Preformed Nanoparticles Research Articles

Synthesis of palladium-rhodium bimetallic nanoparticles for formic acid dehydrogenation

Herein, we report for the first time the synthesis of preformed bimetallic Pd-Rh nanoparticles with different Pd:Rh ratios (nominal molar ratio: 80–20, 60–40, 40–60, 20–80) and the corresponding Pd and Rh monometallic ones by sol immobilization using polyvinyl alcohol (PVA) as protecting agent and NaBH4 as reducing agent, using carbon nanofibers with high graphitization degree (HHT) as the desired support. The synthesized catalysts were characterized by means of Transmission Electron Microscopy (TEM) and inductively coupled plasma optical emission spectroscopy (ICP-OES). TEM shows that the average particle size of the Pd-Rh nanoparticles is the range of 3–4 nm, with the presence of few large agglomerated nanoparticles. For bimetallic catalysts, EDX-STEM analysis of individual nanoparticles demonstrated the presence of random-alloyed nanoparticles even in all cases Rh content is lower than the nominal one (calculated Pd:Rh molar ratio: 90–10, 69–31, 49–51, 40–60). The catalytic performance of the Pd-Rh catalysts was evaluated in the liquid phase dehydrogenation of formic acid to H2. It was found that Pd-Rh molar ratio strongly influences the catalytic performance. Pd-rich catalysts were more active than Rh-rich ones, with the highest activity observed for Pd90:Rh10 (1792 h−1), whereas Pd69:Rh31 (921 h−1) resulted the most stable during recycling tests. Finally, Pd90:Rh10 was chosen as a representative sample for the liquid-phase hydrogenation of muconic acid using formic acid as hydrogen donor, showing good yield to adipic acid.

Engineered magnetoactive collagen hydrogels with tunable and predictable mechanical response.

In the present study, the synthesis of superparamagnetic collagen-based nanocomposite hydrogels with tunable swelling, mechanical and magnetic properties is reported. The fabrication strategy involved the preparation of pristine collagen type-I hydrogels followed by their immersion in highly stable aqueous solutions containing pre-formed double-layer oleic acid-coated hydrophilic magnetite nanoparticles (OA.OA.Fe3O4) at different concentrations, to interrogate nanoparticles' deposition within the 3D fibrous collagen matrix. Besides the investigation of the morphology, composition and magnetic properties of the produced materials, their mechanical properties were experimentally evaluated under confined compressive loading conditions while an exponential constitutive equation was employed to describe their mechanical response. Moreover, the deposition of the nanoparticles in the collagenous matrix was modeled mathematically with respect to the swelling of the gel and the effective stiffness of the matrix. The model recapitulated nanoparticle diffusion and deposition as well as hydrogel swelling, in terms of nanoparticles' size and concentration of OA.OA.Fe3O4 aqueous solution.

(Invited) Pt/Metal Oxide/Ti and Pt/Metal Oxide/Carbon Composite Films for Ethanol Oxidation

Metal oxides such as RuO2 and SnO2 can promote the oxidation of organic fuels at Pt nanoparticles in a number of ways. These include changing the d-band level of the Pt via electron transfer (electronic effect) and providing surface –OH functionality for the oxidation of adsorbed CO (bifunctional effect) [1]. Carbon black coated with a mixture of Ru and Sn oxides has been shown to increase the activity of Pt for ethanol oxidation without a significant loss of selectivity for its complete oxidation to CO2 [2].Here we report on the use of various mixed metal oxide composites prepared by thermal decomposition of metal acetylacetonate complexes (M(acac)n). Oxide layers were deposited onto Ti foil and high surface area carbon electrodes, and drop coated with preformed Pt nanoparticles. Cyclic voltammetry in H2SO4(aq) and polarization experiments in a proton exchange membrane cell were used to study the co-catalytic effects of the oxide layers. The use of acetylacetonate precursors provides a versatile method for screening libraries of oxide supported catalysts, as well as the production and screening of electrodes for fuel cells.Initially, decomposition of Ru(acac)3 and Sn(acac)2 and their mixtures on Ti foil electrodes was investigated. These experiments reproduced the effects previously observed with oxide layers deposited on glassy carbon from KRuO4 and SnCl4 [3]. Deposits formed from both complexes increased the activity for ethanol oxidation of Pt nanoparticles drop coated onto their surfaces, while use of mixtures produced a strong synergistic effect. Deposits formed by thermal decomposition of a variety of other acac complexes, including Ga(acac)3, Zr(acac)4, and In(acac)3, also increased the activity of Pt nanoparticles for ethanol oxidation.Mixed Ru+Sn oxides were also produced by thermal decomposition of Ru(acac)3 and Sn(acac)2 on carbon black, in order to better characterize the oxide deposits and produce catalysts that could be used in fuel cells. X-ray diffraction and energy dispersive X-ray spectrometry confirmed the presence of a mixed oxide. Preformed Pt nanoparticles were adsorbed onto the oxide coated carbon, supported on carbon fiber paper, and the resulting electrodes were evaluated for ethanol oxidation in a proton exchange membrane cell at 80 °C. Acknowledgments: This work was supported by the Natural Sciences and Engineering Research Council of Canada and Memorial University.[1] G.M. Alvarenga, H.M. Villullas, Current Opinion in Electrochemistry, 2017, 4, 39-44[2] D.D. James, R.B. Moghaddam, B. Chen, P.G. Pickup, Journal of the Electrochemical Society, 2018, 165, F215-F219[3] R. B. Moghaddam and P. G. Pickup, Electrochim. Acta, 2012, 65, 210– 215

