Fractionation of oil palm fronds using ethanol-assisted deep eutectic solvent: Influence of ethanol concentration on enhancing enzymatic saccharification and lignin ß-O-4 content.

Numerous fractionation methods have been developed in recent years for separating components such as cellulose, hemicellulose, and lignin from lignocellulosic biomass wastes. Deep eutectic solvents (DES) have recently been widely investigated as captivating green solvents for biomass fractionation. However, most acidic-based deep eutectic solvent fractionation produces condensed lignin with low ß-O-4 content. Besides, most DESs exhibit high viscosity, which results in poor mass transfer properties. This study aimed to address the challenges above by incorporating ethanol into the deep eutectic solvent at various concentrations (10-50 wt%) to fractionate oil palm fronds at a mild condition, i.e., 80 °C, 1 atm. Cellulose residues fractionated with ethanol-assisted deep eutectic solvent showed a maximum glucose yield of 85.8% when 20 wt% of ethanol was incorporated in the deep eutectic solvent, significantly higher than that achieved by pure DES (44.8%). Lignin extracted with ethanol-assisted deep eutectic solvent is lighter in color and higher in ß-O-4 contents (up to 44 ß-O-4 per 100 aromatic units) than pure DES-extracted lignin. Overall, this study has demonstrated that incorporating ethanol into deep eutectic solvents could enhance the applicability of deep eutectic solvents in the complete valorization of lignocellulosic biomass. Highly enzymatic digestible cellulose-rich solid and ß-O-4-rich lignin attained from the fractionation could serve as sustainable precursors for the production of biofuels.

Self-Reconstruction of Sulfate-Terminated Copper Oxide Nanorods for Efficient and Stable 5-Hydroxymethylfurfural Electrooxidation.

The electrochemical 5-hydroxymethylfurfural oxidation reaction (HMFOR) has been regarded as a viable alternative to sustainable biomass valorization. However, the transformation of the catalysts under harsh electrooxidation conditions remains controversial. Herein, we confirm the self-construction of cuprous sulfide nanosheets (Cu2S NSs) into sulfate-terminated copper oxide nanorods (CuO-SO42- NRs) during the first-cycle of the HMFOR, which achieves a near-quantitative synthesis of 2,5-furandicarboxylic acid (FDCA) with a >99.9% yield and faradaic efficiency without deactivation in 15 successive cycles. Electrochemical impedance spectroscopies confirm that the surface SO42- effectively reduces the onset potential for HMFOR, while in situ Raman spectroscopies identify a reversible transformation from CuII-O to CuIII-OOH in HMFOR. Furthermore, density functional theory calculations reveal that the surface SO42- weakens the Cu-OH bonds in CuOOH to promote the rate-determining step of its coupling with the C atom in HMF-H* resulting from HMF hydrogenation, which synergistically enhances the catalytic activity of CuO-SO42- NRs toward HMF-to-FDCA conversion.

A Network of Processes for Biorefining Burdock Seeds and Roots.

In this work, a novel sustainable approach was proposed for the integral valorisation of Arctium lappa (burdock) seeds and roots. Firstly, a preliminary recovery of bioactive compounds, including unsaturated fatty acids, was performed. Then, simple sugars (i.e., fructose and sucrose) and phenolic compounds were extracted by using compressed fluids (supercritical CO2 and propane). Consequently, a complete characterisation of raw biomass and extraction residues was carried out to determine the starting chemical composition in terms of residual lipids, proteins, hemicellulose, cellulose, lignin, and ash content. Subsequently, three alternative ways to utilise extraction residues were proposed and successfully tested: (i) enzymatic hydrolysis operated by Cellulases (Thricoderma resei) of raw and residual biomass to glucose, (ii) direct ethanolysis to produce ethyl levulinate; and (iii) pyrolysis to obtain biochar to be used as supports for the synthesis of sulfonated magnetic iron-carbon catalysts (Fe-SMCC) to be applied in the dehydration of fructose for the synthesis of 5-hydroxymethylfurfural (5-HMF). The development of these advanced approaches enabled the full utilisation of this resource through the production of fine chemicals and value-added compounds in line with the principles of the circular economy.

Aerobic Oxidative Synthesis of Formamides from Amines and Bioderived Formyl Surrogates.

