Graphene Oxide Facilitates Transformation of Waste PET into MOF Nanorods in Ionic Liquids.

Although though ionic liquids (IL) are rapidly emerging as highly efficient reagents for the depolymerization of waste plastics, their high cost and adverse impact on the environment make the overall process not only expensive but also environmentally harmful. In this manuscript, we report that graphene oxide (GO) facilitates the transformation of waste polyethylene terephthalate (PET) to Ni-MOF (metal organic framework) nanorods anchored on reduced graphene oxide (Ni-MOF@rGO) through NMP (N-Methyl-2-pyrrolidone)-based coordination in ionic liquids. Morphological studies using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed mesoporous three-dimensional structures of micrometer-long Ni-MOF nanorods anchored on reduced graphene substrates (Ni-MOF@rGO ), whereas structural studies using XRD and Raman spectra demonstrated the crystallinity of Ni-MOF nanorods. Chemical analysis of Ni-MOF@rGO carried out using X-ray photoelectron spectroscopy demonstrated that nickel moieties exist in an electroactive OH-Ni-OH state, which was further confirmed by nanoscale elemental maps recorded using energy-dispersive X-ray spectroscopy (EDS). The applicability of Ni-MOF@rGO as an electro-catalyst in a urea-enhanced water oxidation reaction (UOR) is reported. Furthermore, the ability of our newly developed NMP-based IL to grow MOF nanocubes on carbon nanotubes and MOF nano-islands on carbon fibers is also reported.

Coordination Polymer Framework-Derived Ni-N-Doped Carbon Nanotubes for Electro-Oxidation of Urea.

Electrochemical oxidation of urea (UOR) is critical in the removal of urea from wastewater and energy conservation and storage. Nickel-based catalysts are widely used for urea-ORR, but in all cases, the nickel must be hybridized with carbon materials to improve its conductivity. In this manuscript, we demonstrate the synthesis of a nickel-decorated carbon nanotube (Ni-NCNT) by simple microwave pyrolysis of Dabco (1,4-diazabicyclo[2.2.2]octane)-based coordination polymer frameworks (CPF). The surface structure, morphology and chemical composition of Ni-NCNT were characterized by Raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy (EDS) analysis. SEM studies showed micrometer-long bamboo-shaped CNTs with nickel nanoparticles anchored to the walls and inside the nanotubes. A structural study by TEM and Raman spectra showed that carbon nanotubes are rich in defects due to the presence of nitrogen, and this was confirmed by energy-dispersive X-ray spectroscopy (EDS) maps. When applied as electrocatalysts in urea oxidation reactions (UOR), our newly developed Ni-NCNT shows excellent electrocatalytic activity and stability, making it a versatile catalyst in energy generation and mitigating water contamination.

DABCO Derived Nitrogen-Doped Carbon Nanotubes for Oxygen Reduction Reaction (ORR) and Removal of Hexavalent Chromium from Contaminated Water.

Though chemically-derived reduced graphene oxide (CDG) from graphite oxide (GO) precursors is a widely practiced procedure for the large-scale production of graphene, the quality and quantity of thus obtained CDG is dependent on the reduction strategy used. In this work, we report an all-solid-state, residue-free, microwave process for the reduction of graphene oxide and subsequent growth of carbon nanotube 'separators' from a single precursor, namely DABCO (1,4-diazabicyclo[2.2.2]octane). The utility of our newly developed technique in efficiently and effectively reducing graphene oxide and in growing nitrogen-doped carbon nanotubes via catalysts like palladium and iron into unique mesoporous, 3-D hierarchical carbon nanostructures is demonstrated. The applicability of the thus obtained palladium embedded in Pd@NCNT-rGO nanoarchitectures for the oxygen reduction reaction (ORR) is investigated. When carbon fiber (CF) was used as the substrate, three-dimensional Fe@NCNT-CF were obtained, whose capability as versatile adsorbents for hexavalent chromium ion removal from contaminated waters was also demonstrated.

Metal Organic Frameworks Derived Fe-N-C Nanostructures as High-Performance Electrodes for Sodium Ion Batteries and Electromagnetic Interference (EMI) Shielding.

