Journal of CO2 Utilization 1 (2013) 1827

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Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Review

Thermal, electrochemical, and photochemical conversion of CO2 to fuels and value-added products
Boxun Hu a, Curtis Guild a, Steven L. Suib a,b,*
a b

Department of Chemistry, University of Connecticut, Unit 3060, 55 North Eagleville Road, Storrs, CT 06269-3060, USA Institute of Materials Science, University of Connecticut, USA

A R T I C L E I N F O

A B S T R A C T

Article history: Received 27 December 2012 Received in revised form 14 March 2013 Accepted 15 March 2013 Available online 24 April 2013 Keywords: Review Carbon dioxide Activation

This review compares various alternate fuels and value-added products from conversion of carbon dioxide such as simple molecules to higher hydrocarbon fuels and polymers. Different methods of activation are summarized that lead to different products. We summarize the advantages and disadvantages of different methods of conversion of carbon dioxide. An overall summary is given at the end of the review that discusses future approaches and promising approaches. 2013 Elsevier Ltd. All rights reserved.

Contents 1. 2. 3. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thermodynamics and kinetics of CO2 conversion . . . . . . . . . . . . . . . . . . . CO2 conversion to fuel and value-added products . . . . . . . . . . . . . . . . . . . CO2 conversion to CO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. CO production by reduction of CO2 . . . . . . . . . . . . . . . . . 3.1.1. CO production by electrocatalysis. . . . . . . . . . . . . . . . . . . 3.1.2. CO production by plasma . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.3. Synthesis gas production by reforming . . . . . . . . . . . . . . 3.1.4. CO2 conversion to HCOOH and HCHO . . . . . . . . . . . . . . . . . . . . . . . 3.2. CO2 conversion to CH3OH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. CO2 conversion to long chain hydrocarbons and oxygenates . . . . . 3.4. CO2 as building blocks for oxygen-rich compounds and polymers 3.5. Prospective in CO2 conversion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 19 19 19 19 20 21 21 22 22 23 24 25 26 26

4.

1. Introduction Carbon dioxide (CO2) utilization technologies have emerged to reduce CO2 emissions by developing benecial uses of CO2 [14]. In todays world, two major environmental concerns attributed in

* Corresponding author at: Department of Chemistry, University of Connecticut, Unit 3060, 55 North Eagleville Road, Storrs, CT 06269-3060, USA. Tel.: +1 860 486 2797; fax: +1 860 486 2981. E-mail address: steven.suib@uconn.edu (S.L. Suib). 2212-9820/$ see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jcou.2013.03.004

part to buildup of carbon dioxide (CO2), the acidication of the oceans and global warming [5,6]. These issues are consequences in part to atmospheric CO2 concentrations (ACC) rising around the globe. Fossil fuel consumption has caused ACC increases from 280 parts per million (ppm) in pre-industrial times to 382 ppm in 2006 according to the National Oceanic and Atmospheric Administration (NOAA). Currently, the atmospheric CO2 concentration is still steadily increasing at a rate of about 1.9 ppm/year. In tandem with this, the international energy outlook (2011) has projected that world energy consumption will increase 53 percent from 2008 to 2035 [7]. Scientists from the Intergovernmental Panel on Climate

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Change (IPCC) have suggested that 350 ppm CO2 is likely the safe upper limit for atmospheric greenhouse gases [8]. To realize this goal, CO2 must be captured and either stored or converted into global warming neutral impact compounds. Utilization of CO2 provides an attractive avenue for this objective. CO2 is extensively used for enhanced oil recovery, urea and polymer synthesis as a monomer feedstock, the food and beverage industry as a propellant, and chemical production [9]. However, only less than 1% of global anthropogenic CO2 generated are utilized to these ends. The rest is released to the atmosphere due to lack of economical technologies to convert these C1 sources to commodity products, and therein lack of demand. CO2 conversion to fuel and value-added products is an ideal route for CO2 utilization due to the simultaneous disposal of CO2 and the benet that many products can be used as alternate transportation fuels. CO2 is a kinetically and thermodynamically stable molecule, thus CO2 conversion reactions are endothermic and need efcient catalysts to obtain high yield. Various renewable energies such as solar, wind, and hydroelectric are proposed as energy sources for CO2 conversion. These largely intermittent kinetic energies are stored in the alternate fuels in the stable form of chemical energy that can be transported and used on demand. These synthetic fuels will sustain new and expanding markets in transportation. Furthermore, the synthetic fuels produced by CO2 utilization are compatible with current hydrocarbon-based automobiles and transportation systems. The products of carbon dioxide conversion can supplement or replace chemical feedstocks in the chemical, pharmaceutical, and polymer industries. This review summarizes the various alternate fuels and valueadded products from CO2 conversion in order of products from simple molecules to higher hydrocarbon fuels and polymers. Each product may be produced by several methods. The pros and cons of different conversion approaches are compared, with the intent of giving direction to the reader in selecting a proper approach to meet specic needs. Many good reviews and books [3,10] have described CO2 utilization by photocatalytic synthesis [4,1113], electrochemical reduction [14,15], plasma [16], and other methods [1,17,18]. We do not attempt to duplicate these references but summarize possible reaction mechanisms, unique catalyst and experimental design, structure-activity relationships, and energy efciency. These issues provide help in understanding the product selectivity and catalytic activity of each system, and evaluate the potential practical applications of the process. 2. Thermodynamics and kinetics of CO2 conversion Fig. 1 gives the Gibbs free energy of CO2 and the products converted from CO2 (CRC Handbook of Chemistry and Physics) [19]. CO2 molecules have a highly stable linear and centrosymmetric (O5 5C5 5O) structure. The difference in Gibbs free energy (DG) between the product and reactants at specic reaction is the driving force shown in Eq. (1):

