Equilibrium and kinetic studies on the extraction of gadolinium(III) from nitrate medium by di‐2‐ethylhexylphosphoric acid in kerosene using a single drop technique

The liquid–liquid extraction of Gd(III) from aqueous nitrate medium was studied using di‐2‐ethylhexylphosphoric acid (HDEHP) in kerosene. On the basis of the slope analysis data, the composition of the extracted species was found to be [Gd A₃(HA)] with the extraction equilibrium constant (K_ex) = (1.48 ± 0.042) × 10^?12 mol dm^?3. The results of the effect of temperature on the value of the equilibrium extraction constant indicated the endothermic character of the extraction system. The kinetics of the forward extraction of Gd³⁺ from nitrate medium by HDEHP in kerosene was investigated using the single drop column technique. The rate of flux (mass transfer per unit area) was found to be proportional to [Gd(III)], [H₂A₂]_(o), [NO₃^?], and [H⁺]^?1 in the liquid drop organic phase. The forward extraction rate constant, k_f, was 2.24 × 10^?3 m s^?1 using the equation: Copyright © 2005 Society of Chemical Industry     

Start‐up and enrichment of a granular anammox SBR to treat high nitrogen load wastewaters

BACKGROUND: Landfill leachate is characterized by low biodegradable organic matter that presents difficulties for the complete biological nitrogen removal usually performed by conventional biological nitrification/denitrification processes. To achieve this, the anaerobic ammonium oxidation (anammox) process is a promising biological treatment. This paper presents an anammox start‐up and enrichment methodology for treating high nitrogen load wastewaters using sequencing batch reactor (SBR) technology. RESULTS: The methodology is based on the gradual increase of the nitrite‐to‐ammonium molar ratio in the influent (from 0.76 to 1.32 mole NO₂^?‐N mole^?1NH₄⁺‐N) and on the exponential increase of the nitrogen loading rate (NLR, from 0.01 to 1.60 kg N m^?3 d^?1). 60 days after start‐up, anammox organisms were identified by polymerase chain reaction (PCR) technique as Candidatus Brocadia anammoxidans. After one year of operation, NLR had reached a value of 1.60 kg N m^?3 d^?1 with a nitrogen (ammonium plus nitrite) removal efficiency of 99.7%. The anammox biomass activity was verified by nitrogen mass balances with 1.32 ± 0.05 mole of nitrite removed per mole of ammonium removed and 0.23 ± 0.05 mole of nitrate produced per mole of ammonium removed. Also, enrichment of anammox bacteria was quantified by fluorescence in situ hybridization (FISH) analysis as 85.0 ± 1.8%. CONCLUSIONS: This paper provides a methodology for the enrichment of the anammox biomass in a SBR to treat high nitrogen loaded wastewaters. Copyright © 2007 Society of Chemical Industry     

Simultaneous nitrification and denitrification with electricity generation in dual‐cathode microbial fuel cells

BACKGROUND: Nitrogen removal using microbial fuel cells (MFCs) is of great interest owing to the potential benefits of bioenergy production. In this study, simultaneous nitrification and denitrification in dual‐cathode MFCs was investigated. RESULTS: The dual‐cathode MFCs investigated were capable of generating electricity and removing nitrogen, influenced by operating methods, nitrogen loading rates and external resistance. Depending on the ammonium concentration in the anode chamber, 84–97% of the ammonium nitrogen was removed via nitrification in the aerobic cathode. The removals of nitrate and total nitrogen were relatively low (～50%) at the influent ammonium concentration of 80 mg NH₄⁺‐N L^?1, but were significantly improved to more than 90% at a lower ammonium input (40 and 20 mg NH₄⁺‐N L^?1). When the electrode couples were electrically connected for different purposes, with high power output from the anode/aerobic cathode and high current generation from the anode/anoxic cathode, nitrogen removal was also improved. An investigation of aeration suggested that factors other than carbon supply, possibly inefficient reactor configuration, also limited the performance of the developed MFC. CONCLUSION: The experimental results demonstrated that the proposed pathway was feasible with effective nitrogen and organic removal. This study provided valuable information for the further development of a continuously operated dual‐cathode MFC system. Copyright © 2011 Society of Chemical Industry     

Fabrication of BaZr0.1Ce0.7Y0.2O3 – δ ‐Based Proton‐Conducting Solid Oxide Fuel Cells Co‐Fired at 1,150 °C

