Characterization of a high performing passive direct formic acid fuel cell

Small fuel cells are considered likely replacements for batteries in portable power applications. In this paper, the performance of a passive air breathing direct formic acid fuel cell (DFAFC) at room temperature is reported. The passive fuel cell, with a palladium anode catalyst, produces an excellent cell performance at 30 °C. It produced a high open cell potential of 0.9 V with ambient air. It produced current densities of 139 and 336 mA cm⁻² at 0.72 and 0.53 V, respectively. Its maximum power density was 177 mW cm⁻² at 0.53 V. Our passive air breathing fuel cell runs successfully with formic acid concentration up to 10 and 12 M with little degradation in performance. In this paper, its constant voltage test at 0.72 V is also demonstrated using 10 M formic acid. Additionally, a reference electrode was used to determine distinct anode and cathode electrode performances for our passive air breathing DFAFC.     

Characterization of direct formic acid fuel cells by Impedance Studies: In comparison of direct methanol fuel cells

We characterized direct liquid fuel cells by electrochemical impedance spectroscopy (EIS) combined with reversible hydrogen electrode (RHE) under fuel cell operating conditions. EIS has been successfully implemented as an in-situ diagnostic tool using an impedance setup with RHE, capable of singling out individual contributions to the overall polarization of fuel cells and separating the anode and cathode contributions. While a direct methanol fuel cell (DMFC) anode was subject to substantial poisoning by reaction intermediates due to better accessibility of methanol to catalyst surface regardless of anode diffusion media, a direct formic acid fuel cell (DFAFC) anode suffered from significant mass transfer limitation depending on the anode diffusion media property and formic acid concentration. The high frequency resistance of a DFAFC cathode increased linearly with an increase of formic acid concentration by membrane dehydration effect. Interestingly, on both the DMFC and DFAFC cathodes, decrease in the mixed charge transfer resistance with an increase of fuel crossover was observed together with a drop in the cathode potential.     

木质纤维素类生物质稀酸水解技术研究进展

稀酸水解技术被广泛应用于木质纤维素类生物质制取燃料乙醇,是目前经济性最好的酶水解预处理技术.文章从稀酸水解工艺出发,综述了近年来稀酸水解技术中非常有发展前景的高温液态水和超低酸水解技术在国内外的研发现状,归纳了常用的5种水解反应器的处理性能,并对比分析了其优缺点,最后提出了稀酸水解技术在工艺及反应器设计方面的发展方向,为后续研究打下了基础.     

Real contribution of formic acid in direct formic acid fuel cell: Investigation of origin and guiding for micro structure design

We first experimentally verified the real contribution of formic acid (FA) in the direct formic acid fuel cell (DFAFC). By comparing the cell performance of the fuel cell fueled with FA and methanol, we found that FA not only acts as fuel in the fuel cell, but is also of benefit to proton conducting and triple phase boundary (TPB) building in the anode. Considering the real contribution and the special mass transfer behavior of FA in the fuel cell, the anode was reasonably designed and optimized. Carbon cloth was selected as the optimized anode diffusion layer to achieve quick methanol transfer from fuel reservoir to anode catalyst. The decal method was proved to be the better choice for membrane electrode assembly (MEA) fabrication than the traditional hot pressing because it can result in better TPB building and lowering the FA crossover. DFAFC performed approximately 60% better after these anodic micro structure optimizations.     

Platinum-macrocycle co-catalysts for electro-oxidation of formic acid

In this paper, it was found that the electrocatalytic activity of a Pt electrode for the electro-oxidation of formic acid could be dramatically enhanced with the modification of macrocycle compounds, such as iron-tetrasulfophthalocyanine (FeTSPc). The electro-oxidation of formic acid on a modified Pt electrode with FeTSPc occurs mainly through a direct pathway. A series of macrocycle compounds were also investigated as modifiers and exhibited a promotion effect similar to the Pt electrode. Therefore, platinum-macrocycle co-catalysts can promote the electro-oxidation of formic acid through a highly effective route, and are potential catalyst materials for a direct formic acid fuel cell (DFAFC).     

