On the origin of the high capacitance of nitrogen-containing carbon nanotubes in acidic and alkaline electrolytes

The synthesis of nitrogenated carbon nanotubes (N-CNTs) with up to 6.1 wt% N, via the use of pyridine as the nitrogen containing carbon precursor, can provide a facile route to significantly enhance the low intrinsic specific capacitance of carbon nanotubes. The nitrogen functionalities determine this, at least, five-fold increase of the specific capacitance.

High-Pressure Methane Storage in Porous Materials: Are Carbon Materials in the Pole Position?

Natural gas storage on porous materials (ANG) is a promising alternative to conventional on-board compressed (CNG) or liquefied natural gas (LNG). To date, Metal–organic framework (MOF) materials have apparently been the only system published in the literature that is able to reach the new Department of Energy (DOE) value of 263 cm3 (STP: 273.15 K, 1 atm)/cm3; however, this value was obtained by using the ideal single-crystal density to calculate the volumetric capacity. Here, we prove experimentally, and for the first time, that properly designed activated carbon materials can really achieve the new DOE value while avoiding the additional drawback usually associated with MOF materials (i.e., the low mechanical stability under pressure (conforming), which is required for any practical application).

Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids

The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim+][NTf2−], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH–CO2−] by a radical–radical coupling after the simultaneous reduction of CO2 and [C2mim+]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim+] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH–CO2−] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H+][NTf2−], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim+][NTf2−], with Pt(110) being the most active electrode studied.

Changes in the storage and sink of carbon dioxide in subsurface atmospheres controlled by climate-driven processes: the case of the Ojo Guareña karst system

A comprehensive environmental monitoring program was conducted in the Ojo Guareña cave system (Spain), one of the longest cave systems in Europe, to assess the magnitude of the spatiotemporal changes in carbon dioxide gas (CO2) in the cave–soil–atmosphere profile. The key climate-driven processes involved in gas exchange, primarily gas diffusion and cave ventilation due to advective forces, were characterized. The spatial distributions of both processes were described through measurements of CO2 and its carbon isotopic signal (δ13C[CO2]) from exterior, soil and cave air samples analyzed by cavity ring-down spectroscopy (CRDS). The trigger mechanisms of air advection (temperature or air density differences or barometric imbalances) were controlled by continuous logging systems. Radon monitoring was also used to characterize the changing airflow that results in a predictable seasonal or daily pattern of CO2 concentrations and its carbon isotopic signal. Large daily oscillations of CO2 levels, ranging from 680 to 1900 ppm day−1 on average, were registered during the daily oscillations of the exterior air temperature around the cave air temperature. These daily variations in CO2 concentration were unobservable once the outside air temperature was continuously below the cave temperature and a prevailing advective-renewal of cave air was established, such that the daily-averaged concentrations of CO2 reached minimum values close to atmospheric background. The daily pulses of CO2 and other tracer gases such as radon (222Rn) were smoothed in the inner cave locations, where fluctuation of both gases was primarily correlated with medium-term changes in air pressure. A pooled analysis of these data provided evidence that atmospheric air that is inhaled into dynamically ventilated caves can then return to the lower troposphere as CO2-rich cave air.

Effect of the porous structure in carbon materials for CO2 capture at atmospheric and high-pressure

Activated carbons prepared from petroleum pitch and using KOH as activating agent exhibit an excellent behavior in CO2 capture both at atmospheric (∼168 mg CO2/g at 298 K) and high pressure (∼1500 mg CO2/g at 298 K and 4.5 MPa). However, an exhaustive evaluation of the adsorption process shows that the optimum carbon structure, in terms of adsorption capacity, depends on the final application. Whereas narrow micropores (pores below 0.6 nm) govern the sorption behavior at 0.1 MPa, large micropores/small mesopores (pores below 2.0–3.0 nm) govern the sorption behavior at high pressure (4.5 MPa). Consequently, an optimum sorbent exhibiting a high working capacity for high pressure applications, e.g., pressure-swing adsorption units, will require a poorly-developed narrow microporous structure together with a highly-developed wide microporous and small mesoporous network. The appropriate design of the preparation conditions gives rise to carbon materials with an extremely high delivery capacity ∼1388 mg CO2/g between 4.5 MPa and 0.1 MPa. Consequently, this study provides guidelines for the design of carbon materials with an improved ability to remove carbon dioxide from the environment at atmospheric and high pressure.

Characterization of a zeolite-templated carbon by electrochemical quartz crystal microbalance and in situ Raman spectroscopy

Electrochemical quartz crystal microbalance was used to monitor the mass changes during the electrochemical characterization of a zeolite-templated carbon (ZTC) in 1 M H2SO4 medium. Under electrochemical oxidation conditions, a high anodic current and a net mass increase were recorded, resulting in the increase of the specific capacitance owing to the contribution of the pseudocapacitance, mainly derived from the hydroquinone–quinone redox couple. Under more severe electrochemical conditions, a net mass loss was observed, revealing that electrochemical gasification took place. Surface chemistry, before and after the electrochemical treatments, was analyzed through temperature programmed desorption experiments. Furthermore, in situ Raman spectroscopy was used to further characterize the structural changes produced in ZTC under the electrochemical conditions applied, supporting that high potential values produce the electrochemical oxidation and degradation of the carbon material.