Dense proton‐conducting BaZr_0.1Ce_0.7Y_0.2O_{3 – δ} (BZCY) electrolyte membranes were successfully fabricated on NiO–BZCY anode substrates at a low temperature of 1,150 °C via a combined co‐press and co‐firing process. To fabricate full cells, the LaSr₃Co_1.5Fe_1.5O_{10 – δ}–BZCY composite cathode layer was fixed to the electrolyte membrane by two means of one‐step co‐firing and two‐step co‐firing, respectively. The SEM results revealed that the cathode layer bonded more closely to the electrolyte membrane via the one‐step co‐firing process. Correspondingly, determined from the electrochemical impedance spectroscopy measured under open current conditions, the electrode polarisation and Ohmic resistances of the one‐step co‐fired cell were dramatically lower than the other one for its excellent interface adhesion. With humidified hydrogen (2% H₂O) as the fuel and static air as the oxidant, the maximum power density of the one‐step co‐fired single cell achieved 328 mW cm^–2 at 700 °C, showing a much better performance than that of the two‐step co‐fired single cell, which was 264 mW cm^–2 at 700 °C.     

Enhanced proton conductivity from phosphoric acid‐incorporated 3D polyacrylamide‐graft‐starch hydrogel materials for high‐temperature proton exchange membranes

To enhance anhydrous proton conductivity of high‐temperature proton exchange membranes (PEMs), we report here the realization of H₃PO₄‐imbibed three‐dimensional (3D) polyacrylamide‐graft‐starch (PAAm‐g‐starch) hydrogel materials as high‐temperature PEMs using the unique absorption and retention of crosslinked PAAm‐g‐starch to concentrated H₃PO₄ aqueous solution. The 3D framework of PAAm‐g‐starch matrix provides enormous space to keep H₃PO₄ into the porous structure, which can be controlled by adjusting crosslinking agent and initiator dosages. Results show that the H₃PO₄ loading and therefore the proton conductivities of the membranes are significantly enhanced by increasing the amount of crosslinking agent and initiator dosages. Proton conductivities as high as 0.109 S cm^?1 at 180°C under fully anhydrous state are recorded. The high conductivities at high temperatures in combination with the simple preparation, low cost, and scalable matrices demonstrate the potential use of PAAm‐g‐starch hydrogel materials in high‐temperature proton exchange membrane fuel cells. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40622.     

A “proton pump” concept for the investigation of proton transport and anode kinetics in proton exchange membrane fuel cells

A novel concept for the measurement of proton transport properties and electrode kinetics in proton exchange membrane fuel cells (PEMFC) is presented. The “proton pump” is essentially a fuel cell operated with pure nitrogen or very low hydrogen partial pressure instead of oxygen-containing gas on the cathode side, avoiding the complicated electrode kinetics of oxygen reduction. In this first study using this concept, we investigated the proton transport in high temperature PEMFC based on polybenzimidazole (PBI)/phosphoric acid membranes. The impedance spectra of the proton pump allow the clear distinction between anode and cathode kinetics and proton transport in the membrane. Identifying and analyzing the contribution of the anodic processes in the impedance spectra enabled the quantitative investigation of anode kinetics based on the Butler-Volmer equation. The proton transport was investigated in more detail in the current saturation region, where proton transport turned out to be the limiting process in case of sufficient H₂ supply at the anode. The maximum proton transport capacity of the PBI/phosphoric acid membrane was found to be comparable to those of Nafion^® membranes.     

Carbon‐supported perovskite oxides as oxygen reduction reaction catalyst in single chambered microbial fuel cells

BACKGROUND: Pt‐free cathodic catalyst is needed for microbial fuel cells (MFCs). Perovskite‐type oxide could be a substitute for Pt because it has been proved to be a highly active and low‐cost oxygen reduction catalyst in chemical fuel cells. RESULTS: A nano‐sized La_0.4Ca_0.6Co_0.9Fe_0.1O₃ perovskite‐type oxide on a carbon support (LCCF/C) was prepared and tested for its performance and stability (15 cycles) in MFCs. An exchange current density of 7.030 × 10^?5 (A cm^?2) was obtained with fresh LCCF/C cathode and is increased to 7.438 × 10^?5 (A cm^?2) after 15 cycles operating in MFCs. A power density of 405 mW m^?2 was achieved with the LCCF/C cathode at the 2nd cycle which was between those of Pt/C (560 mW m^?2) and C (339 mW m^?2) cathodes. At the end of the 15th cycle, the lowest decay (due to biofouling) rate on the open circuit voltage (2%) and the maximum power density (15%) were observed with LCCF/C cathode compared with those of Pt/C (4%, 17%) and C (22%, 69%) cathodes, respectively. CONCLUSIONS: This study demonstrated that perovskite‐type oxide on carbon support catalysts could be a potential substitute for Pt for cathodic oxygen reduction reaction (ORR) in air‐cathode MFCs. © 2012 Society of Chemical Industry     

