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Journal of CO2 Utilization 1 (2013) 18–27

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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. ß 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 beneficial uses of CO2 [1–4]. In today’s 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 ß 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 acidification 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

Hu et al. which is then transferred to a photocatalyst complex. and energy efficiency. and polymer industries. DS is the entropy change. such as photoreduction. applied potentials serve to facilitate the electrochemical reduction of CO2. 1 gives the Gibbs free energy of CO2 and the products converted from CO2 (CRC Handbook of Chemistry and Physics) [19]. Several technical routes lead to the CO2 conversion to CO. Different types of catalysts are involved in these processes. dry. Kubiak and Kumar reported the photo-assisted electrochemical reduction of CO2 to CO on Re(bipy-But)(CO)3Cl((bipy-But) = 4. and hydroelectric are proposed as energy sources for CO2 conversion. structure-activity relationships. These polymerization reactions run at mild conditions with high turnover numbers. The products of carbon dioxide conversion can supplement or replace chemical feedstocks in the chemical. 3. 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. Solar radiation varies across the globe from altitude. CO production by reduction of CO2 Mimicking nature’s photosynthesis process. Each product may be produced by several methods. electrocatalysis. the synthetic fuels produced by CO2 utilization are compatible with current hydrocarbon-based automobiles and transportation systems. CO2 must be captured and either stored or converted into global warming neutral impact compounds.17. (2): 6CO2 ðgÞ þ 6H2 OðlÞ þ hn ! C6 H12 O6 ðsÞ þ 6O2 ðgÞ (2) There are several kinds of driving forces for the CO2 conversion. Lewis and Nocera have proposed to convert and store solar energy in chemicals (H2. Third. First. 3. The net result of these processes is the conversion of different types of energies into chemical energy. CO2 conversion to fuel and value-added products is an ideal route for CO2 utilization due to the simultaneous disposal of CO2 and the benefit that many products can be used as alternate transportation fuels. Secondly.11–13]. inorganic nanocatalysts promote conversion to valueadded olefins in the Fischer–Tropsch synthesis. wind. Most conversions of CO2 to these listed products are endothermic reactions like natural photosynthesis as shown in Eq. electrochemical reduction [14. / Journal of CO2 Utilization 1 (2013) 18–27 19 Change (IPCC) have suggested that 350 ppm CO2 is likely the safe upper limit for atmospheric greenhouse gases [8]. CO2 conversion to CO CO2 conversion to CO (carbon monoxide) looks like the simplest route for CO2 reduction. Utilization of CO2 provides an attractive avenue for this objective. These synthetic fuels will sustain new and expanding markets in transportation. 2. and hydrocarbons) via the photosynthetic process [21]. the food and beverage industry as a propellant. Various renewable energies such as solar. and (tri-) reforming. 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.18]. To realize this goal. Semiconductors absorb photons to make excited electrons transfer from a valence band to the conducting band. with the intent of giving direction to the reader in selecting a proper approach to meet specific needs. CO2 reacts with other monomeric species to form polymers. and evaluate the potential practical applications of the process. such as methane and hydrogen. plasma [16]. and T is temperature. solar radiation for flat-plates facing south at a fixed tilt in New York City is about 2–6 kWh/m2/day [22]. These exhibit rates faster than . In a practical operation. CO2 will react with other reactants with higher Gibbs free energy.B.10] have described CO2 utilization by photocatalytic synthesis [4. plasma. which reduces CO2 to CO and other useful organic compounds (Fig. and chemical production [9]. CO2 conversion to fuel and value-added products 3. highly efficient artificial enzymes lower the activation energy required for photoreduction of CO2. Such photoelectrocatalytic processes should be distinguished from purely photocatalytic routes. Thermodynamics and kinetics of CO2 conversion Fig. pharmaceutical. methanol. in nature. Last but not least. CO2 is a kinetically and thermodynamically stable molecule. two or more types of principles may function simultaneously and make the CO2 conversion more efficient. only less than 1% of global anthropogenic CO2 generated are utilized to these ends. and other methods [1.40 -ditert-butyl-2. urea and polymer synthesis as a monomer feedstock. However. thus CO2 conversion reactions are endothermic and need efficient catalysts to obtain high yield. We do not attempt to duplicate these references but summarize possible reaction mechanisms. The rest is released to the atmosphere due to lack of economical technologies to convert these C1 sources to commodity products. CO2 is extensively used for enhanced oil recovery. For example. while not catalytic.and bi-reforming. Many good reviews and books [3. unique catalyst and experimental design. electrolysis. The pros and cons of different conversion approaches are compared. To meet with global energy demands. (1): Fig.1.15].2-bipyridine)/p-type silicon with a Faradaic efficiency DG ¼ DH ¼ T DS (1) where DH is the enthalpy change. The difference in Gibbs free energy (DG) between the product and reactants at specific reaction is the driving force shown in Eq.1. 2). atmospheric conditions. and therein lack of demand. CO is a feedstock or intermediate for the production of methanol and hydrocarbon fuels via the Fischer– Tropsch synthesis [20]. These issues provide help in understanding the product selectivity and catalytic activity of each system. CO2 molecules have a highly stable linear and centrosymmetric (O5 5C5 5O) structure. and season. photoreduction of CO2 is one of the most alluring methods for CO2 conversion due to the abundance and free access of sunlight. though the cost of the catalysts is still a concern. and many of these are transition metal complexes.1. Fourth. height. Gibbs free energy of CO2 and its related products. A typical photoreduction electrode is composed of a semiconductor and photocatalysts. Furthermore. 1.