Performance of a direct formic acid fuel cell fabricated by ultrasonic spraying

The performances of a direct formic acid fuel cells (DFAFCs) comprising anode catalyst layers prepared via the following three different coating techniques are tested: direct paint (DP), ultrasonic spraying on the diffusion layer (US-D), and ultrasonic spraying directly on the membrane (US-M). These tests confirm that the ultrasonic spraying is a suitable method for the fabricating DFAFC anodes. Palladium black was used for the anode catalyst and a commercially available Pt/C cathode electrode was used for all tests. Scanning electron microscopy (SEM) revealed deep cracks caused by the porous substrate in the catalyst layers prepared by DP and by ultrasonic spraying on the diffusion layer. However, catalyst layers prepared by ultrasonic spraying directly on the membrane were less cracked and less porous, with small Pd particles. The catalyst layer prepared by ultrasonic spraying directly on the membrane showed the highest electrochemical surface area (ECSA) among the three anodes. In performance tests, ultrasonic spraying on the membrane yielded the highest power output because it produces the lowest ohmic resistance, the lowest anode potential, and the highest ECSA. By coating the catalyst membrane directly with ultrasonic spraying, we prepared a DFAFC with maximum power density as high as 245 mW cm^?2 using 5 M formic acid with 2 mg cm^?2 of catalyst loading.     

Direct synthesis of formic acid as hydrogen carrier from CO2 for cleaner power generation through direct formic acid fuel cell

The objective of this work is to develop a process flow modeling for the synthesis of formic acid from CO₂ and H₂ for energy storage and transport purposes. The use of formic acid as an energy storage medium is promising due to difficulties in hydrogen storage, where formic acid can be stored for a longer time with less losses, and then can be utilized in a direct formic acid fuel cell for cleaner power generation. The process flow is developed using Aspen Plus and Engineering Equation Solver to obtain the energy and mass balances, efficiencies, fuel utilization, and Nernst voltage of the direct formic acid fuel cell. The model is validated against data available in the literature for operating parameters. The results show that the operation parameters such as formic acid formation rate, heat duty, and work values, fuel cell efficiency have a significant influence on the overall performance. The proposed system forms formic acid from gaseous H₂ and CO₂ with an energy efficiency of about 19%. The formed formic acid is initially stored in a tank for energy storage and then used in a direct formic acid fuel cell to produce about 168 kW power with an energy efficiency of 16% at 0.7 V, 25 °C and 1 bar.     

Hydrogen production via electrolysis of aqueous formic acid solutions

Hydrogen was produced via electrolysis of aqueous formic acid solutions, and the effects of the concentrations of formic acid and NaOH on the electrolytic voltage were systematically investigated. The voltage is found to be related to the actual formic acid concentration. When the actual formic acid concentration is higher than 0.8 × 10⁻⁹ M, the initial electrolytic voltage can be as low as 0.30 V, which is much lower than the open circuit voltage in a proton exchange membrane fuel cell. The electrolytic voltage increases with the increase of the current density. Specifically at 1.0 M NaOH and 4.0 M HCOOH, the steady voltage value increases from 0.62 to 0.70 V as the current density increases from 1.0 to 6.0 mA/cm². At 3.0 M HCOOH and 2.5 M NaOH, the hydrogen production rate is 53 μmol/h under 8.0 mA/cm², which is promising for practical industrial-scale hydrogen production.     

Electro-oxidation of formic acid on carbon supported Pt-Os catalyst

Pt-Os (3:1)/C catalyst was prepared through the route of thermal decomposition of metallic carbonyl cluster. TEM image showed Pt-Os nanoparticles were well dispersed on carbon substrate with an average particle size of 2.2 ± 0.9 nm. XRD pattern indicated Pt-Os has a face-centered cubic crystal structure. Characterized by cyclic voltammetry and chronoamperometry, Pt-Os (3:1)/C catalyst shows a superior electro-catalytic activity to formic acid oxidation in comparison with Pt/C catalyst. This improved electro-catalytic performace was mainly due to the fine dispersion of Pt-Os nano particles and bi-functional effect.     

