Carbon Dioxide Reduction Metallurgy

Edited by: Neale R. Neelameggham, and Ramana G. Reddy

TMS (The Minerals, Metals & Materials Society), 2008

REDUCTION OF CARBON DIOXIDE TO FORMATE IN AN

ELECTROCHEMICAL MEMBRANE REACTOR IN KHCO3 BUFFER
SOLUTIONS
K.Subramanian1 *, G.Gomathi1, K.Asokan1.
1
Central Electrochemical Research Institute (CSIR), Karaikudi – 630 006, India
(*author for correspondence, e-mail: sivas_tsia@cecri.res.in )

Key words: Carbon Dioxide, Flow Cell, Formate, Ion-Exchange Membrane, Cd, Pb, Sn,
Zn Plated Stainless Steel Woven Mesh Cathodes, Iridium Oxide Film Anode

Abstract

An electrochemical reactor with anode and cathode chambers separated by a composite perfluoro
polymer cation exchange membrane was designed, fabricated and used for the reduction of
dissolved carbon dioxide under ambient conditions to formate. The flow reactor enhanced the
mass transfer of carbon dioxide compared to the batch reactor. Experiments were conducted
using two different perfluoro polymer membranes - Nafion 961. Efficacy of CO2 reduction on
various cathode materials (Cd, Pb, Sn and Zn plated stainless steel woven mesh) were
determined. Optimum values of flow rate and current density were evaluated for the energy
efficient formation of formate in aqueous KHCO3 (pH 7.5-8.5) buffer solutions.

1.Introduction:

The recent research works on the electrochemical reduction of carbon dioxide to various organic
chemicals are of both fundamental and preparative interest. Carbon dioxide is abundant in nature
in large volumes. Huge amounts of CO2 are produced by human and industrial activities. It is a
practically infinite carbon source for the chemical industry, namely, for the manufacturing of
aliphatic alcohols, aldehydes and hydrocarbons and aliphatic and aromatic carboxylic acids.
Attempts are being made to reduce CO2 electrochemically to useful products [1, 2].
Electrochemistry is a viable means for removing CO2 from the atmosphere, and converting it
into more valuable chemicals [3]. Formic acid and its alkali metal formate are one among these
products obtained in electrochemical methods [4-8].
Studies [9,10,11] were carried out for the electro reduction of CO2 in buffered (e.g. K2HPO4),
and somewhat buffered (viz. 0.1–0.5 M KHCO3) solutions. In un-buffered solutions, the
electrode local pH can vary widely from the bulk. In the somewhat buffered solutions, the
equilibrium concentration of H2CO3 is very low and the kinetics of the reactions
CO2(aq) + H2O ↔ H2CO3 and CO2(aq) + OH- ↔HCO3- are limited.
In the present study, CO2 (gas) is saturated in dilute KHCO3 solution and hence CO2(gas) is in
equilibrium with the solution, therefore CO2 (aq) concentration is a constant at a given pressure
and temperature. For the aqueous electrolyte in equilibrium with CO2 gas at a partial pressure of
101.3 kPa and a temperature of 298 K, CO2(aq) is 0.03416 M (i.e. ignoring the effect of ionic
strength) [12] .
Masahi Azuma et al [11] have studied the formation of formic acid in a CO2-saturated 0.05 mol
dm-3 solution (pH 8) using Nafion 417 ion-exchange membrane as separator in a H-type glass
cell. They have considered the formation of formic acid instead of potassium formate in a cation
ion-exchange membrane separated electrolytic cell. Hui Li and Colin Oloman [13, 14] have
reported to have developed a bench scale continuous reactor for the electro reduction of carbon
dioxide to formate using ion-exchange membrane as separator.

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The present study is aimed at the development of an energy efficient electrochemical process for
formation of formate by the reduction of CO2. A filter press type flow reactor for the electro
chemical reduction of CO2 to form formate at constant current density has been designed and
fabricated. Use of perfluoro polymer based cation exchange membrane ensures alkaline
conditions in the anode chamber for formation of oxygen at lower anodic potential. Cd, Pb, Sn
and Zn plated stainless steel woven mesh are the cathode materials studied. IrO2/Ta2O5 film
coated expanded titanium mesh is the anode. The flow cell is fitted with Nafion 961 cation
exchange membrane. 0.5M KHCO3 (pH 8) is the electrolyte. In order to increase the electrical
conductivity of the electrolyte, K2SO4 is added. Unless otherwise stated, a constant temperature
of 298 K is maintained throughout the studies.

