• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.362-367
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• 2009

Recently, the use of formic acid as a fuel for direct liquid fuel cells has emerged as a promising alternative to methanol. In the work presented herein, we evaluated direct formic acid fuel cells(DFAFCs) with various components under operating conditions, for example, the thickness of the proton exchange membrane, concentration of formic acid, gas diffusion layer, and commercial catalyst. The thickness of the proton exchange membrane influenced performance related to the fuel cross-over. To optimize the cell performance, we investigated on the proper concentration of formic acid and catalyst for the formic acid oxidation. Consequently, membrance-electrode assembly(MEA) consisted of $Nafion^{(R)}$-115 and the Pt-Ru black as a anode catalyst showed the maximum performance. This performance was superior to the DMFCs' one.

• Applied Chemistry for Engineering
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• v.19 no.6
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• pp.583-591
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• 2008

Recently, as a demand for the portable device is surged, there are needs to develop a new fuel cell system for replacing the conventionally used secondary battery. For this purpose, it becomes important to develop direct formic acid fuel cell (DFAFC) that uses formic acid as a fuel. The formic acid can offer typical advantages such as excellent non-toxicity of the level to be used as food additive, smaller crossover flux through electrolyte, and high reaction capability caused by high theoretical electromotive force (EMF). With the typical merits of formic acid, the efforts for optimizing reaction catalyst and cell design are being made to enhance performance and long term stability of DFAFC. As a result, to date, the DFAFC having the power density of more than $300mW/cm^2$ was developed. In this paper, basic performing theory and configuration of DFAFC are initially introduced and future opportunities of DFAFC including the development of catalyst for the anode electrode and electrolyte, and design for the optimization of cell structure are discussed.

• 한국신재생에너지학회:학술대회논문집
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• 2008.10a
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• pp.29-32
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• 2008

The cell performance of direct formic acid fuel cell (DFAFC) having catalysts coated by electrospray was analyzed. Pd catalyst was used for the anode electrode and Pd catalyst loading amount and formic acid feed rate dependances of fuel cell performance were evaluated. When loading amount of Pd is in between 3mg/$cm^2$ and 7mg/$cm^2$ and formic acid feed rate is 5ml/min., 3mg/$cm^2$ sample showed better potential at 129 mA/$cm^2$ and power density due to difference in mass transfer limitation. However, when the feed rate is greater than 10ml/min., the opposite tendency was observed between 3mg/$cm^2$ and 7mg/$cm^2$ samples. The result was attributed to improvement in electrochemical reaction of the Pd. Based on the above results, In DFAFC including Pd catalyst that was coated by electrospray, 0.537V as the maximum potential at 129 mA/$cm^2$ was attained.

• Applied Chemistry for Engineering
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• v.27 no.2
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• pp.123-127
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• 2016

Methanol fuel cells having advantages of relatively favorable reaction kinetics and higher energy density have attracted increasing interests as best alternative to hydrogen fuel cell because of H2 production, storage and distribution issues. While there have been extensive research works on developing key components such as electrocatalysts as well as their physicochemical properties in practical formic acid fuel cells, there have also been urgent requests for investigating which fuel sources will be more suitable for direct liquid fuel cells in future. In this mini-review, we highlight the overall interest and outlook of formic acid fuel cells in terms of electrocatalysts, fuel supply and crossover, water management, fuel cell efficiency and system integration in comparison with methanol fuel cells.

• Journal of Hydrogen and New Energy
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• v.27 no.3
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• pp.283-289
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• 2016

In this study, electrochemical characterizations of PdCu/C catalysts that are synthesized by modified polyol method are investigated. Most of all, amount of ethylene glycol (EG) that is used as main component for catalyst synthesis is mainly modulated to optimize synthetic condition of the PdCu/C catalyst, For evaluations about catalytic activity and performance of direct formic acid fuel cell (DFAFC), half cell and full cell tests are implemented. As a result, when amount of EG is 4M, catalytic activities of the PdCu/C catalyst such as peak current of formic acid oxidation and active surface area are best, while maximum power density of DFAFC using the optimized PdCu/C catalyst is better than that using commercial Pd/C (30 wt%) by 6%. Based on that, PdCu/C catalyst synthesized by modified polyol method plays a critical role in improving (i) catalytic activity for formic acid oxidation and (ii) DFAFC performance by employing as anodic catalyst.

