# Generation of Useful Hydrocarbons and Hydrogen during Photocatalytic Decomposition of Acetic Acid on CuO/Rutile Photocatalysts

Authors: Sylwia Mozia
Journal: International Journal of Photoenergy
 (2009)

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## Abstract

The presented
studies have focused on a photocatalytic
generation of useful hydrocarbons, mainly
methane and ethane, from acetic acid underN2 atmosphere. CuO-loaded rutile, as well as unmodified rutile and anatase-phase TiO2 photocatalysts were applied in the experiments.  The
efficiency of the catalysts towards methane generation changed in
the following order: Cu-TiO2 (10% Cu) > crude TiO2≈Cu-TiO2 (20% Cu) > Cu-TiO2 (5% Cu) > rutile. The amount of CH4 produced in the presence of the catalyst containing 10 wt% of Cu was higher for ca. 33% than in case of pure rutile. The concentration of ethane was 14–16 times lower than the amount of methane, regardless of the catalyst used. Low concentrations of hydrogen were also detected in the gaseous mixtures. After 5 hours of the process conducted with the catalyst containing 5–20 wt% of Cu the concentration of hydrogen amounted to 0.06–0.14 vol.%, respectively.


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## Body

## 1. Introduction

Energy has progressively become a major global concern due to the depletion of natural resources and the global warming problem. Moreover, although the oil prices, compared to the prices in summer last year, have recently decreased due to the global recession, it is impossible to predict what oil prices will be next year. In view of this, the development of renewable energy sources is very important. Among numerous alternative energy sources, bioenergy, especially biogas, seems to be the most environmentally friendly and economically viable one. Moreover, except from being the source of energy, the biogas could be an effective solution to the wastes and wastewaters problem.Biogas typically refers to a mixture of gases, mainly methane and carbon dioxide, produced by the anaerobic digestion or fermentation of organic matter under anaerobic conditions. Other compounds present in the biogas could be N2, H2, H2S, O2, CO, H2O, and NH3. The composition of biogas varies depending on the origin of wastes used in the anaerobic digestion process as well as the process conditions.The traditional production of biogas based on anaerobic digestion technology requires the presence of particular kinds of bacteria. The methanogenic bacteria are highly sensitive to the O2 concentration in the system and their activities depend on the concentrations of fatty and acetic acids, and the pH value [1]. In addition, bacteria are not able to treat substances which are biorecalcitrant (e.g., herbicides) or bactericide. This reduces the number of possible sources for biogas generation to those which do not contain substances dangerous to the bacteria [2].In view of this, it seems to be beneficial to find another solution for conversion of wastewaters into useful energy (biogas). In our opinion, such a solution could be development of biogas production via photocatalytic decomposition of organic compounds. Photocatalysis is not specific (or almost not) for particular substrates what means that could be applied for any type of wastewaters, regardless of its toxicity. Therefore, different biogas sources could be utilized for photocatalytic generation of biogas, or “photo-biogas”.Most of the already published papers [3–11] on photocatalytic production of methane concern reduction of CO2 under UV light in the presence of pure or modified TiO2. The reactions were carried out either in liquid or in gaseous phase. The efficient photoreduction of carbon dioxide in aqueous medium was found to be difficult since the solubility of carbon dioxide is rather low (ca. 0.03 mol/dm3 at ambient conditions) [11]. Therefore, attempts to conduct the process in gaseous phase were made [12–14]. Generation of methane from CO2 is often proposed as a method of solving the global warming problem. Another very important environmental problem is treatment of wastewaters. As was mentioned earlier, the photocatalytic production of methane from sewage is supposed to be helpful in solving this problem.Literature data concerning photocatalytic generation of methane from organic compounds in liquid phase are very limited. All of them concern production of CH4 from aliphatic acids [15–18] and alcohols [19]. In 1970’s Kraeutler and Bard [15–17] published a series of papers concerning photocatalytic decarboxylation of acetic acid in the presence of Pt/TiO2 catalyst. The main products of the reaction were methane and carbon dioxide. Similarly, Sakata et al. [18] observed formation of methane and ethane during photodecomposition of acetic and propionic acids in the presence of TiO2 and Pt/TiO2.One of the crucial points in the photocatalytic generation of methane from organic compounds is development of an effective photocatalyst. Most of literature data on the photocatalytic production of methane in aqueous phase show application of TiO2 or Pt/TiO2 photocatalysts [15–18]. In the presented studies we have focused on preparation of CuO-modified rutile photocatalysts and their application in photocatalytic generation of methane in N2 atmosphere. CuO was selected on a basis of literature data [3, 20–23]. For example, Slamet et al. [3] found that CuO was very effective modifying agent in photoreduction of CO2. The authors investigated the effect of modification of TiO2 with CuO, Cu2O and Cu and found that CuO was the most active modifier compared to the other species. Sreethawong and Yoshikawa [23] reported that CuO/TiO2 photocatalysts exhibited significant activity in photocatalytic hydrogen evolution. Taking into consideration these data, CuO was selected as a modifying agent in the presented experiments. Acetic acid was used as a source of the “photobiogas”. Application of acetic acid as a model compound seems to be reasonable since amongst the final by-products of photocatalytic degradation of most organic compounds in water different aliphatic acids, including CH3COOH, are present.


