Unraveling the roles of microporous and micro-mesoporous structures of carbon supports on iron oxide properties and As (V) removal performance in contaminated water.

This study investigates the impact of microporous (SP-C) and micro-mesoporous carbon (DP-C) supports on the dispersion and phase transformation of iron oxides and their arsenic (V) removal efficiency. The research demonstrates that carbon-supported iron oxide sorbents exhibit superior As(V) uptake capacity compared to unsupported Fe2O3, attributed to reduced iron oxide crystallite sizes and As(V) adsorption on carbon supports. Maximum As(V) uptake capacities of 23.8 mg/g and 18.9 mg/g were achieved for Fe/SP-C and Fe/DP-C at 30 wt% and 50 wt% iron loading, respectively. The study reveals a nonlinear relationship between As(V) sorption capacity and iron oxide crystallite size after excluding As(V) adsorption capacity on carbon supports, suggesting the iron oxide phase (Fe3O4) plays a role in determining adsorption capacity. Iron oxide-loaded DP-C sorbents exhibit faster adsorption rates at low As(V) concentrations (5 mg/L) than SP-C sorbents due to their bimodal pore structure. Adsorption behavior varies at higher As(V) concentrations (45 mg/L), with Fe/DP-C reaching maximum capacity more slowly due to limited available adsorptive sites. All adsorbents maintained near-complete As(V) removal efficiency over five cycles. The findings provide insights for designing more efficient adsorbents for As(V) removal from contaminated water sources.

Potassium Permanganate-Impregnated Amorphous Silica-Alumina Derived from Sugar Cane Bagasse Ash as an Ethylene Scavenger for Extending Shelf Life of Mango Fruits.

Ethylene, a plant hormone, is a gas that plays a crucial role in fruit ripening and senescence. In this work, a novel ethylene scavenger was prepared from amorphous silica-alumina derived from sugar cane bagasse ash (SC-ASA) and used to prolong the shelf life of mango fruits during storage. KMnO4 at 2, 4, or 6 wt %/w was loaded on SC-ASA using an impregnation method. The results showed that 4% w/w KMnO4 loaded on SC-ASA (4KM/SC-ASA) was superior for ethylene removal at an initial ethylene concentration of 400 µL L-1 for 120 min under ambient conditions (25-27 °C and 70-75% relative humidity), resulting in 100% ethylene removal. The kinetic study of ethylene removal showed that the adsorption data were best fitted with a pseudo-first-order kinetic model. The effects of 4KM/SC-ASA as sachets on the quality changes of the mango fruits were investigated, with the results showing that mango fruits packed in cardboard boxes with 4KM/SC-ASA had significantly delayed ripening, low levels of ethylene production, respiration, and weight loss, high fruit firmness, low total soluble solids, and high acidity compared to those of the control treatment. These findings should contribute to developing an ethylene scavenger to extend the shelf life of fruits, reduce the waste of the sugar and ethanol industries, and make it a valuable material.

Production of PLA/cellulose derived from pineapple leaves as bio-degradable mulch film.

Mulch films were fabricated from polylactic acid (PLA) with cellulose nanocrystals (PNC) extracted from pineapple leaves. The PNC was modified by incorporating 4 wt% triethoxyvinylsilane (TEVS), designated as 4PNC, to enhance its interaction with PLA. The films incorporated varying concentrations of PNC (1, 2, 4, and 8 wt%). The results indicated that higher PNC concentrations increased the water vapor permeability (WVP) and biodegradability of the composite films, while reducing light transmission. Films containing 4PNC, particularly at 4 wt% (PLA/4PNC-4), exhibited an 11.18 % increase in elongation at break compared to neat PLA films. Moreover, these films showed reduced light transmission, correlating with decreased weed growth, reduced WVP, and enhanced barrier properties, indicative of improved soil moisture retention. Additionally, PLA films with 4PNC demonstrated greater thermal degradation stability than those with unmodified PNC, suggesting enhanced heat resistance. However, there was no significant difference in aerobic biodegradation between the PLA films with PNC and those with 4PNC. This study confirms that TEVS-modified cellulose significantly enhances the properties of bio-composite films, making them more suitable for mulch film applications.

