H2 generation from steam gasification of swine manure over nickel-loaded perovskite oxides catalysts.

In this study, nickel-loaded perovskite oxides catalysts were synthesized via the impregnation of 10%Ni on XTiO3 (X = Ce, Sr, La, Ba, Ca, and Fe) supports and employed in the catalytic steam gasification of swine manure to produce H2-rich syngas for the first time. The synthesized catalysts were characterized using BET, H2-TPR, XRD, HR-TEM, and EDX analysis. Briefly, using perovskite supports resulted in the production of ultrafine catalyst nanoparticles with a uniform dispersion of Ni particles. According to the catalytic activity test, the gas yield showed the increment as 10% Ni/LaTiO3 < 10% Ni/FeTiO3 < 10% Ni/CeTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. Meanwhile, zero coke formation was achieved due to the oxygen mobility of prepared catalysts. Also, the increase in the H2 production for the applied catalysts was in the sequence as 10% Ni/CeTiO3 < 10% Ni/FeTiO3 < 10% Ni/LaTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. The maximum H2 selectivity (∼48 vol%) obtained by10% Ni/CaTiO3 was probably due to the synergistic effect of Ni and Ti on enhancing the water-gas shift reaction, and Ca on creating the maximum oxygen mobility compared to other alkaline earth metals doped at the A place of perovskite. Overall, this study provides a suitable solution for enhanced H2 production through steam gasification of swine manure along with suggesting the appropriate supports to prevent Ni deactivation by lowering coke formation at the same time.

Fabrication of Ni/TiO2 visible light responsive photocatalyst for decomposition of oxytetracycline.

Nickel-impregnated TiO2 photocatalyst (NiTP) responding to visible light was prepared by the liquid phase plasma (LPP) method, and its photoactivity was evaluated in degrading an antibiotic (oxytetracycline, OTC). For preparing the photocatalyst, nickel was uniformly impregnated onto TiO2 (P-25) powder, and the nickel content increased as the number of LPP reactions increased. In addition, the morphology and lattice of NiTP were observed through various instrumental analyses, and it was confirmed that NiO-type nanoparticles were impregnated in NiTP. Fundamentally, as the amount of impregnated nickel in the TiO2 powder increased sufficiently, the band gap energy of TiO2 decreased, and eventually, the NiTP excited by visible light was synthesized. Further, OTC had a decomposition reaction pathway in which active radicals generated in OTC photocatalytic reaction under NiTP were finally mineralized through reactions such as decarboxamidation, hydration, deamination, demethylation, and dehydroxylation. In effect, we succeeded in synthesizing a photocatalyst useable under visible light by performing only the LPP single process and developed a new advanced oxidation process (AOP) that can remove toxic antibiotics.

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%.

Valorization of biomass through gasification for green hydrogen generation: A comprehensive review.

Green and sustainable hydrogen from biomass gasification processes is one of the promising ways to alternate fossil fuels-based hydrogen production. First off, an overview of green hydrogen generation from biomass gasification processes is presented and the corresponding possible gasification reactions and the effect of respective experimental criteria are explained in detail. In addition, a comprehensive explanation of the catalytic effect on tar reduction and hydrogen generation via catalytic gasification is presented regarding the functional mechanisms of various types of catalysts. Furthermore, the commercialization aspects, the associated technical challenges and barriers, and the prospects of a biomass gasification process for green hydrogen generation are discussed. Finally, this comprehensive review provides the related advancements, challenges, and great insight of biomass gasification for the green hydrogen generation to realize a sustainable hydrogen society via biomass valorization.

Removal of oxytetracycline from water by liquid-phase plasma process with an iron precipitated TiO2 photocatalyst.

