Solar Light Photocatalytic CO2 Reduction: General Considerations and Selected Bench-Mark Photocatalysts

The reduction of carbon dioxide to useful chemicals has received a great deal of attention as an alternative to the depletion of fossil resources without altering the atmospheric CO₂ balance. As the chemical reduction of CO₂ is energetically uphill due to its remarkable thermodynamic stability, this process requires a significant transfer of energy. Achievements in the fields of photocatalysis during the last decade sparked increased interest in the possibility of using sunlight to reduce CO₂. In this review we discuss some general features associated with the photocatalytic reduction of CO₂ for the production of solar fuels, with considerations to be taken into account of the photocatalyst design, of the limitations arising from the lack of visible light response of titania, of the use of co-catalysts to overcome this shortcoming, together with several strategies that have been applied to enhance the photocatalytic efficiency of CO₂ reduction. The aim is not to provide an exhaustive review of the area, but to present general aspects to be considered, and then to outline which are currently the most efficient photocatalytic systems.     

Photocatalytic Reduction of CO2 with H2O on Ti-Containing Porous Silica Thin Film Photocatalysts

Two different Ti-containing porous silica thin films having a hexagonal and cubic pore structure were synthesized and used as photocatalysts for the reduction of CO₂ with H₂O at 323 K. UV irradiation of the Ti-containing porous silica thin films in the presence of CO₂ and H₂O led to the formation of CH₄ and CH₃OH with a high quantum yield of 0.28%. These porous silica thin film photocatalysts having a hexagonal pore structure exhibited higher reactivity than the Ti-MCM-41 powder photocatalysts with the same pore structure.     

Comparing Molecular Mechanisms in Solar NH3 Production and Relations with CO2 Reduction

Molecular mechanisms for N₂ fixation (solar NH₃) and CO₂ conversion to C2+ products in enzymatic conversion (nitrogenase), electrocatalysis, metal complexes and plasma catalysis are analyzed and compared. It is evidenced that differently from what is present in thermal and plasma catalysis, the electrocatalytic path requires not only the direct coordination and hydrogenation of undissociated N₂ molecules, but it is necessary to realize features present in the nitrogenase mechanism. There is the need for (i) a multi-electron and -proton simultaneous transfer, not as sequential steps, (ii) forming bridging metal hydride species, (iii) generating intermediates stabilized by bridging multiple metal atoms and (iv) the capability of the same sites to be effective both in N₂ fixation and in CO_x reduction to C2+ products. Only iron oxide/hydroxide stabilized at defective sites of nanocarbons was found to have these features. This comparison of the molecular mechanisms in solar NH₃ production and CO₂ reduction is proposed to be a source of inspiration to develop the next generation electrocatalysts to address the challenging transition to future sustainable energy and chemistry beyond fossil fuels.     

Photocatalytic reaction of H2O+CO2 over pure and doped Rh/TiO2

In the photocatalytic reduction of carbon dioxide to formic acid, formaldehyde and methanol in aqueous suspensions of TiO₂ and Rh/TiO₂, the effects of doping the TiO₂ with W⁶⁺ were investigated.This laboratory is a part of the Center for Catalysis, Surface and Material Science at the University of Szeged.     

内循环光催化反应器降解甲基橙废水的研究

利用自行研制的内循环光催化反应器，以紫外灯光为光源、二氧化钛为催化剂，降解甲基橙废水。试验表明，催化剂、传质、废水色度对光催化降解效率影响显著。本反应器具有良好的气－液－固传质。在最佳实验条件下废水色度去除率≥90％，取得了较好的处理效果。光催化技术对废水的深度处理有广阔的应用前景。     

Complexes in the Photocatalytic Reaction of CO(2) and H(2)O: Theoretical Studies

Complexes (H(2)O/CO(2), e-(H(2)O/CO(2)) and h(+)-(H(2)O/CO(2))) in the reaction system of CO(2) photoreduction with H(2)O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H(2)O/CO(2) captured photo-induced electron and hole produced e-(H(2)O/CO(2)) and h(+)-(H(2)O/CO(2)), respectively. The results revealed that CO(2) and H(2)O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO(2) and H(2)O, which might be attributed to the synergistic effect and which could not be captured experimentally.     

