Jitendra N. Tiwari

Noncovalent Functionalization of Graphene and Graphene Oxide for Energy Materials, Biosensing, Catalytic, and Biomedical Applications

This Review focuses on noncovalent functionalization of graphene and graphene oxide with various species involving biomolecules, polymers, drugs, metals and metal oxide-based nanoparticles, quantum dots, magnetic nanostructures, other carbon allotropes (fullerenes, nanodiamonds, and carbon nanotubes), and graphene analogues (MoS2, WS2). A brief description of π-π interactions, van der Waals forces, ionic interactions, and hydrogen bonding allowing noncovalent modification of graphene and graphene oxide is first given. The main part of this Review is devoted to tailored functionalization for applications in drug delivery, energy materials, solar cells, water splitting, biosensing, bioimaging, environmental, catalytic, photocatalytic, and biomedical technologies. A significant part of this Review explores the possibilities of graphene/graphene oxide-based 3D superstructures and their use in lithium-ion batteries. This Review ends with a look at challenges and future prospects of noncovalently modified graphene and graphene oxide.

Engineered Carbon-Nanomaterial-Based Electrochemical Sensors for Biomolecules

The study of electrochemical behavior of bioactive molecules has become one of the most rapidly developing scientific fields. Biotechnology and biomedical engineering fields have a vested interest in constructing more precise and accurate voltammetric/amperometric biosensors. One rapidly growing area of biosensor design involves incorporation of carbon-based nanomaterials in working electrodes, such as one-dimensional carbon nanotubes, two-dimensional graphene, and graphene oxide. In this review article, we give a brief overview describing the voltammetric techniques and how these techniques are applied in biosensing, as well as the details surrounding important biosensing concepts of sensitivity and limits of detection. Building on these important concepts, we show how the sensitivity and limit of detection can be tuned by including carbon-based nanomaterials in the fabrication of biosensors. The sensing of biomolecules including glucose, dopamine, proteins, enzymes, uric acid, DNA, RNA, and H2O2 traditionally employs enzymes in detection; however, these enzymes denature easily, and as such, enzymeless methods are highly desired. Here we draw an important distinction between enzymeless and enzyme-containing carbon-nanomaterial-based biosensors. The review ends with an outlook of future concepts that can be employed in biosensor fabrication, as well as limitations of already proposed materials and how such sensing can be enhanced. As such, this review can act as a roadmap to guide researchers toward concepts that can be employed in the design of next generation biosensors, while also highlighting the current advancements in the field.

Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries.

Interconnected Pt-nanodendrite/DNA/reduced-graphene-oxide hybrid showing remarkable oxygen reduction activity and stability.

Controlling the morphology and size of platinum nanodendrites (PtDs) is a key factor in improving their catalytic activity and stability. Here, we report the synthesis of PtDs on genomic-double-stranded-DNA/reduced-graphene-oxide (gdsDNA/rGO) by the NaBH4 reduction of H(2)PtCl(6) in the presence of plant gdsDNA. Compared to industrially adopted catalysts (i.e., state-of-the-art Pt/C catalyst, Pt/rGO, Pt(3)Co, etc.), the as-synthesized PtDs/gdsDNA/rGO hybrid displays very high oxygen reduction reaction (ORR) catalytic activities (much higher than the 2015 U.S. Department of Energy (DOE) target values), which are the rate-determining steps in electrochemical energy devices, in terms of onset-potential, half-wave potential, specific-activity, mass-activity, stability, and durability. Moreover, the hybrid exhibits a highly stable mass activity for the ORR over a wide pH range of 1-13. These exceptional properties would make the hybrid applicable in next-generation electrochemical energy devices.

Highly Selective and Stable Carbon Dioxide Uptake in Polyindole-Derived Microporous Carbon Materials

Adsorption with solid sorbents is considered to be one of the most promising methods for the capture of carbon dioxide (CO₂) from power plant flue gases. In this study, microporous carbon materials used for CO₂ capture were synthesized by the chemical activation of polyindole nanofibers (PIF) at temperatures from 500 to 800 °C using KOH, which resulted in nitrogen (N)-doped carbon materials. The N-doped carbon materials were found to be microporous with an optimal adsorption pore size for CO₂ of 0.6 nm and a maximum (Brunauer-Emmett-Teller) BET surface area of 1185 m(2) g(-1). The PIF activated at 600 °C (PIF6) has a surface area of 527 m(2) g(-1) and a maximum CO₂ storage capacity of 3.2 mmol g(-1) at 25 °C and 1 bar. This high CO₂ uptake is attributed to its highly microporous character and optimum N content. Additionally, PIF6 material displays a high CO₂ uptake at low pressure (1.81 mmol g(-1) at 0.2 bar and 25 °C), which is the best low pressure CO₂ uptake reported for carbon-based materials. The adsorption capacity of this material remained remarkably stable even after 10 cycles. The isosteric heat of adsorption was calculated to be in the range of 42.7-24.1 kJ mol(-1). Besides the excellent CO₂ uptake and stability, PIF6 also exhibits high selectivity values for CO₂ over N₂, CH₄, and H₂ of 58.9, 12.3, and 101.1 at 25 °C, respectively, and these values are significantly higher than reported values.