Herein we present a new strategy for the oxidative synthesis of formamides from various types of amines and bioderived formyl sources (DHA, GLA and GLCA) and molecular oxygen (O2) as oxidant on g-C3N4 supported Cu catalysts. Combined characterization data from EPR, XAFS, XRD and XPS revealed the formation of single CuN4 sites on supported Cuphen/C3N4 catalysts. EPR spin trapping experiments disclosed ⋅OOH radicals as reactive oxygen species and ⋅NR1R2 radicals being responsible for the initial C-C bond cleavage. Control experiments and DFT calculations showed that the successive C-C bond cleavage in DHA proceeds via a reaction mechanism co-mediated by ⋅NR1R2 and ⋅OOH radicals based on the well-equilibrated CuII and CuI cycle. Our catalyst has much higher activity (TOF) than those based on noble metals.

Selective Stereoretention of Carbohydrates upon C-C Cleavage Enabling D-Glyceric Acid Production with High Optical Purity over a Ag/γ-Al2O3 Catalyst.

Chiral carboxylic acid production from renewable biomass by chemocatalysis is vitally important for reducing our carbon footprint, but remains underdeveloped. We herein establish a strategy that make use of a stereogenic center of biomass to achieve a rare example of D-glyceric acid production with the highest yield (86.8 %) reported to date as well as an excellent ee value (>99 %). Unlike traditional asymmetric catalysis, chiral catalysts/additives are not required. Ample experiments combined with quantum chemical calculations established the origins of the stereogenic center and catalyst performance. The chirality at C4 in D-xylose was proved to be retained and successfully delivered to C2 in D-glyceric acid during C-C cleavage. The remarkable cooperative-roles of Ag+ and Ag0 in the constructed Ag/γ-Al2O3 catalyst are disclosed as the crucial contributors. Ag+ was responsible for low-temperature activation of D-xylose, while Ag0 facilitated the generation of active O* from O2. Ag+ and active O* cooperatively promoted the precise cleavage of the C2-C3 bond, and more importantly O* allowed the immediate fast oxidization of the D-glyceraldehyde intermediate to stabilize D-glyceric acid, thereby inhibiting the side reaction that induced racemization. This strategy makes a significant breakthrough in overcoming the limitation of poor enantioselectivity in current chemocatalytic conversion of biomass.

Valorization of cellulosic fiber derived from waste biomass of constructed wetland as a potential reinforcement in polymeric composites: A technological approach to achieve circular economy.

This study establishes the suitability of cellulosic fibers derived from Canna indica waste biomass for utilization as a reinforcement in natural fiber polymeric composites. The waste biomass was harvested from constructed wetlands engaged in the treatment of municipal wastewater from a gated community. The extracted Canna indica (CI) fibers were studied for their physicochemical, mechanical, structural, crystallographic, and thermal characteristics and proposed as a potential alternative to synthetic fiber. The CI fibers contained a relatively higher amount of cellulose (60 wt%) and a low wax fraction (0.5 wt%) - which is advantageous for its gainful utilization as a reinforcement. The CI fibers were thermally stable up to 237 °C and have an average fiber length, diameter, and density of 4.3 mm, 842 µm, and 0.75 g/cm3, respectively. The mean maximum tensile strength and Young's modulus were found to be 113 ± 6.82 MPa and 0.8 ± 7.91 GPa, respectively. The nano-indentation test displayed the nano hardness and modulus as 0.3 ± 0.6 GPa and 1.62 ± 0.2 GPa, respectively. The crystallographic properties of CI fibers consisted of an 87.45% crystallinity index and 3.2 nm crystallite size. The morphological attributes of CI fibers showed rough surfaces and shallow cavities on the surfaces of the fibers suggesting the suitability for its utilization as a reinforcement. It is argued that this technological approach can potentially achieve circular economy through valorization of Canna indica biomass harvested from natural wastewater treatment plants.

Valorization of rice biomass by a green approach to release phenolic compounds and their antioxidant activities.

In the present context, we have assessed the green approach for the extraction of phenolics from agro-residues of rice viz., rice bran, and rice straw using water as an extracting solvent. The extraction was optimized with respect to time, temperature, pH, and solid (agro-residues) to liquid (water) ratio. The hydrolysates obtained were determined for phenolics and their antioxidant activities. The maximum total phenolic content (61.32 mg/100 g GAE), flavonoid content (13.19 mg/100 g QE), and tannin content (58.33 mg/100 g TAE) were obtained for rice bran followed by rice straw at pH 5, 1:20 (solid: liquid) for 10 min of extraction. Also, higher antioxidant properties (78.03% for DPPH, 86.45% for ABTS, and 0.85 absorbance at 700 nm for FRAP) were observed for the extracts of rice bran. Caffeic acid, gallic acid, p-coumaric acid, syringic acid, ferulic acid, 2,5-dihydroxy benzoic acid, kaemferol, quercetin, and epicatechin were analyzed by HPLC in both the rice biomass used. This study significantly converts rice biomass to antioxidative phenolic compounds under simple extraction conditions favoring the waste management process and also adding value to the waste biomass.

Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation.

Because of the global necessity to decrease CO2 emissions, biomass-based fuels have become an interesting option to explore; although, bio-oils need to be upgraded, for example, by catalytic hydrodeoxygenation (HDO), to reduce oxygen content. This reaction generally requires bifunctional catalysts with both metal and acid sites. For that purpose, Pt-Al2O3 and Ni-Al2O3 catalysts containing heteropolyacids (HPA) were prepared. HPAs were added by two different methods: the impregnation of a H3PW12O40 solution onto the support and a physical mixture of the support with Cs2.5H0.5PW12O40. The catalysts were characterized by powder X-ray diffraction, Infrared, UV-Vis, Raman, X-ray photoelectron spectroscopy and NH3-TPD experiments. The presence of H3PW12O40 was confirmed by Raman, UV-Vis and X-ray photoelectron spectroscopy, while the presence of Cs2.5H0.5PW12O40 was confirmed by all of the techniques. However, HPW was shown to strongly interact with the supports, especially in the case of Pt-Al2O3. These catalysts were tested in the HDO of guaiacol, at 300 °C, under H2 and at atmospheric pressure. Ni-based catalysts led to higher conversion and selectivity to deoxygenated compound values, such as benzene. This is attributed to both a higher metal and acidic contents of these catalysts. Among all tested catalysts, HPW/Ni-Al2O3 was shown to be the most promising, although it suffered a more severe deactivation with time-on-stream.

Coffee Pulp Gasification for Syngas Obtention and Methane Production Simulation Using Ni Catalysts Supported on Al2O3 and ZrO2 in a Packed Bed Reactor.

The methanation of CO2 is of great interest in power-to-gas systems and contributes to the mitigation of climate change through carbon dioxide capture and the subsequent production of high-added-value products. This study investigated CO2 methanation with three Ni catalysts supported on Al2O3 and ZrO2, which were simulated using a mathematical model of a packed bed reactor designed based on their chemical kinetics reported in the literature. The simulated reactive system was fed with syngas obtained from residual coffee pulp obtained after a solvent phytochemical extraction process under several gasification conditions. The results reflect a high degree of influence of the catalyst support, preparation method, and syngas composition on CO2 and H2 conversions and CH4 selectivity. For all the syngas compositions, the Ni/ZrO2 catalysts showed the best values for CO2 conversion and H2 conversion for the Ni/Al2O3 catalyst except in gasification at 700 °C and using the Ni/ZrO2p catalyst.

Subcritical Water Extraction to Valorize Grape Biomass-A Step Closer to Circular Economy.

With the increase in the world population, the overexploitation of the planet's natural resources is becoming a worldwide concern. Changes in the way humankind thinks about production and consumption must be undertaken to protect our planet and our way of living. For this change to occur, sustainable development together with a circular economic approach and responsible consumption are key points. Agriculture activities are responsible for more than 10% of the greenhouse gas emissions; moreover, by 2050, it is expected that food production will increase by 60%. The valorization of food waste is therefore of high importance to decrease the environmental footprint of agricultural activities. Fruits and vegetables are wildly consumed worldwide, and grapes are one of the main producers of greenhouse gases. Grape biomass is rich in bioactive compounds that can be used for the food, pharmaceutical and cosmetic industries, and their extraction from this food residue has been the target of several studies. Among the extraction techniques used for the recovery of bioactive compounds from food waste, subcritical water extraction (SWE) has been the least explored. SWE has several advantages over other extraction techniques such as microwave and ultrasound extraction, allowing high yields with the use of only water as the solvent. Therefore, it can be considered a green extraction method following two of the principles of green chemistry: the use of less hazardous synthesis (principle number 3) and the use of safer solvents and auxiliaries (principle number 5). In addition, two of the green extraction principles for natural products are also followed: the use of alternative solvents or water (principle number 2) and the use of a reduced, robust, controlled and safe unit operation (principle number 5). This review is an overview of the extraction process using the SWE of grape biomass in a perspective of the circular economy through valorization of the bioactive compounds extracted. Future perspectives applied to the SWE are also discussed, as well as its ability to be a green extraction technique.

