900 catalyst, while the PtY/C-900 catalyst remained unchanged. Although these results suggested that the high ORR activity of the PtY/C-900 catalyst did not originate from Pt-Y alloy formation, it is clear that the Pt-Y system is a promising ORR catalyst which merits further investigation.     

Carbon-supported Pd-Co bimetallic nanoparticles as electrocatalysts for the oxygen reduction reaction

Carbon-supported Pd-Co bimetallic nanoparticle electrocatalysts of different Pd/Co atomic ratios were prepared by a modified polyol reduction. Electrocatalytic activities of the catalysts for the oxygen reduction reaction (ORR) have been investigated based on the porous rotating disk and disk-ring electrode techniques. As-prepared Pd-Co bimetallic nanoparticles evidence a single-phase fcc disordered structure, and the mean particle size is found to decrease with increase in Co content. A typical TEM image of the Pd₂Co/C catalyst, heat-treated at 500 °C, reveals a mean particle diameter is ca. 8.3 nm with a relatively narrow size distribution. For synthesized Pd-Co catalysts, the highest catalytic activity for the ORR, when supported on carbon (i.e., Pd-Co/C) was found for a Pd:Co atomic ratio of 2:1 and heat treatment at ca. 500 °C, corresponding to a Pd–Pd mean interatomic distance of ca. 0.273 nm. Kinetic analysis based on the rotating disk and disk-ring electrode measurements reveals that the ORR on Pd-Co/C catalysts undergoes a four-electron process in forming water. Because the Pd-Co/C catalyst is inactive for the adsorption and oxidation of methanol, it may function as a methanol-tolerant ORR catalyst in a direct methanol fuel cell.     

High surface area synthesis,electrochemical activity,and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H₂SO₄. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.     

Evaluation of the catalytic activity of Pd-Ag alloys on ethanol oxidation and oxygen reduction reactions in alkaline medium

Pd-Ag alloys containing different amounts of Ag (8, 21 and 34 at.%) were prepared in order to evaluate their catalytic activity towards the ethanol oxidation (EOR) and oxygen reduction (ORR) reactions. A sequential electroless deposition of Ag and Pd on a stainless steel disc, followed by annealing at 650 °C under Ar stream, was used as the alloy electrode deposition process.From half-cell measurements in a 1.0 M NaOH electrolyte at ≅20 °C, it was found that alloying Pd with Ag leads to an increases of the ORR and EOR kinetics, relative to Pd. Among the alloys under study, the 21 at.% Ag content alloy presents the highest catalytic activity for the EOR and the lowest Ag content alloy (8 at.% Ag) shows the highest ORR activity. Moreover, it was found that the selectivity of Pd-Ag alloys towards ORR is sustained when ethanol is present in the electrolyte.     

High temperature water electrolysis in solid oxide cells

Hydrogen production via high temperature steam electrolysis is a promising technology as it involves less electrical energy consumption compared to conventional low temperature water electrolysis, as consequence of the more favourable thermodynamic and electrochemical kinetic conditions for the reaction. This paper reports on the Solid Oxide Electrolyser Cell (SOEC) performance as function of the operating parameters temperature, humidity and current density. Current–voltage measurements are coupled with impedance spectroscopy, in order to identify the different loss terms in the cell behaviour coming from the electrolyte resistance and the electrode processes. Remarkably high electrical-to-hydrogen energy conversion efficiencies are achieved (e.g., cell voltages of 1.0 and 1.25 V at −1 A cm⁻² and 900 and 800 °C, respectively). Results obtained, moreover, show that an important limitation for the electrolysis reaction, at least at moderate absolute humidity values below about 70 vol.% can be the steam diffusion in the hydrogen/steam electrode.     

