Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Iron pyrite films prepared by sulfur vapor transport

Iron films deposited via thermal evaporation, with a thickness between 100 and 250 nm, were converted into FeS₂ by open sulfur transport using nitrogen as a gas vector. The films thus obtained constituted a single pyrite phase and were optically highly absorbing. The sulfurization process was optimized. As a result, sample temperature and conversion time were found to be the major determining parameters. The films were characterized using several methods. The crystallinity and phase identification were determined by X-ray diffractometry. Scanning electron microscopy showed a homogeneous surface of both iron and pyrite layers. Optical transmission measurements confirmed the highly absorbing character of FeS₂ and allowed the determination of direct (1.35 eV) and indirect (0.82 eV) transitions.     

Improvement of oxygen mass transfer estimation from oxygen concentration measurements in bubble column reactors

An original procedure has been established for estimating the overall volumetric mass transfer coefficient using the oxygen concentration curves resulting from the usual gassing-in and gassing-out method. This procedure was applied to experimental data obtained in a small scale bubble column using both tap water and a coalescence-inhibiting liquid mixture that represents the coalescence behavior of biological media. It is based on the analysis of the characteristics times of the system, including those of the hydrodynamics of the two phases, the sensor dynamics and the system inertia when the gas composition is modified. A numerical procedure was developed to estimate the characteristic time of the system inertia t_i, using the assumption that this inertia is nearly independent of superficial gas velocity U_G. The calculations confirmed that the optimized t_i value was nearly independent of U_G and of the coalescence behavior of the liquid phase. Additionally, the resulting K_La_L values for tap water were closer to the correlation of Shah et al. [1982. Design parameters estimations for bubble column reactors. A.I.Ch.E. Journal 28, 353-379] than those of other conventional models. Finally, the original procedure was also reported to reduce significantly the square sum deviation between the predicted and the measured oxygen response curves.     

Solar cookers for outdoors and indoors

The solar cooking process has been investigated to develop safe, simple, portable, and reliable solar cookers. The concept of insulated and vapor-tight pots has been introduced and applied to oven, point-focus and heat-pipe cookers. A new, flat-plate cooker with heat pipes has been developed. It requires no tracking and allows cooking to be done in the shade or indoors. Also, a novel-portable cooker, the Mina Oven, featuring a vapor-tight pot and an integral collector with reflector flaps, has been constructed and tested. A second portable cooker that has been developed is the Arafa Cooker, which comprises a parabolic dish focused at a glazed and insulated receiver. Experiments indicated that all cookers yielded satisfactory performance, with cooking times of 25–45 min per kg of food per m² of solar collection area while operating from 10 a.m. to 4 p.m.     

SOLUBILITY AND DIFFUSIVITY OF GASES IN AN ORGANIC SOLUTION OF AMINE

Solubilities and diffusivities of carbon dioxide and nitrous oxide in a mixture of toluene and isopropanol organic solution of cyclohexylamine were measured at 20°C in the range of pressures of solute from 1 to 3 bars. This was performed with an original chromatographic technique taking into account the presence of the product of the reaction.     

Simultaneous measurement of gas hold-up and mass transfer coefficient by tracer dynamic technique in “Emulsair” reactor with an emulsion-venturi distributor

Hydrodynamics and gas-liquid mass transfer have been investigated in an “Emulsair” reactor with cocurrent downflow of gas and liquid. This consists of a cylindrical tank with conical bottom topped by an emulsion-venturi as the gas-liquid distributor in which the gas is self-aspired by action of the kinetic energy of the liquid recirculation. An original tracer dynamic technique using the CO₂-N₂/water system that enables the simultaneous measurement of overall gas hold-up and overall volumetric mass transfer coefficient has been developed and validated using conventional techniques, such as volume expansion for gas hold-up and dynamic oxygenation for mass transfer. It has been shown that gas hold-up and K_La_L can be deduced from the moments of experimental response curves using a CO₂ pulse in the gas feed. Experimental results have proved that hydrodynamics and mass transfer in the Emulsair reactor are strongly influenced by the flow regime in the divergent. Two different regimes have been observed depending on the liquid recirculation flow rate: annular and homogeneous bubbling flows. In both regimes, self-aspired gas flow rate, gas hold-up and K_La_L have been reported to increase with the liquid flow rate. The operation effectiveness, estimated from the gas-to-liquid flow rate ratio, has been shown to pass through a maximum around 0.59 as a function of liquid recirculation. A comparison with the literature proved that this maximum is higher than those observed for other kinds of gas-liquid reactors equipped with a venturi. Correlations for mass transfer estimation have been derived and are in agreement with the literature.     

Study of Hydrodynamics,Mixing and Gas‐Liquid Mass Transfer in a Split‐Rectangular Airlift Reactor

Global hydrodynamic characteristics, liquid mixing and gas‐liquid mass transfer for a 63 L split‐rectangular airlift reactor were studied. Correlations for gas holdup and overall liquid circulation velocity were derived for the air‐water system as a function of the specific power input; these were compared to data and correlations for reactor volumes between 4.7 L and 4600 L. A partial recirculation of small bubbles in the riser was observed when U_gr > 0.03 m/s, which was attributed to the use of a single‐orifice nozzle as the gas phase distributor. The dimensionless mixing time and the overall axial dispersion coefficient were nearly constant for the range of gas flow rates studied. However, values of K_L/d_B were greater than those reported in previous studies and this is caused by the partial recirculation of the gas phase in the riser. While scale effects remain slight, the use of a gas distributor favouring this partial recirculation seems adequate for mass transfer in split‐rectangular airlift reactors.     

Investigations on mode-division multiplexed free-space optical transmission for inter-satellite communication link

Wireless Networks - Inter-satellite data transmission links are very crucial for providing global inter-connectivity. We report designing and investigations on high date rate inter-satellite...