This study developed a new water treatment method using liquid-phase plasma (LPP) process that can decompose oxytetracycline (OTC) remaining in the aquatic environment. Relatedly, the OTC causes damage to the human body and cannot be removed by traditional water treatment methods. The study also prepared Fe/TiO2 photocatalyst responding to visible light using the LPP process. In particular, the OTC decomposition efficiency of the LPP process improved by more than 10% with the use of the Fe/TiO2 photocatalyst as compared to that of the one with the use of bare TiO2 photocatalyst. Further, the optimal LPP process parameters and Fe/TiO2 photocatalyst amount in the LPP process for OTC decomposition were established in the study. Finally, the degradation pathway of the OTC in the LPP process was found based on the five intermediates of the LPP reaction that were detected by the liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) analysis. In particular, the decomposition pathway was estimated to be involving the mineralization of the OTC through demethylation, deamination, dehydration, and ring cleavage.

Comparison of Pore Structures of Cellulose-Based Activated Carbon Fibers and Their Applications for Electrode Materials.

This study presents the first investigation of cellulose-based activated carbon fibers (RACFs) prepared as electrode materials for the electric double-layer capacitor (EDLC) in lieu of activated carbon, to determine its efficacy as a low-cost, environmentally friendly enhancement alternative to nanocarbon materials. The RACFs were prepared by steam activation and their textural properties were studied by Brunauer-Emmett-Teller and non-localized density functional theory equations with N2/77K adsorption isotherms. The crystallite structure of the RACFs was observed by X-ray diffraction. The RACFs were applied as an electrode material for an EDLC and compared with commercial activated carbon (YP-50F). The electrochemical performance of the EDLC was analyzed using galvanostatic charge/discharge curves, cyclic voltammetry, and electrochemical impedance spectroscopy. The results show that the texture properties of the activated carbon fibers were influenced by the activation time. Crucially, the specific surface area, total pore volume, and mesopore volume ratio of the RACF with a 70-min activation time (RACF-70) were 2150 m2/g, 1.03 cm3/g and 31.1%, respectively. Further, electrochemical performance analysis found that the specific capacitance of RACF-70 increased from 82.6 to 103.6 F/g (at 2 mA/cm2). The overall high specific capacitance and low resistance of the RACFs were probably influenced by the pore structure that developed outstanding impedance properties. The results of this work demonstrate that RACFs have promising application value as performance enhancing EDLC electrode materials.

Suppression of the hazardous substances in catalytically upgraded bio-heavy oil as a precautious measure for clean air pollution controls.

Bio-heavy oil (BHO) is a renewable fuel, but its efficient use is problematic because its combustion may emit hazardous air pollutants (e.g., polycyclic aromatic hydrocarbon (PAH) compounds, NOx, and SOx). Herein, catalytic fast pyrolysis over HZSM-5 zeolite was applied to upgrading BHO to drop-in fuel-range hydrocarbons with reduced contents of hazardous species such as PAH compounds and N- and S-containing species (NOx and SOx precursors). The effects of HZSM-5 desilication and linear low-density polyethylene (LLDPE) addition to the feedstock on hydrocarbon production were explored. The apparent activation energy for the thermal decomposition of BHO was up to 37.5% lowered by desilicated HZSM-5 (DeHZSM-5) compared with HZSM-5. Co-pyrolyzing LLDPE with BHO increased the content of drop-in fuel-range hydrocarbons and decreased the content of PAH compounds. The DeHZSM-5 was effective in producing drop-in fuel-range hydrocarbons from a mixture of BHO and LLDPE and suppressing the formation of N- and S-containing species and PAH compounds. The DeHZSM-5 enhanced the hydrocarbon production by up to 58.5% because of its enhanced porosity and high acid site density compared to its parent HZSM-5. This study experimentally validated that BHO can be upgraded to less hazardous fuel via catalytic fast co-pyrolysis with LLDPE over DeHZSM-5.

Preparation and Characterization of Silver-Iron Bimetallic Nanoparticles on Activated Carbon Using Plasma in Liquid Process.

