A novel approach for the facile synthesis of zinc oxide/carbon hybrid systems from corn distillers soluble: Surface modification and characterization for sustainable remediation.

Sustainable, efficient, and environmentally friendly ways to tailor the carbonaceous materials from bio sources with desired functionalities remain a challenge around the world. In this study, we represent a novel approach to synthesize carbon hybrid material based on Zinc Oxide/carbon (ZnO/C) hybrid systems by catalytic hydrothermal process via crosslinking reaction through nucleation and growth of ZnO particles at the functional groups of oxidized carbon material. This research explored the volarization of Condensed Corn Distillers Soluble (CDS) as a carbon precursor to synthesize biobased carbon spheres. Surface modification of the produced carbon spheres took place using zinc chloride (ZnCl2) during hydrothermal carbonization (HTC). Zinc chloride (ZnCl2) was used to function as a catalyst during HTC and functioned as a ZnO source to synthesize (ZnO/C) hybrid systems. Design Expert software v13 was used to design the hydrothermal carbonization (HTC) experiments and response surface methodology was used to find the optimized conditions for the preparation of carbon hybrid systems. The hydrothermal synthesis process introduced 3D stone like zinc oxide particles onto the carbon matrix. These particles were self-assembled onto the carbon framework to produce carbon hybrid systems with unique physical, chemical, structural and functional properties. Herein, the obtained carbon hybrid systems (ZnO/C) were investigated and discussed in detail. ZnO/C hybrid systems were analyzed for surface morphology using scanning electron microscopy (SEM) that presented a 3D spherical interconnected phase and XRD analyses were used for phase crystallinity that showed new crystalline phases such as hopeite and zincite after the ZnCl2 incorporation. Surface functional groups were also analyzed by FTIR and results confirmed the presence of hydrophilic groups such as -OH, CC, and COOH on the surface of ZnO/C hybrid carbon systems. This study provided the insightful guidance for tailoring novel design of multifunctional carbon material as an adsorbent/catalyst for various applications of sustainable remediation.

Designing 3D Ternary Hybrid Composites Composed of Graphene, Biochar and Manganese Dioxide as High-Performance Supercapacitor Electrodes.

Biochar derived from waste biomass has proven to be an encouraging novel electrode material in supercapacitors. In this work, luffa sponge-derived activated carbon with a special structure is produced through carbonization and KOH activation. The reduced graphene oxide (rGO) and manganese dioxide (MnO2) are in-situ synthesized on luffa-activated carbon (LAC) to improve the supercapacitive behavior. The structure and morphology of LAC, LAC-rGO and LAC-rGO-MnO2 are characterized by the employment of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), BET analysis, Raman spectroscopy and scanning electron microscopy (SEM). The electrochemical performance of electrodes is performed in two and three-electrode systems. In the asymmetrical two-electrode system, the LAC-rGO-MnO2//Co3O4-rGO device shows high specific capacitance (SC), high-rate capability and excellent cycle reversibly in a wide potential window of 0-1.8 V. The maximum specific capacitance (SC) of the asymmetric device is 586 F g-1 at a scan rate of 2 mV s-1. More importantly, the LAC-rGO-MnO2//Co3O4-rGO device exhibits a specific energy of 31.4 W h kg-1 at a specific power of 400 W kg-1. Overall, the synergistic effect between the ternary structures of microporous LAC, rGO sheets and MnO2 nanoparticles leads to the introduction of high-performance hierarchical supercapacitor electrodes.

In vitro plant tissue culture as the fifth generation of bioenergy.

Developing and applying a novel and sustainable energy crop is essential to reach an efficient and economically feasible technology for bioenergy production. In this study, plant tissue culture, also referred to as in vitro culture, is introduced as one of the most promising and environmentally friendly methods for the sustainable supply of biofuels. The current study investigates the potential of in vitro -grown industrial hemp calli obtained from leaf, root, and stem explants as a new generation of energy crop. For this purpose, the in vitro grown explants were first fully characterized in terms of elemental and chemical composition. Secondly, HTL experiments were designed by Design Expert 11 with a particular focus on biocrude. Finally, the chemical components, functional groups, and petroleum-like hydrocarbons present in the biocrude were identified by PY-GCMS. A 22.61 wt.% biocrude was produced for the sample grown through callogenesis of the leaf (CL). The obtained biocrude for CL consisted of 19.55% acids, 0.42% N compounds, 15.44% ketones, 16.03% aldehydes, 2.21% furans, 20.01% aromatics, 5.2% alcohols, and 19.88% hydrocarbons. To the best of the authors' knowledge, this is the first report that in vitro -grown biomass is hydrothermally liquefied toward biocrude production; the current work paves the way for integrating plant tissue culture and thermochemical processes for the generation of biofuels and value-added chemicals.

A state-of-the-art review on algae pyrolysis for bioenergy and biochar production.

