Solvent Research Articles

Metal‐Organic Framework Hosted Silicon for Long‐Cycling, Low‐Cost, and Flexible Batteries

AbstractDeveloping biodegradable electrodes is a significant step toward environmental sustainability and cost reduction in battery technology. This paper presents a new approach that utilizes metal‐organic framework (MOF)‐encapsulated silicon nanoparticles (SiNPs) as the active anode material within a cellulose‐based electrode. The electrode is free‐standing, flexible, biodegradable, and significantly reduces the strain experienced by SiNPs during volume expansion, resulting in improved capacity and cycle life stability of SiNPs. The high porosity of the electrode creates efficient lithium (Li+) ion transport channels and enhances electrolyte absorption, thus promoting effective contact between the electrolyte and active material. The outcome is rapid electrode kinetics and a highly reversible discharge capacity of 1744.6 mAh g−1 at 0.5 A g−1 versus Li/Li+ over 1000 cycles. Further, full cell tests are conducted that demonstrate a stable cycle performance exceeding 3400 cycles, with an initial discharge capacity retention of 80.5% at 0.5 A g−1. By employing cellulose and avoiding toxic organic solvents and binders, the proposed approach is promising for a substantial reduction of the production costs of Li‐ion batteries. The scalability of the proposed method further enhances its practical viability, offering intriguing economic implications for the future of battery technology.

Entropically and enthalpically driven self-assembly of a naphthalimide-based luminescent organic π-amphiphile in water.

The self-assembly of π conjugated systems in water has emerged as an efficient method for the development of functional materials for biological applications. But the process is more difficult to understand and to control in water compared to organic solvents due to hydrophobic effects. For π-conjugated molecules, self-assembly in solution generally occurs due to either an enthalpic or entropic gain, but designing π systems that undergo self-assembly via both an entropically and enthalpically favorable process is challenging. Herein, we elucidate in detail the self-assembly of a luminescent naphthalene monoamide-based dipolar π-bolaamphiphile appended with a primary amine and triethylene glycol monomethyl ether (NMI-W) side chain into a vesicular nanostructure. By utilizing a detailed isothermal titration calorimetry (ITC) experiment, we have calculated the thermodynamic parameters associated with the self-assembly of NMI-W in water. Interestingly, the NMI-W shows both entropically and enthalpically favorable robust self-assembly into a vesicular structure, which can encapsulate both hydrophilic and hydrophobic guest molecules. The synergistic effect of dipole-dipole, π-π stacking and hydrophobic interactions of the NMI chromophore is found to be very crucial in driving self-assembly in an aqueous medium as revealed by various experiments and molecular dynamics.

New Materials for Thin-Film Solid-Phase Microextraction (TF-SPME) and Their Use for Isolation and Preconcentration of Selected Compounds from Aqueous, Biological and Food Matrices.

Determination of a broad spectrum of analytes, carried out with analytical instruments in samples with complex matrices, including environmental, biological, and food samples, involves the development of new and selective sorption phases used in microextraction techniques that allow their isolation from the matrix. SPME solid-phase microextraction is compatible with green analytical chemistry among the sample preparation techniques, as it reduces the use of toxic organic solvents to the minimum necessary. Over the past two decades, it has undergone impressive progress, resulting in the development of the thin-film solid-phase microextraction technique, TF-SPME (the thin-film solid-phase microextraction), which is characterized by a much larger surface area of the sorption phase compared to that of the SPME fiber. TF-SPME devices, in the form of a mostly rectangular metal or polymer substrate onto which a thin film of sorption phase is applied, are characterized, among others, by a higher sorption capacity. In comparison with microextraction carried out on SPME fiber, they enable faster microextraction of analytes. The active phase on which analyte sorption occurs can be applied to the substrate through techniques such as dip coating, spin coating, electrospinning, rod coating, and spray coating. The dynamic development of materials chemistry makes it possible to use increasingly advanced materials as selective sorption phases in the TF-SPME technique: polymers, conducting polymers, molecularly imprinted polymers, organometallic frameworks, carbon nanomaterials, aptamers, polymeric ionic liquids, and deep eutectic solvents. Therefore, TF-SPME has been successfully used to prepare analytical samples to determine a broad spectrum of analytes in sample matrices: environmental, biological, and food. The work will be a review of the above-mentioned issues.

