Four different types of crystalline and fibrillar nanocellulosic materials with different functional groups (sulfate, carboxylate, amino-silane) are produced and used to disperse commercial multiwalled carbon nanotubes (MWCNT). Aqueous nanocellulose/MWCNT dispersions are drop-cast on tetrahedral amorphous carbon (ta-C) substrates to obtain highly stable composite electrodes. Their electrochemical properties are studied using cyclic voltammetry (CV) measurements with Ru­(NH3)6 2+/3+, IrCl6 2–/3– redox probes, in electrolytes of different ionic strengths. All studied nanocellulose/MWCNT composites show excellent stability over a wide potential range (−0.6 to +1 V) in different electrolytes. Highly anionic and more porous fibrillar nanocellulosic composites indicate strong electrostatic and physical enrichment of cationic Ru­(NH3)6 2+/3+ in lower-ionic-strength electrolytes, while lesser anionic and denser crystalline nanocellulosic composites show no such effects. This study provides essential insights into developing tailorable nanocellulose/carbon nanomaterial hybrid platforms for different electrochemical applications, by altering the constituent nanocellulosic material properties.

Nanocellulose has emerged as a promising green dispersant for carbon nanotubes (CNTs), and there is an increasing trend in developing nanocellulose/CNT hybrid materials for electrochemical detection of various small molecules. However, there have been very few comprehensive studies investigating the role of nanocellulosic material properties upon the electroanalytical performance of the resultant hybrid electrodes. In this work, we demonstrate the influence of both nanocellulose functionalization and geometry, utilizing sulfated cellulose nanocrystals, sulfated cellulose nanofibers, and TEMPO-oxidized cellulose nanofibers. Transmission electron microscopy tomography enables direct visualization of the effect of nanocellulosic materials on the hybrid architectures. High resolution X-ray absorption spectroscopy verifies that the chemical nature of CNTs in the different hybrids is unmodified. Electroanalytical performances of the different nanocellulose/CNT hybrid electrodes are critically evaluated using physiologically relevant biomolecules with different charge such as, dopamine (cationic), paracetamol (neutral), and uric acid (anionic). The hybrid electrode containing fibrillar nanocellulose geometry with a high degree of sulfate group functionalization provides the highest electroanalytical sensitivity and strongest enrichment towards all studied analytes. These results clearly demonstrate for the first time, the extent of tailorability upon the electroanalytical response of nanocellulose/CNT hybrid electrodes towards different biomolecules, offered simply by the choice of nanocellulosic materials.

Linking structural and compositional features with the observed electrochemical performance is often ambiguous and sensitive to known and unknown impurities. Here an extensive experimental investigation augmented by computational analyses is linked to the electrochemical characterization of in situ nitrogen-doped tetrahedral amorphous carbon thin films (ta-C:N). Raman spectroscopy combined with X-ray reflectivity shows nitrogen disrupting the sp3 C–C structure of the reference ta-C, supported by the observations of graphitic nitrogen substitution in X-ray absorption spectroscopy. The surface roughness also increases, as observed in atomic force microscopy and atomic-level computational analyses. These changes are linked to significant increases in the hydrogen and oxygen content of the films by utilizing time-of-flight elastic recoil detection analysis. The conductivity of the films increases as a function of the nitrogen content, which is seen as a facile reversible outer-sphere redox reaction on ta-C:N electrodes. However, for the surface-sensitive inner-sphere redox (ISR) analytes, it is shown that the electrochemical response instead follows the oxygen and hydrogen content. We argue that the passivation of the required surface adsorption sites by hydrogen decreases the rates of all of the chemically different ISR probes investigated on nitrogenated surfaces significantly below that of the nitrogen-free reference sample. This hypothesis can be used to readily rationalize many of the contradictory electrochemical results reported in the literature.

Here, a new class of transflective oxide metaparticles that are able to capture solar radiation in a selective manner based on their size and morphology is demonstrated. The metaparticles possess an electronic polarization response “polarizonics” and show a specular reflective color at the visible frequencies. As a specific highlight, a resonating ultrathin reflective while transparent metacomposite, i.e., a transflective coating is designed. Further, a perfect solar absorber is devised whose function is morphology controlled and supplemented by the transflective coating via the selective interference concept. The multidisciplinary approach presented here enables design of materials with customized functionalities, bridging the sustainable nanochemistry to nanoengineering and proposes a new way for solving challenges in energy and solar harvesting.

Protein fouling is a critical issue in the development of electrochemical sensors for medical applications, as it can significantly impact their sensitivity, stability, and reliability. Modifying planar electrodes with conductive nanomaterials that possess a high surface area, such as carbon nanotubes (CNTs), has been shown to significantly improve fouling resistance and sensitivity. However, the inherent hydrophobicity of CNTs and their poor dispersibility in solvents pose challenges in optimizing such electrode architectures for maximum sensitivity. Fortunately, nanocellulosic materials offer an efficient and sustainable approach to achieving effective functional and hybrid nanoscale architectures by enabling stable aqueous dispersions of carbon nanomaterials. Additionally, the inherent hygroscopicity and fouling-resistant nature of nanocellulosic materials can provide superior functionalities in such composites. In this study, we evaluate the fouling behavior of two nanocellulose (NC)/multiwalled carbon nanotube (MWCNT) composite electrode systems: one using sulfated cellulose nanofibers and another using sulfated cellulose nanocrystals. We compare these composites to commercial MWCNT electrodes without nanocellulose and analyze their behavior in physiologically relevant fouling environments of varying complexity using common outer-and inner-sphere redox probes. Additionally, we use quartz crystal microgravimetry with dissipation monitoring (QCM-D) to investigate the behavior of amorphous carbon surfaces and nanocellulosic materials in fouling environments. Our results demonstrate that the NC/MWCNT composite electrodes provide significant advantages for measurement reliability, sensitivity, and selectivity over only MWCNT-based electrodes, even in complex physiological monitoring environments such as human plasma.