Hydrogen uptake of manganese oxide-multiwalled carbon nanotube composites

Hydrogen uptake of pristine multi-walled carbon nanotubes is increased more than three-fold at 298 K and hydrogen pressure of 4.0 MPa, upon addition of hydrogen spillover catalyst manganese oxide, from 0.26 to 0.94 wt%. Simple and convenient in situ reduction method is used to prepare Mn-oxide/MWCNTs composite. XRD, FESEM, and TEM demonstrates nanostructural characterization of pristine MWCNTs and composite. TGA analysis of Mn-oxide/MWCNTs composites showed a single monotonous fall related to MWCNTs gasification. Enhancement of hydrogen storage capacity of composite is attributed to spillover mechanism owing to decoration of Mn-oxide nanoparticles on outer surface of MWCNTs. Hydrogen uptake follows monotonous dependence on hydrogen pressure. Oxide-MWCNTs composite not only shows high hydrogen storage capacity as compared to pristine, but also exhibit significant cyclic stability upon successive adsorption–desorption cycles.     

Hydrogen storage of nanostructured TiO2-impregnated carbon nanotubes

Hydrogen uptake study of carbon nanotubes (CNTs) impregnated with TiO₂-nanorods and nanotubes has been performed at room temperature and moderate hydrogen pressures of 8–18 atm. Under hydrothermal synthesis conditions, nanorods (NRs) and nanoparticles (NPs) are found to form either of the two polymorphic phases, i.e., nanorods are formed of predominantly anatase phase while nanoparticles are formed of rutile phase. NRs and NPs are introduced into the CNT matrix via the wetness-impregnation method. These composites store up to 0.40 wt.% of hydrogen at 298 K and 18 atm, which is nearly five times higher the hydrogen uptake of pristine CNTs. The excess amount of hydrogen stored in TiO₂-impregnated CNTs is determined from the amount of TiO₂ in the sample and the measured hydrogen uptake of TiO₂ nanoparticles. Higher hydrogen uptake of NP-impregnated CNTs when compared pristine CNTs is accounted for by considering initial binding of hydrogen on TiO₂ and subsequent spillover in CNT–TiO₂-NPs.     

Hydrogen uptake of cobalt and copper oxide-multiwalled carbon nanotube composites

Hydrogen storage capacity of a pristine multi-walled carbon nanotubes is increased 10-fold at 298 K and an equilibrium hydrogen pressure of ～23 atm, upon addition of a hydrogen spillover catalyst cobalt- and copper oxide, from 0.09 to 0.9 wt.%. In situ reduction method is utilized to synthesize Co-oxide/MWCNTs and Cu-oxide/MWCNTs composite. Blocking of channels and pores of MWCNTs by oxide nanoparticles during preparation method is responsible for low BET specific surface area of composites compared to pristine sample. X-ray diffraction, scanning, and transmission electron microscopy demonstrates nanostructural characterization of MWCNTs and composites. Thermogravimetric analysis of two oxide/MWCNTs composites showed a single monotonous fall related to MWCNTs gasification. Enhancement of hydrogen storage of both composites is attributed to the spillover mechanism due to decoration of Co and Cu-oxide nanoparticles on the outer surface of MWCNTs.     

An overview of hydrogen generation by hydrolysis of Al and its alloys with the addition of carbon-based materials

Al and its alloys are studied extensively for hydrogen generation through water splitting. Alloying Al with metal activators such as bismuth, indium, gallium, etc., leads to the formation of micro galvanic cells during hydrolysis reaction, resulting in an improved hydrogen generation rate. Activation of Al by adding carbon-based materials such as graphite, carbon nanotubes (CNTs), graphene, etc., can instantaneously generate hydrogen at room temperature. When carbon particles are desorbed from the Al matrix during hydrolysis, new Al is exposed, resulting in an increased reaction rate. In Al-Graphite composites which form core-shell structures, H₂O molecules penetrate through the graphite layers and break down the core-shell structure during hydrolysis, and the new Al surfaces are exposed to water. It was found that Al with nano bismuth and graphene nanosheets showed better hydrogen generation rate and hydrogen yield. Graphene nanosheets control the agglomeration of Al and enhance the specific surface area for hydrolysis. During the hydrolysis of Al-CNTs composites, CNTs act as a cathode, resulting in galvanic corrosion between CNTs and the Al matrix. CNTs can also effectively control the agglomeration of Al during ball milling. Spark plasma sintered Al–Bi-CNT composites showed an enhanced hydrogen generation rate during hydrolysis. This paper presents an overview of hydrogen generation by hydrolysis of Al and its alloys, emphasising the addition of carbon-based materials such as graphite, graphene, CNTs, etc.     

Thermal performance of stearic acid/carbon nanotube composite phase change materials for energy storage prepared by ball milling

In this work, stearic acid/carbon nanotubes composite phase change materials (SA/CNTs composite PCMs) were fabricated by ball milling for the first time to enhance the heat conduction of SA and prevent the delamination of SA and CNTs components. The results of suspension stability study conducted using a gravity sedimentation method showed that polyvinylpyrrolidone (PVP) used as dispersant has the best effect on the stability of composite PCMs. Then, the thermal cycling test further proved the stability of prepared composite. The SEM and FT‐IR results revealed that ball milling led to the formation of highly homogeneous composites. The thermal properties of the fabricated SA/CNTs composites with CNTs contents of 2, 6, and 10 wt.% characterized by differential scanning calorimetry (DSC) demonstrated that their phase change temperatures varied slightly while the latent heat decreased with the increased CNTs content. Furthermore, the thermal conductivity of the SA/CNTs composites were greater than that of pure SA by 61.5%, 92.3%, and 119.2%, respectively. The addition of CNTs also increased the thermal release rates of the prepared PCMs and decreased their storage rates. Therefore, the produced materials can be potentially used in thermal management.     