Use of various processes for pilot plant treatment of wastewater from a wood‐processing factory

The wastewater from a wood‐processing factory is characterized by a high COD, chlorides and nitrogen content. Various treatment processes were applied to treat this wastewater in pilot‐scale units. By applying one‐stage denitrification–activated sludge biological treatment it was not possible to remove nitrogen. Nitrification was inhibited by wastewater compounds. By applying a second stage of a nitrification biofilter it was possible to have a high degree of nitrification. The denitrification was complete. With biological methods the reduction of COD, and ‐N and ‐N concentrations to acceptable values was not achievable. Physical–Chemical methods as H₂O₂/UV, electrolysis and ozonation were used as post‐treatment of effluents from the biological system. Radical degradation, initiated by the powerful hydroxyl radicals which are generated from H₂O₂ by UV activation, is used for wastewater post‐treatment. The combination of H₂O₂/UV was not suitable for post‐treatment of this wastewater. With electrolysis, ‐N and COD removal can be complete. The total amount of ammonia and organic nitrogen converted to nitrate nitrogen for current density of 1.15 Adm^?2 and energy consumption of 71.6 kWhm^?3 was 0.35 gdm^?3. Further biological denitrification is required for ‐N removal to permitted values. Energy consumption for the elimination of 1 kg COD was 40.4 kWh and 35.8 kWh for current densities of 0.7 Adm^?2 and 1.15 Adm^?2 respectively. The energy required to reach the limit value of COD equal to 150 mgdm^?3 for current density of 1.15 Adm^?2 was 71.6 kWhm^?3. With ozonation, the COD removal can be complete. Further biological nitrification–denitrification is required to remove ‐N and ‐N to permitted values. At pH 7.0, in order to reach the limit value of COD equal to 150 mgdm^?3, specific ozone dose was 6.0 g per g of COD removed and the total amount of ammonia and organic nitrogen converted to nitrate nitrogen was 0.25 gdm^?3. The total equivalent energy required is estimated to be 75.0 kWhm^?3. © 2001 Society of Chemical Industry     

A Review on Metal‐Free Doped Carbon Materials Used as Oxygen Reduction Catalysts in Solid Electrolyte Proton Exchange Fuel Cells

Within the last decade, metal‐free heteroatom doped carbon nanomaterials have gained attention as effective electrocatalysts for the oxygen reduction reaction (ORR) in many electrochemical systems. Since then, reports have stated that the ORR catalytic activity, onset potential, and H₂O production selectivity of these materials is similar to that of platinum‐based catalysts. These statements rely on cyclic voltammetry (CV) and rotating disc electrode (RDE) measurements in liquid alkaline electrolyte. However, fuel cell researchers aim to replace the costly platinum catalysts in the more prominent acidic solid electrolyte proton exchange fuel cell (PEFC). In this respect, there are only a few reports of unpromising activity, stability, and H₂O production selectivity. In addition, only few reports have been presented on the implementation of such materials in cathode catalyst layers of actual PEFC devices. This mini‐review aims to summarize and evaluate results of these reports. Material synthesis, cell power, open circuit voltage, stability properties, and proposed active sites are reviewed. To date, the highest reported PEFC power densities with guaranteed metal‐free heteroatom doped carbon cathode catalysts have reached up to 321 mW cm⁻²; which although a promising value is substantially short of values obtained for platinum based catalysts.     