Fig. 1. Gibbs free energy of CO2 and its related products.

in nature, though the cost of the catalysts is still a concern. Secondly, inorganic nanocatalysts promote conversion to valueadded olens in the FischerTropsch synthesis. Third, while not catalytic, applied potentials serve to facilitate the electrochemical reduction of CO2. Fourth, CO2 will react with other reactants with higher Gibbs free energy, such as methane and hydrogen. Last but not least, CO2 reacts with other monomeric species to form polymers. These polymerization reactions run at mild conditions with high turnover numbers. In a practical operation, two or more types of principles may function simultaneously and make the CO2 conversion more efcient. The net result of these processes is the conversion of different types of energies into chemical energy. 3. CO2 conversion to fuel and value-added products 3.1. CO2 conversion to CO CO2 conversion to CO (carbon monoxide) looks like the simplest route for CO2 reduction. CO is a feedstock or intermediate for the production of methanol and hydrocarbon fuels via the Fischer Tropsch synthesis [20]. Several technical routes lead to the CO2 conversion to CO, such as photoreduction, electrolysis, plasma, electrocatalysis, dry- and bi-reforming, and (tri-) reforming. Different types of catalysts are involved in these processes. 3.1.1. CO production by reduction of CO2 Mimicking natures photosynthesis process, photoreduction of CO2 is one of the most alluring methods for CO2 conversion due to the abundance and free access of sunlight. To meet with global energy demands, Lewis and Nocera have proposed to convert and store solar energy in chemicals (H2, methanol, and hydrocarbons) via the photosynthetic process [21]. Solar radiation varies across the globe from altitude, height, atmospheric conditions, and season. For example, solar radiation for at-plates facing south at a xed tilt in New York City is about 26 kWh/m2/day [22]. A typical photoreduction electrode is composed of a semiconductor and photocatalysts, and many of these are transition metal complexes. Semiconductors absorb photons to make excited electrons transfer from a valence band to the conducting band, which is then transferred to a photocatalyst complex, which reduces CO2 to CO and other useful organic compounds (Fig. 2). Such photoelectrocatalytic processes should be distinguished from purely photocatalytic routes. Kubiak and Kumar reported the photo-assisted electrochemical reduction of CO2 to CO on Re(bipy-But)(CO)3Cl((bipy-But) = 4,40 -ditert-butyl-2,2-bipyridine)/p-type silicon with a Faradaic efciency

DG DH T DS

(1)

where DH is the enthalpy change, DS is the entropy change, and T is temperature. Most conversions of CO2 to these listed products are endothermic reactions like natural photosynthesis as shown in Eq. (2): 6CO2 g 6H2 Ol hn ! C6 H12 O6 s 6O2 g (2)

There are several kinds of driving forces for the CO2 conversion. First, highly efcient articial enzymes lower the activation energy required for photoreduction of CO2. These exhibit rates faster than

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Fig. 2. Illustration of semiconductor catalysts for photoreduction of CO2.

production has been conducted in either liquid electrolytes or solid oxide electrolytes. Low operation temperature is one of the advantages of using liquid electrolytes, but low temperature often leads to low selectivity and low reaction rates. In aqueous solution, the selectivity for the above carbon species is low due to the competition of the hydrogen evolution reaction with CO2 reduction. Highly acidic electrolytes exhibit similar behavior for CO2 reduction. Electrocatalysis cells based on solid electrolytes (alumina, yttrium-stabilized zirconia) show high conversion rates and selectivity to CO, but require higher operating temperatures (around 8001000 8C) to achieve a high oxygen ion conductivity of the electrolyte. Electrode stability based on heat expansion is also a concern as electrodes may crack or delaminate from the electrolyte structure. For the aqueous CO2 reduction reaction (Eq. (3)): CO2ad e ! CO2 aq (3)

of 97 3%, and a short-circuit quantum efciency of 61% for light-tochemical energy conversion, and an overall efciency of about 10% for the conversion of polychromatic light [23]. Smieja et al. further reported that the electron transfer from the electrode to the catalyst can be controlled by modifying the p-Si surface with phenylethyl groups. The interaction experiments of the electrocatalyst with the targeted catalytic substrate CO2, H2O, and CH3OH show that the reaction with CO2 is about 25 times faster than that with H2O, and 50 times faster than that with CH3OH. Calculations based on density functional theory (DFT) show that the nature of the binding of CO2 to the anion forms a Re(bipy-tBu)(CO)3(CO2)K complex [24]. Kaneco has developed metal-modied p-InP photoelectrodes for the photoelectrochemical reduction of CO2 in the LiOH/ methanol-based electrolyte. Ag, Au, Pd, and Cu deposited p-InP photoelectrodes show higher selectivity to CO than that to H2. Ag deposited p-InP photoelectrode show maximum current efciency of carbon monoxide (rf = 80.4%) and Pd deposited pInP photoelectrode has the highest selectivity to CO (100%) [25]. CO is produced via one electron reduction reaction of CO2 and  CO2 is an intermediate. The Gibbs energy differences of CO(g) splitting on many different metals change the catalytic selectivities. Compared to electrochemical reduction at the same metallic electrodes, onset potentials on Pb, Ag, Au, and Ni deposited photoelectrodes are lower (about 0.250.95 V less). The activation energy barrier in the wide-scale application of photoreduction is the efciency of the catalyst vs. the cost of the materials used for synthesis. If the cost of photocatalysts and photoelectrocatalysts can be lowered and the efciencies and lifetimes are improved, the photo-assisted electrochemical reduction of CO2 could have possible practical applications. 3.1.2. CO production by electrocatalysis Electricity is an easily accessible convenient energy, and can be readily produced by a variety of renewable (wind, hydro, solar) energy sources. The captured kinetic energy can be converted to electricity, and then stored in the form of chemical fuels by electrocatalysis, electrochemical reduction, electrolysis, and plasma-assisted catalytic reduction. CO2 electrocatalysis for CO

