Tetrafluoroborate salts of diazotized Azure A (AA-N), Neutral Red (NR-N) and Congo Red (CR-N) dyes were prepared and reacted with multiwalled carbon nanotubes (MWCNTs) at room temperature, in water without any reducing agent. The as-modified MWCNTs were examined by IRATR, Raman spectroscopy, XPS, TGA, TEM, and cyclic voltammetry. The diazonium band located at ∼2350 cm in the diazotized dye IR spectra vanished after attachment to the nanotubes whereas the Raman D/G peak ratio slightly increased after dye covalent attachment at a high initial diazonium/CNT mass ratio. XPS measurements show the loss of F 1s from the BF anion together with a clear change in the high-resolution C 1s region from the modified nanotubes. Thermogravimetric analyses proved substantial mass loadings of the organic grafts leveling off at 40.5, 34.3, and 50.7 wt % for AA, NR, and CR, respectively. High-resolution TEM pictures confirmed the presence of 1.5-7-nm-thick continuous amorphous layers on the nanotubes assigned to the aryl layers from the dyes. Cyclic voltammetry studies in acetonitrile (ACN) confirmed the grafting of the dyes; the latter retain their electrochemical behavior in the grafted state. The experimental results correlate remarkably well with quantum chemical calculations that indicate high binding energies between the dyes and the CNTs accounting for true covalent bonding (140-185 kJ/mol with the CNT-aryl distance <1.6 nm), though attachment by π stacking also contributes to obtaining stable hybrids. Finally, the pH-responsive character of the robust hybrids was demonstrated by a higher degree of protonation of Neutral Red-grafted CNTs at pH 2 compared to that of the neutral aqueous medium. This work demonstrates that diazotized dyes can be employed for the surface modification of MWCNTs in a very simple and efficient manner in water and at room temperature. The hybrids could be employed for many purposes such as optically pH-responsive materials, biosensors, and optothermal composite actuators to name a few.

4-benzenethiol-functionalized High Surface Area Graphite powder was prepared and decorated with bimetallic Cu 100-x Rh x nanoparticles (NPs) to serve as electrocatalysts for the reduction of nitrates. In the first step, the HSAG powder was grafted with in situ generated diazonium compounds from 4-aminothiophenol (ATP), in acidic medium using NaNO 2 for the diazotization process. The surface composition was tuned using different initial quantities of ATP. The surface XPS-determined S/C atomic ratio was found to increase stepwise with the initial amine quantity. In a second step, the grafted and untreated HSAG powders were decorated with Cu 100-x Rh x NPs by a wet chemical method and the elemental composition of the end composites assessed by EDS-SEM and ICP, whereas TEM and EDS-TEM served to characterize the NPs morphology and their composition at the nanometer scale. In all cases, the NP size was invariably found to be ~1.7 nm but with a size distribution becoming narrower under increasing grafting rate and the global composition enriched in copper. Voltammetry was performed with a cavity microelectrode to evaluate the electrocatalytic performances of the composites for nitrate reduction. Increasing diazonium grafting led to a progressive reduction of the peak current intensity and a shift of the peak potentials towards cathodic values. Maximum intensity was obtained for 0.005 µmol of diazonium salt per mg of HSAG, with a gain of 40 % in comparison to the best untreated sample. This improvement and a change of the voltammogram characteristics after grafting seem to result from modifications of the local composition at the level of NPs that differs from the global composition. This work conclusively shows that diazonium surface modification is important not only to attach electrocatalytic NPs to carbon supports but also to provide narrower size distribution of the electrocatalysts together with finely tuned catalytic properties.