Algae, as a feedstock with minimum land footprint, is considered a promising biomass for sustainable fuels, chemicals, and materials. Unlike lignocellulosic biomass, algae consist mainly of lipids, carbohydrates, and proteins. This review focusses on the bio-oil and biochar co-products of algae-pyrolysis and presents the current state-of-the-art in the pyrolysis technologies and key applications of algal biochar. Algal biochar holds potential to be a cost-effective fertilizer, as it has high P, N and other nutrient contents. Beyond soil applications, algae-derived biochar has many other applications, such as wastewater-treatment, due to its porous structure and strong ion-exchange capacity. High specific capacitance and stability also make algal biochar a potential supercapacitor material. Furthermore, algal biochar can be great catalysts (or catalyst supports). This review sheds light on a wide range of algae-pyrolysis related topics, including advanced-pyrolysis techniques and the potential biochar applications in soil amendment, energy storage, catalysts, chemical industries, and wastewater-treatment plants.

Effects of FeCl3 Catalytic Hydrothermal Carbonization on Chemical Activation of Corn Wet Distillers' Fiber.

Corn wet distillers' fiber (corn fiber) is a byproduct of the corn-ethanol production process, with high potential as a precursor for activated carbon due to its moderate nitrogen content and availability. However, there has been limited investigation into activated carbons from the corn fiber. In this work, we produce activated carbons from the corn fiber using three procedures, including direct KOH activation, hydrothermal carbonization (HTC) followed by KOH activation, and FeCl3-catalyzed HTC followed by KOH activation. Catalytic HTC with FeCl3 was found to slightly increase the degree of carbonization relative to uncatalyzed HTC while also removing the nitrogen content at increasing concentrations and slightly increasing the porosity. The resulting activated carbon samples are then characterized by thermal gravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and nitrogen analysis. The two-step process resulted in activated carbon with substantially higher surface areas than the one-step process (1220 vs 789 m2/g), as well as much higher thermal stability and nitrogen content (up to 1.20%). The results show that the corn fiber has potential for activated carbon production, with the two-step HTC followed by the activation process producing more favorable material properties than direct activation.

Integrated hybrid architecture of metal and biochar for high performance asymmetric supercapacitors.

Two state-of-the-art electrodes were successfully synthesized and used to assemble both symmetric and asymmetric type supercapacitors. 3DFAB was fabricated by direct pyrolysis of green macroalgae in the presence of NaOH. Possible NaOH activation mechanisms are proposed, which explains the formation of oxygen functional groups through quick penetration of OH- and NaOH into the vacancies. To obtain CoTLM, the tile-like architecture of cobalt oxides was introduced to the 3D interconnected functional algal biochar (3DFAB) by a simple one-pot hydrothermal method under mild conditions. For the symmetric supercapacitors, the maximum specific capacitance of RAB, 3DFAB, and CoTLM were 158, 296, and 445 F g-1 at the current density of 1 A g-1. Regarding cobalt-based asymmetric systems, the maximum capacitance for the 3DFAB//CoTLM was 411 F g-1. This asymmetric supercapacitor device also retained 100.9% of its initial capacitance after 4000 cycles at the current density of 4 A g-1. Unbuffered aqueous electrolyte and the unique morphological structure used in this study might catapult forward commercialization of such advanced energy storage devices.

Experimental studies on high-quality bio-oil production via pyrolysis of Azolla by the use of a three metallic/modified pyrochar catalyst.

In this study, the potential of the pyrolysis method to overcome the negative effects of Azolla-filiculoides in infected areas was thoroughly investigated. Non-catalytic pyrolysis experiments were conducted at a temperature range of 400-700 °C. The highest possible bio-oil yield (35 wt%) was attained at 500 °C. To achieve the best chemical composition of bio-oil and higher amount of synthesis gas the catalytic pyrolysis were conducted in a dual-bed quartz reactor at the optimum temperature (500 °C). Although, all three catalysts (pyro-char, modified pyro-char (MPC), and Mg-Ni-Mo/MPC) showed almost an impressive performance in promotion of the common reactions, Mg-Ni-Mo/MPC catalyst have illustrated the stunning results by increasing the percentage of furan compounds from 5.25% to 33.07%, and decreasing the acid compounds from 25.56% to 9.09%. Using GC-MS and GC-FID liquid and gaseous products were fully analyzed. The carbon-based catalysts were also evaluated via FTIR, FESEM, EDX, and BET analyses.

Pyrolysis of marine biomass to produce bio-oil and its upgrading using a novel multi-metal catalyst prepared from the spent car catalytic converter.

In order to reduce the economic and environmental consequences caused by spent car catalyst, we herein report for the first time a novel promising multi-metal catalyst prepared from spent car catalytic converters to upgrade the pyrolysis bio-oils. The physico-chemical properties of prepared catalyst were characterized by XRD, EDS, FESEM, and FT-IR analyses. The thermal stability of the multi-metal catalyst was studied with TGA. To investigate the activity of the catalyst, Conversion of Cladophora glomerata (C. glomerata) into bio-products was carried out via a fixed bed reactor with and without catalyst at the temperature of 500°C. Although the catalyst didn't catalyze the gasification reaction, bio-oil was upgraded over the catalyst. The main effect of the catalyst on the bio-oil components is deoxygenating of nitrogen compounds and promotion the ketonization reaction, which converts acid to ketone and declines the corrosive nature of bio-oil.