where CO2* is a radical anion as an intermediate. The equilibrium potential (E vs. SCE, pH 7.0) is highly negative at 2.14 V. Ionic liquid electrolytes such as 1-ethyl-3-methylimidazolium tetrauoroborate (EMIM-BF4) lower the potential for formation of the CO2 intermediate, most likely by complexation via a weak bonding between CO2 and BF4 anions. Very recently, Rosen et al. [26] reported that CO2 can be reduced at an applied voltage of 1.5 V. This electrocatalytic system (Pt/Naon/(Ag, EMIM-BF4)) reduces CO2 to carbon monoxide (CO) at very low overpotentials (<0.2 V). The system continuously produced CO for more than 7 h at Faradaic efciencies greater than 96%. Another approach to lower overpotentials is electrocatalytic reduction of CO2 by carbon monoxide dehydrogenase (CODH), a naturally occurring enzyme [27,28]. Shin achieved a current efciency of 100% at 0.57 V vs. NHE in a 0.1 M phosphate buffer (pH 6.3) with no overpotential with CODH catalysts [28]. Coordination complexes of tetraaza-macrocycles, porphyrins, and phthalocyanines have been extensively studied for electrochemical reduction of CO2 [2932]. These catalysts have been reviewed by Costamagna et al. [29] The key step for CO2 electroreduction is the coordination of a CO2 molecule to external nitrogen of the phthalocyanine or naphthalocyanine ring. CO has been produced with current efciencies up to ca. 75% with redoxinactive lithium metals [30], while the current efciencies for Co and Fe redox metals increase up to 97.4 and 84.6%, respectively [31]. The electrocatalytic activity of these catalysts for CO2 reduction has been enhanced by using high pressures (20 atm) of CO2 and gas diffusion electrodes (GDE). Interestingly, high-area metal (Fe, Ni, Cu, Pd) electrocatalysts supported on microporous activated carbon bers (ACF) have exhibited similar effects to high CO2 pressure, exhibiting relatively high partial current density (up to 63 mA/cm2) for CO2 reduction on ACF/Ni compared to lower partial current density (<10 mA/cm2) on nonactivated carbon bers [33]. Different Pt electrocatalysts are compared in Table 1. Centi and Perathoner developed a reverse proton exchange membrane (PEM) fuel cell for electrocatalytic reduction of CO2 [34]. CO was continuously produced in the gas phase in signicant amounts (about 103 higher with respect to hydrocarbons). Nanostructured

Table 1 Comparison of Pt electrocatalysts in CO2 reduction in 0.5 M KHCO3 solution. The percentage of C10 limits the products in the trap, and signicant amounts of gas phase CO products are not counted. Electrocatalysts 2 nm Pt/GDM(E-TEK) 3 nm Pt/GDM 5.4 nm Pt-C/GDM PtIr-C/GDM Work conditions Semi-half continuous, 20 8C, 20 mA, 1 h Rate or I efciency 2 102 mol/h 4.5 102 mol/h 7.4 102 mol/h CO: 6580% H2: 1030% Products and selectivity 10% 60% 70% 98% C10, CO* C10, CO* C10, CO* CO/H2 (1:2), formate < 1.5% Refs. [34]

80 mA/cm2, 25 8C, 2 V vs. SCE

[35]

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carbon supported Pt nanoparticles (3 nm) catalysts have the highest activity among three different catalysts and supports. The nanometer scale of the catalysts signicantly increased the catalytic activity. Hydrocarbons were produced for the rst time using electrocatalytic reduction of CO2, and the hydrocarbon production will be included in Section 3.4. Newman and Delacourt designed a PEM electrolysiscell for simultaneous electrochemical reduction of CO2 and H2O to make syngas CO + H2. A current density of 30 mA/cm2 has been achieved using silver-based cathode catalysts in these electrolysis cells [35]. Higher current density (135 mA/cm2) was achieved on supported Au catalysts [36]. Solid oxide electrolysis cells (SOECs) have been developed for the CO2 reduction [37]. Mogensen and Ebbesen have studied reduction of H2O and CO2 in a Ni/YSZ electrode supported SOEC. CO was produced via the reverse water gas shift reaction with higher current densities (0.251 A/cm2) [38,39]. A degradation study using impedance spectroscopy shows that ve electrode processes contribute to the cell resistance [39]. Other SOECs using Pt paste electrodes were much less active compared to nano-size Pt catalysts, and no quantitative CO products have been reported [40,41]. 3.1.3. CO production by plasma Plasmas are fast and clean methods to convert CO2 to CO and O2. Numerous works have been performed in the plasma-assisted CO2 reduction to CO [4247]. Early work was performed in 1990s under the international cooperation of The University of Connecticut, Nagasaki University, and Fujitsu Laboratories Limited. The decomposition of CO2 in fan-type ac glow discharge plasma reactors and dielectric-barrier discharge (DBD)-plasma reactors was investigated. CO2 decomposition was promoted by a synergetic effect between plasma excitation in the gas phase and catalytic actions of the metal (Au, Cu, Pt, Pd, and Rh) coated electrode surface. CO was the main carbonaceous product with moderate conversions at 30.5% and selectivities >80%. The energy efciency ($36%) of plasma methods need to be improved [48], and Spencer et al. reported a theoretical energy cost analysis method to evaluate the effectiveness of plasma systems [46]. Other metal (Al, Cu, Ti, and Fe) electrodes for plasma activation in CH4/ CO2 were tested in Lius group [49,50], and titanium showed the highest activity, for reasons still under investigation [51]. DBD plasmas have been used in CH4/CO2 reforming for producing alkanes, alkenes, oxygenates, and syngas (CO + H2) at ambient

