Nitrogen self-doped activated carbons via the direct activation of Samanea saman leaves for high energy density supercapacitors.

In this study, nitrogen self-doped activated carbons (ACs) obtained via the direct activation of Samanea saman green leaves (SSLs) for high energy density supercapacitors were investigated. The SSL-derived direct-activated carbons (hereinafter referred to SD-ACs) were synthesized by impregnating sodium hydroxide as an activating agent and heating up to 720 °C without a hydrothermal carbonization or pyrolysis step. The optimum condition was investigated by varying the weight ratio of raw SSLs to NaOH. Surpassing the ACs derived from the two-step convention method, SD-ACs showed superior properties, including a higher surface area (2930 m2 g-1), total pore volume (1.37 cm3 g-1) and nitrogen content (4.6 at%). Moreover, SD-ACs exhibited enhanced electrochemical properties with specific gravimetric and volumetric capacitances of 179 F g-1 and 88 F cm-3 in an organic electrolyte, respectively, a high capacitance retention of approximately 87% at a current density of 0.5 A g-1 and excellent cycling stability of 97.5% after 3000 cycles at a current density of 5 A g-1. Moreover, the potential window of the supercapacitor cell was extended to 3.5 V with a significantly enhanced energy density of up to 79 W h kg-1. These results demonstrate that the direct activation of nitrogen-enriched SSLs offers advantages in terms of simplicity, low-cost and sustainable synthetic route to achieve nitrogen self-doped ACs for high energy density supercapacitors, which exhibit superior properties to that of ACs prepared via the conventional method.

Preparation and electrochemical performance of nitrogen-enriched activated carbon derived from silkworm pupae waste.

In this study, nitrogen-enriched activated carbon from silkworm pupae waste (P-AC) was successfully prepared and its electrochemical performances in aqueous and organic electrolytes were investigated. Silkworm pupae waste is beneficial because it is a nitrogen-enriched, inexpensive, and locally available material. The preparation process includes hydrothermal treatment of the silkworm pupae waste at 200 °C, and chemical activation using zinc chloride at activation temperatures of 700, 800 and 900 °C (P700, P800, and P900, respectively). The nitrogen content in the P-ACs was approximately 3.8-6.4 at%, decreasing with activation temperature, while the surface area was approximately 1062-1267 m2 g-1, increasing with activation temperature. Compared to a commercial AC, the P-ACs show higher nitrogen content but lower surface area. Furthermore, the P800 exhibited superior specific capacitance (154.6 and 91.6 F g-1 in aqueous and organic electrolytes) compared to a commercial AC despite possessing smaller surface area. The high nitrogen content enhanced the pseudocapacitance and improved the electrical conductivity of the P-ACs. These properties were confirmed by relatively low series and charge transfer resistances, a capacity retention higher than 88% at a current density of 0.5 A g-1 and excellent cycling stability demonstrated by maintaining 97.6% of its capacitance after 3000 cycles. These results demonstrate that silkworm pupae waste is a viable source of nitrogen-enriched AC for application in supercapacitors.

Dynamics and mechanism of structural diffusion in linear hydrogen bond.

Dynamics and mechanism of proton transfer in a protonated hydrogen bond (H-bond) chain were studied, using the CH(3)OH(2)(+)(CH(3)OH)(n) complexes, n = 1-4, as model systems. The present investigations used B3LYP/TZVP calculations and Born-Oppenheimer MD (BOMD) simulations at 350 K to obtain characteristic H-bond structures, energetic and IR spectra of the transferring protons in the gas phase and continuum liquid. The static and dynamic results were compared with the H(3)O(+)(H(2)O)(n) and CH(3)OH(2)(+)(H(2)O)(n) complexes, n = 1-4. It was found that the H-bond chains with n = 1 and 3 represent the most active intermediate states and the CH(3)OH(2)(+)(CH(3)OH)(n) complexes possess the lowest threshold frequency of proton transfer. The IR spectra obtained from BOMD simulations revealed that the thermal energy fluctuation and dynamics help promote proton transfer in the shared-proton structure with n = 3 by lowering the vibrational energy for the interconversion between the oscillatory shuttling and structural diffusion motions, leading to a higher population of the structural diffusion motion than in the shared-proton structure with n = 1. Additional explanation on the previously proposed mechanisms was introduced, with the emphases on the energetic of the transferring proton, the fluctuation of the number of the CH(3)OH molecules in the H-bond chain, and the quasi-dynamic equilibriums between the shared-proton structure (n = 3) and the close-contact structures (n ≥ 4). The latter prohibits proton transfer reaction in the H-bond chain from being concerted, since the rate of the structural diffusion depends upon the lifetime of the shared-proton intermediate state.