Metal organic framework (MOF)-derived carbon nanostructures (MDC) synthesized by either calcinations or carbonization or pyrolysis are emerging as attractive materials for a wide range of applications like batteries, super-capacitors, sensors, water treatment, etc. But the process of transformation of MOFs into MDCs is time-consuming, with reactions requiring inert atmospheres and reaction time typically running into hours. In this manuscript, we report the transformation of 1,4-diazabicyclo[2.2.2]octane, (DABCO)-based MOFs into iron nitride nanoparticles embedded in nitrogen-doped carbon nanotubes by simple, fast and facile microwave pyrolysis. By using graphene oxide and carbon fiber as microwave susceptible surfaces, three-dimensional nitrogen-doped carbon nanotubes vertically grown on reduced graphene oxide (MDNCNT@rGO) and carbon fibers (MDCNT@CF), respectively, were obtained, whose utility as anode material in sodium-ion batteries (MDNCNT@rGO) and for EMI (electromagnetic interference) shielding material (MDCNT@CF) is reported.

Metal Organic Framework Derived MnO2-Carbon Nanotubes for Efficient Oxygen Reduction Reaction and Arsenic Removal from Contaminated Water.

Even though manganese oxides are attractive materials for batteries, super-capacitors and electro-catalysts for oxygen reduction reactions, in most practical applications MnO2 needs to be hybridized with conductive carbon nano-structures to overcome its inherent poor electrical conductivity. In this manuscript we report microwave-assisted synthesis of MnO2 embedded carbon nanotubes (MnO2@CNT) from Mn-H3BTC (benzene-1,3,5-carboxylic acid) metal organic frameworks (MOF) precursors. Using graphene oxide as microwave susceptible surface, MnO2 nano-particles embedded in three dimensional reduced graphene oxide (rGO) -CNT frameworks (MnO2@CNT-rGO) were synthesized which when applied as electro-catalysts in oxygen reduction reaction (ORR) demonstrated comparable half-wave potential to commercial Pt/C, better stability, and excellent immunity to methanol crossover effect in alkaline media. When carbon fiber (CF) was used as substrate, three-dimensional MnO2@CNT-CF were obtained whose utility as effective adsorbents for arsenic removal from contaminated waters is demonstrated.

Transforming Waste Poly(Ethylene Terephthalate) into Nitrogen Doped Carbon Nanotubes and Its Utility in Oxygen Reduction Reaction and Bisphenol-A Removal from Contaminated Water.

Till date, waste plastics are either down-cycled to cheap products like fibers or burnt in incinerators to generate heat. In this manuscript, we report a simple and effective technique for microwave induced transformation of waste polyethylene terephthalate (wPET) to carbon nano-tubes (CNT). Iron nano-particles dispersed on graphene substrate acted as catalyst for CNT growth whereas urea served the dual role of de-polymerisation of wPET and also as nitrogen doping agent. Application of our newly synthesized 3-D meso-porous graphene-nitrogen doped carbon nanotube- iron electrode (Fe@NCNT-rGO) as electro-catalyst for oxygen reduction reaction (ORR) shows a positive half-wave potential (E1/2) of 0.75 V vs. RHE (reversible hydrogen electrode), nearly ideal four-electron pathway and excellent methanol tolerance when compared to commercial 20% Pt/C. The utility of Fe@NCNT-rGO for removal of bisphenol A from contaminated waters is also reported.

Extraction of Microfibrillar Cellulose From Waste Paper by NaOH/Urethane Aqueous System and Its Utility in Removal of Lead from Contaminated Water.

Though recycling of waste paper is widely practiced but usually it is downgraded to lower valued recycled waste paper. Based on this concern, we report the development of novel NaOH/urethane aqueous system for extraction of microfibrillated cellulose from waste paper. The purity of so obtained microfibrillated cellulose (MFC) was evaluated by morphological tests using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and by evaluation of physicochemical properties using Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Morphologies of MFC studied by SEM and TEM showed that the size of purified cellulose fibrils reduced when compared to that of waste paper but fibrils are cleaner and smoother due to the removal of talc and lignin. XRD analysis revealed that MFC exhibits good crystallinity. The utility of sulfonated and pristine microfibrillar cellulose in removal of lead from contaminated water is also reported. Our results show that renewable, sustainable, cheap, and waste biomass like waste paper can be used for producing valuable second-generation high-value products.

Vitamin Derived Nitrogen Doped Carbon Nanotubes for Efficient Oxygen Reduction Reaction and Arsenic Removal from Contaminated Water.