The mono and bi-metallic nanoparticles have conspicuous properties and are widely used in the environment, energy, and medical fields. In this study, bimetallic nanoparticles composed of silver and iron were precipitated on the surface of activated carbon in a single process using plasma in liquid process (PLP). Silver-iron ions and various radicals were actively generated in the aqueous reactant solution by the PLP. Although metals were precipitated on AC depending on the number of precursors added to the aqueous reactant solution, the standard reduction potential of silver ions was higher than that of iron ions, so silver precipitated on AC. The silver precipitate on AC was a mixture of metallic silver and silver oxide, and iron was present as Fe3O4. Spherical nanoparticles, 100-120 nm in size, were observed on the surface of the Ag-Fe/AC composite. The composition of the bimetallic nanoparticles could be controlled by considering the ionization tendency and standard reduction potential of metal ions and controlling the concentration of the precursors. The PLP presented in this study can be applied to the preparing method of bimetallic nanoparticle/carbon materials and can be expected to be used in the prepare of energy and environmental materials such as MFC and absorption materials for removing pollutants.

Hydrogen Production through Catalytic Water Splitting Using Liquid-Phase Plasma over Bismuth Ferrite Catalyst.

This study examined the H2 production characteristics from a decomposition reaction using liquid-phase plasma with a bismuth ferrite catalyst. The catalyst was prepared using a sol-gel reaction method. The physicochemical and optical properties of bismuth ferrite were analyzed. H2 production was carried out from a distilled water and aqueous methanol solution by direct irradiation via liquid-phase plasma. The catalyst absorbed visible-light over 610 nm. The measured bandgap of the bismuth ferrite was approximately 2.0 eV. The liquid-phase plasma emitted UV and visible-light simultaneously according to optical emission spectrometry. Bismuth ferrite induced a higher H2 production rate than the TiO2 photocatalyst because it responds to both UV and visible light generated from the liquid-phase plasma.

Bamboo-Based Mesoporous Activated Carbon for High-Power-Density Electric Double-Layer Capacitors.

Demand for hybrid energy storage systems is growing, but electric double-layer capacitors (EDLCs) have insufficient output characteristics because of the microporous structure of the activated carbon electrode material. Commercially, activated carbon is prepared from coconut shells, which yield an activated carbon material (YP-50F) rich in micropores, whereas mesopores are desired in EDLCs. In this study, we prepared mesoporous activated carbon (PB-AC) using a readily available, environmentally friendly resource: bamboo. Crucially, modification using phosphoric acid and steam activation was carried out, which enabled the tuning of the crystal structure and the pore characteristics of the product. The structural characteristics and textural properties of the PB-AC were determined, and the specific surface area and mesopore volume ratio of the PB-AC product were 960-2700 m2/g and 7.5-44.5%, respectively. The high specific surface area and mesopore-rich nature originate from the phosphoric acid treatment. Finally, PB-AC was used as the electrode material in EDLCs, and the specific capacitance was found to be 86.7 F/g for the phosphoric-acid-treated sample steam activated at 900 °C for 60 min; this capacitance is 35% better than that of the commercial YP-50F (64.2 F/g), indicating that bamboo is a suitable material for the production of activated carbon.

Acetaldehyde Adsorption Characteristics of Ag/ACF Composite Prepared by Liquid Phase Plasma Method.

Ag particles were precipitated on an activated carbon fiber (ACF) surface using a liquid phase plasma (LPP) method to prepare a Ag/ACF composite. The efficiency was examined by applying it as an adsorbent in the acetaldehyde adsorption experiment. Field-emission scanning electron microscopy and energy-dispersive X-ray spectrometry confirmed that Ag particles were distributed uniformly on an ACF surface. X-ray diffraction and X-ray photoelectron spectroscopy confirmed that metallic silver (Ag0) and silver oxide (Ag2O) precipitated simultaneously on the ACF surface. Although the precipitated Ag particles blocked the pores of the ACF, the specific surface area of the Ag/ACF composite material decreased, but the adsorption capacity of acetaldehyde was improved. The AA adsorption of ACF and Ag/ACF composites performed in this study was suitable for the Dose-Response model.

Waste furniture gasification using rice husk based char catalysts for enhanced hydrogen generation.

