Online analysis of carbon dioxide from a direct ethanol fuel cell

Carbon dioxide yields from a direct ethanol fuel cell have been monitored by using a commercial infrared CO₂ monitor. The time dependence is reported as a function of temperature, current density, and anode catalyst (Pt vs. PtRu). Yields increased strongly with temperature, with a Faradaic yield of 76% being obtained at 100 °C with a Pt black anode. PtRu gave lower yields than Pt by a factor of ca. 3 at 80 and 100 °C, but higher yields than Pt at ambient temperature. The superior ability of PtRu to strip adsorbed CO is important at low temperatures, but not a key factor at 100 °C.     

Overview of the development of CO-tolerant anode electrocatalysts for proton-exchange membrane fuel cells

Poisoning of Pt anode electrocatalysts by carbon monoxide (CO) is deemed to be one of the most significant barriers to be overcome in the development of proton-exchange membrane fuel cell systems (PEMFCs). The use of CO-tolerant electrocatalysts serves as the most hopeful way to solve this problem. It is well established that Pt-based alloy systems of CO-tolerant electrocatalysts can substantially withstand the presence of CO in the fuel stream. Based on literature starting in 2000, a few efforts have still been conducted at developing a more CO-tolerant anode electrocatalyst than the traditional Pt/C or PtRu/C systems. This review introduces and discusses these efforts.Pt-based electrocatalysts, including PtSn/C, PtMo/C (atomic ratio = 5:1), PtRuMo/C (Mo = 10 wt.%), PtRu–H_xMoO₃/C and PtRu/(C nanotubes), appear to be poisoned by CO at the same, or a lower, level than traditional Pt/C or PtRu/C electrocatalysts. Platinum-free electrocatalysts, such as PdAu/C, have proven to be less strongly poisoned by CO than PtRu/C counterparts at temperatures of 60 °C.A greater tolerance to CO can be achieved by modifying the structure of the electrocatalyst. This involves the use of a composite or double-layer that is designed to make the CO react with one of the electrocatalyst in advance while the main hydrogen reacts at another layer with a traditional Pt/C electrocatalyst.     

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H₂ and CO/H₂ (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.     

A study on composite PtRu(1:1)-PtSn(3:1) anode catalyst for PEMFC

Composite PtRu(1:1)/C-PtSn(3:1)/C catalyst layers with various geometries and loadings were designed for a proton exchange membrane fuel cell (PEMFC) anode to improve carbon monoxide (CO) tolerance of the conventional PtRu(1:1)/C catalyst. The idea was based on an experimental finding that the onset potential of the PtSn for CO oxidation was lower than that of the PtRu and the resultant expectation that there seemed to be a possibility of using the PtSn as a CO filter. The CO tolerance of the composite catalyst of each design was judged by the cell performance obtained through a single cell test using H₂/CO gases of various CO concentrations and compared to that of the PtRu/C catalyst. The highest CO tolerance among the composite catalysts tested in this study was obtained for the one with geometry of double layers in the order of PtRu/C and PtSn/C from the electrolyte layer and with respective PtRu and PtSn loadings of 0.25 and 0.12 mg cm⁻². The cell with this composite catalyst showed better performance than the one with the PtRu/C catalyst. When a H₂/100 ppmCO gas was used as the fuel in the single cell test, the cell voltages were measured to be 0.49 and 0.44 V at a current density of 500 mA cm⁻², respectively for the cell with the composite and PtRu/C catalyst.     

