Sewage sludge steam gasification over bimetallic mesoporous Al-MCM48 catalysts for efficient hydrogen generation.

This study explored the potential of steam gasification of sewage sludge over different temperatures (non-catalytic) and bimetallic (Ni-Fe and Ni-Co) mesoporous Al-MCM48 (3-5% Al basis). The higher temperature (800 °C) resulted in higher gas yield (36.74 wt%) and syngas (H2 and CO) selectivity (35.30 vol% and 11.66 vol%). Moreover, catalytic approach displayed that the Al-MCM48 was effective support because the incorporation of nickel increased the efficiency of gasification reactions compared to HZSM-5 (30). It mainly comes from the presence of mesopores and higher surface area (710.05 m2/g) providing more reaction sites and higher stability (less coke formation). Furthermore, the addition of promoters such as Co and Fe allowed the formation of Ni-Fe and Ni-Co alloys, resulting in even higher gas yield and overall H2 and CO selectivity due to the promotion of related reactions such as tar cracking, Boudouard, water gas shift and reforming and so on. Ni-Co alloy catalyst (10% Ni-5% Co/Al-MCM48) resulted in the highest H2 (∼52 vol%) selectivity due to the enhanced Ni dispersion and synergy effect between Ni and Co. Moreover, the application of bi-metal alloy on Al-MCM48 showed no coke formation and significantly reduced CO2 and hydrocarbon selectivity in the product gas. Overall, this study presented a promising solution for sewage sludge disposal in terms of clean H2 generation, reduction in CO2 and higher stability of metal based catalysts at the same time.

Household food waste conversion to biohydrogen via steam gasification over copper and nickel-loaded SBA-15 catalysts.

Household food waste (FW) was converted into biohydrogen-rich gas via steam gasification over Ni and bimetallic Ni (Cu-Ni and Co-Ni) catalysts supported on mesoporous SBA-15. The effect of catalyst method on steam gasification efficiency of each catalyst was investigated using incipient wetness impregnation, deposition precipitation, and ethylenediaminetetraacetic acid metal complex impregnation methods. H2-TPR confirmed the synergistic interaction of the dopants (Co and Cu) and Ni. Furthermore, XRD and HR-TEM revealed that the size of the Ni particle varied depending on the method of catalyst synthesis, confirming the formation of solid solutions in Co- or Cu-doped Ni/SBA-15 catalysts due to dopant insertion into the Ni. Notably, the exceptional activity of the Cu-Ni/SBA-15-EMC catalyst in FW steam gasification was attributed to the fine distribution of the concise Ni nanoparticles (9 nm), which resulted in the highest hydrogen selectivity (62 vol%), gas yield (73.6 wt%). Likewise, Cu-Ni solid solution decreased coke to 0.08 wt%.

Enhanced CO2 electroconversion of Rhodobacter sphaeroides by cobalt-phosphate complex assisted water oxidation.

CO2 can be a next generation feedstock for electricity-driven bioproduction due to its abundance and availability. Microbial electrosynthesis (MES), a promising technique for CO2 electroconversion, provides an attractive route for the production of valuable products from CO2, but issues surrounding efficiency and reasonable productivity should be resolved. Improving the anode performance for water oxidation under neutral pH is one of the most important aspects to advance current MES. Here, we introduce cobalt-phosphate (Co-Pi) assisted water oxidation at the counter electrode (i.e., anode) to upgrade the MES performance at pH 7.0. We show that CO2 can be converted by photochemoautotrophic bacterium, Rhodobacter sphaeroides into organic acids and carotenoids in the MES reactor. Planktonic cells of R. sphareroides in the Co-Pi anode equipped MES reactor was ca. 1.5-fold higher than in the control condition (w/o Co-Pi). The faradaic efficiency of the Co-Pi anode equipped MES reactor was remarkably higher (58.3%) than that of the bare anode (27.8%). While the system can improve the CO2 electroconversion nonetheless there are some further optimizations are necessary.

Hydrogen-rich gas production via steam gasification of food waste over basic oxides (MgO/CaO/SrO) promoted-Ni/Al2O3 catalysts.