Present study provides biohydrogen production methods from waste furniture via catalytic steam gasification with bio-char catalysts (raw char, KOH-activated char and steam-activated char). Total gas yield for the prepared chars was in the order of KOH-activated char > steam-activated char > raw char, whereas, H2 selectivity was in the sequence of raw char > steam-activated char > KOH-activated char. Though KOH-activated char showed the highest gas yield, highest H2 selectivity was obtained at the gasification experiment with raw char due to the large amount of Ca and K and its reasonable surface area (146.89 m2/g). Although the activation of raw biochar results in the increase of gas yield, it has the negative effect on H2 generation due to the removal of alkali and alkaline earth metals for the KOH activated char and steam-activated char. This study shows that raw bio-char could be a potential solution for eco-friendly hydrogen production.

Effect of palladium on the black mass-based catalyst prepared from spent Zn/Mn alkaline batteries for catalytic combustion of volatile organic compounds.

A large amount of spent batteries is produced annually. When spente batteries are buried, their harmful components may contaminate soil and water. Therefore, recycling of spent batteries is essential for environmental reasons. We evaluated the BM (black mass) of spent Zn/Mn alkaline batteries as a catalyst substance for the catalytic combustion of volatile organic compounds (VOCs: benzene, toluene, and o-xylene). The SBM catalyst (black mass-based catalyst) was prepared by treating BM with 0.1 N of sulfuric acid solution. Major elements of the SBM catalyst were manganese, zinc, iron, aluminum, potassium, and sodium except for carbon. In addition, to find out the additive effect of palladium on the SBM catalyst, we prepared the Pd/SBM catalysts using a conventional impregnation method. We investigated the physicochemical properties of the SBM and Pd/SBM catalysts by instrumental analysis. Benzene, toluene, and o-xylene (BTX) were oxidized completely over the SBM catalyst at reaction temperatures less than 410, 340, and 410 °C, respectively (gas hourly space velocity: 40,000 h-1). As expected, for the Pd/SBM catalysts, increasing the palladium loading on the SBM from 0.1 wt% to 1.0 wt% increased the conversions of BTX. In the 1.0 wt% Pd/SBM catalyst, the reaction temperatures for catalytic combustion of BTX were greatly reduced to 310, 260, and 250 °C, respectively (gas hourly space velocity: 40,000 h-1). Instrumental analysis indicated that the increase in activity by adding palladium resulted from the active ingredient (palladium oxide: PdO) and better redox properties.

Catalytic steam gasification of food waste using Ni-loaded rice husk derived biochar for hydrogen production.

The disposal of food waste (FW) is a major cause of environmental contamination. This study reports an environmentally friendly FW disposal method in the form of catalytic steam gasification using various types of Ni-loaded chars (untreated char, steam-treated char, and ZnCl2-treated char). The results were also compared with the gasification results from the Ni catalysts supported on commercial α-alumina (Ni/α-Al2O3). The Ni/steam-treated char showed the maximum hydrogen generation (0.471 mol/(g feedstock•g cat)) because of the high reducibility, high nickel dispersion, large amount of inherent K and Ca, and moderate surface area. The overall gas and H2 yield were observed in the following order: Ni/steam-treated char > Ni/ZnCl2 treated char > Ni/untreated char > Ni/α-Al2O3. Brunauer-Emmett-Teller analysis of various catalysts showed that the treated chars have a mesoporous structure, and the X-ray diffraction, X-ray fluorescence spectroscopy, scanning electron microscopy - energy dispersive spectroscopy showed that the presence of silica in the chars providing the stable support for the Ni loading and prevented coke formation. The chars obtained from biomass pretreatment could be a potential solution for preventing coke formation at high temperatures, thereby increasing the gas yield and enhancing hydrogen generation.

Production of value-added aromatics from wasted COVID-19 mask via catalytic pyrolysis.