Synthesis and Characterization of Environmentally Friendly ß-Cyclodextrin Cross-Linked Cellulose/Poly(vinyl alcohol) Hydrogels for Adsorption of Malathion.

The widespread use of malathion enhances agricultural plant productivity by eliminating pests, weeds, and diseases, but it may lead to serious environmental pollution and potential health risks for humans and animals. To mitigate these issues, environmentally friendly hydrogel adsorbents for malathion were synthesized using biodegradable polymers, specifically cellulose, ß-cyclodextrin (ß-CD), poly(vinyl alcohol) (PVA), and biobased epichlorohydrin as a cross-linker. This study investigated the effects of the cellulose-to-PVA ratio and epichlorohydrin (ECH) content on the properties and malathion adsorption capabilities of ß-CD/cellulose/PVA hydrogels. It was found that the gel content of the hydrogels increased with a higher cellulose-to PVA and ECH ratio, whereas the swelling ratio decreased, indicating a denser structure that impedes water permeation. In addition, various parameters affecting the malathion adsorption capacity of the hydrogel, namely, contact time, pH, hydrogel dosage, initial concentration of malathion, and temperature, were studied. The hydrogel prepared with a ß-CD/cellulose/PVA ratio of 20:40:40 and 9 mL of ECH exhibited the highest malathion adsorption rate and capacity, which indicated an equilibrium adsorption capacity of 656.41 mg g-1 at an initial malathion concentration of 1000 mg L-1. Fourier transform infrared spectroscopy (FTIR), ζ-potential, and X-ray photoelectron spectroscopy (XPS) and NMR spectroscopy confirmed malathion adsorption within the hydrogel. The adsorption process followed intraparticle diffusion kinetics and corresponded to Freundlich isotherms, indicating multilayer adsorption on heterogeneous substrates within the adsorbent, facilitated by diffusion.

Functionalization of cellulose nanocrystals extracted from pineapple leaves as a UV-absorbing agent in poly(lactic acid).

The cinnamate functionalization of cellulose nanocrystals (Cin-CNCs) was investigated as a potential organic reinforcing and UV-shielding agent in polylactic acid (PLA) films. Acid hydrolysis was used to extract cellulose nanocrystals (CNCs) from pineapple leaves. Through esterification with cinnamoyl chloride, the cinnamate group was grafted onto the CNC surface and the resulting Cin-CNCs were incorporated in PLA films as reinforcing and UV-shielding agents. The PLA nanocomposite films were prepared using a solution-casting method and were tested for mechanical/thermal properties, gas permeability, and UV absorption. Importantly, the functionalization of cinnamate on CNCs substantially improved the dispersion of fillers on the PLA matrix. The PLA films containing 3 wt% Cin-CNCs exhibited high transparency and UV absorption in the visible region. On the other hand, PLA films filled with pristine CNCs did not exhibit any UV-shielding properties. The mechanical properties revealed that adding 3 wt% Cin-CNCs to PLA increased its tensile strength and Young's modulus by 70% and 37%, respectively, compared to neat PLA. In addition, the incorporation of Cin-CNCs substantially improved water vapor and oxygen permeability. At 3 wt% Cin-CNC addition, the water vapor and oxygen permeability of PLA films were reduced by 54% and 55%, respectively. This study demonstrated the great potential in utilizing Cin-CNCs as effective gas barriers, dispersible nanoparticles, and UV-absorbing, nano-reinforcing agents in PLA films.

Pineapple-Leaf-Derived, Copper-PAN-Modified Regenerated Cellulose Sheet Used as a Hydrogen Sulfide Indicator.