Food waste, a renewable resource, was converted to H2-rich gas via a catalytic steam gasification process. The effects of basic oxides (MgO, CaO, and SrO) with 10 wt% Ni/Al2O3 on the gasification properties of food waste were investigated using a U-shaped gasifier. All catalysts prepared by the precipitation method were analyzed by X-ray diffraction, H2-temperature-programmed reduction, NH3-temperature-programmed desorption, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The Ni/Al2O3 catalyst was reduced incompletely, and low nickel concentrations were detected on the surface of the alumina. The basic oxides minimized the number of acid sites and suppressed the formation of nickel-aluminate (NiAlxOy) phase in catalyst. In addition, the basic oxides shifted nickel-aluminate reduction reaction to lower temperatures. It resulted in enhancing nickel concentration on the catalyst surface and increasing gas yield and hydrogen selectivity. The low gas yield of the Ni/Al2O3 catalyst was attributed to the low nickel concentration on the surface. The maximum gas yield (66.0 wt%) and hydrogen selectivity (63.8 vol%) of the 10 wt% SrO- 10 wt% Ni/Al2O3 catalyst correlated with the highly dispersed nickel on the surface and low acidity. Furthermore, coke deposition during steam gasification varied with the surface acidity of the catalysts and less coke was formed on 10 wt% SrO- 10 wt% Ni/Al2O3 due to efficient tar cracking. This study showed that the steam gasification efficiency of the Ni/Al2O3 catalyst could be improved significantly by the addition of SrO.

Valorization of hazardous COVID-19 mask waste while minimizing hazardous byproducts using catalytic gasification.

This study proposes a method to valorize hazardous waste such as used COVID-19 face mask via catalytic gasification over Ni-loaded ZSM-5 type zeolites. The 25% Ni was found as an optimal loading on ZSM-5 in terms of H2 production. Among different zeolites (ZSM-5(30), ZSM-5(80), ZSM-5(280), mesoporous (m)-ZSM-5(30), and HY(30)), 25% Ni/m-ZSM-5(30) led to the highest H2 selectivity (45.04 vol%), most likely because of the highest Ni dispersion on the m-ZSM-5(30) surface, high porosity, and acid site density of the m-ZSM-5(30). The content of N-containing species (e.g., caprolactum and nitriles) in the gasification product was also reduced, when steam was used as gasifying agent, which is the source of potentially hazardous air pollutants (e.g., NOx). The increase in the SiO2/Al2O3 ratio resulted in lower tar conversion and lower H2 generation. At comparable conditions, steam gasification of the mask led to ~15 vol% higher H2 selectivity than air gasification. Overall, the Ni-loaded zeolite catalyst can not only suppress the formation of hazardous substances but also enhance the production of hydrogen from the hazardous waste material such as COVID-19 mask waste.

Effect of eggshell- and homo-type Ni/Al2O3 catalysts on the pyrolysis of food waste under CO2 atmosphere.

This study highlights the potential of pyrolysis of food waste (FW) with Ni-based catalysts under CO2 atmosphere as an environmentally benign disposal technique. FW was pyrolyzed with homo-type Ni/Al2O3 (Ni-HO) or eggshell-type Ni/Al2O3 (Ni-EG) catalysts under flowing CO2 (50 mL/min) at temperatures from 500 to 700 °C for 1 h. A higher gas yield (42.05 wt%) and a lower condensable yield (36.28 wt%) were achieved for catalytic pyrolysis with Ni-EG than with Ni-HO (34.94 wt% and 40.06 wt%, respectively). In particular, the maximum volumetric content of H2 (21.48%) and CO (28.43%) and the lowest content of C2-C4 (19.22%) were obtained using the Ni-EG. The formation of cyclic species (e.g., benzene derivatives) in bio-oil was also effectively suppressed (24.87%) when the Ni-EG catalyst and CO2 medium were concurrently utilized for the FW pyrolysis. Accordingly, the simultaneous use of the Ni-EG catalyst and CO2 contributed to altering the carbon distribution of the pyrolytic products from condensable species to value-added gaseous products by facilitating ring-opening reactions and free radical mechanisms. This study should suggest that CO2-assisted catalytic pyrolysis over the Ni-EG catalyst would be an eco-friendly and sustainable strategy for disposal of FW which also provides a clean and high-quality source of energy.

Biohydrogen production from catalytic conversion of food waste via steam and air gasification using eggshell- and homo-type Ni/Al2O3 catalysts.

