Measuring the Capacitance of Carbon in Ionic Liquids: From Graphite to Graphene.

The physical electrochemistry of the carbon/ionic liquids interface underpins the processes occurring in a vast range of applications spanning electrochemical energy storage, iontronic devices, and lubrication. Elucidating the charge storage mechanisms at the carbon/electrolyte interface will lead to a better understanding of the operational principles of such systems. Herein, we probe the charge stored at the electrochemical double layer formed between model carbon systems, ranging from single-layer graphene to graphite and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI). The effect of the number of graphene layers on the overall capacitance of the interface is investigated. We demonstrate that in pure EMIM-TFSI and at moderate potential biases, the electronic properties of graphene and graphite govern the overall capacitance of the interface, while the electrolyte contribution to the latter is less significant. In mixtures of EMIM-TFSI with solvents of varying relative permittivity, the complex interplay between electrolyte ions and solvent molecules is shown to influence the charge stored at the interface, which under certain conditions overcomes the effects of relative permittivity. This work provides additional experimental insights into the continuously advancing topic of electrochemical double-layer structure at the interface between room temperature ionic liquids and carbon materials.

Dielectric-free electrowetting on graphene.

Electrowetting is a simple way to induce the spreading and retraction of electrolyte droplets. This method is widely used in "device" applications, where a dielectric layer is applied between the electrolyte and the conducting substrate. Recent work, including contributions from our own laboratory, have shown that reversible electrowetting can be achieved directly on conductors. We have shown that graphite surfaces, in particular when combined with highly concentrated electrolyte solutions, show a strong wetting effect. The process is driven by the interactions between the electrolyte ions and the surface, hence models of double-layer capacitance are able to explain changes in the equilibrium contact angles. Herein, we extend the approach to the investigation of electrowetting on graphene samples of varying thickness, prepared by chemical vapor deposition. We show that the use of highly concentrated aqueous electrolytes induces a clear yet subtle electrowetting response due to the adsorption of ions and the suppression of the negative effect introduced by the surface impurities accumulating during the transfer process. The latter have been previously reported to fully hinder electrowetting at lower electrolyte concentrations. An amplified wetting response is recorded in the presence of strongly adsorbed/intercalated anions in both aqueous and non-aqueous electrolytes. The phenomenon is interpreted based on the anion-graphene interactions and their influence on the energetics of the interface. By monitoring the dynamics of wetting, an irreversible behaviour is identified in all cases as a consequence of the irreversibility of anion adsorption and/or intercalation. Finally, the effect of the underlying reactions on the timescales of wetting is also examined.

In Situ Derived Hybrid Carbon Molecular Sieve Membranes with Tailored Ultramicroporosity for Efficient Gas Separation.

Fine control of ultramicroporosity (<7 Å) in carbon molecular sieve (CMS) membranes is highly desirable for challenging gas separation processes. Here, a versatile approach is proposed to fabricate hybrid CMS (HCMS) membranes with unique textural properties as well as tunable ultramicroporosity. The HCMS membranes are formed by pyrolysis of a polymer nanocomposite precursor containing metal-organic frameworks (MOFs) as a carbonizable nanoporous filler. The MOF-derived carbonaceous phase displays good compatibility with the polymer-derived carbon matrix due to the homogeneity of the two carbon phases, substantially enhancing the mechanical robustness of the resultant HCMS membranes. Detailed structural analyses reveal that the in situ pyrolysis of embedded MOFs induces more densified and interconnected carbon structures in HCMS membranes compared to those in conventional CMS membranes, leading to bimodal and narrow pore size distributions in the ultramicroporous region. Eventually, the HCMS membranes exhibit far superior gas separation performances with a strong size-sieving ability than the conventional polymers and CMS membranes, especially for closely sized gas pairs (Δd < 0.5 Å) including CO2 /CH4 and C3 H6 /C3 H8 separations. More importantly, the developed HCMS material is successfully prepared into a thin-film composite (TFC) membrane (≈1 µm), demonstrating its practical feasibility for use in industrial mixed-gas operation conditions.

Defect Engineering in Metal-Organic Frameworks Towards Advanced Mixed Matrix Membranes for Efficient Propylene/Propane Separation.

Highly permselective and durable membrane materials have been sought for energy-efficient C3 H6 /C3 H8 separation. Mixed-matrix membranes (MMMs) comprising a polymer matrix and metal-organic frameworks (MOFs) are promising candidates for this application; however, rational matching of filler-matrix is challenging and their separation performances need to be further improved. Here, we propose a novel strategy of "defect engineering" in MOFs as an additional degree of freedom to design advanced MMMs. MMMs incorporated with defect-engineered MOFs exhibit exceptionally high C3 H6 permeability and maintained C3 H6 /C3 H8 selectivity, especially with enhanced stability under industrial mixed-gas conditions. The gas transport, sorption, and material characterizations reveal that the defect sites in MOFs provide the resulting MMMs with not only ultrafast diffusion pathways but also favorable C3 H6 sorption by forming complexation with unsaturated open metal sites, confirmed by in situ FT-IR studies. Most importantly, the concept is also valid for different polymer matrices and gas pairs, demonstrating its versatile potential in other fields.

