Effects of different palladium content loading on the hydrogen storage capacity of double-walled carbon nanotubes

The effects of different amounts palladium loading on the hydrogen sorption characteristics of double-walled carbon nanotubes (DWCNTs) have been investigated. The physical properties of the pristine DWCNTs and Pd/DWCNTs were systematically characterized by X-ray diffraction, transmission electron microscopy, and Brunauer–Emmett–Teller surface area measurements. Pd nanoparticles were loaded on DWCNT surfaces for the dissociation of H₂ into atomic hydrogen, which spills over to the defect sites on the DWCNTs. When we use different Pd content, the particle size and dispersion will be different, which affects the hydrogen storage capacity of the DWCNTs. In this work, the hydrogen storage capacities were measured at ambient temperature and found to be 1.7, 1.85, 3.0, and 2.0 wt% for pristine DWCNTS, 1.0 wt%Pd/DWCNTs, 2.0 wt%Pd/DWCNTs, and 3.0 wt%Pd/DWCNTs, respectively. We found that the hydrogen storage capacity can be enhanced by loading with Pd nanoparticles and selecting a suitable content. Furthermore, the sorption can be attributed to the chemical reaction between the atomic hydrogen and the dangling bonds of the DWCNTs.     

Chemical processing of double-walled carbon nanotubes for enhanced hydrogen storage

Double-walled carbon nanotubes (DWCNTs) were modified for enhanced hydrogen storage by employing a combination of two techniques: KOH activation for the formation of defects on DWCNT surfaces and loading of the DWCNTs with nanocrystalline Pd. The physical properties of the pristine DWCNTs and chemically modified DWCNTs were systematically characterised by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and Brunauer–Emmett–Teller (BET) surface area measurements. The amounts of hydrogen storage capacity were measured at ambient temperature and found to be 1.7, 2.0, 3.7, and 2.8 wt% for pristine DWCNTS, 2 wt% Pd DWCNTs, activated DWCNTs, and 2 wt% Pd activated DWCNTs, respectively. Hydrogen molecules could be adsorbed on defect sites created by chemical activation in DWCNTs through van der Waals forces. For Pd nanoparticle loaded DWCNTs, H₂ molecules could be dissociated into atomic hydrogen and adsorbed on defect sites. We found that the hydrogen storage capacity of DWCNTs can be significantly enhanced by chemical activation or loading with Pd nanoparticles.     

Effect of thermal fluorination on the hydrogen storage capacity of multi-walled carbon nanotubes

Thermal fluorination of multi-walled carbon nanotubes (MWCNTs) was performed to improve their hydrogen storage capacity, based on three considerations. First, the surface of the MWCNTs was altered by thermal fluorination to create a pathway for the storage of hydrogen molecules inside the MWCNTs. These surface treatments increased the number of MWCNT defects through attack by fluorine radicals. The defects were identified using Raman peaks and TEM images. Second, thermal fluorination changed the pore structure by enlarging the specific surface area and the pore volume, which increased the number of hydrogen adsorption sites. Last, the induced fluorine groups enhanced the hydrogen storage capacity through attraction effects on the electron in the hydrogen molecules due to the high electronegativity of fluorine. In conclusion, thermal fluorination increased the hydrogen storage capacity of MWCNTs four-fold to 1.69 wt%.     

Helical confinement effects on hydrogen storage in double-walled carbon nanotubes

Molecular configurations are some of the important factors that strongly affect the hydrogen adsorption in carbon nanotubes (CNTs). A Quantum Molecular dynamics simulations are performed to study the adsorption isotherm of torsional double-walled carbon nanotubes (DWCNTs) filled with hydrogen molecules. The considered key factors that affect the hydrogen storage responses of the DWCNTs are the adsorption energy and the surface tension effect. Our simulated results show that 2-sided effect is observed and kinetic diameter of H₂ molecules is shortened approximately 4.11% under helical confinement. The results further reveal that the amounts of hydrogen storage wt% are computed at 77 K and found to be 1.77 wt% and 3.92 wt% for pristine and twisted-DWCNTs, respectively. Finally, it is shown that the adsorption heat, which reflects surface property, is twisted dependent.     