pH 7. Ag. The captured kinetic energy can be converted to electricity. Interestingly. The equilibrium potential (E vs. 75% with redoxinactive lithium metals [30]. Smieja et al. the selectivity for the above carbon species is low due to the competition of the hydrogen evolution reaction with CO2 reduction. The Gibbs energy differences of CO(g) splitting on many different metals change the catalytic selectivities. and 50 times faster than that with CH3OH. The system continuously produced CO for more than 7 h at Faradaic efficiencies greater than 96%. CO was continuously produced in the gas phase in significant amounts (about 103 higher with respect to hydrocarbons).57 V vs. The percentage of C10 limits the products in the trap.2.2 V). 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 fibers [33]. but low temperature often leads to low selectivity and low reaction rates.25–0. For the aqueous CO2 reduction reaction (Eq. high-area metal (Fe. electrochemical reduction. CO2 electrocatalysis for CO where CO2* is a radical anion as an intermediate. and plasma-assisted catalytic reduction. SCE.4 Â 102 mol/h CO: 65–80% H2: 10–30% Products and selectivity 10% 60% 70% 98% C10. formate < 1. Rosen et al.20 B. Ag. CO* C10. Cu. The activation energy barrier in the wide-scale application of photoreduction is the efficiency of the catalyst vs. H2O. EMIM-BF4)) reduces CO2 to carbon monoxide (CO) at very low overpotentials (<0.4 and 84. / Journal of CO2 Utilization 1 (2013) 18–27 Fig.0) is highly negative at À2.4 nm Pt-C/GDM Pt–Ir-C/GDM Work conditions Semi-half continuous. [26] reported that CO2 can be reduced at an applied voltage of 1.3) with no overpotential with CODH catalysts [28]. CO production by electrocatalysis Electricity is an easily accessible convenient energy. À2 V vs. Electrocatalysis cells based on solid electrolytes (alumina. and significant amounts of gas phase CO products are not counted. Centi and Perathoner developed a reverse proton exchange membrane (PEM) fuel cell for electrocatalytic reduction of CO2 [34]. Au. and can be readily produced by a variety of renewable (wind. Very recently. and an overall efficiency of about 10% for the conversion of polychromatic light [23].14 V. This electrocatalytic system (Pt/Nafion/(Ag. [34] 80 mA/cm2. respectively [31]. 2. but require higher operating temperatures (around 800–1000 8C) to achieve a high oxygen ion conductivity of the electrolyte. solar) energy sources.4%) and Pd deposited pInP photoelectrode has the highest selectivity to CO (100%) [25]. Pd. If the cost of photocatalysts and photoelectrocatalysts can be lowered and the efficiencies and lifetimes are improved. and Cu deposited p-InP photoelectrodes show higher selectivity to CO than that to H2. a naturally occurring enzyme [27. 20 8C. CO* CO/H2 (1:2). CO* C10. Electrode stability based on heat expansion is also a concern as electrodes may crack or delaminate from the electrolyte structure. Pd) electrocatalysts supported on microporous activated carbon fibers (ACF) have exhibited similar effects to high CO2 pressure. 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). and phthalocyanines have been extensively studied for electrochemical reduction of CO2 [29–32]. In aqueous solution. Kaneco has developed metal-modified p-InP photoelectrodes for the photoelectrochemical reduction of CO2 in the LiOH/ methanol-based electrolyte. Different Pt electrocatalysts are compared in Table 1. electrolysis. 20 mA. SCE [35] . Electrocatalysts 2 nm Pt/GDM(E-TEK) 3 nm Pt/GDM 5. The interaction experiments of the electrocatalyst with the targeted catalytic substrate CO2. Highly acidic electrolytes exhibit similar behavior for CO2 reduction. Low operation temperature is one of the advantages of using liquid electrolytes.1 M phosphate buffer (pH 6. CO is produced via one electron reduction reaction of CO2 and  CO2 is an intermediate. and CH3OH show that the reaction with CO2 is about 25 times faster than that with H2O. the photo-assisted electrochemical reduction of CO2 could have possible practical applications. Shin achieved a current efficiency of 100% at À0. Ag deposited p-InP photoelectrode show maximum current efficiency of carbon monoxide (rf = 80. and then stored in the form of chemical fuels by electrocatalysis.5 M KHCO3 solution. Nanostructured Table 1 Comparison of Pt electrocatalysts in CO2 reduction in 0.5 Â 102 mol/h 7. yttrium-stabilized zirconia) show high conversion rates and selectivity to CO. and Ni deposited photoelectrodes are lower (about 0. onset potentials on Pb. Hu et al. (3)): CO2ðadÞ þ eÀ ! CO2 Ã ðaqÞ (3) of 97 Æ 3%. Another approach to lower overpotentials is electrocatalytic reduction of CO2 by carbon monoxide dehydrogenase (CODH).5 V.1. production has been conducted in either liquid electrolytes or solid oxide electrolytes. porphyrins. the cost of the materials used for synthesis. Ionic liquid electrolytes such as 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) lower the potential for formation of the CO2À intermediate. 