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Journal of CO2 Utilization

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Short communication

STEP carbon capture The barium advantage

Stuart Licht *, Baochen Cui, Baohui Wang
Department of Chemistry, The George Washington University, Washington, DC 20052, USA

A R T I C L E I N F O

A B S T R A C T

Article history: Received 19 December 2012 Received in revised form 29 January 2013 Accepted 22 March 2013 Keywords: Carbon capture Climate change Solar energy Electrolysis Barium carbonate

We have recently introduced the theory of the Solar Thermal Electrochemical Process for carbon capture and utilization (STEP carbon). We have also provided experimental validation of that theory using electrolysis of molten lithium and eutectic alkali carbonates at high ($50%) solar efciency and high rate, and delineated the materials required to use STEP carbon to decrease atmospheric CO2 to preindustrial levels in ten years. In this communication an effective, alternative STEP carbon electrolyte is introduced. It is demonstrated thermodynamically that barium carbonate can provide more than an order of magnitude greater afnity for direct carbon dioxide absorption from the air than our prior lithium carbonate electrolyte. It is demonstrated experimentally that molten barium carbonate mixtures provide an effective medium for the direct electrolytic reduction of absorbed carbon dioxide at high rate and lower energy. The products of the electrolysis are graphite, which is readily stored as a valued added commodity for future generations, and oxygen. The electrolyte is not consumed in this carbon dioxide splitting process. 2013 Elsevier Ltd. All rights reserved.

1. Introduction The Solar Thermal Electrochemical Process (STEP) provides a comprehensive solution to decrease the atmospheric carbon dioxide level. Theory of the process was introduced in 2009 as an extension of our earlier theory and experiment of efcient solar water splitting [1]. Experimental verication of this process has been presented from 2010 through the present [2,3] for an increasing portfolio of societal staples (STEP cement [3], STEP iron [4], STEP fuels [2,5], STEP magnesium and bleach [6], and other processes [7]). As examples, STEP iron or cement produces the metal from hematite or limestone, but without the CO2 emissions associated with the millennia old iron carbothermal or lime kiln processes, and STEP fuels uses solar energy efciently to produce H2 or CO at high rate to be used directly, or to generate hydrocarbon fuels. In the STEP process, solar energy in the form of heat diminishes the energy required by endothermic electrochemical splitting. Energetically forbidden reactions become allowed with the application of concentrated solar thermal energy. Solar energy efciencies in excess of 50% have been reported [2]; high concentrations of reactants in new molten salt chemistries yield facile kinetics and novel products [3,4] at high 0.1 to amp to amps cm2 rates at inexpensive (e.g. steel or nickel) electrodes. The STEP process is described in the supplementary section.

* Corresponding author at: Department of Chemistry, The George Washington University, 2121 Eye St., NW Washington, DC 20052, USA. Tel.: +1 703 726 8225. E-mail address: slicht@gwu.edu (S. Licht). 2212-9820/$ see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jcou.2013.03.006

One of the advantages of the STEP carbon chemistry process is that CO2 concentration, capture, separation and utilization in a single step. Prior initiatives to decrease atmospheric carbon dioxide are multiple-component coupled processes. Generally, these initiatives start with one of several energy consuming processes to increase the CO2 concentration [8], and then either sequester the concentrated CO2 (such as through pumping into a reservoir [9], or chemical [10] or biological [11] immobilization) or utilize the concentrated CO2 (such as by gas phase [12], aqueous [13] or photocatalytic [14,15] reduction to fuels). Instead, in STEP carbon atmospheric carbon dioxide is directly captured and converted to carbon in a single process. Carbon dioxide, bubbled into molten carbonate solutions, is absorbed (through reactive equilibration with oxide to become more carbonate). Simultaneously, carbonate it is directly split by electrolysis releasing oxide, oxygen gas at the anode and carbon (graphite) at the cathode. The oxide released by electrolysis then absorbs more carbon dioxide and the process is ongoing (CO2 in, and carbon and oxygen out). Hence, STEP is a single, combined CO2 absorption, capture, storage and utilization process. Graphite provides among the most dense, stable media for storage of captured carbon dioxide, as well as a valuable economic resource. Solar thermal energy, absorbed by heating the molten carbonate, decreases the energy required to drive the electrolysis and increases the solar energy efciency of STEP carbon. Molten carbonates provide a million-fold concentration increase of reducible tetravalent carbon sites per cubic centimeter, compared to air, facilitating carbon utilization. This substantial, direct increase in reactive carbon, decreases both the thermodynamic and kinetic energies required to drive the splitting

