An extremely simple and rapid (seconds) approach is reported to directly synthesize gram quantities of P-doped graphitic porous carbon materials with controlled P bond configuration. For the first time, it is demonstrated that the P-doped carbon materials can be used as a selective metal free catalyst for aerobic oxidation reactions. The work function of P-doped carbon materials, its connectivity to the P bond configuration, and the correlation with its catalytic efficiency are studied and established. In direct contrast to N-doped graphene, the P-doped carbon materials with higher work function show high activity in catalytic aerobic oxidation. The selectivity trend for the electron donating and withdrawing properties of the functional groups attached to the aromatic ring of benzyl alcohols is also different from other metal free carbon based catalysts. A unique catalytic mechanism is demonstrated, which differs from both GO and N-doped graphene obtained by high temperature nitrification. The unique and unexpected catalytic pathway endows the P-doped materials with not only good catalytic efficiency but also recyclability. This, combined with a rapid, energy saving approach that permits fabrication on a large scale, suggests that the P-doped porous materials are promising materials for "green catalysis" due to their higher theoretical surface area, sustainability, environmental friendliness, and low cost.
Transition-metal-catalyzed alkylation reactions of arenes have become a central transformation in organic synthesis. Herein, we report the first general strategy for alkylation of arenes with styrenes and alcohols catalyzed by carbon-based materials, exploiting the unique property of graphenes to produce valuable diarylalkane products in high yields and excellent regioselectivity. The protocol is characterized by a wide substrate scope and excellent functional group tolerance. Notably, this process constitutes the first general application of graphenes to promote direct C-C bond formation utilizing polar functional groups anchored on the GO surface, thus opening the door for an array of functional group alkylations using benign and readily available graphene materials. Mechanistic studies suggest that the reaction proceeds via a tandem catalysis mechanism in which both of the coupling partners are activated by interaction with the GO surface.
Hummers method is commonly used for the fabrication of graphene oxide (GO) from graphite particles. The oxidation process also leads to the cutting of graphene sheets into small pieces. From a thermodynamic perspective, it seems improbable that the aggressive, somewhat random oxidative cutting process could directly result in graphene nanosheets without destroying the intrinsic π-conjugated structures and the associated exotic properties of graphene. In Hummers method, both KMnO4 and NO2(+) (nitronium ions) in concentrated H2SO4 solutions act as oxidants via different oxidation mechanisms. From both experimental observations and theoretical calculations, it appears that KMnO4 plays a major role in the observed oxidative cutting and unzipping processes. We find that KMnO4 also limits nitronium oxidative etching of graphene basal planes, therefore slowing down graphene fracturing processes for nanosheet fabrication. By intentionally excluding KMnO4 and exploiting pure nitronium ion oxidation, aided by the unique thermal and kinetic effects induced by microwave heating, we find that graphite particles can be converted into graphene nanosheets with their π-conjugated aromatic structures and properties largely retained. Without the need of any postreduction processes to remove the high concentration of oxygenated groups that results from Hummers GO formation, the graphene nanosheets as-fabricated exhibit strong absorption, which is nearly wavelength-independent in the visible and near-infrared (NIR) regions, an optical property typical for intrinsic graphene sheets. For the first time, we demonstrate that strong photoacoustic signals can be generated from these graphene nanosheets with NIR excitation. The photo-to-acoustic conversion is weakly dependent on the wavelength of the NIR excitation, which is different from all other NIR photoacoustic contrast agents previously reported.