## 2. Experimental

The catalysts used in this study were prepared from crude TiO2 obtained directly from the Chemical Factory “Police” (Poland). The crude TiO2 was modified with CuCl2·2H2O as follows. A defined amount of TiO2 was introduced into a beaker containing aqueous solution of modifying agent and stirred for 22 hours. After that water was evaporated and the samples were dried at 105°C for 24 hours in an oven. Such prepared samples were calcinated at 700°C in Ar atmosphere (5 dm3/h) for 1 hour. The amount of Cu introduced to the samples was 5, 10 or 20 wt%.  In order to compare the results, a sample containing rutile phase without CuO was prepared by annealing of crude TiO2 at 800°C for 1 hour in air. At the temperature of 700°C, which was applied for preparation of CuO/rutile catalysts, the anatase phase, not rutile, was obtained. Therefore, the temperature of 800°C was selected for preparation of pure rutile without CuO.X-ray diffraction (XRD) analyses were performed on a powder diffractometer Philips X’Pert PRO (CuKα, 35 kV, 30 mA). UV-VIS/DR spectra were recorded using Jasco V 530 spectrometer (Japan) equipped with the integrating sphere accessory for diffuse reflectance spectra. BaSO4 was used as a reference.The photocatalytic reaction was conducted in a cylindrical glass reactor containing 0.35 dm3 of CH3COOH (1 mol/dm3) and 0.35 g of a catalyst. At the beginning of the experiment N2 was bubbled through the reactor for at least 3 hours to ensure that the dissolved oxygen was eliminated. Then, the UV lamp (λmax=365 nm), positioned in the center of the reactor, was turned on to start the photoreaction. Gaseous products were analyzed using GC SRI 8610C equipped with TCD and HID detectors, and Shincarbon (carbon molecular sieve; 4 m, 1 mm, 10–120 mesh) and molecular sieve 5A (2 m, 2 mm, 80–100 mesh) columns. Helium was used as a carrier gas.


