Effects of alkali promoters on the textural and catalytic properties of mesoporous Fe–Al–Cu catalysts for water gas shift reaction

Mesoporous Fe₂O₃–Al₂O₃–CuO catalysts promoted with alkali oxides were synthesized and used in water gas shift reaction (WGSR) at high temperatures for hydrogen purification. These chromium-free catalysts were characterized using nitrogen adsorption/desorption, hydrogen temperature programmed reduction, X-ray diffraction (XRD), and transmission electron microscopy techniques. The synthesized catalysts with narrow single-modal pore size distribution in mesopore region possessed high specific surface area. The catalytic results revealed that except Cs, the addition of other alkali promoters declined the catalytic activity. However, all catalysts showed higher catalytic performance than the conventional commercial catalyst. The results showed an optimum content of Cs promoter (3 wt.%) for the promoted Fe–Al–Cu catalyst (3 wt.% Cs-FAC), which exhibited the highest activity in WGSR at high temperature.     

Promotional effect of transition metal doping on the properties of KF/CaO catalyst for biodiesel synthesis

A series of heterogeneous KF/CaO catalysts modified with transition metals (lanthanum, cerium, and zirconium) were prepared via wet impregnation method and applied to the trsansesterification process of waste cooking oil (WCO) as feedstock with methanol to biodiesel production. The structure, performance of the solid catalysts was characterized by X-ray diffraction (XRD), temperature programmed desorption of CO₂ (CO₂-TPD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The effect of methanol/oil molar ratio, ¹reaction time, reaction temperature, catalyst amount, and stability was investigated. The results showed that 10 wt% of lanthanum, cerium, and zirconium improved the catalytic activity of KF/CaO catalyst. The maximum catalytic activity using the lanthanum doping of 10wt% on KF/CaO catalyst was reached 98.7% under the optimal reaction condition of methanol/oil molar ratio of 12:1, reaction for 1 h at reaction temperature of 65°C, and 4% (wt/wt oil) catalyst amount. In addition, the FAME yield of KF/CaO/La catalyst remained higher than 95% after 10 cycles. The promotional effect of lanthanum doping could be attributed to the enhancement of the basicity strength of KF/CaO catalyst and block the leach of Ca²⁺ in the transesterification reaction.     

ZrxMg1-xO supported cobalt catalysts for methane decomposition into COx-free hydrogen and carbon nanotubes

Zirconia-magnesia supported cobalt catalysts with various Zr/Mg atomic ratios were prepared and evaluated for non-oxidative catalytic decomposition of methane to produce CO_x-free hydrogen and carbon nanotube. The catalytic performance of the catalysts was performed in a continuous fixed bed flow reactor at 700°C under atmospheric pressure. The fresh and spent catalysts were characterized by XRD, TPR, BET, TEM, and Raman spectroscopy. The results showed that the change in Zr/Mg ratio of the mixed oxide support has a significant effect on the catalytic performance of the active Co metal. The catalyst 30%Co/Zr_0.8Mg_0.2 showed the highest activity and stability within the used series of catalysts with hydrogen yield reached up to 79%. Both Co/Mg_1.0 and Co/Zr_1.0 showed poor stability due to strong Co-Mg interaction and aggregation of Co species on Zr support, respectively. All catalysts produced mainly MWCNTs with different diameters depending on the Zr/Mg ratio. The outer diameter increased with increasing Zr content in the catalyst due to the enlargement of the particle size of cobalt as a result of aggregation.     

Dry reforming of methane over oil palm shell activated carbon and ZSM-5 supported cobalt catalysts

In this study, cobalt supported oil palm shell activated carbon (Co/OPS-AC) and ZSM-5 zeolite (Co/ZSM-5) catalysts have been prepared for dry reforming of methane. Cobalt ratios of 6.0 and 14.0 wt% were deposited via wet impregnation method to the OPS-AC and ZSM-5 catalysts. The catalysts were characterized by XRD, N₂ adsorption--desorption isotherms, BET surface area, SEM, FESEM-EDX, TPR-H₂, and TPD-NH₃. The dry reforming of methane was performed using a micro reactor system under the condition of 10,000 ml/h.g-cat, 3 atm, CH₄/CO₂ ratio of 1.2:1.0 and temperature range from 923 K to 1023 K. The gaseous products were analyzed by gas chromatography (GC) with thermal conductivity detector (TCD) and further quantified to determine the conversions of CH₄ and CO₂, and the yields of CO and H₂. Experimental results revealed both catalysts exhibited lower conversions of CO₂ and CH₄ with the increase in temperature from 923 K to 1023 K. The reduced conversions may be due to the formation of carboneous substance on the catalyst known as coking. Comparatively, Co/OPS-AC gave higher conversions of CO₂ and CH₄ as well as higher yields of H₂ and CO as it has a higher surface area than Co/ZSM-5 which subsequently rendered higher activity for the reforming of methane. With the increasing cobalt loadings and reaction temperature, OPS-AC(14) catalyst exhibited improved activity and H₂/CO ratio. Based on these results, cobalt supported OPS activated carbon catalyst was suggested to be more effective for CO₂ and CH₄ conversions.     

