Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

On the speed of the eddy-driven jet and the width of the Hadley cell in the Southern Hemisphere

A strong correlation between the speed of the eddy-driven jet and the width of the Hadley cell is found to exist in the Southern Hemisphere, both in reanalysis data and in twenty-first-century integrations from the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report multimodel archive. Analysis of the space–time spectra of eddy momentum flux reveals that variations in eddy-driven jet speed are related to changes in the mean phase speed of midlatitude eddies. An increase in eddy phase speeds induces a poleward shift of the critical latitudes and a poleward expansion of the region of subtropical wave breaking. The associated changes in eddy momentum flux convergence are balanced by anomalous meridional winds consistent with a wider Hadley cell. At the same time, faster eddies are also associated with a strengthened poleward eddy momentum flux, sustaining a stronger westerly jet in midlatitudes. The proposed mechanism is consistent with the seasonal dependence of the interannual variability of the Hadley cell width and appears to explain at least part of the projected twenty-first-century trends.

The relationship between the ITCZ and the Southern Hemispheric eddy-driven jet

We study the effect of a thermal forcing confined to the midlatitudes of one hemisphere on the eddy-driven jet in the opposite hemisphere. We demonstrate the existence of an “interhemispheric teleconnection,” whereby warming (cooling) the Northern Hemisphere causes both the intertropical convergence zone (ITCZ) and the Southern Hemispheric midlatitude jet to shift northward (southward). The interhemispheric teleconnection is effected by a change in the asymmetry of the Hadley cells: as the ITCZ shifts away from the Equator, the cross-equatorial Hadley cell intensifies, fluxing more momentum toward the subtropics and sustaining a stronger subtropical jet. Changes in subtropical jet strength, in turn, alter the propagation of extratropical waves into the tropics, affecting eddy momentum fluxes and the eddy-driven westerlies. The relevance of this mechanism is demonstrated in the context of future climate change simulations, where shifts of the ITCZ are significantly related to shifts of the Southern Hemispheric eddy-driven jet in austral winter. The possible relevance of the proposed mechanism to paleoclimates is discussed, particularly with regard to theories of ice age terminations.

Southern Hemisphere jet latitude biases in CMIP5 models linked to shortwave cloud forcing

Substantial biases in shortwave cloud forcing (SWCF) of up to ±30 W m−2are found in the midlatitudes of the Southern Hemisphere in the historical simulations of 34 CMIP5 coupled general circulation models. The SWCF biases are shown to induce surface temperature anomalies localized in the midlatitudes, and are significantly correlated with the mean latitude of the eddy-driven jet, with a negative SWCF bias corresponding to an equatorward jet latitude bias. Aquaplanet model experiments are performed to demonstrate that the jet latitude biases are primarily induced by the midlatitude SWCF anomalies, such that the jet moves toward (away from) regions of enhanced (reduced) temperature gradients. The results underline the necessity of accurately representing cloud radiative forcings in state-of-the-art coupled models.

Trends in the CERES dataset, 2000–13: the effects of sea ice and jet shifts and comparison to climate models

We review the effects of dynamical variability on clouds and radiation in observations and models and discuss their implications for cloud feedbacks. Jet shifts produce robust meridional dipoles in upper-level clouds and longwave cloud-radiative effect (CRE), but low-level clouds, which do not simply shift with the jet, dominate the shortwave CRE. Because the effect of jet variability on CRE is relatively small, future poleward jet shifts with global warming are only a second-order contribution to the total CRE changes around the midlatitudes, suggesting a dominant role for thermodynamic effects. This implies that constraining the dynamical response is unlikely to reduce the uncertainty in extratropical cloud feedback. However, we argue that uncertainty in the cloud-radiative response does affect the atmospheric circulation response to global warming, by modulating patterns of diabatic forcing. How cloud feedbacks can affect the dynamical response to global warming is an important topic of future research.

The response of the Southern Hemispheric eddy-driven jet to future changes in shortwave radiation in CMIP5

A strong relationship is found between changes in the meridional gradient of absorbed shortwave radiation (ASR) and Southern Hemispheric jet shifts in 21st century climate simulations of CMIP5 (Coupled Model Intercomparison Project phase 5) coupled models. The relationship is such that models with increases in the meridional ASR gradient around the southern midlatitudes, and therefore increases in midlatitude baroclinicity, tend to produce a larger poleward jet shift. The ASR changes are shown to be dominated by changes in cloud properties, with sea ice declines playing a secondary role. We demonstrate that the ASR changes are the cause, and not the result, of the intermodel differences in jet response by comparing coupled simulations with experiments in which sea surface temperature increases are prescribed. Our results highlight the importance of reducing the uncertainty in cloud feedbacks in order to constrain future circulation changes.

