Sustainable Carbon Source from Almond Shell Waste: Synthesis, Characterization, and Electrochemical Properties
This study demonstrates the complete transformation of almond shell waste into a high-performance carbon material for carbon paste electrode (CPE) fabrication. The biocarbon was synthesized via carbonization at 800 °C and subsequently activated with CO2, resulting in a semicrystalline structure rich in carbonyl groups-consistent with its lignocellulosic origin (34.25% cellulose, 13.48% hemicellulose, 48.03% lignin). Carbonization increased the total pore volume of carbonized almond (CAR_ALD) by nearly 13-fold and the specific surface area by over two orders of magnitude compared to raw almond (RAW_ALD), while CO2 activation further enhanced activated almond's (ACT_ALD) surface area (~19%) and pore volume (~35%). To improve electrochemical performance, Bi2O3 doped with Sm was applied as a surface modifier. Comprehensive characterization (N2 physisorption X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopic Analysis (FTIR), X-Ray Photoelectron Spectroscopic Analysis (XPS), Thermogravimetric and Differential Thermal Analysis (TG-DTA), Cyclic voltammetry (CV), Electrochemical impedance spectroscopy (EIS)) confirmed the material's structural integrity, graphitic features, and successful modifier incorporation. Electrochemical testing revealed the highest current response (48 µA) for the CPE fabricated from CAR_ALD/Bi2O3-Sm, indicating superior electrocatalytic activity and reduced charge transfer resistance. Notably, this is the first report of a fully functional CPE working electrode fabricated entirely from waste material.
https://doi.org/10.3390/ma19010008
The Influence of Various Modifications of Hazelnut Shell Flour as Potential Filler in Plywood Technology
This study investigates the potential of utilizing hazelnut shells (HS) as an innovative filler in three-layer plywood technology, addressing the growing need for sustainable, high-performance materials. Traditional plywood production relies on adhesives enhanced with various fillers to improve physical, mechanical, and operational characteristics. This research explores using native, chemically modified, and activated carbon derived from hazelnut shells as fillers in urea-formaldehyde (UF) resin. The produced plywood's mechanical properties, water absorption, and formaldehyde emissions were thoroughly analyzed. Key findings demonstrate that incorporating 10 part by weight (pbw) native hazelnut shell flour significantly enhances the modulus of rupture (MOR) to 138.6 N mm-2 and modulus of elasticity (MOE) to 13,311 N mm-2. Chemically modified hazelnut shell flour achieves optimal results at 5 pbw, while activated carbon from hazelnut shells, even at 1 pbw, markedly improves bonding strength (2.79 N mm-2 referred to 0.81 N mm-2 for reference sample without filler added). Notably, activated carbon effectively reduces formaldehyde emissions (2.72 mg 100 g-1 oven dry panel referred to 3.32 mg 100 g-1 oven dry panel for reference samples with 10 pbw filler) and improves water resistance, indicating better further dimensional stability and lower environmental impact. The study also shows that excessive filler content negatively affects strength parameters, confirming the importance of optimizing filler concentration. These results highlight the potential of hazelnut shells as an eco-friendly alternative filler in plywood production, contributing to waste valorization and environmental sustainability. This study supports the practical application of hazelnut shell fillers, promoting a circular economy and reducing reliance on traditional, less sustainable materials, thus providing a valuable solution for the wood composite industry.
https://doi.org/10.3390/ma17164128
The Impact of Nutshell Biochar on the Environment as an Alternative Fuel or as a Soil Amendment.
Walnut, pistachio, and peanut nutshells were treated by pyrolysis to biochar and analyzed for their possible usage as fuels or soil fertilizers. All the samples were pyrolyzed to five different temperatures, i.e., 250 °C, 300 °C, 350 °C, 450 °C, and 550 °C. Proximate and elemental analyses were carried out for all the samples, as well as calorific value and stoichiometric analysis. For sample usage as a soil amendment, phytotoxicity testing was performed and the content of phenolics, flavonoids, tannin, juglone, and antioxidant activity were determined. To characterize the chemical composition of walnut, pistachio, and peanut shells, lignin, cellulose, holocellulose, hemicellulose, and extractives were determined. As a result, it was found that walnut shells and pistachio shells are best pyrolyzed at the temperature of 300 °C and peanut shells at the temperature of 550 °C for their use as alternative fuels. The highest measured net calorific value was in pistachio shells, which were biochar pyrolyzed at 550 °C, of 31.35 MJ kg−1. On the other hand, walnut biochar pyrolyzed at 550 °C had the highest ash share of 10.12% wt. For their use as soil fertilizers, peanut shells were the most suitable when pyrolyzed at 300 °C, walnut shells at 300 and 350 °C, and pistachio shells at 350 °C. https://doi.org/10.3390/ma16052074
Fluoride Bio-Sorption Efficiency and Antimicrobial Potency of Macadamia Nut Shells.
