Enhanced biobased carbon materials made from softwood bark via a steam explosion preprocessing step for reactive orange 16 dye adsorption.

The growing textile industry produces large volumes of hazardous wastewater containing dyes, which stresses the need for cheap, efficient adsorbing technologies. This study investigates a novel preprocessing method for producing activated carbons from abundantly available softwood bark. The preprocessing involved a continuous steam explosion preconditioning step, chemical activation with ZnCl2, pyrolysis at 600 and 800 °C, and washing. The activated carbons were subsequently characterized by SEM, XPS, Raman and FTIR prior to evaluation for their effectiveness in adsorbing reactive orange 16 and two synthetic dyehouse effluents. Results showed that the steam-exploded carbon, pyrolyzed at 600 °C, obtained the highest BET specific surface area (1308 m2/g), the best Langmuir maximum adsorption of reactive orange 16 (218 mg g-1) and synthetic dyehouse effluents (>70 % removal) of the tested carbons. Finally, steam explosion preconditioning could open up new and potentially more sustainable process routes for producing functionalized active carbons.

Morphology and phosphate distribution in bottom ash particles from fixed-bed co-combustion of sewage sludge and two agricultural residues.

The purpose of this study was to provide detailed knowledge of the morphological properties of ash particles, including the volumetric fractions and 3D distributions of phosphates that lay within them. The ash particles came from digested sewage sludge co-combusted with K- and Si-rich wheat straw or K-rich sunflower husks. X-ray micro-tomography were combined with elemental composition and crystalline phase information to analyse the ash particles in 3D. Analyses of differences in the X-ray attenuation enabled calculation of 3D phosphate distributions that showed high heterogeneity in the slag particles. This is underscored by a distinct absence of phosphates in iron-rich and silicon-rich parts. The slag from silicate-based wheat straw mixtures had lower average attenuation than that from sunflower husks mixtures, which contained more calcium. Calculated shares of phosphates between 7 and 17 vol% were obtained, where the highest value for a single assigned phosphate was observed in hard slag from wheat straw with 10 % sewage sludge. The porosity was notably higher for particles from pure wheat straw combustion (62 vol%), compared to the other samples (15-35 vol%). A high open pore volume fraction (60-97 vol%) indicates that a large part of the pores can be accessed by the surroundings. For all samples, more than 60 % of the discrete (closed) pores had an equivalent diameter < 30 µm, while the largest volume fraction consisted of pores with an equivalent diameter > 75 µm. Slag from sunflower husk mixtures had larger pore volumes and a greater relative number of discrete pores >75 µm compared to wheat straw mixtures.

Wood waste-based functionalized natural hydrochar for the effective removal of Ce(III) ions from aqueous solution.

In this study, a sustainable and easily prepared hydrochar from wood waste was studied to adsorb and recover the rare earth element cerium (Ce(III)) from an aqueous solution. The results revealed that the hydrochar contains several surface functional groups (e.g., C-O, C = O, OH, COOH), which largely influenced its adsorption capacity. The effect of pH strongly influenced the Ce(III) removal, achieving its maximum removal efficiency at pH 6.0 and very low adsorption capacity under an acidic solution. The hydrochar proved to be highly efficient in Ce(III) adsorption reaching a maximum adsorption capacity of 327.9 mg g-1 at 298 K. The kinetic and equilibrium process were better fitted by the general order and Liu isotherm model, respectively. Possible mechanisms of Ce(III) adsorption on the hydrochar structure could be explained by electrostatic interactions and chelation between surface functional groups and the Ce(III). Furthermore, the hydrochar exhibited an excellent regeneration capacity upon using 1 mol L-1 of sulfuric acid (H2SO4) as eluent, and it was reused for three cycles without losing its adsorption performance. This research proposes a sustainable approach for developing an efficient adsorbent with excellent physicochemical and adsorption properties for Ce(III) removal.

Sustainable Biomass-Derived Carbon Electrodes for Potassium and Aluminum Batteries: Conceptualizing the Key Parameters for Improved Performance.

