Optimizing Hydrogen Production: Influence of Promoters in Methane Decomposition on Titania-Modified-Zirconia Supported Fe Catalyst.

This study addresses the pivotal challenge of hydrogen production through methane decomposition, offering a pathway to achieving clean energy goals. Investigating the utilization of titania-modified zirconia dual redox supports (10TiZr) in iron or doped iron-based catalysts for the CH4 decomposition reaction, our research involves a thorough characterization process. This includes analyses of the surface area porosity, X-ray diffraction, Raman-infrared spectroscopy, and temperature-programmed reduction/oxidation. The observed sustained enhancement in catalytic activity over extended durations suggests the in situ formation of catalytically active sites. The introduction of Co or Ni into the 30Fe/10TiZr catalyst leads to the generation of a higher density of reducible species. Furthermore, the Ni-promoted 30Fe/10TiZr catalyst exhibits a lower crystallinity, indicating superior dispersion. Notably, the cobalt-promoted 30Fe/10TiZr catalyst achieves over 80% CH4 conversion and H2 yield within 3 h. Additionally, the Ni-promoted 30Fe/10TiZr catalyst attains a remarkable 87% CH4 conversion and 82% H2 yield after 3 h of the continuous process.

Fluoride Removal Using Nanofiltration-Ranged Polyamide Thin-Film Nanocomposite Membrane Incorporated Titanium Oxide Nanosheets.

Drinking water defluoridation has attracted significant attention in the scientific community, from which membrane technology, by exploring thin film nanocomposite (TFN) membranes, has demonstrated a great potential for treating fluoride-contaminated water. This study investigates the development of a TFN membrane by integrating titanium oxide nanosheets (TiO2 NSs) into the polyamide (PA) layer using interfacial polymerization. The characterization results suggest that successfully incorporating TiO2 NSs into the PA layer of the TFN membrane led to a surface with a high negative charge, hydrophilic properties, and a smooth surface at the nanoscale. The TFN membrane, containing 80 ppm of TiO2 NSs, demonstrated a notably high fluoride rejection rate of 98%. The Donnan-steric-pore-model-dielectric-exclusion model was employed to analyze the effect of embedding TiO2 NSs into the PA layer of TFN on membrane properties, including charge density (Xd), the pore radius (rp), and pore dielectric constant (εp). The results indicated that embedding TiO2 NSs increased Xd and decreased the εp by less than the TFC membrane without significantly affecting the rp. The resulting TFN membrane demonstrates promising potential for application in water treatment systems, providing an effective and sustainable solution for fluoride remediation in drinking water.

Impact of Sr Addition on Zirconia-Alumina-Supported Ni Catalyst for COx-Free CH4 Production via CO2 Methanation.

Zirconia-alumina-supported Ni (5Ni/10ZrO2+Al2O3) and Sr-promoted 5Ni/10ZrO2+Al2O3 are prepared, tested for carbon dioxide (CO2) methanation at 400 °C, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, surface area and porosity, infrared spectroscopy, and temperature-programmed reduction/desorption techniques. The CO2 methanation is found to depend on the dispersion of Nickel (Ni) sites as well as the extent of stabilization of CO2-interacted species. The Ni active sites are mainly derived from the reduction of 'moderately interacted NiO species'. The dispersion of Ni over 1 wt % Sr-promoted 5Ni/10ZrO2+Al2O3 is 1.38 times that of the unpromoted catalyst, and it attains 72.5% CO2 conversion (against 65% over the unpromoted catalyst). However, increasing strontium (Sr) loading to 2 wt % does not affect the Ni dispersion much, but the concentration of strong basic sites is increased, which achieves 80.6% CO2 conversion. The 5Ni4Sr/10ZrO2+Al2O3 catalyst has the highest density of strong basic sites and the highest concentration of active sites with maximum Ni dispersion. This catalyst displays exceptional performance and achieves approximately 80% CO2 conversion and 70% methane (CH4) yield for up to 25 h on steam. The unique acidic-basic profiles composed of strong basic and moderate acid sites facilitate the sequential hydrogenation of formate species in the COx-free CH4 route.