3. These catalysts have been reviewed by Costamagna et al.5% Refs.95 V less). [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 efficiencies up to ca. and a short-circuit quantum efficiency of 61% for light-tochemical energy conversion. Illustration of semiconductor catalysts for photoreduction of CO2. while the current efficiencies for Co and Fe redox metals increase up to 97.28]. Compared to electrochemical reduction at the same metallic electrodes. 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]. hydro. NHE in a 0. most likely by complexation via a weak bonding between CO2 and BF4 anions. Au. Ni.6%. 25 8C. 1 h Rate or I efficiency 2 Â 102 mol/h 4. Coordination complexes of tetraaza-macrocycles. further reported that the electron transfer from the electrode to the catalyst can be controlled by modifying the p-Si surface with phenylethyl groups.

4. and no quantitative CO products have been reported [40.50]. which can be a valuable co-reactant with carbon dioxide.54]. For transportation.2 kg/GJ Fuel input) for the ITRPP-SC (Fig. which from an energetic and life cycle analysis perspective appears to be a questionable approach to limit CO2 emissions. reported a theoretical energy cost analysis method to evaluate the effectiveness of plasma systems [46]. this conventional chemical process by ammines needs high thermal power in order to regenerate the solvent. though can be used in industrial power applications. Mogensen and Ebbesen have studied reduction of H2O and CO2 in a Ni/YSZ electrode supported SOEC.41]. Synthesis gas production by reforming While carbon dioxide is the primary focus of this paper. The nanometer scale of the catalysts significantly increased the catalytic activity. Hydrocarbons were produced for the first time using electrocatalytic reduction of CO2.24] to synthesize alternate transportation fuels via the Fischer–Tropsch synthesis. and Fe) electrodes for plasma activation in CH4/ CO2 were tested in Liu’s group [49.4 kg/GJ Fuel input) and 84% (8. Other SOECs using Pt paste electrodes were much less active compared to nano-size Pt catalysts. The power plant efficiency 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.1. The energy and environmental analysis of integrated trireforming power plants (ITRPP) has been reported by Minutillo and Perna [58. Cu. coal gas.5% and selectivities >80%. A degradation study using impedance spectroscopy shows that five electrode processes contribute to the cell resistance [39]. Fig. There is considerable debate on the meaning of CO2 reforming with methane. 3. Source: adapted from Ref. The reduction in CO2 emissions has been estimated at 83% (15. Pd. Power plant CO2 emission mixture has residue oxygen. Newman and Delacourt designed a PEM electrolysiscell for simultaneous electrochemical reduction of CO2 and H2O to make syngas CO + H2. CH4/CO2 reforming to form syngas (CO/H2) is an important process [23. The energy efficiency ($3–6%) of plasma methods need to be improved [48].9 vs. oxygenates. as part of the refining process the fractions of CO2 isolated often come with a high fraction of methane. DBD plasmas have been used in CH4/CO2 reforming for producing alkanes. and landfill gas. The decomposition of CO2 in fan-type ac glow discharge plasma reactors and dielectric-barrier discharge (DBD)-plasma reactors was investigated. / Journal of CO2 Utilization 1 (2013) 18–27 21 carbon supported Pt nanoparticles (3 nm) catalysts have the highest activity among three different catalysts and supports. 3. As an added benefit. 3) and ITRPP-CC respectively. Ti. the reformation of methane to fuel precursors prevents methane from escaping into the environment and preserves carbon into the hydrocarbon production cycle.1.4 vs. which uses syngas as its feedstock. Hu et al. Early work was performed in 1990s under the international cooperation of The University of Connecticut. With new capture technology development. A few good reviews are recommended [55–57]. CO production by plasma Plasmas are fast and clean methods to convert CO2 to CO and O2.59]. 