The development of sustainable, safe, low-cost, high energy and density power-density energy storage devices is most needed to electrify our modern needs to reach a carbon-neutral society by ~2050. Batteries are the backbones of future sustainable energy sources for both stationary off-grid and mobile plug-in electric vehicle applications. Biomass-derived carbon materials are extensively researched as efficient and sustainable electrode/anode candidates for lithium/sodium-ion chemistries due to their well-developed tailored textures (closed pores and defects) and large microcrystalline interlayer spacing and therefore opens-up their potential applications in sustainable potassium and aluminum batteries. The main purpose of this perspective is to brief the use of biomass residues for the preparation of carbon electrodes for potassium and aluminum batteries annexed to the biomass-derived carbon physicochemical structures and their aligned electrochemical properties. In addition, we presented an outlook as well as some challenges faced in this promising area of research. We believe that this review enlightens the readers with useful insights and a reasonable understanding of issues and challenges faced in the preparation, physicochemical properties and application of biomass-derived carbon materials as anodes and cathode candidates for potassium and aluminum batteries, respectively. In addition, this review can further help material scientists to seek out novel electrode materials from different types of biomasses, which opens up new avenues in the fabrication/development of next-generation sustainable and high-energy density batteries.

Facile Synthesis of Sustainable Activated Biochars with Different Pore Structures as Efficient Additive-Carbon-Free Anodes for Lithium- and Sodium-Ion Batteries.

The present work elucidates facile one-pot synthesis from biomass forestry waste (Norway spruce bark) and its chemical activation yielding high specific surface area (S BET) biochars as efficient lithium- and sodium-ion storage anodes. The chemically activated biochar using ZnCl2 (Biochar-1) produced a highly mesoporous carbon containing 96.1% mesopores in its structure as compared to only 56.1% mesoporosity from KOH-activated biochars (Biochar-2). The latter exhibited a lower degree of graphitization with disordered and defective carbon structures, while the former presented more formation of ordered graphite sheets in its structure as analyzed from Raman spectra. In addition, both biochars presented a high degree of functionalities on their surfaces but Biochar-1 presented a pyridinic-nitrogen group, which helps improve its electrochemical response. When tested electrochemically, Biochar-1 showed an excellent rate capability and the longest capacity retentions of 370 mA h g-1 at 100 mA g-1 (100 cycles), 332.4 mA h g-1 at 500 mA g-1 (1000 cycles), and 319 mA h g-1 at 1000 mA g-1 after 5000 cycles, rendering as an alternative biomass anode for lithium-ion batteries (LIBs). Moreover, as a negative electrode in sodium-ion batteries, Biochar-1 delivered discharge capacities of 147.7 mA h g-1 at 50 mA g-1 (140 cycles) and 126 mA h g-1 at 100 mA g-1 after 440 cycles.

Preparation and Characterization of Pulp and Paper Mill Sludge-Activated Biochars Using Alkaline Activation: A Box-Behnken Design Approach.

This study utilized pulp and paper mill sludge as a carbon source to produce activated biochar adsorbents. The response surface methodology (RSM) application for predicting and optimizing the activated biochar preparation conditions was investigated. Biochars were prepared based on a Box-Behnken design (BBD) approach with three independent factors (i.e., pyrolysis temperature, holding time, and KOH:biomass ratio), and the responses evaluated were specific surface area (SSA), micropore area (S micro), and mesopore area (S meso). According to the RSM and BBD analysis, a pyrolysis temperature of 800 °C for 3 h of holding and an impregnation ratio of 1:1 (biomass:KOH) are the optimum conditions for obtaining the highest SSA (885 m2 g-1). Maximized S micro was reached at 800 °C, 1 h and the ratio of 1:1, and for maximizing S meso (569.16 m2 g-1), 800 °C, 2 h and ratio 1:1.5 (445-473 m2 g-1) were employed. The biochars presented different micro- and mesoporosity characteristics depending on pyrolysis conditions. Elemental analysis showed that biochars exhibited high carbon and oxygen content. Raman analysis indicated that all biochars had disordered carbon structures with structural defects, which can boost their properties, e.g., by improving their adsorption performances. The hydrophobicity-hydrophilicity experiments showed very hydrophobic biochar surfaces. The biochars were used as adsorbents for diclofenac and amoxicillin. They presented very high adsorption performances, which could be explained by the pore filling, hydrophobic surface, and π-π electron-donor-acceptor interactions between aromatic rings of both adsorbent and adsorbate. The biochar with the highest surface area (and highest uptake performance) was subjected to regeneration tests, showing that it can be reused multiple times.

3-Aminopropyl-triethoxysilane-Functionalized Tannin-Rich Grape Biomass for the Adsorption of Methyl Orange Dye: Synthesis, Characterization, and the Adsorption Mechanism.