PREDICTION OF CO2 FREEZE-OUT CONDITIONS AND CO2 HYDRATE FORMATION CONDITIONS WITH A SINGLE EQUATION OF STATE

A recent study by Eggeman and Chaffin (2005 Eggeman , T. , and Chafin , S. ( 2005 ). Beware of pitfalls of CO₂ freezing predictions , Chem. Eng. Prog. , 101 ( 3 ), 39 – 44 . [Google Scholar]), which showed large discrepancies in CO₂ freeze-out conditions as predicted by several commercial simulators, prompted a reexamination of using the TBS equation of state for phase equilibrium calculations involving solids. Salim and Trebble (1994 Salim , P. , and Trebble , M. A. ( 1994 ). Modelling of solid phases in thermodynamic calculations via translation of a cubic equation of state at the triple point , Fluid Phase Equilib. , 93 , 75 – 99 .[Crossref] , [Google Scholar]) had previously presented a methodology for extending the Trebble-Bishnoi-Salim (TBS) equation of state (Salim, 1990 Salim , P. ( 1990 ). A modified Trebble-Bishnoi equation of state, M.Sc. thesis , University of Calgary . [Google Scholar]) to calculations involving a solid phase. In this study, the CO₂ freeze-out conditions in CO₂/CH₄ and CO₂/C₂H₆ mixtures are calculated from the TBS equation of state, and it is shown that they provide a better data fit than the traditional Poynting correction method. Furthermore, since the use of an equation of state in SLE/SVE calculations does not require the explicit assumption of a pure solid phase, the model was assessed for its ability to correlate CO₂ gas hydrate equilibrium conditions. Gas hydrates were simply treated as an impure solid phase, and it was seen that the predictions of gas hydrate equilibrium were in very good agreement with the experimental data. Computationally, the use of the TBS equation of state has the advantage, over the model of Yokozeki (2005 Yokozeki , A. ( 2005 ). Methane gas hydrates viewed through unified solid-liquid-vapour equation of state , Int. J. Thermophys. , 26 ( 3 ), 743 – 765 . [Google Scholar]), that it does not require a modifying factor (c_b) in the repulsive term to handle the presence of hydrates; they are instead handled using a unique binary interaction parameter for the hydrate phase.     

Insights of Fe2O3 and MoO3 Electrodes for Electrocatalytic CO2 Reduction in Aprotic Media

Transition metal oxides (TMO) have been successfully used as electrocatalytically active materials for CO₂ reduction in some studies. Because of the lack of understanding of the catalytic behavior of TMOs, electrochemical methods are used to investigate the CO₂ reduction in thin-film nanostructured electrodes. In this context, nanostructured thin films of Fe₂O₃ and MoO₃ in an aprotic medium of acetonitrile have been used to study the CO₂ reduction reaction. In addition, a synergistic effect between CO₂ and the TMO surface is observed. Faradic cathodic processes not only start at lower potentials than those reported with metal electrodes, but also an increase in capacitive currents is observed, which is directly related to an increase in oxygen vacancies. Finally, the results obtained show CO as a product of the reduction.     

Photocatalytic activity of porous titania nanocrystals prepared by nanoscale permeation process in supercritical CO2: Effects of supercritical conditions

Porous TiO₂ nanocrystals (PTN) were synthesized using activated carbon templates with supercritical CO₂ by using the nanoscale permeation (NP) process. The photoactivity of PTN was tested by methylene blue (MB) degradation. Compared with the commercially available P-25, all PTN exhibited significant photocatalytic degradation of MB mainly due to their porous structure with high surface area, high hydroxy concentration and small crystalline size. The optimum temperature and pressure are found to be 60 °C and 26 MPa, under which obtained PTN-1 shows the highest photoactivity and slow deactivation for MB degradation after 15 trials.     