Steam and air gasification with 5 wt% Ni/Al2O3 eggshell (Ni-EG) and homo (Ni-H) catalysts were performed for the first time to produce biohydrogen from food waste. The steam gasification produced comparably higher gas yield than air gasification. In non-catalytic experiments, steam gasification generated a higher volume percent of H2, whereas more CO, CO2, CH4, and C2-C4 were produced in air gasification. Ni-EG demonstrated higher potential to obtain H2-rich gases with a low C2-C4 content compared to that obtained by Ni-H, particularly in steam gasification at 800 °C, which produced gaseous products with 59.48 vol% H2. The long-term activity of both catalysts in steam gasification was evaluated, and Ni-EG exhibited higher stability than Ni-H. The ideal distribution of Ni species on the outer region of γ-Al2O3 pellets in Ni-EG resulted in higher activity, stability, and selectivity than Ni-H in both steam and air gasification.

Elevated conversion of CO2 to versatile formate by a newly discovered formate dehydrogenase from Rhodobacter aestuarii.

Due to climate change, recent research interests have increased towards CO2 utilization as a strategy to mitigate the atmospheric CO2 level. Herein, we aimed to explore formate dehydrogenases (FDHs) from chemoautotroph to discover an efficient and O2-tolerant biocatalyst for catalyzing the CO2 reduction to a versatile formate. Through genome-mining and phylogenetic analysis, the FDH from Rhodobacter aestuarii (RaFDH) was newly discovered as a promising O2-tolernat CO2 reductase and was successfully expressed in Escherichia coli. In this study, the optimum conditions and turnover rates of RaFDH were examined for CO2 reduction and formate oxidation. In particular, the RaFDH-driven CO2 reduction far surpassed the formate oxidation with a turnover rate of 48.3 and 15.6 min-1, respectively. The outstanding superiority of RaFDH towards CO2 reduction can be applicable for constructing a feasible electroenzymatic system that produce a versatile formate from CO2 as a cheap, abundant, and renewable resource.

Acetaldehyde removal and increased H2/CO gas yield from biomass gasification over metal-loaded Kraft lignin char catalyst.

Acetaldehyde removal tests were performed to compare the catalytic activity of the Kraft lignin char (KC), KOH-treated Kraft lignin char (KKC), and activated carbon (AC) along with their impregnation with Mn in a plasma reactor. The gasification characteristics (syngas content, and H2/CO ratio) of yellow poplar were investigated using nickel catalysts supported on KC, KKC, AC, and γ-Al2O3 in a U-type quartz reactor. KKC and Mn/KKC improved significantly the surface area and contents of O and N functional groups over the raw char. In particular, Mn/KKC showed the highest acetaldehyde-removal efficiency. The catalytic activity of Ni-impregnated KC, KKC, AC, and γ-Al2O3 decreased in the order of Ni/KKC > Ni/AC > Ni/KC > Ni/γ-Al2O3 for the gas yield and Ni/γ-Al2O3 >Ni/KC > Ni/AC >Ni/KKC for the oil yield, respectively. The Ni/KKC provides a more conducive environment for gasification, resulting in larger amounts of syngas (H2 and CO) in the product gases. Moreover, Ni impregnated with char may be the most inexpensive and effective solution for achieving maximum tar reduction and syngas generation.

Catalytic Pyrolysis of Pinus densiflora Over Mesoporous Al2O3 Catalysts.

The thermal and catalytic pyrolysis of Pinus densiflora (P. densiflora) were performed to test the catalytic cracking efficiency of two mesoporous Al2O3 catalysts with different surface areas. Thermogravimetric analysis (TGA) of P. densiflora showed that the differential TG (DTG) peak heights obtained from catalytic pyrolysis were smaller than those of non-catalytic pyrolysis due to the conversion of the reaction intermediates to coke. Pyrolyzer-gas chromatography/mass spectrometry analysis/flame ionization detection (Py-GC/MS/FID) suggested that using the Al2O3 catalysts, the yields of phenols and levoglucosan decreased with a concomitant increase in the yields of aldehydes, alcohol, ketones, and furans. Between the two catalysts, Al2O3-B prepared by spray pyrolysis showed higher cracking efficiency than Al2O3-A prepared by hydrothermal method because of its larger surface area.

Hydrodeoxygenation of Pyrolysis Bio-Oil Over Ni Impregnated Mesoporous Materials.

The catalytic hydrodeoxygenation (HDO) of bio-oil over Ni-supported mesoporous materials was performed using a high pressure autoclave reactor. The actual pyrolysis oil of cork oak wood was used as a sample, and Ni/Al-SBA-15 and Ni/Al-MSU-F were used as catalysts. In addition, supercritical ethanol was added as solvent. Both Ni-supported mesoporous catalysts showed efficient HDO reaction ability. A higher heating value and pH of bio-oil were achieved by the HDO reaction over both catalysts and upgraded bio-oil had a lower viscosity. Compared to Ni/Al-MSU-F, Ni/Al- SBA-15 produced more upgraded bio-oil with a lower oxygen content and higher heating value via a catalytic HDO process.