Evaluating the potential of CNT-supported Co catalyst used for gas pollution removal in the incineration flue gas

This study investigated the use of Cu/Al₂O₃, Co/Al₂O₃, Fe/Al₂O₃, and Ni/Al₂O₃ catalysts for the growth of carbon nanotubes (CNTs). These CNTs were used as support for Co catalyst preparation and Co/CNT catalysts were applied to a catalytic reaction to remove BTEX, PAHs, SO₂, NO, and CO simultaneously in a pilot-scale incineration system. The analyzed results of EDS and XRD showed low metal content and good dispersion characteristics of the Al₂O₃-supported catalysts by excess-solution impregnation. FESEM analyzed results showed that the CNTs that were synthesized from Co, Fe, and Ni catalysts had a diameter of 20 nm, whereas those synthesized from Cu/Al₂O₃ had a diameter of 50 nm. Pilot-scale test results demonstrated that the Co/CNT catalyst effectively removed air pollutants in the catalytic reaction and that there was no obvious deactivation by Pb, water vapor, and coke deposited in the process. The thermal stabilization at 250 °C and hydrophobicity properties of CNTs enhanced the application of CNT catalysts in flue gas.     

Combined steam-dry reforming of toluene in syngas over CaNiRu/Al2O3 catalysts

Cracking, steam reforming, dry reforming, and combined steam and dry reforming of toluene in model syngas were performed using catalysts to simulate tar removal produced during biomass gasification. The catalysts were prepared by adding Ru, Ca, and Mn to Ni-based catalysts, and their properties were measured using BET, pulse CO chemisorption, XRD and TG. In steam and dry reforming of toluene, a high toluene conversion was observed with increasing Ca content in the catalyst and catalysts containing Ca showed a higher activity than those containing Mn. In combined steam-dry reforming with syngas, 1%CaNiRu/Al₂O₃ indicated a conversion of 93.9% at 800°C.     

Experimental evaluation of the catalytic efficiency of calcium based natural and modified catalyst for biodiesel synthesis

Transesterification of a mixture of vegetable oils with methanol using metal oxide catalysts derived from snail shell (SS) for biodiesel production was investigated. The metal oxides obtained from calcined snail shells in the temperature range of 650°–950 °C and modified by loading different potassium salts were used as a catalyst in the process. The catalysts were characterized by FT-IR, XRD, SEM-EDS, XPS and TGA. Catalytic activities of developed catalysts were also tested by Hammet indicator method and ion exchange method. The best calcination conditions were observed at 850°C for 4 hours based on biodiesel yield. The KF loaded snail shell gave highest biodiesel yield of 98 ± 1% in a batch reactor with highest basicity (15.9 mmoles/g) and basic strength measured by Hammet method. The optimized reaction conditions were: reaction temperature 65°C, reaction time 3 hours, methanol to oil molar ratio 9:1 and catalyst concentration 3wt%. Leaching and reusability tests confirm the stability of the catalyst as it encounters only 3% of leaching and small changes in catalytic activity up to five runs in terms of biodiesel yield.     

Design and optimization of new La1−xCexNi1−yFeyO3 (x,y = 0–0.4) nano catalysts in dry reforming of methane

The paper reports the production of syngas from dry reforming of methane (DRM) over La_1?xCe_xNi_1?yFe_yO₃ (x, y = 0–0.4) perovskites. A series of La_1?xCe_xNi_1?yFe_yO₃ were designed by central composite design (CCD) and synthesized by a sol–gel auto combustion method. Artificial neural network (ANN) approach was used to determine the relationship between preparation and operational parameters on the performance of the catalysts in the DRM process. Nickel mole fraction, lanthanum mole fraction, calcination temperature, and reaction temperature were considered as input variables, and conversion of methane was considered as the output variable. An ANN model with nine neurons in the hidden layer was the suitable in predicting conversion of methane. The genetic algorithm (GA) was subsequently used to determine the optimal preparation condition for enhancing the conversion of methane. La_0.6Ce_0.4Ni_0.99Fe_0.01O₃ catalyst, calcined at 756°C was obtained to be the most active catalyst owing to the optimal composition of nickel and lanthanum in the catalyst formulation.     

