Capacitive and Infrared Gas Sensors for the Assessment of the Methane Number of LNG Fuels.

Liquid Natural Gas (LNG) is an energy source that is becoming more important in energy transition, as the world is facing lower the CO2 emissions and backup sources for wind and solar energy are needed. LNG is becoming a major player not only as fuel for power plants, but also in transport and mobility. However, the composition of LNG varies significantly between the various production locations around the world, and the layering of hydrocarbons with different molecular weights takes place even in LNG containers. This is especially critical for LNG engines, in which the ignition properties of the gas depend heavily on the fuel quality or Methane Number (MN) of the gas. For optimized engine operation and motor management, this fuel quality should be measured regularly, preferably online and by a small and low-cost sensor. This paper presents two sensor solutions for the assessment of the full gas composition. For both sensors, the standard deviation in the composition of the relevant hydrocarbons was low enough to calculate the Methane Number with an accuracy of approximately 1 MN unit. It was demonstrated that the electronic capacitive sensor was better suited to assess the higher hydrocarbons, whereas the infrared sensor showed higher selectivity for the lower hydrocarbons.

A Versatile Capacitive Sensing Platform for the Assessment of the Composition in Gas Mixtures.

The energy market is facing a major transition, in which natural gas and renewable gasses will play an important role. However, changing gas sources and compositions will force the gas transporters, gas engine manufacturers, and gas grid operators to monitor the gas quality in a more intensive way. This leads to the need for lower cost, smaller, and easy to install gas quality sensors. A new approach is proposed in this study that is based on the chemical interactions of the various gas components and responsive layers applied to an array of capacitive interdigitated electrodes. For Liquid Natural Gas (LNG), containing a relative high concentration of higher hydrocarbons, an array of ten capacitive chips is proposed, that is sufficient to calculate the full composition, and can be used to calculate energy parameters, such as Wobbe Index, Calorific Value, and Methane Number. A first prototype was realized that was small enough to be inserted in low and medium pressure gas pipes and LNG engine fuel lines. Adding the pressure and temperature data to the chip readings enables the determination of the concentrations of the various alkanes, hydrogen, nitrogen, and carbon dioxide, including small fluctuations in water vapor pressure. The sensitivity and selectivity of the new sensor is compared to a compact analyzer employing tunable filter infrared spectrometry.

Sunlight-Fueled, Low-Temperature Ru-Catalyzed Conversion of CO2 and H2 to CH4 with a High Photon-to-Methane Efficiency.

Methane, which has a high energy storage density and is safely stored and transported in our existing infrastructure, can be produced through conversion of the undesired energy carrier H2 with CO2. Methane production with standard transition-metal catalysts requires high-temperature activation (300-500 °C). Alternatively, semiconductor metal oxide photocatalysts can be used, but they require high-intensity UV light. Here, we report a Ru metal catalyst that facilitates methanation below 250 °C using sunlight as an energy source. Although at low solar intensity (1 sun) the activity of the Ru catalyst is mainly attributed to thermal effects, we identified a large nonthermal contribution at slightly elevated intensities (5.7 and 8.5 sun) resulting in a high photon-to-methane efficiency of up to 55% over the whole solar spectrum. We attribute the excellent sunlight-harvesting ability of the catalyst and the high photon-to-methane efficiency to its UV-vis-NIR plasmonic absorption. Our highly efficient conversion of H2 to methane is a promising technology to simultaneously accelerate the energy transition and reduce CO2 emissions.

Compositional and electric field dependence of the dissociation of charge transfer excitons in alternating polyfluorene copolymer/fullerene blends.

The electro-optical properties of thin films of electron donor-acceptor blends of a fluorene copolymer (PF10TBT) and a fullerene derivative (PCBM) were studied. Transmission electron microscopy shows that in these films nanocrystalline PCBM clusters are formed at high PCBM content. For all concentrations, a charge transfer (CT) transition is observed with absorption spectroscopy, photoluminescence, and electroluminescence. The CT emission is used as a probe to investigate the dissociation of CT excited states at the donor-acceptor interface in photovoltaic devices, as a function of an applied external electric field and PCBM concentration. We find that the maximum of the CT emission shifts to lower energy and decreases in intensity with higher PCBM content. We explain the red shift of the emission and the lowering of the open-circuit voltage (V(OC)) of photovoltaic devices prepared from these blends with the higher relative permittivity of PCBM (epsilon(r) = 4.0) compared to that of the polymer (epsilon(r) = 3.4), stabilizing the energy (E(CT)) of CT states and of the free charge carriers in blends with higher PCBM concentration. We show that the CT state has a short decay time (tau = ca. 4 ns) that is reduced by the application of an external electric field or with increasing PCBM content. The field-induced quenching can be explained quantitatively with the Onsager-Braun model for the dissociation of the CT states when including a high electron mobility in nanocrystalline PCBM clusters. Furthermore, photoinduced absorption spectroscopy shows that increasing the PCBM concentration reduces the yield of neutral triplet excitons forming via electron-hole recombination, and increases the lifetime of radical cations. The presence of nanocrystalline domains with high local carrier mobility of at least one of the two components in an organic heterojunction may explain efficient dissociation of CT states into free charge carriers.

Charge transfer absorption for pi-conjugated polymers and oligomers mixed with electron acceptors.

Pi-conjugated polymers and oligomers show charge transfer (CT) absorption bands when mixed with electron acceptors in chloroform solution. This is attributed to the formation of (ground state) donor-acceptor complexes in solution. By varying the concentration of the donor and acceptor, the extinction coefficient for the CT absorption and the association constant of donor and acceptor are estimated. The spectral position of the CT bands correlates with the electrochemical oxidation potential of the pi-conjugated donor and the reduction potential of the acceptor.

Large area liquid crystal monodomain field-effect transistors.

Butyl, hexyl, and decyl derivatives of the liquid-crystalline organic semiconductor 5,5' '-bis(5-alkyl-2-thienylethynyl)-2,2':5',2' '-terthiophene were synthesized and studied with respect to their structural, optical, and electrical properties. By means of an optimized thermal annealing scheme the hexyl and decyl compounds could be processed into self-assembled monodomain films of up to 150 mm in diameter. These were investigated with X-ray diffractometry, which revealed a clearly single-crystalline monoclinic morphology with lamellae parallel to the substrate. Within the lamellae the molecules were found to arrange with a tilt of about 50 degrees with the rubbing direction of the polyimide alignment layer. The resulting, close side-to-side packing was confirmed by measurements of the UV/vis absorption, which showed a dichroic ratio of 19 and indicated H-aggregation. AFM analyses revealed self-affinity in the surface roughness of the monodomain. The compounds showed bipolar charge transport in TOF measurements, with hole mobilities reaching up to 0.02 cm(2)/Vs and maximum electron mobilities around 0.002 cm(2)/Vs. The hexyl derivative was processed into large-area monodomain top-gate field-effect transistors, which were stable for months and showed anisotropic hole mobilities of up to 0.02 cm(2)/Vs. Compared to multidomain bottom-gate transistors the monodomain formation allowed for a mobility increase by 1 order of magnitude.