Crystals morphology of ethylenediaminetetraacetatozincate triethylenediaminium and tetramethylethylenediaminium

Trimethylenediamine ethylenediaminetetraacetate zincate trihydrate [HN(CH2CH2)3NH]ZnL · 3H2О and tetramethylethylenediamine ethylenediaminetetraacetate zincate dihydrate [H(CH3)2NCH2CH2N(CH3)2H]ZnL · 2H2О were synthesized by reacting zinc oxide with ethylenediaminetetraacetic acid (H4L) and then with its triethylenediamine or tetramethylethylenediamine salts. The resulting compounds precipitate from aqueous or organic solvents in the form of thread-like, cubic and pyramidal crystals, which are characterized by elemental analysis, scanning electron microscopy, IR spectroscopy, thermogravimetry and differential scanning calorimetry.

Carboxyl-Group-Bearing Metal Corroles of Cobalt, Manganese and Copper for Electrocatalytic Hydrogen Evolution.

5,15-bis(perfluorophenyl)-10-(4-carboxyphenyl) corrole and its Co(III), Mn(III), and Cu(III) corrole complexes were synthesized. The electrocatalytic hydrogen evolution reaction (HER) of these metal corrole complexes was investigated using different proton sources (AcOH, trifluoroacetic acid, and TsOH) in an organic dimethylformamide solvent. The electrocatalytic HER may proceed through EECC, EECEC, or EEECEC pathways (where E represents electron transfer and C represents proton binding) depending on the acidity and concentration of the proton source used. The Co corrole complex exhibits remarkable hydrogen production performance, achieving a turnover frequency of 201 s-1 and a catalytic efficiency of 1.00. The examined metal corrole complexes also exhibit good HER activity in aqueous solution, with their catalytic activity following an order of 1-Co > 1-Cu > 1-Mn in both organic and aqueous phases.

Effect of Solvent and Cholesterol on Liposome Production by the Reverse-Phase Evaporation (RPE) Method.

Liposomal drug delivery is a promising approach for delivering therapeutics effectively. While most liposomes are designed to be nanometer-sized for efficient cellular uptake, micron-sized liposomes are gaining interest due to their larger drug-loading capacity. When combined with macroscale structures, such as implants and hydrogels, they offer prolonged therapeutic delivery. This study investigates how solvents affect the production of micron-sized liposomes, with or without cholesterol, using the reverse-phase evaporation (RPE) method. Although the RPE method is established for producing micron-sized liposomes, the influence of solvents on liposome size and uniformity is not well understood. The study explores whether controlling the size of inverse micelles, an intermediate product, through the use of different organic solvents affects the final liposome size. Three solvents─diethyl ether, methanol, and acetone─were tested for their effect on the formation of inverse micelles and liposomes and their sizes. Results showed that without cholesterol, diethyl ether produced uniform inverse micelles, leading to mostly nanosized liposomes. Methanol and acetone resulted in phase separation, preventing uniform liposome formation, although some micron-sized liposomes appeared. The acetone sample yielded mostly oil droplets. The results showed that forming inverse micelles lead to nanosized liposomes. With cholesterol, phase separation was dominant in methanol, but micron-sized liposomes still formed. Across all cases, cholesterol reduced the liposome size. The findings reveal that inverse micelles are not always reliable predictors of the final liposome size and that the RPE method is highly sensitive to solvent polarity and lipid-solvent interactions. Overall, the findings of this study provide valuable insights into how the choice of solvent and lipid composition can influence the production of liposomes via the RPE method. These insights are critical for optimizing liposome production and influencing future designs of liposomal drug delivery systems.

Structural Design of Hybrid Manganese(II) Halides for High Quantum Efficiency and Specific Response to Methanol.

Manganese(II) halides have been a new generation of optoelectronic materials due to their fascinating luminescent properties, however, lacking specific solvent-responsive analogues with high quantum efficiency. Herein, we prepared three single crystals, [Pr(MIm)2][MnBr4] ([Pr(MIm)2]2+ = 1,3-di(methylimidazolium)-propane, Compound 1), [Pr(EIm)2][MnBr4] ([Pr(EIm)2]2+ = 1,3-di(ethylimidazolium)-propane, Compound 2), and [Bu(MIm)2][MnBr4] ([Bu(MIm)2]2+ = 1,4-di(methylimidazolium)-butane, Compound 3), where different Bola-type cations were chosen as organic components to separate [MnBr4]2- tetrahedrons. All three compounds emitted bright green light with excellent quantum yields of 95.3, 80.0, and 96.2%, benefiting from the large Mn···Mn distance. More interestingly, Compound 3 showed a highly selective response to methanol in a series of tested organic solvents, with a rapid and reversible change in emission color from green to red. The single crystal of [Bu(MIm)2][MnBr4]·CH3OH with red emission proved that the luminescence switching was attributed to the adsorption of CH3OH molecules into the lattice space in the form of the O-H···Br hydrogen bonds. To our knowledge, for tetrahedrally coordinated Mn(II) species, the reversible emission color switching between green and red triggered by a solvent without the change of coordination number is achieved for the first time, providing promising applications for the specific detection of methanol.