Improving hydrogen storage in Ni-doped carbon nanospheres

The effect of nickel distribution and content in Ni-doped carbon nanospheres on hydrogen storage capacity under conditions of moderate temperature and pressure was studied. It was found that the nickel distribution, obtained by using different doping techniques and conditions, has a noticeable influence on hydrogen storage capacity. The samples with the most homogeneous nickel distribution, obtained by pre-oxidising the carbon nanospheres, displayed the highest storage capacity. In addition, storage capacity is influenced by the amount of nickel. It was found a higher storage capacity in samples containing 5 wt.% of Ni. This is due to the greater interactions between the nickel and the support that produce a higher activation of the solid through a spillover effect.     

Investigation of hydrogen storage capacity of multi-walled carbon nanotubes deposited with Pd or V

This work presents the synthesis and characterization of multi-walled carbon nanotubes (multi-walled CNTs) deposited with Pd or V and their hydrogen storage capacity measured by Sievert's volumetric apparatus. The CNTs were grown by the CVD method using LPG and LaNi₅ as the carbon source and catalyst, respectively. Pd was impregnated on the CNTs by the reflux method with hydrogen gas as a reducing agent, while V was embedded on the CNTs by the vapor deposition method. The average metal particle size deposited on the CNTs was around 5.8 nm for Pd and 3.6 nm for V. Hydrogen adsorption experiments were performed at room temperature and at −196 °C under a hydrogen pressure of 65 bar. At −196 °C, the treated CNTs had a maximum hydrogen uptake of 1.21 wt%, while the CNTs deposited with Pd (Pd-CNTs) and CNTs deposited with V (V-CNTs) possessed lower surface areas, inducing lower hydrogen adsorption capacities of 0.37 and 0.4 wt%, respectively. For hydrogen sorption at room temperature, the CNTs decorated with the metal nanoparticles had a higher hydrogen uptake compared to the treated CNTs. Hydrogen adsorption capacity was 0.125 and 0.1 wt% for the Pd-CNTs and V-CNTs, respectively, while the hydrogen uptake of the treated CNTs was <0.01 wt%. For the second cycle, only half of the first hydrogen uptake was obtained, and this was attributed to the re-crystallization of the defect sites on the carbon substrate after the first hydrogen desorption.     

Optimizing the conditions of multi-walled carbon nanotubes surface activation and loading metal nanoparticles for enhanced hydrogen storage

In this study, the effect of surface activation of multi-walled carbon nanotubes (MWCNTs) by KOH along with loading of cobalt and lithium nanoparticles on the surface of MWCNTs are investigated. In the first step, surface activation parameters, i.e. MWCNT/KOH weight ratio, activation temperature, and activation time are optimized to give the highest hydrogen uptake. According to obtained results, the optimum synthesis conditions are MWCNT/KOH weight ratio of 1:5, 800 °C, and 1 h of activation duration. Afterward, cobalt and lithium metal nanoparticles are doped discretely on the surface of activated nanotubes. It is demonstrated that amounts of loaded cobalt and lithium metals are 5.5 and 1.9% wt, respectively. In addition, it is revealed that the amount of hydrogen storage capacity for cobalt-loaded and lithium-loaded MWCNTs are 1.06% wt. and 1.33% wt., respectively (at 278 K) which are higher than the capacity of pristine and activated MWCNT samples.     

Synergistic effect of CNT bridge formation and spillover mechanism on enhanced hydrogen storage by iron doped carbon aerogel

In the present, enhanced hydrogen sorption over activated iron-doped carbon aerogel (CA) through the spillover effect was taken up. Iron doped carbon aerogel was prepared through sol-gel polymerization of resorcinol-formaldehyde (R–F) with sodium carbonate as a catalyst. Iron doping was made at 1, 5, and 10 wt % levels. It has been further inferred that the presence of nano iron caused carbon nanotube (CNT) formation in the carbon matrix during the carbonization and activation processes. Fe doped CAs were characterized by XRD, SEM, BET, FTIR, and TEM. Hydrogen sorption by 1, 5, and 10% Fe doped CAs at liquid nitrogen temperature (77K) and up to 25 atm. had storage capacities as 1.47 wt%, 1.38 wt%, and 1.28 wt%, respectively. Activation of CAs brought a significant increase in the storage capacity (∼3.80 wt%), which could have been driven by the presence of CNT in the matrix and an increase in the microporosity on activation.     