conditions [52]. There is considerable debate on the meaning of CO2 reforming with methane, which from an energetic and life cycle analysis perspective appears to be a questionable approach to limit CO2 emissions. 3.1.4. Synthesis gas production by reforming While carbon dioxide is the primary focus of this paper, as part of the rening process the fractions of CO2 isolated often come with a high fraction of methane, which can be a valuable co-reactant with carbon dioxide. Methane itself has a global warming potential (GWP) of 30 (GWP of CO2 = 1). Methane is abundant in shale gas, coal gas, nature gas, and landll gas. For transportation, methane is not practical as a fuel due to its stability and requirements for transport, though can be used in industrial power applications. CH4/CO2 reforming to form syngas (CO/H2) is an important process [23,24] to synthesize alternate transportation fuels via the FischerTropsch synthesis, which uses syngas as its feedstock. As an added benet, the reformation of methane to fuel precursors prevents methane from escaping into the environment and preserves carbon into the hydrocarbon production cycle. Considerable work has been conducted in CH4/CO2 reforming [53,54]. A few good reviews are recommended [5557]. Power plant CO2 emission mixture has residue oxygen, which is a poison for most CO2 reduction catalysts by promoting the watergas shift reaction. Separating the oxygen from the carbonaceous gases adds considerable cost and complexity to CO2 conversion efforts, thus leading to the tri-reforming process that has been developed at Pennsylvania State University. The three-step reaction process avoids the separation step and has the promise of being cost-efcient for producing industrially useful synthesis gas. The energy and environmental analysis of integrated trireforming power plants (ITRPP) has been reported by Minutillo and Perna [58,59]. The reduction in CO2 emissions has been estimated at 83% (15.4 vs. 93.4 kg/GJ Fuel input) and 84% (8.9 vs. 56.2 kg/GJ Fuel input) for the ITRPP-SC (Fig. 3) and ITRPP-CC respectively. The power plant efciency is not penalized by using the tri-reforming process because the produced syngas can be used to generate chemicals and/or to feed fuel cell-based power plants. Furthermore, this conventional chemical process by ammines needs high thermal power in order to regenerate the solvent. With new capture technology development, the lower energy requirements for regeneration will lower the cost.

Fig. 3. Flow chart of the integrated tri-reforming power plant-steam cycle (ITRPP-SC). Source: adapted from Ref. [58].

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CO2 reforming with CH4 is an example of CO2 being used as a soft oxidant, where the dioxide is dissociated into CO and surface oxygen, and oxygen abstracts hydrogen from methane to form water via the water-gas shift reaction. This type of oxidative reaction has been extended into the oxidative coupling and oligomerization of CH4 [60,61] and dehydrogenation of alkanes (C2H6, C3H8, etc.) [6266] and alkyl aromatics [67,68]. The emergence, application and mechanistic pathways of these systems have been reviewed by Park and Ansari [1]. Due to the abundant availability, non-toxic, economic and mild oxidizing properties of CO2, these green methods are economical and energy efcient and they have potential industrial applications for the development of various useful chemicals. Shale gas contains mainly methane ($60%) and light alkanes (C2C6). With the rapid increase of shale gas production in the US and other countries, the facile production of ethylene [63], propene [69], butene [70], and hexene[71] from shale gas using the method of oxidative coupling of CH4 and dehydrogenation of alkanes is promised to lower production costs of these compounds. 3.2. CO2 conversion to HCOOH and HCHO Formic acid (HCOOH) and formaldehyde (HCHO) are the simplest oxygenates produced from the reduction of CO2 with H2O (or proton solvents). Generally, they are resulting products of CO2 reduction with protons in an electrochemical reaction, and they are intermediates in the formation of methanol and higher hydrocarbons. The selectivities of HCOOH, HCHO, and CH3OH are largely dependent on the reduction methods and catalysts used. Yadav et al. [72] recently reported an efcient articial photosynthetic production of formic acid from CO2 using a graphene coupled multianthraquinone-substituted porphyrin photocatalyst. Under 0.5 cm3/min of CO2, quantitative formic acid products were measured with a gas chromatograph but no quantum efciency was reported. About 46% of the total solar light source available on earth is in the visible light range. Visible light driven photocatalysts give an alluring prospect in the production of fuels using solar energy, although currently most catalysts exhibit efciencies too low for practical applications. Graphene exhibits high electron mobility and acts as an electron reservoir; as such a major research effort into graphenes electrochemical and electrical properties is in effect as of this writing. There is great potential for further accelerating the photoreduction reaction of CO2. A signicant question here is whether in the HCOOH synthesis by this photochemical approach the effective mechanism involves an electrode for H2 photogeneration coupled with a catalyst to catalyze the reaction between CO2 and H2, probably in the liquid phase. These photocatalysts are apparently not stable. Another photoreduction system reported by Sato et al. is composed of a p-type semiconductor photosensitizer (N-Ta2O5) and a Ru complex reducing catalyst in an acetonitrile/triethanolamine solution. This system has achieved a selectivity of more than 75% for HCOOH using visible-light. The highest turnover numbers (89) have been achieved (Fig. 4) using the N-Ta2O5 photosensitizer but the quantum efciency of 1.9% at 405 nm is low [73]. Several different electrocatalytic reduction methods/catalysts have been developed for continuous electrocatalytic reduction of CO2 to oxygenate products, including HCOOH and HCHO. In aqueous KHCO3 electrolyte, Pt and less expensive Co and Fe nanocatalysts were respectively loaded on carbon nanotubes for electrocatalytic reduction of CO2, with oxygenates (isopropanol, methanol, ethanol, acetone, and acetaldehyde) isolated as the