Effect of calcium based catalyst on production of synthesis gas in gasification of waste bamboo chopsticks

This study investigated the effects of calcium based catalyst (calcium oxide) on variation of gas composition in catalytic gasification reaction stages by controlling the gasification temperature between 600 °C and 900 °C whilst varying a catalyst/biomass ratio from 0 to 0.2 w/w. The tested biomass generated from used bamboo chopsticks were used as the feedstock. To assess the gas composition variation, the ratio of H₂/CO, H₂/CO₂, CO/CO₂, and 3H₂/CH₄ are four important factors that affect the performance of catalytic gasification process. The maximum ratio of H₂/CO increased from 0.23 to 0.72 in the gasification temperature range between 600 °C and 900 °C and 0%–20% calcium based catalyst addition ratio. This is due to enhanced H₂ production as a result of the facilitated water–gas shift reaction. The ratios of CO/CO₂ and 3H₂/CH₄ increased significantly from 0.9 to 2.1 and from 2.6 to 4.1, respectively, when the gasification temperature increased from 600 °C to 900 °C and 20% catalyst addition ratio. Obviously, the high temperature and catalyst addition are favorable for production of CO and H₂ during gasification of tested biomass. In conclusion, the tested mineral calcium based catalyst (CaO) can help facilitating the reaction rate of partial oxidation and water–gas shift reaction, enhancing the quality of synthesis gas, and reduction of the gasification reaction time. This catalyst has potential application in gasification of waste bamboo chopsticks in the future.     

Fabrication and performance evaluation of graphene-supported PtRu electrocatalyst for high-temperature electrochemical hydrogen purification

The main aim of this study is to investigate the high-temperature electrochemical hydrogen purification (HT-ECHP) performances of graphene nanoplatelet (GNP) support material decorated with platinum (Pt) and platinum-ruthenium (PtRu) nanoparticles prepared by microwave irradiation technique. Prepared catalysts coupled to the phosphoric acid doped polybenzimidazole (PBI) membrane for HT-ECHP application. The structural and electrochemical properties of the catalysts were examined by thermogravimetric analysis (TGA), X-Ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Transition electron microscopy (TEM) and cyclic voltammetry (CV) analyses. The characterization results indicate that the catalysts provided the necessary properties for HT-ECHP application. The HT-ECHP performances are investigated with reformate gas mixture containing hydrogen (H₂), carbon dioxide (CO₂) and carbon monoxide (CO) in the range of 140–180 °C. The results show that the electrochemical purification performances of the catalysts increase with increasing operating temperature. The highest H₂ purification performance is obtained with PtRu/GNP catalyst. The high electrochemical H₂ purification performance of the PtRu/GNP catalyst can be attributed to the strong synergistic interactions between Pt and Ru particles decorated on the GNP. These results advocate that the PtRu/GNP catalyst is a hopeful catalyst for HT-ECHP application.     

Characterisation of the electrochemical water gas shift reactor (EWGSR) operated with hydrogen and carbon monoxide rich feed gas

Water gas shift units are used to raise the H₂ yield of reforming processes by converting CO to CO₂ and additional H₂. Additional subsequent processes are required to separate H₂ from the product gas stream to obtain pure H₂. This study investigates a novel electrochemical membrane reactor, where the water gas shift reaction occurs electrochemically. The reactor is operated at 393 K and 403 K with electrical energy to enable hydrogen purification in terms of electrochemical pumping, as well as a simultaneous electrochemical CO oxidation to increase the yield of purified H₂. The experimental results show the influence of several operation parameters upon its operation characteristics (e.g. cell voltage, electrochemical CO oxidation, the energy demand, etc.). The process yielded high overall exergy efficiencies of, e.g. 78.3%, whereas the anodic outlet stream contributed with 35%-units, and the purified hydrogen with 43.3%-units.     

Study of Ce-Pt/γ-Al2O3 for the selective oxidation of CO in H2 for application to PEFCs: Effect of gases

In order to supply pure hydrogen to proton exchange membrane (PEM) fuel cells and avoid CO poisoning, selective CO oxidation in H₂ was studied over Ce-Pt/γ-Al₂O₃. Adding the Ce promoted the CO conversion and selectivity of Pt/γ-Al₂O₃ with changing loading weights of Pt and Ce, oxygen concentration, residence time, and the composition of gases (H₂O, CO₂, and N₂). At 250 °C, adding H₂O to the feed gas enhanced the CO conversion due to the water–gas shift reaction. While, adding CO₂ to the feed gas suppressed the CO conversion due to the reversible water–gas shift reaction. In situ BET and XRD tests showed that well-dispersed metallic Pt particles (−2 nm) existed on the Ce oxide over the alumina support, which helps to supply oxygen to the Pt for a high activity of CO oxidation and selectivity.     