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process. Molten carbonate contains $10 mol reducible tetravalent carbon/liter. Air contains 0.04% CO2, equivalent to 1 105 mol of tetravalent carbon/liter. Carbonates higher concentration of active, reducible tetravalent carbon sites, logarithmically decreases the electrolysis potential, and can facilitate charge transfer at low electrolysis potentials. We have previously investigated molten alkali carbonates as the STEP carbon electrolysis medium for direct CO2 capture and utilization. In particular, lithium carbonate [8], and alkali carbonate eutectics are effective [8,9]. Li2CO3 is more conductive than Na2CO3 or K2CO3 [16]. Li2O is highly soluble in this media, to support facile carbon dioxide dissolution [4c]. Finally, Li2O is less corrosive than Na2O or K2O in molten carbonates [17], or molten chlorides [18], permitting the effective use of inexpensive (nickel) anode and (steel) cathode materials. 2. Experimental Solar thermal congurations driving STEP syntheses and STEP carbon have been detailed in previous publications [24]. This study focuses only on advances in the STEP electrochemical reactor component. Congurations of the electrochemical reactor have also been detailed in previous publications [24,16,17]. Barium carbonate (Alfa Aeasar, 99%), lithium carbonate (Alfa Aeasar, 99%), barium oxide (STREM, 99.5%) and lithium oxide (Alfa Aeasar, 99.5%), are used in the electrolysis and solubility studies. The electrolysis uses 40 g of the molten carbonate mix, contained, as will be noted, in either a pure alumina (AdValue, 99.6%) crucible, or a nickel (Alfa Aesar 35906 low-form 20 mL) crucible. In the alumina crucible cell, the cathode consists of a at disk formed by coiling a 26.5 cm long 0.12 cm diameter steel wire, and is situated horizontally 1 cm below the oxygen anode a at disk formed by coiling a 32 cm long 0.10 cm diameter pure nickel wire. In the nickel crucible cell, the anode consists of the inner crucible walls, and a steel foil cathode (0.00300 Precision Brand 16255) situated in the middle of the crucible and bent either into a vertical cylinder or folded n shape.

of Ca2+) then the oxide product in Eq. (4) leads to an additional, recoverable, product (such as lime, CaO). The decomposition of calcium carbonate at $900 8C (to CaO and CO2) is the basis of lime formation for cement production [3]. Unlike calcium carbonate, barium carbonate is highly stable and only melts at 1923 8C. In this study we introduce a new, barium containing, electrolyte for STEP carbon. Barium carbonate has several (iiii) advantages compared to pure lithium carbonate/ lithium oxide electrolytes. (i) Barium is fourfold more prevalent than lithium in the earths crust, and hence a more available resource for STEP carbon implementation. We have previously calculated that sufcient lithium carbonate is available to decrease atmospheric carbon dioxide to pre-industrial levels in ten years [2,16]. (ii) It will be shown that the equilibrium of barium carbonate favors even greater reactive absorption of CO2 to carbonate than lithium carbonate, and that molten electrolytes containing barium carbonate also promote facile reduction and capture of carbon dioxide. (iii) Barium oxide is even less corrosive toward metals than lithium oxide further stabilizing the STEP electrodes and cell casing. In general the strength of an oxide in melts to donate an electron pair (Lewis basicity) decreases in the order: K2O > Na2O > Li2O > BaO > CaO > MgO > Fe2O3 > Al2O3 > TiO2 > B2O3 > SiO2 > P2O5 [18]. Fig. 1 left compares our calculated domains in which carbon dioxide will be absorbed to form carbonate, constrained by the area above the curve for the equilibrium constant of: MCO3 MO CO2 ; M Ba or Li2 ; K pCO2 aMO aMCO3 (4)

3. Results and discussion Oxides dissolved in molten carbonates play a critical role, not only in the rapid reactive absorption of carbon dioxide gas, and its dissolution as carbonate: Dissolution : CO2 gas O2 moltenmiscible ! CO3 2 moltenmiscible (1)

but also in facilitating the molten carbonate electrolytic splitting of the dissolved carbon dioxide: Electrolysis : CO3 2 moltenmiscible ! C solid O2 moltenmiscible 3O2 gas (2)

A high miscible oxide concentration promotes rapid carbon dioxide uptake and facile carbon dioxide splitting, and these collectively yield carbon dioxide splitting without change in the electrolyte in accord with [2]: NetEqs1and2 : CO2 gas ! Csolid O2 gas (3)