Fig. 4. Turnover number for HCOOH formation from visible-light-induced selective CO2 reduction using Ru complex electrocatalysts. Source: adapted from Ref. [73].

primary products; [74] In a microuidic reactor, nanosize Pt electrocatalysts reduced CO2 to formic acid at high Faradaic (89%) and energetic efciencies (45%) [73]. Solid oxide electrolyzers have attracted strong interest in recent years due to high efciency in the conversion of electrical energy into chemical energy [37,38,7577]. Co-electrolysis of CO2 and H2O using Ni/YSZ electrodes reported the formation of CO and H2, attributed to the water-gas shift reaction [38]. The electrocatalysis reactions of CO2 and H2O on Pt and ZnO nanocatalysts form HCHO in the gas headspace, and HCHO further forms paraformaldehyde polymers in condensed water [78]. A high CO2 conversion ($8%) was reported in the continuous gas-phase reduction. Compared to electrocatalytic reduction in liquid electrolyte, product separation in the gas phase reduction is not required. Recent efforts and opportunities in the heterogeneous electrochemical conversion of carbon dioxide have been described by Whipple and Kenis [15]. Compared to the production of HCOOH and HCHO by photoreduction of CO2, electrocatalytic reduction of CO2 has a much higher energy efciency (3345%); the electrocatalytic system is less complicated; also, the operation unit can be more compact and continuously achieve high time/space yield of the reactor. Therefore, large-scale utilization of electrocatalytic process is technically possible. Another process relevant here is the reduction of CO2 to HCOOH using biomass methods [139]. 3.3. CO2 conversion to CH3OH Methanol as a key commodity has become an important part of our global economy. From building blocks for plastics, paints, and organic solvents to clean fuels applied in fuel cells and combustion engines, 50 million tons of methanol have been consumed in 2011. George Olah (Nobel Prize 1994) has proposed repurposing the hydrocarbon fossil fuel network into a methanol economy in which methanol gathered by CO2 reduction and bioconversion is used as a feedstock for transportation and energy storage. For industrial production of methanol from synthesis gas (CO, CO2, and H2), the mixture of copper, zinc oxide, and alumina has achieved high selectivity to methanol (99.8%) at 250300 8C and 510 MPa in the Lurgi MegaMethanol process [79] and ICI processes [80,81]. CO2 precipitates in the methanol synthesis via the reverse watergas shift reaction. Park, Lim, and their coworkers found that an optimal CO2 fraction can maximize the methanol yield and the CO2 fraction also depends on the reaction temperature [82]. This may indirectly show that CO2 contributes to the formation of methanol. Not all of the equilibria have been considered in this work. The active sites of Cu/ZnO/Al2O3 catalysts proposed by Behrens et al. consist of Cu steps decorated with Zn atoms, all stabilized by a

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series of well-dened bulk defects and surface species that need to be present jointly for the system to work [83]. Methanol can be produced directly from carbon dioxide sources by catalytic hydrogenation and photo-assisted electrochemical reduction. Relevant reactions for hydrogenation from CO2 are as Eqs. (4)(6): CO2 g 3H2 g $ CH3 OHl H2 Ol DH298 K 49:9 kJ=mol (4) CO2 g H2 g $ COg H2 Og COg 2H2 g $ CH3 OHl DH298 K 41 kJ=mol (5) (6)

Pyridinium and its substituted derivatives exhibit effective and stable homogeneous electrocatalytic performance for the aqueous multiple-electron/proton reduction of carbon dioxide to products such as formic acid, formaldehyde, and methanol [95]. A p-GaP semiconductor has reduced CO2 in pyridine to methanol with 44% quantum efciency and near 100% selectivity at 0.5 V vs. SCE and under 365 nm illumination [96]. Organic molecules can reduce CO2 to highly reduced species through multiple electron transfers without the need for a metal-based multi-electron transfer. This unique electrocatalyst shows that a single catalyst has the ability to reduce multiple species. But the separation of methanol and related health issues should be considered. 3.4. CO2 conversion to long chain hydrocarbons and oxygenates From the thermodynamic and kinetic point of view, CO2 conversion to long chain hydrocarbons and oxygenates is more challenge than to simple CO, CH4, HCOOH, and HCHO. These valuable liquid state fuels have higher energy density and are more convenient to store and transport. The worlds current transportation infrastructure and vehicles are designed for consuming these liquid fuels. In Section 3.1, various methods for CO2/H2O conversion to syngas CO and H2 have been introduced. Syngas can be converted to liquid fuel via FischerTropsch synthesis (Eq. (7)). xH2 g yCOg ! aCn H2n2 l=g bCn H2n l=g cCn H2n1 OHl dCn1 H2n1 CHOl eCn1 H2n1 COOHl zH2 Ol (7)

