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Heavy metal ions are a naturally occurring element that is toxic. The overuse of these heavy metal-based compounds in industry, agriculture, domestic, and technological practices leads to exposure in the environment that may have adverse effects on human health and the ecology. Considering their toxicity, the detection of metal ions is crucial, and many analytical methods are used to monitor them. Electrochemical methods have attracted considerable attention due to good sensitivity, low detection limit, and short analysis time and portability. To increase the sensitivity and selectivity of detection, research has focused on developing high surface area nanostructured electrode materials including inorganic, organic, polymer, and corresponding hybrid-based composites. The properties of graphene, a family of 2D layered material, has ignited the scientific community to discover other layered materials and explore their electrochemical sensing application toward toxic metal ions. This chapter provides an overview of materials developed for detection of heavy metal ions contaminants, particularly the graphene and functionalized graphene-based nanomaterials.

A new single layer graphene oxide hybrid polymeric material was fabricated in which the fullerene moieties covalently attached to the edges of surface of SLGO sheets were coordinated to palladium atom in an η2-fasion, SLGO-php-C60/Pd. The polymer was characterized by SEM, TEM, FT-IR and Raman techniques. The newly formed material exhibited reversible electrochemical activity in the negative potential range due to the reduction of fullerene cages with an overall electrochemical behavior resembling that of typical organic conducting polymers. The electron density of states calculated using DFT method clearly confirmed the fullerene cage reduction via electron transfer from the low-lying SLGO states. Therefore, coordination polymers of fullerene moieties bonded to the graphene sheets are easier to reduce in comparison to the coordination polymers of pristine C60. In addition, the spectroscopic and electrochemical properties of SLGO-php-C60/Pd hybrid polymeric material were also compared with php-C60/Pd polymer and SLGO-php-C60 hybrid films to seek film morphology-property relations. The present study extends the application of graphene oxide providing electrically conducting, redox-active polymer material for different applications.

Photocatalytic behavior of a recently synthesized, single layer graphene oxide (SLGO) decorated with an electron donor, zinc phthalocyanine (ZnPc) and an electron acceptor, fulleropyrrolidine (C60) donor-acceptor hybrid is demonstrated. Electron accumulation in the form of one-electron reduced product of methyl viologen was obtained in high yields in an electron pooling experiment involving the ZnPc-SLGO-C60 hybrid and a sacrificial electron donor compared with control hybrids involving either ZnPc-SLGO or SLGO-C60 hybrids. This novel property of ZnPc-SLGO-C60 hybrid has been ascribed to the proximity effect offered by GO with covalently linked donor and acceptor entities on its surface. The present studies reveal that the ZnPc-SLGO-C60 hybrid is a suitable catalyst for solar fuel production.

A (carbon nanotube)–(fullerene–ferrocene dyad polymer) composite, pyr-SWCNTs/(C60Fc-Pd), was devised and tested as an active material of a symmetrical device for electric energy storage. The composite was redox conducting at both positive and negative potentials due to the Fc/Fc+ and C60–/C60 electrode process of the ferrocene and fullerene moiety of the dyad, respectively. The composite was prepared, first, by electrophoretic deposition of a film of noncovalently modified with 1-pyrenebutyric acid stacked single-wall carbon nanotubes (pyr-SWCNTs). Then, this film was coated, by potentiodynamic electropolymerization, with a film of the palladium-doped polymer of 2′-ferrocenylfulleropyrrolidine (C60Fc-Pd). The AFM imaging showed that the C60Fc-Pd film was uniformly built of 40–150 nm diameter globules of C60Fc-Pd while the film formed a tangle of pyr-SWCNTs bundles wrapped with clusters of ∼45 nm diameter globules of C60Fc-Pd. The XPS measurements identified interactions between the Pd and C60 moieties in ...

The molecular self-assembly of surfactants on the surface of single-walled carbon nanotubes (SWCNT) is currently a common strategy for the tuning of nanotube properties and the stabilization of carbon nanotube dispersions. Here, we report direct measurements of the degree of interfacial ordering for sodium dodecyl sulfate (SDS) surfactants adsorbed on colloidal, single-chirality enriched, SWCNTs within a solid film and investigate the dependence of surface alkyl chain order on the surfactant concentration in the precursor solution. The degree of order for the SWCNT-bound SDS molecules, is probed by vibrational sum frequency generation (VSFG) spectroscopy. We find concrete evidence for the presence of highly ordered surface structures at sufficiently high SDS concentrations, attributed here to cylindrical-like micelle assemblies with the SWCNT at the core. As the SDS concentration decreases, the interfacial order is found to decrease as well, generating a more disordered or random adsorption of surfactants on the nanotube surfaces.

The superoxide anion radical, O2•−, induced C60 electropolymerization mechanism was refined by simultaneous cyclic voltammetric (CV) and vis-NIR spectroelectrochemical as well as mass spectrometric (MALDI-TOF) characterization of the one- and two-electron reduction products of C60 in the presence of O2 in a mixed organic solvent solution. The C60 polymer (C60-O) film was also investigated by Raman spectroscopy and imaged by atomic force microscopy (AFM) both at the early and advanced polymerization stage. While the spectroelectrochemical behavior of the C60/C60•− couple in the presence of O2 was similar to that in its absence, at more negative potentials corresponding to C602− and O2•− formation C602− participated in a chemical follow-up reaction resulting in a product lacking any diagnostic absorption band in the vis-NIR range. Although the main peak in the MS spectrum of the one-electron reduction product was that of C60 at m/z of 720, several additional peaks in the m/z range of 739−760 appeared, indic...

