Cellulose Nanofibrils Surface Research Articles

Surface Modification of Cellulose Films By Dielectric Barrier Discharge for Organic Photovoltaics Encapsulation

Organic photovoltaics (OPV) are the third generation of solar cells and are more and more attractive for industrial applications. OPV present numerous advantages, such as flexibility, low cost, light weight, large-area production.[1,2] Nonetheless, OPV are not as efficient as the conventional crystalline silicon photovoltaic (PV) cells. Recently, power conversion efficiency (PCE) has reached 18% for OPV, while conventional PV remains around 30% [3]. In this sense, additional works are necessary to improve their processability. Moreover, components of OPV are highly sensitive to water or oxygen, which strongly affect OPV stability in time when used in harsh conditions. Therefore, development of new barrier coatings are today essential to reduce OPV degradation and increase their shelf life. According to the literature, encapsulation can be performed following three strategies: (i) glass-glass encapsulation, (ii) flexible polymer lamination and (iii) thin film direct deposition. Glass-glass encapsulation provides great protection, with good optical properties but it remains fragile and is not compatible with roll-to-roll processes. On the other hand, although, flexible polymer lamination is suitable for roll-to-roll processes, adhesion between the front and back barriers is still complex to deal with, leading sometimes to partial encapsulation, thus increasing OPV degradation. Finally, direct deposition allows to obtain thin films with excellent optical and oxygen and humidity barrier properties. To date, most of thin layers are synthesized under vacuum [1,2]. This work focus on the development new barrier coatings at atmospheric pressure, compatible with roll-to-roll processes using cellulose nanofibrils with excellent oxygen barrier properties [4]. Being hydrophilic, the surface of cellulose nanofibrils have been modified to improve the water barrier properties. Wettability modification (WCA ~ 140°) was successfully achieved with an atmospheric pressure dielectric barrier discharge to control the fragmentation/reticulation of 2,4,6,8-Tetramethylcyclotetrasiloxane (TMCTS).

Tuning the surface charge of rice straw-derived cellulose nanofibril membrane separator for electrochemical performance enhancement of supercapacitors

The electrochemical performance of supercapacitors has often overlooked the effect of surface charge on cellulose-based separators. Cellulose nanofibrils (CNFs) produced by 2,2,6,6-tetramethylpipridine-1-oxyl (TEMPO) oxidation possess a high anionic surface charge due to the presence of carboxylate groups, which could affect the transport of electrolyte ions. In this work, the surface of CNFs is modified with a cationic polyelectrolyte, namely polydiallydimethylammonium chloride (PDADMAC), to yield a nearly-zero surface charge CNF membrane derived from rice straw. The surface modification of CNFs using 20 wt% PDADMAC results in CNF-M2, with a surface charge of +5.3 mV, notable porosity (64 %), excellent electrolyte uptake (225 %), and improved ionic conductivity (5.0 mS cm−1). A symmetric supercapacitor assembled with CNF-M2 as a separator, exhibits enhanced specific capacitance (185.3 F g−1 at 0.1 A g−1), energy density (37.1 Wh kg−1 at a power density of 0.24 kW kg−1), and is able to maintain 100 % capacitance retention over 10,000 cycles in 1.0 M Na2SO4 aqueous electrolyte solution. This surface modification leads to 1.2–1.4 times increase in energy and power densities compared to the unmodified CNF membrane. Thus, the nearly-zero surface charge of the modified CNF membrane holds promise as a separator that elevates the performance of supercapacitors.

Reversible Surface Engineering of Cellulose Elementary Fibrils: From Ultralong Nanocelluloses to Advanced Cellulosic Materials.

Cellulose nanofibrils (CNFs) are supramolecular assemblies of cellulose chains that provide outstanding mechanical support and structural functions for cellulosic organisms. However, traditional chemical pretreatments and mechanical defibrillation of natural cellulose produce irreversible surface functionalization and adverse effects of morphology of the CNFs, respectively, which limit the utilization of CNFs in nanoassembly and surface functionalization. Herein, this work presents a facile and energetically efficient surface engineering strategy to completely exfoliate cellulose elementary fibrils from various bioresources, which provides CNFs with ultrahigh aspect ratios (≈1400) and reversible surface. During the mild process of swelling and esterification, the crystallinity and the morphology of the elementary fibrils are retained, resulting in high yields (98%) with low energy consumption (12.4kJ g-1). In particular, on the CNF surface, the surface hydroxyl groups are restored by removal of the carboxyl moieties via saponification, which offers a significant opportunity for reconstitution of stronger hydrogen bonding interfaces. Therefore, the resultant CNFs can be used as sustainable building blocks for construction of multidimensional advanced cellulosic materials, e.g., 1D filaments, 2D films, and 3D aerogels. The proposed surface engineering strategy provides a new platform for fully utilizing the characteristics of the cellulose elementary fibrils in the development of high-performance cellulosic materials.

