Single atom (Pd/Pt) supported on graphitic carbon nitride as efficient photocatalyst for visible-light reduction of carbon dioxide

Reducing carbon dioxide (CO2) to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single palladium/platinum (Pd/Pt) atoms supported on graphitic carbon nitride (g-C3N4), i.e. Pd/g-C3N4 and Pt/g-C3N4, acting as photocatalysts for CO2 reduction were investigated by density function theory (DFT) calcu-lations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, depositing atom catalysts on g-C3N4 significantly enhances the visible light absorption, rendering them ideal for visible light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.

New empirical expressions to correlate solubilities of solids in supercritical carbon dioxide

Supercritical processes are gaining importance in the last few years in the food, environmental and pharmaceutical product processing. The design of any supercritical process needs accurate experimental data on solubilities of solids in the supercritical fluids (SCFs). The empirical equations are quite successful in correlating the solubilities of solid compounds in SCF both in the presence and absence of cosolvents. In this work, existing solvate complex models are discussed and a new set of empirical equations is proposed. These equations correlate the solubilities of solids in supercritical carbon dioxide (both in the presence and absence of cosolvents) as a function of temperature, density of supercritical carbon dioxide and the mole fraction of cosolvent. The accuracy of the proposed models was evaluated by correlating 15 binary and 18 ternary systems. The proposed models provided the best overall correlations. (C) 2009 Elsevier BA/. All rights reserved.

Effect of Chain Length of Alcohol on the Lipase-Catalyzed Esterification of Propionic Acid in Supercritical Carbon Dioxide

The esterification of propionic acid was investigated using three different alcohols, namely, isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol. The variation of conversion with time for the synthesis of isoamyl propionate was investigated in the presence of five enzymes. Novozym 435 showed the highest activity, and this was used as the enzyme for investigating the various parameters that influence the esterification reaction. The Ping-Pong Bi-Bi model with inhibition by both acid and alcohol was used to model the experimental data and determine the kinetics of the esterification reaction.

Importance of carbon dioxide physiological forcing to future climate change

An increase in atmospheric carbon dioxide (CO2) concentration influences climate both directly through its radiative effect (i.e., trapping longwave radiation) and indirectly through its physiological effect (i.e., reducing transpiration of land plants). Here we compare the climate response to radiative and physiological effects of increased CO2 using the National Center for Atmospheric Research (NCAR) coupled Community Land and Community Atmosphere Model. In response to a doubling of CO2, the radiative effect of CO2 causes mean surface air temperature over land to increase by 2.86 ± 0.02 K (± 1 standard error), whereas the physiological effects of CO2 on land plants alone causes air temperature over land to increase by 0.42 ± 0.02 K. Combined, these two effects cause a land surface warming of 3.33 ± 0.03 K. The radiative effect of doubling CO2 increases global runoff by 5.2 ± 0.6%, primarily by increasing precipitation over the continents. The physiological effect increases runoff by 8.4 ± 0.6%, primarily by diminishing evapotranspiration from the continents. Combined, these two effects cause a 14.9 ± 0.7% increase in runoff. Relative humidity remains roughly constant in response to CO2-radiative forcing, whereas relative humidity over land decreases in response to CO2-physiological forcing as a result of reduced plant transpiration. Our study points to an emerging consensus that the physiological effects of increasing atmospheric CO2 on land plants will increase global warming beyond that caused by the radiative effects of CO2.

Synthesis of biodiesel in supercritical alcohols and supercritical carbon dioxide

Biodiesel was synthesized in supercritical fluids by two routes: non-catalytically in supercritical alcohols and by enzyme catalysis in supercritical carbon dioxide. Two oils, sesame oil and mustard oil, and two alcohols, methanol and ethanol, were used for the synthesis. Complete conversion was observed for synthesis in supercritical alcohols whereas only a maximum of 70% conversion was observed for the enzymatic synthesis in supercritical carbon dioxide. For the synthesis in supercritical alcohols, the activation energies and pseudo-first order rate constants were determined. For the reactions in supercritical carbon dioxide, a mechanism based on ping pong bi-bi was proposed and the kinetic parameters were determined. (C) 2009 Elsevier Ltd. All rights reserved.