Hydrogen storage in coiled carbon nanotubes

We report a density functional calculation of the adsorption of molecular hydrogen on the external surface of coiled carbon nanotube (CCNT). Binding energies of single molecule have been studied as a function of three different orientations and at three different sites like hexagon, pentagon and heptagon. The binding energy values are larger than linear (5,5) armchair nanotube, which has approximately same diameter as that of coiled carbon nanotube. The curvature and topology of CCNT are responsible for this considerable enhancement. The system with full coverage is also studied. When the nanotube surface is fully covered with one molecule per graphitic hexagon, pentagon and heptagon gives the 6.8 wt% storage capacity. The binding energy per molecule decreases due to repulsive interactions between neighbor molecules. It gives good storage medium for hydrogen. Almost it meets the DOE target.     

Decorating carbon nanotubes with Ni particles using an electroless deposition technique for hydrogen storage applications

A facile and low-cost electroless deposition technique is utilized to decorate multi-walled carbon nanotubes (CNTs) with Ni. The obtained composites are attempted to use as hydrogen storage materials, whose performance is evaluated with a high-pressure microbalance. Effects of the concentration of plating solution, deposition time, and reaction temperature on the loading amount, particle size, morphology, and distribution density of Ni are studied using a transmission electron microscope. With proper deposition parameters, highly dispersed Ni nanoparticles with a uniform diameter can be fabricated on CNTs, causing a notable hydrogen spillover reaction on the composite. The optimum hydrogen storage capacity of the prepared Ni-decorated CNTs with a average diameter of 5 nm, measured at 6.89 MPa and 25 °C, is 1.02 wt%, which is almost three times higher than that (0.35 wt%) of pristine CNTs.     

Synthesis and hydrogen storage capacity of exfoliated turbostratic carbon nanofibers

Turbostratic carbon nanofibers (CNFs) with a rough surface, open pore walls, and a defect structure were continuously produced by the thermal decomposition of alcohol in the presence of an iron catalyst and a sulfur promoter at 1100 °C under a nitrogen atmosphere in a vertical chemical vapor deposition reactor. A graphite exfoliation technique using intercalation and thermal shock was employed to expand the graphene layers of the as-produced turbostratic CNFs. The hydrogen storage capacity of the turbostratic CNF samples was measured using the volumetric method with a pressure of up to 1 MPa at 77 K. The hydrogen storage capacities of the as-produced and exfoliated turbostratic CNFs were 1.5 and 5 wt%, respectively. The defects on the surface and expandable graphitic structure are considered important keys to increasing the hydrogen uptake in turbostratic CNFs.     

Aerogel sheet of carbon nanotubes decorated with palladium nanoparticles for hydrogen gas sensing

In the development of hydrogen sensors, it is required to meet the demands of both high sensor performance as well as the ease of fabrication for mass production. For this purpose we proposed a chemiresistive hydrogen sensors based on an aerogel sheet of carbon nanotubes decorated with palladium nanoparticles (CNT/Pd sheet). The fabrication process is straightforward that a dry-spun CNT aerogel sheet is suspended between concentric electrodes followed by depositing Pd nanoparticles on CNT sheets by thermal evaporation. The present CNT/Pd sheet sensors can detect hydrogen at concentrations as low as 2 ppm at room temperature with a detection range from 2 to 1000 ppm. The aerogel nature of CNT/Pd sheet contributes to low detection limit and broad detection range of the CNT/Pd sensor. Relations between hydrogen concentration and sensor response and response time, and the effects of temperature on sensor performance were investigated.     