Hydrotalcites for adsorption of CO2 at high temperature

Adsorption of carbon dioxide by hydrotalcites was investigated by using a gravimetric method at 450 ‡C. Hydrotalcites possessed higher adsorption capacity of CO₂ than other basic materials such as MgO and Al₂O₃. Two different preparation methods of hydrotalcite with varying Mg/Al ratio were employed to determine their effects on the adsorption capacity of CO₂. In addition, varying amounts of K₂CO₃ were impregnated on the hydrotalcite to further increase its adsorption capacity of CO₂. The hydrotalcite prepared by the high supersaturation method with Mg/Al=2 showed the most favorable adsorption-desorption pattern with high adsorption capacity of CO₂. K₂CO₃ impregnation on the hydrotalcite increased the adsorption capacity of CO₂ because it changed both the chemical and the physical properties of the hydrotalcite. The optimum amount of K₂CO₃ impregnation was 20 wt%. The hydrotalcite prepared by the high supersaturation method with Mg/Al=2 and 20 wt% K₂CO₃ impregnation has the highest adsorption capacity of CO₂ with 0.77 mmol CO₂/g at 450 ‡C and 800 mmHg.     

In situ XAFS Studies on the Effects of the Hydrophobic–Hydrophilic Properties of Ti-Beta Zeolites in the Photocatalytic Reduction of CO2 with H2O

The photocatalytic reduction of CO₂ with H₂O to produce CH₄ and CH₃OH was found to proceed in the gas phase at 323 K with different reactivities and selectivities on hydrophilic Ti-Beta(OH) and hydrophobic Ti-Beta(F) zeolites prepared in the OH^– and F^– media, respectively. In situ XAFS measurements have revealed that these differences are attributed to the differences in the affinity for the adsorption of H₂O molecules on the highly dispersed tetrahedrally coordinated titanium oxide species depending on the hydrophobic–hydrophilic properties of zeolites.     

Synthesis of Silica Nanofluid and Application to CO2 Absorption

Abstract

This study focused on the synthesis of stable nanofluids and their direct application to the CO₂ absorption process. A sol-gel process was used as the synthesis method of nanoparticles in nanofluid. The particle size and stability were determined by SEM image and zeta potential of the nanofluid. Three types of nanofluids containing approximately 30 nm, 70 nm, and 120 nm particles were synthesized and all nanofluids had a stable zeta potential of approximately ? 45 mV. Addition of nanoparticles increased the average absorption rate of 76% during the first 1 minute and total absorption amount of 24% in water. The capacity coefficient of CO₂ absorption in the nanofluid is 4 times higher than water without nanoparticles, because the small bubble sizes in the nanofluid have large mass transfer areas and high solubility.     

EFFICIENT DESULFURIZATION IN O2/CO2 COMBUSTION: DEPENDENCE ON COMBUSTION CONDITIONS AND SORBENT PROPERTIES

Based on experiments on desulfurization, CaSO₄ decomposition, and a system approach using theoretical analysis, efficient in-furnace desulfurization in O₂/CO₂ combustion was investigated. The influence of combustion conditions and sorbent properties on system desulfurization efficiency was clarified. The global desulfurization efficiency was found to increase with O₂ purity. The global desulfurization efficiency in a dry recycle was higher than that in a wet recycle. The global efficiency of in-furnace desulfurization decreased with initial O₂ concentration. As the temperature increased, the global desulfurization efficiency increased first and then decreased due to the decomposition of CaSO₄. In the temperature range investigated, the global desulfurization efficiency in O₂/CO₂ coal combustion was much higher than that of conventional coal combustion in air. The global desulfurization efficiency decreased with sorbent size. When the particle radius decreased to one quarter, the global desulfurization efficiency doubled, becoming as high as 80%. The global desulfurization efficiency was very different among the three sorbents investigated, whether in O₂/CO₂ combustion or in conventional air combustion. The global desulfurization efficiency increased in the order of Ca(OH)₂, scallop, and limestone in O₂/CO₂ combustion, but in the order of scallop, Ca(OH)₂, and limestone in conventional air combustion. Nevertheless, all three sorbents demonstrated much higher desulfurization efficiency in O₂/CO₂ combustion than in conventional air combustion.     