## 3. Results and Discussion

Figure1 presents XRD patterns of crude TiO2 and photocatalysts modified with CuO. It can be observed that crude TiO2 contained almost pure (97%) anatase phase. The diffraction lines were weak and broad suggesting poor crystallinity of the sample. The crystallite size of anatase in the crude TiO2 was 9 nm. The catalysts containing 5 and 10 wt% Cu were composed of rutile and CuO only. In case of the sample containing 20 wt% of Cu, except from rutile and CuO phases, CuCl was also identified. The presence of CuCl suggests that the amount of CuCl2 used was too high and the transformation of CuCl2 to CuO was not complete under the conditions applied. Some amount of copper (II) was reduced to copper (I) forming CuCl. The sample prepared by calcination of crude TiO2 at 800°C and denoted later as rutile consisted of 97% of rutile and 3% of anatase [24].  As was mentioned earlier (see Section 2),  the temperature of 800°C  was selected because application of calcination temperature of  700°C resulted not in rutile, but anatase phase. These data clearly show that the presence of CuO strongly affects the temperature of phase transformation from anatase to rutile. Such a phenomenon was already reported in literature [25]. Francisco and Mastelaro [25] explained it by catalyzing properties of copper oxide. CuO probably catalyzes the mass transport to the nucleation region of rutile phase, promoting rutile nuclei growth, thus favoring the phase transition. CuO is responsible for a higher number of defects inside the anatase phase, in such a way that formation and growth of a higher number of rutile nuclei into TiO2 anatase take place faster.  The mechanism responsible for such a modification is an excess of oxygen vacancies that accelerates the transition and the crystallite growth [25].XRD patterns of crude TiO2 and Cu-modified photocatalysts: (a) crude TiO2; (b) photocatalyst containing 10 wt% Cu; (c) photocatalyst containing 20 wt% Cu. •-rutile; Δ-anatase; □-CuO; ▾-CuCl.
(a)(b)(c)The crystallite size of rutile calculated on a basis of the Scherrer equation was similar for pure rutile and CuO/rutile catalysts and ranged from 300 to 320 nm, respectively. However, since 100 nm is generally considered the upper limit for XRD crystal size measurements, these data cannot be interpreted as accurate dimensions of the rutile crystals. The only conclusion could be that crystallite sizes of rutile in all of the samples (i.e., pure rutile and CuO/TiO2) were similar. This might lead to the conclusion that the crystallite size of rutile, being almost the same for all the samples, should not affect the photocatalytic behavior of the CuO-modified rutile.Figure2 shows UV-Vis/DR spectra of crude TiO2, rutile and Cu-modified catalysts. It can be observed that all the spectra of CuO-rutile photocatalysts exhibit a similar course and are red shifted for over 30 nm relative to crude TiO2, what indicates a decrease of the band gap energy. This decrease was associated with phase transformation from anatase to rutile. A similar red shift relative to crude TiO2 can be observed in case of pure rutile. To determine the band gap energy (Eg) of the samples, the Kubelka-Munk method was used. The Eg values were calculated from the (F(R)hν)1/2 versus hν plots, where F(R)=(1-R)/2R  [26]. The absorption edge for crude TiO2 was found to be 378 nm, which value corresponded to the band gap energy of Eg=3.28 eV. The absorption edges determined for pure rutile and CuO-rutile samples were 412 and 414 nm, what corresponded to Eg of 3.01 and 2.99 eV, respectively. From Figure 2 it can be also found that CuO-rutile catalysts absorbed more visible light than pure TiO2. The increased absorption in the Vis region was due to grey color of the CuO-modified photocatalysts.Figure 2
UV/Vis-DR spectra of crude TiO2, rutile and Cu-rutile photocatalysts.The TiO2 and Cu-TiO2 photocatalysts were applied for the photocatalytic decomposition of acetic acid under N2 atmosphere. The reaction was conducted for 5 hours. Figure 3 presents changes of concentration of methane in gaseous mixtures versus time of irradiation.Figure 3
Photocatalytic generation of methane on different photocatalysts.For the initial 2 hours of the process, no significant difference in the amount of methane generated on different catalysts was observed. The concentration of CH4 was in the range of 0.24–0.28 vol.% what corresponded to 0.12–0.14 mmolCH4/molCH3COOH. However, with increasing time of irradiation the differences between the amounts of methane formed with application of different catalysts were becoming more significant. After 5 hours of irradiation the pure rutile was found to be the least efficient catalyst. The amount of methane formed in the presence of rutile was ca. 0.6 vol.%, what corresponded to 0.29 mmolCH4/molCH3COOH. The highest amount of methane was generated in case of the catalyst containing 10 wt% of Cu. After 5 hours of irradiation the concentration of CH4 in gaseous mixture was 0.88 vol.% (0.43 mmolCH4/molCH3COOH). On the basis of the results presented in Figure 3, the efficiency of the catalysts toward methane generation can be put in the following order: Cu-TiO2 (10% Cu) > crude TiO2≈ Cu-TiO2 (20% Cu) > Cu-TiO2 (5% Cu) > rutile. It should be noticed here that all the rutile catalysts containing CuO were more active than pure rutile. The amount of methane generated on Cu-rutile photocatalyst was higher than that obtained in case of pure rutile for ca. 16, 33 and 24%, for catalysts containing 5–20 wt% of  Cu, respectively.Taking into consideration the above results, the catalyst containing 10 wt% of Cu was further applied in a long term process. Irradiation was conducted for 28 hours. It was found that the amount of methane generated was continuously increasing with increasing time of irradiation. After 5 hours of the process the concentration of methane in gas amounted to 0.88 vol.