JOURNAL OF APPLIED ELECTROCHEMISTRY 28 (1998) 10731081

Thermo-electrochemical reduction of sulfate to sulde using a graphite cathode

A thermoelectrochemical process which allows reduction of sulfate to sulde with current eciency of 80% using graphitic carbon as an electrode is presented. The mechanism which requires undissociated sulde (6.5 M H2SO4) and works at temperatures close to 120 C, proceeds at low overpotential and in the absence of hydrogen evolution. A molecular model describing the interaction of H2SO4 with the carbon lattice of graphite leading to the liberation of H2S is discussed on the basis of electrochemical and photoelectron spectroscopic data. Applications of this process in energy and environmental technology (sulde as energy source for CO2 reducing chemoautotrophic bacteria) and for elimination of sulfuric acid waste are discussed.
Keywords: biomass production, CO2 reducing chemoautotropic bacteria, graphite cathode, sulfate, sulfuric acid, thermoelectrochemical reduction

1. Introduction Electrolytic reduction of sulfate (as H2SO4) to H2S and its precipitation as a nonhazardous metal sulde is a possible means of eliminating sulfuric acid waste. A further potential application is to provide the sulde as energy carrier to sulde oxidizing chemoautotrophic bacteria (Thiobacillus ferrooxidans) in order to convert CO2 and H2O to biomass (carbohydrates, proteins, lipids) via the Calvin Cycle [1]. In this process the reformed sulfate is recycled using photovoltaic electricity and solar heat for the reduction process. Up to now, aside from reduction via chemical reactions (e.g. reduction by means of Fe2+ in acid solution) or biomimetic reduction [2], only a thermal reduction of H2SO4 at about 1000 C is known. The liberation of H2S and S, observed long ago, along with H2 during the electrolysis of concentrated H2SO4 using a Pt cathode [36], is not due to a direct electrochemical reduction of the H2SO4 but very probably due to the reduction by means of the hydrogen in the atomic state liberated from water splitting. This fact has been conrmed in this work as shown later. Massive reduction of sulfate to sulde takes place in geological environments, especially in geothermally active regions along ocean ridges where sulfate containing seawater enters the heated ocean oor and sulde is emitted via so called `black smokers', which are the energy source of a very dynamic biomass system, mediated by sulde oxidizing and archaeobacteria. A direct electrochemical reduction of sulfate to H2S in aqueous solution can be described according to the overall reaction
0021-891X

H2 SO4 8 H 8 e @ H2 S 4 H2 O A
A

Since such an 8 e -transition process is very unlikely to occur, the following reaction steps most probably take place: A 2 H2 SO4 8 H 8 e @ H2 S2 O6 2 H2 O io 25  C 0X220 V A H2 S2 O6 2 H 2 e @ 2 H2 SO3 io 25  C 0X564 V A H2 SO3 4 H e @ S 3 H2 O io 25  C 0X449 V S 2 H 2 e @ H2 Saq A io 25  C 0X143 V 5 4 3 2

A one step reduction of H2SO4 to H2SO3 may also be considered according to A H2 SO4 2 H 2 e @ H2 SO3 H2 O io 25  C 0X172 V 6

In cyclic voltammetric experiments using a RuS2 single crystal as a working electrode [10], peaks have been found which indicate the occurrence of Reactions 4, 5 and 6. On the anodic side, where the main reaction A 4 H 2 O @ 2 O 2 8 H 8 e io 25  C 1X230 V 7 takes place, other reactions can also occur which lead to the production of O3, H2O2, SO2 and S2 O2 , 5 8 depending on the concentration of H2SO4, the tem1073