2.Experimental details

2.1 Electrodes
2.1.1 Cathodes: Stainless steel (SS 316) woven wire mesh (wire diameter 0.2 mm) was chosen as
the substrate. Ten layers of the substrate mesh, each of geometrical area 15 × 10 x 1 cm3 have
been degreased, washed well with water and etched in hydrofluoric acid for few minutes. They
have been immersed in the respective plating baths for getting Cd, Pb and Sn and Zn deposits.
The layers have been kept one over the other and pressed together to form a porous sponge like
electrode, which is mounted in the cell as cathode. The effective geometrical area of the cathode
so formed has a geometrical area of 150 cm2. This type of arrangement enhances the residence
time of CO2 in the cathode chamber.

2.1.2 Anode: Anode is prepared by applying a thin layer of a solution containing IrCl3 and TaCl5
dissolved in isopropanol, on flattened and pretreated expanded titanium mesh of geometrical area
15 x 10 cm2 and baking in oxygen atmosphere at 723 K in a preheated furnace. Active film
thickness is built up to 5-6 μm through a layer by layer deposition.

2.2. Membrane
The anode and cathode are separated by Nafion 961 (Dupont, USA) cation exchange membrane.
The Nafion 961 membrane has a thick (100µm) perfluoro sulphonic acid polymer layer on one
side of the thin PTFE fiber woven matrix, while the other side has a thin (10µm) of perfluoro
carboxylic acid polymer layer. The membrane is in K+ form, and before putting into operation, it
is pretreated by immersing in distilled water for at least 12 hours.

2.3 Electrolyser assembly

The anode and cathode chambers are made from solid polypropylene materials. The anode and
cathode chambers are identical and have the dimensions of 15 ×10 ×1 cm. The chambers have
provisions for feeding electrolyte and draining out the cell effluent. Nafion 961 cation exchange
membrane is placed between the anode and cathode chambers. The reactor is assembled in a leak
proof manner by placing EPDM gaskets between the chambers and the membrane. Nafion 961
membrane is mounted in such a way that the carboxylic acid layer faces the anode and the
sulphonic acid layer faces the cathode. The anode and cathode chambers are arranged in such a
way that the anolyte and catholyte flow is in countercurrent direction. The gap between the
electrodes and membrane is kept constant at 3 mm. The reactor stack is held tightly in place
using mild steel back plates and stainless bolts and nuts.

2.4. Electro reduction of CO2

All the chemicals are of analar grade and all solutions have been prepared using triple distilled
water. The experiments are carried out at 298 ± 1 K. Carbon dioxide is absorbed at atmospheric
pressure in potassium bicarbonate solution (0.5M KHCO3 in 0.05M K2SO4, pH 8) in a vertical
absorption column. The amount of gas absorbed is determined by volumetric analysis. The CO2

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absorbed solution is the catholyte and 0.5 M KOH solution is the anolyte. Formate formed is
determined by high-pressure liquid chromatography (HPLC - SHIMADZU, JAPAN) and values
are counter checked by the bromometric method [15]. DC current from a constant current
generator (Aplab-, 0-2 A, 0-35V) is applied to the reactor and cell voltage is recorded at regular
intervals. Peristaltic pumps are used for feeding the electrolyte to the electrode chambers. The
effect of electrolyte flow rate and applied current density on current efficiency for formate
production has been studied for an operating time of one hour. Current in the range of 0.15 A to
0.6 A has been applied to the cell.

2.5.Experimental set up
The hold up volume of anode and cathode chamber is 120 ml. As the flow rates are very small,
two peristaltic pumps are used. The effluent from the cathode chamber is collected and analyzed
for formate. The effluent from the anode chamber is collected and analysed for KOH depletion.

3.Principle of membrane cell process for electrochemical reduction of CO2

The cation exchange membrane used, selectively allows the transport of K+ ions from the anode
chamber to the cathode chamber along with associated water molecules. It suppresses the back
migration of HCOO- ions from the cathode to anode chamber. The predominant reaction
occurring in the anode chamber (pH 14) is oxygen evolution.