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. A current density of 30 mA/cm2 has been achieved using silver-based cathode catalysts in these electrolysis cells [35]. Cu. CO was the main carbonaceous product with moderate conversions at 30. Flow chart of the integrated tri-reforming power plant-steam cycle (ITRPP-SC). Considerable work has been conducted in CH4/CO2 reforming [53. and Fujitsu Laboratories Limited. 56. nature gas. which is a poison for most CO2 reduction catalysts by promoting the watergas shift reaction. Other metal (Al.39]. CO was produced via the reverse water gas shift reaction with higher current densities (0. and Rh) coated electrode surface. Nagasaki University. for reasons still under investigation [51]. and the hydrocarbon production will be included in Section 3. . Methane is abundant in shale gas. Furthermore. The three-step reaction process avoids the separation step and has the promise of being cost-efficient for producing industrially useful synthesis gas. Higher current density (135 mA/cm2) was achieved on supported Au catalysts [36]. Methane itself has a global warming potential (GWP) of 30 (GWP of CO2 = 1). and titanium showed the highest activity. and syngas (CO + H2) at ambient conditions [52]. 93. the lower energy requirements for regeneration will lower the cost. CO2 decomposition was promoted by a synergetic effect between plasma excitation in the gas phase and catalytic actions of the metal (Au. alkenes. methane is not practical as a fuel due to its stability and requirements for transport.25–1 A/cm2) [38. Numerous works have been performed in the plasma-assisted CO2 reduction to CO [42–47]. and Spencer et al. 3. Solid oxide electrolysis cells (SOECs) have been developed for the CO2 reduction [37]. [58]. Pt.4.3.B.

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.38. This type of oxidative reaction has been extended into the oxidative coupling and oligomerization of CH4 [60. / Journal of CO2 Utilization 1 (2013) 18–27 CO2 reforming with CH4 is an example of CO2 being used as a soft oxidant. 4) using the N-Ta2O5 photosensitizer but the quantum efficiency of 1. and they are intermediates in the formation of methanol and higher hydrocarbons. Visible light driven photocatalysts give an alluring prospect in the production of fuels using solar energy. Park.75–77]. and alumina has achieved high selectivity to methanol (99. Shale gas contains mainly methane ($60%) and light alkanes (C2–C6). The active sites of Cu/ZnO/Al2O3 catalysts proposed by Behrens et al. Compared to electrocatalytic reduction in liquid electrolyte. propene [69]. consist of Cu steps decorated with Zn atoms. [72] recently reported an efficient artificial photosynthetic production of formic acid from CO2 using a graphene coupled multianthraquinone-substituted porphyrin photocatalyst. butene [70]. CO2 conversion to CH3OH Methanol as a key commodity has become an important part of our global economy. Yadav et al. as such a major research effort into graphene’s electrochemical and electrical properties is in effect as of this writing. and CH3OH are largely dependent on the reduction methods and catalysts used. 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). etc. Hu et al. From building blocks for plastics. application and mechanistic pathways of these systems have been reviewed by Park and Ansari [1]. methanol. Another photoreduction system reported by Sato et al.9% at 405 nm is low [73]. The highest turnover numbers (89) have been achieved (Fig. The emergence. non-toxic. and acetaldehyde) isolated as the Fig. 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. nanosize Pt electrocatalysts reduced CO2 to formic acid at high Faradaic (89%) and energetic efficiencies (45%) [73]. paints. is composed of a p-type semiconductor photosensitizer (N-Ta2O5) and a Ru complex reducing catalyst in an acetonitrile/triethanolamine solution. Therefore.) [62–66] and alkyl aromatics [67. economic and mild oxidizing properties of CO2. the mixture of copper. all stabilized by a . Due to the abundant availability. the facile production of ethylene [63]. these green methods are economical and energy efficient and they have potential industrial applications for the development of various useful chemicals. There is great potential for further accelerating the photoreduction reaction of CO2. 