Sustainable biofuel synthesis from non-edible oils: a mesoporous ZSM-5/Ni/Pt catalyst approach.

This work examines the hydrodeoxygenation (HDO) activity of non-edible oils using a high surface area catalyst. The HDO activity was thoroughly examined and contrasted using the high surface area catalyst Ni/Pt-ZSM-5 as well as other supports like MCM-48 and H-beta. Ni/Pt bimetals supported on mesoporous ZSM-5 were created via reverse order impregnation to facilitate HDO of non-edible oils. Techniques such as XRD, FT-IR, BET, HR-TEM, HR-SEM, TPD, and TGA were used to characterize the produced catalysts. The synthesized catalysts considerably influenced the hydrodeoxygenation activities for the synthesis of lengthy chain hydrocarbons in a stainless-steel reactor with a high-pressure fixed bed between 300 and 375 °C under 10-40 bar hydrogen pressure. High levels of Ni/Pt-ZSM-5 acidity, textural, and H2 consumption qualities were discovered. Distributions of the products were also reviewed, along with comparisons of the structure-activity connections.

Microwave-assisted synthesis of Limonia acidissima Groff gum stabilized palladium nanoparticles for colorimetric glucose sensing.

Herein, we present a novel microwave-assisted method for the synthesis of palladium nanoparticles (PdNPs) supported by Limonia acidissima Groff tree extract gum. The synthesized PdNPs were characterized using various analytical techniques, including FTIR, SEM, TEM, UV-visible, and powder XRD analyses. TEM and XRD analysis confirmed that the synthesized LAG-PdNPs are highly crystalline nature spherical shapes with an average size diameter of 7-9 nm. We employed these gum-capped PdNPs to investigate their peroxidase-like activity for colorimetric detection of hydrogen peroxide (H2O2) and glucose. The oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2, catalyzed by PdNPs, produces oxidation products quantified at 652 nm using spectrophotometry. The catalytic activity of PdNPs was optimized with respect to temperature and pH. The developed method exhibited a linear range of detection from 1 to 50 µm, with detection limits of 0.35 µm for H2O2 and 0.60 µm for glucose.

Ni-Fe bimetallic catalysts with high dispersion supported by SBA-15 evaluated for the selective oxidation of benzyl alcohol to benzaldehyde.

A wetness impregnation method was used to impregnate the substrate with a substantial quantity of oleic acid together with a metal precursor, leading to significantly dispersed Ni-Fe bimetallic catalysts based on mesoporous SBA-15. Using a wide variety of characterization methods, such as XRD, BET, and TEM Analysis, the physiochemical properties of the catalyst were determined. The addition of the metal does not have any effect on the structural characteristics of the SBA-15 catalyst, as validated by transmission electron microscopy (TEM), which shows that the prepared SBA-15 supported catalyst has a hexagonal mesoporous structure. The catalytic capabilities of the Ni-Fe-SBA-15 catalysts were evaluated in the conversion of BzOH using tert-butyl hydroperoxide (TBHP) as an oxidant and acetonitrile as a solvent. The Ni/Fe-SBA-15 (NFS-15) catalytic composition is the best of the developed catalysts, with a maximum conversion of 98% and a selectivity of 99%. In-depth investigations were conducted into the molar ratio of TBHP to BzOH, the dosage of the catalyst, the reaction rate, temperature, and solvent. The recycling investigations indicate that the synthesized Ni/Fe-SBA-15 (NFS-15) catalyst seems to be more durable up to seven successive cycles.

Hydrogen Production via Methane Decomposition over Alumina Doped with Titanium Oxide-Supported Iron Catalyst for Various Calcination Temperatures.

