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Catalytic Processes for Activation of CO2

Narcís Homsa,b, Jamil Toyirc and Pilar Ramírez de la Piscinaa,    aDepartament de Química Inorgànica and Institut de Nanociència i Nanotecnologia, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain, bCatalonia Institute for Energy Research (IREC), Jardins de les Dones de Negre 1, 08930 Barcelona, Spain, cUniversité Sidi Mohamed Ben Abdellah, Faculté Polydisciplinaire, B.P 1223, Taza, Morocco

1.1 Introduction

CO2 can be considered a carbon source rather than just a greenhouse gas (GHG) that needs to be mitigated. As a result of tough policies on GHG emissions, CO2 has turned out to be a strategic carbon source, available as free or even with a financial return if adequate technology is applied for CO2 capture and recycling. From this perspective, an attractive opportunity is emerging for a new CO2-based economy. The chemical recycling of CO2 and its reuse in the production of fuels or other chemicals is attractive from both an environmental perspective and in terms of fossil source independency. CO2 is released as a by-product in the chemical and petrochemical industry and in fermentation processes and currently, new technological possibilities based on membranes and absorbents are opening up for its separation and capture. High purity CO2 is available from such sources; indeed, some such emissions are already used in the production of chemicals such as CO2 from the ammonia industry which is fed to urea plants or CO2 from fermentation which is recycled into the beverage industry after appropriate cleaning. Moreover, large-scale emissions of CO2 come from power plants fueled by natural gas and from the cement industry; in these cases undesired impurities must be taken into account before the CO2 becomes useful. However, these sources can be considered an opportunity for large-scale recycling of CO2. In what follows we will consider different options for the reuse of CO2 by means of chemical recycling.

. Nevertheless, CO2 use is thermodynamically possible via numerous reactions involving its reduction or its incorporation into other compounds.

O bond(s) and the formation of new C—H or C—C bond(s) can be accomplished using a reductant. In this case, the action of an appropriate catalyst can convert CO2 into a potential energy vector. This recycling pathway requires a large input of energy and usually H2 as the reductant, and leads to fuels such as methane and methanol. In this context, two aspects must be taken into account: the production of H2 and the energy source. If the energy comes from renewable sources and the H2 does not come from fossil fuels, does the overall process merit further interest. Nowadays, we can engage optimized electrolysis of water to supply the H2, thus avoiding the fossil fuel starting material. The use of non-constant wind energy or electrical energy produced at night can be used to obtain H2, thereby matching the necessity to store such excess energy. In fact, storage of H2 itself is necessary; one nice way to accomplish this is to incorporate the hydrogen into a liquid fuel. Then, since the products obtained from the catalytic hydrogenation of CO2 can be directly used as fuels, overall this process could be seen as a means of electrical energy storage and transport. However, the recycling of CO2 to fuels implies its immediate release into the environment.

O bond(s). However, to accomplish a desired reaction, the action of a catalyst is also usually necessary. In this CO2 recycling pathway, different parameters need to be taken into account to determine the viability of a proposed process. The amount of CO2 fixed and the overall energy balance of the complete chemical route, together with the value of the product produced, could indicate how feasible this process is. Large-scale production of highly valued polymers could be performed using recycled CO2, thus also diminishing the use of fossil resources. In this way, if highly stable long-life materials are produced, the CO2 storage could be very long term and therefore the release of CO2 into the environment could be very slow.

In recent years, extensive research has been carried out into these aspects of CO2 reuse and numerous publications have appeared [1–12]. This chapter therefore presents recent advances in the conversion of CO2 into fuels and desirable chemical products by using heterogeneously catalyzed processes, which are summarized in Figure 1.1.

Figure 1.1 Catalytic routes for CO2 activation in heterogeneous phase leading to fuels and chemicals.

The chapter is divided in different sections. After the Introduction, the second section is dedicated to the reactions of CO2 with hydrogen; particular attention is paid to large-scale processes that produce synfuels: methanol, dimethyl ether (DME), methane and higher hydrocarbons and alcohols. Then, CO2-reforming processes of methane and alcohols, and dehydrogenation processes using CO2 are presented in Section 1.3. Catalytic processes based on CO2 insertion into organic compounds to form carbonates or carboxylic acids are discussed in Section 1.4. In the last part, future trends in the catalytic conversion of CO2 are presented with a particular focus on processes that aim to produce strategic chemicals or fuels using renewable energy sources.

1.2 Reactions of CO2 with hydrogen

1.2.1 Hydrogenation of CO2 to Methanol

Methanol is extensively used as a starting material for the production of several bulk chemicals and liquid fuels [2]. Furthermore, the use of methanol as a medium for the storage and transportation of hydrogen and as fuel in direct methanol fuel cells (DMFC) could increase demand for it in a future.

Nowadays, methanol production uses syngas (a CO/CO2/H2 mixture) produced from fossil sources and Cu/ZnO-based catalysts. However, methanol production from CO2 and hydrogen (Eq. (1.1)) is now considered a serious alternative which could contribute to mitigate CO2. In a recent book, Nobel Laureate Olah [6] set out the concept of the methanol economy based on the production of methanol by chemical recycling of CO2.

(1.1)

In fact, initial attempts to produce methanol in industry were performed in the 1920s using CO2 from fermentation processes. The catalysts used at that time were similar to those currently commercialized for the production of methanol from syngas [6]. However, to match the performances of the process using syngas, the process of methanol synthesis from CO2 and H2 requires a highly effective catalyst in terms of activity, stability, and selectivity. Achieving high selectivity is difficult because the formation of products other than methanol, such as hydrocarbons and higher alcohols, is thermodynamically favored. Moreover, the reverse water-gas shift reaction (RWGS, Eq. (1.2)) may be kinetically favored under methanol synthesis conditions.

(1.2)

The most important research into methanol production from CO2 and H2 has been reviewed in a number of recent publications [2,11–13]. Although a wide range of metal-based catalysts have been studied for methanol synthesis, particular attention has been paid to copper-based catalysts [11]. Table 1.1 compiles several representative reported catalysts.

Table 1.1

Catalytic Behavior of Various Catalysts for Methanol Synthesis from CO2 and H2

aPrepared by coprecipitation and tested at bench scale for a long-term operation.

bPrepared by co-impregnation, short-term operation.

cPrepared by incipient wetness, short-term operation.

dPrepared by leaching, initial activity.