In the absence of CO2 (gas), molten carbonate electrolysis leads to a buildup of oxide (along with the carbon and oxygen products), expressed as Eq. (2). If the spectator cation, from the molten or dissolved carbonate, leads to a soluble oxide (as in the case of Ba2+ or 2Li+) then the oxide product in equation 2 is miscible. However if the spectator cation leads to an insoluble oxide (such as in the case

In this domain, the oxide will spontaneously react with carbon dioxide to form the carbonate, when pCO2 aMO =aMCO3 > K . It is evident that this domain is signicantly larger for barium, compared to lithium, carbonate. This opens up a larger window of opportunity for carbon dioxide utilization by barium carbonate. The thermodynamic equilibrium conditions were calculated using the known enthalpy and entropy as a function of temperature of Li2O, BaO, CO2 BaCO3 and Li2CO3 [1921]. We calculate the freeenergy of Eq. (4), and from this calculate the thermodynamic equilibrium constant as a function of temperature. Unlike lithium carbonate which melts at 723 8C and provides an effective molten electrolyte for CO2 splitting, barium carbonate is a solid in this temperature. The driving force for the reactive absorption of CO2 to carbonate is greater for BaCO3 than Li2CO3, but how will barium carbonate as a solid provide an effective medium for electrolytic carbon dioxide splitting? While pure barium carbonate is not liquid at temperatures below 1000 8C, mixtures of barium and lithium carbonate readily melt. Components of the phase diagram including this large zone of liquid solution was reported in 1941 [2224], and the large range of pure liquid, miscible BaCO3Li2CO3 mixes [16] is presented in the bottom of Fig. 1. The reported quantitative composition of miscible molten carbonate and oxide salts varies in the literature, although solubility trends (such as the high solubility of barium carbonated in molten carbonate) are consistent. We suggest these quantitative variations are related to factors affecting solubility of carbonate/ oxide salt mixtures, such as the (increasing) partial pressure of CO2 in the atmosphere and (small) water uptake into these electrolytes. Experimentally, we observe the facile reaction of CO2 with dissolved oxide in molten carbonate. When air is bubbled through 750 8C molten mix of 65 wt% BaCO3, 24% Li2CO3, 11% Li2O, the electrolyte gains mass through the reaction of airborne CO2 with the dissolved oxide, and the rate is proportional to the rate of ow, and the concentration of CO2 in the gas. At constant air ow, and comparing the pure Li2CO3 to the barium mix electrolyte (each with 11 wt% Li2O), the experimental rate of CO2 uptake from the air

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Fig. 1. Left: Comparison of the equilibrium constant for Li2CO3 and BaCO3, decomposition of carbonate or absorption of CO2 as calculated from the thermochemistry of the carbonate, carbon dioxide and oxide components. Right: Phase diagram of the BaCO3Li2CO3 system (100% or 0% respectively indicate pure barium or lithium carbonate); modied from Ref. [24]. The 705 8C Li2O/Li2CO3 mix melting point is noted for comparison, but not shown on the curve.

is more rapid in the barium mix electrolyte (0.108 g after 4 h) than in the pure lithium electrolyte (0.064 g after 4 h) in 33 g of electrolyte. Using air, rather than pure CO2, the rate of mass gain is limited by the rate at which air (0.03% CO2) can be bubbled into the molten 750 8C carbonate. With pure CO2 through 33 g of 750 8C electrolyte, the reaction nears completion (over 4 g mass) based on the available 11 wt% Li2O. The capability to remove CO2, whether from high concentration industrial sources, or directly from the atmosphere, by reactive absorption in molten carbonate is driven by higher concentrations of dissolved oxide. Although common inorganic oxides do not melt at temperatures less than 1500 8C, they can dissolve in molten carbonates at temperatures less than 1000 8C. Fig. 2 compares the solubility of several oxides and carbonates in one molten lithium carbonate (Li2CO3) as a function of temperature. Note, the large difference for the calcium salts between the high solubility of calcium carbonate and low solubility of calcium oxide. However another alkali earth, the barium salts act in a different manner. As seen in the gure barium oxide has a considerably advantage in solubility compared to lithium, and is two orders of magnitude more soluble than calcium oxide. As with the barium carbonate (Fig. 1 right), barium oxide is highly soluble. Not shown in the