In this study, wasted mask is chosen as a pyrolysis feedstock whose generation has incredibly increased these days due to COVID-19. We suggest a way to produce value-added chemicals (e.g., aromatic compounds) from the mask with high amounts through catalytic fast pyrolysis (CFP). To this end, the effects of zeolite catalyst properties on the upgradation efficiency of pyrolytic products produced from pyrolysis of wasted mask were investigated. The compositions and yields of pyrolytic gases and oils were characterized as functions of pyrolysis temperature and the type of zeolite catalyst (HBeta, HY, and HZSM-5), including the mesoporous catalyst of Al-MCM-41. The mask was pyrolyzed in a fixed bed reactor, and the pyrolysis gases evolved in the reactor was routed to a secondary reactor inside which the zeolite catalyst was loaded. It was chosen 550 °C as the CFP temperature to compare the catalyst performance for the production of benzene, toluene, ethylbenzene, and xylene (BTEX) because this temperature gave the highest oil yield (80.7 wt%) during the non-catalytic pyrolysis process. The large pore zeolite group of HBeta and HY led to 134% and 67% higher BTEX concentrations than HZSM-5, respectively, likely because they had larger pores, higher surface areas, and higher acid site density than the HZSM-5. This is the first report of the effect of zeolite characteristics on BTEX production via CFP.

Photocatalytic Reaction Properties of TiO2-Supported on the Long Lasting Phosphor: Sr4Al14O25:Eu2+,Dy3.

The TiO2/Sr4Al14O25:Eu2+,Dy3+ photocatalytic composite was prepared by depositing the nano-crystalline titanium dioxide layer on the long-lasting phosphor substrate of strontium aluminate, using a low-pressure chemical vapor deposition (LP-CVD). The photocatalysis characteristic was studied by examining the photodegradation of benzene (C6H6) gas under UV, visible light illumination, and in the darkness. The photocatalytic composite of TiO2-deposited Sr4Al14O25:Eu2+,Dy3+ showed an active photocatalytic reactivity under UV-light as well as visible-light illumination. The mechanism of the photocatalysis reaction for the TiO2-deposited strontium aluminate phosphor composite was interpreted in point of the energy band structure and phosphorescent emission. The coupling of nanocrystalline TiO2 with the strontium aluminate phosphor might result in an energy band bending at the interface of TiO2/Sr4Al14O25:Eu2+,Dy3+, making the titanium dioxide at the junction to be photo-reactive even in a visible wavelength region. In addition, the depth profile of Auger electron spectroscopy (AES) confirmed a possible formation of oxygen vacancies at the interface between TiO2 and Sr4Al14O25:Eu2+,Dy3+. Then, oxygen defects create extra electrons which may excited subsequently to the conduction band and participate in a photocatalytic reaction, resulting in an enhancement of the photodecomposition of benzene. The LP-CVD TiO2-strontium aluminate phosphor was also photoactive in the darkness because of light emission from the long lasting phosphor. Also, the TiO2-deposited Sr4Al14O25:Eu2+,Dy3+ long lasting phosphor was analyzed by a XRD (X-ray diffraction), TEM (transmission electron microscopy), UV/visible spectroscopy and AES.

Catalytic Oxidation of Toluene with Ozone Over the Ru-Mn/Desilicated Nanoporous H-Zeolite Socony Mobil-5 at Room Temperature.

In this study, the effect of Ru-Mn bimetallic catalysts in combination with a zeolite support on the removal of toluene in the presence of ozone at room temperature was investigated. Desili-cated HZSM-5 (DZSM) was fabricated and applied as a Ru-Mn support for the removal of toluene (100 ppm) in the presence of ozone (1000 ppm) at room temperature. The surface area, pore volume, and average pore size of Ru-Mn with a DZSM support (RuMn/DZSM) were measured and compared with those of Ru-Mn/HZSM-5 (RuMn/HZSM). The pore size of RuMn/DZSM (69 Å) was much larger than that of RuMn/HZSM-5 (5.5 Å). In addition, the pore volumes of RuMn/DZSM and RuMn/HZSM were 0.64 and 0.25 cm³/g, respectively. Furthermore, the ratios of Mn³+/Mn4+ and Ovacancy/Olattice of RuMn/DZSM were larger than those of RuMn/HZSM-5. The removal efficiency of toluene of RuMn/DZSM was higher than that of RuMn/HZSM due to its larger pore volume, pore size, and the increased ratios of Mn³+/Mn4+ and Ovacancy/Olattice.