Unprecedentedly Low CO2 Transport through Vertically Aligned, Conical Silicon Nanotube Membranes.

Nanotube membranes could show significantly enhanced permeance and selectivity for gas separations. Up until now, studies have primarily focused on applying carbon nanotubes to membranes to achieve ultrafast mass transport. Here, we report the first preparation of silicon nanotube (SiNT) membranes via a template-assisted method and investigate the gas transport behavior through these SiNT membranes using single- and mixed-gas permeation experiments. The SiNT membranes consist of conical cylinder-shaped nanotubes vertically aligned on a porous silicon wafer substrate. The diameter of the SiNT pore mouths are 10 and 30 nm, and the average inner diameter of the tube body is 80 nm. Interestingly, among the gases tested, we found an unprecedentedly low CO2 permeance through the SiNT membranes in single-gas permeation experiments, exceeding the theoretical Knudsen selectivity toward small gases/CO2 separation. This behavior was caused by the reduction of CO2 permeability through the blocking effect of CO2 adsorbed in the narrow pore channels of the SiNT cone regions, indicating that CO2 molecules have a high affinity to the native silicon oxide layer (∼2 nm) that is formed on the inner walls of SiNTs. SiNT membranes also exhibited enhanced gas permeance and water flux as compared to classic theoretical models and, as such, may prove useful as a new type of nanotube material for use in membrane applications.

Origin of CO2-philic Sorption by Graphene Oxide Layered Nanosheets and Their Derivatives.

Graphene oxide (GO) is a promising 2D material for adsorbents and membranes, in particular, for the CO2 separation process. However, CO2 diffusion and sorption in GO and its layered structures are still not well understood because of its heterogeneous structure. Here we report CO2 sorption in GO and its derivatives (e.g., reduced GO (rGO)) in powders and films. These CO2 sorption behaviors reveal that GO is highly CO2-philic via complex CO2-functional-group-surface interactions, as compared with graphite and rGOs. Even in highly interlocked, lamellar GO films, CO2 molecules above a certain threshold pressure can diffuse into GO interlayers, causing GO films to swell and leading to dramatic increases in CO2 sorption. Intercalated water in GO interlayers can be removed by preferential CO2 sorption without any changes in the GO chemical structure. This finding helps to explain the origin of CO2 affinity with GO and has implications for preparing anhydrous GO assemblies for various applications.

Understanding Gas Transport Behavior through Few-Layer Graphene Oxide Membranes Controlled by Tortuosity and Interlayer Spacing.

Here, we elucidate the gas transport behavior through few-layer graphene oxide membranes (FGOMs) that have a systematically controlled diffusion pathway, including tortuosity and channel width. The obtained unusual gas permeation order (especially, CH4 > O2 > N2) of the FGOM provides strong evidence that gas molecules can indeed penetrate through the empty voids created by horizontally assembled GO, which allows selective gas transport features. These unique transport features of the FGOM originate from its continuously connected channel structure, which is an analogue of an ultrapermeable glassy polymer with extremely large free volumes in dense films. Furthermore, variation of the channel width in the range of 0.50-0.55 nm leads to notable changes in the gas permeance orders related to CH4, indicating that there is a transition region for switching the gas transport mechanism between a molecular sieving character and the solution-diffusion model.

Reductive dechlorination of DNAPL mixtures with Fe(II/III)-L and Fe(II)-C: Evaluation using a kinetic model for the competitions.

A kinetic model for the competitions was applied to understand the reductive dechlorination of tertiary DNAPL mixtures containing PCE, TCE, and 1,1,1-TCA. The model assumed that the mass transfer rates were sufficiently rapid that the target compounds in the solution and the DNAPL mixture were in phase equilibrium. Dechlorination was achieved using either a mixture of Fe(II), Fe(III), and Ca(OH)2 (Fe(II/III)-L) or a mixture of Fe(II) and Portland cement (Fe(II)-C). PCE in the DNAPL mixtures was gradually reduced and it was reduced more rapidly using Fe(II)-C than Fe(II/III)-L. A constant total TCE concentration in the DNAPL mixtures was observed, which implied that the rate of loss of TCE by dechlorination and possibly other processes was equal to the rate of production of TCE by PCE dechlorination. On the other hand, 1,1,1-TCA in the DNAPL mixtures was removed rapidly and its degradation rate by Fe(II/III)-L was faster than by Fe(II)-C. The coefficients in the kinetic model (ki, Ki) were observed to decrease in the order 1,1,1-TCA>PCE>TCE, for both Fe(II/III)-L and Fe(II)-C. The concentrations of target compounds in solution were the effective solubilities, because of the assumption of phase equilibrium and were calculated with Rault's Law. The concentration changes observed were an increase and then a decrease for PCE, a sharp and then gradual increase for TCE, and a dramatic decrease for 1,1,1-TCA. The fraction of initial and theoretical reductive capacity revealed that Fe(II)-C had ability to degrade target compounds.