%, whereas after 28 hours the amount of methane increased up to 3.66 vol.%.Another gaseous products which were identified in the reaction mixture were carbon dioxide and ethane. Figure4 shows a comparison of the amount of these compounds generated after 5 hours of irradiation. From the obtained data it was found that the main products of acetic acid decomposition were methane and carbon dioxide. The lowest concentrations of CH4 and CO2 in the gaseous mixture were obtained in case of pure rutile, whereas the highest—in case of rutile containing 10 wt% of Cu. The ratio of CH4/CO2 formation was found to be in the range of 0.94–0.98 in case of CuO-modified TiO2, ca. 1.1 in case of crude TiO2 and about 1.2 for rutile. These data clearly show that for pure TiO2 the amount of methane was higher than the amount of CO2. On the contrary in case of the CuO-rutile catalysts the concentration of CO2 was higher than concentration of CH4. In Figure 4 it can be also observed that the amount of ethane was significantly lower than the amount of methane and carbon dioxide, regardless of the catalyst used. The lowest concentration of ethane after 5 hours of irradiation was observed for rutile (0.043 vol.%) and the highest for CuO/rutile catalyst containing 10 wt% of Cu (0.062 vol.%). The ratio of CH4/C2H6 was found to be about 14–16.Figure 4
A comparison of the amount of products obtained after 5 hours of reaction conducted with different photocatalysts.Taking into consideration that the main gaseous products identified were methane and carbon dioxide and that the CH4/CO2 ratio was about 1, it might be concluded that the photodecomposition of acetic acid followed the so-called “photo-Kolbe” reaction pathway [15–17]:(1)CH3COOH→CH4+CO2.
Reaction (1) represents the photocatalytic decarboxylation of acetic acid under anaerobic conditions. The reaction is initiated by photogenerated holes and can be also written as follows [27]:(2)CH3COOH+h+→CH3•+CO2+H+,(3)H++e-→H•,(4)CH3•+H•→CH4.
The reaction of the formation of ethane from acetic acid can be presented as follows [18]:(5)2CH3COOH→C2H6+2CO2+H2,
or, taking into consideration the recombination of methyl radicals [27]:(6)CH3•+CH3•→C2H6.
Reactions (5) and (6) in the discussed system are minor ones, what can be concluded on a basis of the obtained data (Figure 4) showing that the amount of ethane was significantly lower than that of methane.From Figure4 it can be also found that amongst the gaseous products of the reaction hydrogen was present. Changes of H2 concentration in time of the experiment are presented in Figure 5. It can be observed that in case of crude TiO2 and pure rutile the amount of hydrogen was significantly lower than of the Cu-modified photocatalysts. In case of the catalysts containing CuO the H2 concentration was increasing with increasing Cu loading. After 5 hours of irradiation about 0.06–0.14 vol.% of H2 was obtained for photocatalysts containing 5–20 wt% of Cu, respectively.Figure 5
Photocatalytic generation of hydrogen on different photocatalysts.The photocatalytic evolution of hydrogen in the presence of sacrificial agents has been already described in the literature [18, 20–22, 26–34]. In general, when the reducing agent, or hole scavenger, such as alcohol [20, 23, 26–29], organic acid [18, 30, 31] or sulfide ion [32, 33], is present in the solution, the photogenerated holes react with the reducing agent. As a result the photocatalyst is enriched with electrons and H2 evolution reaction is enhanced [34]:(7)2H++2e-→H2.According to Kudo and Miseki [34] the hydrogen evolution in the presence of sacrificial agent does not mean the “water splitting”. Water splitting means to split water into H2 and O2 in a stoichiometric amount in the absence of sacrificial reagents [34].The photocatalytic hydrogen evolution can be enhanced by modification of TiO2. Literature data [20–23] show that CuO/TiO2 photocatalysts are very effective in H2 generation. The TiO2 acts as the primary catalyst and CuO acts as a cocatalyst, helping charge separation [20]. After absorption of a photon (hν) with sufficient energy, that is, equal or higher than the band gap energy (Eg) of TiO2, the electrons and holes are generated. The hole scavenger consumes holes in the valence band rapidly leaving electrons in the conduction band of TiO2. The conduction band (CB) of CuO is positioned below the CB of TiO2 which allows transfer of electrons from the CB of TiO2 to the CB of CuO. These results in a more negative CB potential of CuO and, as a result, enhanced hydrogen evolution. The yield of H2 evolution greatly relies on the competition between the trapping of the excited electrons by cocatalyst active sites followed by reduction reaction and the electron-hole recombination [23]. As was mentioned earlier, the amount of hydrogen in case of the Cu-modified photocatalysts was significantly higher than in case of pure TiO2. This might lead to a conclusion that the limited hydrogen evolution in case of crude TiO2 and rutile resulted from rapid recombination of holes and electrons, since the separation of electron-hole pairs in case of pure TiO2 is not as efficient as in the presence of CuO.The source of hydrogen in case of the photocatalytic reactions conducted in the presence of sacrificial agents is still under debate. Bandara et al. [20] have argued that H2 is produced from water. They have drawn such a conclusion on a basis of the experiment performed with application of absolute methanol. During this process no H2 evolution was observed. On the other hand, Sakata et al. [18] proposed that H2 formation is due to photocatalytic decomposition of acetic acid:(8)CH3COOH+h+→•CH3+CO2+H+,(9)•CH3+•OH→CH3OH,
or(10)CH3COOH+2•OH→HOCH2COOH+H2O.
In the next step, CH3OH and HOCH2COOH are decomposed into carbon dioxide and hydrogen:(11)CH3OH+H2O→CO2+3H2,(12)HOCH2COOH+H2O→2CO2+3H2.