Regenerated cellulose (RC) produced from waste pineapple leaves was used to develop a colorimetric sensor as a Cu-PAN sheet (RCS). Microcrystalline cellulose derived from dried pineapple leaves was combined with Cu-PAN, dissolved in NaOH and urea, and made into an RC sheet using Na2SO4 as a coagulant. The RCS was used as an H2S indicator at various H2S concentrations (0-50 ppm) and temperatures (5-25 °C). The RCS color changed from purple to New York pink when exposed to H2S. A colorimeter method was used to develop prediction curves with values of R2 > 0.95 for H2S concentrations at 5-25 °C. The physicochemical properties of fresh and spent RCS were characterized using various techniques (Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and thermogravimetric analysis). In addition, when stored at 5 and 25 °C for 90 days, the RCS had outstanding stability. The developed RCS could be applied to food packaging as an intelligent indicator of meat spoilage.

Oxidative coupling of methane-comparisons of MnTiO3-Na2WO4 and MnOx-TiO2-Na2WO4 catalysts on different silica supports.

The oxidative coupling of methane (OCM) converts CH4 to value-added chemicals (C2+), such as olefins and paraffin. For a series of MnTiO3-Na2WO4 (MnTiO3-NW) and MnOx-TiO2-Na2WO4 (Mn-Ti-NW), the effect of loading of MnTiO3 or MnOx-TiO2, respectively, on two different supports (sol-gel SiO2 (SG) and commercial fumed SiO2 (CS)) was examined. The catalyst with the highest C2+ yield (21.6% with 60.8% C2+ selectivity and 35.6% CH4 conversion) was 10 wt% MnTiO3-NW/SG with an olefins/paraffin ratio of 2.2. The catalyst surfaces with low oxygen-binding energies were associated with high CH4 conversion. Stability tests conducted for over 24 h revealed that SG-supported catalysts were more durable than those on CS because the active phase (especially Na2WO4) was more stable in SG than in CS. With the use of SG, the activity of MnTiO3-NW was not substantially different from that of Mn-Ti-NW, especially at high metal loading.

Effects of Mg, Ca, Sr, and Ba Dopants on the Performance of La2O3 Catalysts for the Oxidative Coupling of Methane.

Oxidative coupling of methane (OCM) is a reaction to directly convert methane into high value-added hydrocarbons (C2+) such as ethylene and ethane using molecular oxygen and a catalyst. This work investigated lanthanum oxide catalysts for OCM, which were promoted with alkaline-earth metal oxides (Mg, Ca, Sr, and Ba) and prepared by the solution-mixing method. The synthesized catalysts were characterized using X-ray powder diffraction, CO2-programmed desorption, and X-ray photoelectron spectroscopy. The comparative performance of each promoter showed that promising lanthanum-loaded alkaline-earth metal oxide catalysts were La-Sr and La-Ba. In contrast, the combination of La with Ca or Mg did not lead to a clear improvement of C2+ yield. The most promising LaSr50 catalyst exhibited the highest C2+ yield of 17.2%, with a 56.0% C2+ selectivity and a 30.9% CH4 conversion. Catalyst characterization indicated that their activity was strongly associated with moderate basic sites and surface-adsorbed oxygen species of O2 -. Moreover, the catalyst was stable over 25 h at a reactor temperature of 700 °C.

Sustainable utilization of waste glycerol for 1,3-propanediol production over Pt/WOx/Al2O3 catalysts: Effects of catalyst pore sizes and optimization of synthesis conditions.