DH298 K 90:8 kJ=mol

While the overall reaction of CO2 hydrogenation is exothermic (DH = 49.9 kJ/mol), the rate determination step is activating CO2 in the reverse water-gas shift reaction (Eq. (5)). Transitional metal oxides (Fe3O4, Mn3O4, and Co3O4) and Raney copper are active RWGS catalysts at temperatures of about 300 8C. The kinetics and mechanisms of the WGS reaction have been extensively studied on Fe, Cu, Ni, and Au catalysts [8489]. Formate (HCOO), carbonate (CO32), and carboxylate (HOCO) intermediates play an important role in the synthesis of hydrocarbon fuel [84]. The active sites have been proposed by density functional theory (DFT) calculations [83,85,86]. More details about the WGS reaction can be found [90]. Copper oxide is a catalyst for the WGS reaction. Cu/Zr/Al2O3 catalysts work for both CO and CO2 hydrogenation in the methanol synthesis. Logically, doping metals, which function as catalysts in the RWGS reaction, would promote CO2 hydrogenation. DFT calculations and Kinetic Monte Carlo (KMC) simulations on metaldoped Cu(1 1 1) surfaces have shown that the overall methanol yield increased in the sequence: Au/Cu(1 1 1) < Cu(1 1 1) < Pd/ Cu(1 1 1) < Rh/Cu(1 1 1) < Pt/Cu(1 1 1) < Ni/Cu(1 1 1) [91]. A considerable research effort has been made on CO2 activation by visible light photocatalysts due to the natural abundance of sunlight (Table 2). Due to the high energy requirements, this method is often paired with electrochemical methods via photoelectrocatalysis to push the reaction. The catalysts traditionally used are transition metal complexes, TiO2, ZnO, CdS, and functionalized metal surfaces. While TiO2 does not have the ideal conducting band energy for dissociating CO2 (both the CB and CO2 dissociation energies occur at $0.24 V), its anatase phase presents a viable candidate for implementation due to its UV active band gap (3.2 eV), its non-toxicity, and stability. A wide variety of CO2 photoreduction has been performed on the surface of TiO2 under UV irradiation [92,93]. Mesoporous zeolite supported Ti-oxides mainly produced methane and methanol. Addition of Pt increases CH4 over methanol. The insight into the mechanistic aspects of CO2 photoreduction using TiO2/mesoporous materials is included in Indrakantis review [12]. Bi2S3/CdS hetero-junction photocatalysts exhibit a high yield of 613 mmol methanol/g catalysts under visible light irradiation [94]. Low potentials of conduction bands of Bi2S3 and CdS favor the formation of methanol.

where n is a positive integer, a, b, c, d, e, and z stand for the product fractions. x na b c d e a c y na b c d e z na b c d ea d 2e Alkane products (CnH(2n+2)) are unbranched hydrocarbons, suitable for diesel fuel and jet fuel. In addition, competing reactions also produce alkenes (CnH2n), as well as oxygenated hydrocarbons (alcohols (CnH(2n+1)OH), aldehydes Cn1H2n1CHO, and carboxylic acids Cn1H2n1COOH). Various types of FTS catalysts with different catalytic selectivity have been developed for the selective production of diesel fuel, light olens, and high alcohols. The FTS process has been used for the production of synthetic fuels for more than 50 years. A few companies (Sasol, PetroSA, and Shell) currently produce commercial synthetic fuels and ne chemicals by the FTS process. Considerable work has been reported in catalytic hydrogenation of CO2 to formic acid [97,98], methanol [99], and jet fuels [100] using homogeneous and heterogeneous catalysts. CO2 hydrogenation using FischerTropsch catalysts has shown the advantages over homogeneous catalysts in terms of solvent separation,

Table 2 Photoreduction and electrocatalytic reduction results of CO2 to methanol using different catalytic systems. Catalytic-system Bi2S3/CdS + CO2 + NaOH/Na2SO3/H2O p-GaP + 10 mM pyridine + CO2 Pyridinium-KCl-H2O + CO2 TiO2/FSM16 zeolite Pt-TiO2/Y-zeolite Working conditions Catalysts + visible light 0.5 V vs. SCE, 365 nm Hydrogenated Pd or Pt, 50 mA cm2 CO2 + H2O, 328 K CO2 + H2O, 328 K Products and selectivity 613 mmol CH3OH/g cat. 100% CH3OH HCOOH CH3OH CH4 CH3OH CH4, CH3OH Energy eff. NA Quant. 44% Farad. 62% Farad. 33% NA NA Refs. [94] [96] [95] [92] [93]

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B. Hu et al. / Journal of CO2 Utilization 1 (2013) 1827

Table 3 Product selectivity, olen/parafn ratio, and CO2 conversion over three different Fe FTS catalysts. Catalysts GHSV (h1) Temp. (K) Conv. (%) Selectivity (%) CO, CH4 15%Fe/10%K/g-Al2O3 6%Fe/4%K/28%Mn 2%Fe/4%Mn/12%K/4% Ce 3600 3360 270 673 593 563 51 45 50.4 37.4 31.3 37.7 C2C6 62.6 68.7 62.3 C /C
5 5

