Microalgae are increasingly viewed as renewable biological resources for a wide range of chemical compounds that can be used as or transformed into biomaterials through biorefining to foster the bioeconomy of the future. Besides the well-established biofuel potential of microalgae, key microalgal bioactive compounds, such as lipids, proteins, polysaccharides, pigments, vitamins, and polyphenols, possess a wide range of biomedical and nutritional attributes. Hence, microalgae can find value-added applications in the nutraceutical, pharmaceutical, cosmetics, personal care, animal food, and agricultural industries. Microalgal biomass can be processed into biomaterials for use in dyes, paints, bioplastics, biopolymers, and nanoparticles, or as hydrochar and biochar in solid fuel cells and soil amendments. Equally important is the use of microalgae in environmental applications, where they can serve in heavy metal bioremediation, wastewater treatment, and carbon sequestration thanks to their nutrient uptake and adsorptive properties. The present article provides a comprehensive review of microalgae specifically focused on biomaterial production and environmental applications in an effort to assess their current status and spur further deployment into the commercial arena.
Theobroma cacao L. species, cultivated worldwide for its valuable beans, generates up to 72% weight of the fruit as waste. The lack of reutilization technologies in the cocoa agroindustry has hindered the exploitation of valuable bio-components applicable to the generation of high value added bioproducts. One such bioproduct is microfibrillated cellulose (MFC), a biopolymer that stands out for its desirable mechanical properties and biocompatibility in biomedical, packing, 3D printing, and construction applications. In this study, we isolated microfibrillated cellulose (MFC) from cocoa pod husk (CPH) via oxalic acid hydrolysis combined with a steam explosion. MFC isolation started with the Solid/Liquid extraction via Soxhlet, followed by mild citric acid hydrolysis, diluted alkaline hydrolysis, and bleaching pre-treatments. A Response Surface Methodology (RSM) was used to optimize the hydrolysis reaction at levels between 110 and 125 °C, 30–90 min at 5–10% (w/v) oxalic acid concentration. The cellulose-rich fraction was characterized by Fourier-Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD), and Scanning Electron Microscopy (SEM) analyses. Characterization analyses revealed a cellulose-rich polymer with fibers ranging from 6 to 10 μm, a maximum thermal degradation temperature of 350 °C, and a crystallinity index of 63.4% (peak height method) and 29.0% (amorphous subtraction method). The optimized hydrolysis conditions were 125 °C, 30 min, at 5% w/v oxalic acid: with a 75.7% yield. These results compare with MFC obtained through highly concentrated inorganic acid hydrolysis from different biomass sources. Thus, we show a reliable and greener alternative chemical treatment for the obtention of MFC.
Catalytic biomass pyrolysis is one of the most promising routes for obtaining bio-sustainable products that replace petroleum derivatives. This study evaluates the production of aromatic compounds (benzene, toluene, and xylene (BTX)) from the catalytic pyrolysis of lignocellulosic biomass (Pinus radiata (PR) and Eucalyptus globulus (EG)). Chilean natural zeolite (NZ) was used as a catalyst for pyrolysis reactions, which was modified by double ion exchange (H2NZ) and transition metals impregnation (Cu5H2NZ and Ni5H2NZ). The catalysts were characterized by nitrogen adsorption, X-ray diffraction (XRD), ammonium programmed desorption (TPD-NH3), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). Analytical pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) allowed us to study the influence of natural and modified zeolite catalysts on BTX production. XRD analysis confirmed the presence of metal oxides (CuO and NiO) in the zeolite framework, and SEM-EDS confirmed successful metal impregnation (6.20% for Cu5H2NZ and 6.97% for Ni5H2NZ). Py-GC/MS revealed a reduction in oxygenated compounds such as esters, ketones, and phenols, along with an increase in aromatic compounds in PR from 2.92% w/w (without catalyst) to 20.89% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/5, and in EG from 2.69% w/w (without catalyst) to 30.53% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/2.5. These increases can be attributed to acidic sites within the catalyst pores or on their surface, facilitating deoxygenation reactions such as dehydration, decarboxylation, decarbonylation, aldol condensation, and aromatization. Overall, this study demonstrated that the catalytic biomass pyrolysis process using Chilean natural zeolite modified with double ion exchange and impregnated with transition metals (Cu and Ni) could be highly advantageous for achieving significant conversion of oxygenated compounds into hydrocarbons and, consequently, improving the quality of the condensed pyrolysis vapors.
Herein, the green synthesis of silver nanoparticles (AgNPs), assisted by LED light, using the aqueous extracts of agroindustrial waste products, such as avocado seeds (ASs), cocoa pod husks (CPHs), and orange peels (OPs), is presented. Surface plasmon resonance analysis showed faster and complete NP formation when irradiated with blue LED light. Green and red light irradiation showed non- and limited nanoparticle formation. TEM analyses confirmed the semispherical morphology of the synthesized AgNPs, with the exception of OP–AgNPs, which showed agglomeration during the light irradiation. For AS–AgNPs and CPH–AgNPs, the average particle diameter was about 15 nm. Interestingly, the CPH extract demonstrated faster nanoparticle formation as compared to the AS extract (100 min vs. 250 min irradiation time, respectively). FTIR spectroscopy assessed the involvement of diverse functional groups of the bioactive phytochemicals present in the plant extracts during nanoparticle photobiosynthesis. The antioxidant activity, as determined by ferric reducing antioxidant power (FRAP) assay, varied from 1323.72 µmol TE/mL in the AS aqueous extract to 836.50 µmol TE/mL in the CPH aqueous extract. The total polyphenol content was determined according to the Folin–Ciocalteu procedure; the AS aqueous extract exhibited a higher polyphenol content (1.54 mg GAE/g) than did the CPH aqueous extract (0.948 mg GAE/g). In vitro antibacterial assays revealed that the AS–AgNPs exhibited promising antibacterial properties against pathogenic bacteria (E. Coli), whereas the CPH–AgNPs showed antibacterial activity against S. aureus and E. coli. The green synthesis of AgNPs using AS, CPH, and OP aqueous extracts reported in this work is environmentally friendly and cost-effective, and it paves the way for future studies related to agroindustrial waste valorization for the production of advanced nanomaterials, such as antibacterial AgNPs, for potential biomedical, industrial, and environmental applications.