Crude oil sorbent based on cellulose nanofibrils-methacrylate grafted copolymers

Hydrophobic composites of cellulose nanofibrils (CNF) with acrylic polymers are obtained by methyl methacrylate (MMA) and butyl methacrylate (BMA) polymerization in Pickering emulsion, stabilized with cellulose nanofibrils. Successful modification of CNF surface by grafting MMA or BMA was confirmed by infrared spectroscopy, gel permeation chromatography, and scanning electron microscopy. The obtained composites were also characterized by simultaneous thermal analysis and wetting contact angle measurement. Composites based on CNF exhibit good thermal and oil sorption properties.

Effect of different electronegative oxygen atoms of cellulose nanofibrils on the formation and photocatalytic property of ZnO/cellulose composite

Cellulose is widely employed as a template in supporting and dispersing ZnO. The oxygen atom of the hydroxyl (–OH) groups of cellulose have a significant impact on the morphology and photocatalytic property of ZnO. This work aims to investigate the effect of different electronegative oxygen atoms of cellulose nanofibrils (CNF) on the formation and photocatalytic properties of ZnO/cellulose composites. The interaction between cellulose and ZnO has been achieved by controlling cellulose fiber size and regulating the electronegativity of oxygen atoms on the CNF surface. The results indicate that etherized CNF (ECNF) with the highest degree of etherification substitution (1.7) and the best electronegativity (−34.6 mV) can synthesize the ZnO/cellulose composite with the largest loading content of ZnO (58.9%) and the best photocatalytic activity for MO degradation (91.1%). It can be concluded that the intenser electrostatic interaction between oxygen atoms on the CNF surface and ZnO can facilitate the fixation and growth of more high-quality ZnO nanoflowers, thus improving the photocatalytic property. In a word, this work can provide a novel perspective for the efficient preparation of ZnO/cellulose composites with designable morphology and structure.

Polyester–melamine coil coating formulation reinforced with surface-modified cellulose nanofibrils

In light of the need to redesign industrially produced materials by utilizing renewable resources, nanoscopic forms of cellulose are regarded as a valuable asset. In this work, the potential of cellulose nanofibrils (CNFs) as an unconventional nanoadditive for a polyester–melamine coil coating formulation is explored. CNFs, hydrophilic nanomaterials with high aspect ratios, were successfully incorporated in the solvent-borne formulation. Coatings were prepared with extremely low loadings of the nanoadditive (0.5 and 0.7 wt%). At these concentrations, the volume fraction of the nanofibrils in the coatings was calculated to be close to their percolation threshold. Two different pathways of CNF surface modification were applied to allow for a good compatibilization in the resin matrix, and the formulations were cured in two different settings. The effective compatibilization of the nanoadditive led to a significant variation of the viscoelastic properties in the coatings containing CNFs. The results from dynamic mechanical analysis (DMA) highlighted the effect of CNFs on the crosslinked network at the nanoscale, resulting in an increase in Tg. Additionally, an increase in the stress at break and Young's modulus was determined by tensile testing, while satisfactory elongation at break was preserved. Other relevant effects induced by the presence of CNFs on the properties of the coatings were highlighted, such as a significant matt effect, increased surface roughness and lower scratch resistance. A preliminary evaluation of the water barrier properties by electrochemical impedance spectroscopy (EIS) is also presented, suggesting that the incorporation of a hydrophilic nanoadditive did not lead to a deterioration of the coatings' performance.