gures is our additional observation that barium oxide and barium carbonate are also soluble in molten sodiumpotassium carbonate eutectics, such as measured in, Na1.23K0.77CO3 which also can provide alternative electrolytes to support carbon dioxide uptake and splitting. High current is required for the economic viability of industrial electrochemical processes such as in aluminum production, and high current at low voltage will also be required for electrolytic carbon dioxide splitting processes for CO2 removal from the air or from industrial stacks. Fig. 3 demonstrates that not only Li2CO3, but also barium mix molten carbonates can sustain high rates of CO2 electrolysis at low energy, both under air and under CO2. High CO2 level concentrations are found in smoke stacks and a variety of industrial ues including those associated with fossil fuels and iron or cement production. We have previously reported on the facile kinetics, and high sustainable current density for carbon dioxide splitting to carbon (at the cathode) and oxygen (at the anode) in molten carbonates. Hence the measured potential during the electrolysis in lithium carbonate at 750 8C: is 1.45 V for J = 1 A cm2 using a planar steel or platinum wire cathode and excess (60 fold-higher) area anode, while it is 1.6 V, for J = 1 A cm2 with a wire nickel anode with excess cathode area. We have

Fig. 2. Solubility in molten lithium carbonate of various oxides and calcium carbonate.

Fig. 3. Electrolysis currents for carbon dioxide splitting in various electrolytes.

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previously reported on the low energy for carbon dioxide splitting to in molten carbonates. The open circuit measured potential of the electrolysis E(J = 0 A cm2) decreases with increasing temperature from 1.1 V at 750 8C, to 0.9 V at 850 8C and 0.7 V at 950 8C, and the cathode product gradually shifts from 100% (solid) carbon at 750 8C to a product of 100% (gas phase) carbon monoxide at 950 8C [16]. Interestingly, we observe that added lithium oxide further decreases the observed electrolysis potential, providing evidence of a peroxide intermediate at the anode during oxygen formation [4c].

Fig. 3 presents the low electrolysis energy and high electrolysis current in various molten carbonate electrolytes including barium carbonate using a Ni anode and steel cathode. The constant current electrolysis potential increases when the radial diffusion at a wire electrode is replaced by the planar diffusion to a at electrode, and decreases with increase in the surface area. Substantial electrode surface area increases can be achieved through simple macroscopic change such as use of a coiled long wire, or a folded foil, electrode, or microscopic changes in morphology, such as by

Fig. 4. Molten carbonate electrolysis readily converts CO2 to a storable carbon product. Cells, carbon product and variation of the electrolysis potential with time are shown. Each electrolysis is at 750 8C for 4 h at 1 A in the indicated electrolyte mix. The pink and yellow electrolysis curves are conducted in an alumina crucible, which contains a coiled Ni wire anode over a coiled steel wire cathode (photographed) immersed in the molten electrolyte. Subsequent to the electrolysis the components are removed and photographed showing the anode and electrolyte (top middle), and below them is the cathode with the typical thick deposited carbon product. The lower electrolysis curve is conducted with alternate cathodes (photographed) and a Ni crucible that also serves as the anode along with a folded steel foil cathode.