Intermolecular Anionic Mixed‐Valence and π‐Dimer Complexes of ortho‐Pentannulated Bisazacoronene Diimide

AbstractThis study reports the serendipitous discovery of intermolecular anionic mixed‐valence (MV) and π‐dimer species in ortho‐pentannulated BisAzaCoroneneDiimides (BACDs) during their electrochemical reduction in a non‐aqueous solvent. A library of nitrogen‐containing extended PDIs was synthesized via an aza‐benzannulation reaction followed by a Pd‐catalysed ortho‐pentannulation reaction. Ortho‐pentannulated BACDs revealed strong aggregation abilities in solution. Concentration‐dependent UV/Vis absorption spectra, variable temperature 1H NMR experiments, and atomic force microscopy coupled to molecular dynamics support their self‐assembly into columnar aggregates. Cyclic voltammetry experiments in dichloromethane reveal prominent splitting of the first reduction wave, attributed to the formation of unprecedented intermolecular anionic MV and π‐dimers in organic solvent. These species were thoroughly characterized by real‐time spectroelectrochemistry, electrochemical simulations and theoretical calculations. Remarkably, this work underscores the tuneable nature of AzaBenzannulatedPerylene Diimides (AzaBPDIs) and BACDs, emphasizing their potential as a promising scaffold for designing supramolecular materials with long‐range radical anion delocalization. The observation of this phenomenon provides insights into the fundamental behaviour of supramolecular organic semiconductors, thereby paving the way for the development of novel electronic devices and electron‐deficient materials.

Intermolecular Anionic Mixed-Valence and π-Dimer Complexes of ortho-Pentannulated Bisazacoronene Diimide.

This study reports the serendipitous discovery of intermolecular anionic mixed-valence (MV) and π-dimer species in ortho-pentannulated BisAzaCoroneneDiimides (BACDs) during their electrochemical reduction in a non-aqueous solvent. A library of nitrogen-containing extended PDIs was synthesized via an aza-benzannulation reaction followed by a Pd-catalysed ortho-pentannulation reaction. Ortho-pentannulated BACDs revealed strong aggregation abilities in solution. Concentration-dependent UV/Vis absorption spectra, variable temperature 1H NMR experiments, and atomic force microscopy coupled to molecular dynamics support their self-assembly into columnar aggregates. Cyclic voltammetry experiments in dichloromethane reveal prominent splitting of the first reduction wave, attributed to the formation of unprecedented intermolecular anionic MV and π-dimers in organic solvent. These species were thoroughly characterized by real-time spectroelectrochemistry, electrochemical simulations and theoretical calculations. Remarkably, this work underscores the tuneable nature of AzaBenzannulatedPerylene Diimides (AzaBPDIs) and BACDs, emphasizing their potential as a promising scaffold for designing supramolecular materials with long-range radical anion delocalization. The observation of this phenomenon provides insights into the fundamental behaviour of supramolecular organic semiconductors, thereby paving the way for the development of novel electronic devices and electron-deficient materials.

Facile fabrication of green and sustainable gelatin-based aerogels for marine oil spill recovery

Efficient and rapid cleanup of marine oil spills is crucial for environmental protection and resource recovery. Biomass aerogel has a broad application prospect in oil spill treatment, but is often limited by the complex preparation process and the use of toxic cross-linking agents. In this study, the hydrophobic gelatin-based aerogels (HGAs) were simply prepared for marine oil spill recovery based on self-crosslinking of gelatin, bubbles produced by surfactants and high-speed stirring, and chemical vapor deposition using methyl trichlorosilane (MTCS). The results showed that the HGAs exhibited a three-dimensional porous structure with a water contact angle of 131.6°. Their adsorption capacities for various oils and organic solvents ranged from 60.4 to 146.5 g/g, which was linearly related to the oil density and depended on the number of pores within the material. The oil adsorption by the HGAs reached equilibrium within 30 s, following the pseudo-second-order kinetic model and the HGAs were highly stable in different temperature, pH, and salinity conditions. Simple squeezing can recover 80 % of the spilled oil, and retain 86 % of the initial adsorption capacity after 10 adsorption-squeeze cycles. Additionally, the HGAs had an excellent continuous oil-water separation performance, demonstrating significant potential and practicability in marine oil spill recovery.