Sulphonation of polystyrene‐butadiene rubber with chlorosulphonic acid for proton exchange membrane: Kinetic study

Proton exchange membrane for fuel cell application was synthesized from a hydrophobic polystyrene‐butadiene rubber (PSBR) via sulphonation at different temperatures (22, 35, 55, 65, and 75°C) and varying time with chlorosulphonic acid. Infra‐red spectroscopy (IR) and proton nuclear magnetic resonance (¹H‐NMR) were used to confirm the occurrence of sulphonation. Sulphonation occurred only on the phenyl ring with a maximum degree of sulphonation of 70.96 mole percent. Consequently, 10^?3–10^?2 S/cm proton conductivity was achieved. Two models for the reaction kinetics were investigated: first‐order reversible and first‐order irreversible, respectively. However, the reaction kinetic was found to obey the first‐order reversible model. The activation energy (E_a) of the reaction was calculated to be 41.56 kJ/mol of PSBR repeat unit, which is an indication that the reaction is nonspontaneous. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

PEM fuel cell reaction kinetics in the temperature range of 23-120 °C

The performance of a Nafion 112 based proton exchange membrane (PEM) fuel cell was tested at a temperature range from 23 °C to 120 °C. The fuel cell polarization curves were divided into two different ranges based on current density, namely, <0.4 A/cm² and >0.4 A/cm², respectively. These two ranges were treated separately with respect to electrode kinetics and mass transfer. In the high current density range, a linear increase in membrane electrode assembly (MEA) power density with increasing temperature was observed, indicating the advantages of high temperature operation.Simulation based on electrode reaction kinetic theory, experimental polarization curves, and measured cathodic apparent exchange current densities all gave temperature dependent apparent exchange current densities. Both the calculated partial pressures of O₂ and H₂ gas in the feed streams and the measured electrochemical Pt surface areas (EPSAs) decrease with increasing temperature. They were also used to obtain the intrinsic exchange current densities. A monotonic increase of the intrinsic exchange current densities with increasing temperature in the range of 23-120 °C was observed, suggesting that increasing the temperature does promote intrinsic kinetics of fuel cell reactions.There are two sets of cathode apparent exchange current densities obtained, one set is for the low current density range, and the other is for the high current density range. The different values of cathode current densities in the two current density ranges can be attributed to the different states of the cathode Pt catalyst surface. In the low current density range, the cathode catalyst surface is a Pt/PtO, and in the high current density range, the catalyst surface becomes pure Pt.     

Recent developments in fuel‐processing and proton‐exchange membranes for fuel cells

In recent years, great progress has been made in the development of proton‐exchange membrane fuel cells (PEMFCs) for both mobile and stationary applications. This review covers two types of new membranes: (1) carbon dioxide‐selective membranes for hydrogen purification and (2) proton‐exchange membranes; both of these are crucial to the widespread application of PEMFCs. On hydrogen purification for fuel cells, the new facilitated transport membranes synthesized from incorporating amino groups in polymer networks have shown high CO₂ permeability and selectivity versus H₂. The membranes can be used in fuel processing to produce high‐purity hydrogen (with less than 10 ppm CO and 10 ppb H₂S) for fuel cells. On proton‐exchange membranes, the new sulfonated polybenzimidazole copolymer‐based membranes can outperform Nafion^® under various conditions, particularly at high temperatures and low relative humidities. Copyright © 2010 Society of Chemical Industry     

Modification of sulfonated poly(ether ether ketone) membranes by impregnation with the ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate for proton exchange membrane fuel cell applications

Sulfonated poly(ether ether ketone) (SPEEK) membranes were modified by impregnation with the ionic liquid (IL) 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMI.BF₄) by immersion into an IL aqueous solution for different periods of time. The modified membranes were investigated by thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), ion exchange capacity (IEC), and conductivity. The SPEEK membrane immersed into the IL aqueous solution for 2 min showed greater dimensional and thermal stability than the pristine SPEEK membrane, and achieved higher decomposition temperatures. It also presented a higher conductivity value (1.0 mS cm^?1), indicating that BMI.BF₄ is a promoter of proton conductivity. The membrane electrode assembly (MEA) produced reached maximum values of power density of 0.13 W cm^?2 and current density of 0.54 A cm^?2 during fuel cell operation. The results indicate that the SPEEK membrane modified by immersion for 2 min is promising for use in a proton exchange membrane fuel cell. Its performance yielded values very close to those obtained with Nafion, which reaches maximum values of power density of 0.19 W cm^?2 and current density of 0.77 A cm^?2. POLYM. ENG. SCI. 56:1037–1044, 2016. © 2016 Society of Plastics Engineers     

Sorption of NaOH and NaOC6H5 on quaternary ammonium resin in a fixed‐bed adsorber