2OH- Æ ½ O2 + H2O + 2e Eo= + 0.40 V vs. NHE (1)

The main reaction occurring in the cathode chamber is the cathodic splitting of water molecule
followed by the formation of formate ions.

CO2 + H2O + 2eÆ HCOO- + OH- (pH 0) Eo = -0.199 V vs NHE (2)

- -
CO2 + H2O + 2eÆ HCOO + OH (pH 8) Eo = -0.64 V vs NHE (3)

In a cation exchange membrane electrolyser, two moles of K+ are transported to cathode chamber
from anode chamber for every one mole of formate ion formed at the cathode. Formate ions
combine with potassium ions transported to form potassium formate and another K+ gives
electrical neutrality to the OH- produced at the cathode. The overall equilibrium cell voltage
would be –1.04 V.
The principle of the process is illustrated in Figure 1. Competing reactions, namely H2 evolution
and CO formation affect the efficiency of the reactor to a significant extent.

CO2 + H2O + 2e → CO + OH- (pH 0) Eo = -0.101 V vs NHE (4)

CO2 + H2O + 2e → CO + OH- (pH 8) Eo = -0.541 V vs NHE (5)

2 H2O + 2 e→ 2OH- + H2 (pH 8) Eo = -0.472 V vs NHE (6)

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 Fig.1: Membrane reactor for electrochemical reduction of CO2 to formate

4.Results and discussion

Carbon dioxide gas is reduced electrochemically in aqueous electrolyte solutions of 0.5 M

KHCO3 (pH 8) to potassium formate. The solubility of Carbon dioxide in aqueous electrolyte
solutions at 101.3 kPa pressure and 298 K is about 0.03416 mol dm-3. The availability of active
species, CO2 for electro reduction, is extremely low at the vicinity of the electrode surface and it
seriously interferes with the rate of mass transfer. In batch type electrolytic reactors, depletion of
CO2 at the surface takes place first and CO2 from the bulk has to diffuse to the electrode surface,
resulting in mass transfer controlled kinetic phenomena. During the above process, several other
competitive side reactions suppress the primary reaction though the cathode has good electro
catalytic properties for reduction of carbon dioxide to formate. When the dynamic supply of
specific active species is ensured to electrode surface, the mass transfer effects is minimized to
certain extent. Hence, it is envisaged [9] that a continuous flow reactor is more efficient for the
electro reduction of CO2 in CO2 saturated aqueous electrolytes to formate. Like any other
electrochemical process, the desired product can be obtained if the electrodes specific to the
particular reaction product are used. In an electrochemical flow reactor, the catholyte containing
the dissolved carbon dioxide is fed continuously to the reactor. The dissolved carbon dioxide in
the aqueous solution reacts as electrolyte at the cathode, is electrochemically reduced and flows
out continuously in the form as formate. In the flow cell, reaction specificity is obtained by the
proper choice of cathode material, electrochemical reactor design and process parameters.
The Electrochemical reduction of carbon dioxide has been carried out at different cathode
materials, namely Cadmium, Lead, Tin and Zinc. Their performance is compared with respect to
concentration of formate formed, current efficiency and cell voltage. The variation of formate
formed, for different cathode materials, as a function of catholyte flow rate at a constant current
density of 2 mA cm-2 is shown in Figure 2.

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Fig.2: Variation of amount of formate formed with respect to flow rate of catholyte feed at Cd,
Pb, Sn and Zn surfaces, current density: 2 mA cm-2, T:298 K, Charge : 0.3 Ah

Fig.3: Variation of amount of formate formed with respect to flow rate of catholyte feed, at
Cadmium (Cd) surface at current densities: 2.0, 2.5 and 3.0mA cm-2, T:298 K, Charge : 0.3 Ah

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 Fig.4: Variation of amount of formate formed with respect to flow rate of catholyte feed, at
Lead(Pb) surface at current densities: 2.0, 2.5 and 3.0mA cm-2, T:298 K, Charge : 0.3 Ah