Supramolecular donor-acceptor hybrids composed of few-layer graphene as an electron acceptor and phthalocyanine or porphyrin bearing four pyrene entities as photosensitizer donors have been synthesized, and occurrence of ultrafast charge separation in the order of 10(11)-10(12) s(-1) due to close proximity of the donor and acceptor entities is demonstrated.

Photoinduced charge separation processes of three-layer supramolecular hybrids, fullerene-porphyrin-SWCNT, which are constructed from semiconducting (7,6)- and (6,5)-enriched SWCNTs and self-assembled via π-π interacting long alkyl chain substituted porphyrins (tetrakis(4-dodecyloxyphenyl)porphyrins; abbreviated as MP(alkyl)(4)) (M = Zn and H(2)), to which imidazole functionalized fullerene[60] (C(60)Im) is coordinated, have been investigated in organic solvents. The intermolecular alkyl-π and π-π interactions between the MP(alkyl)(4) and SWCNTs, in addition, coordination between C(60)Im and Zn ion in the porphyrin cavity are visualized using DFT calculations at the B3LYP/3-21G(*) level, predicting donor-acceptor interactions between them in the ground and excited states. The donor-acceptor nanohybrids thus formed are characterized by TEM imaging, steady-state absorption and fluorescence spectra. The time-resolved fluorescence studies of MP(alkyl)(4) in two-layered nanohybrids (MP(alkyl)(4)/SWCNT) revealed efficient quenching of the singlet excited states of MP(alkyl)(4) ((1)MP*(alkyl)(4)) with the rate constants of charge separation (k(CS)) in the range of (1-9) × 10(9) s(-1). A nanosecond transient absorption technique confirmed the electron transfer products, MP˙(+)(alkyl)(4)/SWCNT˙(-) and/or MP˙(-)(alkyl)(4)/SWCNT˙(+) for the two-layer nanohybrids. Upon further coordination of C(60)Im to ZnP, acceleration of charge separation via(1)ZnP* in C(60)Im→ZnP(alkyl)(4)/SWCNT is observed to form C(60)˙(-)Im→ZnP˙(+)(alkyl)(4)/SWCNT and C(60)˙(-)Im→ZnP(alkyl)(4)/SWCNT˙(+) charge separated states as supported by the transient absorption spectra. These characteristic absorptions decay with rate constants due to charge recombination (k(CR)) in the range of (6-10) × 10(6) s(-1), corresponding to the lifetimes of the radical ion-pairs of 100-170 ns. The electron transfer in the nanohybrids has further been utilized for light-to-electricity conversion by the construction of proof-of-concept photoelectrochemical solar cells.

A non-covalent double-decker binding strategy is employed to construct functional supramolecular single-wall carbon nanotubes (SWCNT)-tetrapyrrole hybrids capable of undergoing photoinduced electron transfer and performing direct conversion of light into electricity. To accomplish this, two semiconducting SWCNTs of different diameters (6,5 and 7,6) were modified via π-π stacking of pyrene functionalized with an alkyl ammonium cation (PyrNH(3)(+)). Such modified nanotubes were subsequently assembled via dipole-cation binding of zinc porphyrin with one (1) or four benzo-18-crown-6 cavities (2) or phthalocyanine with four benzo-18-crown-6 cavities at the ring periphery (3), employed as visible-light photosensitizers. Upon charactering the conjugates using TEM and optical techniques, electron transfer via photoexcited zinc porphyrin and phthalocyanine was investigated using time-resolved emission and transient absorption techniques. Higher charge-separation efficiency is established for SWCNT(7,6) with a narrow band gap than the thin SWCNT(6,5) with a wide band gap. Photoelectrochemical studies using FTO/SnO(2) electrodes modified with these donor-acceptor conjugates unanimously demonstrated the ability of these conjugates to convert light energy into electricity. The photocurrent generation followed the trend observed for charge separation, that is, incident-photon-to-current efficiency (IPCE) of a maximum of 12 % is achieved for photocells with FTO/SnO(2)/SWCNT(7,6)/PyrNH(3)(+):1.

Graphene oxide decorated with an electron donor, zinc(II) phthalocyanine, and an electron acceptor, fullerene, has been synthesized, and photoinduced electron transfer leading to charge-separation is reported.

Dialkyl (3-aryl-l,2,4-oxadiazol-5-yl)phosphonate6sa -h have been obtained by 1,3-dipolar cycloaddition of arenenitrile oxides 5a-f to dialkyl phosphorocyanidates (4a and 4b) in yields ranging between 30% and 58%. A standardized method for obtaining cyanidates 4a and 4b has been established. The diethyl thiophosphorocyanidate (4c) is less reactive than 4a and 4b, only the 3-(4'-nitrophenyl) derivative 6i being obtainable. While the IR and NMFt spectra of 6a-i were unexceptional, their UV spectra showed evidence of conjugative interaction in high degrees between the phosphonate and heterocyclic moieties as well as a varying conjugative interaction between the heterocyclic and aryl moieties. The oxadiazoles 6a-h are thermally labile and yield trialkyl phosphates 7 as the only identifiable products. A mechanism based on the intermediacy of monomeric alkyl metaphosphate 11 in the formation of trialkyl phosphate was postulated, and supportive evidence in the form of trapping the metaphosphate with acetophenone has been obtained.