Facile approach to the synthesis of 3D platinum nanoflowers and their electrochemical characteristics

Three-dimensional (3D) platinum nanoflowers have been successfully synthesized by potentiostatic pulse plating method on a silicon substrate, and electrochemical study shows that the nanostructured Pt catalyst has an excellent electrocatalytic activity toward methanol and CO oxidation due to preferential (100) and (110) surface orientations on the Pt nanoflowers.

Synthesis of Pt Nanopetals on Highly Ordered Silicon Nanocones for Enhanced Methanol Electrooxidation Activity

Platinum (Pt) nanopetals were electrodeposited on highly ordered silicon nanocones (SiNCs) and explored as the electrocatalyst for methanol oxidation reaction (MOR) for direct methanol fuel cells applications. Highly ordered SiNCs array fabricated using the porous anodic aluminum oxide as the template had a high surface area. Well-dispersed Pt nanopetals possessing high electrocatalytic surface area was synthesized by pulse-electrodeposition on the SiNCs. Pt nanopetals loaded on highly ordered SiNC support exhibited very good catalytic activity for MOR and a high tolerance against CO poisoning, as compared to Pt nanoflowers/flat Si, Pt nanoparticles/flat Si, and many previously reported works. The abundance of a large surface area for facile transport of methanol, SiO(2) sites in the vicinity of the SiNCs, as well as less contact area between the Pt nanopetals catalyst and SiNCs are suggested to be the major factors enhancing the electrocatalytic performance of the Pt nanopetal/SiNC electrode. Moreover, we believe this new nanostructure (Pt nanopetals/SiNCs) will enable many new advances in nanotechnology.

Facile synthesis of continuous Pt island networks and their electrochemical properties for methanol electrooxidation.

A two-dimensional continuous Pt island network was successfully synthesized by pulse-potentiostatic electrodeposition on a flat silicon substrate, which showed markedly enhanced catalytic activity toward methanol electrooxidation and high CO tolerance, probably due to the synergistic effect of the Pt island catalyst and surrounding SiO(2) surface layer.

A Promising Approach to the Synthesis of 3D Nanoporous Graphitic Carbon as a Unique Electrocatalyst Support for Methanol Oxidation

A 3D nanoporous graphitic carbon (g-C) material is synthesized by using an adamantane (C(10)H(16)) flame, and utilized to support a Pt(50)-Ru(50) alloy catalyst. The physico-chemical properties of the Pt(50)-Ru(50)/3D nanoporous g-C electrode are examined by a range of spectroscopy techniques as well as Brunauer-Emmett-Teller surface area analysis. Cyclic voltammetry measurements are used for electrochemical characterization of the Pt(50)-Ru(50)/3D nanoporous g-C electrode. The electrochemical investigations show that the supported Pt(50)-Ru(50) has excellent activity and stability towards methanol electro-oxidation. Good CO tolerance is also shown, and considered to be due to the presence of Ru nanoparticles. It is proposed that Ru is able to promote the oxidation of strongly adsorbed CO on Pt by supplying an oxygen source: Ru(OH)(ad). Moreover, the presence of 3D nanopores in the g-C support may also contribute to the observed higher current density by virtue of the easy transport of methanol and the oxidation products through these nanopores.

Accelerated Bone Regeneration by Two-Photon Photoactivated Carbon Nitride Nanosheets

Human bone marrow-derived mesenchymal stem cells (hBMSCs) present promising opportunities for therapeutic medicine. Carbon derivatives showed only marginal enhancement in stem cell differentiation toward bone formation. Here we report that red-light absorbing carbon nitride (C3N4) sheets lead to remarkable proliferation and osteogenic differentiation by runt-related transcription factor 2 (Runx2) activation, a key transcription factor associated with osteoblast differentiation. Accordingly, highly effective hBMSCs-driven mice bone regeneration under red light is achieved (91% recovery after 4 weeks compared to 36% recovery in the standard control group in phosphate-buffered saline without red light). This fast bone regeneration is attributed to the deep penetration strength of red light into cellular membranes via tissue and the resulting efficient cell stimulation by enhanced photocurrent upon two-photon excitation of C3N4 sheets near cells. Given that the photoinduced charge transfer can increase cytosolic Ca2+ accumulation, this increase would promote nucleotide synthesis and cellular proliferation/differentiation. The cell stimulation enhances hBMSC differentiation toward bone formation, demonstrating the therapeutic potential of near-infrared two-photon absorption of C3N4 sheets in bone regeneration and fracture healing.