This paper presents the potential application of macadamia nut shells (MNS) in the bio-sorption of fluoride and its antimicrobial potency against common pathogens encountered in surface water resources. The efficiency of MNS in the sorption of fluoride was determined using batch mode experiments, while the antimicrobial potency was investigated using the well disc diffusion assay method. The maximum fluoride sorption capacity of 1.26 mg/g was recorded at an initial fluoride concentration of 5 mg/L, adsorbent dosage of 0.5 g/100 mL, contact time of 120 min and initial pH of 6. The adsorption kinetics data were better described with a pseudo second order model, indicating the dominance of the chemisorption mechanisms. The Langmuir adsorption isotherm model described the isotherm data suggesting a monolayered adsorption. The thermodynamic parameters, ∆Gº and ∆Hº, confirmed that F- sorption by MNS is a spontaneous and endothermic process. The bio-sorbent was regenerated for seven continuous cycles when HCl was used as regenerating solution. The antimicrobial studies revealed that MNS has minimal activity towards Escherichia coli, Staphylococcus aureus and Klebsiella pneumoniae. The MNS showed potentials for application in bio-sorption of fluoride. However, the doping of MNS with metal ions is recommended to enhance its anti-microbial potency. https://doi.org/10.3390/ma15031065
The Utilisation of Solid Fuels Derived from Waste Pistachio Shells in Direct Carbon Solid Oxide Fuel Cells.
The comprehensive results regarding the physicochemical properties of carbonaceous materials that are obtained from pistachio shells support their usage as solid fuels to supply direct carbon solid oxide fuel cells (DC-SOFCs). The influence of preparation conditions on variations in the chemical composition, morphology of the biochar powders, and degree of graphitization of carbonaceous materials were investigated. Based on structural investigations (X-ray diffraction analysis and Raman spectroscopy), it was observed that disordered carbon particles developed during the application of thermal treatments. The use of X-ray fluorescence enabled a comparative analysis of the chemical composition of the inorganic matter in biocarbon-based samples. Additionally, the gasification of carbonaceous-based samples vs. time at a temperature of 850 °C was investigated in a H2O or CO2 gas atmosphere. The analysis demonstrated the conversion rate of biochar obtained from pistachio shells to H2, CH4 and CO during steam gasification. The electrochemical investigations of the DC-SOFCs that were supplied with biochars obtained from pistachio shells were characterized by satisfactory values for the current and power densities at a temperature range of 700-850 °C. However, a higher power output of the DC-SOFCs was observed when CO2 was introduced to the anode chamber. Therefore, the impact of the Boudouard reaction on the performance of DC-SOFCs was confirmed. The chars that were prepared from pistachio shells were adequate for solid fuels for utilization in DC-SOFCs. https://doi.org/10.3390/ma14226755
An Evaluation of the Impact of the Amount of Potassium Hydroxide on the Porous Structure Development of Activated Carbons.
This paper presents the results of an evaluation of the impact of the amount of potassium hydroxide on the obtained porous structure of the activated carbons derived from the shells of pistachios, hazelnuts, and pecans by carbonization and subsequent chemical activation with potassium hydroxide by different adsorption methods: Brunauer-Emmett-Teller, Dubinin-Raduskevich, the new numerical clustering-based adsorption analysis, Quenched Solid Density Functional Theory, and 2D-Non-linear Density Functional Theory for Heterogeneous Surfaces, applied to nitrogen adsorption isotherms at -196 °C. Based on the conducted research, a significant potential for the production of activated carbons from waste materials, such as nut shells, has been demonstrated. All the activated carbons obtained in the present study at the activator/char mass ratio R = 4 exhibited the most developed porous structure, and thus very good adsorption properties. However, activated carbons obtained from pecan shells deserve special attention, as they were characterized by the most homogeneous surface among all the samples analyzed, i.e., by a very desirable feature in most adsorption processes. The paper demonstrates the necessity of using different methods to analyze the porous structure of activated carbons in order to obtain a complete picture of the studied texture. This is because only a full spectrum of information allows for correctly selecting the appropriate technology and conditions for the production of activated carbons dedicated to specific industrial applications. As shown in this work, relying only on the simplest methods of adsorption isotherm analysis can lead to erroneous conclusions due to lack of complete information on the analyzed porous structure. This work thus also explains how and why the usual characterizations of the porous structure of activated carbons derived from lignocellulosic biomass should not be taken at face value. On the contrary, it is advisable to cross reference several models to get a precise idea of the adsorbent properties of these materials, and therefore to propose the most suitable production technology, as well as the conditions of the preparation process.