Synergistic Effect in Au-Cu Bimetallic Catalysts for the Valorization of Lignin-Derived Compounds

The selective oxidation of veratryl alcohol as lignin-derived compound was studied under mild conditions, using Au-Cu catalysts synthesized from pre-formed nanoparticles with different Au:Cu molar ratios. Bimetallic catalysts show higher activity compared to monometallic counterparts, highlighting a clear synergistic effect. By comparing the physico-chemical surface properties of catalysts supported on carbon and Al2O3, we were able to establish a strong support effect, with alumina-based catalysts being more active than carbon-supported ones. Moreover, TEM and X-ray photoelectron spectroscopy (XPS) analyses showed a different composition of nanoparticles (NPs) and metal exposure, and we established that Au is the active phase of the reaction. The co-presence of Au and Cu species, and their different interaction with the support, enabled obtaining more than 70% conversion of veratryl alcohol to veratryl aldehyde as a unique product. Moreover, the Au1Cu1 supported on alumina catalyst was recovered by filtration and reused without significant loss of activity and selectivity up to four times.

Simple Method to Supply Organic Nanoparticles with Excitation-Wavelength-Dependent Photoluminescence.

Organic fluorescent nanoparticles (FNPs) have become increasingly prevalent in a variety of applications but the creation of organic FNPs using a simple procedure and that possess diverse morphology, multicolor luminescence, and high brightness has been challenging. Herein, a facile strategy to prepare this class of organic FNPs is established by way of preformed organic nanoparticles themselves. It was found that as long as the nanoparticles contained aromatic/heterocyclic rings in their base unit and regardless of morphologies (e.g., small-molecule micelles, polymeric micelles, reverse micelles, solid microspheres, and vesicles), simple UV irradiation can result in the particles exhibiting excitation-wavelength-dependent photoluminescence with considerable quantum yields (∼8.3-16.7% for tested particles). Upon initial investigation of the mechanism, the photoluminescence behavior was attributed to a polycyclic aromatic hydrocarbon (PAH) process. Furthermore, the application of the synthesized organic FNPs in cancer cell imaging is demonstrated as just one of the many potential applications. The straightforward method to supply preformed organic nanoparticles with photoluminescence would be attractive for scientists in both academia and industry.

Preformed Pd-Based Nanoparticles for the Liquid Phase Decomposition of Formic Acid: Effect of Stabiliser, Support and Au–Pd Ratio

Hydrogen is one of the most promising energy carriers for the production of electricity based on fuel cell hydrogen technology. Recently, hydrogen storage chemicals, such as formic acid, have been proposed to be part of the long-term solution towards hydrogen economy for the future of our planet. Herein we report the synthesis of preformed Pd nanoparticles using colloidal methodology varying a range of specific experimental parameters, such as the amount of the stabiliser and reducing agent, nature of support and Pd loading of the support. The aforementioned parameters have shown to affect mean Pd particle size, Pd oxidation, atomic content of Pd on the surface as well as on the catalytic performance towards formic acid decomposition. Reusability studies were carried out using the most active monometallic Pd material with a small loss of activity after five uses. The catalytic performance based on the Au–Pd atomic ratio was evaluated and the optimum catalytic performance was found to be with the Au/Pd atomic ratio of 1/3, indicating that the presence of a small amount of Pd is essential to promote significantly Au activity for the liquid phase decomposition of formic acid. Thorough characterisation has been carried out by means of XPS, SEM-EDX, TEM and BET. The observed catalytic performance is discussed in terms of the structure/morphology and composition of the supported Pd and Au–Pd nanoparticles.