The overall reaction summarizing (8)–(12) can be written as follows:(13)CH3COOH+2H2O→2CO2+4H2.
The photocatalytic decomposition of methanol was also presented as follows [29]:(14)CH3OH→HCHO+3H2,(15)HCHO+H2O→HCO2H+H2,(16)HCO2H→CO2+H2.
From the mechanism proposed by Sakata et al. [18] it can be found that H2 is produced from methanol and glycolic acid, which are formed from acetic acid ( (9) and (10). These two reactions are possible when hydroxyl radicals are present in the solution. However, in the low pH region the amount of OH• radicals formed is not high due to low concentration of OH-. Therefore, the amount of methanol and glycolic acid which might be produced in the reactions (9) and (10) should be rather low. This leads to a conclusion that in the low pH region the reaction (13) is of minor importance [18]. In view of this, it is more probable that the hydrogen ions come mainly from decomposition of acetic acid presented by (8), rather than from decomposition of methanol or glycolic acid (reactions (11) and (12). Water could be also involved in H2 generation through the reaction (7), however, according to Jang et al. [33] its effect should be insignificant due to the low concentration of protons in neutral water. Summing up, the photocatalytic evolution of H2 in the presence of acetic acid as a sacrificial agent was probably mainly due to reduction of protons (H+) generated during decomposition of CH3COOH (8) . Moreover, it can be also supposed that some amount of hydrogen was generated from by-products of acetic acid decomposition, such as methanol and glycolic acid, as well as from water molecules. However, the H2 evolution during the latter two processes compared to the overall hydrogen evolution is supposed to be of minor importance.An evidence for the supposition that the source of hydrogen is acetic acid, not water, might be also the ratio of methane to carbon dioxide concentrations (Figure4). As was mentioned earlier, in case of crude TiO2 and rutile the amount of methane was higher than the amount of CO2, whereas for CuO-TiO2 catalysts the concentration of CH4 was lower than CO2. This might suggest that in case of these two types of photocatalysts some other reactions, despite of those described by (1)–(6) took place. One explanation might be generation of hydrogen from acetic acid. Assuming that both, methane and at least part of the hydrogen were produced from acetic acid, the amounts of these compounds should depend on the efficiency of the reactions of their formation. Thus, the higher amount of H2, the lower amount of CH4 should be generated, since H+  would take part in reaction (7) instead of (1)-(4). In case of pure TiO2 the amount of H2 was very low and therefore the CH4/CO2 ratio was above 1. For the CuO-TiO2 catalysts higher amount of hydrogen was generated, what might be supposed to be a reason of a decrease of CH4 concentration. Moreover, the effect of C2H6 and possibly higher hydrocarbons formation on methane concentration in the reaction mixture should be also taken into consideration. However, taking into account that the amount of C2H6 was comparable for all the catalysts used (0.02–0.03 mmolC2H6/molCH3COOH after 5 hours of irradiation) the effect of ethane generation on CH4/CO2 ratio seems to be of lower importance. Besides, it might be also supposed that a certain amount of carbon dioxide was reduced to CH4, what might be concluded from the fact that the concentration of CO2 in case of crude TiO2 and rutile was lower than that of methane. Literature data [3, 8, 9, 35] show that the reduction of carbon dioxide in the presence of various types of modified TiO2 is possible. However, in order to state unequivocally what affects the CH4/CO2 ratio in the presence of pure TiO2 and CuO/TiO2 catalysts, further investigations are necessary.Summing up, from the presented data (Figures3 and 4) it can be clearly seen that the most active photocatalyst towards hydrocarbons (i.e., methane and ethane) generation was Cu-TiO2 containing 10 wt% Cu. Since the crystallite size of rutile in all of the Cu-modified photocatalysts as well as in pure rutile could be assumed to be comparable, it might be supposed that the highest photoactivity of Cu-TiO2 (10% Cu) was associated with the amount of CuO present in this sample. The photocatalytic activity of rutile-type samples increased as follows: pure rutile < Cu-TiO2 (5% Cu) < Cu-TiO2 (10% Cu), what suggests that 5 wt% of Cu was below the optimum value. Taking into consideration that in case of the Cu-TiO2 containing 20 wt% Cu the yield of CH4 formation decreased, one might draw a conclusion that this sample was overloaded with CuO. This overloading might have led to a “shading effect” of CuO [3], which means that particles of copper oxide covered most of active sites of titania. As a result, the TiO2 surface accessible to acetic acid molecules decreased and the yield of the “photo-Kolbe” reaction also decreased. However, the efficiency of photocatalysts toward hydrogen evolution (Figures 4 and 5) was as follows: Cu-TiO2 (20% Cu) > Cu-TiO2 (10% Cu) > Cu-TiO2 (5% Cu) > rutile ≈ crude TiO2. These results show that the catalyst which was the most effective in methane production (i.e., containing 10 wt% Cu) was the second one in case of hydrogen generation. Therefore, the explanation about “shading effect” of CuO in case of the catalyst containing 20 wt% Cu seems to be unsatisfactory. In view of these, more probable explanation is that at higher CuO content, higher amount of acetic acid molecules took place in the reaction of H2 formation rather than CH4 generation. Therefore, since the amount of substrate, that is, CH3COOH, was always the same, the increased production of hydrogen should lead to a decreased production of methane, what was observed in the discussed experiments.