Super effective Zn-Fe-doped TiO2 nanofibers as photocatalyst for ammonia borane hydrolysis

In this study, the photocatalytic activity of TiO₂ nanofibers toward ammonia borane hydrolysis has been strongly modified by doping the nanostructure by ZnO and Fe₂O₃ oxides. Due to the differences in the work function and band gap energy among the three semiconductors (TiO₂, ZnO and Fe₂O₃), illumination of TiO₂ leads to accumulate the electrons and holes on the conduction and valance bands of Fe₂O₃ and ZnO, respectively. Accordingly, the experimental results indicated that the surface of the obtained nanofibers is very active which results in an instant hydrolysis of ammonia borane molecules reaching the active zone surrounding the nanofibers. Moreover, negative activation energy was determined as increasing the temperature led to decrease the photocatalytic performance. Furthermore, kinetic studies indicated that the heterogeneous catalytic reaction describing the ammonia borane hydrolysis process is zero order which additionally supports the super activity of the introduced nanofibers. It was also observed that Fe₂O₃ content in the introduced nanofibers has distinct influence as the best performance was obtained at 1 wt%. The modified TiO₂ nanofibers were prepared by calcination of electrospun nanofibers composed of titanium isopropoxide, zinc acetate and iron acetate in air at 700 °C for 1 h. Overall, the present study opens a new avenue to overcome the fast electrons/holes recombination dilemma facing TiO₂-based nanostructures.     

Producing biodiesel from waste animal oil by modified ZnO

Biodiesel produced by transesterification of waste animal oil is a promising green fuel in the future. ZnO-Al₂O₃ and ZnO/Zn₂Al composition oxides were prepared by co-precipitation method and impregnation method, respectively. The above catalysts were characterized by X-ray diffraction (XRD), Brunauer--Emmett--Teller (BET) and CO₂ adsorption and temperature-programmed desorption (CO₂-TPD) and show that the high activity for the catalyst is attributed to its high alkalinity. The reaction parameters were optimized and the results show that the transesterification ratio of waste animal oil can reach 98.7% with 10% ZnO/Zn₂Al catalyst after 2 h. Moreover, 10%ZnO/Zn₂Al compound oxides can be active for the successive cycles. The glycerol as a predominant by-product after transesterification is of high purity with high use value.     

Production of soybean ethanol-based biodiesel using CaO heterogeneous catalysts promoted by Zn,K and Mg

This article focuses on the optimization of the production of fatty acid ethyl esters from soybean oil using CaO-based heterogeneous catalysts. Three different catalytic promoters were evaluated: Magnesium, zinc, and potassium. The reaction has evaluated the promoter content (promoter to calcium molar ratio), catalyst load, alcohol to oil molar ratio, and temperature. Response surface methodology (RSM) was used to evaluate the influence of each variable on the yield of biodiesel. The addition of K₂O or MgO in the catalyst has enhanced the yield in fatty acid ethyl esters, while the use of ZnO as a promoter was not successful.     

Production of bio-oil from algal biomass and its upgradation to biodiesel using CaO-based heterogeneous catalysts

The present article deals with the production of bio-oil from algal biomass as well as the preparation and characterization of noble CaO-based heterogeneous catalyst for upgradation of bio-oil to biodiesel. The bio-oil has been extracted from algal biomass using hexane as solvent in soxhlet apparatus and upgraded to biodiesel by transesterification using noble CaO-based heterogeneous catalysts. Catalyst with TiO₂:CaO molar ratio of 0.25 and calcination temperature of 700°C has been found to be most suitable among all the catalysts developed. Characterization of the catalysts has been done by using X-ray diffraction (XRD), scanning electron microscope (SEM), and thermo-gravimetric analysis (TGA). The input--output model has been developed to correlate experimental and predicted value of biodiesel yield. Optimization of process parameters has been done using response surface methodology. Various properties and elemental composition of algal bio-oil and biodiesel have been determined and compared with biodiesel.     