Monolithic metal-containing TiO2 aerogels assembled from crystalline pre-formed nanoparticles as efficient photocatalysts for H2 generation

Nanoparticle-based aerogels are 3-dimensional (3D) assemblies of macroscopic size that maintain the intrinsic properties of the initial nanoparticles. Accordingly, they bear immense potential to become an emerging platform for designing new and efficient photocatalysts. However, to take full advantage of this strategy, understanding of the multiscale processes occurring in such 3D-architectures is essential. Here, we prepared aerogels by co-assembling spherical Au, Pd, and PdAu with TiO2 nanoparticles and investigated their photocatalytic properties for hydrogen generation. During gelation, the anatase nanoparticles undergo oriented attachment, homogeneously entrapping the metal nanoparticles in the growing network. The aerogels offer a high porosity with a mean pore size of ca. 34 nm and a large surface area of about 450 m2 g−1. The porous structure enhances the light-harvesting, reagent transport, and electron migration process, generating 3.5-fold more hydrogen in comparison to the corresponding powders.

Pt/Ru–Sn Oxide/Carbon Catalysts for Ethanol Oxidation

Mixed Ru–Sn oxides have been deposited onto a high surface area carbon support by thermal decomposition of Ru and Sn acetylacetonate (acac) complexes. Adsorption of preformed Pt nanoparticles produced catalysts with enhanced low potential activity for the oxidation of ethanol in aqueous sulfuric acid at ambient temperature and in a proton exchange membrane (PEM) cell at 80 °C. Varying the oxide composition between Ru0.38Sn0.62O2 and Ru0.67Sn0.33O2 did not influence the catalyst’s activity greatly but did increase stability in the sulfuric acid solution. Higher stability was observed in the PEM cell, where a Pt/Ru0.55Sn0.45O2/C anode provided much higher currents than a commercial Pt/C catalyst for ethanol oxidation at low potentials. Anodes for direct ethanol fuel cells can be fabricated by coating a carbon fibre paper backing layer consecutively with carbon black, Ru(acac)3 + Sn(acac)2, and Pt nanoparticles, with appropriate thermal processing.

Dominant role of iron oxides in magnetic circular dichroism of plasmonic-magnetic Au-Fe3−xO4 heterodimer nanostructures

Plasmon-tuned magneto-optical (MO) properties enable design concepts of MO devices with various nanoarchitectures. In this study, magnetic circular dichroism (MCD) is presented in plasmonic-magnetic Au-Fe3−xO4 heterodimer nanostructures dispersed in solution. The heterodimers are synthesized by thermal decomposition of Fe(III) precursors in the presence of preformed Au nanoparticles. The extinction spectrum exhibits a localized surface plasmon resonance (LSPR) peak, which is red-shifted with respect to the isolated Au particle resonance. On the other hand, the MCD response is overwhelmingly dominated by iron oxide counterparts consisting of multiphase magnetite (Fe3O4)/maghemite (γ-Fe2O3). No appreciable LSPR-enhancement in the MO response is found. As for the effect of the magnetic component on the LSPR behavior of Au, a decrease in the magnetoplasmonic response is observed. This suggests a reduction of the effective magnetic field to the Au counterparts, which can probably be due to magnetic shielding by the iron oxides in the near vicinity of Au nanoparticles.

Organizing Crystalline Functionalized Pentacene Using Periodicity of Poly(Vinyl Alcohol).