Sequential Extraction and Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy Monitoring in the Biorefining of Brewer's Spent Grain.

The brewing industry plays a significant role in producing a substantial annual volume of by-products, which contributes to the global accumulation of food waste. The primary by-product generated is brewer's spent grain (BSG), a lignocellulosic biomass rich in proteins, fiber, and moisture content. Leveraging biorefining and valorization techniques for BSG represents a promising strategy to enhance sustainability, resilience, and circularity within the brewing chain. To date, most studies have focused on extracting proteins from BSG. Yet, it is crucial to note that the fiber part of BSG also holds considerable potential for biorefining processes. This study introduces a novel sequential extraction method designed to integrally recover the major components of BSG. Notably, it introduces a reactive extraction approach that enables the simultaneous extraction and tuneable functionalization of the hemicellulose component. Additionally, the study assesses the utility of the attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy as a user-friendly tool to monitor and evaluate the effectiveness of the fractionation process. This spectroscopic technique can provide valuable insights into the changes and composition of BSG throughout the extraction process.

Surface-Controlled CdS/Ti3 C2 MXene Schottky Junction for Highly Selective and Active Photocatalytic Dehydrogenation-Reductive Amination.

Photocatalytic valorization and selective transformation of biomass-derived platform compounds offer great opportunities for efficient utilization of renewable resources under mild conditions. Here, the novel three-dimensional hierarchical flower-like CdS/Ti3 C2 Schottky junction (MCdS) composed of surface-controlled CdS and pretreated Ti3 C2 MXene is created for photocatalytic dehydrogenation-reductive amination of biomass-derived amino acid production under ambient temperature with unprecedented activity and selectivity. Schottky junction efficiently promotes photoexcited charge migration and separation and inhibits photogenerated electron-hole recombination, which results in a super-high activity. Meanwhile, CdS with the reduced surface energy supplies sufficient hydrogen sources for imine reduction and induces the preferential orientation of alanine, thus contributing superior selectivity. Moreover, a wide range of hydroxyl acids are successfully converted into corresponding amino acids and even one-pot conversion of glucose to alanine is easily achieved over MCdS. This work illustrates the mechanism of crystal orientation control and heterojunction construction in controlling catalytic behavior of photocatalytic nanoreactor, providing a paradigm for construction of MXene-based heterostructure.

Regulation of Redox Molecular Junctions in Covalent Organic Frameworks for H2 O2 Photosynthesis Coupled with Biomass Valorization.

H2 O2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value-added products. Here, a series of COFs (i.e. Cu3 -BT-COF, Cu3 -pT-COF and TFP-BT-COF) with regulated redox molecular junctions have been prepared to study H2 O2 photosynthesis coupled with furfuryl alcohol (FFA) photo-oxidation to furoic acid (FA). The FA generation efficiency of Cu3 -BT-COF was found to be 575 mM g-1 (conversion ≈100 % and selectivity >99 %) and the H2 O2 production rate can reach up to 187 000 µM g-1 , which is much higher than Cu3 -pT-COF, TFP-BT-COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H2 O2 production and FFA photo-oxidation to increase the efficiency. This is the first report about COFs for H2 O2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous-crystalline catalysts in this field.

Lignocellulose-degrading fungi newly isolated from central Morocco are potent biocatalysts for olive pomace valorization.

The investigation of lignocellulolytic catalysts is an important feature to face the challenges of lignocellulosic biomass valorization. In central Morocco, fungi were isolated from decaying wood, soil, olive crushing by-products and their compost. One hundred fifty-five isolates were submitted to a selective screening, which served to distinguish 83% of lignocellulolytic isolates. Then, a collection of 56 fungi was subjected to morphological and molecular identification with the ITS5 and ITS4 primers. This approach showed that 45% of the fungal population belonged to the genus Penicillium, followed by Aspergillus 14%, and Fusarium 11%. Alternaria, Trichoderma, Paecilomyces, Cladosporium, Trichocladium, Circinella, and Doratomyces genera are founded with a minority occurrence. Finally, validation of the enzymatic profile was done for 20 isolates, by testing their enzymatic performance on a liquid medium in the presence of cellulose, lignin, and olive pomace. The maximum protein production of 788 µg ml-1 was reached by an Alternaria strain, which produced also 10.6 IU ml-1 of endoglucanase. Thus, a ß-glucosidase activity of 5.1 IU ml-1 was obtained by a Penicillium strain isolated from decaying wood. Regarding ligninolytic activities, olive pomace was the most suitable substrate to detect these activities. Decaying wood strains presented the most remarkable results with 1.1 IU ml-1, 0.7 IU ml-1 et 0.3 IU ml-1 for laccase, LiP and MnP, respectively. The use of the selected fungi and olive pomace as local biomass are important factors for the development of green processes targeting the valorization of this by-product into high-value molecules.