Refs

3.6 2.9 (11.2) 4.4

[117] [118] [102]

operation cost, and catalytic activity. But different from CO hydrogenation, CO2 is thermodynamically stable and is practically an inert gas. The reverse water-gas shift (RWGS) reaction (Eq. (5)) is the key step for CO2 hydrogenation. Fe [101104], Co [105,106], and Ru [107,108] catalysts supported on silica, gamma alumina, zeolite, titania, and carbon nanomaterials have been investigated. Addition of potassium (0.5 3%) can promote the growth of the long chain hydrocarbons [109,110], but higher potassium contents impede the catalytic activity, and can even kill cobalt catalysts [111]. Manganese oxide [112] and ceria [104] are added as promoters due to the improvement of RWGS activity [101]. Addition of Cu and Ru in iron catalysts increases the CO2 conversion [108], and Cu sites play the role of forming hydroxyl groups and produce higher alcohols due to the synergetic effect among copper, potassium, and iron catalytic sites [113]. Except catalysts design, a new concept of FTS reactor design has been proposed by Rahimpour to increase gasoline yield and reduce undesired products [114116]. Several efcient CO2 hydrogenation catalysts have been recently reported for higher hydrocarbon (>C2+) synthesis (Table 3). Without Mn promoters for the production of light olens, the reaction temperature (where t is the absolute temperature) in a xed bed reactor is higher as 673 K, and also the H2/CO2 (1:3) is low [117]. With addition of MnO2 nanober supports, the reaction temperature in a xed fed reactor decreased to 593 K, the selectivity to C2+ hydrocarbons increased about 6%. The interfaces of Fe/Mn supports signicantly affect the ratio of olens/parafns. Fe supported K-OMS-2 nanocatalysts have highest selectivity to light olens (C5/C = 11.2) [118]. For the ceria modied Fe/Mn/K catalysts in a stirred tank reactor, addition of ceria increase 22% of CO2 conversion and 5% of increase in olen formation due to an increase of RWGS activity compared to the catalysts without ceria, less Fe content in catalysts still leads to high activity for CO2 conversion due to excellent Fe dispersion [102]. The product distributions of Mn promoted catalysts show deviated AndersonSchultzFlory distributions due to secondary reactions and olen adsorption and insertion [119,120]. Long chain hydrocarbons (up to C9) have been synthesized by other CO2 conversion methods, such as electrocatalytic reduction using Pt nanoparticles on carbon-based electrodes [34]. But the electrocatalytic reduction experiments showed that the surface reaction-chain growth was very slow about 20 min for the conversion of ethane to propane due to low reaction temperature (298 K) [34]. The product distribution is different

from that expected from the AndersonSchultzFlory (ASF) distribution for FischerTropsch synthesis. This may be due to strong readsorption of intermediates in nanostructured (porous) carbon. Direct analyses in real time-time of ight-mass spectroscopy (DART-TOF-MS) analysis of post-reaction catalysts can examine the adsorbed species [118]. Syngas, light hydrocarbons, and liquid fuels have been synthesized by CO2/CH4 reforming using plasmas [52,121]. The conversions and selectivities are determined by the CH4/CO2 feed ratio, residence time, and input power. The hydrocarbon distribution also did not follow an ASF distribution. Carbon lms were formed without zeolite A [121]. Copper electrodes are effective for the formation of hydrocarbons in the CO2 electrochemical reduction in the aqueous solution (Table 4) [122124]. Ogura et al. reported that ethylene has been produced with a high selectivity (69%) and a total current efciency of 97% using copper (I) halide/copper electrodes [124,125]. Copper alloy did not produce ethylene although AuCu lowers the over potentials required [124,126]. AuCu catalysts need to work under the same conditions for comparison. A pathway of CO2 to C2H4 was through the formation of carboxylic acid COOH groups and adsorbed intermediates like CH2CO, which is supported by the formation of C1C3 carboxylic acids. Li and Kanan reported that Cu2O layers formed on annealed Cu foil at 500 8C is more active than polycrystalline Cu electrodes [127], but Cu2O electrodes are still less selective than copper (I) halide/copper electrodes. 30% of HCOOH in the products are also produced, indicating that the same pathway is followed. These experiments suggest that Cu+ ions are the active sites for the selective ethylene production. 3.5. CO2 as building blocks for oxygen-rich compounds and polymers CO2 can be utilized as a monomeric building block to synthesize various value-added oxygen-rich compounds and polymers at mild conditions. Since polycarbonate (Eq. (8)) was synthesized by S. Inoue and co-workers using CO2 and propylene oxide in the presence of ZnEt2 and H2O in 1969 [128], considerable efforts have been put into developing a copolymer synthesis based on CO2 [129131], More active and controllable catalysts [132,133] based on Zn, Co, and Cr complexes show very high activity with a turnover number up to 26,000, as well as excellent control for the copolymerization of CO2 and cyclohexene (or propylene) oxide (Eq. (9)).