An association model for the solubilities of pharmaceuticals in supercritical carbon dioxide

The equilibrium solubility of a pharmaceutical compound. 1,5-dimethy1-2-phenyl-4-propan-2-ylpyrazol-3-one (propyphenazone, isopropylantipyrine) in supercritical carbon dioxide (SCCO2) was experimentally determined by a saturation method at 308, 318 and 328 K. over the pressure range of 9.0-19.0 MPa. The solubility data satisfied the self-consistency test, proposed by Mendez-Santiago and Teja. A new association model was derived to correlate the solubilities of pharmaceutical compounds in SCCO2. Solubility data from 54 different pharmaceutical compounds including steroids, antibiotics, anti-inflammatory, antioxidants, statins and specific functional drugs were collected from literature. The model successfully correlated the experimental results for the solubilities of all these compounds in SCCO2 within 12% AARD. (C) 2010 Elsevier B.V. All rights reserved.

Carbon dioxide and methane exchange between a boreal pristine lake and the atmosphere

Lakes serve as sites for terrestrially fixed carbon to be remineralized and transferred back to the atmosphere. Their role in regional carbon cycling is especially important in the Boreal Zone, where lakes can cover up to 20% of the land area. Boreal lakes are often characterized by the presence of a brown water colour, which implies high levels of dissolved organic carbon from the surrounding terrestrial ecosystem, but the load of inorganic carbon from the catchment is largely unknown. Organic carbon is transformed to methane (CH4) and carbon dioxide (CO2) in biological processes that result in lake water gas concentrations that increase above atmospheric equilibrium, thus making boreal lakes as sources of these important greenhouse gases. However, flux estimates are often based on sporadic sampling and modelling and actual flux measurements are scarce. Thus, the detailed temporal flux dynamics of greenhouse gases are still largely unknown. ----- One aim here was to reveal the natural dynamics of CH4 and CO2 concentrations and fluxes in a small boreal lake. The other aim was to test the applicability of a measuring technique for CO2 flux, i.e. the eddy covariance (EC) technique, and a computational method for estimation of primary production and community respiration, both commonly used in terrestrial research, in this lake. Continuous surface water CO2 concentration measurements, also needed in free-water applications to estimate primary production and community respiration, were used over two open water periods in a study of CO2 concentration dynamics. Traditional methods were also used to measure gas concentration and fluxes. The study lake, Valkea-Kotinen, is a small, humic, headwater lake within an old-growth forest catchment with no local anthropogenic disturbance and thus possible changes in gas dynamics reflect the natural variability in lake ecosystems. CH4 accumulated under the ice and in the hypolimnion during summer stratification. The surface water CH4 concentration was always above atmospheric equilibrium and thus the lake was a continuous source of CH4 to the atmosphere. However, the annual CH4 fluxes were small, i.e. 0.11 mol m-2 yr-1, and the timing of fluxes differed from that of other published estimates. The highest fluxes are usually measured in spring after ice melt but in Lake Valkea-Kotinen CH4 was effectively oxidised in spring and highest effluxes occurred in autumn after summer stratification period. CO2 also accumulated under the ice and the hypolimnetic CO2 concentration increased steadily during stratification period. The surface water CO2 concentration was highest in spring and in autumn, whereas during the stable stratification it was sometimes under atmospheric equilibrium. It showed diel, daily and seasonal variation; the diel cycle was clearly driven by light and thus reflected the metabolism of the lacustrine ecosystem. However, the diel cycle was sometimes blurred by injection of hypolimnetic water rich in CO2 and the surface water CO2 concentration was thus controlled by stratification dynamics. The highest CO2 fluxes were measured in spring, autumn and during those hypolimnetic injections causing bursts of CO2 comparable with the spring and autumn fluxes. The annual fluxes averaged 77 (±11 SD) g C m-2 yr-1. In estimating the importance of the lake in recycling terrestrial carbon, the flux was normalized to the catchment area and this normalized flux was compared with net ecosystem production estimates of -50 to 200 g C m-2 yr-1 from unmanaged forests in corresponding temperature and precipitation regimes in the literature. Within this range the flux of Lake Valkea-Kotinen yielded from the increase in source of the surrounding forest by 20% to decrease in sink by 5%. The free water approach gave primary production and community respiration estimates of 5- and 16-fold, respectively, compared with traditional bottle incubations during a 5-day testing period in autumn. The results are in parallel with findings in the literature. Both methods adopted from the terrestrial community also proved useful in lake studies. A large percentage of the EC data was rejected, due to the unfulfilled prerequisites of the method. However, the amount of data accepted remained large compared with what would be feasible with traditional methods. Use of the EC method revealed underestimation of the widely used gas exchange model and suggests simultaneous measurements of actual turbulence at the water surface with comparison of the different gas flux methods to revise the parameterization of the gas transfer velocity used in the models.