Isolation and Characterization of Stigmasterol from Psidium guajava Leaves: A Promising Bioactive Compound with Therapeutic Potential

This study aimed to isolate and characterize bioactive compounds from the leaves of Psidium guajava Linn. The hydroethanolic extract yielded 32% (80 g) from the crude material, which was subjected to column chromatography for fractionation. Structural elucidation of the isolated compound was performed using 1D and 2D Nuclear Magnetic Resonance (NMR) spectroscopy, including COSY, HSQC, and HMBC experiments. The spectral data confirmed the presence of stigmasterol, characterized by its distinct chemical shifts and long-range correlations between carbon and proton atoms. Stigmasterol was isolated as a white, crystalline solid and identified by its unique physio-chemical properties, such as solubility in organic solvents, a melting point of 163-164°C, and molecular formula C29H48O. This compound is known for its significant biological activities, including antibacterial, antimalarial, anti-inflammatory, antioxidant, and anticancer effects. By employing advanced techniques like 1D and 2D NMR spectroscopy, the study provides precise structural elucidation of stigmasterol, contributing to natural product research and reinforcing the medicinal potential of guava leaves as a source of pharmacologically active compounds. This adds to the existing knowledge of the plant’s bioactive components and their applications in medicinal chemistry

Mesoporous Silica Supported Hydrophilic Ionic Liquid Gel Microspheres for Solvent-Free Deep Oxidative Desulfurization.

Solvent-free oxidative desulfurization can avoid environmental pollution caused by organic solvents as well as prevent loss of fuel during the oil-water separation process. In this work, first, hydrophilic ionic liquid gel microspheres with [BMIM]BF4 and PHEMA as the dispersion medium and gel network, respectively, were successfully prepared by using mesoporous silica microspheres as a supporting skeleton capable of stabilizing the gel through an anchoring effect, and then the catalyst [BMIM]PW and oxidant H2O2 were incorporated into the gel microspheres to construct a liquid compartment microreactor for deep desulfurization. The prepared microreactor (SiO2@[BMIM]PW/ILG-microspheres) has excellent extraction-catalytic capacity and exhibited ∼100% desulfurization ratio for a model oil of n-heptane with 500 ppm of DBT at 60 °C for 3 h without solvents. Additionally, the prepared microreactor can absorb hydrophilic desulfurization products after the reaction and has advantages of reusability and simple recovery without polluting the fuel oil, which is beneficial for potential petroleum industrial application.

Diethylene glycol-zinc chloride based deep eutectic solvent for green extraction of bixin compound

Deep eutectic solvents (DESs) are ionic liquid alternatives that replace volatile and flammable organic solvents. DESs are formed by hydrogen bond interaction between the hydrogen bond donor (HBD) and the hydrogen bond acceptor (HBA). We prepared DES using zinc chloride (ZnCl2) as HBA and diethylene glycol (DEG) as HBD. Formed DES was applied to extract the bixin contained in annatto seeds. The homogenous liquid mixtures were analysed for their pH, viscosity, density, conductivity, thermal properties, and solubility in various solvents. Bixin extracted using DES was identified by thin-layer chromatography (TLC), UV–Vis spectrophotometer, Fourier Transform Infra-Red (FTIR), and Proton Nuclear Magnetic Resonance (1HNMR). The mixtures with a mole fraction of ZnCl2 0.1 (DES1), 0.2 (DES2), and 0.3 (DES3) are liquid at room temperature. The analysis results prove that bixin has been successfully extracted using DES, where DES1 was better for bixin extraction than DES2 and DES3, with extracted bixin levels of 32.42, 28.84, and 0.46 mg g-1 by dry seeds mass, respectively. In this case, DES1, DES2, and DES3 could extract 62.17, 55.31, and 0.88 % of bixin from the entire total bixin contained in annatto seeds. The DES can be used for bixin extraction using a relatively simple method based on the results obtained.