Nanoparticles of acenes exhibit highly efficient intermolecular singlet fission (SF). Recent reports indicate that altering the morphology of 6,13-bis-(triisopropylsilylethynyl)pentacene (TIPS-Pn) nanoparticles has a profound influence on their SF dynamics. Here, we show that poly(vinyl alcohol) (PVA) induces a phase transition in preformed TIPS-Pn nanoparticles. These nanoparticles are amorphous when initially formed but crystalline after addition of PVA. Surface characterization indicates that a diffuse PVA layer surrounds the nanoparticles. We propose that a periodic interaction between the hydroxyl groups of PVA and TIPS groups of TIPS-Pn on the nanoparticle surface induces a large-scale structural rearrangement to yield crystalline TIPS-Pn. Such reorganization in preformed organic nanoparticles is unprecedented, and we believe that this is the first report of such an effect induced by polymer adsorption. Transient absorption spectroscopic results reveal that SF within these nanoparticles is accelerated by an order of magnitude upon structural rearrangement.

Co3O4/BiVO4 Heterostructures for Photochemical Water Oxidation: The Role of Synthesis Parameters and Preparation Route for the Physico-Chemical Properties and the Catalytic Activity

Abstract The synthesis conditions of the semiconductor BiVO4 have marked influence on its physicochemical and photocatalytic properties. In this work, a pH-controlled co-precipitation route was systematically investigated. Special attention was paid to the pH value during co-precipitation and co-precipitate post-treatment. In a sacrificial photocatalytic water oxidation test, the highest activity was observed for a sample precipitated at pH = 1 and 70 °C, which was post treated at 600 °C in air for 3 h after washing and drying. The activity was further improved by another 90% by the addition of the Co3O4-based co-catalyst. Good synergy between semiconductor and co-catalyst was obtained for the deposition of pre-formed nanoparticles at a loading of 0.1 w% (physical impregnation). The effects of different synthesis conditions of the semiconductor and impregnation method for the co-catalyst on the structure, morphology and optical properties of the catalysts were investigated by PXRD, SEM, UV-vis spectroscopy, and TEM, while the water oxidation activity was compared in the dark and with the aid of visible light using cerium (IV) or silver (I) as sacrificial agents, respectively, with the aim of establishing structure-activity correlations. The roles of semiconductor particle anisotropy and co-catalyst particle distribution for optimal photo-activity in the oxygen evolution reaction are discussed.

Laser‐Guided Microcanvas Printing of Multicolor Upconversion Nanoparticles on Molybdenum Disulfide Monolayer

AbstractScanning focused laser beams incident on nanomaterials have provided a nondestructive and facile technique to fabricate micropatterns of a wide variety of hybrid materials. Conventionally, the technique is limited to localized chemical modification or in situ reduction of specific metal ions en route to heterogeneous material systems. However, as hybrid structures continue to be an essential form to couple various material properties and bring forth nanostructures with designable traits, the need for a flexible technique to interface nanomaterials presynthesized in higher quality remains an important challenge. Herein, a technique for laser‐guided microcanvas formation by anchoring preformed upconversion nanoparticles at specific sites on a MoS2 monolayer surface is presented. The technique expands the building blocks in laser‐produced hybrid structures to include presynthesized nanomaterials. The upconversion microstructures are formed via a microbubble‐assisted mechanism, with distinct emission contrast against the background. The proof‐of‐concept production of a multicolor upconversion microcanvas marks the potential for full‐color high‐resolution displays while the technique opens up the possibility of fabricating an expandable range of new hybrid structures.

Interface tailoring of SnO2–TiO2 photocatalysts modified with anionic/cationic surfactants

SnO2–TiO2 nanocomposites are prepared by growing TiO2 nanoparticles onto the preformed SnO2 nanoparticles. The SnO2 core nanoparticles ware obtained in the presence of two different surfactants, namely hexadecyltrimethyl ammonium bromide and polyethylene glycol 600 (PEG600), by chemical precipitation followed by a thermal treatment at 500 °C. The TiO2 was obtained directly on modified SnO2 nanoparticles by a sol–gel process. A sample without surfactants was prepared in the same conditions. The processes involved during annealing of precursors were revealed by TGA-FTIR. The crystalline and mesoporous structures of samples were evidenced by XRD, HRTEM and by N2 adsorption–desorption isotherms. XPS investigations highlighted the interface modifications due to the presence of cationic or anionic moieties resulted from the thermal decomposition of surfactants. Combined UPS and UV–Vis measurements allowed the determination of the oxidation energies, band gaps and energy bands alignment of nanocomposites. The photocatalytic activity based on reactive oxygen species (ROS) generation was studied toward degradation of RhB under visible-light irradiation and by the use of EPR coupled with spin-trapping technique. It was found that the generated ROS are only of ·OH type and, this specific process, is analyzed in terms of energy bands alignment.