In particular, Cu/ZnO-based catalysts are among the most useful systems for the catalytic hydrogenation of CO2 to methanol [13–17]. The addition of other components such as ZrO2, Al2O3, Ga2O3, and SiO2 has been extensively studied [16,18]. Saito et al. developed high performance multicomponent catalysts based on Cu/ZnO/ZrO2/Al2O3 and prepared via co-precipitation using metal nitrates and sodium carbonate [16]. Several functions have been proposed for ZnO in these co-precipitated Cu/ZnO-based catalysts: (i) ZnO may favor the formation of appropriate precursors during preparation of the catalyst, which leads to higher dispersion; (ii) in the presence of Al2O3, ZnO may show refractory behavior and attenuate the unavoidable agglomeration of Cu particles which takes place during a long-term operation; (iii) ZnO may avoid the poisoning of Cu particles by feed gas impurities such as sulfides and chlorides; and (iv) ZnO, as a basic oxide, may neutralize the acidity of Al2O3, thus preventing the transformation of methanol to DME. However, in such catalysts, the effect of the texture of ZnO on the interaction with Cu and on the dispersion of Cu particles is difficult to determine. The activity of the multicomponent catalyst is proportional to the surface area of copper. The presence of Al2O3 or ZrO2 increases the total surface area as well as the dispersion of Cu particles on the surface. The presence of other components such as Ga2O3 or SiO2 increases the performance of the multicomponent catalyst. Ga2O3 increases the activity per unit of Cu surface area. Both Cu+ and Cu⁰ species are essential to catalyze the reaction and Ga2O3 regulates the ratio of Cu+/Cu⁰ throughout the reaction maintaining it near optimal.

A Cu/ZnO/ZrO2/Al2O3/SiO2 catalyst was used in a small bench plant with a capacity of 50 kg-CH3OH/day. The plant was equipped with facilities for recycling unreacted gases and gaseous products and it was operated under practical reaction conditions for methanol synthesis from CO2 and H2 (523 K; 5 MPa) [16]. The Cu/ZnO/ZrO2/Al2O3/SiO2 was highly stable during long-term methanol synthesis and showed selectivity to methanol of 99.7%. The purity of the crude methanol produced in the bench plant was 99.9% by weight; higher than that of the crude methanol commercially produced from syngas.

The crystallization of the Cu particles during the operation of co-precipitated Cu/ZnO-based catalysts has been related to the presence of sodium nitrate [16]. In an attempt to avoid these problems, Toyir et al. [19,20] reported the use of supported Cu–Ga2O3 catalysts prepared by co-impregnation using zinc oxides of different surface areas. Methanol synthesis on silica-supported Cu–ZnO–Ga2O3 catalysts was also studied. The promoting effect of Ga2O3 was associated with the Ga2O3 particle size. Small Ga2O3 particles favor the formation of an intermediate state of copper between Cu⁰ and Cu²+, probably Cu+. In addition, Toyir et al. found that the use of methoxide and acetylacetonate precursors for the preparation of a Cu–Ga2O3/ZnO catalyst yields better dispersion of copper than in catalysts prepared from nitrate precursors [20]. SiO2-supported multicomponent catalysts, especially when hydrophobic silica is used, are effective and fairly stable during the production of methanol at temperatures up to 543 K [20].

There is not definitive agreement yet about a unified and rationalized mechanism for methanol synthesis from CO2 hydrogenation where elementary steps are completely evidenced and active centers defined. Several key mechanistic questions have not yet been settled. For many years, CO hydrogenation was assumed to be the main reaction pathway for methanol synthesis until isotopic labeling experiments conducted by Chinchen et al. strongly suggested that CO2 is the main source for CH3OH synthesis [15]. In connection with the results obtained by Chinchen et al., numerous experimental results have supported the route from CO2[21,22]. Recently, a combined DFT (density functional theory) and KMC (kinetic Monte Carlo) study was carried out by Yang et al. [23] to study the effects of metal dopants on the catalytic performance of the Cu(1 1 1) surface in CH3OH synthesis via CO2 hydrogenation. On Cu(1 1 1) and Au/Cu(1 1 1), CH3OH is mainly produced via formate species.

Scheme 1.1 displays a simplified reaction mechanism based on key intermediate surface species in which six atoms of hydrogen are consumed to convert one molecule of CO2 into one molecule of CH3OH and one molecule of H2O.

Scheme 1.1 CO2 hydrogenation to methanol via formation of formate species over a Cu/ZnO-based catalyst.

In a recent microkinetic-based DFT analysis of the mechanism of methanol synthesis on Cu from CO2 and CO [24] indicated that the reaction was structure sensitive and suggested that for a commercial Cu/ZnO/Al2O3 catalyst, an open Cu surface—for example: Cu(1 1 0), Cu(1 0 0) or Cu(2 1 1) partially covered by oxygen—may provide a good model for the active site of methanol synthesis without excluding the involvement of ZnO in a synergetic effect at the Cu–ZnO interface.

Kinetic studies undertaken on CO2 hydrogenation to methanol over Cu/ZnO-based catalysts under realistic conditions were conducted by Saito et al. [16]. In that study, methanol and CO were produced via parallel pathways. Measurement of the yield of methanol and CO as a function of reciprocal space velocity (1/SV) (Figure 1.2) showed that methanol and CO are formed simultaneously at low conversions of CO2 (Eqs. (1.1) and (1.2), respectively).

Figure 1.2 Yields of methanol (circles) and CO (squares) in methanol synthesis from CO2/H2 (1/3, mol/mol) over a Cu/ZnO/ZrO2 catalyst as a function of reciprocal SV (T = 523 K, P = 5 MPa) (adapted from Ref. [16]).

Both water and CO show an inhibitory effect on methanol synthesis over Cu/ZnO-based catalysts although the effect of water is much stronger than that of CO, as shown in Figure 1.3[16].

Figure 1.3 Inhibitory effects of H2O (a) and CO (b) on methanol synthesis and that of H2O on CO formation (c) from CO2/H2 (1/3, mol/mol) over a Cu/ZnO/ZrO2 catalyst. r and ri are the rate and the initial rate of methanol or CO formation before H2O or CO addition; T = 523 K, SV = 180,000 h−1, P = 5 MPa for H2O addition, P = 3.5 MPa for CO addition (adapted from Ref. [16]).

Methanol production using CO2 and H2 is already undertaken on a commercial scale. This process is carried out in two steps in the CAMERE process developed in Korea by KIST [25]. First, CO2 is converted to CO by the RWGS over a ZnAl2O4-based catalyst; then, in a separate reactor, methanol synthesis takes place over CuO/ZnO/ZrO2/Ga2O3 at 513 K and 2.7 MPa.

A commercial plant constructed by the company Carbon Recycling International (CRI) for the production of methanol from CO2 is currently operative in Iceland and uses local geothermal energy sources [26]. Recently in Japan, the construction of a 100 metric ton-per-year demonstration plant producing methanol from CO2 in a single-step was announced. In that case, the CO2 feed is obtained as an industrial by-product in Mitsui’s chemical complex at Osaka. The hydrogen required was planned to be generated from water using renewable energy [27].