Nitrogen doped carbon nanotubes (NCNT) that were prepared by simple microwave pyrolysis of Niacin (Vitamin B3) as noble metal free electrocatalyst for oxygen reduction reaction (ORR) is reported. Our newly developed technique has the distinct features of sustainable and widely available niacin as a bi-functional source of both carbon and nitrogen, whereas the iron catalyst is cheap and the fourth most common element in the Earth's crust. The results of the electrochemical tests show that our newly developed iron impregnated NCNT anchored on reduced graphene substrate (Fe@NCNT-rGO) catalyst exhibit: a positive half-wave potential (E1/2) of 0.75 V vs. RHE (reversible hydrogen electrode), four-electron pathway, and better methanol tolerance when compared to commercial 20% Pt/C. When applied as adsorbent for arsenic removal, our newly discovered NCNT-Fe illustrate the efficient and effective removal of arsenic across a wide range of pH values.

Blister packing of copper hydroxide and titania nanoparticles on graphene and its recycling.

Metal nanoparticles anchored on a graphene substrate find many applications such as sensors, catalysts, lithium ion batteries, etc. However, to date, graphene-metal nanohybrids have been synthesized by either covalent or ionic interactions between the graphene substrate and the metal nanoparticles. In this manuscript, we report a green and facile method to "bubble pack" metal nanoparticles on a graphene substrate by a simple process utilizing eco-friendly ionic liquids in conjunction with microwave heating. Copper nanoparticles bubble packed on graphene showed enhanced glucose sensing when compared to covalently bonded copper/graphene hybrids. Titania nanoparticles bubble packed on graphene when applied as anode materials in lithium ion batteries exhibited two times more lithium ion retention when compared to covalently bonded titania/graphene hybrids. "End of life" disposal of nanomaterials into the environment is a growing area of concern in recent days. One way of dealing with this problem is to extend the life cycle of nanomaterials by reusing the nanomaterials in multiple applications. In this report, we also show the recyclability of our novel bubble packaging material, by etching out the metal nanoparticles resulting in a unique 3D hierarchical graphene nanocup decorated graphene. The applicability of this recycled material in super capacitors is also reported.

Graphene--nanotube--iron hierarchical nanostructure as lithium ion battery anode.

In this study, we report a novel route via microwave irradiation to synthesize a bio-inspired hierarchical graphene--nanotube--iron three-dimensional nanostructure as an anode material in lithium-ion batteries. The nanostructure comprises vertically aligned carbon nanotubes grown directly on graphene sheets along with shorter branches of carbon nanotubes stemming out from both the graphene sheets and the vertically aligned carbon nanotubes. This bio-inspired hierarchical structure provides a three-dimensional conductive network for efficient charge-transfer and prevents the agglomeration and restacking of the graphene sheets enabling Li-ions to have greater access to the electrode material. In addition, functional iron-oxide nanoparticles decorated within the three-dimensional hierarchical structure provides outstanding lithium storage characteristics, resulting in very high specific capacities. The anode material delivers a reversible capacity of ~1024 mA · h · g(-1) even after prolonged cycling along with a Coulombic efficiency in excess of 99%, which reflects the ability of the hierarchical network to prevent agglomeration of the iron-oxide nanoparticles.

Defect-engineered three-dimensional graphene-nanotube-palladium nanostructures with ultrahigh capacitance.

The development of three-dimensional carbon-based nanostructures is the next step forward for boosting industrial applications of carbon nanomaterials such as graphenes and carbon nanotubes. Some defects, which have been considered as detrimental factors for maintaining exceptional materials properties of two-dimensional graphene, can be actively used to synthesize three-dimensional graphene-based carbon nanostructures. Here we describe a fast and heretofore unreported defect-engineered method to synthesize three-dimensional carbon nanohybrid structures with strong bonding between graphene nanoplatelets and carbon nanotubes using simple microwave irradiation and an ionic liquid. Our one-pot method utilizes defect-engineered sequential processes: microwave-based defect generation on graphene nanoplatelets, anchoring of palladium nanoparticles on these defects, and subsequent growth of carbon nanotubes by use of an ionic liquid. The unique three-dimensional nanostructures showed an ultrahigh redox capacitance due to high porosity, a high surface-to-volume ratio from the spacer role of vertically standing one-dimensional carbon nanotubes on graphene sheets, and capacitance-like redox response of the palladium nanoparticles. The proposed defect-engineered method could lead to novel routes to synthesizing three-dimensional graphene-based nanostructures with exceptionally high performance in energy storage systems.

A coagulation technique for purification of graphene sheets with graphene-reinforced PVA hydrogel as byproduct.

A simple and rapid coagulation method to separate graphene from partially or incompletely reduced graphene oxide is developed in this study. Our isolation technique is not only simple and effective but also can be applied to a quality control in graphene production. Interestingly, the byproduct of our technique is valuable graphene-reinforced PVA hydrogel.