A biomass amino silica-functionalized material was successfully prepared by a simple sol-gel method. 3-Aminopropyltriethoxysilane (APTES) was added to a tannin-rich grape residue to improve its physicochemical properties and enhance the adsorption performance. The APTES functionalization led to significant changes in the material's characteristics. The functionalized material was efficiently applied in the removal of methyl orange (MO) due to its unique characteristics, such as an abundance of functional groups on its surface. The adsorption process suggests that the electrostatic interactions were the main acting mechanism of the MO dye removal, although other interactions can also take place. The functionalized biomass achieved a very high MO dye maximum adsorption capacity (Q max) of 361.8 mg g-1. The temperature positively affected the MO removal, and the thermodynamic studies indicated that the adsorption of MO onto APTES-functionalized biomass was spontaneous and endothermic, and enthalpy is driven in the physisorption mode. The regeneration performance revealed that the APTES-functionalized biomass material could be easily recycled and reused by maintaining very good performance even after five cycles. The adsorbent material was also employed to treat two simulated dye house effluents, which showed 48% removal. At last, the APTES biomass-based material may find significant applications as a multifunctional adsorbent and can be used further to separate pollutants from wastewater.

Facile Synthesis of Sustainable Biomass-Derived Porous Biochars as Promising Electrode Materials for High-Performance Supercapacitor Applications.

Preparing sustainable and highly efficient biochars as electrodes remains a challenge for building green energy storage devices. In this study, efficient carbon electrodes for supercapacitors were prepared via a facile and sustainable single-step pyrolysis method using spruce bark as a biomass precursor. Herein, biochars activated by KOH and ZnCl2 are explored as templates to be applied to prepare electrodes for supercapacitors. The physical and chemical properties of biochars for application as supercapacitors electrodes were strongly affected by factors such as the nature of the activators and the meso/microporosity, which is a critical condition that affects the internal resistance and diffusive conditions for the charge accumulation process in a real supercapacitor. Results confirmed a lower internal resistance and higher phase angle for devices prepared with ZnCl2 in association with a higher mesoporosity degree and distribution of Zn residues into the matrix. The ZnCl2-activated biochar electrodes' areal capacitance reached values of 342 mF cm-2 due to the interaction of electrical double-layer capacitance/pseudocapacitance mechanisms in a matrix that favors hydrophilic interactions and the permeation of electrolytes into the pores. The results obtained in this work strongly suggest that the spruce bark can be considered a high-efficiency precursor for biobased electrode preparation to be employed in SCs.

Process Parameters Optimization, Characterization, and Application of KOH-Activated Norway Spruce Bark Graphitic Biochars for Efficient Azo Dye Adsorption.

In this work, Norway spruce bark was used as a precursor to prepare activated biochars (BCs) via chemical activation with potassium hydroxide (KOH) as a chemical activator. A Box-Behnken design (BBD) was conducted to evaluate and identify the optimal conditions to reach high specific surface area and high mass yield of BC samples. The studied BC preparation parameters and their levels were as follows: pyrolysis temperature (700, 800, and 900 °C), holding time (1, 2, and 3 h), and ratio of the biomass: chemical activator of 1: 1, 1.5, and 2. The planned BBD yielded BC with extremely high SSA values, up to 2209 m2·g-1. In addition, the BCs were physiochemically characterized, and the results indicated that the BCs exhibited disordered carbon structures and presented a high quantity of O-bearing functional groups on their surfaces, which might improve their adsorption performance towards organic pollutant removal. The BC with the highest SSA value was then employed as an adsorbent to remove Evans blue dye (EB) and colorful effluents. The kinetic study followed a general-order (GO) model, as the most suitable model to describe the experimental data, while the Redlich-Peterson model fitted the equilibrium data better. The EB adsorption capacity was 396.1 mg·g-1. The employment of the BC in the treatment of synthetic effluents, with several dyes and other organic and inorganic compounds, returned a high percentage of removal degree up to 87.7%. Desorption and cyclability tests showed that the biochar can be efficiently regenerated, maintaining an adsorption capacity of 75% after 4 adsorption-desorption cycles. The results of this work pointed out that Norway spruce bark indeed is a promising precursor for producing biochars with very promising properties.

Morphological characterisation of ash particles from co-combustion of sewage sludge and wheat straw with X-ray microtomography.