1.2.2 Dimethyl Ether Synthesis

Currently there is much interest in the production of DME because of its diverse uses. DME is a valuable chemical; is a useful precursor for the preparation of other organic compounds and is also used as an aerosol propellant. Moreover, several potential applications of DME are envisaged in the transportation sector. DME can act as a clean fuel when burned in engines that are properly optimized. In addition, DME is expected to be an alternative for application in direct fuel cells. DME is produced by the dehydration of methanol:

(1.3)

There are two processes currently available for DME production using syngas. Indirect synthesis first produces methanol and then uses an acid catalyst such as alumina or phosphoric acid-modified γ-Al2O3, to dehydrate the methanol (Eq. (1.3)).

Alternatively, DME can be produced by direct synthesis using a bifunctional catalyst that permits methanol synthesis and dehydration in the same unit of the process, with no methanol isolation and purification. The single-step process is more attractive since the in situ dehydration of methanol to DME is a reasonable way to overcome the severe limitations of the thermodynamic equilibrium of methanol synthesis. The favorable thermodynamics of the dehydration reaction increases oxygenate yields and the degree of conversion in DME synthesis is significantly higher than in methanol synthesis, even at low pressure [28].

Although DME can be produced using CO2/H2 by single-step or two-step processes, there are few reports of direct synthesis of DME using CO2/H2 (Eq. (1.4)) [29–33:]

(1.4)

Typical catalysts for this reaction are Cu-based catalysts supported on moderate acidic zeolites such as NaHZSM-5 and reviewed by Wang et al. [11]. The effect of the addition of several promoters to Cu-based catalysts has been studied. A small amount of Mo added to HZSM-5-supported Cu markedly enhances the catalytic activity [34]. Meanwhile, the addition of Pd to Cu–Zn–Al–Zr/HZSM-5 leads to a catalyst which is more favorable for DME production than for CO formation [35]. Table 1.2 summarizes several representative systems for DME synthesis.

Table 1.2

Representative Catalysts for DME Synthesis from CO2 and H2 (data from Ref. [11])

1.2.3 Formic Acid Synthesis

Formic acid is an important chemical with numerous applications. Furthermore, formic acid has been considered as a suitable hydrogen storage material for potential fuel cell applications. The decomposition of formic acid yields only H2 and CO2 without CO formation. If an appropriate process of HCOOH production from CO2 was implemented, the co-produced CO2 would easily be recyclable via hydrogenation to form HCOOH once more [36].

The current industrial methods used for HCOOH production employ CO as a raw material [37]. As an alternative, the hydrogenation of abundant and inexpensive CO2 could be advantageous and deserves exploration [38].

Thermodynamically, CO2 hydrogenation to formic acid (Eq. (1.5)) is disfavored

(1.5)

In an aqueous medium, extremely high CO2/H2 pressures must be used to reach only very small equilibrium concentrations of HCOOH [39]. In homogeneous phase, a base is used to shift the unfavorable equilibrium and form HCOO−. Jessop et al. have shown that the proton transfer to the base drives the reaction (Eq. (1.6)) [40]:

(1.6)

The most significant results for the catalytic hydrogenation of CO2 to formic acid have been obtained in homogeneous phase using organometallic complexes [36], mainly rhodium, ruthenium, and iridium systems [36,40,41]. Under CO2 supercritical conditions (scCO2), improved catalytic behavior of several systems has been reported; this has been related to the high miscibility of H2 and scCO2, the ease of separation of the products and improved mass-transfer and heat-transfer properties [40]. High rates of hydrogenation were obtained using soluble RuXY(P(CH3)3)4 catalysts (X, Y = H, Cl or OOCCH3) in scCO2[40].

Most researchers intended to form HCOOH via CO2 hydrogenation over homogeneous catalysts and propose the use of high-boiling nitrogenous bases in polar solvents. However, technical hurdles such as catalyst and solvent removal and the limited amounts of HCOOH formed per mol of high molecular weight amine represent serious drawbacks. A new process for the hydrogenation of CO2 to formic acid using ruthenium complexes has recently been developed by BASF [42]. To shift the unfavorable equilibrium, the process uses amines such as NHex3 instead of the commonly used NEt3. The process was claimed to be advantageous because the formic acid can be isolated easily in mild conditions by thermal cleavage of the HCOOH/NHex3 adducts.

Very recently, attempts have been made by Preti et al. to find a heterogeneous supported metal catalyst [43]. A gold-based catalyst has been developed for CO2 hydrogenation in the presence of neat NEt3 to form HCOOH/NEt3 adducts. The HCOOH/NEt3 adducts could be separated simply by drawing them directly, catalyst free, from the reactor under pressure. A continuous production process for catalyst-free and solvent-free adducts has been demonstrated using a robust titania-supported gold catalyst [43].

Other approaches consisting of the immobilization of an active complex onto a support are being studied to find more practical systems for the hydrogenation of CO2 to formic acid. Zhang et al. [44] recently reported that ruthenium complexes immobilized over amine-functionalized silica working in basic ionic liquid yield satisfactory results for the hydrogenation of CO2 to formic acid which can easily be collected. The method offers the possibility to directly reusing the ionic liquid and catalyst after a simple separation step.

1.2.4 CO2 Hydrogenation to CH4

The catalytic hydrogenation of CO2 to form methane (Sabatier reaction, Eq. (1.7)) is the most favored reaction in the series of CO2 hydrogenation reactions that produce hydrocarbons and alcohols [45].

(1.7)

The full reduction of CO2 into methane requires the transfer of eight electrons which leads to significant kinetic limitations. The reaction is highly exothermic and the removal of heat from the reactor is an important issue. Therefore, processes using high-performance catalysts and adequate reactors are required to achieve satisfactory rates and selectivity.

Applications of the CO2 methanation process include H2 purification used in ammonia manufacture [46] and can also be used to remove CO2 from confined spaces [47]. In gas chromatography, converters of CO and CO2 to methane can allow improved sensitivity in CO and CO2 quantification. If renewably generated H2 is used to carry CO2 methanation, then the methane produced can be used as a supplementary fuel; this could be a way of recycling CO2 in a natural gas power plant [48,49].

The catalytic hydrogenation of CO2 to methane has been widely studied using numerous supported catalysts based on metals from groups 8–10 [49,50]. Supported Ni-based catalysts are the most useful and studied systems for CO2 methanation. An important focus of research has been the influence of the support on the performance of the catalyst. The interaction between Ni and highly dispersive supports determines the catalytic performances of Ni-based catalysts used for methane production from CO2[11].

At low temperatures, noble metals (e.g., Ru, Pd, and Pt) show better activity and stability than Ni [51]. Highly dispersed Ru nanoparticles supported on TiO2 produce high methanation yields, which can reach 100% at 433 K [52]. Recently, Jacquemin et al. reported the possibility of producing methane from CO2 and H2 over Rh/g-Al2O3 at low temperatures (298–423 K) and atmospheric pressure [49].

For higher temperature operation (723 K) Park et al. recently reported a Pd–Mg/SiO2 catalyst synthesized from a reverse micro-emulsion that is fairly active and selective for CO2 methanation [50].