The role of evaporating showers in the transfer of sting-jet momentum to the surface

The most damaging winds in a severe extratropical cyclone often occur just ahead of the evaporating ends of cloud filaments emanating from the so-called cloud head. These winds are associated with low-level jets (LLJs), sometimes occurring just above the boundary layer. The question then arises as to how the high momentum is transferred to the surface. An opportunity to address this question arose when the severe ‘St Jude's Day’ windstorm travelled across southern England on 28 October 2013. We have carried out a mesoanalysis of a network of 1 min resolution automatic weather stations and high-resolution Doppler radar scans from the sensitive S-band Chilbolton Advanced Meteorological Radar (CAMRa), along with satellite and radar network imagery and numerical weather prediction products. We show that, although the damaging winds occurred in a relatively dry region of the cyclone, there was evidence within the LLJ of abundant precipitation residues from shallow convective clouds that were evaporating in a localized region of descent. We find that pockets of high momentum were transported towards the surface by the few remaining actively precipitating convective clouds within the LLJ and also by precipitation-free convection in the boundary layer that was able to entrain evaporatively cooled air from the LLJ. The boundary-layer convection was organized in along-wind rolls separated by 500 to about 3000 m, the spacing varying according to the vertical extent of the convection. The spacing was greatest where the strongest winds penetrated to the surface. A run with a medium-resolution version of the Weather Research and Forecasting (WRF) model was able to reproduce the properties of the observed LLJ. It confirmed the LLJ to be a sting jet, which descended over the leading edge of a weaker cold-conveyor-belt jet.

Climatic simulations of the eastern Andes low-level jet and its dependency on convective parameterizations

The South American low level jet (SALLJ) of the Eastern Andes is investigated with Regional Climate Model version 3 (RegCM3) simulations during the 2002-2003 austral summer using two convective parameterizations (Grell and Emanuel). The simulated SALLJ is compared with the special observations of SALLJEX (SALLJ Experiment). Both the Grell and Emanuel schemes adequately simulate the low level flow over South America. However, there are some intensity differences. Due to the larger (smaller) convective activity, the Emanuel (Grell) scheme simulates more intense (weaker) low level wind than analysis in the tropics and subtropics. The objectives criteria of Sugahara (SJ) and Bonner (BJ) were used for LLJ identification. When applied to the observations, both criteria suggest a larger frequency of the SALLJ in Santa Cruz, followed by Mariscal, Trinidad and Asuncin. In Mariscal and Asuncin, the diurnal cycle indicates that SJ occurs mainly at 12 UTCs (morning), while the BJ criterion presents the SALLJ as more homogenously distributed. The concentration into two of the four-times-a-day observations does not allow conclusions about the diurnal cycle in Santa Cruz and Trinidad. The simulated wind profiles result in a lower than observed frequency of SALLJ using both the SJ and BJ criteria, with fewer events obtained with the BJ. Due to the stronger simulated winds, the Emanuel scheme produces an equal or greater relative frequency of SALLJ than the Grell scheme. However, the Grell scheme using the SJ criterion simulates the SALLJ diurnal cycle closer to the observed one. Although some discrepancies between observed and simulated mean vertical profiles of the horizontal wind are noted, there is large agreement between the composites of the vertical structure of the SALLJ, especially when the SJ criterion is used with the Grell scheme. On an intraseasonal scale, a larger southward displacement of SALLJ in February and December when compared with January has been noted. The Grell and Emanuel schemes simulated this observed oscillation in the low-level flow. However, the spatial pattern and intensity of rainfall and circulation anomalies simulated by the Grell scheme are closer to the analyses than those obtained with the Emanuel scheme.

Reduction kinetics of NiO-YSZ composite for application in solid oxide fuel cell

A porous nickel-8 mol% yttria stabilized zirconia (Ni-8YSZ) composite, used as anode for solid oxide fuel cell, was obtained by reduction of NiO-8YSZ cermet. The first goal was the evaluation of the temperature effect of powder processing by thermogravimetry. In addition, the influence of porosity in the reduction kinetic of the sample sintered at 1450 A degrees C was evaluated. The final porosity produced in NiO-8YSZ composite by pore former was 30.4 and 37.9 vol.%, respectively, for 10 and 15 mass% of corn starch. The sample with 15 mass% of corn starch promotes a reduction rate almost twice higher than sample with 10 mass% of corn starch. The porosity introduced by the reduction of NiO was 23 vol.%.

Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO(2) start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H(2)/CO, the formation of CO(2) is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. (C) 2008 Elsevier Ltd. All rights reserved.