Metal Nano Networks by Potential-Controlled In Situ Assembling of Gold/Silver Nanoparticles.

Non‐spherical Au/Ag nanoparticles can be generated by chemical reduction of silver ions in the presence of preformed gold nanoparticles. The process of particle formation can be controlled by concentrations of ligands and reducing agent. The formation of ellipsoidal, nanorod‐ and peanut‐shaped nanoparticles as well as of more complex fractal nanoassemblies can be explained by changes in particle surface state, electrochemical potential formation and particle‐internal self‐polarization effects. It is possible to create highly fractal nanoassemblies with sizes between the mid‐nanometer and the lower micrometer range. The assemblies are marked by high optical absorption and complex nano‐networks of very high surface‐to‐volume ratios and a granular base structure.

Green Synthesis of a Cu/SiO2 Catalyst for Efficient H2-SCR of NO

In this work, the synthesis of Cu/SiO2 catalysts starting from pre-formed copper nanoparticle (CuNP) colloidal suspensions was carried out. Two different protocols for the CuNP synthesis were tested: (i) a green approach using water as solvent and ascorbic acid as reducer and stabilizing agent, and (ii) a second solvothermal method involving the use of diethylene glycol as solvent, sodium hypophosphite (NaH2PO2) as reducer, and polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB) as stabilizing agents. In addition, and for the sake of comparison, a third catalyst was prepared by solid state conventional grinding of CuO with SiO2. The catalysts were tested in the environmentally relevant catalytic reduction of NOX with H2, in a temperature range from 300 to 500 °C. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR) cycles, Raman spectroscopy, and N2 adsorption for specific surface BET measurements. From these techniques CuO and Cu(0) species were detected depending on the synthesis protocol. CuNP size and size distribution in the colloid suspensions were determined by transmission electronic microscopy (TEM). The catalyst prepared from the aqueous suspension (CuAsc/SiO2) exhibited higher NO conversion (100%) and selectivity (85%) toward N2 at the lower reaction evaluated temperature (300 °C). The CuCTAB/SiO2 catalyst obtained by the solvothermal approach showed activity at high reaction temperature (400 °C) preferentially. The metal–support mechanical mixture exhibited a negligible response at low temperature and low conversion (68%) and selectivity (88%) at 500 °C. Nanoparticle size and distribution on the support, together with the metal–support interaction, were postulated as the most plausible parameters governing the catalytic performance of the different Cu/SiO2 materials.

Preformed Au colloidal nanoparticles immobilised on NiO as highly efficient heterogeneous catalysts for reduction of 4-nitrophenol to 4-aminophenol

A facile approach to synthesise highly active and stable Au/NiO catalysts for the hydrogenation of nitro-aromatics is reported. Preformed gold nanoparticles have been immobilized onto NiO using a colloidal method. In this article, the reduction of 4-nitrophenol with NaBH4 has been used as a model reaction to investigate the catalytic activity of synthesised Au/NiO catalysts. In addition, we report a systematic study of the reduction kinetics, and the influence of specific reaction parameters such as (i) temperature, (ii) stirring rate, (iii) sodium borohydride concentration and (iv) substrate/metal molar ratio. The reaction has been performed at a substrate/metal molar ratio of 7.4, a ratio significantly higher than previously reported. Reusability of the catalyst has been examined, with little to no decrease in activity observed over 5 catalytic cycles. Systematic variation of Au loading reveals the successful synthesis of low cost and efficient Au/NiO catalysts at very low Au content and using high substrate/metal molar ratios.

Electrochemical Detection of Dopamine Based on Functionalized Electrodes

The rapid electrochemical identification and quantification of neurotransmitters being a challenge in the ever-growing field of neuroelectronics, we aimed to facilitate the electrochemical selective detection of dopamine by functionalizing commercially available electrodes through the deposition of a thin film containing pre-formed gold nanoparticles. The influence of different parameters and experimental conditions, such as buffer solution, fiber material, concentration, and cyclic voltammetry (CV) cycle number, were tested during neurotransmitter detection. In each case, without drastically changing the outcome of the functionalization process, the selectivity towards dopamine was improved. The detected oxidation current for dopamine was increased by 92%, while ascorbic acid and serotonin oxidation currents were lowered by 66% under the best conditions. Moreover, dopamine sensing was successfully achieved in tandem with home-made triple electrodes and an in-house built potentiostat at a high scan rate mode.