Turning an environmental problem into an opportunity: potential use of biochar derived from a harmful marine biomass named Cladophora glomerata as anode electrode for Li-ion batteries.

The electrochemical performance of lithium ion battery was enhanced by using biochar derived from Cladophora glomerata (C. glomerata) as widespread green macroalgae in most areas of the Iran's Caspian sea coast. By the utilization of the structure of the biochar, micro-/macro-ordered porous carbon with olive-shaped structure was successfully achieved through pyrolysis at 500 °C, which is the optimal temperature for biofuel production, and was activated with HCl. The biochar and HCl treatment biochar (HTB) were applied as anode electrode in lithium ion batteries. Then, electrochemical measurements were conducted on the electrodes via galvanostatic charge-discharge, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) analyses. The electrochemical results indicated a higher specific discharge capacity (700 mAh g-1) and good cycling stability for HTB at the current density of 0.1 A g-1 as compared to the biochar. The reason that HTB electrode works better than the biochar could be due to the higher surface area, formation functional groups, removal impurities, and formation some micropores after HCl treatment. The biochar derived from marine biomass and treatment process developed here could provide a promising path for the low-cost, renewable, and environmentally friendly electrode materials. Graphical abstract Algal-biochar into Li-ion Battery.

Catalytic upgrading of bio-products derived from pyrolysis of red macroalgae Gracilaria gracilis with a promising novel micro/mesoporous catalyst.

Conversion of Gracilaria gracilis (G. gracilis) into bio-products was carried out via pyrolysis at different temperatures to determine its potential for phenol-rich bio-oil. Co-Mo supported on zeolites (HZSM-5), mesoporous (HMS) catalysts and their composites (ZH) were investigated and compared to each other on catalytic pyrolysis processes. In non-catalytic tests, the maximum weight percentage of bio-oil was 42wt% at 500°C and had the maximum amount of phenol (6.28wt%). in the catalytic tests by ZH composites; the addition of zeolite content in the structure of composites significantly decreased total concentrations of acetic acid and formic acid from 9.56 to 8.12wt% and slightly decreased phenol and furfural concentrations from 6.65 and 6.98 to 5.88 and 5.49wt%, respectively. Furthermore, the best selectivity for hydrogen yield (6.08mmol/g macroalgae) and lowest amount of acetic acid (5.4wt%) was observed for CoMo/ZH-20 catalyst, that is synthesized by 20wt% of zeolite.

Hydrothermal gasification of Cladophora glomerata macroalgae over its hydrochar as a catalyst for hydrogen-rich gas production.

A tubular batch micro-reactor system was used for hydrothermal gasification (HTG) of Cladophora glomerata (C. glomerata) as green macroalgae found in the southern coast of the Caspian Sea, Iran. Non-catalytic tests were performed to determine the optimum condition for hydrogen production. Hydrochar, as a solid residue of non-catalytic HTG was characterized by BET, FESEM, and ICP-OES methods to determine its physiochemical properties. Surface area and pore volume of C. glomerata increased drastically after HTG. Also, the aqueous products were identified and quantified by GC-MS and GC-FID methods. Hydrochar was loaded to the reactor to determine its catalytic effect on HTG. HTG was promoted by inorganic compounds in the hydrochar and its porosity. The maximum hydrogen yield of 9.63mmol/g was observed in the presence of algal hydrochar with the weight ratio of 0.4 to feedstock. Also, acids production was inhibited while phenol production was promoted in the presence of hydrochar.

Promotion of hydrogen-rich gas and phenolic-rich bio-oil production from green macroalgae Cladophora glomerata via pyrolysis over its bio-char.

Conversion of Cladophora glomerata (C. glomerata) as a Caspian Sea's green macroalgae into gaseous, liquid and solid products was carried out via pyrolysis at different temperatures to determine its potential for bio-oil and hydrogen-rich gas production for further industrial utilization. Non-catalytic tests were performed to determine the optimum condition for bio-oil production. The highest portion of bio-oil was retrieved at 500°C. The catalytic test was performed using the bio-char derived at 500°C as a catalyst. Effect of the addition of the algal bio-char on the composition of the bio-oil and also gaseous products was investigated. Pyrolysis derived bio-char was characterized by BET, FESEM and ICP method to show its surface area, porosity, and presence of inorganic metals on its surface, respectively. Phenols were increased from 8.5 to 20.76area% by the addition of bio-char. Moreover, the hydrogen concentration and hydrogen selectivity were also enhanced by the factors of 1.37, 1.59 respectively.