50 million tons of methanol have been consumed in 2011. About 46% of the total solar light source available on earth is in the visible light range. Graphene exhibits high electron mobility and acts as an electron reservoir. These photocatalysts are apparently not stable.5 cm3/min of CO2. including HCOOH and HCHO. acetone. and oxygen abstracts hydrogen from methane to form water via the water-gas shift reaction. Lim. zinc oxide. With the rapid increase of shale gas production in the US and other countries. large-scale utilization of electrocatalytic process is technically possible.3. For industrial production of methanol from synthesis gas (CO. primary products. quantitative formic acid products were measured with a gas chromatograph but no quantum efficiency was reported. Not all of the equilibria have been considered in this work. Several different electrocatalytic reduction methods/catalysts have been developed for continuous electrocatalytic reduction of CO2 to oxygenate products. and organic solvents to clean fuels applied in fuel cells and combustion engines. Recent efforts and opportunities in the heterogeneous electrochemical conversion of carbon dioxide have been described by Whipple and Kenis [15]. Generally.22 B. with oxygenates (isopropanol. Pt and less expensive Co and Fe nanocatalysts were respectively loaded on carbon nanotubes for electrocatalytic reduction of CO2. CO2 precipitates in the methanol synthesis via the reverse watergas shift reaction. also. In aqueous KHCO3 electrolyte. Source: adapted from Ref. 3. attributed to the water-gas shift reaction [38]. 4. where the dioxide is dissociated into CO and surface oxygen. The electrocatalysis reactions of CO2 and H2O on Pt and ZnO nanocatalysts form HCHO in the gas headspace. This system has achieved a selectivity of more than 75% for HCOOH using visible-light. A high CO2 conversion ($8%) was reported in the continuous gas-phase reduction. [74] In a microfluidic reactor. Compared to the production of HCOOH and HCHO by photoreduction of CO2. ethanol.2. probably in the liquid phase. electrocatalytic reduction of CO2 has a much higher energy efficiency (33–45%).8%) at 250–300 8C and 5–10 MPa in the Lurgi MegaMethanol process [79] and ICI processes [80. Turnover number for HCOOH formation from visible-light-induced selective CO2 reduction using Ru complex electrocatalysts. Under 0. and HCHO further forms paraformaldehyde polymers in condensed water [78].81]. The selectivities of HCOOH. and H2). [73]. Solid oxide electrolyzers have attracted strong interest in recent years due to high efficiency in the conversion of electrical energy into chemical energy [37. they are resulting products of CO2À reduction with protons in an electrochemical reaction. Another process relevant here is the reduction of CO2 to HCOOH using biomass methods [139].68]. C3H8.61] and dehydrogenation of alkanes (C2H6. the operation unit can be more compact and continuously achieve high time/space yield of the reactor. CO2. although currently most catalysts exhibit efficiencies too low for practical applications. HCHO. the electrocatalytic system is less complicated. 3. product separation in the gas phase reduction is not required. A significant 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. 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. Co-electrolysis of CO2 and H2O using Ni/YSZ electrodes reported the formation of CO and H2.

as well as oxygenated hydrocarbons (alcohols (CnH(2n+1)OH). Various types of FTS catalysts with different catalytic selectivity have been developed for the selective production of diesel fuel.B. Mesoporous zeolite supported Ti-oxides mainly produced methane and methanol. The active sites have been proposed by density functional theory (DFT) calculations [83. b. 50 mA cmÀ2 CO2 + H2O. Cu/Zr/Al2O3 catalysts work for both CO and CO2 hydrogenation in the methanol synthesis. NA Quant. Bi2S3/CdS hetero-junction photocatalysts exhibit a high yield of 613 mmol methanol/g catalysts under visible light irradiation [94]. its anatase phase presents a viable candidate for implementation due to its UV active band gap (3. (4)–(6): CO2 ðgÞ þ 3H2 ðgÞ $ CH3 OHðlÞ þ H2 OðlÞ ðDH298 K ¼ À49:9 kJ=molÞ (4) CO2 ðgÞ þ H2 ðgÞ $ COðgÞ þ H2 OðgÞ COðgÞ þ 2H2 ðgÞ $ CH3 OHðlÞ ðDH298 K ¼ 41 kJ=molÞ (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. and HCHO. methanol [99]. and Shell) currently produce commercial synthetic fuels and fine chemicals by the FTS process. The world’s current transportation