The decomposition of methane has been chosen as an alternative method for producing hydrogen. In this study, 20 % Fe was used as the active metal part of the catalyst. To better comprehend the impact of the supporting catalytic properties, alumina and titania-alumina composite were investigated as supports. Iron-based catalysts were prepared by impregnation method and then calcined at different temperatures (300 °C, 500 °C, and 800 °C). The catalysts were examined at 800 °C under atmospheric pressure with a 15 mL/min total flow rate and 2 : 1 CH4 to N2 feed ratio. The textural and morphological characteristics of the fresh calcined and spent catalysts were investigated. The catalytic activity and stability data demonstrated that Fe supported over TiO2-Al2O3 calcined at 500 °C performed the best of all evaluated catalysts with a more than 80 % hydrogen yield. The Raman spectra result showed that graphitic carbon was produced for all used titanium dioxide catalysts. Moreover, according to transmission electron microscopy (TEM) results, the carbon deposited on the catalysts' surface is carbon nanotubes (CNT).

Correlation between the particle size, structural and photoluminescence spectra of nano NiCr2O4 and La doped NiCr2O4 materials.

Nano NiCr2O4 undoped and La doped NiCr2O4 nanorods array were successfully prepared by solution based conventional method[sbcm]. The synthesized samples were characterized by the diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) spectroscopy for finding optical properties. Further, the samples structure confirmed by Fourier transforms infrared (FTIR), and X-ray diffraction (XRD)techniques. High-resolution transmission electron microscopy (HRTEM) analysis revealed the attachment of NiCr2O4 nanorods on surface of nanoparticles. From the results, it was found that the reaction time, band gap energy, and particle size strongly influenced by changing the concentration of La in NiCr2O4. This work is notable for its examination of the impact of the precursor on the optical and structural characteristics of samples of La-doped and undoped NiCr2O4. This was the first time the investigation had been done. The average particle size of the La-doped and undoped NiCr2O4 samples is between 16 and 24 nm.

Alumina-Magnesia-Supported Ni for Hydrogen Production via the Dry Reforming of Methane: A Cost-Effective Catalyst System.

5Ni/MgO and 5Ni/γAl2O3 are pronounced in the line of cheap catalyst systems for the dry reforming of methane. However, the lower reducibility of 5Ni/MgO and the significant coke deposition over 5Ni/γAl2O3 limit their applicability as potential DRM catalysts. The mixing capacity of MgO and Al2O3 may overcome these limitations without increasing the catalyst cost. Herein, a 5Ni/xMg(100 - x)Al (x = 0, 20, 30, 60, 70, and 100 wt. %) catalyst system is prepared, investigated, and characterized with X-ray diffraction, surface area and porosity measurements, H2-temperature programmed reduction, UV-Vis-IR spectroscopy, Raman spectroscopy, thermogravimetry, and transmission electron microscopy. Upon the addition of 20 wt. % MgO into the Al2O3 support, 5Ni/20Mg80Al is expanded and carries both stable Ni sites (derived through the reduction of NiAl2O4) and a variety of CO2-interacting species. CH4 decomposition at Ni sites and the potential oxidation of carbon deposits by CO2-interacting species over 5Ni/20Mg80Al results in a higher 61% H2-yield (against ~55% H2-yield over 5Ni/γAl2O3) with an excellent carbon-resistant property. In the major magnesia support system, the 5Ni/60Mg40Al catalyst carries stable Ni sites derived from MgNiO2 and "strongly interacted NiO-species". The H2-yield over the 5Ni/60Mg40Al catalyst moves to 71%, even against a high coke deposition, indicating fine tuning between the carbon formation and diffusion rates. Ni dispersed over magnesia-alumina with weight ratios of 7/3 and 3/7 exhibit good resistance to coke. Weight ratios of 2/8 and 7/3 contain an adequate amount of reducible and CO2-interactive species responsible for producing over 60% of H2-yield. Weight ratio 6/4 has a proper coke diffusion mechanism in addition to achieving a maximum of 71% H2-yield.

Understanding Coke Deposition Vis-à-Vis DRM Activity over Magnesia-Alumina Supported Ni-Fe, Ni-Co, Ni-Ce, and Ni-Sr Catalysts.