Recycling of waste glycerol derived from biodiesel production to high value-added chemicals is essential for sustainable development of Bio-Circular-Green Economy. This work studied the conversion of glycerol to 1,3-propanediol over Pt/WOx/Al2O3 catalysts, pointing out the impacts of catalyst pore sizes and operating conditions for maximizing the yield of 1,3-propanediol. The results suggested that both pore confinement effect and number of available reactive metals as well as operating conditions determined the glycerol conversion and 1,3-propanediol selectivity. The small-pore 5Pt/WOx/S-Al2O3 catalyst (6.1 nm) gave a higher Pt dispersion (32.0%), a smaller Pt crystallite size (3.5 nm) and a higher number of acidity (0.47 mmol NH3 g-1) compared to those of the large-pore 5Pt/WOx/L-Al2O3 catalyst (40.3 nm). However, glycerol conversion and 1,3-propanediol yield over the small-pore 5Pt/WOx/S-Al2O3 catalyst were significantly lower than those of the large-pore Pt/WOx/L-Al2O3 catalyst, suggesting that the diffusional restriction within the small-pore catalyst suppressed transportation of molecules to expose catalytic active sites, favoring the excessive hydrogenolysis of 1,3-propanediol, giving rise to undesirable products. The best 1,3-propanediol yield of 32.8% at 78% glycerol conversion were achieved over the 5Pt/WOx/L-Al2O3 under optimal reaction condition of 220 °C, 6 MPa, 5 h reaction time and amount of catalyst to glycerol ratio of 0.25 g mL-1. However, the 1,3-propanediol yield and glycerol conversion decreased to 19.6% and 51% after the 4th reaction-regeneration which were attributed to the carbonaceous deposition and the agglomeration of Pt particles.

Modification of pineapple leaf fibers with aminosilanes as adsorbents for H2S removal.

Pineapple leaves were used as a natural fiber source to prepare various modified microcrystalline cellulose (MCC) samples as sorbents for H2S sorption. Pineapple leaf fibers were first extracted from pineapple leaves, followed by hydrolyzing to produce MCC before various modifications using primary amine (3-aminopropyltrimethoxysilane, APS), secondary amine (N-methyl-3-aminopropyltrimethoxysilane, MAPS), or tertiary amine (N,N-dimethyl-3-aminopropyltrimethoxysilane, DAPS). The characterization results proved that all the aminosilane groups were successfully grafted onto the MCC. In addition, the thermal stability and the porosity of the modified sorbents were enhanced relative to those of unmodified MCC. The H2S sorption studies of MCC modified with APS, MAPS, and DAPS at 0, 3, or 5%w/w showed that MCC-MAPS had better H2S sorption performance than MCC-APS and MCC-DAPS, respectively, when comparing the H2S sorption performance at the same loading level. The optimum H2S sorption performance of each aminosilane group was achieved from MCC-APS at 5%, MCC-MAPS at 3%, and MCC-DAPS at 5%. An additional study of H2S sorption of these three sorbents in the presence of CO2 showed that MCC-DAPS at 5% was the best sorbent for selective H2S removal. Our results indicated that MCC modified with the aminosilane groups, especially MAPS, were promising materials for H2S sorption, with potential application in gas separation.

Highly efficient TiO2-supported Co-Cu catalysts for conversion of glycerol to 1,2-propanediol.

Glycerol is a low-cost byproduct of the biodiesel manufacturing process, which can be used to synthesize various value-added chemicals. Among them, 1,2-propanediol (1,2-PDO) is of great interest because it can be used as an intermediate and additive in many applications. This work investigated the hydrogenolysis of glycerol to 1,2-PDO over Co-Cu bimetallic catalysts supported on TiO2 (denoted as CoCu/TiO2) in aqueous media. The catalysts were prepared using the co-impregnation method and their physicochemical properties were characterized using several techniques. The addition of appropriate Cu increased the glycerol conversion and the 1,2-PDO yield. The highest 1,2-PDO yield was achieved over a 15Co0.5Cu/TiO2 catalyst at 69.5% (glycerol conversion of 95.2% and 1,2-PDO selectivity of 73.0%). In the study on the effects of operating conditions, increasing the reaction temperature, initial pressure, and reaction time increased the glycerol conversion but decreased the selectivity to 1,2-PDO due to the degradation of formed 1,2-PDO to lower alcohols (1-propanol and 2-propanol). The reaction conditions to obtain the maximum 1,2-PDO yield were a catalyst-to-glycerol ratio of 0.028, a reaction temperature of 250 °C, an initial H2 pressure of 4 MPa, and a reaction time of 4 h.