Heterostructure CdS/ZnS nanoparticles as a visible light-driven photocatalyst for hydrogen generation from water

(CdS)_x/(ZnS)_1–x nanoparticles were synthesized as a visible light-driven photocatalyst using the stepped microemulsion technique with a series of the ratio factors (x). The photocatalytic test results showed that (CdS)_x/(ZnS)_1-x with x = 0.8 had the highest photo-reactivity for H₂ production from water under visible light. The composite (CdS)_0.8/(ZnS)_0.2 catalyst had a heterogeneous structure that exhibited a much greater photocatalytic hydrogen production activity than either pure CdS or the homogeneous Cd_0.8Zn_0.2S solid solution. ZnS deposition also was shown to largely improve the stability of CdS in the heterostructured CdS/ZnS catalyst. Thermal treatment of the catalyst, i.e., annealing (CdS)_0.8/(ZnS)_0.2 at 723 K, improved the crystallinity of the catalyst and increased its photocatalytic H₂ production rate by more than 36 times. Deposition of Ru on the surface of the catalyst particles by in situ photo-deposition further increased the photo-H₂ generation rate by 3 times. The photocatalyst of 0.5%Ru/CdS/ZnS achieved the highest H₂ production activity, at a rate of 12650 μmol/g-h and with a light to hydrogen energy conversion efficiency of 6.5%.     

Synthesis and use of a catalyst in the production of biodiesel from Pongamia pinnata seed oil with dimethyl carbonate

The preparation of sodium methoxide-treated algae catalysts and their activity in the transesterification of Pongamia pinnata seed oil by dimethyl carbonate were investigated. We also investigated the effect of the sodium methoxide-treated algae catalyst on the biodiesel yield. The development of sodium methoxide-treated algae catalysts can overcome most problems associated with dissolution in dimethyl carbonate. The products were analyzed using gas chromatography-mass spectroscopy to identify the fatty acid methyl esters in the biodiesel produced. The molar ratio of Pongamia pinnata seed oil to dimethyl carbonate in transesterification in the presence of the sodium methoxide-treated algae catalyst was observed to play a substantial role in this study, wherein the Pongamia pinnata seed oil conversion increased with increasing catalyst concentration. The highest percent conversion rate was 97%. With intense research focus and development, an ideal catalyst can indeed be developed for optimal biodiesel production that is both economically feasible and environmentally benign.     

Nanocatalyzed biodiesel synthesis from the oily contents of Marine brown alga Dictyota dichotoma

This research article demonstrates biodiesel synthesis through the methanolysis of the oily contents (4.02 ± 0.27% w/w on dried basis) of Dictyota dichotoma collected from the coast of Hawksbay, Pakistan. The metal oxides (CaO, MgO, ZnO, and TiO₂) used as nanocatalysts were refluxed (5% K₂SO₄), calcinated (850 °C) and characterized by Atomic Force Microscopy (AFM) which produced 93.2% w/w FAME (biodiesel) at relatively mild condition (5% catalyst, 65 °C, 3 h, 18:1 molar ratio) using CaO. Whereas, MgO, ZnO, and TiO₂ produced 92.4%, 72.5%, and 31.8% w/w FAME, respectively at elevated condition (225 °C). Thus, CaO was considered to be the best catalyst among the others. This tri-phase reaction require continuous fast mixing and the yield depends on the reaction parameters like catalyst amount, temperature, reaction time and molar ratio (methanol: oil). The reusability of these heterogeneous catalysts simplified the purification step, reduced the waste generation and make the final product technically and economically viable.     

The proton exchange membrane fuel cell systems using methanolysis of sodium borohydride as a hydrogen source with cobalt catalysts

Constant hydrogen generation via a hydrogen generator is evaluated from the methanolysis of sodium borohydride (NaBH₄) using Co/Al₂O₃ and MnO_x/Al₂O₃ catalysts. Chemical borohydrides coupled with catalysts can be used for compact storage and to create efficient generation systems. Thus, we first report the catalytic activity of MnO_x/Al₂O₃, which is synthesized using the simple wet-impregnation method, for the methanolysis reaction. The results indicate that both catalysts can effectively accelerate the methanolysis reaction and provide constant hydrogen generation rates. Thus, we integrate this hydrogen generation system into a proton exchange membrane fuel cell stack (PEMFC) to determine whether it can be used as a portable power supply. As a result, this fuel cell system operates at 40 W for 1 hr using the hydrogen source supplied from the catalytic methanolysis reaction.     

Transesterification of Pistacia chinensis seed oil using a porous cellulose-based magnetic heterogeneous catalyst

In the present work, a novel cellulose-based porous heterogeneous solid acid catalyst encapsulation of ferriferous oxide (Fe₃O₄) and sulfonated graphene (GO-SO₃H) into cellulose to form composite porous microspheres catalyst (GO-SO₃H/CM@Fe₃O₄)was synthesized and evaluated for biodiesel production from Pistacia chinensis seed oil. The SEM, EDS and FTIR analysis revealed that the catalyst GO-SO₃H/CM@Fe₃O₄ owned stronger active sites and GO-SO₃H dispersed well in porous surface and inside of cellulose support. Under the optimum conditions, microwave-assisted transesterification process was carried out with the best catalyst amount, i.e. 5 wt% GO-SO₃H/CM@Fe₃O₄ (weight ratio of GO-SO₃H/cellulose), and conversion yield reached 94%. The prepared catalyst could be easily separated from reaction solution by extra magnetic field and reclaimed at least five runs.     