The catalytic conversion of CH4 and CO2 into H2-rich syngas is known as the dry reforming of methane (DRM). The dissociation of CH4 over active sites, coupled with the oxidation or polymerization of CH4-x (x = 1-4), plays a crucial role in determining in determining the DRM product yield and coke deposition. Herein, a series of bimetallic-supported catalysts are prepared by the dispersion of Ni-M (M = Ce, Co, Fe, and Sr) over 60 wt% MgO-40 wt% Al2O3 (60Mg40Al) support. Catalysts are tested for DRM and characterized with XRD, surface area and porosity, temperature-programmed reduction/desorption, UV-VIS-Raman spectroscopy, and thermogravimetry. 2.5Ni2.5Sr/60Mg40Al and 2.5Ni2.5Fe/60Mg40Al, and 2.5Ni2.5Ce/60Mg40Al and 2.5Ni2.5Co/60Mg40Al have similar CO2 interaction profiles. The 2.5Ni2.5Sr/60Mg40Al catalyst nurtures inert-type coke, whereas 2.5Ni2.5Fe/60Mg40Al accelerates the deposition of huge coke, which results in catalytic inferiority. The higher activity over 2.5Ni2.5Ce/60Mg40Al is due to the instant lattice oxygen-endowing capacity for oxidizing coke. Retaining a high DRM activity (54% H2-yield) up to 24 h even against a huge coke deposition (weight loss 46%) over 2.5Ni2.5Co/60Mg40Al is due to the timely diffusion of coke far from the active sites or the mounting of active sites over the carbon nanotube.

Comparative risk assessment studies estimating the hazard posed by long-term consumption of PPCPs in river water.

This study assesses the risk due to Emerging Contaminants (ECs), present in Indian rivers - Ganga (650 million inhabitants), Yamuna (57 million inhabitants), and Musi (7,500,000 inhabitants), 13 ECs in total, have been used for risk assessment studies. Their concentrations (e.g., Fluconazole: 236950 µg/l, Ciprofloxacin: 31000 µg/l, Caffeine: 21.57 µg/l, etc.) were higher than the threshold concentrations for safe consumption (e.g. Fluconazole allowable level is 3.8 µg/l, and Ciprofloxacin allowable level is 0.51 µg/l). Three different pathways of emerging contaminants (ECs) transfer (oral water ingestion, oral fish ingestion, and dermal water contact) have been considered and the study is carried out in 2 ways: (i) deterministic and (ii) probabilistic approaches (using Monte Carlo iterative methods with 10000 simulations) with the aid of a software - Risk (version 7.5). The risk value, quantified by Hazard Quotient (HQ) is higher than the allowable limit of 1 for several compounds in the three rivers like Fluconazole (HQ = 18276.713), Ciprofloxacin (HQ = 278.675), Voriconazole (HQ = 14.578), Cetirizine (HQ = 1006.917), Moxifloxacin (HQ = 8.076), Caffeine (HQ = 55.150), and Ibuprofen (HQ = 9.503). Results show that Fluconazole and Caffeine pose the maximum risk in the rivers via the "oral pathway" that allows maximum transfer of the ECs present in the river (93% and 82% contribution to total risk). The risk values vary from nearly 25 times to 19000 times the United States Environmental Protection Agency (USEPA) threshold limit of 1 (e.g., Caffeine Infant Risk = 25.990 and Fluconazole Adult Risk = 18276.713). The most susceptible age group, from this study, is "Adults" (19-70 years old), who stand the chance of experiencing the adverse health hazards associated with prolonged over-exposure to the ECs present in the river waters. Musi has the maximum concentration of pollutants and requires immediate remediation measures. Further, both methods indicate that nearly 60-70% of the population in all the three study areas are at risk of developing health hazards associated with over-exposure to ECs regularly, making the areas inhabitable.

Sr Promoted Ni/W-Zr Catalysts for Highly Efficient CO2 Methanation: Unveiling the Role of Surface Basicity.