Two main mechanisms have been proposed for the methanation of CO2 (Scheme 1.2). The first involves the formation of CO and its subsequent conversion to methane [53–55]. In the second mechanism, CO2 is directly hydrogenated without intermediate CO formation [56]. Possible key intermediates in the first mechanism are the adsorbed formyl species (HCO)ads or surface carbon (Cads) whose hydrogenation produces methane [57]. In the second mechanism, hydrogen carbonate (HCO3)ads and formate (HCOO)ads surface species have been considered as possible intermediates [56]. The hydrogenation of active formates adsorbed on the metal-support interface has been suggested as the key step in the formation of methane via this mechanism.

Scheme 1.2 Simplified pathways of CO2 methanation on supported metal catalysts.

To distinguish between the two mechanisms, Peebles et al. carried out methanation of CO2 on clean Ni(1 0 0) surfaces [53]. Large amounts of CO were formed, with activation energies of 88.7 kJ mol−1 and 72.8–82.4 kJ mol−1 for CH4 and CO formation, respectively. The absolute CH4 production rates were very close to those for methanation of CO. The results were more consistent with the mechanism involving (CO)ads and (C)ads intermediates. Recently, the dissociation of CO2 into CO and oxygen on the surface of Rh/g-Al2O3 has been evidenced via in situ DRIFT studies [49].

1.2.5 CO Production via the Reverse Water-Gas Shift Reaction (RWGS)

CO2 can be reduced to CO by the catalytic RWGS reaction (Eq. (1.2)):

(1.2)

At moderate temperatures, the equilibrium constant is low and a key aim is to increase the conversion of the reactants. CO2 or H2 concentration could be increased and then the excess CO2 or H2 recirculated in the process. However, the equilibrium conversion values are limited; as an example, only 65% conversion of CO2 is achieved with H2/CO2 = 3 at 900 K. Removing water vapor from the reactor can also be used to drive the equilibrium toward CO production.

The RWGS should be taken into account in all reactions using CO2 and H2. Indeed, the RWGS is a key reaction in the production of methanol (Section 1.2.1. above) and in the hydrogenation of CO2 into higher hydrocarbons or alcohols, which are presented below. For separate utilization of the RWGS in processes which first require reduction of CO2 to CO, active catalysts for the water-gas shift (WGS) reaction are generally used. Cu-based catalysts, supported noble metal catalysts and CeO2-based catalysts have particularly been studied for the RWGS reaction [4,11].

The effects of several components on the performance of Cu/ZnO-based catalysts for the RWGS have been studied [58]. Table 1.3 summarizes some representative Cu-based catalysts.

Table 1.3

Activity of Various Cu-based Catalysts on RWGS

Reaction conditions: T = 523 K; P = 0.15 MPa, CO2/H2 = 1/3 (mol/mol).

Data processed from Ref. [58].

A Cu/ZnO/ZrO2/Al2O3 catalyst is considered to be suitable for practical use. The addition of a small amount of colloidal silica to a Cu/ZnO-based catalyst greatly improves its long-term stability in the RWGS, as in methanol synthesis from CO2 and H2. As for methanol synthesis, a linear relationship between the activity of the catalyst in the RWGS and the metallic copper surface was found [16,59]. However, the RWGS is more favored on metallic copper than on partially oxidized copper [60].

Although much work has been devoted to studying the mechanism of the RWGS, mainly over Cu-based catalysts, this remains controversial [4]. Two principal reaction pathways, the redox and formate decomposition mechanisms, have been proposed to explain the mechanism of CO formation in the RWGS. For the redox mechanism, the concept of the oxidation and reduction cycle is suggested. CO2 oxidizes Cu⁰ and generates CO (Eq. (1.8)). H2 reduces Cu+ to Cu⁰ and forms H2O (Eq. (1.9)) [61]. FTIR spectroscopy studies carried out by Fujita et al. with CO2 alone over a Cu/ZnO catalyst indicate that CO2 dissociates to CO [62].

(1.8)

(1.9)

The formate-based pathway involves a role for H2 in the formation of formate intermediate surface species from adsorbed CO2[63–66] CO is then produced by formate decomposition. Participation of Cu⁰ in the formation of formate intermediates has also been proposed [66].

1.2.6 Higher Hydrocarbon Synthesis

The effective production of higher hydrocarbons from the reaction between CO2 and H2 is difficult. Indirect approaches based on Fischer-Tropsch (FT) and methanol synthesis are adopted to achieve a selective synthesis using CO2[67]. In the FT-synthesis approach, the two-step process comprises: (i) the RWGS and (ii) FT synthesis. In the methanol-mediated process, CO2 and H2 produce methanol, which subsequently transforms into hydrocarbons such as the gasoline fraction.

Whatever the pathway adopted, the active catalyst should be designed to have a dual function so as to operate in the proposed consecutive steps, as shown in the Scheme 1.3.

Scheme 1.3 Pathways for CO2 hydrogenation to higher hydrocarbons.

With a CO2/H2 mixture, cobalt catalysts used for FT synthesis from syngas lead to a high production of methane and a deviation from the Anderson-Schultz-Flory (ASF) distribution occurs [68,69]. CO2 hydrogenation over FT iron-based catalysts yields higher percentages of alkenes than cobalt-based catalysts do, but FT iron-based catalysts show high selectivity to undesired products, especially methane [70]. The modification of FT-based catalysts by adding effective promoters and using appropriate supports arose as a promising way to prepare an effective catalyst for producing long-chain hydrocarbons from CO2. The addition of a controlled amount of manganese to an iron catalyst suppresses methane formation and increases the alkene/alkane ratio [70]. Both structural and electronic changes have been invoked to explain the promoting effects of Mn. Potassium added to Mn–Fe–based catalysts has been shown to act as an electronic promoter rather than a structural one, leading to higher conversion of CO2 and a lower methane yield [70]. A substantial increase in the alkene/alkane ratio with a shift toward longer hydrocarbon chains was also observed [70]. Copper can often replace Mn as a dopant in iron-based CO2 hydrogenation catalysts since besides being a RWGS catalyst, Cu enhances the hydrogenation capacity of the iron. The choice of support for the promoted catalysts above mentioned depends strongly on being able to ensure catalytic stability by avoiding the sintering of active dispersed particles during the reaction [67,70].

For the methanol-mediated process, an effective catalyst should be active for methanol synthesis and for performing the conversion of methanol to (CHx) species which will in turn be transformed to higher olefins and paraffins via C—C bond formation; in this case an ASF distribution is not expected.