Optimizing chemistry at the surface of prodrug-loaded cellulose nanofibrils with MAS-DNP

Studying the surface chemistry of functionalized cellulose nanofibrils at atomic scale is an ongoing challenge, mainly because FT-IR, NMR, XPS and RAMAN spectroscopy are limited in sensitivity or resolution. Herein, we show that dynamic nuclear polarization (DNP) enhanced 13C and 15N solid-state NMR is a uniquely suited technique to optimize the drug loading on nanocellulose using aqueous heterogenous chemistry. We compare the efficiency of two conventional coupling agents (DMTMM vs EDC/NHS) to bind a complex prodrug of ciprofloxacin designed for controlled drug release. Besides quantifying the drug grafting, we also evidence the challenge to control the concurrent prodrug adsorption and to optimize washing procedures. We notably highlight the presence of an unexpected prodrug cleavage mechanism triggered by carboxylates at the surface of the cellulose nanofibrils.

Responses of Rat Mesenchymal Stromal Cells to Nanocellulose with Different Functional Groups.

Cellulose nanofibrils (CNFs) are multiscale hydrophilic biocompatible polysaccharide materials derived from wood and plants. TEMPO-mediated oxidation of CNFs (TO-CNF) turns some of the primary hydroxyl groups to carboxylate and aldehyde groups. Unlike carboxylic functional groups, there is little or no information about the biological role of the aldehyde groups on the surface of wood-based CNFs. In this work, we replaced the aldehyde groups in the TO-CNF samples with carboxyl groups by another oxidation treatment (TO-O-CNF) or with primary alcohols with terminal hydroxyl groups by a reduction reaction (TO-R-CNF). Rat mesenchymal stem/stromal cells (MSCs) derived from bone marrow were seeded on polystyrene tissue culture plates (TCP) coated with CNFs with and without aldehyde groups. TCP and TCP coated with bacterial nanocellulose (BNC) were used as control groups. Protein adsorption measurements demonstrated that more proteins were adsorbed from cell culture media on all CNF surfaces compared to BNC. Live/dead and lactate dehydrogenase assays confirmed that all nanocellulose biomaterials supported excellent cell viability. Interestingly, TO-R-CNF samples, which have no aldehyde groups, showed better cell spreading than BNC and comparable results to TCP. Unlike TO-O-CNF surfaces, which have no aldehyde groups either, TO-R-CNF stimulated cells, in osteogenic medium, to have higher alkaline phosphatase activity and to form more biomineralization than TCP and TO-CNF groups. These findings indicate that the presence of aldehyde groups (280 ± 14 μmol/g) on the surface of TEMPO-oxidized CNFs might have little or no effect on attachment, proliferation, and osteogenic differentiation of MSCs.

Development of a β-cyclodextrin-chitosan polymer as active coating for cellulosic surfaces and capturing of microcystin-LR

In the search for more environmentally friendly adsorbent materials, the use of polysaccharides results attractive. Especially, as they can be used as coatings to add functionality to common materials as a new avenue to explore. Their inherent tendency to adsorb into each other is valuable as it adds a variety of functional groups on the outmost surface layer. Our project focuses on the pre-modification of the bio-polymer chitosan (Ch) with a 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) oxidized β-cyclodextrin (Ch-TOCD), which was then adsorbed onto the cellulose nanofibrils (CNF) surface. Furthermore, the mechanism driving the adsorption of the modified chitosan onto the cellulose backbone was studied by using three different Ch-TOCD conjugates possessing different degrees of substitutions. This was conducted to evaluate whether the adsorption was guided by the change of the available electrostatic interactions between the amino (Ch) and the residual carboxyl groups of cellulose or if the adsorption was driven by the dispersive forces of the hydroxyl groups from both polysaccharides. Finally, to assess the viability of the added hydrophobic cavities (Ch-TOCD conjugate), the capture of an amphipathic toxin categorized as a monitored pollutant (microcystin-LR) was followed by Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) on a surface level and by High-performance liquid chromatography (HPLC) when the Ch-TOCD coating was applied in CNF beads. Results showed that the adsorption of Ch-TOCD was accomplished at similar levels independent of the degree of substitution. The highest adsorbed amounts of microcystin-LR were 20.5 mg/g on the model coated CNF surface, and 2.36 mg/g on the CNF coated beads. The successful coating of two nanocellulose systems and the positive adsorption of the microcystin suggest a broad-scale application of this bio-based, low energy input coating in high-end fields such as drug delivery, textile, and water restoration.

Polyoxometalate/Cellulose Nanofibrils Aerogels for Highly Efficient Oxidative Desulfurization.