This study explores the employment of CO2 methanation for carbon dioxide utilization and global warming mitigation. For the first time, in this work, we combine the interesting properties of the WO3-ZrO2 support and the benefits of Sr to improve the performance of Ni-based catalysts in this reaction. Sr loading on 5Ni/W-Zr samples is increased to 3 wt %, resulting in improved surface basicity through strong basic site formation. After 300 min, the 5Ni + 3Sr/W-Zr catalyst exhibits high activity and stability, achieving 90% CO2 conversion and 82% CH4 yield compared to 62 and 57% on 5Ni/W-Zr. Limited sintering and absence of carbon deposits are confirmed by temperature-programmed oxidation, XRD, Raman, and TEM analyses at 350 °C for 300 min. Sr promotion creates additional CO2 adsorption and conversion sites, enhancing the catalytic performance.

Exploring Modified Rice Straw Biochar as a Sustainable Solution for Simultaneous Cr(VI) and Pb(II) Removal from Wastewater: Characterization, Mechanism Insights, and Application Feasibility.

This study aimed to investigate the efficacy of a rice straw biosorbent in batch adsorption for the removal of chromium (Cr(VI)) and lead (Pb(II)) heavy-metal ions from wastewater. The biosorbent was chemically synthesized and activated by using concentrated sulfuric acid. The produced biosorbent was then characterized by using Fourier transform infrared (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) analyses, which provided insights into surface morphology and functional groups. The study examined the effects of pH, rice straw dose, ion concentration, and contact time on metal ion adsorption. Optimal conditions for efficient removal (95.57% for Cr(VI) and 85.68% for Pb(II)) were achieved at a pH of 2.0, a biosorbent dose of 2 g/L, an initial concentration of 20 mg/L, and a contact time of 50 min in synthetic solutions. The isotherms and kinetics model fitting results found that both metal ion adsorption processes were multilayer on the hetero surface of rice straw biosorbent via rate diffusion kinetics. Thermodynamic investigations were conducted, and the results strongly indicate that the adsorption process is endothermic and spontaneous. Notably, the results indicated that the highest desorption rate was achieved by adding 0.3 N HCl to the system.

Cellulose graphitic carbon directed iron oxide interfaced polypyrrole electrode materials for high performance supercapacitors.

The rising demand for green and clean energy urges the enlargement of economical and proficient electrode materials for supercapacitors. Herein, we designed a novel electrode material by porous cellulose graphitic carbon (CC) derived from bio-waste cornhusk via the pyrolysis route, and α-Fe2O3 decorated nanostructure with CC (CCIO) was achieved in situ pyrolysis of corn-husk and Fe(NO3)3·9H2O metal salt followed by a coating of polypyrrole (CCIOP). The CC, CCIO, and CCIOP nanocomposite electrodes were characterized by XRD, Raman, FTIR, FE-SEM/EDX, FE-TEM, XPS, and BET analysis. The CCIOP nanocomposite electrode exhibits an enhanced specific capacitance (Csp) of 290.9 F/g, which is substantial to its pristine CC (128.3 F/g), PPy (140.3 F/g), and CCIO (190.7 F/g). The Csp of CCIOP in a three-electrode system, using 1 M Na2SO4 electrolyte exhibits excellent capacity retention of 79.1 % even at a high current density of 10 A/g. The as-fabricated asymmetric supercapacitor (ASC) delivered a remarkable capacity retention of 88.7 % with a coulombic efficiency of 98.8 % even after 3000 cycles. The study shows successful utilization of cellulose from bio-waste cornhusk into a substantial template applicable in future alternative energy storage devices.

Isomerization of C7 and C8 through Ionic Liquids Supported by a Fe/SBA-15 Catalyst.