Improving hydrogen storage in modified carbon materials

The hydrogen adsorption capacity of different types of carbon nanofibers (Platelet, Fishbone and Ribbon) and amorphous carbon has been measured as a function of pressure and temperature. Results have showed as the more graphitic/ordered carbon materials adsorbed less hydrogen than the more amorphous ones. After that and, with the aim of improve the hydrogen adsorption capacity of these carbon materials, they were functionalizated (oxygen surface groups incorporation) and Ni-modificated. Results also showed an important increase of the H₂ adsorption capacity despite the porosity loss that took place after the treatments. Due to the advantages of functionalization and Ni-modification, both treatments were applied at the same time over the most promising carbon materials from the H₂ adsorption point of view, observing again an improvement of the hydrogen adsorption capacity. Finally, the H₂ adsorption capacity of chemically activated carbon materials increased considerably due the pore structure development and even more if activated materials were Ni-modificated.     

Hydrogen storage capacity at high pressure of raw and purified single wall carbon nanotubes produced with a solar reactor

Samples of single wall carbon nanotubes (SWNTs) were prepared using a solar reactor. Graphite targets containing different catalysts (Ni/Co, Ni/Y, Ni/Ce) allowed the synthesis of SWNTs soot in which nanotubes had different diameter distributions. Several consecutive stages of HCl treatment and thermal oxidation in air (HCl protocol) purified the samples. Another protocol involving HNO₃ treatment and H₂O₂ oxidation (HNO₃ protocol) was also used. Isotherms of hydrogen adsorption were volumetrically measured at 253 K under pressures below 6 MPa on raw and treated samples. The highest adsorption capacity (0.7  wt%) was measured on raw soot. HCl protocol clearly increases the BET surface area (_SBET)$(S_{\mathrm{BET}})$ and the microporous volume (_W0(_N2))$(W_0({\mathrm{N}}_2))$ measured by N₂ at 77 K of the treated samples with respect to the as-produced materials, whereas HNO₃ protocol decreases them. A correlation between textural properties and hydrogen storage capacities is discussed.     

Hydrogen storage behaviors of platinum-supported multi-walled carbon nanotubes

In this work, the hydrogen storage behaviors of multi-walled carbon nanotubes (MWNTs) loaded by crystalline platinum (Pt) particles were studied. The microstructure of the Pt/MWNTs was characterized by X-ray diffraction and transmission electron microscopy. The pore structure and total pore volumes of the Pt/MWNTs were analyzed by N₂/77 K adsorption isotherms. The hydrogen storage capacity of the Pt/MWNTs was evaluated at 298 K and 100 bar. From the experimental results, it was found that Pt particles were homogeneously distributed on the MWNT surfaces. The amount of hydrogen storage capacity increased in proportion to the Pt content, with Pt-5/MWNTs exhibiting the largest hydrogen storage capacity. The superior amount of hydrogen storage was linked to an increase in the number of active sites and the optimum-controlled micropore volume for hydrogen adsorption due to the well-dispersed Pt particles. Therefore, it can be concluded that Pt particles play an important role in hydrogen storage characteristics due to the hydrogen spillover effect.     

Topological defects embedded large-sized single-walled carbon nanotubes for hydrogen storage: A molecular dynamics study