infrastructure and vehicles are designed for consuming these liquid fuels. this method is often paired with electrochemical methods via photoelectrocatalysis to push the reaction. (5)). and carboxylate (HOCOÀ) intermediates play an important role in the synthesis of hydrocarbon fuel [84]. (7)). But the separation of methanol and related health issues should be considered. Considerable work has been reported in catalytic hydrogenation of CO2 to formic acid [97. and Co3O4) and Raney copper are active RWGS catalysts at temperatures of about 300 8C. A considerable research effort has been made on CO2 activation by visible light photocatalysts due to the natural abundance of sunlight (Table 2). Addition of Pt increases CH4 over methanol. a.86]. The FTS process has been used for the production of synthetic fuels for more than 50 years. CO2 hydrogenation using Fischer–Tropsch catalysts has shown the advantages over homogeneous catalysts in terms of solvent separation. 44% Farad. TiO2. e. These valuable liquid state fuels have higher energy density and are more convenient to store and transport. A few companies (Sasol. doping metals. Syngas can be converted to liquid fuel via Fischer–Tropsch synthesis (Eq. CO2 conversion to long chain hydrocarbons and oxygenates From the thermodynamic and kinetic point of view. d. various methods for CO2/H2O conversion to syngas – CO and H2 have been introduced. its non-toxicity.2 eV). Methanol can be produced directly from carbon dioxide sources by catalytic hydrogenation and photo-assisted electrochemical reduction. and carboxylic acids CnÀ1H2nÀ1COOH). HCOOH.93]. where n is a positive integer. 365 nm Hydrogenated Pd or Pt. and methanol [95].98]. CH4. suitable for diesel fuel and jet fuel. Hu et al. 62% Farad. and high alcohols. In addition. SCE and under 365 nm illumination [96]. In Section 3. Low potentials of conduction bands of Bi2S3 and CdS favor the formation of methanol.4. and Au catalysts [84–89].5 V vs. Logically. 328 K Products and selectivity 613 mmol CH3OH/g cat. Cu. aldehydes CnÀ1H2nÀ1CHO. SCE. The kinetics and mechanisms of the WGS reaction have been extensively studied on Fe. While TiO2 does not have the ideal conducting band energy for dissociating CO2 (both the CB and CO2 dissociation energies occur at $0. xH2 ðgÞ þ yCOðgÞ ! aCn Hð2nþ2Þ ðl=gÞ þ bCn H2n ðl=gÞþ cCn Hð2nþ1Þ OHðlÞ þ dCnÀ1 H2nÀ1 CHOðlÞ þ eCnÀ1 H2nÀ1 COOHðlÞ þ zH2 OðlÞ (7) ðDH298 K ¼ À90:8 kJ=molÞ While the overall reaction of CO2 hydrogenation is exothermic (DH = À49. Table 2 Photoreduction and electrocatalytic reduction results of CO2 to methanol using different catalytic systems. 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].24 V).5 V vs. and jet fuels [100] using homogeneous and heterogeneous catalysts. competing reactions also produce alkenes (CnH2n). A p-GaP semiconductor has reduced CO2 in pyridine to methanol with 44% quantum efficiency and near 100% selectivity at À0. Due to the high energy requirements. CH3OH Energy eff. The insight into the mechanistic aspects of CO2 photoreduction using TiO2/mesoporous materials is included in Indrakanti’s review [12]. formaldehyde. 100% CH3OH HCOOH CH3OH CH4 CH3OH CH4. More details about the WGS reaction can be found [90]. c. the rate determination step is activating CO2 in the reverse water-gas shift reaction (Eq. and functionalized metal surfaces. The catalysts traditionally used are transition metal complexes. / Journal of CO2 Utilization 1 (2013) 18–27 23 series of well-defined bulk defects and surface species that need to be present jointly for the system to work [83]. ZnO. which function as catalysts in the RWGS reaction. A wide variety of CO2 photoreduction has been performed on the surface of TiO2 under UV irradiation [92.85. 328 K CO2 + H2O. Formate (HCOOÀ). carbonate (CO32À). Transitional metal oxides (Fe3O4. CO2 conversion to long chain hydrocarbons and oxygenates is more challenge than to simple CO. [94] [96] [95] [92] [93] . x ¼ nða þ b þ c þ d þ eÞ þ a þ c y ¼ nða þ b þ c þ d þ eÞ z ¼ nða þ b þ c þ d þ eÞa À d À 2e Alkane products (CnH(2n+2)) are unbranched hydrocarbons. Relevant reactions for hydrogenation from CO2 are as Eqs. and z stand for the product fractions. 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. light olefins.1. CdS. PetroSA. 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 À0. and stability. Mn3O4. Copper oxide is a catalyst for the WGS reaction.9 kJ/mol). 33% NA NA Refs. 3. Ni. would promote CO2 hydrogenation.