1998 Chapman & Hall

1074

B. A. BILAL AND H. TRIBUTSCH

perature, the electrode material and the current density. The standard potential of Reaction 7 is the thermodynamic value of the voltage of water splitting under standard conditions, since the standard potential of the reaction A 2 H 2 e @ H2 io 25  C 0X000 V 8 is by denition zero. Only the part of the overvoltage needed for water splitting depends on the pH, since both anodic and cathodic standard potentials for water splitting depend in the same manner on pH. Equations 26 show that the reduction is favoured by acid solution. At such low pH, the standard potentials of Reactions 4, 5 and 6 are within the stability range of water (Eo)H/pH diagram). Thus the electrochemical reduction of sulfate in aqueous solution is thermodynamically possible. The fact that such reduction has not been demonstrated up to now indicates that the sulfate reduction is apparently kinetically inhibited and needs high overvoltage to take place. The largest component of the overvoltage is due to the inhibited charge transfer from the electrode surface to the sulfate in solution, depending on the electrode material, the temperature, the current density and the physical and chemical conditions of the H2SO4, particularly the degree of association between H+ and SO2 which inuences the electron distri4 bution along the SO bond. In this work, the conditions for a decrease of the activation energy for the reduction process were examined.

2. Experimental details Figure 1 shows the apparatus used for the electrochemical reduction of sulfate. It consists of a glass U-tube (dia. 30 mm, height 250 mm) whose tops are tightly tted to reuxe's, electrodes and thermometers. The electrolyte solution was blanketed by a moderately owing air stream moving the gases produced at the electrodes from the cell atmosphere; gases produced at the cathode were passed into lead acetate (or copper sulfate) solution allowing quantitative precipitation of the sulde produced. A spiralshaped platinum wire of 1 mm in diameter and 400 mm in length was used as the anode. Apart from a graphite cathode (a block with the surface F 18.2 cm2 which was connected tightly at its cylindrical top above the electrolyte surface with a Pt wire), similar spirals of Pt, Ag and Cu were also used as cathode in test experiments. H2SO4 solutions of dierent concentrations, up to 10 M, as well as aqueous Na2SO4 (1 M, pH 0, adjusted with H2SO4) and molten Na2SO4(H2O)10 (melting point, 30 C) were used as electrolytes. Electrolyte temperatures up to 145 C were used using a 300 W reector lamp. The voltage was successively increased from 0.6 up to 2.5 V. The interaction of the H2SO4 with the surface of the graphite electrode was investigated by means of photoelectron spectroscopy. The generation of H2S and its use for CO2-xation was tested by preticipitating H2S and Cu2+ solution and by cultivating Thiobacillus ferrooxidans on the resulting CuS precipitate.

Fig. 1. Apparatus for electrolytic reduction of H2SO4.

THERMO-ELECTROCHEMICAL REDUCTION OF SULFATE TO SULFIDE

1075

3. Results In aqueous Na2SO4 solution (pH 0), and also in molten Na2SO4(H2O)10, no reduction of sulfate was obtained at any of the cathode materials mentioned above, even at temperatures up to 145 C, and U 2.5 V. The results of the H2SO4 reduction are summarized in Table 1. Fig. 2 shows those obtained using a graphite cathode. Ag and Cu, which have a relatively high hydrogen overvoltage, reacted with concentrated H2SO4 at about 145 C to form SO2 which is easily reduced to H2S, forming Ag2S as well as CuS. At moderate H2SO4 concentrations around 6 M and the corresponding boiling temperature, no reduction was observed even at a voltage U 2.5 V. In the case of Pt as cathode, formation of H2S was only observed after water splitting (H2-evolution) took place. 3.1. Graphite cathode A direct electrochemical reduction of sulfate with liberation of traces of H2S was already obtained at gH2 SO4 5 M, boiling temperature (113 C) and a voltage lower than that of water splitting. At higher