SOLUBILITY OF CO2AND H2S IN A MIXED SOLVENT

Mixed solvents are a combination of chemical and physical solvents and have some advantages over traditional treating solvents for the removal of acid gases from gas streams. The solubility of H₂S and CO₂in a mixed solvent consisting of AMP (2-amino-2-methyl-l-propanol), sulfolane, and water has been measured at 40 and 100°C at partial pressures of the acid gas to 6000 kPa. The solubility in the mixed solvent was compared with the solubility in an aqueous solution of equivalent amine concentration. At solution loadings less than 1 mol acid gas/mol amine, the solubility of the acid gas is lower in the mixed solvent than in the corresponding amine solvent. At higher loadings, the trend is reversed and the solubility is greater in the mixed solvent. The results are rationalized in terms of the effect of the physical solvent component on the chemical reaction and physical vapor-liquid equilibria. The solubility model of Deshmukh and Mather was used to correlate the data.     

Periodic CO2 Dosing Strategy for Dunaliella salina Batch Culture

A periodic CO₂ dosing strategy for D. salina 19/30 batch culture is proposed. A model of periodic CO₂ dosing including dosing time calculation, dosing interval estimation and final chlorophyll yield prediction was established. In experiments, 5% CO₂/95% N₂ gas was periodically dosed into D. salina culture. Two different gas dosing flow rates were tested. The corresponding dosing time for each flow rate was estimated via the model (10 min·d⁻¹ for 0.7 L·min⁻¹ and 36 min·d⁻¹ for 0.3 L·min⁻¹). Daily pH measurements showed that the pH of these cultures dosed periodically was always kept between 7.5 and 9.5, which highlights that periodic gas supply can maintain a suitable range of pH for microalgal growth without expensive buffers. Notably the culture dosed for set daily intervals was seen to have similar growth to the culture supplied constantly, but with much higher CO₂ capture efficiency (11%–18%) compared to continuous dosing (0.25%). It shows great potential for using periodic gas supply to reduce cost, wasted gas and energy use.     

A Fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO₂ and CO₂/H₂ on a silica-supported caesium-doped copper catalyst. Adsorption of CO₂ on a “caesium”/silica surface resulted in the formation of CO₂ ⁻ and complexed CO species. Exposure of CO₂ to a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm⁻¹. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and H₂, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.     

H2+CO2 Synergistic Plasma Positioning Carboxyl Defects in g-C3N4 with Engineered Electronic Structure and Active Sites for Efficient Photocatalytic H2 Evolution