Polyoxometalate (POM) presents great potential in oxidative desulfurization (ODS) reaction. However, the high dissolubility of POM in common solvents makes it difficult to recycle. Besides, the small specific surface area of POM also limits the interaction between them and the substrate. Depositing polyoxometalates onto three-dimensional (3D) network structured materials could largely expand the application of POM. Here, the surfaces of cellulose nanofibrils (CNFs) were modified with very few (3-Aminopropyl) trimethoxysilane (APTS) to endow positive charges on the surfaces of CNFs, and then phosphotungstic acid (PTA) was loaded to obtain the aerogel A-CNF/PTA as the ODS catalyst. FT-IR indicated the successful deposition of PTA onto aminosilane modified CNF surfaces. UV-VIS further suggested the stability of PTA in the aerogels. BET and SEM results suggested the increased specific surface area and the relatively uniform 3D network structure of the prepared aerogels. TGA analysis indicated that the thermal stability of the aerogel A-CNF/PTA50% was a little higher than that of the pure CNF aerogel. Most importantly, the aerogel A-CNF/PTA50% showed good catalytic performance for ODS. Catalysis results showed that the substrate conversion rate of the aerogel A-CNF/PTA50% reached 100% within 120 min at room temperature. Even after five cycles, the substrate conversion rate of the aerogel A-CNF/PTA50% still reached 91.2% during the dynamic catalytic process. This work provides a scalable and facile way to stably deposit POM onto 3D structured materials.

Chemical treatment of biomass wastes as carbon dot carriers for solar-driven water purification

A purely chemical method is demonstrated to treat a variety of biomass wastes for extracting cellulose nanofibrils (CNFs) with a consistent property. By hydrothermal reaction, carbon dots (CDs) can be easily grafted on the surface of CNFs to act as photo-thermal agents and enable fast water evaporation rate at 2.5 kg m−2h−1 with about 96.45% solar-to-vapor efficiency under one sun irradiation. This derives from good hydration ability of this system, which lowers the evaporation enthalpy. Moreover, this system not only adsorbs dye contaminants effectively by the formation of hydrogen bonds, but also possesses long-term antifouling solar desalination by means of rationally drilled millimeter-sized channels. Given the sustainable biomass resources and scalable fabrication process, this work offers a promising strategy towards construct low-cost evaporators with the excellent water purification performance.

Fabrication and Characterization of Hydrophobic Cellulose Nanofibrils/Silica Nanocomposites with Hexadecyltrimethoxysilane.

Cellulose nanofibrils (CNFs) have attracted much attention because of their renewability and potential biocompatibility. However, CNFs are extremely hydrophilic due to the presence of a large number of hydroxyl groups, limiting their use as a water-resistant material. In this work, we controlled the adsorption behavior of silica nanoparticles on the surface of CNFs by adjusting the synthesis conditions. The silica nanoparticle size and packing efficiency on the CNF surface could be controlled by varying the ammonium hydroxide and water concentrations. In addition, hexadecyltrimethoxysilane (HDTMS) was successfully grafted onto CNF or CNF/silica nanocomposite surfaces, and the quantitative content of organic/inorganic substances in HDTMS was analyzed through XPS and TGA. The HDTMS-modified CNF/silica nanocomposites were more advantageous in terms of hydrophobicity than the HDTMS-modified CNF composites. This is because the silica nanoparticles were adsorbed on the surface of the CNFs, increasing the surface roughness and simultaneously increasing the amount of HDTMS. As a result, the HDTMS-modified CNFs showed a water contact angle (WCA) of ~80°, whereas HDTMS-modified CNF/silica nanocomposites obtained superhydrophobicity, with a WCA of up to ~159°. This study can provide a reference for the expansion of recyclable eco-friendly coating materials via the adsorption of silica nanoparticles and hydrophobic modification of CNF materials.

Highly Efficient Iron Oxide Nanoparticles Immobilized on Cellulose Nanofibril Aerogels for Arsenic Removal from Water.

The application and optimal operation of nanoparticle adsorbents in fixed-bed columns or industrial-scale water treatment applications are limited. This limitation is generally due to the tendency of nanoparticles to aggregate, the use of non-sustainable and inefficient polymeric resins as supporting materials in fixed-bed columns, or low adsorption capacity. In this study, magnesium-doped amorphous iron oxide nanoparticles (IONPs) were synthesized and immobilized on the surface of cellulose nanofibrils (CNFs) within a lightweight porous aerogel for arsenic removal from water. The IONPs had a specific surface area of 165 m2 g−1. The IONP-containing CNF aerogels were stable in water and under constant agitation due to the induced crosslinking using an epichlorohydrin crosslinker. The adsorption kinetics showed that both As(III) and As(V) adsorption followed a pseudo second-order kinetic model, and the equilibrium adsorption isotherm was best fitted using the Langmuir model. The maximum adsorption capacities of CNF-IONP aerogel for As(III) and As(V) were 48 and 91 mg As g-IONP−1, respectively. The optimum IONP concentration in the aerogel was 12.5 wt.%, which resulted in a maximum arsenic removal, minimal mass loss, and negligible leaching of iron into water.