Hydrogen purification for fuel cell using CuO/CeO(2)-Al(2)O(3) catalyst

CuO/CeO(2), CuO/Al(2)O(3) and CuO/CeO(2)-Al(2)O(3) catalysts, with CuO loading varying from 1 to 5 wt.%, were prepared by the citrate method and applied to the preferential oxidation of carbon monoxide in a reaction medium containing large amounts of hydrogen (PROX-CO). The compounds were characterized ex situ by X-ray diffraction, specific surface area measurements, temperature-programmed reduction and temperature-programmed reduction of oxidized surfaces; XANES-PROX in situ experiments were also carried out to study the copper oxidation state under PROX-CO conditions. These analyses showed that in the reaction medium the Cu(0) is present as dispersed particles. On the ceria, these metallic particles are smaller and more finely dispersed, resulting in a stronger metal-support interaction than in CuO/Al(2)O(3) or CuO/CeO(2)-Al(2)O(3) catalysts, providing higher PROX-CO activity and better selectivity in the conversion of CO to CO(2) despite the greater BET area presented by samples supported on alumina. It is also shown that the lower CuO content, the higher metal dispersion and consequently the catalytic activity. The redox properties of the ceria support also contributed to catalytic performance. (C) 2010 Elsevier B.V. All rights reserved.

Potential oscillations in a proton exchange membrane fuel cell with a Pd-Pt/C anode

We report in this paper the occurrence of potential oscillations in a proton exchange membrane fuel cell (PEMFC) with a Pd-Pt/C anode, fed with H(2)/100 ppm CO, and operated at 30 degrees C. We demonstrate that the use of Pd-Pt/C anode enables the emergence of dynamic instabilities in a PEMFC. Oscillations are characterized by the presence of very high oscillation amplitude, ca. 0.8 V. which is almost twice that observed in a PEMFC with a Pt-Ru/C anode under similar conditions. The effects of the H(2)/CO flow rate and cell current density on the oscillatory dynamics were investigated and the mechanism rationalized in terms of the CO oxidation and adsorption processes. We also discuss the fundamental aspects concerning the operation of a PEMFC under oscillatory regime in terms of the benefit resulting from the higher average power output. (c) 2010 Elsevier B.V. All rights reserved.

The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H(2)S-Pt/C interaction products

The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H(2),similar to 20% N(2), and 8 ppm hydrogen sulfide (H(2)S). Cell performance losses are calculated by evaluating cell potential reduction due to H(2)S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H(2)S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H(2)S-contaminated anode feeding stream. (C) 2011 Elsevier B.V. All rights reserved.

Ink-Jet Printing of Color Optical Filters for LCD Applications

At the age of multi-media, portable electronic devices such as mobile phones, personal digital assistant and handheld gaming systems have increased the demand for high performance displays with low cost production. Inkjet printing color optical filters (COF) for LCD applications seem to be an interesting alternative to decrease the production costs. The advantage of inkjet printing technology is to be fast, accurate, easy to run and cheaper than other technologies. In this master thesis work, we used various disciplines such as optical microscopy, rheology, inkjet printing, profilometering and colorimetry. The specific aim of the thesis was to investigate the feasibility of using company-A pigment formulation in inkjet production of COF for active matrix LCD applications. Ideal viscosity parameters were determined from 10 to 20mPa·s for easy inkjet printing at room temperature. The red pigments used are fully dispersed into the solvent and present an excellent homogenous repartition after printing. Thickness investigations revealed that the printed COF were equal or slightly thicker than typically manufactured ones. The colorimetry investigations demonstrated color coordinates very close to the NTSC red standard. LED backlighting seems to be a valuable solution to combine with the printed COF regarding to the spectrum and color analysis. The results on this thesis will increase the understanding of inkjet printing company-A pigments to produce COF for LCD applications.

In Bio-Fuel We Trust

In bio-fuel we trust. Or do we? In this chapter, ethnographic material from Sweden is used to discuss ways sin which trust may influence the choice of bio-fuel for heating purposes. The meaning and substance of trust or distrust, as well as the very conditions for trust, are elaborated on in relation to solar and bio-pellet systems, district heating with bio-fuel, and traditional fireplaces. An important conclusion of this chapter is that the degree to which people perceive others as being like themselves or not tends to be decisive for whether these others are to be trusted, and therefore worth listening to. The context and situation in which a certain heating system is being chosen does not only involve trust in individuals, however, but in companies and the authorities, as well as in the arterfacts themselves. An example is given on how distrust of district heating companies led house owners to reject an offer of district heating despite the comfort and environmental benefit this could have provided. it is shown how this distrust might be resolved by making the rhythm of households and sitrict heating companies more in step with one another. The strong emotional attachment to and deep-felt trust in the traditional fireplace is also analysed, and a question is put forward as to whether these feelings could be transferred to modern bio-pellet stoves. Finally, our great and assured trust in bio-fuel as a main solution to global climate change is shortly commented upon and partly questioned.