Propylene Epoxidation to Propylene Oxide Over RuO2, CuO, TeO2, and TiO2 Supported on Modified Mesoporous Silicas.

Direct gas phase epoxidation of propylene to propylene oxide (PO) using O2 is a challenging problem in catalysis research. Silica-supported ruthenium-copper-based catalysts have been recently reported to be promising for propylene epoxidation. In this work, mesoporous silica supports modified with RuO2, CuO, and TeO2 with and without TiO2 were investigated for propylene epoxidation to PO. The prepared catalysts were divided into two groups. The first group consisted of mesoporous silica supports modified with RuO2, CuO, and TeO2, and the second group consisted of the same components as the first group but adding TiO2. The prepared supports and catalysts were characterized using BET surface area analysis and other advanced instrument techniques. It was found that the catalyst made with RuO2 and TeO2 impregnated onto porous silica modified with CuO and TiO2 (denoted as RuTe/CuTiSi) exhibited an excellent PO formation of 344 gPO h-1 kg-1cat, which was superior to that of the other prepared catalysts. Moreover, the addition of TiO2 into the catalyst greatly improved the PO formation rate and the arrangement of active components in the catalyst and strongly influenced catalytic performance.

Synthesis of Value-Added Chemicals via Oxidative Coupling of Methanes over Na2WO4-TiO2-MnO x /SiO2 Catalysts with Alkali or Alkali Earth Oxide Additives.

Na2WO4-TiO2-MnO x /SiO2 (SM) catalysts with alkali (Li, K, Rb, Cs) or alkali earth (Mg, Ca, Sr, Ba) oxide additives, which were prepared using incipient wetness impregnation, were investigated for oxidative coupling of methane (OCM) to value-added hydrocarbons (C2+). A screening test that was performed on the catalysts revealed that SM with Sr (SM-Sr) had the highest yield of C2+. X-ray photoelectron spectroscopy analyses indicated that the catalysts with a relatively low binding energy of W 4f7/2 facilitated a high CH4 conversion. A combination of crystalline MnTiO3, Mn2O3, α-cristobalite, Na2WO4, and TiO2 phases was identified as an essential component for a remarkable improvement in the activity of the catalysts in the OCM reaction. In attempts to optimize the C2+ yield, 0.25 wt % Sr onto SM-Sr achieved the highest C2+ yield at 22.9% with a 62.5% C2+ selectivity and a 36.6% CH4 conversion. A stability test of the optimal catalyst showed that after 24 h of testing, its activity decreased by 18.7%.

Removal of Heavy Metal Ions Using Modified Celluloses Prepared from Pineapple Leaf Fiber.

Since large amounts of pineapple leaves are abandoned after harvest in agricultural areas, the possibility of developing value-added products from them is of interest. In this work, cellulose fiber was extracted from pineapple leaves and modified with ethylenediaminetetraacetic acid (EDTA) and carboxymethyl (CM) groups to produce Cell-EDTA and Cell-CM, respectively, which were then used as heavy metal ion adsorbents. A solution of either lead ion (Pb2+) or cadmium ion (Cd2+) was used as wastewater for the purpose of studying adsorption efficiencies. The adsorption efficiencies of Cell-EDTA and Cell-CM were significantly higher than those of the unmodified cellulose in the pH range 1-7. Maximum adsorptions toward Pb2+ and Cd2+ were, for Cell-EDTA, 41.2 and 33.2 mg g-1, respectively, and, for Cell-CM, 63.4 and 23.0 mg g-1, respectively. The adsorption behaviors of Cell-CM for Pb2+ and Cd2+ fitted well with a pseudo-first-order model, but those of Cell-EDTA for Pb2+ and Cd2+ fitted well with a pseudo-second-order model. All of the adsorption behaviors could be described using the Langmuir adsorption isotherm. Desorption studies of Pb2+ and Cd2+ on both adsorbents using 1 M HCl suggested that regenerability of Cell-EDTA was, for both adsorbates, better than that of Cell-CM. Moreover, adsorption measurements in a mixture of Pb2+ and Cd2+ at various ratios showed that for both adsorbents the adsorption of Pb2+ was higher than that of Cd2+, while the adsorption selectivity for Pb2+ of Cell-CM was greater than that of Cell-EDTA. This study showed that the modified cellulosic adsorbents made from pineapple leaves were able to efficiently adsorb metal ions.