H2SO4 concentration (6.7 M), traces of H2S were already detected at U 0.6 V at 116 C as well as at boiling temperature (121 C). The limiting current of the equipment used (36 lA) was too low for a possible quantitative determination as PbS in reasonable time. It is dicult to predict the thermodynamic limit of the voltage necessary for the reduction at such conditions of temperature and concentration, since neither the partial molar entropy nor the overvoltage of Reactions 6, 4 and 5 are known as functions of these conditions. However, the relatively low values of the standard potentials of these reactions, explain that the reduction at 0.6 V (or perhaps even less) is possible. The liberation at U 1.5 V (still much lower than that of water splitting observed at U 1.9 V) of H2S became much stronger. The current eciency (fraction of the current liberating H2S and quantitatively determined as PbS) increased drastically with increasing temperature: 1% at 102 C and current density i 0.025 mA cmA2, 45% at 116 C, i 0.20 mA cmA2 and 60% at 121 C, i 0.017 mA cmA2. At 1.9 V, eciency maximum of 2% at 102 C, i 0.17 mA cmA2, 58% at 116 C, i 0.151 mA cmA2 and 80% at 121 C, i 0.147 mA cmA2. These results clearly show that a

Fig. 2. Current eciency of the reduction of H2SO4 at graphite cathode as a function of cell voltage: (curve A: 6.7 M, 121 C), (curve B: 6.7 M, 116 C), (curve C: 6.7 M, 102 C) and (curve D: 9.7 M, 145 C).

1076 Table 1. Results of the reduction of H2SO4 Expt. CH2 SO4 /M Cathode T /C U /V i /mA cmA2

B. A. BILAL AND H. TRIBUTSCH

Current eciency /% converted to H2S H2S-traces

Remarks

(1) (2)

5 5

Pt C

113 113

1.82.2 1.8

0.143.32 0.13

No formation of H2S, only water splitting Still no water splitting, but traces of H2S were detected with Pb (CH3COO)2 paper Traces of H2S before water splitting at 1.9 V No formation of H2S, but water splitting. Traces of H2S were observed Direct reduction before water splitting took place at 1.9 V. The yield decrease between 1.99 and 2.2 V is due to the consumption of current, mainly in water splitting Direct reduction, but only traces of H2S could be detected with Pb (CH3COO)2 paper. Because of very low current used, no quantitative determination was possible Direct reduction before water splitting occurred around 1.9 V, where a yield maximum is obtained. Yield decrease at U > 1.9 V due to the same reason as in expt. 4 The same observation as in expt. 5 Higher yield at 1.5 and 1.9 V due to the higher temperature, but lower yield at U=2.02.2 V very probably due higher rate of water splitting The yield of H2S is much lower than in expts 5 and 6, because of the formation of sulfur which was observed at the cathode. Probably H2Sx was formed, since a black yellow precipitate was obtained in Pb (CH3COO)2 solution. PbS is obtained in Pb (CH3COO)2 solution and sulfur was formed at the cathode

1.92.2 (3) 6.7 Pt 121 1.92.11 2.2 1.5 1.9 2.2

0.232.29 H2 0.211.23 2.11 0.025 0.17 1.67

S-traces H2S-traces 1 2 0.5

(4)

6.7

102

(5)

6.7

116

0.6

(2 lA cmA2)

(6)

6.7

121

1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 0.6 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2

0.20 0.027 0.057 0.080 0.151 0.252 0.895 1.452 (1.95 lA cmA2) 0.017 0.024 0.055 0.076 0.147 0.247 0.846 1.456 0.056 0.075 0.148 1.46

45 46.5 48 51 58 46 36 29 60 61 63 67 80 61 23 15 20 21 22 24.5

(7)

9.7

145

1.7 1.8 1.9 2.2

(8)

9.7

Pt

145

1.92.1

0.221.24

H2Sx?