Investigation of grain boundary formation in PtRu/C catalyst obtained in a polyol process with post-treatment

The grain boundary formation in PtRu/C catalyst obtained in a polyol process with post-treatment was investigated by scanning transmission electron microscopy, transmission electron microscopy (TEM) and High resolution TEM. The crystalline structure and surface composition of the PtRu/C catalysts were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical activities were evaluated by CO stripping voltammetry and linear sweep voltammetry measurements in combination with in situ IR reflection-absorption spectroscopy. As-prepared isolated spherical nanoparticles on the carbon support started to interconnect after washing procedure, and the interconnection between the particles was greatly promoted by reduction post-treatment at 80 °C; grain boundary formation occurred in the interconnected particles with increasing reduction temperature to 200 °C, and the particles reconstructed severely with further increasing reduction temperature to 400 °C. The defects at the grain boundary served as active sites for methanol electro-oxidation by weakening CO_ads adsorption on Pt sites and facilitating OH_ads formation, and the PtRu/C catalyst treated in 5% H₂/Ar at 200 °C for 10 h had the greatest catalytic activity for methanol electro-oxidation among the PtRu/C catalysts treated under various atmospheres and temperatures.     

High pressure palladium membrane reactor for the high temperature water-gas shift reaction

The water-gas shift (WGS) catalytic membrane reactor (CMR) incorporating a composite Pd-membrane and operating at elevated temperatures and pressures can greatly contribute to the efficiency enhancement of several methods of H₂ production and green power generation. To this end, mixed gas permeation experiments and WGS CMR experiments have been conducted with a porous Inconel supported, electroless plated Pd-membrane to better understand the functioning and capabilities of those processes. Binary mixtures of H₂/He, H₂/CO₂, and a ternary mixture of H₂, CO₂ and CO were separated by the composite membrane at 350, 400, and 450 °C, 14.4 bar (P_tube = 1 bar), and space velocities up to 45,000 h⁻¹. H₂ permeation inhibition caused by reversible surface binding was observed due to the presence of both CO and CO₂ in the mixtures and membrane inhibition coefficients were estimated. Furthermore, WGS CMR experiments were conducted with a CO and steam feed at 14.4 bar (P_tube = 1 bar), H₂O/CO ratios of 1.1-2.6, and GHSVs of up to 2900 h⁻¹, considering the effect of the H₂O/CO ratio as well as temperature on the reactor performance. Experiments were also conducted with a simulated syngas feed at 14.0 bar (P_tube  = 1 bar), and 400-450 °C, assessing the effect of the space velocity on the reactor performance. A maximum CO conversion of 98.2% was achieved with a H₂ recovery of 81.2% at 450 °C. An optimal operating temperature for high CO conversion was identified at approximately 450 °C, and high CO conversion and H₂ recovery were achieved at 450 °C with high throughput, made possible by the 14.4 bar reaction pressure.     

Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells

The electrooxidation of methoxy methane (dimethyl ether) was studied at different Pt-based electrocatalysts in a standard three-electrode electrochemical cell. It was shown that alloying platinum with ruthenium or tin leads to shift the onset of the oxidation wave towards lower potentials. On the other hand, the maximum current density achieved was lower with a bimetallic catalyst compared to that obtained with a Pt catalyst. The direct oxidation of dimethoxy methane in a fuel cell was carried out with Pt/C, PtRu/C and PtSn/C catalysts. When Pt/C catalyst is used in the anode, it was shown that the pressure of the fuel and the temperature of the cell played important roles to enhance the fuel cell electrical performance. An increase of the pressure from 1 to 3 bar leads to multiply by two times the maximum achieved power density. An increase of the temperature from 90 to 110 °C has the same effect. When PtRu/C catalyst is used in the anode, it was shown that the electrical performance of the cell was only a little bit enhanced. The maximum power density only increased from 50 to 60 mW cm⁻² at 110 °C using a Pt/C anode and a Pt_0.8Ru_0.2/C anode, respectively. But, the maximum power density is achieved at lower current densities, i.e. higher cell voltages. The addition of ruthenium to platinum has other effect: it introduces a large potential drop at relatively low current densities. With the Pt_0.5Ru_0.5/C anode, it has not been possible to applied current densities higher than 20 mA cm⁻² under fuel cell operating conditions, whereas 250 and almost 400 mA cm⁻² were achieved with Pt_0.8Ru_0.2/C and Pt/C anodes. The Pt_0.9Sn_0.1/C anode leads to higher power densities at low current densities and to the same maximum power density as the Pt/C anode.     

H2 production via water gas shift in a composite Pd membrane reactor prepared by the pore-plating method

In this work, H₂ production via catalytic water gas shift reaction in a composite Pd membrane reactor prepared by the ELP “pore-plating” method has been carried out. A completely dense membrane with a Pd thickness of about 10.2 μm over oxidized porous stainless steel support has been prepared. Firstly, permeation measurements with pure gases (H₂ and N₂) and mixtures (H₂ with N_2, CO or CO₂) at four different temperatures (ranging from 350 to 450 °C) and trans-membrane pressure differences up to 2.5 bar have been carried out. The hydrogen permeance when feeding pure hydrogen is within the range 2.68–3.96·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5, while it decreases until 0.66–1.35·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 for gas mixtures. Furthermore, the membrane has been also tested in a WGS membrane reactor packed with a commercial oxide Fe–Cr catalyst by using a typical methane reformer outlet (dry basis: 70%H₂–18%CO–12%CO₂) and a stoichiometric H₂O/CO ratio. The performance of the reactor was evaluated in terms of CO conversion at different temperatures (ranging from 350 °C to 400 °C) and trans-membrane pressures (from 2.0 to 3.0 bar), at fixed gas hourly space velocity (GHSV) of 5000 h⁻¹. At these conditions, the membrane maintained its integrity and the membrane reactor was able to achieve up to the 59% of CO conversion as compared with 32% of CO conversion reached with conventional packed-bed reactor at the same operating conditions.     

Three-dimensional numerical modeling on high pressure membrane reactors for high temperature water-gas shift reaction

This study presents a three-dimensional numerical model that simulates the H₂ production from coal-derived syngas via a water-gas shift reaction in membrane reactors. The reactor was operated at a temperature of 900 °C, the typical syngas temperature at gasifier exit. The effects of membrane permeance, syngas composition, reactant residence time, sweep gas flow rate and steam-to-carbon (S/C) ratio on reactor performance were examined. Using CO conversion and H₂ recovery to characterize the reactor performance, it was found that the reactor performance can be enhanced using higher sweep gas flow rate, membrane permeance and S/C ratio. However, CO conversion and H₂ recovery limiting values were found when these parameters were further increased. The numerical results also indicated that the reactor performance degraded with increasing CO₂ content in the syngas composition.     