Synthesis of Dimethyl Ether via CO2 Hydrogenation: Effect of the Drying Technique of Alumina on Properties and Performance of Alumina-Supported Copper Catalysts.

Thermal treatment during catalyst preparation is one of the important factors affecting the characteristics and performance of a catalyst. To improve the catalytic performance of an alumina-supported copper catalyst prepared by an impregnation method for dimethyl ether (DME) synthesis from CO2, the effects of the use of hot air and infrared drying as well as calcination at 600 and 900 °C to prepare alumina supports were investigated. Infrared drying could shorten the required drying time by 75% when compared with hot air drying. Infrared drying could also help maintain the pore size and pore volume of the supports, leading to their larger surface areas. Different drying techniques were additionally noted to result in different sizes and shapes of the pores as well as to different copper distributions and intensities of acid sites of the catalyst. An increase in the calcination temperature resulted in a decrease in the surface area of the supports because of particle aggregation. The drying technique exhibited a more significant effect than calcination temperature on the space-time yield of DME. A catalyst utilizing the support prepared by infrared drying and then calcined at 600 °C exhibited the highest yield of DME (40.9 gDME kgcat -1 h-1) at a reaction temperature of 300 °C. Stability of the optimal catalyst, when monitored over a 24 h period, was noted to be excellent.

Novel Hybrid Conductor of Irregularly Patterned Graphene Mesh and Silver Nanowire Networks.

We prepared the hybrid conductor of the Ag nanowire (NW) network and irregularly patterned graphene (GP) mesh with enhanced optical transmittance (~98.5%) and mechano-electric stability (ΔR/Ro: ~42.4% at 200,000 (200k) cycles) under 6.7% strain. Irregularly patterned GP meshes were prepared with a bottom-side etching method using chemical etchant (HNO3). The GP mesh pattern was judiciously and easily tuned by the regulation of treatment time (0-180 min) and concentration (0-20 M) of chemical etchants. As-formed hybrid conductor of Ag NW and GP mesh exhibit enhanced/controllable electrical-optical properties and mechano-electric stabilities; hybrid conductor exhibits enhanced optical transmittance (TT = 98.5%) and improved conductivity (ΔRs: 22%) compared with that of a conventional hybrid conductor at similar TT. It is also noteworthy that our hybrid conductor shows far superior mechano-electric stability (ΔR/Ro: ~42.4% at 200k cycles; TT: ~98.5%) to that of controls (Ag NW (ΔR/Ro: ~293% at 200k cycles), Ag NW-pristine GP hybrid (ΔR/Ro: ~121% at 200k cycles)) ascribed to our unique hybrid structure.

Production of Glycerol Carbonate from Glycerol over Templated-Sodium-Aluminate Catalysts Prepared Using a Spray-Drying Method.

Glycerol carbonate (GLC) was synthesized from glycerol and dimethyl carbonate (DMC) over sodium aluminate (NaAlO2) catalysts. The catalysts were prepared using a spray-drying method and compared with those prepared using the conventional hot-air drying method. Polyvinylpyrrolidone and glycerol were used as a catalyst template to increase the surface area and porosity of the catalysts. Additionally, different operating conditions were investigated such as the catalyst concentration, glycerol-to-DMC ratio, reaction temperature, reaction time, and catalyst reusability. The NaAlO2 catalyst prepared using the spray-drying method with 30 wt % glycerol as the template yielded the maximum GLC (85%) with 100% GLC selectivity.