Fig.5: Variation of amount of formate formed with respect to flow rate of catholyte feed, at Tin
(Sn) surface at current densities: 2.0, 2.5 and 3.0mA cm-2, T:298 K, Charge : 0.3 Ah

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 Fig.6: Variation of amount of formate formed with respect to flow rate of catholyte feed, at
Zinc(Zn) surface at current densities: 2.0, 2.5 and 3.0mA cm-2, T:298 K, Charge : 0.3 Ah

Fig.7: Variation of current efficiency with respect to flow rate of Carbon dioxide absorbed 0.5
M KHCO3 buffer catholyte feed on Cadmium (Cd) surface, at current densities: 2.0, 2.5, and 3.0
mA cm-2, T:298 K, Charge : 0.3 Ah

The effect of flow rate on the concentration of formate obtained at various current densities for
Cd, Pb, Sn and Zn are shown in Figures 3, 4, 5 and 6 respectively. Figures 7, 8, 9, and 10 show
the effect of catholyte feed on the current efficiency for formate formation for Cd, Pb, Sn and Zn
respectively. Figure 11 shows the comparative performance of Sn and Zn cathodes. In the above
Figures, it is generally observed that current efficiency as well as the amount of the formate
formed increase with flow rate reach maximum values at a flow rate of 13 ml minute-1, thereafter
values of amount of formate slightly decreases, but current efficiency reaches a more or less
stable value with increase in flow rate. Increase in flow rate of catholyte increases the mass
transfer of carbon-dioxide to the electrode surface, leading to an increase in the concentration of
carbon dioxide available for electrode reaction, producing more amount of formate. But after
reaching the flow rate range of 13 ml minute-1, the amount of formate starts to decrease with
increase in flow rate for all the cathodes studied . This may be due to the shorter residence time
for enrichment of formate concentration in the cell liquor. On the other hand, the current
efficiency becomes more or less stable after reaching the flow rate of 13 ml minute-1.

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 Fig.8 Variation of current efficiency with respect to flow rate of Carbon dioxide absorbed 0.5 M
KHCO3 buffer catholyte feed on Lead(Pb) surface, at current densities: 2.0, 2.5, and 3.0 mA cm-2,
T:298 K, Charge : 0.3 Ah

Fig.9: Variation of current efficiency with respect to flow rate of Carbon dioxide absorbed 0.5
M KHCO3 buffer catholyte feed on Tin (Sn) surface, at current densities: 2.0, 2.5, and 3.0 mA cm-
2
, T:298 K, Charge : 0.3 Ah

When comparing the performance of the cathode materials at the optimum flow rate (13 ml
minute-1) of catholyte, formate concentrations of 0.0179, 0.0245, 0.0217, and 0.0103 mol dm-3
and maximum current efficiency value of 70, 90, 85 and 40 were obtained for Cd, Pb, Sn and Zn
respectively. The maximum formate concentration of 0.0245 mol dm-3 and maximum current
efficiency of 90% could be achieved on Pb cathode.

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 Fig.10: Variation of current efficiency with respect to flow rate of Carbon dioxide absorbed 0.5
M KHCO3 buffer catholyte feed on Zinc(Zn) surface, at current densities: 2.0, 2.5, and 3.0 mA cm-
2
, T:298 K, Charge : 0.3 Ah

Fig.11: Comparison of Tin and Zinc cathodes in the performance for current efficiency with respect to
catholyte flow rate at current densities: 2.0, 2.5, and 3.0 mA cm-2, T:298 K, Charge : 0.3 Ah

The performance characteristics of the cathodes studied may be given in terms of current
efficiency and concentration of formate is in the order Pb ≈ Sn >Cd>>Zn. The optimum flow
rate of the catholyte for electrolyser designed and operated is 13 ml minute-1.