On the influence of hydrothermal treatment pH on the performance of Bi2WO6 as photocatalyst in the glycerol photoreforming.

Solar driven semiconductor-based photoreforming of biomass derivatives, such as glycerol is a sustainable alternative towards green hydrogen evolution concerted with production of chemical feedstocks. In this work, we have investigated the influence of the pH of the hydrothermal treatment on the efficiency of Bi2WO6 as photocatalyst in the glycerol photoreforming. Bi2WO6 is pointed as a promising material for this application due its adequate band gap and the ability to promote hole transfer directly to glycerol without formation of non-selective ⋅OH radicals. Samples prepared at neutral to moderate alkaline conditions (pH = 7-9) are highly crystalline, while those prepared in acidic media (pH = 0-2) exhibit higher concentrations of oxygen vacancies. At pH = 13, the non-stoichiometric Bi(III)-rich phase Bi3.84W0.16O6.24 is formed. All samples were fully characterized towards their optical and morphological properties. UV-Vis irradiation of the photocatalysts modified with 1% m/m Pt and in the presence of 5% v/v aqueous glycerol solution leads to H2 evolution and glycerol oxidation. The sample prepared at pH = 0 exhibited the highest photonic efficiency (ξ) for H2 evolution (1.4 ± 0.1%) among the investigated samples with 99% selectivity for simultaneous formic acid formation. Similar performance was observed for the non-stoichiometric Bi3.84W0.16O6.24 sample (ξ = 1.2 ± 0.1% and 88% selectivity for formic acid), whereas the more crystalline sample prepared at pH = 9 was less active (ξ = 0.9 ± 0.1%) and leads to multiple oxidation products. The different behaviors were rationalized based on the role of oxygen vacancies as active adsorption and redox sites at the semiconductor surface, stablishing clear relationships between the semiconductor structure and its photocatalytic performance. The present work contributes for the rational development of specific photocatalysts for glycerol photoreforming.

Biomass-based micronutrient fertilizers and biofortification of raspberries fruits.

The increasing amount of bio-waste creates the need to develop a method for efficient management based on processes that are more environmentally friendly than incineration and composting. This research aimed to utilize the waste of raspberry seeds after supercritical CO2 extraction. The biomass was enriched with micronutrients by the biosorption process to prepare micronutrient fertilizers for organic farming and biofortification of raspberries fruits. It was observed that at 100% dose of micronutrients, raspberry crop yield increased by 3%, and transfer of micronutrients to fruit biomass increased by 4.7%, 6.4%, and 8.8% (Cu, Mn, Zn, respectively) compared to commercial fertilizer. The supply of micronutrients at a dose of 150% led to a significant increase in micronutrient content of 3%, 41%, and 8% (Cu, Mn, and Zn, respectively) compared to commercial fertilizer. Research shows that the application of higher doses of micronutrients leads to the enrichment of edible parts of fruits, and fertilizers ensure environmental safety. The fruits contained on average 11.5% more microelements compared to the groups fertilized with the commercial product. The fruit yield (9.09-10.4 Mg per hectare) and the sugar content (9.82-10.2%) were also the highest. The micronutrients released from fertilizers and available to plants throughout the vegetation period affect the increase in yield, especially in the case of plants fruiting several times a year.

Solid-state co-culture fermentation of simulated food waste with filamentous fungi for production of bio-pigments.

The use of waste stream residues as feedstock for material production simultaneously helps reduce dependence on fossil-based resources and to shift toward a circular economy. This study explores the conversion of food waste into valuable chemicals, namely, bio-pigments. Here, a simulated food waste feedstock was converted into pigments via solid-state fermentation with the filamentous fungus Talaromyces albobiverticillius (NRRL 2120). Pigments including monascorubrin, rubropunctatin, and 7-(2-hydroxyethyl)-monascorubramine were identified as products of the fermentation via ultra-performance liquid chromatography coupled with quadrupole-time-of-flight electrospray ionization mass spectrometry. Pigments were obtained at concentrations of 32.5, 20.9, and 22.4 AU/gram dry substrate for pigments absorbing at 400, 475, and 500 nm, respectively. Pigment production was further enhanced by co-culturing T. albobiverticillius with Trichoderma reesei (NRRL 3652), and ultimately yielded 63.8, 35.6, and 43.6 AU/gds at the same respective wavelengths. This represents the highest reported production of pigments via solid-state fermentation of a non-supplemented waste stream feedstock. KEY POINTS: • Simulated food waste underwent solid-state fermentation via filamentous fungi. • Bio-pigments were obtained from fermentation of the simulated food waste. • Co-culturing multiple fungal species substantially improved pigment production.