Inui [71] reported selective synthesis of lower olefins using a two-stage packed reactor in which methanol is first produced over a Pd-modified Cu–ZnO–Al2O3–Cr2O3 catalyst. In the second stage, methanol is converted to hydrocarbons over a SAPO–34 zeolite. More than 90% selectivity to C2–C4 olefins was found; SAPO-34 was claimed to be suitable for lower olefin synthesis because of its weak acidity and narrow pore structure. A two-stage series reactor system was also studied for the synthesis of the gasoline fraction using CO2[71]. In addition to a methanol synthesis catalyst, MFI-type metallosilicates such as H–Fe-silicate and H–Ga–silicate were optimum for the conversion of methanol to the gasoline fraction. Hydrocarbon synthesis via a methanol-mediated process in a single-bed reactor was demonstrated for the synthesis of isoalkanes. The choice of support is crucial because surface characteristics of pore structures and inner electric fields strongly influence catalytic performances. In fact, the effects of the type of zeolite on catalytic activity for the synthesis of isoalkanes from CO2 hydrogenation were studied over Fe–Zn–Zr/zeolite catalysts [72]. The distribution of hydrocarbon products is influenced by the structure and acidity of the zeolites [73]. HY zeolite is most effective for isoalkane synthesis due to the presence of medium and strong acid sites. The reaction paths of isoalkane formation over an Fe–Zn–Zr/HY catalyst indicate that methanol is synthesized directly from CO2 hydrogenation, and the RWGS is not an indispensable step for hydrocarbon formation [74].

Best performances in terms of CO2 conversion and selectivity to desirable products in CO2 hydrogenation to higher hydrocarbons have been achieved in fluidized-bed and slurry reactors. They were also beneficial for the removal of heat generated due to the highly exothermic nature of the reaction [75]. In particular, hydrogenation of CO2 to hydrocarbons proceeded in fluidized-bed and slurry reactors over an Fe/Cu/Al/K catalyst yields better catalytic performance than a fixed-bed reactor [75]. However, some technological hurdles still have to be overcome, particularly the deactivation and inhibitory effects of the water produced. In this respect, the utilization of a permeoselective silica membrane to remove water in situ has been proposed to improve the productivity of long-chain hydrocarbons [76].

1.2.7 CO2 Hydrogenation to Higher Alcohols

The possibilities for safe transport and the excellent compatibility with gasoline of higher alcohols make them better suited than methanol for fuel applications [4]. However, if for methanol synthesis Cu/ZnO-based catalysts are the reference, a catalyst of similar performance for the synthesis of higher alcohols from CO2 and H2 is yet to be developed [77].

Higher alcohol synthesis from syngas (Eq. (1.10)) is thermodynamically more favorable than from CO2/H2 (Eq. (1.11)) and produces less water. However, the heat released is lower when CO2/H2 is used making the process less complicated to control.

(1.10)

(1.11)

So far there is no generally accepted mechanism for higher alcohol synthesis from CO2/H2[78,79]. The most cited route for higher alcohol formation through CO2 hydrogenation is summarized in Scheme 1.4[78,79]. The proposed mechanism involves two competitive paths (A and B). Elementary steps involved in path A are the reduction of CO2 to CO followed by CO dissociation [79]. Dissociated CO is then hydrogenated to produce surface hydrocarbon species (CHx). CHx fragments either lead to methane (or higher hydrocarbons) by hydrogenation or form adsorbed C2 oxygenates by CO insertion. The adsorbed oxygenated C2 species are subsequently hydrogenated to form C2H5OH or transformed to higher oxygenates by interaction with adsorbed CHx species to form higher alcohols according to a C—C bond formation/hydrogenation process [79]. The competitive path, B, involves the reduction of CO2 by hydrogenation (without dissociation) to produce methanol as a by-product. Questions regarding the rate-limiting step and the selectivity controlling steps together with their relationship with active(s) site(s) are still being studied.

Scheme 1.4 Simplified scheme of higher alcohol synthesis from CO2 and H2.

An active catalyst for the synthesis of higher alcohols should catalyze the key elementary processes: (i) CO2 reduction to CO; (ii) hydrogen-assisted dissociation of CO; and (iii) CO insertion/C—C bond formation with subsequent hydrogenation. The design of the catalyst depends on the target product.

In the absence of commercial catalysts with production rates for higher alcohols at the levels needed to achieve economic viability, potential catalysts can be divided into four broad categories: (i) modified methanol synthesis catalysts (Cu/Zn-based and Cu/Mn-based); (ii) modified molybdenum-based catalysts (sulfides and oxides); (iii) rhodium-based catalysts; and (iv) modified FT catalysts.

Ethanol is produced more readily on Rh-based catalysts [79]. For higher alcohols synthesis, straight-chain alcohols are produced over both molybdenum sulfide-type catalysts and modified FT catalysts, such as Co/Cu-based catalysts [80]. The selective synthesis of branched alcohols still suffers from lacking desirable yields because high pressures and temperatures are still required to perform high activity and selectivity [81]. K and/or Cs-promoted Cu/Zn/Cr catalysts show interesting activity for the synthesis of isobutanol[81] Copper crystallites supported on modified MgO (Cu/Mg/Ce/K) and ZrO2/ZnO/MnO promoted by alkali and palladium (Zr/Zn/Mn/Pd/K) are also active for isobutanol synthesis from syngas or CO2/H2 [81].

The most successful catalysts for higher alcohol synthesis are rhodium based, which is prohibitively expensive for large-scale production. It is possible to produce mixtures of methanol and higher alcohols from syngas by alkali promotion of the methanol synthesis catalysts and by appropriate modification of the reaction conditions [82]. Along these lines, attempts have been made to circumvent the use of rhodium by modifying the Cu/ZnO methanol synthesis catalyst for the synthesis of ethanol and higher alcohols. In work reported by Inui et al., a supported Rh catalyst, an Fe-based modified FT catalyst, and a Cu-based modified methanol synthesis catalyst were combined in different ways [83,84]. Unfortunately, these catalysts failed to produce sufficient quantities of higher alcohols to be viable on an industrial scale.

1.3 CO2-assisted reactions

1.3.1 CO2 Reforming of Methane

Catalytic reforming of methane with CO2 (Eq. (1.12)), also known as dry reforming of methane, has recently received considerable attention because of the simultaneous consumption of two major greenhouse gases.

(1.12)

At a practical level, reforming with CO2, rather than H2O, is attractive because this reaction can be employed in areas where water is not available and yields syngas with lower H2/CO ratios, which is a useful feedstock for the FT synthesis of long-chain hydrocarbons [85]. In solid oxide fuel cell applications, internal reforming with CO2 is expected to be more convenient, as CO2 is a mild oxidant and could avoid the negative impact of using steam, such as thermomechanical constraints [86]. In other situations, a combination of CO2 and steam reforming may be advantageous [87]. The performance of noble metals (Ru, Rh, Pd, Ir, and Pt) and other transition metals, such as Ni, supported on Al2O3, SiO2, ZrO2, La2O3, and CeO2 has been widely studied in dry reforming of methane [88].