We report a novel cancer-targeted nanomedicine platform for imaging and prospect for future treatment of unresected ovarian cancer tumors by intraoperative multimodal phototherapy. To develop the required theranostic system, novel low-oxygen graphene nanosheets were chemically modified with polypropylenimine dendrimers loaded with phthalocyanine (Pc) as a photosensitizer. Such a molecular design prevents fluorescence quenching of the Pc by graphene nanosheets, providing the possibility of fluorescence imaging. Furthermore, the developed nanoplatform was conjugated with poly(ethylene glycol), to improve biocompatibility, and with luteinizing hormone-releasing hormone (LHRH) peptide, for tumor-targeted delivery. Notably, a low-power near-infrared (NIR) irradiation of single wavelength was used for both heat generation by the graphene nanosheets (photothermal therapy [PTT]) and for reactive oxygen species (ROS)-production by Pc (photodynamic therapy [PDT]). The combinatorial phototherapy resulted in an enhanced destruction of ovarian cancer cells, with a killing efficacy of 90%–95% at low Pc and low-oxygen graphene dosages, presumably conferring cytotoxicity to the synergistic effects of generated ROS and mild hyperthermia. An animal study confirmed that Pc loaded into the nanoplatform can be employed as a NIR fluorescence agent for imaging-guided drug delivery. Hence, the newly developed Pc-graphene nanoplatform has the significant potential as an effective NIR theranostic probe for imaging and combinatorial phototherapy.
The π-plasmon band of SWNTs can be used to selectively and sensitively detect Fe3+via the conjugation of Fe3+ selective siderophores.
The unique properties of a holey graphene sheet, referred to as a graphene sheet with nanoholes in its basal plane, lead to wide range of applications that cannot be achieved by its nonporous counterpart. However, the large-scale solution-based production requires graphene oxide (GO) or reduced GO (rGO) as the starting materials, which take hours to days for fabrication. Here, an unexpected discovery that GO with or without holes can be controllably, directly, and rapidly (tens of seconds) fabricated from graphite powder via a one-step-one-pot microwave assisted reaction with a production yield of 120 wt% of graphite is reported. Furthermore, a fast and low temperature approach is developed for simultaneous nitrogen (N) doping and reduction of GO sheets. The N-doped holey rGO sheets demonstrate remarkable electrocatalytic capabilities for the electrochemical oxygen reduction reaction. The existence of the nanoholes provides a "short cut" for efficient mass transport and dramatically increases edges and surface area, therefore, creates more catalytic centers. The capability of rapid fabrication and N-doping as well as reduction of holey GO can lead to development of an efficient catalyst that can replace previous coin metals for energy generation and storage, such as fuel cells and metal-air batteries.
We report on magnetic susceptibility, NMR, and EPR measurements of pristine and Fe-doped micro- and nanosized graphenes (LGr and NGr), prepared by a unique microwave enabled technique from graphite particles. Significant orbital diamagnetism in the studied compounds (∼70% of that of bulk graphite) is revealed. At T < 30 K, a weak paramagnetism due to edge π-electronic spin states is observed. Reduction on the lateral size of the graphene sheets results in the suppression of orbital diamagnetism and strengthening of the paramagnetic contribution due to an increased number of open edges in NGr. Significant acceleration of 13C nuclear spin–lattice relaxation under iron doping of both LGr and NGr samples is attributed to the interaction of nuclear spins with paramagnetic Fe ions and indicates that the latter are anchored to the graphene edges. The amount of Fe ions attached to the edges of NGr-Fe is ∼6.6 times higher than that of LGr-Fe. This finding reveals the noticeable capability of nanographene to fix Fe ions on its periphery terminated by various oxygen-containing groups and atomic hydrogen. Several schemes for such fixation are proposed.
A highly porous graphitic carbon material, dually-doped with P and S, was studied as a metal free catalyst for aerobic oxidation reactions. Catalytic mechanism studies suggest that the active centers, originated from P-and S-doping, additively/synergistically catalyze the aerobic oxidation of benzylic alcohols but with different pathways. For the first time, catalytic centers stemming from S-doping were experimentally identified to be exocyclic S species (C-S-C, sulfur out of the carbon ring), which are different from those proposed for electrochemical oxygen reduction reactions (ORR) with a 4epathway and oxygen evaluation reactions (OER). Notably, all the catalytic sites from both P and S doping share a similar "protruding out" pyramid structure, which is in contrast to the planar structure of the catalytic sites in Nor B-doped graphitic materials. The unique geometric structure of the catalytic sites can minimize substrate steric hindrance effects, endowing the P, S co-doped catalysts with a wide substrate scope and functional group tolerance. Furthermore, the unambiguous distinguishment of the catalytic sites from those in OER and ORR provides valuable guidance for designing and developing carbon materials with controlled active sites to satisfy different catalytic applications.
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