Lean methane premixed combustion over a catalytically stabilized zirconia foam burner

This study experimentally investigates lean methane/air premixed combustion in a catalytic zirconia foam burner. The burner is packed with an inert perforated alumina plate at the inlet preheating zone and with catalytic zirconia foams at the combustion zone. Catalytic foams are prepared by using a modified perovskite catalyst (LaMn_0.4Co_0.6O₃), in which the transition metal ion Co is partially substituted by Mn and supported by inert zirconia foam. Results indicate that the flame stability limits of both catalytic and inert burners expand with increasing equivalence ratios. The stable combustion region of the catalytic burner is larger than that of the inert burner. The heterogeneous catalytic combustion effect can decrease and increase the lower and upper flame stability limits, respectively. The central temperatures of the flame fronts are higher in the catalytic burner than in the inert burner. The pressure drops of the catalytic burner are almost equal to those of the inert burner in cold flows but are significantly higher than those in the inert burner in reaction flows. Less amounts of carbon monoxide, nitric oxides, and unburned hydrocarbon emissions are detected in the catalytic burner relative to the inert burner. The thermal radiation efficiencies of the catalytic burner vary between 0.24 and 0.39 and are favorably superior to those of the inert burner, ranging from 0.11 to 0.20.     

Ferric-manganese doped sulphated zirconia nanoparticles catalyst for single-step biodiesel production from waste cooking oil: Characterization and optimization

Biodiesel of waste cooking oil origin is gaining attention as a replacement for current fossil fuels, as its low-priced, recycled feedstock shall prevent food source competition, which is estimated to happen with current biodiesel production processes. As a result, waste cooking oil has been claimed to be a highly potential feedstock for biodiesel production. In the present research work, Fe-Mn doped sulphated zirconia catalyst was synthesized and used in simultaneous esterification and transesterification of waste cooking oil to biodiesel synthesis. The catalyst was prepared through the impregnation method and characterized by using XRD, TPD-NH_3, FT-IR, BET, and TEM. Response surface methodology (RSM) in conjunction with the central composite design (CCD) was applied to statistically evaluate and optimize the biodiesel preparation process. It was found that the synthesis of biodiesel achieved an optimum level of 97.2% waste cooking oil methyl ester’s (WCOME’s) yield at the following reaction conditions: methanol/oil molar ratio: 10:1, catalyst concentration: 3.0 wt %, and reaction temperature: 160 °C. The extremely high WCOME’s yield of 97.2% was proved to be due to high acidity, surface area, and large pore diameter; reactants can easily diffuse into the interior pore of the catalyst and allow them to be in contact with active sites that enhance catalytic activity.     

High-affinity ouabain receptors: primary membrane sensors for ionizing radiation

Although the high sensitivity of the Na/K pump in cell membrane to ionizing radiation is well known in literature, the individual role of different isoforms of pump in determination of its radio-sensitivity is not clear yet. This is the subject of the present investigation. Using isotope, electro-physiological and enzymological methods, the effect of γ-ionizing radiation on cell membrane voltage-current characteristics, acetylcholine-induced membrane current, ²²Na⁺ and ⁴⁵Ca²⁺ exchange between cells and bathing solution, Na+K⁺-ATPase activity, dose-dependent ouabain binding with cell membrane, intracellular cAMP and membrane phosphorylation in snail neurons were studied. The changes in neurons as a result of 30-min γ-radiation exposure of snails to 5.16 Ci/kg at the end of the first 30 min of post-radiation period were as follows: the increase in membrane ionic conductance reversed the ouabain sensitivity of acetylcholine-induced currents, stimulation of ²²Na⁺ and ⁴⁵Ca²⁺ uptakes, inhibition of Na/K pump, activation Na/Ca exchange in reversed mode, increase in ouabain binding with high-affinity α₃ and decrease with α₂ middle-affinity receptors, decrease in intracellular cAMP content and membrane dephosphorylation. On the basis of the obtained data, it is suggested that both α₃ and α₂ catalytic subunits of Na⁺+K⁺-ATPase serve primary membrane sensors through the activation of which the biological effect of γ-radiation on neurons is realized. The IR has activation effects on α₃-dependent Na⁺/Ca²⁺ exchange in forward and its inactivation on α₂-dependent reverse modes.