Proton transfer reactions and dynamics of sulfonic acid group in Nafion®.

Proton transfer reactions and dynamics of the hydrophilic group (-SO(3)H) in Nafion® were studied at low hydration levels using the complexes formed from CF(3)SO(3)H, H(3)O(+) and nH(2)O, 1 ≤n≤ 3, as model systems. The equilibrium structures obtained from DFT calculations suggested at least two structural diffusion pathways at the -SO(3)H group namely, the "pass-through" and "pass-by" mechanisms. The former involves the protonation and deprotonation at the -SO(3)H group, whereas the latter the proton transfer in the adjacent Zundel complex. Analyses of the asymmetric O-H stretching frequencies (ν(OH)) of the hydrogen bond (H-bond) protons showed the threshold frequencies (ν(OH*)) of proton transfer in the range of 1700 to 2200 cm(-1). Born-Oppenheimer Molecular Dynamics (BOMD) simulations at 350 K anticipated slightly lower threshold frequencies (ν(A)(OH*,MD)), with two characteristic asymmetric O-H stretching frequencies being the spectral signatures of proton transfer in the H-bond complexes. The lower frequency (ν(A)(OH,MD))) is associated with the oscillatory shuttling motion and the higher frequency (ν(B)(OH,MD))) the structural diffusion motion. Comparison of the present results with BOMD simulations on protonated water clusters indicated that the -SO(3)H group facilitates proton transfer by reducing the vibrational energy for the interconversion between the two dynamic states (Δν), resulting in a higher population of the H-bonds with the structural diffusion motion. One could therefore conclude that the -SO(3)H groups in Nafion® act as active binding sites which provide appropriate structural, energetic and dynamic conditions for effective structural diffusion processes in a proton exchange membrane fuel cell (PEMFC). The present results suggested for the first time a possibility to discuss the tendency of proton transfer in H-bond using Δν(BA)(OH,MD)) and provided theoretical bases and guidelines for the investigations of proton transfer reactions in theory and experiment.

Mechanisms of proton transfer in Nafion: elementary reactions at the sulfonic acid groups.

Proton transfer reactions at the sulfonic acid groups in Nafion were theoretically studied, using complexes formed from triflic acid (CF3SO3H), H3O+ and H2O, as model systems. The investigations began with searching for potential precursors and transition states at low hydration levels, using the test-particle model (T-model), density functional theory (DFT) and ab initio calculations. They were employed as starting configurations in Born-Oppenheimer molecular dynamics (BOMD) simulations at 298 K, from which elementary reactions were analyzed and categorized. For the H3O+-H2O complexes, BOMD simulations suggested that a quasi-dynamic equilibrium could be established between the Eigen and Zundel complexes, and that was considered to be one of the most important elementary reactions in the proton transfer process. The average lifetime of H3O+ obtained from BOMD simulations is close to the lowest limit, estimated from low-frequency vibrational spectroscopy. It was demonstrated that proton transfer reactions at -SO3H are not concerted, due to the thermal energy fluctuation and the existence of various quasi-dynamic equilibria, and -SO3H could directly and indirectly mediate proton transfer reactions through the formation of proton defects, as well as the -SO3- and -SO3H2+ transition states.