Isomerization is extensively utilized in the petroleum industry, and this study demonstrates an energy-efficient process utilizing an ionic liquid catalyst. 1-Ethyl-3-methylimidazolium triflate [Emim][TFO] as an ionic liquid was immobilized on solid support Fe/SBA-15. Variants of the catalyst were developed with the Fe constant at 5% and different ratios of ionic liquid. In the catalyst Fe/[Emim][TFO]/SBA-15, the metal Fe was loaded via the impregnation method, and subsequently, the ionic liquid variants Fe/[Emim][TFO](10)/SBA-15, Fe/[Emim][TFO](20)/SBA-15, and Fe/[Emim][TFO](30)/SBA-15 were synthesized. The physical properties of the synthesized catalyst were studied using standard characteristic techniques. The process performance was studied for variants of each parameter, which include temperature, hydrogen flow rate, pressure, and weight hourly space velocity. The iso-products of n-heptane and n-octane were obtained with an appreciable conversion of >90% and a selectivity of >95% with the catalyst Fe/[Emim][TFO](20)/SBA-15 among the other synthesized catalysts. The process yielded a high quantum of iso-products with negligible cracked products at a low temperature of 140 °C. The catalyst Fe/[Emim][TFO](20)/SBA-15 at 140 °C delivered the highest yield of iso-alkanes among the three catalysts. Iso-alkanes are instrumental tools for increasing the octane number of a fuel. This study delivers high iso-alkane content fuel, which can provide the best anti knock capability and enhance fuel efficiency for the life of modern high-powered engines. The results demonstrate a process that is energy-efficient, economic, and environmentally friendly.

Methane Decomposition to Hydrogen Over Zirconia-Supported Fe Catalysts-Effects of the Modified Support.

Methane decomposition is a promising route to synthesize COx -free hydrogen and carbon nanomaterials (CNMs ). In this work, the impregnation method was employed for the preparation of the catalysts. Systematic investigations on the activity and stability of Fe-based catalysts were carried out in a packed-bed micro-activity reactor at 800 °C with a feed gas flow rate of 18 mL/min. The effect of doping Y2 O3 , MgO, SiO2 and TiO2 over ZrO2 on the catalytic performance was also studied. BET revealed that the specific surface areas and pore volumes are increased after SiO2 , TiO2 , and Y2 O3 are added to ZrO2 while MgO had a negative impact and hence a little decrease in specific surface area is observed. The catalytic activity results showed that the Fe-based catalyst supported over TiO2 -doped ZrO2 that is, Fe-TiZr, demonstrated the highest activity and stability, with a maximum methane conversion of 81.3 % during 180 min time-on-stream. At 800 °C, a maximum initial methane conversion of 73 %, 38 %, 64 %, and 69 % and a final carbon yield of 121 wt. %, 55 wt. %, 354 wt. %, and 174 wt. % was achieved using Fe-MgZr, Fe-SiZr, Fe-TiZr and Fe-YZr catalysts, respectively. Moreover, bulk deposition of uniform carbon nanotubes with a high degree of graphitization and different diameters was observed over the catalysts.

Biodiesel production from Sisymbrium irio as a potential novel biomass waste feedstock using homemade titania catalyst.

Biomass waste streams are a possible feedstock for a range of eco-friendly products and a crucial alternative energy source for achieving carbon neutrality; therefore, the efficient management of biomass waste has taken on a greater significance in recent years. Due to its well-comparable physic-chemical properties with fossil diesel, biodiesel is a potential substitute for fossil fuel. This study aimed to synthesize biodiesel from the widely available non-edible seed oil of Sisymbrium irio L. (a member of the Brassicaceae family) via a transesterification procedure over a homemade TiO2 catalyst. At 1:16 oil to methanol ratio, 93% biodiesel yield was obtained over 20 mg catalyst at 60 °C and 60 min. The ASTM methods were used to analyze the fuel properties. The quantitative and qualitative analysis was performed by FT-IR, GC-MS, and NMR spectroscopy. GC-MS study confirms 16 different types of fatty acids of methyl esters. FT-IR analysis showed important peaks that confirm the successful occurrence of biodiesel. 1H-NMR and 13C-NMR showed important peaks for converting triglycerides into corresponding FAMEs. The acid value (0.42 mg KOH/mg/kg), flash point (106 °C), and water content (0.034) of biodiesel are below the specified limit of ASTM D6751 whereas kinetic viscosity (3.72 mm2/s), density (0.874 kg/L), cloud point (- 4.3 °C) and pour point (- 9.6 °C) and high heating value (41.62 MJ/kg) fall within the specified range of ASTM D6751 test limit. The Unsaturation degree and oxidative stability of biodiesel are above ASTM D6751 test limit. The physic-chemical properties of the SIB confirm that it is eco-friendly fuel and a competitive source for manufacturing biodiesel on a commercial scale. Furthermore, the SIB is engine friendly and has good fuel efficacy.