Dry reforming conditions are thermodynamically favorable for several side reactions such as methane decomposition (Eq. (1.13)), Boudouard equilibrium (Eq. (1.14)), RWGS (Eq. (1.2)), methanation (Eq. (1.7)), and steam reforming (Eq. (1.15)).

(1.13)

(1.14)

(1.15)

Carbon deposition caused by CH4 decomposition (Eq. (1.13)), and/or Boudouard equilibrium (Eq. (1.14)) is the major cause of catalyst deactivation during dry reforming of methane [89].

The inhibition of carbon deposition has been studied using different metals, supports and promoters [88,90]. Noble metals have been found to show higher resistance toward carbon deposit formation than non-noble metals such as Ni [91,92]. Among the materials tested, Rh-based catalysts exhibit high activity and stability. Moreover, the use of a support with a low concentration of Lewis acid sites and/or the presence of basic sites results in enhanced catalyst activity, and lower coke deposition therefore leading to more stable catalysts [93].

Although several mechanisms have been proposed for the reaction [94–98] many issues are still being addressed in order to develop a consistent model to explain the activation modes of CH4 and CO2, the implication of the metal(s) and the support, the rate-limiting step(s) and the crucial issue of carbon deposit formation [98].

A limited number of industrial processes use the CO2/CH4 reforming reaction [99–102]. Dry reforming is essentially used to produce pure CO from natural gas (the CALCOR process [103] or to obtain an equimolar H2/CO syngas as a feedstock for further chemical synthesis (the SPARG process) [104].

New applications of CO2 reforming that upgrade coke oven gases have recently been reported [105]. CO2 reforming of a mixture of H2, CH4, and CO over Ni/g-Al2O3 followed by methanol synthesis has been considered. Catalyst deactivation by coke deposition and sintering, still need to be solved to devise an optimum application.

1.3.2 CO2 Reforming of Ethanol and Higher Alcohols

Although ethanol steam reforming, partial oxidation, and autothermal reforming have been widely studied, dry reforming is much less known (Eq. (1.16)) [106–111.]

(1.16)

Bellido et al. reported an efficient Ni/Y2O3-ZrO2 catalyst for the dry reforming of ethanol. The catalyst was prepared by a polymerization method and exhibits a CO2 conversion of 61% at 1073 K [111]. Besides hydrogen production, recent studies demonstrate a value-added use of ethanol reforming with CO2 to produce carbon nanofilaments [112]. Alternative use of a mixed steam/CO2 reforming of ethanol has been shown to be advantageous in some situations where it is necessary to find a good compromise between activity, stability, and heat control [113]. Although one industrial patent claims the reforming of various alcohols, water is added as a means of adjusting the H2/CO ratio, and CO2 is considered as inert [114].

1.3.3 Oxidative Dehydrogenation in the Presence of CO2

The utilization of CO2 as an oxygen source is an alternative method for converting light paraffins to valuable olefins with better yields than conventional non-oxidative dehydrogenation processes [115]. The latter is equilibrium-limited and highly endothermic [116]. Oxidative dehydrogenation (ODH) is an irreversible and exothermic process which can be carried out at lower temperatures without carbon deposition. The presence of CO2, a mild oxidant, as a substitute for oxygen allows better olefin selectivity [117–119]. Recent work on ODH in the presence of CO2 has focused on the production of propene [117,120].

Effective catalysts for the ODH of propane in the presence of CO2 are supported catalysts based on active species, such as Cr [120,121], Ga [118], and In [117]. Elsewhere, Duprez and col. recently reviewed other promising applications of ODH in the presence of CO2 to produce valuable olefins such as isobutene [115].

One of the most relevant applications of CO2-assisted reactions is the dehydrogenation of ethylbenzene to styrene; a very important monomer in the modern petrochemical industry. The dehydrogenation process is considered an attractive way to respond to the increasing industrial demand for styrene [115]. The commercial process in which steam is co-fed with the ethylbenzene suffers from energy loss and catalyst deactivation, due to coking. The catalyst slowly deactivates and typically needs to be replaced every 1–2 years. In the presence of CO2, Fe/Ca/Al oxide catalysts exhibit high performance in the dehydrogenation of ethylbenzene to styrene with much slower deactivation [122,123]. In this process the reaction was considered to proceed 45% via a one-step pathway (Eq. (1.17)) and 55% via a two-step pathway (Eqs. (1.18) and (1.2)).

(1.17)

Two-step path:

(1.18)

(1.2)

The use of CeO2 as a dopant in V2O5-based catalysts supported on ZrO2–SiO2[124], Al2O3[125], and TiO2–ZrO2[126,127] has been reported to improve the activity and stability of the catalysts in ethylbenzene dehydrogenation in the presence of CO2 by preventing coke formation. An improved selectivity to styrene was obtained over mesoporous silica (SBA-15)-supported CeO2–ZrO2[128].

To summarize, several efficient catalytic systems have been developed for promising CO2-assisted processes; their redox properties dominate the catalytic activity. CO2 acts as a mild oxidant and can play several roles depending on the catalyst and the reaction; CO2 can produce active oxygen species and reoxidize the reduced oxides, participating in the redox cycle. Moreover, CO2 can play a role in reducing coking through the oxidation of carbon species.

1.4 CO2 insertion reactions

This section deals with the catalytic conversion routes of CO2 which incorporate the whole CO2 molecule into organic substrates. We will focus here on the synthesis of organic carbonates and carboxylic acids using catalytic processes in heterogeneous phase. Several reviews cover different specific aspects of these transformations of CO2[129–132]. These reactions are of great interest from an industrial point of view because the synthetic target has direct potential applications as a valuable chemical or a useful platform for further organic synthesis. Moreover, the use of CO2 in these syntheses may contribute to the development of clean synthetic methods, in some cases avoiding the use of highly toxic and harmful substances, and the formation of undesired by-products. The organic molecules obtained constitute stable substrates that can be important in carbon management strategies and could ensure the long-term storage of CO2. These processes can be contemplated under the concept of low energy input reactions because the CO2 molecule is not broken down. The development of new heterogeneous catalysts to replace the homogeneous catalysts mainly used in these reactions is very important for reasons of cost and product separation as well as for catalyst stability and recovery.

1.4.1 Organic Carbonates

Several organic carbonates such as dimethyl carbonate (DMC), diphenyl carbonate (DPC), ethylene carbonate (EC), propylene carbonate (PC), and styrene carbonate (SC) are important in industry. They are used in the synthesis of polycarbonates and polyurethanes, which are among the most extensively used plastics. In addition, they can be employed in lithium-ion batteries and are used as aprotic polar solvents [129,130].

Organic carbonates were first produced on a commercial scale from phosgene. Research into alternative routes has caused great interest for many years because of the high toxicity of phosgene and the generation of HCl as a by-product of the process. For DMC production, the oxidative carbonylation of methanol catalyzed by cuprous chloride in a slurry reactor, and the carbon monoxide-methyl nitrite process using a Pd²+ catalyst have been developed industrially [131,132].