Thermally Robust Porous Bimetallic (Ni xPt1- x) Alloy Mesocrystals within Carbon Framework: High-Performance Catalysts for Oxygen Reduction and Hydrogenation Reactions.

Thermally stable porous bimetallic (Ni xPt1- x) alloy mesocrystals within a carbon framework are produced via an aerosol-assisted process for high-performance catalysts for the oxygen reduction reaction (ORR) and hydrogenation. The porous Ni xPt1- x alloy has a robust composite of alloy nanoparticles with an adjustable composition and a porous carbon skeleton. Porous Ni xPt1- x alloys exhibit high thermal stability, retaining their crystalline structure and morphology at 550 °C for 6 h, as observed in thermal treatment tests under various conditions (time, temperature, and atmosphere). The porous Ni xPt1- x alloy as a catalyst for the hydrogenation of propylene has high conversion efficiency (>80%) and low activation energy ( Ea < 20 kJ/mol) at ≥80 °C through the suitable control of the element composition and a pore structure. As a catalyst for the ORR, the catalytic activity of the porous Ni xPt1- x alloy is superior to that of conventional Pt/C (0.115 mA) (0.853 mA/cmPt2 at 0.9 V/cmPt2). This is attributed to the homogeneous alloying of the metal components (Ni and Pt) and the increased accessibility of the reactants to the catalyst, resulting from the unique morphology of the porous Ni xPt1- x alloy, i.e., hierarchical structure with high porosity.

High-Performance Asymmetric Supercapacitors of MnCo2O4 Nanofibers and N-Doped Reduced Graphene Oxide Aerogel.

The working potential of symmetric supercapacitors is not so wide because one type of material used for the supercapacitor electrodes prefers either positive or negative charge to both charges. To address this problem, a novel asymmetrical supercapacitor (ASC) of battery-type MnCo2O4 nanofibers (NFs)//N-doped reduced graphene oxide aerogel (N-rGOAE) was fabricated in this work. The MnCo2O4 NFs at the positive electrode store the negative charges, i.e., solvated OH-, while the N-rGOAE at the negative electrode stores the positive charges, i.e., solvated K+. An as-fabricated aqueous-based MnCo2O4//N-rGOAE ASC device can provide a wide operating potential of 1.8 V and high energy density and power density at 54 W h kg-1 and 9851 W kg-1, respectively, with 85.2% capacity retention over 3000 cycles. To understand the charge storage reaction mechanism of the MnCo2O4, the synchrotron-based X-ray absorption spectroscopy (XAS) technique was also used to determine the oxidation states of Co and Mn at the MnCo2O4 electrode after being electrochemically tested. The oxidation number of Co is oxidized from +2.76 to +2.85 after charging and reduced back to +2.75 after discharging. On the other hand, the oxidation state of Mn is reduced from +3.62 to +3.44 after charging and oxidized to +3.58 after discharging. Understanding in the oxidation states of Co and Mn at the MnCo2O4 electrode here leads to the awareness of the uncertain charge storage mechanism of the spinel-type oxide materials. High-performance ASC here in this work may be practically used in high-power applications.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors.

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGOae) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO2 during the charging process is 7.4 µg cm-2. Whilst, the mass change of the solvated ions at the N-rGOae electrode is 8.4 µg cm-2. An asymmetric supercapacitor of MnO2//N-rGOae (CR2016) provides a maximum specific capacitance of ca. 467 F g-1 at 1 A g-1, a maximum specific power of 39 kW kg-1 and a specific energy of 40 Wh kg-1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO2//N-rGOae supercapacitor may be practically used in high power and energy applications.