High performance Pd-based catalysts for oxidation of formic acid

Two novel catalysts for anode oxidation of formic acid, Pd₂Co/C and Pd₄Co₂Ir/C, were prepared by an organic colloid method with sodium citrate as a complexing agent. These two catalysts showed better performance towards the anodic oxidation of formic acid than Pd/C catalyst and commercial Pt/C catalyst. Compared with Pd/C catalyst, potentials of the anodic peak of formic acid at the Pd₂Co/C and Pd₄Co₂Ir/C catalyst electrodes shifted towards negative value by 140 and 50 mV, respectively, meanwhile showed higher current densities. At potential of 0.05 V (vs. SCE), the current density for Pd₄Co₂Ir/C catalyst is as high as up to 13.7 mA cm⁻², which is twice of that for Pd/C catalyst, and six times of that for commercial Pt/C catalyst. The alloy catalysts were nanostructured with a diameter of ca. 3–5 nm and well dispersed on carbon according to X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements. The composition of alloy catalysts was analyzed by energy dispersive X-ray analysis (EDX). Pd₄Co₂Ir/C catalyst showed the highest activity and best stability making it the best potential candidate for application in a direct formic acid fuel cell (DFAFC).     

Catalytic reduction of CO2 by Al–Sn-CNTs composite for synthesizing formic acid

Electrochemical reduction and photocatalytic reduction of CO₂ have attracted more and more attention, but they also face the problem of low utilization efficiency of electricity and solar energy. In this study, a new strategy of applying a novel Al–Sn-CNTs composite in electrochemical corrosion process was proposed to reduce CO₂ without additional electricity and light. In the Al–Sn-CNTs/CO₂ system, micro galvanic cell with Al as anode and Sn or CNTs as cathode was formed, and CO₂ was reduced to formic acid on the cathode surface. The cumulative formic acid concentration of the Al–Sn-CNTs/CO₂ system achieved 21.18 mg/L within 60 min under the conditions of initial pH 9.0, Cl⁻ concentration 10 mmol/L, and Al–Sn-CNTs composite dosage 2 g/L. Based on the morphology, crystal structure and electrochemical test results of the Al–Sn-CNTs composite, a possible mechanism of CO₂ reduction to formic acid in the Al–Sn-CNTs/CO₂ system was proposed.     

Facile synthesis of PdAu/C by cold plasma for efficient dehydrogenation of formic acid

Decomposition of formic acid biomass to generate hydrogen is vital for coping with fossil energy depletion, environmental pollution, and developing clean, efficient, safe, and sustainable modern energy system. In this study, a PdAu/C−C bimetallic catalyst was prepared by the co-impregnation method followed by an atmospheric pressure (AP) cold plasma treatment to synthesize PdAu/C−P catalysts. The resulting PdAu/C−P showed excellent catalytic activity for the formic acid dehydrogenation (FAD) reaction. The total volume of H₂ and CO₂ released from the FAD reaction was about 375 mL after 4 h at 50 °C, and the initial turnover frequency (TOF_initial) was 808.6 h⁻¹. We used X−ray diffractometry (XRD), temperature programmed reduction (TPR) and high-resolution transmission electron microscopy (HRTEM) to show that plasma can effectively promote the redispersion of Pd−Au particles on the surface of the support. The average particle size of PdAu/C−P (3.5 ± 1.5 nm) was less than PdAu/C−C (4.4 ± 1.9 nm) and uniformly distributed. X-ray photoelectron spectroscopy (XPS), TPR, and HRTEM showed that PdAu/C−P has a higher degree of alloying. In addition, the strong electric field in the plasma facilitated more metal sites located on the outer surface of the support in PdAu/C−P, and the atomic ratio of M/C (M = Pd and Au) (0.0134) was much larger than that of PdAu/C−C (0.0060). The apparent activation energy (E_a) of PdAu/C−P for the FAD reaction was only 27.25 kJ mol⁻¹, and it had much higher activity and stability than the commercial Pd/C (Sigma−Aldrich). The total volume of H₂ and CO₂ produced over the PdAu/C−P for three cycles was 1.33, 5.87, and 8.56 times that of commercial Pd/C. Overall, the cold plasma enhanced the degree of alloying, promoted the redispersion of agglomerated particles, and regulated the surface enrichment of the active metal components. This is of great significance for guiding the preparation of high−performance multi-metal catalysts by cold plasma.     