The sorption behaviours of NaOH and NaOC₆H₆₅ on quaternary ammonium resin with functional groups of ‐NMe⁺₄CI^? (hydrophilicity) and ‐NBu⁺₄Cl^? (lipophilicity) in an aqueous fixed‐bed adsorber were investigated. The types of resins and salts, salt concentration, and operating temperature were evaluated to achieve the optimum sorption conditions. The probability distribution function of the breakthrough curve was employed to describe the sorption system. The parameters of probability distribution function, sorption rate, exchange capability, height of mass‐transfer zone and degree of saturation were also obtained. The effective exchange capacities for hydrophilic resins were found to be smaller than those for lipophilic resins. The sorption capability of NaOC₆H₅ in the resin was larger than that of NaOH.     

Inhibition of sulfide on the simultaneous removal of nitrate and p‐cresol by a denitrifying sludge

BACKGROUND: Many industrial discharges, such as those generated from petrochemical refineries, contain large amounts of sulfurous, nitrogenous and organic contaminants. Denitrification has emerged as a suitable technology for the simultaneous removal of these pollutants in a single reactor unit; however, more evidence is demanded to clarify the limitations of denitrification on the simultaneous removal of sulfide and phenolic contaminants and to optimize the biological process. The aim of this study was to evaluate the capacity of a denitrifying sludge to simultaneously convert sulfide and p‐cresol via denitrification. RESULTS: Sulfide was the preferred electron donor over p‐cresol, imposing a 5 h lag phase (required for complete sulfide removal) on organotrophic denitrification. Addition of sulfide (20 mg S^2? L^?1) to p‐cresol‐amended denitrifying cultures also decreased the reduction rate of nitrate and nitrite, as well as the production rate of nitrogen gas. Nitrite reduction rate was the most affected step by sulfide, decreasing from 35 to 21 mg N (g VSS d)^?1. A synergistic inhibitory effect of nitrate and sulfide was also observed on nitrite reduction. Despite the effects of sulfide on the respiratory rates monitored, complete removal of nitrate, sulfide and p‐cresol could be achieved after 48 h of incubation. CONCLUSION: Our results suggest that simultaneous removal of sulfide and p‐cresol could be achieved in denitrifying reactors, but a large hydraulic residence time may be required to sustain an efficient process due to inhibitory effects of sulfide. Copyright © 2008 Society of Chemical Industry     

Self Humidifying Hybrid Anion–Cation Membrane Fuel Cell Operated Under Dry Conditions

Hybrid fuel cells composed of a low‐pH proton conductive membrane in contact with a high‐pH anion conductive membrane were investigated. The effect of relative humidity (RH), ionomer content in the anion‐conductive electrode and the inlet gas flow rates were evaluated. The formation of water at the junction of the anion conductive member and proton conductive membrane is especially interesting because it can self‐humidify the fuel cell when dry gases are used. In situ alternative current (AC) impedance spectroscopy was used as a diagnostic tool to understand the performance limitations under different test conditions. The cell output increased at low RH compared to a traditional proton exchange membrane fuel cell. The cell current under dry conditions was limited by the availability of oxygen in the catalyst sites due to flooding in the electrode layer. The ionomer fraction of the high‐pH cathode plays a significant role in the cell performance. At high gas feed rates, water removal from the electrode layers increased and mitigated the effects of flooding. The hybrid cells were operated at steady‐state operation at 0.58 V and 200 mA cm^–2 using dry H₂/O₂ feeds at 80 °C.     

Preparation and characterization of UV‐grafted ion‐exchange textiles in continuous electrodeionization

Ion‐exchange textiles (IETs) suitable for use in continuous electrodeionization (CEDI) stacks were prepared using the ultraviolet (UV)‐induced grafting of acrylic acid and sodium styrene sulfonate for cation‐exchange textiles, or 2‐hydroxyethyl methacrylate and vinylbenzyl trimethyl ammonium chloride for anion‐exchange textiles, onto nonwoven polypropylene fabric using benzophenone as photoinitiator. Although the ion‐exchange capacity (2.2 meq g^?1) of the prepared strong acid cation‐exchange textile was lower than that of IRN77 strong acid cation‐exchange resin (4.2 meq g^?1), the overall rate constant of IET was very high due to its low crosslinking and high specific surface area. There was no significant difference between the two different media in terms of the Co(II) removal rate. Furthermore, the current efficiency for IETs was higher than that of IRN77 cation‐exchange resin during a CEDI operation, with efficiencies of 60% and 20%, respectively. The IET also showed the faster exchange kinetics. Therefore, IETs prepared in this study proved to have desirable ion‐conducting characteristics within the CEDI systems. Also this study revealed that the primary removal mechanism in CEDI is the transport of ions through a medium and not the ionic capacity of a medium. Copyright © 2004 Society of Chemical Industry     