Combustion of phosphorus-rich residual streams can produce nutrient-rich ashes and these can be used either in further processing or as materials for direct nutrient recycling. The latter requires knowledge on morphological parameters of such ash particles that may impact plant growth, nutrient availability, and soil physical properties. The present work aims to determine the porosity, pore size, and specific surface area of ash particles, and discuss these properties in light of literature concerning interaction with soil water and plant roots. Bottom ash particles from combustion of sewage sludge and wheat straw and their co-combustion were analysed with X-ray microtomography. Image analysis provided information on morphology, specific surface area, porosity, and pore structure on a micrometre scale resolution. Co-combusting sewage sludge with wheat straw resulted in differences in ash particles' porosity and pore structure compared to combustion of pure fuels. Pure wheat straw ash displayed 62 vol% porosity while there was no apparent difference between 10 wt% or 30 wt% mixtures of sewage sludge, with a porosity of 29-31 vol%. Open pore volume comprise the largest part of the porosity (72-99 vol%) enabling interaction between surrounding pore water and nutrients. Overall, the ash particles display large open volume fractions and thin particle walls which may lead to rapid weathering and extensive interaction with soil water. The particles generally contained pore openings over 200 µm towards the surroundings, which provide opportunities for interaction with microbes and roots from a variety of plant species in addition to nutrient transport by soil water.

A Short Review on the Electrochemical Performance of Hierarchical and Nitrogen-Doped Activated Biocarbon-Based Electrodes for Supercapacitors.

Cheap and efficient carbon electrodes (CEs) for energy storage systems (ESS) such as supercapacitors (SCs) and batteries are an increasing priority issue, among other things, due to a globally increasing share of intermittent electricity production (solar and wind) and electrification of transport. The increasing consumption of portable and non-portable electronic devices justifies research that enables environmentally and economically sustainable production (materials, processing techniques, and product design) of products with a high electrochemical performance at an acceptable cost. Among all the currently explored CEs materials, biomass-based activated carbons (AC) present enormous potential due to their availability and low-cost, easy processing methods, physicochemical stability, and methods for self-doping. Nitrogen doping methods in CEs for SCs have been demonstrated to enhance its conductivities, surface wettability, and induced pseudocapacitance effect, thereby delivering improved energy/power densities with versatile properties. Herein, a short review is presented, focusing on the different types of natural carbon sources for preparing CEs towards the fabrication of SCs with high electrochemical performance. The influences of ACs' pore characteristics (micro and mesoporosity) and nitrogen doping on the overall electrochemical performance (EP) are addressed.

Sustainable Biomass Activated Carbons as Electrodes for Battery and Supercapacitors-A Mini-Review.

Some recent developments in the preparation of biomass carbon electrodes (CEs) using various biomass residues for application in energy storage devices, such as batteries and supercapacitors, are presented in this work. The application of biomass residues as the primary precursor for the production of CEs has been increasing over the last years due to it being a renewable source with comparably low processing cost, providing prerequisites for a process that is economically and technically sustainable. Electrochemical energy storage technology is key to the sustainable development of autonomous and wearable electronic devices. This article highlights the application of various types of biomass in the production of CEs by using different types of pyrolysis and experimental conditions and denotes some possible effects on their final characteristics. An overview is provided on the use of different biomass types for the synthesis of CEs with efficient electrochemical properties for batteries and supercapacitors. This review showed that, from different biomass residues, it is possible to obtain CEs with different electrochemical properties and that they can be successfully applied in high-performance batteries and supercapacitors. As the research and development of producing CEs still faces a gap by linking the type and composition of biomass residues with the carbon electrodes' electrochemical performances in supercapacitor and battery applications, this work tries to diminish this gap. Physical and chemical characteristics of the CEs, such as porosity, chemical composition, and surface functionalities, are reflected in the electrochemical performances. It is expected that this review not only provides the reader with a good overview of using various biomass residues in the energy storage applications, but also highlights some goals and challenges remaining in the future research and development of this topic.

High quality biofuel pellet production from pre-compacted low density raw materials.

In this study, pre-compaction was evaluated as a method to enhance stable reed canary grass pellet production. An experimental design of the factors raw material moisture content, steam addition, raw material bulk density, and die temperature was used to find production conditions for high quality pellets by multiple linear regression modelling of responses. Response variables being modelled were variability of pelletizer current (as a measurement of uneven production), pellet bulk density, and pellet durability. By pre-compacting the raw material from a bulk density of 150 kg/m3 to 270kg/m3, continuous production could be obtained at minimum raw material moisture content of 13.8%. Bulk density and durability were both highly correlated to raw material moisture content, but showed different optima. Multiple response optimization was used to target process settings for production of high quality reed canary grass pellets with bulk density >650kg/m3 and durability >97.5%.