• Carbon letters
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• v.6 no.1
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• pp.41-46
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• 2005

Plasma carbon blacks of 20~30 nm diameter were synthesized by direct decomposition of natural gas using a hybrid plasma torch system with 50 kW direct current and 4 MHz of radio frequency. The insulating rector which inside diameter of 400 mm and length of 1500 mm, respectively was kept at 300~$400^{\circ}C$ during the preparation. The ultimate analysis of plasma carbon blacks reveals that the raw plasma carbon blacks contains a large quantity of volatile which is mainly consist of hydrogen. Therefore devolatilization of raw plasma carbon blacks were carried out at $900^{\circ}C$ for one hour under nitrogen atmosphere. The devolatilization leads to the decrease in electrical resistivity and surface oxygen functional groups of plasma carbon black significantly. In order to investigate the plasma carbon as a catalyst support, devolatilized plasma black at $900^{\circ}C$ (DPB) supported PtAu catalyst was synthesized by sodium boronhydride reduction method. Electrochemical measurements and direct formic acid fuel cell test indicated that catalytic activity of DPB supported PtAu catalyst for formic acid oxidation was similar to that of Vulcan XC-72 of commercial carbon black supported one.

• Journal of the Korean Electrochemical Society
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• v.15 no.4
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• pp.216-221
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• 2012

Electrochemical reduction of carbon dioxide has been widely studied by many scientists and researchers. Recently, the production of formic acid, which is expensive but highly useful liquid material, is receiving a great attention. However, difficulties in the electrochemical reduction process and analyzing methods impede the researches. Therefore, it is important to design an adequate system, develop the reduction process and establish the analyzing methods for carbon dioxide reduction to formic acid. In this study, the production of formic acid through electrochemical reduction of carbon dioxide was performed and concentration of the product has been analyzed. Large scale batch cell with proton exchange membrane was used in the experiment. The electrochemical experiment has been performed using a series of metal catalysts. Linear sweep voltammetry (LSV) and chronoamperometry were performed for carbon dioxide reduction and electrochemical analysis using silver chloride and platinum electrode as a reference electrode and counter electrode, respectively. The concentration of formic acid generated from the reduction was monitored using high performance liquid chromatography (HPLC). The results validate the appropriateness and effectiveness of the designed system and analyzing tool.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2539-2545
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• 2012

In the present study, we suggest a new way to reactivate performance of direct formic acid fuel cell (DFAFC) and explain its mechanism by employing electrochemical analyses like chronoamperometry (CA) and cyclic voltammogram (CV). For the evaluation of DFAFC performance, palladium (Pd) and platinum (Pt) are used as anode and cathode catalysts, respectively, and are applied to a Nafion membrane by catalyst-coated membrane spraying. After long DFAFC operation performed at 0.2 and 0.4 V and then CV test, DFAFC performance is better than its initial performance. It is attributed to dissolution of anode Pd into $Pd^{2+}$. By characterizations like TEM, Z-potential, CV and electrochemical impedance spectroscopy, it is evaluated that such dissolved $Pd^{2+}$ ions lead to (1) increase in the electrochemically active surface by reduction in Pd particle size and its improved redistribution and (2) increment in the total oxidation charge by fast reaction rate of the Pd dissolution reaction.

• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.270-274
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• 2017

Formic acid has been known as one of key sources of hydrogen. Among various monometallic catalysts, hydrogen can be efficiently produced on Pd catalyst. However, the catalytic activity of Pd is gradually reduced by the blocking of active sites by CO, which is formed from the unwanted indirect oxidation of formic acid. One of promising solutions to overcome such issue is the design of alloy catalyst by adding other metal into Pd since alloying effect (such as ligand and strain effect) can increase the chance to mitigate CO poisoning issue. In this study, we have investigated formic acid deposition on the bimetallic $Pd/Pd_3Fe$ core-shell nanocatalyst using DFT (density functional theory) calculation. In comparison to Pd catalyst, the activation energy of formic acid dehydrogenation is greatly reduced on $Pd/Pd_3Fe$ catalyst. In order to understand the importance of alloying effects in catalysis, we decoupled the strain effect from ligand effect. We found that both strain effect and ligand effect reduced the binding energy of HCOO by 0.03 eV and 0.29 eV, respectively, compared to the pure Pd case. Our DFT analysis of electronic structure suggested that such decrease of HCOO binding energy is related to the dramatic reduction of density of state near the fermi level.

• Journal of Hydrogen and New Energy
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• v.26 no.3
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• pp.227-233
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• 2015

In this study, we evaluate catalytic activity of Pd/C catalyst that is synthesized by modified polyol method. With such formed Pd/C is used as anodic catalyst for direct formic acid fuel cell (DFAFC) and performances of the DFAFC are measured to verify whether the new catalyst is effective for enhancing DFAFC performance and to determine optimal loadings of the Pd/C needed for obtaining best DFAFC performance. Pd particle distribution of the Pd/C catalyst is analyzed by TEM, while its catalytic activity is estimated by using cyclic voltammogram (CV) as measuring formic acid oxidation reaction and active surface area. As a result of that, the Pd/C catalyst synthesized by modified polyol shows better catalytic activity and DFAFC performance with small loading amount of Pd/C. When loading amount of Pd/C is $1.5mgcm^{-2}$, maximum power density of DFAFC adopting the catalyst is $122mWcm^{-2}$.