2.2

2.10

24

THERMO-ELECTROCHEMICAL REDUCTION OF SULFATE TO SULFIDE

1077

higher current eciency is obtained at high temperature (higher degree of association between SO2 4 and H+, parallel with a signicant decrease in the dielectric constant of water with increasing temperature), but not as a consequence of the current density, which varied slightly in the opposite direction due to the decreasing dissociation of the sulfuric acid. The extrapolation of curves A and B in Fig. 2 shows that probably the same current eciency, such as found at 1.5 V, could also be obtained at a cell voltage of 0.6 V if a much bigger electrode surface were used to give a suciently high current to make a quantitative determination possible in reasonable time. At U > 1.9 V a drastic decrease in current efciency was observed, which is due to the rising fraction of the current consumed in water splitting. Curve A in Fig. 2 descends more rapidly than curve B, probably due to the higher part of the current consumed in water splitting at 121 C than at 116 C. This explains the crossing of the curves around U 2.03 V. At higher H2SO4 concentration (9.7 M) and boiling temperature (145 C), and nearly the same current densities as in the case of reduction of 6.7 M H2SO4 at 121 C, the current eciency (even at lower voltage than that of water splitting) is much lower than that obtained in the case of 6.7 M H2SO4 despite similar current densities. This decrease is due to the competing reduction to sulfur which was observed in the cathode chamber. However, the eciency curve increased slightly from 20% at U 1.7 V and, i 0.056 mA cmA2, 22% at U 1.9 V and i 0.148 mA cmA2, to 24.5% at U 2.2 V and i 1.46 mA cmA2 and seems to remain unchanged at higher voltage and current density. This behaviour was unexpected in comparison with that for 6.7 M H2SO4, since it is unlikely that the dierent parts of the current consumed in the production of H2S, sulfur and water splitting (including the entropy term) remain more or less the same with increasing voltage and current density. More detailed experiments, including a quantitative determination of the sulfur and the hydrogen must be carried out to get this point clear. As an additional test for the liberation of H2S during cathodic reduction of H2SO4 on graphite, and in order to demonstrate its relevance for an energy cycle based on sulfur, H2S was precipitated with Cu2+ to give CuS. Thiobacillus ferrooxidans was cultivated on this sulde as the only energy source and bacterial growth was clearly veried. 3.2. Pt cathode Up to 2.2 V and i 3.32 mA cmA2, no formation of H2S, but only water splitting, was observed in 5 M H2SO4 at boiling temperature (113 C). Also, 6.7 M H2SO4, 121 C, U up to 2.1 V and i 1.23 mA cmA2, no formation of H2S took place. Starting at U 2.2 V and i 2.11 mA cmA2, traces of H2S were detected. In 9.7 M H2SO4, 145 C, U 1.9 V and

i 0.22 mA cmA2, very probably a reduction to H2S and sulfur by means of hydrogen arising from water splitting occurred, since the gas products passed into Pb(CH3COO)2 solution gave a black yellow precipitate which was partially soluble in CS2. At U 2.2 V and i 2.10 mA cmA2 the reduction accompanying the stronger water splitting led to the formation of H2S but only with a current eciency of 24%. The photoelectron spectra of a reference graphite without any contact with H2SO4 are shown in Figs. 3A(a), 3B(a), 3C(a) and 4(a). Those of a graphite electrode, after running the reduction experiments, are shown in Figs. 3A(b), 3B(b), 3C(b) and 4(b). Fig. 3A(b) shows the S2p peak at 168.8 eV which refers to sulfur coordinated with 4 O-atoms in sulfate. No signal is observed in Fig. 3A(a). Also the oxygen spectrum O1s in Fig. 3B(b) clearly shows the peak at 531.8 eV refering to the oxygen bond in sulfate, whereas the very at peak in Fig. 3B(a), which is shifted to higher energy and refers to a CO bond, is apparently due to interaction with the atmospheric oxygen (the samples were heated). The Cls spectrum in Fig. 3C(b) shows a peak which is shifted to lower energy and is of much lower intensity in comparison to the peak in Fig. 3C(a). This conrms that the C-atoms at the surface of the graphite electrode are not only bonded to neighbouring C-atoms in the graphite lattice, but also to other atoms. Spectrum 3C(b) shows, furthermore, a shoulder at an energy of about 286 eV which corresponds to a CS bond and is very probably due to a week interaction of the unpaired electrons in the C-atoms with the S-atoms in sulfate. Curves 4(a) and 4(b), which are normalized to the same current, show this aspect more clearly. 4. Discussion 4.1. Electrode material Except for Pt, the materials used as cathodes have a relatively high hydrogen overvoltage in order to suppress the competing hydrogen evolution Reaction 8. Graphite is a material which is, moreover, corrosion resistant (denoted below as C). The layer structure of this material shows hexagonal C-rings with conjugated p-bonds and therefore has a conduction band with delocalized electrons. It oers the interesting possibility that H2SO4 forms an intermediate compound CmxH2SO4 in which the SO of the sulfate may be conjugated with the double p-bond system of the hexagonal C-rings in the layers. This compound may have a lower activation energy of reduction due to easier change transfer from the conduction level in graphite to sulfate. 4.2. Eect of temperature, pressure and concentration Electron transfer to sulfate is assumed to take place more easily when the two negative charges of the free ion are neutralized by means of positive ligands which

