Graphene based materials: Past, present and future

Graphene oxide: preparation, functionalization, and electrochemical applications.

Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries

Since its first isolation in 2004, graphene has become one of the hottest topics in the field of materials science, and its highly appealing properties have led to a plethora of scientific papers. Among the many affected areas of materials science, this 'graphene fever' has influenced particularly the world of electrochemical energy-storage devices. Despite widespread enthusiasm, it is not yet clear whether graphene could really lead to progress in the field. Here we discuss the most recent applications of graphene - both as an active material and as an inactive component - from lithium-ion batteries and electrochemical capacitors to emerging technologies such as metal-air and magnesium-ion batteries. By critically analysing state-of-the-art technologies, we aim to address the benefits and issues of graphene-based materials, as well as outline the most promising results and applications so far.

The role of graphene for electrochemical energy storage

BACKGROUND Synthetic membranes are used for desalination, dialysis, sterile filtration, food processing, dehydration of air and other industrial, medical, and environmental applications due to low energy requirements, compact design, and mechanical simplicity. New applications are emerging from the water-energy nexus, shale gas extraction, and environmental needs such as carbon capture. All membranes exhibit a trade-off between permeability—i.e., how fast molecules pass through a membrane material—and selectivity—i.e., to what extent the desired molecules are separated from the rest. However, biological membranes such as aquaporins and ion channels are both highly permeable and highly selective. Separation based on size difference is common, but there are other ways to either block one component or enhance transport of another through a membrane. Based on increasing molecular understanding of both biological and synthetic membranes, key design criteria for new membranes have emerged: (i) properly sized free-volume elements (or pores), (ii) narrow free-volume element (or pore size) distribution, (iii) a thin active layer, and (iv) highly tuned interactions between permeants of interest and the membrane. Here, we discuss the permeability/selectivity trade-off, highlight similarities and differences between synthetic and biological membranes, describe challenges for existing membranes, and identify fruitful areas of future research. ADVANCES Many organic, inorganic, and hybrid materials have emerged as potential membranes. In addition to polymers, used for most membranes today, materials such as carbon molecular sieves, ceramics, zeolites, various nanomaterials (e.g., graphene, graphene oxide, and metal organic frameworks), and their mixtures with polymers have been explored. Simultaneously, global challenges such as climate change and rapid population growth stimulate the search for efficient water purification and energy-generation technologies, many of which are membrane-based. Additional driving forces include wastewater reuse from shale gas extraction and improvement of chemical and petrochemical separation processes by increasing the use of light hydrocarbons for chemicals manufacturing. OUTLOOK Opportunities for advancing membranes include (i) more mechanically, chemically, and thermally robust materials; (ii) judiciously higher permeability and selectivity for applications where such improvements matter; and (iii) more emphasis on fundamental structure/property/processing relations. There is a pressing need for membranes with improved selectivity, rather than membranes with improved permeability, especially for water purification. Modeling at all length scales is needed to develop a coherent molecular understanding of membrane properties, provide insight for future materials design, and clarify the fundamental basis for trade-off behavior. Basic molecular-level understanding of thermodynamic and diffusion properties of water and ions in charged membranes for desalination and energy applications such as fuel cells is largely incomplete. Fundamental understanding of membrane structure optimization to control transport of minor species (e.g., trace-organic contaminants in desalination membranes, neutral compounds in charged membranes, and heavy hydrocarbons in membranes for natural gas separation) is needed. Laboratory evaluation of membranes is often conducted with highly idealized mixtures, so separation performance in real applications with complex mixtures is poorly understood. Lack of systematic understanding of methodologies to scale promising membranes from the few square centimeters needed for laboratory studies to the thousands of square meters needed for large applications stymies membrane deployment. Nevertheless, opportunities for membranes in both existing and emerging applications, together with an expanding set of membrane materials, hold great promise for membranes to effectively address separations needs.

http://science.sciencemag.org/content/sci/356/6343/eaab0530.full.pdf

Maximizing the right stuff: The trade-off between membrane permeability and selectivity

Ultralight multiwalled carbon nanotube (MWCNT) aerogel is fabricated from a wet gel of well-dispersed pristine MWCNTs. On the basis of a theoretical prediction that increasing interaction potential between CNTs lowers their critical concentration to form an infinite percolation network, poly(3-(trimethoxysilyl) propyl methacrylate) (PTMSPMA) is used to disperse and functionalize MWCNTs where the subsequent hydrolysis and condensation of PTMSPMA introduces strong and permanent chemical bonding between MWCNTs. The interaction is both experimentally and theoretically proven to facilitate the formation of a MWCNT percolation network, which leads to the gelation of MWCNT dispersion at ultralow MWCNT concentration. After removing the liquid component from the MWCNT wet gel, the lightest ever free-standing MWCNT aerogel monolith with a density of 4 mg/cm(3) is obtained. The MWCNT aerogel has an ordered macroporous honeycomb structure with straight and parallel voids in 50-150 μm separated by less than 100 nm thick walls. The entangled MWCNTs generate mesoporous structures on the honeycomb walls, creating aerogels with a surface area of 580 m(2)/g which is much higher than that of pristine MWCNTs (241 m(2)/g). Despite the ultralow density, the MWCNT aerogels have an excellent compression recoverable property as demonstrated by the compression test. The aerogels have an electrical conductivity of 3.2 × 10(-2) S·cm(-1) that can be further increased to 0.67 S·cm(-1) by a high-current pulse method without degrading their structures. The excellent compression recoverable property, hierarchically porous structure with large surface area, and high conductivity grant the MWCNT aerogels exceptional pressure and chemical vapor sensing capabilities.