Convenient Aqueous‐Phase Synthesis of Covalent Organic Frameworks for Anhydrous Proton Conduction

Covalent organic frameworks (COFs) as a kind of emerging materials has been widely concerned. Developing and recovering new COF materials is of great importance for anhydrous proton conduction, most of the synthesis methods are not organic solvent phase or convenient enough, which would inevitably lead to solvent waste and increase environmental burden. Herein, a method of COF synthesis in aqueous phase is developed, which is used for nonpolluting and sustainable fabrication. Benefits from the suitable channels and stability of HCOF‐1, the composite material H3PO4@HCOF‐1 exhibit high proton conductivity (1.29 × 10−4 S cm−1) at 413 K and the crystallinity of HCOF‐1 is maintained well after measurements. This work broadens the scope of COF synthesis and promotes the development of anhydrous proton conduction.

Ultrathin membranes comprising polymers of intrinsic microporosity oligomers for high-performance organic solvent nanofiltration

Microporous organic polymers (MOPs) featuring chemically rigid backbones and permanent micropores are desirable for fabricating molecular selective membranes towards organics separation. However, coordinating facile film processing with high micropore persistence remains a challenge. In this paper, a low molecular weight polymers of intrinsic microporosity was rationally designed by precisely controlling the stoichiometric equilibrium of polymerization monomer. The polymers of intrinsic microporosity oligomers combine rigid and contorted structures with the aqueous solution processability, promoting the formation of 25-nm-thick polyacrylamide nanofilms with enhanced microporosity via support-free interfacial polymerization (SFIP). The resulting composite membranes have superior retention of small molecular solutes and high nonpolar and polar solvent permeances. Experiment and simulation results show that their excellent separation performance is due to substantially open and interconnected microporosity formed in the polymer networks based on rigid and contorted diamines as well as reduced film thickness. This study provides a new sight for using MOPs to construct high-microporosity membranes for precise and rapid molecular sieving.

Recent Updates on Pd‐Incorporated Ionic Liquids Catalyzed Suzuki Cross‐Coupling Reaction: A Mini‐Review

ABSTRACTIonic liquids (ILs) have been recognized for their potential as environmentally friendly solvents when compared to traditional organic solvents. Additionally, their function goes beyond that of solvents, and cocatalysts, as they frequently act as stabilizing agents and ligands for the metal‐active species and intermediates in catalytic systems. This comprehensive review primarily focuses on the application of Pd‐incorporated ILs in catalyzing cross‐coupling Suzuki reactions. The responses play a vital role in creating a wide range of structurally diverse and highly functionalized organic compounds, focusing specifically on nucleopalladation Suzuki coupling reactions. The review provides a detailed summary of the reaction conditions, stereoselectivity and regioselectivity, and the underlying mechanisms. Furthermore, it underscores crucial and characteristic illustrations, displaying the practical implementations of these coupling reactions. The aim of this review is to stimulate further research efforts, with the ultimate goal of expanding our understanding and utilization of ILs in various fields in the future.

Extreme impact enhancement of epoxy using a sulfosuccinate-based anionic surfactant as a new modifier

In this study, disodium lauryl ether sulfosuccinate (DSL or sulfosuccinate), a commercially available anionic surfactant, was employed for the first time as an impact modifier for epoxy resin. Introducing only 5 phr of DLS into the epoxy matrix resulted in a remarkable 189% enhancement in impact strength without a significant detrimental effect on its tensile strength. According to FTIR and SEM results, the strong interaction between the modifier DLS and the epoxy matrix, along with the formation of a nano-blend morphology with a wide interfacial area, can be proposed as two key factors contributing to the remarkable enhancement in impact strength of epoxy/DLS hybrid. The thermal stability of the epoxy was not significantly affected by the incorporation of DLS up to 8 phr. The epoxy/DLS hybrid exhibited lower chemical stability against organic solvents, while the hybrid resistance to acids and bases remained largely unchanged. Based on the obtained results, DLS can be considered as a promising impact modifier for epoxy systems.