https://doi.org/10.3390/ma14082045
Studies of Resistance of PP/Natural Filler Polymer Composites to Decomposition Caused by Fungi
The article discusses the grain morphology of the natural filler from hazelnut and walnut shell flour. It was observed that the geometry of both meals is similar to each other and resembles uneven balls in shape. The heterogeneity and well-developed outer surface of the flour grains allow for filling the voids with the polymer matrix. The analysis of the surface of the SEM images allowed to observe the presence of natural filler flour grains in the entire volume of the produced polymer composites, uneven distribution and small agglomerates, as well as the presence of voids, distributed in the matrix and in the matrix/filler interface. As a result of the visual evaluation of the activity of microorganisms (mycelium) on the surface of the produced polymer composite materials PP/hazelnut and walnut shell flour with a different % share, different fraction, it was found that the best fungistatic effect was shown by the samples marked with the symbol hazelnut at the fraction 315-443 µm. The least fungistatic material was found to be the samples with walnut shell meal filler at the fraction 315-443 µm (F2 and F4), on which the microorganisms achieved significant growth (more than 50% of the test area). The highest value of contact angle was obtained for samples with hazelnut filler fraction 315-443 (C2 and C4), which also confirms its best fungistatic effect.
https://doi.org/10.3390/ma14061368
Performance Characterization of Broad Band Sustainable Sound Absorbers Made of Almond Skins.
In order to limit the environmental impact caused by the use of non-renewable resources, a growing research interest is currently being shown in the reuse of agricultural by-products as new raw materials for green building panels. Moreover, the European directives impose the goal of sustainability supporting the investigation of passive solutions for the reduction of energy consumption. Thus, the promotion of innovative building materials for the enhancement of acoustic and thermal insulation of the buildings is an important issue. The aim of the present research was to evaluate the physical, acoustical, and thermal performances of building panels produced by almond skin residues, derived from the industrial processing of almonds. In this paper different mix designs were investigated using polyvinyl acetate glue and gum Arabic solution as binders. Air-flow resistivity σ and normal incidence sound absorption coefficient α were measured by means of a standing wave tube. Thermal conductivity λ, thermal diffusivity α, volumetric heat capacity ρc were measured using a transient plane source device. Finally, water vapor permeability δp was experimentally determined using the dry cup method. Furthermore, a physical characterization of the specimens in terms of bulk density ρb and porosity η allowed to study the correlation existing between the binder and the aggregates and the consequent acoustical and hygrothermal behavior occurring on the different mix designs. The achieved results suggested the investigated materials comparable to the main products currently existing on the market.
Application of Walnut Shells-Derived Biopolyol in the Synthesis of Rigid Polyurethane Foams.
This study aimed to examine rigid polyurethane (PUR) foam properties that were synthesized from walnut shells (WS)-based polyol. The Fourier Transform Infrared Spectroscopy (FTIR) results revealed that the liquefaction of walnut shells was successfully performed. The three types of polyurethane (PUR) foams were synthesized by replacement of 10, 20, and 30 wt% of a petrochemical polyol with WS-based polyol. The impact of WS-based polyol on the cellular morphology, mechanical, thermal, and insulating characteristics of PUR foams was examined. The produced PUR foams had apparent densities from 37 to 39 kg m-3, depending on the weight ratio of WS-based polyol. PUR foams that were obtained from WS-based polyol exhibited improved mechanical characteristics when compared with PUR foams that were derived from the petrochemical polyol. PUR foams produced from WS-based polyol showed compressive strength from 255 to 310 kPa, flexural strength from 420 to 458 kPa, and impact strength from 340 to 368 kPa. The foams that were produced from WS-based polyol exhibited less uniform cell structure than foams derived from the petrochemical polyol. The thermal conductivity of the PUR foams ranged between 0.026 and 0.032 W m-1K-1, depending on the concentration of WS-based polyol. The addition of WS-based polyol had no significant influence on the thermal degradation characteristics of PUR foams. The maximum temperature of thermal decomposition was observed for PUR foams with the highest loading of WS-based polyol.
Almond shell as a microporous carbon source for sustainable cathodes in lithium–sulfur batteries.
A microporous carbon derived from biomass (almond shells) and activated with phosphoric acid was analysed as a cathodic matrix in Li–S batteries. By studying the parameters of the carbonization process of this biomass residue, certain conditions were determined to obtain a high surface area of carbon (967 m2 g−1) and high porosity (0.49 cm3 g−1). This carbon was capable of accommodating up to 60% by weight of sulfur, infiltrated by the disulphide method. The C–S composite released an initial specific capacity of 915 mAh g−1 in the Li–S cell at a current density of 100 mA g−1 with a high retention capacity of 760 mAh g−1 after 100 cycles and a coulombic efficiency close to 100%. The good performance of the composite was also observed under higher current rates (up to 1000 mA g−1). The overall electrochemical behaviour of this microporous carbon acting as a sulfur host reinforces the possibility of using biomass residues as sustainable sources of materials for energy storage.