Na-intercalated carbon nanotubes-supported platinum nanoparticles as new highly effective catalysts for preferential CO oxidation in H2-rich stream

Na⁺-intercalated carbon nanotubes (Na-CNTs) were obtained by impregnation of CNTs with sodium acetate followed by annealing at high temperatures under argon. Stable Na-CNTs-supported Pt catalysts (Pt/Na-CNT catalysts) were then prepared for hydrogen purification via preferential CO oxidation in a H₂-rich stream (CO-PROX). Characteristic studies show that the content of Na⁺ species in CNTs is increased with increased annealing temperature and the Pt nanoparticles with an average size of 2–3 nm are uniformly dispersed on the surfaces of Na-CNTs. An optimized Pt/Na-CNT catalyst with 5 wt% Pt loading can completely remove CO from 40 °C to 200 °C. This catalyst also exhibits long-term stability for 1000 h at 100 °C in feed gas containing 1% CO, 1% O₂, 50% H₂, 15% CO₂, and 10% H₂O balanced with N₂. The electron transfer between the Pt nanoparticles and Na⁺ species plays an important role in enhancing the CO-PROX performance of the catalyst.     

CO tolerance of nano-architectured Pt–Mo anode electrocatalysts for PEM fuel cells

PEM fuel cell membrane electrode assemblies with Nafion electrolytes and commercial Pt-based cathodes were tested with Pt_0.8Mo_0.2 alloy and MoO_x@Pt core–shell anode electrocatalysts for CO tolerance and short-term stability to corroborate earlier thin-film RDE results. Polarization curves at 70 °C for the Pt_0.8Mo_0.2 alloy in H₂ with 25–1000 ppm CO showed a significant increase in CO tolerance based on peak power densities in comparison to PtRu electrocatalysts. MoO_x@Pt core–shell electrocatalysts, which showed extremely high activity for H₂ in 1000 ppm CO during RDE studies, performed relatively poorly in comparison to the Pt_0.8Mo_0.2 and PtRu alloys for the same total catalyst loading on a per area basis in MEA testing. The discrepancy is attributed to residual stabilizer from the core–shell synthesis impacting catalyst-ionomer interfaces. Nonetheless, the MoO_x@Pt electrochemical performance is superior on a per-gram-of-precious-metal basis to the Pt_0.8Mo_0.2 electrocatalyst for CO concentrations below 100 ppm. Due to cross-membrane Mo migration, the stability of the Mo-containing anode electrocatalysts remains a challenge for developing stable enhanced CO tolerance for low-temperature PEM fuel cells.     

Parametric study of membrane reactors for hydrogen production via high-temperature water gas shift reaction

This study presents numerical studies of hydrogen production performance via water gas shift reaction in membrane reactor. The pre-exponential factor in describing the hydrogen permeation flux is used as the main parameter to account for the membrane permeance variation. The operating pressure, temperature and H₂O/CO molar ratio are chosen in the 1–20 atm, 400–600 °C and 1–3 ranges, respectively. Based on the numerical simulation results three distinct CO conversion regimes exist based on the pre-exponential factor value. For low pre-exponential factors corresponding to low membrane permeance, the CO conversion approaches to that obtained from a conventional reactor without hydrogen removal. For high pre-exponential factor, high CO conversion and H₂ recovery with constant values can be obtained. For intermediate pre-exponential factor range both CO conversion and H₂ recovery vary linearly with the pre-exponential factor. In the high membrane permeation case CO conversion and H₂ recovery approach limiting values as the operating pressure increases. Increasing the H₂O/CO molar ratio results in an increase in CO conversion but decrease in H₂ recovery due to hydrogen permeation driving force reduction. As the feed rate increases in the reaction side both the CO conversion and hydrogen recovery decrease because of decreased reactant residence time. The sweep gas flow rate has a significant effect on hydrogen recovery. Low sweep gas flow rate results in low CO conversion H₂ recovery while limiting CO conversion and hydrogen recovery can be reached for the high membrane permeance and high sweep gas flow rate cases.     