Hydrogen Production from Gadolinium-Promoted Yttrium-Zirconium-Supported Ni Catalysts through Dry Methane Reforming.

Hydrogen production from dry reforming of methane (DRM) not only concerns with green energy but also involves the consumption of two greenhouse gases CH4 and CO2. The lattice oxygen endowing capacity, thermostability, and efficient anchoring of Ni has brought the attention of the DRM community over the yttria-zirconia-supported Ni system (Ni/Y + Zr). Herein, Gd-promoted Ni/Y + Zr is characterized and investigated for hydrogen production through DRM. The H2-TPR → CO2-TPD → H2-TPR cyclic experiment indicates that most of the catalytic active site (Ni) remains present during the DRM reaction over all catalyst systems. Upon Y addition, the tetragonal zirconia-yttrium oxide phase stabilizes the support. Gadolinium promotional addition up to 4 wt % modifies the surface by formation of the cubic zirconium gadolinium oxide phase, limits the size of NiO, and makes reducible NiO moderately interacted species available over the catalyst surface and resists coke deposition. The 5Ni4Gd/Y + Zr catalyst shows about ∼80% yield of hydrogen constantly up to 24 h at 800 °C.

Effect of Adding Gadolinium Oxide Promoter on Nickel Catalyst over Yttrium-Zirconium Oxide Support for Dry Reforming of Methane.

The dry reforming of methane (DRM) was studied for seven hours at 800 °C and 42 L/(g·h) gas hourly space velocity over Ni-based catalysts, promoted with various amounts of gadolinium oxide (x = 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0 wt.%) and supported on mesoporous yttrium-zirconium oxide (YZr). The best catalyst was found to have 4.0 wt.% of gadolinium, which resulted in ∼80% and ∼86% conversions of CH4 and CO2, respectively, and a mole ratio of ∼0.90 H2/CO. The addition of Gd2O3 shifted the diffraction peaks of the support to higher angles, indicating the incorporation of the promoter into the unit cell of the YZr support. The Gd2O3 promoter improved the catalyst basicity and the interaction of NiO with support, which were reflected in the coke resistance (6.0 wt.% carbon deposit on 5Ni+4Gd/YZr; 19.0 wt.% carbon deposit on 5Ni/YZr) and the stability of our catalysts. The Gd2O3 is believed to react with carbon dioxide to form oxycarbonate species and helps to gasify the surface of the catalysts. In addition, the Gd2O3 enhanced the activation of CH4 and its conversion on the metallic nickel sites.

Stability and Activity of Rhodium Promoted Nickel-Based Catalysts in Dry Reforming of Methane.

The rhodium oxide (Rh2O3) doping effect on the activity and stability of nickel catalysts supported over yttria-stabilized zirconia was examined in dry reforming of methane (DRM) by using a tubular reactor, operated at 800 °C. The catalysts were characterized by using several techniques including nitrogen physisorption, X-ray diffraction, transmission electron microscopy, H2-temperature programmed reduction, CO2-temperature programmed Desorption, and temperature gravimetric analysis (TGA). The morphology of Ni-YZr was not affected by the addition of Rh2O3. However, it facilitated the activation of the catalysts and reduced the catalyst's surface basicity. The addition of 4.0 wt.% Rh2O3 gave the optimum conversions of CH4 and CO2 of ~89% and ~92%, respectively. Furthermore, the incorporation of Rh2O3, in the range of 0.0-4.0 wt.% loading, enhanced DRM and decreased the impact of reverse water gas shift, as inferred by the thermodynamics analysis. TGA revealed that the addition of Rh2O3 diminished the carbon formation on the spent catalysts, and hence, boosted the stability, owing to the potential of rhodium for carbon oxidation through gasification reactions. The 4.0 wt.% Rh2O3 loading gave a 12.5% weight loss of carbon. The TEM images displayed filamentous carbon, confirming the TGA results.