Retention Mechanisms of Basic Compounds in Liquid Chromatography with Sodium Dodecyl Sulfate and 1-Hexyl-3-Methylimidazolium Chloride as Mobile Phase Reagents in Two C18 Columns

Reversed-phase liquid chromatography (RPLC) relies on a non-polar stationary phase and a more polar hydro-organic mobile phase, where compound retention is primarily governed by hydrophobicity, with more hydrophobic compounds being retained longer. The introduction of secondary equilibria in the chromatographic system through additives, such as anionic surfactants and ionic liquids (ILs), was proposed to mitigate ionic interactions between positively charged analytes and the anionic free silanol groups in non-endcapped stationary phases, thereby preventing increased retention and peak tailing. Additionally, the combined hydrophobic and ionic interactions between cationic analytes and the ions in these additives was demonstrated to create mixed retention mechanisms that influence retention and selectivity. In this regard, this study investigates aqueous chromatographic systems incorporating both the anionic surfactant sodium dodecyl sulfate (SDS) and the IL 1-hexyl-3-methylimidazolium chloride as mobile phase reagents. This combination of reagents modulates the retention, eliminating the need for organic solvents and resulting in highly sustainable HPLC procedures. The chromatographic behavior was assessed using two different C18 columns (Zorbax Eclipse and XTerra-MS). The strength of solute interactions was estimated by calculating equilibrium parameters and the contributions of hydrophobic and ionic interactions through simple mathematical models. Focusing on the retention of six basic drugs (β-adrenoceptor antagonists), the study highlighted the significant role of ionic interactions. The results demonstrate the feasibility of using aqueous systems combining SDS and an IL for the efficient separation of moderately polar basic compounds without the use of organic solvents.

Multifaceted insights into pentagonal BeP2 monolayer: From electrochemical to mechanical resilience for alkali-ion batteries using DFT

Herein, we elucidated the properties of a pentagonal BeP2 monolayer, emphasizing its robust dynamic, thermal, and mechanical stabilities, as well as its promising electrochemical characteristics. Combining density functional theory (DFT) with a thermodynamic energy decomposition scheme, we identified BeP2 as a potentially excellent 2D material for energy storage devices. It is characterized by large lattice parameters and semi-metallic behavior, exhibiting a zero density of states (DOS) at the Fermi level. It demonstrates favorable open-circuit voltages, low metal ion migration barriers, and negligible structural modifications for Na and K ions. The specific capacities of Li/Na/K reached remarkable values, surpassing those of most previously reported monolayers. Emerging ion battery technology necessitates solid, directly comparable data to establish an optimized standard organic solvent electrolyte. With this objective in mind, we systematically investigated systems combining two Li/Na/K salts with three different alkyl carbonate solvents. Furthermore, we proposed a defect in BeP2 to explore all possible avenues for sustaining the pentagonal BeP2 monolayer (supplementary Fig. S5 and S6). In summary, our findings strongly indicate that the pentagonal BeP2 monolayer holds considerable promise as an anode material for sodium-ion batteries (NIBs) and potassium-ion batteries (KIBs) owing to its high electrochemical and mechanical sustainability and excellent compatibility with electrolytes.

Comparative study of blending techniques in polylactic acid/cellulose nanofibrils green composites for benchtop 3D printing filaments

AbstractAdditive manufacturing for polylactic acid (PLA) reinforced with cellulose nanofibrils (CNF) could unlock fabrication of specialized and user‐specific biomedical devices. However, the process of combining PLA and CNF is challenging and proves complicated with possible irreversible CNF agglomeration and organic solvents leftover, particularly when involving solvent‐casting technique. Direct melt‐blending can mitigate these issues, but there are few reports of a single‐step melting and extrusion process to produce ready‐to‐use 3D printing filaments. This study compares the distribution of CNF fillers within the PLA matrix in PLA/CNF composites made by direct melt‐blending into filaments using a benchtop filament maker, and by solvent‐casting followed by extrusion into filaments. The filaments were 3D‐printed via fused deposition modeling (FDM), followed by tensile testing, morphology, and other characterizations. Uneven filament diameters were observed for the composite filaments prepared via solvent‐casting because of severe agglomeration, resulted in poor printability and tensile properties of filaments and 3D‐printed samples. Direct melt‐blended filament diameters were consistent, resulted in only slight decrease of tensile properties compared to pure PLA, contributing to the highest maximum tensile strength of 3D‐printed sample of 51.47 ± 1.73 MPa at 5% CNF loading. Morphology revealed good integration of CNF into PLA matrix starting at 3% CNF loading. Direct melt‐blending was comparable to the conventional methods, which enables simpler PLA/CNF composite preparation especially for 3D printing.Highlights Better dispersibility achieved by direct melt‐blending than by solvent‐casting. PLA/CNF filaments produced via solvent‐casting suffered severe agglomeration. Direct melt‐blended PLA/CNF5% yielded the highest maximum tensile strength. Morphology reveals good CNF‐PLA integration starting at 3% of CNF loading. Worsened agglomeration causing increased number of voids observed at 10% CNF.