Catalytic Pyrolysis of Korean Pine (Pinus koraiensis) Nut Shell Over Mesoporous Al2O3.

The catalytic pyrolysis of waste Korean pine nut shell (KPNS) over mesoporous Al2O3 was investigated by thermogravimetric analysis (TGA) and pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS). TGA results showed that the thermal and catalytic pyrolysis of KPNS over mesoporous Al2O3 has the same decomposition temperature. On the other hand, the maximum decomposition for the catalytic pyrolysis of KPNS over commercial-Al2O3 shifted to a higher temperature. The Py-GC/MS results indicated that large amounts of oxygen-containing pyrolyzates, such as acids, furans, levoglucosan, and phenols, were produced by the non-catalytic pyrolysis of KPNS. These oxygen-containing pyrolyzates were upgraded efficiently into aromatic hydrocarbons by applying Al2O3 catalysts. Between the two Al2O3 catalysts, mesoporous Al2O3 showed better performance on the formation of aromatic hydrocarbons via the catalytic pyrolysis of KPNS than commercial Al2O3 because of its uniform larger pores.

Stabilization of Hydrogen Production via Methanol Steam Reforming in Microreactor by Al2O3 Nano-Film Enhanced Catalyst Adhesion.

In hydrogen production by methanol steam reforming reaction with microchannel reactor, Al2O3 thin film formed by atomic layer deposition (ALD) was introduced on the surface of microchannel reactor prior to the coating of catalyst particles. Methanol conversion rate and hydrogen production rate, increased in the presence of Al2O3 thin film. Over-view and cross-sectional scanning electron microscopy study showed that the adhesion between catalyst particles and the surface of microchannel reactor enhanced due to the presence of Al2O3 thin film. The improvement of hydrogen production rate inside the channels of microreactor mainly came from the stable fixation of catalyst particles on the surface of microchannels.

Bio-Diesel Production from Deoxygenation Reaction Over Ce0.6Zr0.4O2 Supported Transition Metal (Ni, Cu, Co, and Mo) Catalysts.

Ce0.6Zr0.4O2 supported transition metal (Me = Ni, Cu, Co, and Mo) catalysts have been investigated to screen for the catalytic activity and selectivity for deoxygenation reaction of oleic acid. Me-Ce0.6Zr0.4O2 catalysts were prepared by a co-precipitation method. Ni-Ce0.6Zr0.4O2 catalyst exhibited much higher oleic acid conversion, selectivity for C9 to C17 compounds, and oxygen removal efficiency than the others. This is mainly ascribed to the presence of free Ni species, synergy effects between Ni and Ce0.6Zr0.4O2, and the highest BET surface area.

Catalytic Conversion of Pinus densiflora Over Mesoporous Catalysts Using Pyrolysis Process.

Catalytic pyrolysis experiments were conducted to investigate the possibility of obtaining valuable chemicals from Pinus densiflora, a native Korean tree species occupying 21.4% of the total area under forests in South Korea. Two representative mesoporous catalysts, Al-MCM-41 and Al-MSU-F, as well as hierarchical mesoporous MFI (Meso-MFI) that has both mesopores and micropores, were used as catalysts. Compared to non-catalytic pyrolysis, catalytic pyrolysis was shown to reduce the fractions of levoglucosan, phenolics, and acids in bio-oil, while increasing the fractions of aromatics, PAHs, and furans. Meso-MFI with strong acid sites showed a high selectivity toward aromatics and PAHs, whereas Al-MCM-41 and Al-MSU-F with weak acid sites exhibited a high selectivity toward furanic compounds. The results of this study indicate that choosing a catalyst with an adequate quantity of acidic sites with the required strength is critical for enhancing the production of desired chemicals from Pinus densiflora.

Catalytic Hydrodeoxygenation of Bio-oil Model Compounds over Pt/HY Catalyst.