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25

Table 4 Comparison of Cu-containing electrodes with other metal electrodes in CO2 reduction for ethylene production. Alloy 1: monel metal, Ni + Co: 65%, Cu: 33%, Fe: 2%; NA: not available in the reference. Electrocatalysts Working cond. Product selectivity C2H4 Pure Cu Cu/CuCl Ag/CuCl CuCl only Alloy 1 Ag Pt Cu2O/Cu 3 M KBr, 1.8 V vs. Ag/AgCl 51.9 69.4 64.0 42.9 0.3 1.3 49.9 5 CH4 11.4 4.0 3.8 9.9 5.2 4.9 8.0 NA CO 18.2 7.1 9.3 6.7 5.9 79.6 4.9 8 H2 21.7 9.4 13.0 34.8 93.3 7.4 28.1 >50 CO2 conversion Refs.

h
105 97.2 98 103 108 98.4 98 NA 7.7 9.3 10.2 5.8 1.3 11.6 9.5 NA [124] [124]

4 M KBr, 2 V 0.8 V, 0.5 M NaHCO3

[122] [127]

A high selectivity (100%) and efcient process for the synthesis of cyclic carbonates has been developed by Yang et al. using an electroreduction method in an ionic liquid at room temperature (Eq. (10)) [134,135]. A current efciency as high as 90% was achieved at a constant potential of 2.4 V. Ethylene carbonate is used as a polar solvent with a molecular dipole moment of 4.9 D. Propylene carbonate is a high permittivity component of electrolytes in lithium batteries.

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CN bond formation using CO2 as C1 feedstock for the production of various oxygenates, such as oxazolidinones, quinazolines, carbamates, isocyanates, and polyurethanes has been reviewed by Yang et al. [2]. These commodity chemicals have been synthesized from green methods and have important applications in pharmaceutical and plastic industries. Other important examples of CO2 utilization include carboxylation of aromatics to arylcarboxylic acids with carbon dioxide [140]. Aromatic carboxylic acids were obtained in excellent yield by carboxylation of aromatics with a carbon dioxideAl2Cl6/Al system at 2080 8C. The reaction mechanism was proposed to involve superelectrophilic aluminum chloride activated carbon dioxide reacting with aromatics via a typical electrophilic substitution. 4. Prospective in CO2 conversion Catalysts play a key role in the CO2 conversion to fuels and valued added products. In the past decades, numerous methods and catalysts have been developed to realize enhanced carbon recovery. Current catalytic technologies for CO2 conversion have

Another breakthrough in CO2 utilization was made by Zhang and Yu. Various propiolic acids were synthesized under mild conditions through copper- and copper-N-heterocyclic carbene (NHC)-catalyzed transformation of CO2 to carboxylic acid by CH bond activation and carboxylation of terminal alkyne (Eq. (11)) [136]

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The formation of oxazole 2-carboxylic acid in carboxylation of oxazole (Eq. (12)) has been recently reported by Boogaerts and Nolan using [(NHC)AuOH] complexes in THF at 45 8C [137]. The signicantly strong Au-OH base species permit the facile functionalization of CH bonds without the use of other organometallic reagents.

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Except for production of CC and CO bonds in the above activation of CO2, great success has made in direct formation of CN bonds based on CO2 activation through molecular catalysis (Eq. (13)).

achieved high energy efciency, high reaction rates, and high value products although these are not achieved simultaneously by a single method. An integration of several techniques and strategies may achieve practical production of high value chemical products from CO2. Nanostructured, porous, and functional materials have played and will continue to play an important role in these catalytic conversion processes. With a better understanding of the fundamental structurecompositionactivity relationships of these catalytic systems, the recipes, sizes, shapes, and morphologies of the catalysts can be tuned for better catalytic performance. Modern in situ characterization techniques and theories will promote the rational design of cost-effective catalysts and processes. This review demonstrated that it is technically possible to use CO2 as a carbon source for the synthesis of commodity productsfrom simple CO to liquid fuels and high molecular

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polymers. Unfortunately, these highly endothermic CO2 conversions consume lots of energy. Renewable solar, wind, wave, hydropower, geothermal energy, and waste heat in plants are the rst consideration. CO2 conversion has attracted more interest due to simultaneously reducing emissions and creating value to offset the cost of disposal of CO2. For sustainable large-scale utilization of CO2, the commodity products of CO2 conversion processes should be economically viable and are in high demand. For practical production, evaluations of energy balances and economic feasibilities of the processes are essential. The conversion processes must also take into account the life cycle of the process to ensure that additional CO2 is not produced beyond what is already being removed from or going into the atmosphere. CO2 conversion is one stage of the carbon dioxide cycle. The compatibility of these projects and products with current infrastructure should be considered rst and is vital for the success of research in this area. To develop successful CO2 conversion projects, many technical and commercial barriers need to be overcome. An interdisciplinary study should consider overall design of product ow diagrams, economic analyses, processes, and catalyst development and optimization. Universities and research institutions supported by government agencies and industries mainly contribute to technology development. Industries are commercializing these mature technologies. Government agencies are nancially supporting this research and development of CO2 conversion technologies, and will also regulate and stimulate CO2 conversion technology development. At last, CO2 utilization is a viable solution for repurposing and storing this greenhouse gas, and international cooperation will help mature and apply technologies to achieve the CO2 emission control target. The mechanisms of many of these reactions are not well known. Various reactions are believed to have different intermediates and mechanistic steps. One electron transfer reactions to CO2 (to form carbon dioxide anion radical) inhibits further conversion, while a different mechanism is necessary to produce CO via breaking of CO bonds. Identity of the exact steps in activation of CO2 needs to be done to improve selectivities and yields in these reactions by modifying catalysts based on such data. Other issues that are critical include stability, productivity, cost, environmental friendliness of processes and other factors. Acknowledgements We acknowledge the support of the U. S. Department of Energy, Ofce of Basic Energy Sciences, Division of Chemical, Biological, and Geological Sciences for this work under grant DE-FGO286ER13622.A000. References
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