The application of green solvent in a biorefinery using lignocellulosic biomass as a feedstock.

The high dependence on crude oil for energy utilization leads to a necessity of finding alternative sustainable resources. Solvents are often employed in valorizing the biomass into bioproducts and other value-added chemicals during treatment stages. Unfortunately, despite the effectiveness of conventional solvents, hindrances such as expensive solvents, unfavourable environmental ramifications, and complicated downstream separation systems often occur. Therefore, the scientific community has been actively investigating more cost-effective, environmentally friendly alternatives and possess the excellent dissolving capability for biomass processing. Generally, 'green' solvents are attractive due to their low toxicity, economic value, and biodegradability. Nonetheless, green solvents are not without disadvantages due to their complicated product recovery, recyclability, and high operational cost. This review summarizes and evaluates the recent contributions, including potential advantages, challenges, and drawbacks of green solvents, namely ionic liquids, deep eutectic solvents, water, biomass-derived solvents and carbon dioxide in transforming the lignocellulosic biomass into high-value products. Moreover, research opportunities for future developments and potential upscale implementation of green solvents are also critically discussed.

Molybdenum, Vanadium, and Tungsten-Based Catalysts for Sustainable (ep)Oxidation.

This article gives an overview of the research activity of the LAC2 team at LCC developed at Castres in the field of sustainable chemistry with an emphasis on the collaboration with a research team from the University of Zagreb, Faculty of Science, Croatia. The work is situated within the context of sustainable chemistry for the development of catalytic processes. Those processes imply molecular complexes containing oxido-molybdenum, -vanadium, -tungsten or simple polyoxometalates (POMs) as catalysts for organic solvent-free epoxidation. The studies considered first the influence of the nature of complexes (and related ligands) on the reactivity (assessing mechanisms through DFT calculations) with model substrates. From those model processes, the work has been enlarged to the valorization of biomass resources. A part concerns the activity on vanadium chemistry and the final part concerns the use of POMs as catalysts, from molecular to grafted catalysts, (ep)oxidizing substrates from fossil and biomass resources.

Adsorption of Hexavalent Chromium Using Activated Carbon Produced from Sargassum ssp.: Comparison between Lab Experiments and Molecular Dynamics Simulations.

Adsorption is one of the most successful physicochemical approaches for removing heavy metal contaminants from polluted water. The use of residual biomass for the production of adsorbents has attracted a lot of attention due to its cheap price and environmentally friendly approach. The transformation of Sargassum-an invasive brown macroalga-into activated carbon (AC) via phosphoric acid thermochemical activation was explored in an effort to increase the value of Sargassum seaweed biomass. Several techniques (nitrogen adsorption, pHPZC, Boehm titration, FTIR and XPS) were used to characterize the physicochemical properties of the activated carbons. The SAC600 3/1 was predominantly microporous and mesoporous (39.6% and 60.4%, respectively) and revealed a high specific surface area (1695 m2·g-1). To serve as a comparison element, a commercial reference activated carbon with a large specific surface area (1900 m2·g-1) was also investigated. The influence of several parameters on the adsorption capacity of AC was studied: solution pH, solution temperature, contact time and Cr(VI) concentration. The best adsorption capacities were found at very acid (pH 2) solution pH and at lower temperatures. The adsorption kinetics of SAC600 3/1 fitted well a pseudo-second-order type 1 model and the adsorption isotherm was better described by a Jovanovic-Freundlich isotherm model. Molecular dynamics (MD) simulations confirmed the experimental results and determined that hydroxyl and carboxylate groups are the most influential functional groups in the adsorption process of chromium anions. MD simulations also showed that the addition of MgCl2 to the activated carbon surface before adsorption experiments, slightly increases the adsorption of HCrO4- and CrO42- anions. Finally, this theoretical study was experimentally validated obtaining an increase of 5.6% in chromium uptake.