Ultralight multiwalled carbon nanotube aerogel.

The association of cellular toxicity with the physiochemical properties of graphene-based materials is largely unexplored. A fundamental understanding of this relationship is essential to engineer graphene-based nanomaterials for biomedical applications. Here, an in vitro toxicological assessment of graphene oxide (GO) and reduced graphene oxide (RGO) and in correlation with their physiochemical properties is reported. GO is found to be more toxic than RGO of same size. GO and RGO induce significant increases in both intercellular reactive oxygen species (ROS) levels and messenger RNA (mRNA) levels of heme oxygenase 1 (HO1) and thioredoxin reductase (TrxR). Moreover, a significant amount of DNA damage is observed in GO treated cells, but not in RGO treated cells. Such observations support the hypothesis that oxidative stress mediates the cellular toxicity of GO. Interestingly, oxidative stress induced cytotoxicity reduces with a decreasing extent of oxygen functional group density on the RGO surface. It is concluded that although size of the GO sheet plays a role, the functional group density on the GO sheet is one of the key components in mediating cellular cytotoxicity. By controlling the GO reduction and maintaining the solubility, it is possible to minimize the toxicity of GO and unravel its wide range of biomedical applications.

Oxygenated Functional Group Density on Graphene Oxide: Its Effect on Cell Toxicity

We investigate the low-temperature electron transport properties of chemically reduced graphene oxide (RGO) sheets with different carbon $s{p}^{2}$ fractions of 55$%$ to 80$%$. We show that in the low-bias (Ohmic) regime, the temperature ($T$) dependent resistance ($R$) of all the devices follow Efros-Shklovskii variable range hopping (ES-VRH) $R\ensuremath{\sim}\mathrm{exp}[{({T}_{\mathrm{ES}}/T)}^{1/2}]$ with ${T}_{\mathrm{ES}}$ decreasing from 3.1\ifmmode\times\else\texttimes\fi{}10${}^{4}$ to 0.42\ifmmode\times\else\texttimes\fi{}10${}^{4}$ K and electron localization length increasing from 0.46 to 3.21 nm with increasing $s{p}^{2}$ fraction. From our data, we predict that for the temperature range used in our study, Mott-VRH may not be observed even at 100$%$ $s{p}^{2}$ fraction samples due to residual topological defects and structural disorders. From the localization length, we calculate a band-gap variation of our RGO from 1.43 to 0.21 eV with increasing $s{p}^{2}$ fraction from 55 to 80$%$, which agrees remarkably well with theoretical predictions. We also show that, in the high bias non-Ohmic regime at low temperature, the hopping is field driven and the data follow $R\ensuremath{\sim}\mathrm{exp}[{({E}_{0}/E)}^{1/2}]$ providing further evidence of ES-VRH.

https://link.aps.org/accepted/10.1103/PhysRevB.86.235423

Efros-Shklovskii variable-range hopping in reduced graphene oxide sheets of varying carbonsp2fraction

The development of 3D in vitro models capable of recapitulating native tumor microenvironments could improve the translatability of potential anticancer drugs and treatments. Here, 3D bioprinting techniques are used to build tumor constructs via precise placement of living cells, functional biomaterials, and programmable release capsules. This enables the spatiotemporal control of signaling molecular gradients, thereby dynamically modulating cellular behaviors at a local level. Vascularized tumor models are created to mimic key steps of cancer dissemination (invasion, intravasation, and angiogenesis), based on guided migration of tumor cells and endothelial cells in the context of stromal cells and growth factors. The utility of the metastatic models for drug screening is demonstrated by evaluating the anticancer efficacy of immunotoxins. These 3D vascularized tumor tissues provide a proof-of-concept platform to i) fundamentally explore the molecular mechanisms of tumor progression and metastasis, and ii) preclinically identify therapeutic agents and screen anticancer drugs.

Daeha Joung

Papers

Graphene based materials: Past, present and future

Ultralight multiwalled carbon nanotube aerogel.

Oxygenated Functional Group Density on Graphene Oxide: Its Effect on Cell Toxicity

Efros-Shklovskii variable-range hopping in reduced graphene oxide sheets of varying carbonsp2fraction

3D Bioprinted In Vitro Metastatic Models via Reconstruction of Tumor Microenvironments.