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. The reverse water-gas shift (RWGS) reaction (Eq. The product distributions of Mn promoted catalysts show deviated Anderson–Schultz–Flory distributions due to secondary reactions and olefin adsorption and insertion [119.133] based on Zn. The interfaces of Fe/Mn supports significantly affect the ratio of olefins/paraffins.000. indicating that the same pathway is followed. More active and controllable catalysts [132. Since polycarbonate (Eq.5. Catalysts GHSV (hÀ1) Temp.6 2. residence time. and Cr complexes show very high activity with a turnover number up to 26. / Journal of CO2 Utilization 1 (2013) 18–27 Table 3 Product selectivity. Carbon films were formed without zeolite A [121]. addition of ceria increase 22% of CO2 conversion and 5% of increase in olefin formation due to an increase of RWGS activity compared to the catalysts without ceria. With addition of MnO2 nanofiber supports.2) 4.110]. reported that ethylene has been produced with a high selectivity (69%) and a total current efficiency of 97% using copper (I) halide/copper electrodes [124. 30% of HCOOH in the products are also produced. such as electrocatalytic reduction using Pt nanoparticles on carbon-based electrodes [34]. and Ru [107. titania. Without Mn promoters for the production of light olefins.126]. But different from CO hydrogenation.5– 3%) can promote the growth of the long chain hydrocarbons [109. Co. and carbon nanomaterials have been investigated. and Cu sites play the role of forming hydroxyl groups and produce higher alcohols due to the synergetic effect among copper. A pathway of CO2 to C2H4 was through the formation of carboxylic acid –COOH groups and adsorbed intermediates like –CH2CO. olefin/paraffin ratio. 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.108] catalysts supported on silica. 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]. and iron catalytic sites [113]. Hu et al. Manganese oxide [112] and ceria [104] are added as promoters due to the improvement of RWGS activity [101].24 B.4 37. Inoue and co-workers using CO2 and propylene oxide in the presence of ZnEt2 and H2O in 1969 [128]. Fe [101–104]. less Fe content in catalysts still leads to high activity for CO2 conversion due to excellent Fe dispersion [102]. but higher potassium contents impede the catalytic activity. Copper alloy did not produce ethylene although AuCu lowers the over potentials required [124. and liquid fuels have been synthesized by CO2/CH4 reforming using plasmas [52. Ogura et al. The conversions and selectivities are determined by the CH4/CO2 feed ratio.3 C /C 5 5 – Refs 3.120]. Addition of potassium (0. Syngas. and also the H2/CO2 (1:3) is low [117]. the reaction temperature in a fixed fed reactor decreased to 593 K.6 68. and catalytic activity.9 (11. potassium. as well as excellent control for the copolymerization of CO2 and cyclohexene (or propylene) oxide (Eq.125]. but Cu2O electrodes are still less selective than copper (I) halide/copper electrodes.2) [118]. and can even kill cobalt catalysts [111]. (8) (9) . (9)). Addition of Cu and Ru in iron catalysts increases the CO2 conversion [108]. CO2 is thermodynamically stable and is practically an inert gas. (K) Conv. which is supported by the formation of C1–C3 carboxylic acids. and CO2 conversion over three different Fe FTS catalysts.3 37. light hydrocarbons. Li and Kanan reported that Cu2O layers formed on annealed Cu foil at 500 8C is more active than polycrystalline Cu electrodes [127]. Fe supported K-OMS-2 nanocatalysts have highest selectivity to light olefins (C5/C– = 11.7 C2–C6 62. and input power.4 [117] [118] [102] operation cost. For the ceria modified Fe/Mn/K catalysts in a stirred tank reactor. These experiments suggest that Cu+ ions are the active sites for the selective ethylene production. This may be due to strong readsorption of intermediates in nanostructured (porous) carbon. The product distribution is different from that expected from the Anderson–Schultz–Flory (ASF) distribution for Fischer–Tropsch synthesis. Several efficient CO2 hydrogenation catalysts have been recently reported for higher hydrocarbon (>C2+) synthesis (Table 3).7 62. (5)) is the key step for CO2 hydrogenation. 3. gamma alumina. considerable efforts have been put into developing a copolymer synthesis based on CO2 [129–131]. The hydrocarbon distribution also did not follow an ASF distribution. Co [105. Copper electrodes are effective for the formation of hydrocarbons in the CO2 electrochemical reduction in the aqueous solution (Table 4) [122–124]. a new concept of FTS reactor design has been proposed by Rahimpour to increase gasoline yield and reduce undesired products [114–116].4 31. AuCu catalysts need to work under the same conditions for comparison.106]. (%) Selectivity (%) CO. Except catalysts design. Direct analyses in real time-time of flight-mass spectroscopy (DART-TOF-MS) analysis of post-reaction catalysts can examine the adsorbed species [118]. (8)) was synthesized by S. the reaction temperature (where t is the absolute temperature) in a fixed bed reactor is higher as 673 K.121]. the selectivity to C2+ hydrocarbons increased about 6%. zeolite. Long chain hydrocarbons (up to C9) have been synthesized by other CO2 conversion methods.