Modeling of a flat-plate solar reactor. Degradation of formic acid by the photo-Fenton reaction

This work describes the use of solar radiation to destroy an organic pollutant in aqueous solution, using the photo-Fenton reaction. Formic acid was chosen as the model substrate. A kinetic model that accounts for the dark (Fenton) and the light activated (photo-Fenton) reaction rates in a single mathematical expression has been used. Furthermore, to take into account the irradiated and the nonirradiated liquid volumes, a rigorous mass balance for each one of the reactant species has been applied. Under the adopted operating conditions, an organic pollutant conversion up to 81% was achieved after 1 h of operation. Predictions of the theoretical model were compared with experimental results and good agreement for formic acid and hydrogen peroxide concentration evolutions was obtained. Deviations between model predictions and experimental data were always smaller than 9%. Theoretical and experimental results of the pollutant conversion showed that solar irradiation improves the effectiveness of the Fenton system significantly; a pollutant conversion 175% greater than that obtained with the dark system alone was observed.     

Methanol conditioning for improved performance of formic acid fuel cells

This paper considers the effect of methanol pretreatment on the performance of a direct formic acid fuel cell (DFAFC). We find that conditioning of the cell in methanol results in a substantial increase in current. The current at 60 °C increases from 95 to 320 mA/cm² at 0.3 V. The maximum power density increases from 33 to 119 mW/cm². The cell resistance decreases from 0.37 to 0.32 Ω cm². CO stripping experiments show that the catalyst is not being greatly affected by these changes. Our interpretation of the data is that the anode layer of membrane electrolyte assembly (MEA) undergoes some change during the methanol conditioning. The change improves the performance.     

Solvent effects on high-pressure hydrogen gas generation by dehydrogenation of formic acid using ruthenium complexes

High-pressure H₂ was produced by the selective dehydrogenation of formic acid (DFA) using ruthenium complexes at mild temperatures in various organic solvents and water. Among the solvents studied, 1,4-dioxane was the best candidate for this reaction to generate high gas pressure of 20 MPa at 80 °C using the Ru complex having a dearomatized pyridine-based pincer PN³P* ligand. This complex shows reusability for the high-pressure DFA in 1,4-dioxiane while maintaining the catalytic performance, however, deactivation occurred in other solvents. In dimethyl sulfoxide, its decomposition products may cause catalytic deactivation. The gas pressure generated in 1,4-dioxane was lower than that in water due to the high dissolution of 1,4-dioxane into CO₂ according the vapor-liquid equilibrium calculations. The role of solvent is crucial since it affected the catalytic performance and also the generated gas pressure (H₂ and CO₂) from FA.     

Unusually active palladium-based catalysts for the electrooxidation of formic acid

Formic acid fuel cells offer exciting prospects for powering portable electronic and MEMS devices. Pd-based catalysts further improve the performance of direct formic acid fuel cells while reducing catalyst costs over Pt-based catalysts. This study investigates several Pd-based catalysts, both unsupported and carbon-supported, and compares the electrochemical results with results obtained in an operating fuel cell. Power densities of up to 260 mW cm⁻² were achieved in a fuel cell at 750 mA operating at 30 °C. Carbon-supported catalysts and addition of other metals, such as gold, show potential in further improving the performance of Pd-based catalysts.     

Three-dimensional CFD modeling of a direct formic acid fuel cell

A three-dimensional (3D) with one straight channel computational fluid dynamics (CFD) model is developed by using the ESI-CFD software to investigate the effect of varying operating parameters on the performance of direct formic acid fuel cell (DFAFC) and formic acid crossover from the anode to the cathode side through the membrane. Formic acid concentration (4 M–10 M), temperature (313 K–353 K), anode stoichiometry (1.5–3.0), and cathode stoichiometry (2.0–3.0) are the selected operating parameters in this study. Validation results of the DFAFC are in reasonable agreement with the typical trends reported in the literature on DFAFC performance. Simulation results indicate that formic acid concentration, temperature, anode, and cathode stoichiometry influenced the DFAFC performance and the formic acid crossover. The increments of formic acid concentration or stoichiometric ratio will improve the cell performance; however, the current densities obtained are declining to the increasing temperature. The increase in temperature of the formic acid concentration is found to lead to the decrease in performance. For the formic acid crossover phenomenon, the formic acid crossover flux increases with the increments of formic acid concentration, DFAFC operating temperature, and anode and cathode stoichiometric ratios.     