Carbon Dioxide emissions from an Acacia plantation on peatland in Sumatra, Indonesia

Abstract. Peat surface CO2 emission, groundwater table depth and peat temperature were monitored for two years along transects in an Acacia plantation on thick tropical peat (>4 m) in Sumatra, Indonesia. A total of 2300 emission measurements were taken at 144 locations. The autotrophic root respiration component of the CO2 emission was separated from heterotrophic emissions caused by peat oxidation in three ways: (i) by comparing CO2 emissions within and beyond the tree rooting zone, (ii) by comparing CO2 emissions with and without peat trenching (i.e. cutting any roots remaining in the peat beyond the tree rooting zone), and (iii) by comparing CO2 emissions before and after Acacia tree harvesting. On average, the contribution of root respiration to daytime CO2 emission is 21 % along transects in mature tree stands. At locations 0.5 m from trees this is up to 80 % of the total emissions, but it is negligible at locations more than 1.3 m away. This means that CO2 emission measurements well away from trees are free of any root respiration contribution and thus represent only peat oxidation emission. We find daytime mean annual CO2 emission from peat oxidation alone of 94 t ha−1 yr−1 at a mean water table depth of 0.8 m, and a minimum emission value of 80 t ha−1 yr−1 after correction for the effect of diurnal temperature fluctuations, which resulted in a 14.5 % reduction of the daytime emission. There is a positive correlation between mean long-term water table depths and peat oxidation CO2 emission. However, no such relation is found for instantaneous emission/water table depth within transects and it is clear that factors other than water table depth also affect peat oxidation and total CO2 emissions. The increase in the temperature of the surface peat due to plantation development may explain over 50 % of peat oxidation emissions.

Metathesis of carbon dioxide and phenyl isocyanate catalysed by group(IV) metal alkoxides: An experimental and computational study

The insertion reactions of zirconium(IV) n-butoxide and titanium(IV) n-butoxide with a heterocumulene like carbodiimide, carbon dioxide or phenyl isocyanate are compared. Both give an intermediate which carries out metathesis at elevated temperatures by inserting a second heterocumulene in a head-to-head fashion. The intermediate metallacycle extrudes a new heterocumulene, different from the two that have inserted leading to metathesis. As the reaction is reversible, catalytic metathesis is feasible. In stoichiometric reactions heterocumulene insertion, metathesis and metathesis cum insertion products are observed. However, catalytic amounts of the metal alkoxide primarily led to metathesis products. It is shown that zirconium alkoxides promote catalytic metathesis (isocyanates, carbon dioxide) more efficiently than the corresponding titanium alkoxide. The difference in the metathetic activity of these alkoxides has been explained by a computational study using model complexes Ti(OMe)(4) (1bTi) and Zr(OMe)(4) (1bZr). The computation was carried out at the B3LYP/LANL2DZ level of theory.

Solubilities of Benzene Derivatives in Supercritical Carbon Dioxide

The solubilities of benzene derivatives in supercritical carbon dioxide was determined by the saturation method over the pressure range (9.5 to 14.5) MPa. The solubilities were determined at (308 and 313) K for 1-chloro-2,4-dinitrobenzene and (308, 318, and 328) K for m-dinitrobenzene. At 308K, the solubility (in mole fraction) of 1-chloro-2,4-dinitrobenzene varied from (2.83 to 5.88).10(-3) while the solubility of m-dinitrobenzene increased from (2.05 to 5.54).10(-3) as the pressure increased from (9.5 to 14.5) MPa. However, the solubilities of both compounds decreased with increasing temperature. Models based on the solubility parameter and semiempirical models such as the Mendez-Santiago-Teja model, the Gordillo model, and the association model, were used to correlate the experimental solubility data for the benzene derivatives.

