Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations warrant comprehensive studies. The availability of well-defined pristine graphene starting materials in large quantities remains a key obstacle to the advancement of synthetic graphene chemistry.

We report a fast Staudinger reaction between perfluoroaryl azides (PFAAs) and aryl phosphines, occurring readily under ambient conditions. A rate constant as high as 18 M−1 s−1 was obtained between methyl 4-azido-2,3,5,6-tetrafluorobenzoate and methyl 2-(diphenylphosphanyl)benzoate in CD3CN/D2O. In addition, the iminophosphorane product was stable toward hydrolysis and aza-phosphonium ylide reactions. The PFAA-Staudinger reaction proved to be an excellent bioothorgonal reaction. PFAA-derivatized mannose and galactose were successfully transformed into cell surface glycans and efficiently labeled with phosphine-derivatized fluorescent bovine serum albumin.

Multifunctional cellulose nanocrystals have been synthesized and applied as a new type of glyconanomaterial in lectin binding and bacterial imaging. The cellulose nanocrystals were prepared by TEMPO-mediated oxidation and acidic hydrolysis, followed by functionalization with a quinolone fluorophore and carbohydrate ligands. The cellulose nanocrystals were subsequently applied in interaction studies with carbohydrate-binding proteins and in bacterial imaging. The results show that the functional cellulose nanocrystals could selectively recognize the corresponding cognate lectins. In addition, mannosylated nanocrystals were shown to selectively interact with FimH-presenting E. coli, as detected by TEM and confocal fluorescence microscopy. These glyconanomaterials provide a new application of cellulose nanocrystals in biorecognition and imaging.

The anti-soiling (AS) performance of solar mirrors coated with a highly transparent, superhydrophobic nanoparticle-textured coating has been characterized. The AS coatings were created on the mirror surface by depositing nano-textured silica nanoparticle layers of ∼250 nm thickness using a draw-down coating process, followed by fluorination of the nanoparticles in a molecular vapor deposition process. Highly uniform surface features of the AS-coated mirrors (20 × 30 cm2, no measurable loss in specular reflectance, and water contact angle >165°) provided an outstanding AS performance. A 4× reduction in the rate of dust accumulation as determined by gravimetric measurement of the accumulated dust on coated versus uncoated mirrors was observed. Additional evidence of a significant reduction in soiling rate was determined during measurements of specular reflectance in an outdoor environment test. The adhesion force between a model sand particle and nano-textured coatings in the hydrophobic to superhydrophobic range was also studied. A dramatic decrease in adhesive force acting on the particle was observed with increasing surface hydrophobicity. The results align well with the observed dust accumulation on the AS-coated mirrors. The AS-coated mirror maintains a high reflectivity by shedding dust and resisting dust accumulation, providing a potential benefit when applied to mirrors in the solar field of a concentrated solar power generation plant.

We report the synthesis of a three-dimensional graphene (3DG)–TiO 2 nanocomposite by covalently attaching P25 TiO 2 nanoparticles onto pristine 3DG through a perfluorophenyl azide-mediated coupling reaction. The TiO 2 nanoparticles were robustly attached on the 3DG surface, with minimal particle agglomeration. In photocatalytic CO 2 reduction, the 3DG–TiO 2 nanocomposite demonstrated excellent activity, about 11 times higher than that of the P25 TiO 2 nanoparticles. The enhanced activity can be partially attributed to the highly dispersed state of the P25 TiO 2 nanoparticles on the 3DG substrate. This 3DG-based system offers a new platform for fabricating photocatalytic materials with enhanced activities.