Kinetic Analysis for the Catalytic Pyrolysis of Wood Plastic Composite Over Al-MCM-41.

This study examined the catalytic effects of Al-MCM-41 on the pyrolysis of wood plastic composite via the thermogravimetric analysis (TGA) and model-free kinetic analysis. Al-MCM-41 containing nanopores, with a high BET surface area (633 m²/g) and acidity (SiO2/Al2O3:25), reduced the decomposition temperature of wood and plastic mixtures (PE and PP) in a wood-plastic composite. The average activation energy for the catalytic pyrolysis of wood plastic composite, which was calculated via a model-free kinetic analysis method (Ozawa) of TGA, was also lower at all conversions than those of non-catalytic pyrolysis. This suggests that the pores of Al-MCM-41 and its high cracking efficiency allow the effective diffusion of wood plastic composite components.

Catalytic Performance of Supported Bimetallic Catalysts for Complete Oxidation of Toluene.

The complete oxidation of toluene (as a model volatile organic compound) was studied to determine the influence of adding a transition metal (Mn, Cr, Fe, Co, and Ni) to the 5 Cu/Al catalyst. The physcochemical properties of the catalysts were characterized by Brunauer-Emmett-Teller (BET) surface area analysis, X-ray diffraction (XRD) analysis, field emission transmission electron microscopy (FE/TEM), and hydrogen temperature programmed reduction (H2-TPR). The catalytic activity of the supported bimetallic catalysts followed the order: 5Cu-5Mn/Al > 5Cu-5Cr/Al > 5Cu-5Fe/Al > 5Cu-5Co/Al > 5Cu > 5Cu-5Ni/Al, based on the temperature for T90 of toluene conversion (T90). Two different reaction mechanisms (mixing and the synergistic effect) were operative in the supported bimetallic catalysts except for the 5Cu-5Mn/Al and 5Cu-5Ni/Al catalysts, on the basis of the reaction temperature. The difference between the electronegativity of copper and the added transition metal was associated with the catalytic activity.

Effective toluene oxidation under ozone over mesoporous MnOx/γ-Al2O3 catalyst prepared by solvent deficient method: Effect of Mn precursors on catalytic activity.

In this study, the role of manganese precursors in mesoporous (meso) MnOx/γ-Al2O3 catalysts was examined systematically for toluene oxidation under ozone at ambient temperature (20 °C). The meso MnOx/γ-Al2O3 catalysts developed with Mn(CH3COO)2, MnCl2, Mn(NO3)2.4H2O and MnSO4 were prepared by an innovative single step solvent-deficient method (SDM); the catalysts were labeled as MnOx/Al2O3(A), MnOx/Al2O3(C), MnOx/Al2O3(N), and MnOx/Al2O3(S), respectively. Among all, MnOx/Al2O3(C) showed superior performance both in toluene removal (95%) as well as ozone decomposition (88%) followed by acetate, nitrate and sulphated precursor MnOx/Al2O3. The superior performance of MnOx/Al2O3(C) in the oxidation of toluene to COx is associated with the ozone decomposition over highly dispersed MnOx in which extremely active oxygen radicals (O2-, O22- and O-) are generated to enhance the oxidation ability of the catalysts greatly. In addition, toluene adsorption over acid support played a vital role in this reaction. Hence, the properties such as optimum Mn3+/Mn4+ ratio, acidic sites, and smaller particle size (≤2 nm) examined by XPS, TPD of NH3, and TEM results are playing vital role in the present study. In summary, the MnOx/Al2O3 (C) catalyst has great potential in environmental applications particularly for the elimination of volatile organic compounds with low loading of manganese developed by SDM.