Acyclic organic carbonates can be produced by the catalyzed reaction of alcohols with CO2 (Eq. (1.19)) using metallorganic species, namely organotin-based catalysts in homogeneous phase [129,133]. However, to avoid equilibrium limitations, it is necessary to remove water from the product side, or to use a high pressure of CO2. Molecular sieves cannot be used for removing water because the surface hydroxyls formed are acidic enough to protonate the carbonate and reverse the reaction; organic water traps are better suited [130].

(1.19)

Due to the effectiveness in homogeneous phase of organotin catalysts, supported organotin compounds grafted on different supports have also been explored [134]. Moreover, different solid acid-base catalysts have also been studied. However, most of the systems reported in heterogeneous phase are less effective than those operating in homogeneous phase [131]. New reactor concepts, including the use of membrane reactors for water separation using heterogeneous catalysis, have also been reported [135].

Most of the materials studied in heterogeneous processes are ZrO2-based catalysts, including ZrO2 modified by acidic compounds such as phosphoric acid or ZrO2-supported heteropolyacids [131]. Tomishige et al. reported that the binary oxides CeO2–ZrO2 showed better catalytic activity than ZrO2[136]. The catalytic activity of ZrO2 is attributed to the Brönsted basicity of hydroxyl groups and to the Lewis acid/base pairs present on the surface which act as active centers [137,138]. Detailed studies of DMC synthesis from CO2 and methanol over ZrO2 using in situ Raman and infrared spectroscopies have been reported [138–140]. The results indicate that DMC is produced via a sequential route: (i) dissociative adsorption of methanol to form methoxide species, (ii) CO2 insertion resulting in the formation of monomethyl carbonate, (iii) the transfer of a methyl group from the adsorbed methanol to the monomethyl carbonate. In addition to zirconia-based catalysts, other oxidic systems such as CeOxTi1−xO2, CeO2, and TiO2 have been used to synthesize DMC via the route represented in Eq. (1.19); TiO2 exhibited the lowest catalytic activity [131]. Vanadia-based catalysts such as H3PO4/V2O5 and Cu–Ni/V2O5–SiO2 have also been reported to be useful for continuous production of DMC from CO2 and methanol using fixed-bed reactors [141].

The synthesis of cyclic carbonates via cycloaddition of CO2 to epoxides is carried out industrially using homogeneous catalytic processes (Eq. (1.20)).

(1.20)

In this case, there is no formation of water and this process has been extensively studied in heterogeneous phase [131,132]. Immobilized homogeneous catalysts and catalysts based on metal oxides, zeolites, and smectites have also been developed. A review of this subject has been published by Dai et al. [131]. Metal oxides such as MgO, La2O3, ZrO2, and Nb2O5 are relatively active for the synthesis of cyclic carbonates such as PC and SC via the process represented in Eq. (1.20). Moreover, much higher catalytic activities were observed over mixed metal oxides or mixed metal-non-metal oxides [131]. Mg–Al and Mg-modified Zn–Al mixed oxides, prepared from hydrotalcite precursors are highly effective for these processes [142,143]. The catalytic results point to cooperation between the acid and basic sites of the mixed oxides. Yamaguchi et al. [142] and other researchers [131] proposed a bifunctional mechanism of acid-base catalysis for the synthesis of cyclic carbonates from CO2 and epoxides.

When using zeolites, their basicity can be improved by the incorporation of an alkali metal oxide into the pores of the zeolite. Davis et al. studied the performance of various alkali-modified X-zeolites and Y-zeolites [144]. Occluded alkali metal oxides promote the catalytic activity and that activity increases with the electronegativity of the alkali metal cation. Alkali and alkaline-earth-modified Engelhard titano-silicate-10 (ETS-10) molecular sieve catalysts have also been reported to be useful for the synthesis of PC via Eq. (1.20)[145]. Alkali-modified catalysts are significantly more effective than the alkaline-earth-modified ones. The presence of a small amount of water enhances the rate of cycloaddition toward the formation of the cyclic carbonate without significant formation of glycol as a by-product; Doskocil discussed the role of water adsorbed onto ETS-10 catalysts [146]. Despite abundant research, the yield of cyclic carbonate from epoxides and CO2 achieved through the use of modified zeolites is still low.

Modified smectites have also been used in reactions of the type represented in Eq. (1.20)[131]. Fujita et al. indicated that an Na-modified Mg-containing smectite with K+ added yielded up to 80.7% of PC, without the use of co-catalysts or a solvent [147].

As is generally the case, homogeneous catalysts based on organic bases and organometallic complexes, show better activity and selectivity than the acid-basic solids mentioned above. Some heterogenized homogeneous systems have been studied; we refer here exclusively to supported organometallic complexes. Different types of organometallic complexes of Cr, Co, Ni, Al, Mn, Zn, Ru, and Re have been reported [131]. Chromium-salen complexes were anchored on aminopropyl-functionalized SiO2, ITQ-2, and MCM-41 supports. A Cr-salen complex anchored via covalent linkage through the ligand showed no leaching during SC synthesis via the process represented in Eq. (1.20) and yielded an epoxide conversion of 70% [148]. Mn-salen complexes heterogenized on SiO2 proved to highly active, stable, and reusable catalysts for the PC synthesis via the process represented in Eq. (1.20) under scCO2; a yield of 95% was reported [149]. Other authors have reported [131,132,150] that the covalently immobilized catalyst can lose its halide ligand during the catalytic reaction; the addition of halides as co-catalysts or their introduction into the support could improve catalytic performance.

There are two additional routes by which to synthesize cyclic carbonates: (i) via the reaction of CO2 with a glycol (1,2 diol) (Eq. (1.21)) and (ii) via the oxidative carboxylation of an olefin with CO2 in the presence of oxygen (Eq. (1.22)). However, very few heterogeneous catalysts have been studied in these two routes.

(1.21)

(1.22)

Tomishige et al. found that over CeO2–ZrO2 catalysts, cyclic carbonates such as EC and PC were selectively synthesized via (Eq. (1.21)) with ethylene glycol and propylene glycol respectively [151,152]. Despite EC and PC selectivity reach ca. 100%, the maximum conversion due to equilibrium limitations is low; the removal of water is necessary in this case.

Aresta et al. reported that Nb2O5 was effective for the oxidative carboxylation of styrene with CO2 as in (Eq. (1.22)) [153]. However, the selectivity was as low as ca. 2%. Nevertheless, the use of NbCl5 as a co-catalyst gives a carbonate yield of up to 11%. The use of Ti-modified MCM-41 as a catalyst for the process represented in (Eq. (1.22)) but employing H2O2 as the oxidant and an organic base as a co-catalyst, has also been reported [154].