Kinetics,degradation pathway and reaction mechanism of advanced oxidation of 4‐nitrophenol in water by a UV/H2O2 process

Photooxidation of 4‐nitrophenol (4‐NP) in water by the UV/H₂O₂ advanced oxidation process was carried out in order to investigate the kinetics and pathway of 4‐NP degradation. The experimental results showed that the photodegradation of 4‐NP accorded well with pseudo‐first order kinetics. The effects of different parameters, such as H₂O₂ dosage, pH value and various anion scavengers on the degradation of 4‐NP have been investigated in detail. It was found that acidic conditions are more favorable to the degradation of 4‐NP but many anions, such as HCO₃^?, NO₃^? and Cl^?, slow down the photooxidation rate of 4‐NP. Hydroquinone, 1,2,4‐trihdroxybenzene, 4‐nitropyrogallol, and 4‐nitrocatechol were tentatively identified as the intermediates of 4‐NP degradation by GC/MS after samples were derivatized by N,O‐bis(trimethylsilyl)‐trifluoroacetamide (BSTFA). A degradation pathway was proposed to account for the observed intermediates produced during 4‐NP degradation by the UV/H₂O₂ process. Copyright © 2003 Society of Chemical Industry     

Cation‐exchange kinetics and electrical conductivity studies of an ‘organic‐inorganic’ composite cation‐exchanger: Polypyrrole Th(IV) phosphate

Polypyrrole Th(IV) phosphate, an electrically conducting ‘organic‐inorganic’ cation‐exchange composite material was prepared by the incorporation of an electrically conducting polymer, i.e., polypyrrole, into the matrix of a fibrous type inorganic cation‐exchanger thorium(IV) phosphate. The composite cation‐exchanger has been of interest because of its good ion‐exchange capacity, higher chemical and thermal stability, and high selectivity for heavy metal ions. The temperature dependence of electrical conductivity of this composite system with increasing temperatures was measured on compressed pellets by using four‐in‐line‐probe dc electrical conductivity measuring instrument. The conductivity values lie in the semiconducting region, i.e., in the order of 10^?6 to 10^?4 S cm^?1 that follow the Arrhenius equation. Nernst–Plank equation has been applied to determine some kinetic parameters such as self‐diffusion coefficient (D₀), energy of activation (E_a), and entropy of activation (ΔS*) for Mg(II), Ca(II), Sr(II), Ba(II), Ni(II), Cu(II), Mn(II), and Zn(II) exchange with H⁺ at different temperatures on this composite material. These results are useful for predicting the ion‐exchange process occurring on the surface of this cation‐exchanger. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Pore‐forming technology and performance of MEA for direct methanol fuel cells

BACKGROUND: The commercialization of DMFCs is seriously restricted by its relatively low power density. Lots of work has been concentrated on catalysts with high activity, the optimization of flow path design, development of new kinds of proton exchange membrane and modification of Nafion membrane. Meanwhile, very few reports have involved the structure optimization of the membrane electrode assembly (MEA). To improve the performance of direct methanol fuel cells (DMFCs), the catalyst layer (CL) structures of anode and cathode were optimized by utilizing ammonium carbonate as pore forming agent. RESULTS: The polarization curves showed that in catalyst slurry the optimal content of ammonium carbonate was 50 wt%, and the DMFC performance was enhanced from 75.65 mW cm^?2 to 167.42 mW cm^?2 at 55 °C and 0.2 MPa O₂. Electrochemical impedance spectroscopy and electrochemical active surface area (EASA) testing revealed that the improved performance of optimized MEAs could be mainly attributed to the increasing EASA and the enhanced mass transfer rate of CLs. But poor methanol crossover limited the performance enhancement of MEAs with porous anodes. CONCLUSION: With regard to improving cell performance, this pore‐forming technology is better applied to the cathode catalyst layer to improve its structure rather than the anode catalyst layer. © 2012 Society of Chemical Industry