8 93. 4. With a better understanding of the fundamental structure–composition–activity relationships of these catalytic systems.0 34. Aromatic carboxylic acids were obtained in excellent yield by carboxylation of aromatics with a carbon dioxide–Al2Cl6/Al system at 20–80 8C.5 M NaHCO3 [122] [127] A high selectivity (100%) and efficient process for the synthesis of cyclic carbonates has been developed by Yang et al.1 9. (13)). Various propiolic acids were synthesized under mild conditions through copper. and polyurethanes has been reviewed by Yang et al.3 11. (10)) [134. The significantly strong Au-OH base species permit the facile functionalization of C–H bonds without the use of other organometallic reagents.6 9. / Journal of CO2 Utilization 1 (2013) 18–27 25 Table 4 Comparison of Cu-containing electrodes with other metal electrodes in CO2 reduction for ethylene production. Current catalytic technologies for CO2 conversion have Another breakthrough in CO2 utilization was made by Zhang and Yu.9 8 H2 21.9 D. Propylene carbonate is a high permittivity component of electrolytes in lithium batteries.9 5. À1. An integration of several techniques and strategies may achieve practical production of high value chemical products from CO2. sizes. Modern in situ characterization techniques and theories will promote the rational design of cost-effective catalysts and processes. 0. carbamates. the recipes.9 0.0 42. These commodity chemicals have been synthesized from green methods and have important applications in pharmaceutical and plastic industries.3 1.5 NA [124] [124] 4 M KBr.3 10.135]. NA: not available in the reference. (10) C–N bond formation using CO2 as C1 feedstock for the production of various oxygenates.3 7.2 7.8 V vs.4 13.9 5 CH4 11. This review demonstrated that it is technically possible to use CO2 as a carbon source for the synthesis of commodity products–from simple CO to liquid fuels and high molecular (13) .0 3. Ni + Co: 65%.8 1. achieved high energy efficiency.7 9. using an electroreduction method in an ionic liquid at room temperature (Eq.B.4 64. Other important examples of CO2 utilization include carboxylation of aromatics to arylcarboxylic acids with carbon dioxide [140].4 98 NA 7. isocyanates. Alloy 1: monel metal. A current efficiency as high as 90% was achieved at a constant potential of À2.0 NA CO 18. Prospective in CO2 conversion Catalysts play a key role in the CO2 conversion to fuels and valued added products. high reaction rates. Fe: 2%.8 9. and morphologies of the catalysts can be tuned for better catalytic performance.8 V. Product selectivity C2H4 Pure Cu Cu/CuCl Ag/CuCl CuCl only Alloy 1 Ag Pt Cu2O/Cu 3 M KBr.4 28.6 4. (12)) has been recently reported by Boogaerts and Nolan using [(NHC)AuOH] complexes in THF at 45 8C [137]. Hu et al.9 8.3 49. shapes. Nanostructured. In the past decades. porous. such as oxazolidinones.2 4.9 79. and high value products although these are not achieved simultaneously by a single method. great success has made in direct formation of C–N bonds based on CO2 activation through molecular catalysis (Eq.1 >50 CO2 conversion Refs. The reaction mechanism was proposed to involve superelectrophilic aluminum chloride activated carbon dioxide reacting with aromatics via a typical electrophilic substitution.9 69. and functional materials have played and will continue to play an important role in these catalytic conversion processes. Ethylene carbonate is used as a polar solvent with a molecular dipole moment of 4. quinazolines. Ag/AgCl 51.3 6. Electrocatalysts Working cond. h 105 97. (11)) [136] (11) The formation of oxazole 2-carboxylic acid in carboxylation of oxazole (Eq.2 5.7 9. (12) Except for production of C–C and C–O bonds in the above activation of CO2. Cu: 33%.4 4. numerous methods and catalysts have been developed to realize enhanced carbon recovery.7 5.2 98 103 108 98.and copper-N-heterocyclic carbene (NHC)-catalyzed transformation of CO2 to carboxylic acid by C–H bond activation and carboxylation of terminal alkyne (Eq.4 V. [2]. À2 V À0.

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