The hydrodeoxygenation of a model compound of lignin-derived bio-oil, guaiacol, which can be obtained from the pyrolysis of biomass to bio-oil, has attracted considerable research attention because of its huge potential as a substitute for conventional fuels. In this study, platinum-loaded HY zeolites (Pt/HY) with different Si/Al molar ratios were used as catalysts for the hydrodeoxygenation of guaiacol, anisole, veratrole, and phenol to a range of hydrocarbons, such as cyclohexane. The cyclohexane (major product) yield increased with increasing number of acid sites. To produce bio-oil with the maximum level of cyclohexane and alkylated cyclohexanes, which would be suitable as a substitute for conventional transportation fuels, the Si/Al molar ratio should be optimized to balance the Pt particle-induced hydrogenation with acid site-induced methyl group transfer. The fuel properties of real bio-oil derived from the fast pyrolysis of cork oak was improved using the Pt/HY catalyst.

Heat-Induced Agglomeration of Amorphous Silicon Nanoparticles Toward the Formation of Silicon Thin Film.

The thermal behavior of silicon nanoparticles (Si NPs) was investigated for the preparation of silicon thin film using a solution process. TEM analysis of Si NPs, synthesized by inductively coupled plasma, revealed that the micro-structure of the Si NPs was amorphous and that the Si NPs had melted and merged at a comparatively low temperature (~750 °C) considering bulk melting temperature of silicon (1414 °C). A silicon ink solution was prepared by dispersing amorphous Si NPs in propylene glycol (PG). It was then coated onto a silicon wafer and a quartz plate to form a thin film. These films were annealed in a vacuum or in an N2 environment to increase their film density. N2 annealing at 800 °C and 1000 °C induced the crystallization of the amorphous thin film. An elemental analysis by the SIMS depth profile showed that N2annealing at 1000 °C for 180 min drastically reduced the concentrations of carbon and oxygen inside the silicon thin film. These results indicate that silicon ink prepared using amorphous Si NPs in PG can serve as a proper means of preparing silicon thin film via solution process.

Biodiesel production via the transesterification of soybean oil using waste starfish (Asterina pectinifera).

Calcined waste starfish was used as a base catalyst for the production of biodiesel from soybean oil for the first time. A batch reactor was used for the transesterification reaction. The thermal characteristics and crystal structures of the waste starfish were investigated by thermo-gravimetric analysis and X-ray diffraction. The biodiesel yield was determined by measuring the content of fatty acid methyl esters (FAME). The calcination temperature appeared to be a very important parameter affecting the catalytic activity. The starfish-derived catalyst calcined at 750 °C or higher exhibited high activity for the transesterification reaction. The FAME content increased with increasing catalyst dose and methanol-over-oil ratio.

Catalytic pyrolysis of mandarin residue from the mandarin juice processing industry.

In this study, the catalytic pyrolysis of mandarin residue from the mandarin juice processing industry was carried out using pyrolysis gas chromatography/mass spectroscopy and employing microporous zeolite catalysts, HZSM-5 (SiO2/Al2O3=23 and 80) and HBeta (SiO2/Al2O3=25). The effect of acidity of the catalyst was investigated by comparing the activity of two HZSM-5 catalysts with different SiO2/Al2O3 ratios. The effect of catalyst structure was explored by comparing the results obtained using HZSM-5 (23) and HBeta. Most oxygenates produced from non-catalytic pyrolysis were removed by catalytic upgrading, whereas the yields of mono-aromatics, which are important feedstock materials for the chemical industry, increased considerably, improving the quality of the bio-oil produced. HZSM-5 (23), having the highest acidity among the catalysts used in this study, showed superior catalytic activity to those of HZSM-5 (80) and HBeta. Pt/HZSM-5 (23) and Ga/HZSM-5 (23) resulted in an even higher yield of aromatics.

Characterization of carbon nanotube-cdse hybrid nanomaterials.

MWNT-CdSe hybrid nanomaterials were prepared with carboxylic acid-treated CdSe nanoparticles and amino-functionalized MWNTs. The hybridization of MWNT-CdSe nanomaterials was performed by the formation of covalent bond between MWNT and CdSe. Their covalent bond lengths were varied with changing the linking spacers. Amino-functionalized MWNTs were reacted with CdSe nanoparticles which were functionalized with carboxylic acid groups. Their detailed structures were characterized by FT-IR, XPS, and small angle X-ray scattering. Through small angle X-ray scattering experiments, it was found that the structures of CdSe nanoparticles were not regular, and their sizes were broadly distributed in solution. The longer amino-functionalized MWNTs were thermally decomposed at lower temperature. The photoluminescence (PL) of chemically-linked MWNT-CdSe hybrid nanomaterials were weaker than that of CdSe nanoparticles. In addition, their PL intensities more weakened on the MWNT-CdSe with the longer spacers.