Recyclable Mesoporous Organosilica Nanoparticles Derived from Proline-Valinol Amides for Asymmetric Organocatalysis

Going a step further from bulk organosilicas to nanosized materials, we describe herein the preparation of mesoporous organosilica nanoparticles derived from mono- and bis-silylated proline-valinol amides, both by grafting on preformed mesoporous silica nanoparticles (MSN) and by a co-condensation method in neutral medium using Brij-56/CTAB as templates. This is the first report on the obtention of functionalized MSN by a co-condensation procedure with a structurally complex chiral precursor. The functionalized MSN have been characterized by elemental analysis, 29Si and 13C CP MAS NMR, transmission electron microscopy, scanning electron microscopy, N2-sorption measurements, dynamic light scattering, ζ-potential, and powder X-ray diffraction. We have evaluated the activity of these materials as recyclable catalysts in the asymmetric aldol reaction. The best organocatalysts are those derived from the monosilylated precursor, observing good diastereo- and enantiomeric ratios with a simple and environmentally friendly optimized protocol (water, 0 °C, absence of cocatalyst). The nanocatalyst was easily recovered by centrifugation and recycled up to five runs without loss of activity and selectivity. The use of organosilica nanoparticles reduces the problems of diffusion and low reaction rates encountered with bulk organosilicas.

Phase Control in Hafnia: New Synthesis Approach and Convergence of Average and Local Structure Properties.

Technologically relevant tetragonal/cubic phases of HfO2 can be stabilized at room temperature by doping with trivalent rare earths using various approaches denoted generically as bulk coprecipitation. Using in situ/ex situ X-ray diffraction (XRD), Raman spectroscopy, high-resolution transmission electron microscopy, and in situ/ex situ site-selective, time-gated luminescence spectroscopy, we show that wet impregnation of hafnia nanoparticles with 10% Eu oxide followed by mild calcination in air at 500 °C produces an efficient stabilization of the cubic phase, comparable to that obtained by bulk precipitation. The physical reasons behind the apparently conflictual data concerning the actual crystallographic phase and the local symmetry around the Eu stabilizer and how these can be mediated by luminescence analysis are also discussed. Apparently, the cubic crystal structure symmetry determined by XRD results in a pseudocubic/tetragonal local structure around Eu determined by luminescence. Considering the recent findings on wet impregnated CeO2 and ZrO2, it is concluded that CeO2, ZrO2, and HfO2 represent a unique case of a family of oxides that is extremely tolerant to heavy doping by wet impregnation. In this way, the same batch of preformed nanoparticles can be doped with different lanthanide concentrations or with various lanthanides at a fixed concentration, allowing a systematic and reliable investigation of the effect of doping, lanthanide type, and lanthanide concentration on the various functionalities of these technologically relevant oxides.

Synthesis Method for Cellulose Nanofiber Biotemplated Palladium Composite Aerogels.

Here, a method to synthesize cellulose nanofiber biotemplated palladium composite aerogels is presented. Noble metal aerogel synthesis methods often result in fragile aerogels with poor shape control. The use of carboxymethylated cellulose nanofibers (CNFs) to form a covalently bonded hydrogel allows for the reduction of metal ions such as palladium on the CNFs with control over both nanostructure and macroscopic aerogel monolith shape after supercritical drying. Crosslinking the carboxymethylated cellulose nanofibers is achieved using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) in the presence of ethylenediamine. The CNF hydrogels maintain their shape throughout synthesis steps including covalent crosslinking, equilibration with precursor ions, metal reduction with high concentration reducing agent, rinsing in water, ethanol solvent exchange, and CO2 supercritical drying. Varying the precursor palladium ion concentration allows for control over the metal content in the final aerogel composite through a direct ion chemical reduction rather than relying on the relatively slow coalescence of pre-formed nanoparticles used in other sol-gel techniques. With diffusion as the basis to introduce and remove chemical species into and out of the hydrogel, this method is suitable for smaller bulk geometries and thin films. Characterization of the cellulose nanofiber-palladium composite aerogels with scanning electron microscopy, X-ray diffractometry, thermal gravimetric analysis, nitrogen gas adsorption, electrochemical impedance spectroscopy, and cyclic voltammetry indicates a high surface area, metallized palladium porous structure.