Polymer Films from Cellulose Nanofibrils—Effects from Interfibrillar Interphase on Mechanical Behavior

Dense polymeric films based on network-forming cellulose nanofibrils (CNFs) have excellent mechanical properties but are limited by moisture sensitivity. Here, interfibrillar effects from CNF surface properties are investigated. TEMPO-oxidized CNFs and two native CNFs are prepared with a similar length and width, to exclude geometrical effects. The CNFs have different surface properties in terms of sorbed hemicellulose content, hemicellulose molar mass, and surface charge. Moisture sorption, structural changes, and mechanical properties at different relative humidities are characterized. The presence of sorbed hemicelluloses in the interfibrillar interphase has favorable effects on the mechanical tensile properties. Surface-charged carboxyls increased moisture sorption and film thickness swelling and reduced the mechanical properties. A comparison with biaxially oriented polyethylene terephthalate films provides a perspective into the structure and properties of CNF films. The present study shows the importance of the interfibrillar interface and interphase region for mechanical film properties, including moisture effects.

Influence of cellulose nanofibrils on the rheology, microstructure and strength of alkali activated ground granulated blast-furnace slag: a comparison with ordinary Portland cement

This paper reports on the effect of cellulose nanofibrils (CNFs) on the fresh-state properties of alkali activated ground granulated blast-furnace slag (GGBS). Surface functionalized (oxidized) CNFs were added to alkali activated GGBS water suspensions (hydraulic pastes). The rheological behaviour of the pastes was compared with OPC and interpreted based on the CNF-mineral surface interaction, and on the CNF-water interaction and swelling. The water dispersion of CNFs with different surface functionalization degrees resulted in gels of different viscosity and yield stress, due to their different hydrophilicity and water adsorption properties. On increasing the CNFs surface oxidation degree, the viscosity of the CNF water dispersion decreases and the CNF water adsorption increases, while the viscosity of fresh pastes increases because of the reduced amount of available mixing water. In the hardened state, the hydraulic pastes show differences in mechanical strength related to the type and the amount of CNF influencing the porosity of the matrix as evidenced by the microstructural investigation performed by X-ray microtomography. The presence of higher amounts of CNFs induces the formation of porous agglomerates that may act as stress concentrators due to the swelling ability of nanofibrils.

Facile surface modification of amphiphilic cellulose nanofibrils prepared by aqueous counter collision

The present study concerns the chemical modification of the surfaces of cellulose nanofibrils (CNFs) prepared by aqueous counter collision (ACC). Wood-derived CNFs prepared by ACC were acetylated with acetic anhydride in an aqueous dispersion. The moderately acetylated nanofibrils were more readily dispersible in water than unmodified CNFs, although the original nanofibrous morphology comprising crystalline cellulose I remained almost unchanged. This indicates that the surfaces of the crystalline CNFs had been selectively acetylated, which possibly inhibited self-aggregation between the nanofibrils, thereby facilitating dispersion in the aqueous medium. Despite the absence of additives, the acetylated CNFs were readily adsorbed onto hydrophobic surfaces, and retained their compatibility with water, which improved their ability to stabilize emulsions and coat plastic resin particles in water. The results indicate that the amphiphilic properties of CNFs prepared by ACC can be controlled by this facile surface acetylation method, which potentially increases their usefulness in various fields.

Organocatalyzed ring opening polymerization of lactide from the surface of cellulose nanofibrils

The surface initiated ring opening polymerization (SI-ROP) of cellulose nanofibers (CNF) with rac-Lactide under mild conditions using N,N-dimethyl aminopyridine (DMAP) was investigated. The influence of catalyst amount, monomer-to-initiator (cellulose surface –OH groups) ratio, temperature, and cellulose preconditioning (lyophilization vs solvent exchange) were studied to determine the best SI-ROP conditions, and to understand the effect of the parameters on grafting efficiency. The fibers modified after lyophilization had a PLA content comparable to those obtained with traditional metal catalysts (e.g. tin-(II)ethylhexanoate). Starting from a stable dispersion of CNF in dichloromethane obtained through solvent-exchange showed better results at low catalyst amounts. Furthermore, DMAP was readily removed from the products whereas metal catalysts can be hard to remove from the final material, potentially shortening the material lifespan and making it unfit for some applications. Therefore, the use of an easily removable and more efficient organocatalyst can be considered a good alternative to metal catalysts.