In this paper, we investigate the performance of large-sized single-walled carbon nanotubes (SWCNTs) incorporated with mono vacancy (MV), double vacancy (DV), and Stone-Wales (SW) topological defects as a medium for hydrogen adsorption using molecular dynamics (MD) simulations. A novel potential energy distribution (PED) method is employed with MD simulations to determine the adsorbed hydrogen molecules and associated binding energy. In addition, we extended our work to bundles of defected SWCNT (D-SWCNT) that provided the most prominent adsorption capacity subjected to temperature and pressure variations. In particular, four representative (8,8), (13,13), (19,19), and (33,0) SWCNTs are simulated under various thermodynamic conditions, and collected adsorption isotherms data reveals higher gravimetric density for large-sized SWCNT. At 77 K and 100 bar, the maximum hydrogen uptake in pristine SWCNTs is 6.88–7.73 wt%, depending on the size of the nanotubes. In contrast, the binding energy decreases as the nanotube size increases. At 77 K, (8,8) and (19,19) SWCNTs have average binding energies of 0.043 and 0.021 eV, respectively. Meanwhile, (19,19) SWCNT incorporated with 1% DV defects having 5–8 rings (DV1) and MV defects yields the maximum storage capacity of 9.07 wt% and 8.62 wt%, respectively, at 77 K. Furthermore, the increment of about 43.29% in wt.% is obtained for DV1 defected nanotube relative to pristine SWCNT at 300 K and 100 bar. Moreover, our results indicate the maximum hydrogen uptake of 8.65, 7.15, 2.57, and 1.33 wt% in the square array of DV1 defect embedded SWCNTs at 77, 100, 200, and 300 K, respectively, compared to 9.07, 6.65, 2.24, and 1.11 wt% in the isolated D-SWCNT at identical conditions. As a result, the D-SWCNT bundles are better suited for hydrogen storage at high temperatures than the isolated D-SWCNT. Our present study paves the way to progress toward the efficient usage of D-SWCNTs with few chemical alterations for scaled-up applications.     

H2 storage on single- and multi-walled carbon nanotubes

The adsorption of hydrogen on single-walled and multi-walled carbon nanotubes (CNTs) was investigated at 77 and 298 K, in the pressure range of 0–1000 Torr. The adsorption isotherms indicate that adsorption follows the Langmuir model. Hydrogen uptakes were found to depend strongly on the nature of the CNTs. Single-walled CNTs adsorb significantly higher quantities of hydrogen per unit mass of the solid, while the opposite is true on a per unit surface area basis. This observation implies that adsorption takes place selectively on specific sites on the surface. The hydrogen uptake capacity of CNTs was also found to be affected by the purity of the materials, increasing with increasing purity. Temperature programmed desorption indicated that relatively strong adsorption bonds develop between adsorbent and adsorbate and that a single type of adsorption site exists on the solid surface.     

Investigation of hydrogen storage capacity of various carbon materials

Hydrogen storage capacity of various carbon materials, including activated carbon (AC), single-walled carbon nanohorn, single-walled carbon nanotubes, and graphitic carbon nanofibers, was investigated at 303 and 77 K, respectively. The results showed that hydrogen storage capacity of carbon materials was less than 1 wt% at 303 K, and a super activated carbon, Maxsorb, had the highest capacity (0.67 wt%). By lowering adsorption temperature to 77 K, hydrogen storage capacity of carbon materials increased significantly and Maxsorb could store a large amount of hydrogen (5.7 wt%) at a relatively low pressure of 3 MPa. Hydrogen storage capacity of carbon materials was proportional to their specific surface area and the volume of micropores, and the narrow micropores was preferred to adsorption of hydrogen, indicating that all carbon materials adsorbed hydrogen gas through physical adsorption on the surface.     

The synthesized nickel-doped multi-walled carbon nanotubes for hydrogen storage under moderate pressures

Hydrogen adsorption capacity of Multiwalled carbon nanotubes (MWCNTs) decorated with Nickel (Ni) nanoparticles has been presented at room temperature and under moderate pressures of 4–20 bar. The functionalization of carbon nanotubes was carried by H₂SO₄-HNO₃ reducing agents and the Ni supported MWCNTs (Ni-MWCNTs) were prepared by wet chemical method. The structure and morphology characterization of samples were performed by XRD, TEM, EDX and SEM analyses. These nanotubes then subjected to hydrogenation step by using Sievert's-like apparatus. The hydrogenation of the Ni-MWCNTs was performed at 298 K and moderate hydrogen pressures of 4–20 bar. The obtained results show that there is a correlation between hydrogen storage capacity and hydrogen pressure that; as the pressure was increased, hydrogen uptake capacity enhanced due to physisorption. In addition, maximum hydrogen storage capacity of Ni-MWCNTs was found to be 0.298 wt % at room temperature and under pressure of 20 bar.