Mechanistic insights into hydrogen production from formic acid catalyzed by Pd@N-doped graphene: The role of the nitrogen dopant

The catalytic decomposition of formic acid (HCOOH) is a crucial process for hydrogen production technologies. Herein, periodic density functional theory (DFT) calculations were employed to explore the effect of N-doping on the decomposition of formic acid. We designed a series of single Pd-atoms deposited in the single vacancy of N-doped graphene sheets, namely Pd-DGr, Pd–N1Gr, Pd–N2Gr, and Pd–N3Gr, as the proposed catalysts. Our findings show that H₂ production from HCOOH dehydrogenation on these surfaces proceeds via the formate (HCOO) pathway (Path-I) rather than the carboxylate (COOH) pathway (Path-II). Furthermore, the Pd–N3Gr catalyst shows the greatest catalytic reactivity toward HCOOH dehydrogenation via Path-I, requiring an activation energy (E_a) of 0.38 eV.On the other hand, the undesirable dehydration of HCOOH to carbon monoxide (CO) through COOH (Path-IIIA) or formyl (HCO) (Path-IIIB) intermediates is unlikely to occur on Pd–N3Gr due to a large activation energy. We found that the active species on the catalyst surface increased with N-doping concentration. Additionally, microkinetic simulations of the HCOOH decomposition on these surfaces confirmed the high activity and selectivity of the Pd–N3Gr catalyst toward HCOOH dehydrogenation (Path-I). These calculated results highlight that the Pd–N3Gr catalyst is a promising candidate for the formic acid decomposition reaction to yield hydrogen.     

Amine-functionalized sepiolite: Toward highly efficient palladium nanocatalyst for dehydrogenation of additive-free formic acid

Formic acid has recently come to be considered as a promising material for chemical storage of hydrogen. To date, highly efficient and low-cost heterogeneous catalysts for formic acid dehydrogenation without additive under mild conditions are still limited. In this work, we employed amine-functionalized sepiolite, a typical natural clay mineral with fibrous structure, as support to synthesize a nanocatalyst by the simple impregnation-reduction method. The amine groups on amine functionalized sepiolite support are shown to significantly reduce the average size of Pd nanoparticles (from 7.60 to 2.80 nm) as well as provide a synergistic effect with the Pd nanoparticles, which boosts the rate of additive-free formic acid dehydrogenation (initial turnover frequency (TOF) values of 5587 h⁻¹ at 60 °C, equal to or even better than the most active heterogeneous catalysts). Compared to current catalyst systems, this catalyst can lead to a brighter prospect of cost-efficient heterogeneous catalysts for formic acid dehydrogenation.     

Enhancement of anodic oxidation of formic acid on Pd–Fe bimetallic nanoparticles by thermal treatment

The surface composition and catalytic properties of Pd–Fe bimetallic catalysts with identical bulk composition can be continuously tuned by treatment at different temperatures. The activity of these catalysts in formic acid oxidation was related to the treatment temperature. The thermal treatment temperatures ranged from 400 to 600 °C. The Pd–Fe nanoparticles are characterized by an array of analytical techniques including TEM (transmission electron microscopy), XRD (X-ray diffraction), ICP (inductively coupled plasma) and HS-LEIS (low energy ion scattering spectroscopy). The electrocatalytic activity is examined using cyclic voltammetric and chronoamperometric measurements. The Pd–Fe/C catalyst with 500 °C shows the highest electrocatalytic activity for formic acid oxidation, with a current activity 3 times higher than that of before treated Pd–Fe/C catalyst, 5.6 times higher than that of commercial Pt/C catalyst. The migration of Pd to the surface on the nanoparticle catalysts as well as the electrochemical active surface area of the PdFe–H catalysts was shown to play a major role in enhancing the electrocatalytic activity for catalyst. These findings provided important insights into the correlation between the electrocatalytic activity and the treatment temperature of the nanoengineered bimetallic catalysts.