Single-site and nanosized Fe-Co electrocatalysts for oxygen reduction: Synthesis, characterization and catalytic performance

The impregnation of Ketjen Black (C) with iron and cobalt phthalocyanines (MPc) taken one by one or as a 1:1 stoichiometric mixture, followed by heat treatment at 600 °C under inert atmosphere, gave materials containing arrays of single metal ions coordinated by four nitrogen atoms (M-N₄ units). Increasing the pyrolysis temperature to 800° resulted in the formation of carbon-supported, nanosized metal particles. A key role of the carbon support in determining the material structure at either temperature investigated was demonstrated by TPD, EXAFS, XANES and XRPD studies. These also showed that a Fe-Co alloy is obtained at 800 °C when the impregnation of Ketjen Black involves a mixture of FePc and CoPc. Electrodes coated with the different Fe, Co and Fe-Co materials, containing ca. 3 wt% metal loadings, were scrutinized for the oxygen reduction reaction (ORR) in alkaline media by linear sweep voltammetry. For comparative purposes, two Pt electrocatalysts containing 3 and 20 wt% metal were investigated. The electrochemical activity of all materials was analyzed by Tafel and Koutecky-Levich plots as well as chronopotentiometry. The Fe-containing electrocatalysts have been found to be highly active for the ORR in alkaline media with convective limiting currents as high as 600 A g Fe⁻¹ at room temperature and onset potentials as high as 1.02 V vs. RHE. It has been found that (i) the ORR mass activity of the Pc-derived electrocatalysts is superior to that of the Pt catalysts investigated; (ii) the activity of FePc and FePc-CoPc/C, heat treated at either 600 or 800 °C, is superior to that of the corresponding Co materials; (iii) the electrocatalysts obtained at 600 °C are fairly more active than those obtained at 800 °C.     

Non-precious metal catalysts synthesized from precursors of carbon, nitrogen, and transition metal for oxygen reduction in alkaline fuel cells

Non-precious metal catalysts (NPMCs) synthesized from the precursors of carbon, nitrogen, and transition metals were investigated as an alternate cathode catalyst for alkaline fuel cells (AFCs). The procedures to synthesize the catalyst and the post-treatment were tailored to refine its electrocatalytic properties for oxygen reduction reaction (ORR) in alkaline electrolyte. The results indicated that the performance of NPMCs prepared with carbon-supported ethylenediamine-transition metal composite precursor and subjected to heat-treatment shows comparable activity for oxygen reduction with Pt/C catalyst. The NPMC exhibits an open circuit potential of 0.97 V and a maximum power density of 177 mW cm⁻² at 50 °C when tested in anion exchange membrane (AEM) fuel cells.     

Nickel–carbon nanocomposites prepared using castor oil as precursor: A novel catalyst for ethanol steam reforming

A novel and simple method to prepare nickel-based catalysts for ethanol steam reforming is proposed. The present method was developed using castor oil as a precursor. The results clarify that the nickel–carbon (Ni/C) catalyst has a high activity for ethanol steam reforming. It was observed that the catalytic behavior could be modified according to the experimental conditions employed. Moreover, it is interesting to note that the increase in the catalytic activity of the Ni/C nanocomposite over time, at 500 and 600 °C of reaction temperature, may be associated with the formation of filamentous carbon. The preliminary results indicate that the novel methodology used, led to the obtainment of materials with important properties that can be extended to applications in different catalytic process.     

High temperature iron-based catalysts for hydrogen and nanostructured carbon production by methane decomposition

The production of hydrogen and filamentous carbon by means of methane decomposition was investigated in a fixed-bed reactor using iron-based catalysts. The effect of the textural promoter and the addition of Mo as a dopant affects the catalysts performance substantially: iron catalyst prepared with Al₂O₃ showed slightly higher catalytic performance as compared to those prepared with MgO; Mo addition was found to improve the catalytic performance of the catalyst prepared with MgO, whereas in the catalyst prepared with Al₂O₃ displayed similar or slightly poorer results. Additionally, the influence of the catalyst reduction temperature, the reaction temperature and the space velocity on the hydrogen yield was thoroughly investigated. The study reveals that iron catalysts allow achieving high methane conversions at operating temperatures higher than 800 °C, yielding simultaneously carbon nanofilaments with interesting properties. Thus, at 900 °C reaction temperature and 1 l g⁻¹_cat h⁻¹ space velocity, ca. 93 vol% hydrogen concentration was obtained, which corresponds to a methane conversion of 87%. Additionally, it was found that at temperatures higher than 700 °C, carbon co-product is deposited mainly as multi walled carbon nanotubes. The textural and structural properties of the carbonaceous structures obtained are also presented.