## 4. Conclusions

It was found that it is possible to generate useful hydrocarbons, such as CH4 and C2H6, from acetic acid in the presence of Cu-modified rutile under UV irradiation. The efficiency of the catalysts toward methane generation changed in the following order: Cu-TiO2 (10% Cu) > crude TiO2≈ Cu-TiO2 (20% Cu) > Cu-TiO2 (5% Cu) > rutile. The amount of CH4 produced in the presence of the catalyst containing 10 wt% of Cu was higher for ca. 7% than in case of crude anatase-phase TiO2 and for ca. 33% than in case of pure rutile. The concentration of ethane was 14–16 times lower than the amount of methane. The lowest concentration of C2H6 after 5 hours of irradiation was observed for rutile (0.043 vol.%) and the highest for CuO/rutile catalyst containing 10 wt% of Cu (0.062 vol.%). The mechanism of methane generation from acetic acid followed the photo-Kolbe reaction pathway, what was concluded on a basis of CH4/CO2 ratio, which was found to be ~1. Low concentrations of hydrogen were also detected in the gaseous mixtures. The amount of H2 was increasing with increasing Cu loading. After 5 hours of irradiation about 0.06–0.14 vol.% of H2 was obtained for photocatalysts containing 5–20 wt% of Cu, respectively. On the basis of the experimental data it is supposed that the source of hydrogen was acetic acid, not water.Further investigations on the effectiveness of methane generation in the presence of CuO/TiO2 photocatalyst are in progress.



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