The use of cyclic carbonates has been envisaged as a convenient strategy for the synthesis of DMC [10,129]. The reaction to obtain DMC from an epoxide can be carried out in a two-step reaction (Eqs. 1.20 and 1.23).

(1.23)

The cyclic carbonate produced in a first step can further react with an excess of methanol yielding DMC and valuable dry glycol. The second step can be catalyzed by different acids and bases [155]. Basic metal oxides are more effective and useful for catalyzing the overall reaction; among the catalysts reported, MgO appears to be the most effective [156].

Although oxide catalysts based on CeO2 are not good catalysts for the process represented in (Eq. (1.23)) [115], Corma and col. have shown that appropriate loading of gold nanoparticles onto ceria significantly increases the activity and the selectivity of ceria nanocrystallites in the transalkylation of propylene carbonate by methanol [157].

1.4.2 Carboxylic Acids

The direct carboxylation of hydrocarbons to carboxylic acids is a great opportunity for their synthesis. The carboxylation of saturated hydrocarbons can be considered as the formal insertion of CO2 into a C—H bond with consequent formation of a new C—C bond. The direct conversion of methane and CO2 to higher value-added products has recently been reviewed [158].

In this context, the direct reaction of methane and CO2 to give acetic acid (Eq. (1.24)) in heterogeneous phase could be of great interest to industry. However, the reaction is thermodynamically unfavorable under practical conditions.

(1.24)

The reaction represented in Eq. (1.24) occurs to some extent over supported catalysts based on Rh, Pd, and Pt [130,159,160]. In an attempt to drive Eq. (1.24) to the right-hand side, C2H2 was added to the reactant mixture (CO2+CH4); acetic acid and vinylacetate were produced by using an admixture of Pt/Al2O3 and Zn acetate/C catalysts [161]. Acetic acid is formed in a first step, then Zn acetate/C catalyzes the reaction between the acetic acid and C2H2 and vinylacetate is produced.

Huang et al. tried to overcome thermodynamic limitations [162] by introducing O2 (Eq. (1.25)); using V2O5–PdCl2/Al2O3 as a catalyst, small amounts of CH3COOH were obtained.

(1.25)

The coupling reaction of CO2 with unsaturated compounds has been extensively studied using metallic complexes in the homogeneous phase. However, few examples in the heterogeneous phase have been reported [130].

Over a PtSn/SiO2 catalyst, CO2, C2H4, and H2O react selectively to give lactic acid (Eq. (1.26)) [163] in a fixed-bed reactor. The catalyst was a well-defined PtSn alloy supported on silica. When using H2 instead of H2O as a reactant, several by-products were formed and before the formation of lactic acid, the simultaneous appearance of CO and H2O was observed; the RWGS results in the formation of water which is necessary for the desired reaction (Eq. (1.26)):

(1.26)

An in situ DRIFT-mass spectrometry study reported that the reaction yields lactic acid through a C2-carbonylic species and non-dissociatively coordinated CO2[164]. Other studies carried out using propylene over the same PtSn/SiO2 catalyst did not prove satisfactory results for obtaining hydroxybutanoic acids [165].

1.5 Concluding remarks and outlook

CO2 recycling could have a significant impact on global CO2 emissions if useful fuels can be obtained by direct CO2 conversion routes. However, the source of the energy required to carry out these processes is essential to demonstrate that environmentally benign routes can become feasible. Heterogeneously catalyzed CO2 hydrogenation to methanol as well as the production of DME and synthetic hydrocarbons are already feasible industrial processes and are industrially attractive and economically viable if cheap and clean sources of H2 are available. The transformation of CO2 into polymeric materials is another potential large use of CO2 which deserve further research. Progress toward finding new heterogeneous catalysts is expected to be made. Currently there is some industrial interest in these processes: Bayer announced to plan to market a process to produce polyurethane-based plastics using CO2 as a raw material by 2015 [166]. Additional uses of CO2 in heterogeneously catalyzed processes to obtain valuable products such as olefins through oxidative dehydrogenation processes could be incentivized to become industrial practice.

Finally, other CO2 activation routes are expected to be explored in depth. The electro-catalytic or photo-catalytic activation of CO2 are processes that could be considered for future implementation. The difference between the two processes resides in the source of the electrons. Recent reviews report the electro-catalytic reduction of CO2 to various products including CO, HCHO, HCOOH, CH3OH, and CH4, depending on the conditions, the composition of the electrode and the cell parameters [9,167–169]. Active electro-catalytic metals for the reduction of CO2 are widely described elsewhere [9,170–174]. In most of the cases reported, the rate limiting step is considered to be the reduction of CO2 (Eq. (1.27)).

(1.27)

Consecutive or simultaneous elementary steps involving electron/proton transfer lead to the formation of various products (Eqs. (1.28)–(1.31)).

(1.28)

(1.29)

(1.30)

(1.31)

Important issues still need to be resolved in order to devise efficient processes for the electro-catalytic reduction of CO2; they mainly concern the low solubility of CO2 in aqueous solutions, kinetic limitations, the low selectivity of CO2 reduction, deactivation of electro-catalysts and low tolerance to contaminants [175]. Gas-phase CO2 reduction, based on a gas diffusion electrode (GDE), and solid polymer electrolyte (SPE), has been reported to be a promising approach [176]. If the electrical energy could be supplied through a photo-assisted process, then photo-electrochemical activation of CO2 could be considered. A photo-electro-catalytic device for such a purpose should integrate the photo-anode for water dissociation and the electro-catalyst for CO2 reduction. Developments in this field have recently been reviewed [4,177,178].

Meanwhile, direct photo-catalytic conversion of CO2 is one of the more promising fields of research into CO2 recycling. Under this concept, CO2 could really be considered to be a green molecule from which, by means of renewable solar energy, desirable chemical products and fuels could be sustainably obtained. Appropriate catalytic materials are being studied that would allow these processes to run in the heterogeneous phase and in aqueous solutions, thereby avoiding the use of sacrificial electron donors. Reduction of CO2 and water oxidation can be accomplished by a semiconductor which absorbs light energy and transfers electrons to the redox species thus minimizing electron-hole recombination. The photo-catalytic reduction of CO2 in aqueous solution to produce oxygenates and hydrocarbons can be achieved using various semiconductors mainly under UV radiation. TiO2-based materials, zeolite or silicate-containing highly dispersed TiO2 species, mixed oxides, and metal (Cu)-doped oxides, have all been used [9,176,179–181]. The main challenge is to use visible light for this process [8,182]. Materials based on nanocomposites of AgBr/TiO2 for the photo-catalytic reduction of CO2 to hydrocarbons; and the use of layered double hydroxides Zn–Cu–M(III) (M=Al, Ga) and InTaO4-based materials for the photo-catalytic conversion of CO2 into methanol have been recently reported [183–185]. Further scientific research in this field is needed to facilitate adequate evaluation of future practical