1078

B. A. BILAL AND H. TRIBUTSCH

Fig. 3. (A) Photoelectron spectrum (S2p) in a reference graphite (3A(a)) and in the used graphite electrode (3A(b)). (B) Photoelectron spectrum (01s) in a reference graphite (3B(a)) and in the used electrode (3B,b). (C) Photoelectron spectrum (Cls) in a reference graphite (3C(a)) and in the used graphite electrode (3C(b)).

are electrostatically or covalently bonded to the oxygen. The so caused polarization of the SO-bond shifts the electron density away from the S-atom. Such decrease in the electron density around the S-atom could easily be obtained using protons as positive ligands to from undissociated H2SO4. The dissociation of sulfuric acid is rapidly suppressed with increasing temperature and concentration [7, 8]. Higher temperature not only supplies at least a part of the necessary activation energy, but also leads to a drastically increased association between SO2 and H . Since the degree of 4 dissociation of H2SO4 at constant temperature and given sulfate concentration increases with increasing pressure [7, 8] and, in addition, reactions giving gas products are hindered by pressure increase, no calalytic eect of pressure was expected. The results obtained conrm the above hypothesis, namely that (i) direct reduction of H2SO4 is only possible when the acid is highly undissociated at conditions of fairly high temperature (optimum: 121 C) and

moderately high concentration (optimum: 6.7 M) and (ii) the obviously high activation energy needed for a direct reduction to occur can be drastically reduced when a suitable cathode material such as graphite is used. Figures 5(a)(f) show a proposed mechanism of the reduction of the H2SO4 intermediary bonded between the graphite layers. The tetrahedrally structured H2SO4 has four r bonds and 2 dppp SObonds (Fig. 5(a.1)). The C-atoms at the end of two neighbouring graphite layers have unpaired electrons (Fig. 5(a.2)). Because of the higher energy of the dp pp-bond in comparison to the r CO-bond, each of the unpaired electrons of the two C-atoms is paired with one electron of each of the O-atoms having the dppp-bond to form 2 r CO-bonds with optimum orbital overlapping and two electrons are set free at the S-atom (Fig. 5(a.3)). The second step is assumed to be a charge transfer from the 2 r OS-bonds to the

THERMO-ELECTROCHEMICAL REDUCTION OF SULFATE TO SULFIDE

1079

Fig. 4. Spectrum of Fig. 3C, normalized to the same intensity.

Fig. 5.

1080

B. A. BILAL AND H. TRIBUTSCH

Fig. 5. Postulated mechanism of H2SO4 reduction at graphite cathode.