Absolute Entropy and Energy of Carbon Dioxide Using the Two-Phase Thermodynamic Model

The two-phase thermodynamic (2PT) model is used to determine the absolute entropy and energy of carbon dioxide over a wide range of conditions from molecular dynamics trajectories. The 2PT method determines the thermodynamic properties by applying the proper statistical mechanical partition function to the normal modes of a fluid. The vibrational density of state (DoS), obtained from the Fourier transform of the velocity autocorrelation function, converges quickly, allowing the free energy, entropy, and other thermodynamic properties to be determined from short 20-ps MD trajectories. The anharmonic effects in the vibrations are accounted for by the broadening of the normal modes into bands from sampling the velocities over the trajectory. The low frequency diffusive modes, which lead to finite DoS at zero frequency, are accounted for by considering the DoS as a superposition of gas-phase and solid-phase components (two phases). The analytical decomposition of the DoS allows for an evaluation of properties contributed by different types of molecular motions. We show that this 2PT analysis leads to accurate predictions of entropy and energy of CO2 over a wide range of conditions (from the triple point to the critical point of both the vapor and the liquid phases along the saturation line). This allows the equation of state of CO2 to be determined, which is limited only by the accuracy of the force field. We also validated that the 2PT entropy agrees with that determined from thermodynamic integration, but 2PT requires only a fraction of the time. A complication for CO2 is that its equilibrium configuration is linear, which would have only two rotational modes, but during the dynamics it is never exactly linear, so that there is a third mode from rotational about the axis. In this work, we show how to treat such linear molecules in the 2PT framework.

Enzymatic synthesis of flavors in supercritical carbon dioxide

Commercially important flavor esters of isoamyl alcohol, catalyzed by crude hog pancreas lipase (HPL), were synthesized under solvent-free conditions and in supercritical carbon dioxide. The esters synthesized were isoamyl acetate, isoamyl propionate, isoamyl butyrate, and isoamyl octanoate. Very low yields (3-4%) of isoamyl acetate were obtained, but high yields for the other three esters were obtained under both supercritical and solvent-free conditions. The yields of esters of the even-carbon acids, isoamyl acetate, butyrate, and octanoate, increased with increasing chain length, whereas the yield of isoamyl propionate was higher than that of isoamyl butyrate. The optimum temperature of the reaction was higher under supercritical conditions (45 degreesC) than under solvent-free conditions (35-40 degreesC). The effects of other parameters such as alcohol concentration, water concentration, and enzyme loading were investigated. An increase in the water concentration decreased the conversion significantly in supercritical carbon dioxide but not under solvent-free conditions. The optimum ratio of alcohol to acid was dependent on the extent of inhibition by the acid. Although providing a higher apparent yield by being run in a highly concentrated medium, the overall conversion under solvent-free conditions was lower than that under supercritical conditions for similar enzyme concentrations, indicating that the synthesis of esters in supercritical carbon dioxide might be a viable option.

Solubilities of resorcinol and pyrocatechol and their mixture in supercritical carbon dioxide

The equilibrium solubilities of dihydroxy benzene isomers (resorcinol and pyrocatechol) and its mixture were experimentally determined at different temperatures (308, 318, 328, and 338 K) in the pressure range of 9.8-16.2 MPa. In the ternary system, the solubilities of pyrocatechol increased while the solubilities of resorcinol decreased relative to their binary solubilities. A new association model was developed based on the concept of formation of solvate complex molecules to correlate the solubility of the solid for mixed solids in supercritical carbon dioxide (SCCO(2)). The model equation relates the solubility of solute in terms of the cosolute composition, temperature, pressure and density of SCCO(2). The proposed model correlated the solubilities of sixteen solid systems taken from the literature and current experimental data with an average absolute relative deviation (AARD) of around 4%. (C) 2011 Elsevier B.V. All rights reserved.

Exergetic analysis of carbon dioxide vapour compression refrigeration cycle using the new fundamental equation of state

The purpose of this paper is to present exergy charts for carbon dioxide (CO2) based on the new fundamental equation of state and the results of a thermodynamic analysis of conventional and trans-critical vapour compression refrigeration cycles using the data thereof. The calculation scheme is anchored on the Mathematica platform. There exist upper and lower bounds for the high cycle pressure for a given set of evaporating and pre-throttling temperatures. The maximum possible exergetic efficiency for each case was determined. Empirical correlations for exergetic efficiency and COP, valid in the range of temperatures studied here, are obtained. The exergy losses have been quantified. (C) 2003 Elsevier Ltd. All rights reserved.