Defective functional-group-endowed polymer semiconductors, which have unique photoelectric properties and rapid carrier separation properties, are an emerging type of high-performance photocatalyst for various energy and environmental applications. However, traditional oxidation etching chemical methods struggle to introduce defects or produce special functional group structures gently and controllably, which limits the implementation and application of the defective functional group modification strategy. Here, with the surface carboxyl modification of graphitic carbon nitride (g-C₃N₄) photocatalyst as an example, we show for the first time the feasibility and precise modification potential of the non-thermal plasma method. In this method, the microwave plasma technique is employed to generate highly active plasma in a combined H₂+CO₂ gas environment. The plasma treatment allows for scalable production of high-quality defective carboxyl group-endowed g-C₃N₄ nanosheets with mesopores. The rapid H₂+CO₂ plasma immersion treatment can precisely tune the electronic and band structures of g-C₃N₄ nanosheets within 10 min. This conjoint approach also promotes charge-carrier separation and accelerates the photocatalyst-catalyzed H₂ evolution rate from 1.68 mmol h⁻¹g⁻¹ (raw g-C₃N₄) to 8.53 mmol h⁻¹g⁻¹ (H₂+CO₂-pCN) under Xenon lamp irradiation. The apparent quantum yield (AQY) of the H₂+CO₂-pCN with the presence of 5 wt.% Pt cocatalyst is 4.14% at 450 nm. Combined with density functional theory calculations, we illustrate that the synergistic N vacancy generation and carboxyl species grafting modifies raw g-C₃N₄ materials by introducing ideal defective carboxyl groups into the framework of heptazine ring g-C₃N₄, leading to significantly optimized electronic structure and active sites for efficient photocatalytic H₂ evolution. The 5.08-times enhancement in the photocatalytic H₂ evolution over the as-developed catalysts reveal the potential and maneuverability of the non-thermal plasma method in positioning carboxyl defects and mesoporous morphology. This work presents new understanding about the defect engineering mechanism in g-C₃N₄ semiconductors, and thus paves the way for rational design of effective polymeric photocatalysts through advanced defective functional group engineering techniques evolving CO₂ as the industrial carrier gas.     

Tackling increased CO2 concentration in feeds for existing acid gas removal units: A simulation study based on a customized CO2 kinetics model

A Middle East-based amine sweetening unit, with an overall capacity of about 2.2 BSCFD of gas, is among the world’s largest process plants and currently processes sour gas with 10 mol% of hydrogen sulfide (H₂S) and carbon dioxide (CO₂) put together. Current expectation is that acid gas contents in the feed may increase beyond the design limit of the plant. The present work is an effort to quantify the effects of the feed gas CO₂ increase on the plant and to proffer solutions to handle these effects efficiently. We revised the kinetics of amine-based CO₂ absorption correlation of an existing model using real-data-driven parameters re-estimation. Evolutionary technique that employs particle swarm optimization algorithm is used for this purpose. The new CO₂ kinetic model is inserted in a first-principle process simulator, ProMax® V4.0, in order to analyze various solutions necessary to mitigate the operational challenges due to increased feed CO₂. The process plant with present design and operating conditions is determined to handle up to 8.45 mol% CO₂ contents in the sour gas feed. Further results revealed that methyldiethanolamine, diethanolamine, and dimethyl ether propylene glycol (DEPG) could not handle this high feed CO₂ challenge, even at maximum (design) steam and solvent usage. However, diglycolamine exclusively renders the solution as it treats high CO₂ feed gas efficiently with allowable utility consumption, while satisfying the constraints imposed by product gas specifications.     

The kinetics of CO2 hydrogenation on a Rh foil promoted by titania overlayers

Submonolayer deposits of titania on a Rh foil have been found to increase the rate of CO₂ hydrogenation. The primary product, methane, exhibits a maximum rate at a TiO _x coverage of 0.5 ML which is a factor of 15 higher than that over the clean Rh surface. The rate of ethane formation displays a maximum which is 70 times that over the unpromoted Rh foil; however, the selectivity for methane remains in excess of 99%. The apparent activation energy for methane formation and the dependence of the rate on H₂ and CO₂ partial pressure have been determined both for the bare Rh surface and the titania-promoted surface. These rate parameters show very small variations as titania is added to the Rh catalyst. The methanation of CO₂ is proposed to start with the dissociation of CO₂ into CO_(a) and O_(a), and then proceed through steps which are identical to those for the hydrogenation of CO. The increase in the rate of CO₂ hydrogenation in the presence of titania is attributed to an interaction between the adsorbed CO, released by CO₂ dissociation, and Ti³⁺ ions located at the edge of TiO _x islands covering the surface. Differences in the effects of titania promotion on the methanation of CO₂ and CO are discussed in terms of the mechanisms that have been proposed for these two reactions.