two C-atoms (Fig. 5(b.1)), where a simultaneous rearrangement of the conjugation system occurs in order to form the energetically more stable system with two ketone bonds conjugated with the double bonds of the C-rings in the layers (Fig. 5(b.3)). H2SO4 is hereby reduced to H2O2S (sulfoxylic acid) with two electron pairs at the S-atom (Fig. 5(b.2)). The third step is assumed to be the reduction of the ketone groups to obtain the original form of the graphite layers with C-atoms having unpaired electrons and water as shown in (Fig. 5(c.1)) and (Fig. 5(c.2)). As fourth step it is proposed that the two O-atoms of the tautometric form (Fig. 5(d.1)) of the sulfoxylic acid (in which the S-atom has a r-bond with each of the two H-atoms, one r-bond and one dp-bond with each of the two O-atoms) are again bonded to the original graphite form in (Fig. 5(d.2)) and the same procedure as in the steps before [(Fig. 5(d.1)) + (Fig. 5(d.2)) (Fig. 5(d.3)), Fig. 5(e.1)) H2S + (Fig. 5(e.2)) and (Fig. 5(f.1)) + 4H+ + 4eA (Fig. 5(f.2)) + 2H2O] takes place.

The XPS-measurements appear to be consistent with this model, especially in that they demonstrate a chemical change of the carbon environment, and the presence of sulfur and oxygen in a sulfate environment. The evidence of sulfurcarbon interaction (286 eV), which appears as a shoulder in Fig. 4(b), suggests that we are dealing with a partial interfacial intercalation of the sulfur species during the catalytic reduction process where neighbouring carbon sheets can participate in the chemical interaction. 5. Applications 5.1. Elimination of sulfuric acid waste Sulfuric acid waste arises in many chemical processes. Up to now, the only ways used for its disposal is its environmental harmful release into the sea or conversion at high temperature (1000 C). By means of the above described electrolytic reduction, it is possible to convert the acid to nonhazardous sulde via simple technology. Taking the data for the maximum current eciency in experiment 6, Table 1 (6.7 M

THERMO-ELECTROCHEMICAL REDUCTION OF SULFATE TO SULFIDE

1081

arid areas where no plant photosynthesis is possible. Temperatures around 120 C, necessary for the electrocatalytic reduction of H2SO4 (around 6.5 M) to H2S for the graphite cathode, could be easily obtained using a solar thermal collector and the electric energy may be generated by photovoltaic panels. The energy carrier H2S is precipitated as metal sulde which is fed to CO2 reducing bacteria (Thiobacillus ferrooxidans) to convert it, in the presence of oxygen and water, to biomass (carbohydrates, proteins, lipids) according to the Calvin cycle, where it is reoxidized to SO2 (process veried during this work). 4 After separation of the biomass, the sulfate is separated as H2SO4 by means of anion exchange and recycled for re-reduction (Fig. 6). A detailed description of the sulfate reduction as part of a biomass producing solar powered fuel cycle is given elsewhere [9]. Acknowledgements The authors gratefully acknowledge the assistance of E. Mueller in performing the electrochemical experiments, and thank H. Sehnert for carrying out the XPS-measurements and J. Rojas-Chapana for performing the experiments with Thiobacillus ferrooxidans.
Fig. 6. Diagram of solar powered biomass production process based on thermoelectrochemical reduction of sulfate to sulde.

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] H. Tributsch, Nature 281 (1979) 555. O. A. E. Shigeru and Hideo Togo, Bull. Chem. Soc. Jpn. 56 (1983) 3828. E. Gehrcke, Verh. Phys. Ges. 5 (1903) 263. C. G. Schluederberg, J. Phys. Chem. 12 (1908) 574. W. D. Brandcroft and J. E. Magon, J. Am. Soc. 57 (1935) 2561. H. Homann, Z. Elektroch. 27 (1921) 442. B. A. Bilal and E. Muller, Z. Naturforsch. 48a (1993) 1073. Idem, Ibid. 49a (1994) 939. B. A. Bilal and H. Tributsch, J. Chem. Technol. Biotechnol. to be published.

H2SO4, graphite cathode, T 121 C, U 1.9 V, i 0.147 mA cmA2 and current eciency 80%), 1 kWh is required for reduction of 1.97 mol sulfuric acid to H2S. 5.2. Solar powered bacterial biomass production Figure 6 shows a diagram of a solar powered bacterial production process which could be run even in