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texturing or increasing porosity of the electrode. Other surface area enhancements, such as using the electrolytic cell encasement as either the nickel or steel electrode provide even larger surface area electrodes. As seen in Fig. 3, and consistent with the higher mobility (charge to mass ratio) of the Li+ compared to Ba2+ cation, pure lithium carbonate provides somewhat lower polarization than the barium carbonate electrolyte, but the latter electrolyte provides higher currents when the nickel anode surface area is extended to include the (crucible) cell walls. Fig. 4 presents the representative, voluptuous carbon product formed during a 1 A, 4 h 750 8C electrolysis, as well as the potential measured during such electrolyses. The electrolyte shown (barium carbonate with added lithium carbonate and lithium oxide) is gray/ white prior to the melt, transparent when molten, and gray/white after cooling post-electrolysis. On the top side of Fig. 4, to emphasize the thick, carbon electrolysis product, we use a simple coiled steel wire, with surface area 5 cm2 per side, as a cathode. A nickel anode of the same size lies above the cathode. The carbon product forms on the side of the cathode that faces the anode. Photographs of the alumina crucible cell used in the pink (65 wt% BaCO3, 24% Li2CO3, 11% Li2O) and yellow curve (Li2CO3) electrolyses are included in Fig. 4. The anode and cathode are shown, before electrolysis and also post electrolysis, prior to washing. The top middle photos are of the electrodes and electrolyte subsequent to the pink curve (65 wt% BaCO3, 24% Li2CO3, 11% Li2O) electrolysis, and a similar thick carbon product is formed during the Li2CO3. After extraction and cooling, when it is cathode wire is uncoiled, the product drops off the cathode, and the original wire can be recoiled and reused. Similarly, the anode is unchanged after extraction, cooling and washing. As previously quantied [4c], nickel is highly stable in the lithium carbonate during the electrolysis, with the formation of a protective nickel oxide during oxygen evolution. Enhanced stability of the nickel anode in the barium, compared to lithium, molten carbonate electrolyte is noted here and will be detailed in an expanded study; briey, a vulnerable area of the nickel appears to occur at the molten lithium carbonate/ air interface, and the anode often breaks at this interface. Instead, in the molten barium electrolyte, the anode was stable even at the electrolyte/air interface. In this cell conguration, the measured mass change during the electrolysis is consistent with the change of electrolyte from Li2CO3 to 65 wt% BaCO3, 24% Li2CO3, 11% Li2O, and whether the electrolysis is conducted under air or under carbon dioxide. During the 4 h, 1 A electrolyses the mass respectively changes by 2.6 g lost (Li electrolyte under air), or 1.11 g lost (Ba electrolyte under air), or 0.04 g gain (Ba electrolyte under CO2). The rst value is consistent with the simultaneous electrolysis and Li2CO3 decomposition (lost as carbon dioxide), the second value is consistent with the gas product during the electrolysis (from 4 Ah of charge), and the nal value is consistent with an approximate balance of the gas product and CO2 absorption during the electrolysis. This latter experiment was conducted with a slow ow of CO2 above the electrolysis. As indicated in the discussion of Fig. 1, the mass gain is substantially greater when the CO2 is bubbled through, rather than owed over, the molten electrolyte. The right side of Fig. 4 also presents photographs of an alternate cell conguration, which is driven by a much lower electrolysis potential, and is contained by a nickel crucible, whose walls also serve as a high surface area oxygen generating anode. In the gure, the gray curve electrolysis is conducted in this nickel cell. The required electrolysis potential of 1.51.6 V in 65 wt% BaCO3, 24% Li2CO3, 11% Li2O at 750 8C is $0.8 V less than needed in the coiled disk electrode conguration. The nickel cell uses either of two separate cathode geometries (each photographed before and after the electrolysis in the barium mix electrolyte) both formed from

folded steel foil: a 24 cm2 radial n cathode (either under air (gray potential curve) or under CO2), or a 4 cm2 vertical cylinder. Either cathode is immersed in the center of the Ni crucible lled with molten carbonate. Post electrolysis electrolyte is visible as congealed in the center of the radial n cathodes. As shown, the extracted cathode product is black when formed under CO2, and covered with a speckled off-white overlayer with excess oxide when formed under air (bottom right photo). 4. Conclusions The benets of a new series of barium carbonate electrolytes for facile capture of atmospheric carbon dioxide and its direct conversion to readily storable, energetic solid carbon are demonstrated. Both barium containing, and the previously studied pure lithium, carbonate electrolytes sustain facile reduction and capture of carbon dioxide into a readily storable, useful solid carbon product. In addition the barium containing carbonate electrolytes have several advantages compared to pure lithium carbonate electrolytes. (i) The equilibrium of barium carbonate favors even greater reactive absorption of CO2 than lithium carbonate; (ii) barium is a fourfold more available resource for STEP carbon implementation, and (iii) barium oxide further stabilizes the STEP electrodes and cell casing (is even less corrosive toward metals than lithium oxide). Here, the electrolysis component of the Solar Thermal Electrochemical Process of carbon capture is studied, and an electrolytic cell with inexpensive (nickel and steel) components, provides direct conversion of carbon dioxide to carbon from the atmosphere in a single step. In ongoing experiments (to be reported) at higher temperature, molten barium carbonate mix electrolytes are also an effective medium to study carbon monoxide, hydrogen and hydrocarbon products (in addition to the 750 8C solid carbon product reported here). It is anticipated that sodium and potassium, rather than lithium, salt additions to the barium carbonate electrolyte can decrease the initial electrolyte cost. However, it is emphasized that the electrolyte is not consumed during the electrolysis. Lower fractions of lithium carbonate in the barium carbonate electrolyte mix may further enhance the rate of CO2 absorption and cell stability, while higher fractions will increase electrolyte conductivity and decrease polarization. Acknowledgements The authors are grateful for support of this research by the National Science Foundation (Award 1006568). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.jcou.2013.03.006. References
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