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 Fig.12: Effect of current density on Variation of current efficiency at 13 ml minute-1 flow rate of
catholyte feed on Cd, Pb, Sn and Zn surfaces, T:298 K, duration of passage of current: 1 h

The influence of current density on current efficiency has been studied at constant flow rate of
13 ml minute-1 . Figure 12 shows the influence of current density on the current efficiency of
formate formation on Cd, Pb, Sn and Zn. As the current density increases the current efficiency
increases and reaches a maximum value of 70, 90, 85 and 40 % at a current density range of 2-
2.5 mA cm-2 for Cd, Pb, Sn and Zn respectively. Then it starts to decrease with further increase
in current density. As the current density increases, the rate of reaction increases and the demand
for CO2 electrolyte increases and also the cathode working potential increases. The amount of
CO2 electrolyte is limited at the interface even under the continuous flow conditions. The
increase in cathode potential favours hydrogen evolution along with formate formation. At
current densities, more than 4 mA dm-2 hydrogen evolution reaction is favoured.

Fig.13: Effect of current density on the formate concentration at 13 ml minute-1 flow rate of
catholyte feed of at Cd, Pb, Sn and Zn surfaces, current density: 2 mA cm-2, T:298 K, duration of
passage of current: 1 h

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The effect of current density on concentration of formate formed has been studied at a constant
flow rate of 13 ml minute-1 (Figure 13). The concentration of formate increases slightly with
current density and reaches maximum values and then decreases rapidly. As the current density
increases, the rate of formation of formate increases and on reaching the current density range of
2-2.5 mA cm-2 , the mass transfer rate affects the formate formation reaction on all the cathode
material studied. Variation of cell voltage with time at constant current density of 2 mA cm-2
and flow rate of 13 ml minute-1 is shown in Figure 14.

Fig.14: Variation of cell voltage with time for carbon dioxide reduction in 0.5M KHCO3 + 0.05 M
K2SO4 (pH 8) buffer electrolytes and oxygen evolution in alkaline (0.5 M KOH) solution,
current density : 2 mA cm-2 , flow rate of catholyte: 13 ml minute-1 , cathode materials : Cd, Pb, Sn
and Zn , T:298 K, duration of passage of current: 1 h

On the application of current to cell, the cell voltage increases rapidly, reaches a steady value
and was quite stable up to 35, 50, 45 and 25 minutes for the cathode materials Cd, Pb, Sn and Zn
respectively and there after it increases steeply. The formate formation is accompanied by the
side reaction of hydrogen gas evolution. During the course of operation of cell, the hydrogen gas
accumulates in catholyte chamber and reduces the active electrode area available for formate
formation. The actual current density increases with increase in hydrogen evolution. The Cell
voltage performance of the cathode materials studied is in the order Pb ≈ Sn >Cd>>Zn.

5. Conclusions

An electrochemical flow membrane cell with electrode geometrical area of 150 cm2 for
electrochemical reduction of carbon dioxide absorbed in 0.5 mol dm-3 KHCO3, was operated with
a composite perfluoro sulphonic-carboxylic group ion-exchange Nafion 961 membrane,
IrO2/Ta2O5 film coated titanium anode and with cathode materials such as Cadmium, Lead, Tin
and Zinc coated on stainless steel fine mesh. The reaction occurring at the anode chamber is the
only oxygen evolution and reactions occurring in the cathode chamber are formation formate
ions along with the side reaction of hydrogen evolution. The cell was operated at different
catholyte feed rates and at different current densities and corresponding values for formate
concentration, current efficiency and cell voltage were recorded for each cathode material.
Optimum process parameters for the membrane cell of apparent electrode area of 150 cm-2 were
evaluated. The performance characteristics of the above cathode materials with respect to
concentration of formate formed, current efficiency and cell voltage were evaluated and it is in
the following order Pb ≈ Sn >Cd>>Zn.
A maximum current efficiency of 90% was achieved for the formate production of 24.5 x 10-2
mol dm-3 at an optimum catholyte of flow rate of 13 ml minute-1 at 298 K for lead coated cathode

197
and a maximum current efficiency of 40% was recorded at formate production of 10.1 x 10-2
mol dm-3 for zinc coated cathode. The cell voltage at 2 mA cm-2 was 1.6 V to 1.7 V for the
reactor with lead coated cathode. It is proposed to design and develop catalytic cathodes with
large active area and to make further improvements in cell design for the efficient production of
formate.

Acknowledgement

The authors wish to thank Mr.S.Govindhu, Scientist, CECRI for his help with HPLC analysis
and Mr.M.Ganeshamoorthy and Mr. S.Ashokkumar, CECRI for their technical assistance.

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