Enhanced performance of a cellulose nanofibrils-based triboelectric nanogenerator by tuning the surface polarizability and hydrophobicity

Cellulose is the most abundant natural polymer on earth. Because it is renewable, biodegradable, and biocompatible, it offers distinct advantages as a starting material for bio-based triboelectric nanogenerator (bio-TENG). However, weak polarity, poor hydrophobicity, and insufficient functionalization on the natural cellulose surface severely limit the development of high-performance cellulose-based TENGs. In this work, chemical functionalization is employed to control the surface polarizability and hydrophobicity of cellulose nanofibrils (CNFs). Functional groups on the CNF surface are modified with triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (PFOTES) in a straightforward and facile process. Fluorine-bearing silane chains are grafted to the surface of CNFs, which increases their triboelectric charge density and improves their hydrophobicity. Experimental results demonstrate that the surface polarity of CNFs is greatly improved after PFOTES modification. The PFOTES-CNF-based TENG exhibits good resistance to humidity and long-term cycle stability, and it retains 70% of the initial output performance at 70% ambient humidity. The short-circuit current of the PFOTES-CNF-based TENG reached 9.3 μA, which is about twice that of CNF-based TENG prior to modification. These results clearly indicate that PFOTES can be used to control CNF surface polarizability and hydrophobicity, advancing the search for durable, high-performance, degradable bio-TENGs.

The surface chemistry of a nanocellulose drug carrier unravelled by MAS-DNP.

Cellulose nanofibrils (CNF) are renewable bio-based materials with high specific area, which makes them ideal candidates for multiple emerging applications including for instance on-demand drug release. However, in-depth chemical and structural characterization of the CNF surface chemistry is still an open challenge, especially for low weight percentage of functionalization. This currently prevents the development of efficient, cost-effective and reproducible green synthetic routes and thus the widespread development of targeted and responsive drug-delivery CNF carriers. We show in this work how we use dynamic nuclear polarization (DNP) to overcome the sensitivity limitation of conventional solid-state NMR and gain insight into the surface chemistry of drug-functionalized TEMPO-oxidized cellulose nanofibrils. The DNP enhanced-NMR data can report unambiguously on the presence of trace amounts of TEMPO moieties and depolymerized cellulosic units in the starting material, as well as coupling agents on the CNFs surface (used in the heterogeneous reaction). This enables a precise estimation of the drug loading while differentiating adsorption from covalent bonding (∼1 wt% in our case) as opposed to other analytical techniques such as elemental analysis and conductometric titration that can neither detect the presence of coupling agents, nor differentiate unambiguously between adsorption and grafting. The approach, which does not rely on the use of 13C/15N enriched compounds, will be key to further develop efficient surface chemistry routes and has direct implication for the development of drug delivery applications both in terms of safety and dosage.

Hybridization between cellulose nanofibrils and faceted silver nanoparticles used with surface enhanced Raman scattering for trace dye detection

This research studies the surface enhanced Raman scattering (SERS) activity of cellulose nanofibrils (CNFs) hybridized with faceted silver nanoparticles (AgFNPs) for the detection of organic dyes in aqueous media. Faceted AgNPs were synthesized under environmentally benign conditions using TEMPO-oxidized CNFs as both shape-regulating, reducing and stabilizing agents. Small, zero valent, spherical AgNPs first formed on the CNF surface and transformed into larger and faceted AgNPs when reacting with H2O2 through a thermodynamically driven Ostwald ripening mechanism. The as-synthesized hybrids exhibited strong analytical enhancement in the Raman signal of methylene blue, up to 6.8 × 103 at 448 cm−1 with less than 32% spatial variations and 10% sample-to-sample variability, enabling the detection of dyes in water at the sub part-per million level. The origin of the SERS enhancement came from discrete hotspots of high silver content on the substrate, as characterized by spatially resolved laser ablation inductively coupled plasma mass spectrometry.