Electrooxidation of H2/CO on carbon-supported PtRu-MoOx nanoparticles for polymer electrolyte fuel cells

Ternary PtRu-MoO_x catalysts with various Mo compositions have been investigated as anode electrocatalytic materials for a polymer electrolyte fuel cell fed with H₂/CO mixtures. Electrocatalysts have been prepared using a highly reproducible two step method, which allowed good control over the composition and particle size. All the prepared catalysts record a total metal loading close to 30 wt%, and a Mo load of 0, 1 and 3 wt%, supported on carbon Vulcan XC-72R, keeping the Pt/Ru atomic ratio constant. The incorporation of different amounts of Mo over the PtRu system does not modify structural characteristics such as particle size and crystal phases. However, the surface composition depends largely on the amount of Mo. An increase in the Mo loading to 3 wt% resulted in a decrease of the Pt surface area. The in situ FTIR technique has been used to investigate the CO oxidation process. The extent of CO poisoning was found to be lower for the trimetallic catalysts than for the binary catalyst at a potential below 0.25 V. The fuel cell performance was evaluated at 80 °C in a PEMFC fed with H₂/CO (10 ppm). Polarization curves for the catalysts show that activity depends heavily on composition, with catalysts with a small amount of Mo (1 wt%) displaying the highest CO tolerance. An increase in Mo loading (3 wt%) decreases activity of the PtRuMo, although it also reduces CO poisoning. The presence of Mo⁵⁺ species must be crucial for reducing the saturation coverage of irreversibly adsorbed CO on Pt surface atoms at very low potentials. However, the surface metal ratio of Pt/Mo (wt%) must be higher than 4, in order to keep the enough surface bare platinum sites, which are required for the dissociative adsorption of molecular H₂.     

Selective CO oxidation over a commercial PROX monolith catalyst for hydrogen fuel cell applications

Preferential oxidation (PROX) of CO over noble-metal-containing monolith catalysts is one of the most promising approaches for removing CO to generate low temperature fuel cell quality H₂. The monolith-supported washcoated catalyst comprising Cu and Fe promoted with Pt is highly effective in reducing the CO in practical reformates to less than 10 ppm over a broad range of feed compositions, inlet temperatures and turn down ratios. It is speculated that Pt dissociates the H₂ which then reduces the CuO to its active state. Pt may also act as a cocatalyst for CO adsorption with metal oxides supplying oxygen for PROX reaction. The catalytic system is operated adiabatically with an inlet temperature between roughly 65–120 °C reaching an exit temperature close to 150 °C with no evidence of reverse water gas shift or methanation. The goal was to find the proper operating conditions to achieve <10 ppm CO. Turn down ratios (varying space velocities) at a factor of 4–5 are routinely achieved up to at least 34,000 h⁻¹ with high steam levels of up to 45%. The wide operating window simplifies the control of the PROX reactor and improves the fuel processor’s performance for fast startup and shutdown and responses to transient loads. The catalyst also retains its performance after multiple start and stops modes of operation in reformate.     

Sorbent enhanced hydrogen production from steam gasification of coal integrated with CO2 capture

In this work, CO₂ capture and H₂ production during the steam gasification of coal integrated with CO₂ capture sorbent were investigated using a horizontal fixed bed reactor at atmospheric pressure. Four different temperatures (650, 675, 700, and 750 °C) and three sorbent-to-carbon ratios ([Ca]/[C] = 0, 1, 2) were studied. In the absence of sorbent, the maximum molar fraction of H₂ (64.6%) and conversion of coal (71.3%) were exhibited at the highest temperature (750 °C). The experimental results verified that the presence of sorbent in the steam gasification of coal enhanced the molar fraction of H₂ to more than 80%, with almost all CO₂ was fixed into the sorbent structure, and carbon monoxide (CO) was converted to H₂ and CO₂ through the water gas shift reaction. The steam gasification of coal integrated with CO₂ capture largely depended on the reaction temperature and exhibited optimal conditions at 675 °C. The maximum molar fraction of H₂ (81.7%) and minimum CO₂ concentration (almost 0%) were obtained at 675 °C and a sorbent-to-carbon ratio of 2.