Enhancing thermal conductivity of palmitic acid based phase change materials with carbon nanotubes as fillers

Multi-walled carbon nanotubes (CNTs) as produced are usually entangled and not ready to be dispersed into organic matrix. CNTs were treated by mechano-chemical reaction with ball milling the mixture of potassium hydroxide and the pristine CNTs. Hydroxide radical functional groups have been introduced on the CNT surfaces, which enabled to make stable and homogeneous CNT composites. Treated CNTs were successfully dispersed into the palmitic acid matrix without any surfactant. Transient short-hot-wire apparatus was used to measure the thermal conductivities of these nanotube composites. Nanotube composites have substantially higher thermal conductivities than the base palmitic acid matrix, with the enhancement increasing with the mass fraction of CNTs in both liquid state and solid state. The enhancements of the thermal conductivity are about 30% higher than the reported corresponding values for palmitic acid based phase change nanocomposites containing 1 wt% CNTs treated by concentrated acid mixture.     

Effect of Ni nanoparticle distribution on hydrogen uptake in carbon nanotubes

Ni decoration on carbon nanotubes (CNTs) performed by electroless nickel (EN) deposition is investigated. The effect of Ni particle distribution on hydrogen uptake of CNTs is also studied. The chemical composition, crystal structure and microstructure of the CNTs with or without Ni loading are characterized using an inductively coupled plasma spectrometer (ICP), X-ray diffraction meter (XRD) and transmission electron microscope (TEM) coupled with an energy dispersive spectroscope (EDS). The hydrogen uptake in CNTs with or without Ni loading is measured using a high-pressure microbalance at room temperature under a hydrogen pressure of 6.89 MPa. The experimental results show that fine and well-dispersed metallic Ni nanoparticles can be obtained by EN. The density and particle distribution depend on deposition temperature and time. An enhanced hydrogen storage capacity of CNTs can be obtained by Ni decoration, which provided a spillover reaction. The hydrogen storage capacity of the as-received CNTs was 0.39 wt.%. As much as 1.27 wt.% of hydrogen can be stored when uniformly distributed nano-sized Ni particles are formed on the surface of the CNTs. However, the beneficial effect is lost when the active sites for either physical or chemical adsorption are blocked by excessive Ni loading.     

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.     

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.     

On-demand hydrogen generation by the hydrolysis of ball-milled aluminum composites: A process overview

The hydrolysis of aluminum (Al) is a relatively simple method for on-demand hydrogen generation for niche (low-power, <1 kW) proton exchange membrane fuel cell applications. The hydrolysis of Al in neutral pH water and under standard ambient conditions is prevented by the presence of a thin surficial oxide layer. A promising method to enable Al's spontaneous hydrolysis is by its mechanochemical activation (ball milling) with certain metals (e.g., Bi, Sn, In, Ga). This overview presents several aspects relating to the changes occurring in Al particles during ball milling, e.g., the structural and morphological behavior of Al during ball milling procedures (with and without the presence of activation metals), and the distribution and homogenization of Al and various activation metals. The formation of galvanic cells between anodic Al and cathodic activation metals (relative to Al) is discussed. A summary of the existing Al composites for on-demand hydrogen generation is presented. The paper concludes with a discussion of activation metal recovery, and the effects thereof on the economic feasibility of Al composites for hydrogen generation.     

Dehydrogenation and low-pressure hydrogenation properties of NaAlH4 confined in mesoporous carbon black for hydrogen storage

For hydrogen to be successfully used as an energy carrier in a new renewable energy driven economy, more efficient hydrogen storage technologies have to be found. Solid-state hydrogen storage in complex metal hydrides, such as sodium alanate (NaAlH₄), is a well-researched candidate for this application. A series of NaAlH₄/mesoporous carbon black composites, with high NaAlH₄ content (50–90 wt%), prepared via ball milling have demonstrated significantly lower dehydrogenation temperatures with intense dehydrogenation starting at ∼373 K compared to bulk alanate's ≥ 456 K. Dehydrogenation/hydrogenation cycling experiments have demonstrated partial hydrogenation at 6 MPa H₂ and 423 K. The cycling experiments combined with temperature-programmed dehydrogenation and powder X-ray diffraction have given insight into the fundamental processes driving the H₂ release and uptake in the NaAlH₄/carbon composites. It is established that most of the hydrogenation behavior can be attributed to the Na₃AlH₆ ↔ NaH transition.     

Hydrogen adsorption performance of Cu-BTC/graphene aerogel composite: A combined experimental and computational study

Metal-organic frameworks (MOFs) are reported as potential hydrogen storage materials due to ultrahigh surface area and pore volume. However, most top-performing MOFs for hydrogen storage require strict synthesis conditions and high cost, which limits their wide applications. In this work, Cu-BTC/graphene aerogel (GA) composite is prepared at room temperature with improved hydrogen uptake at 100 bar compared with pristine Cu-BTC. To understand the mechanism of the enhanced hydrogen uptakes in the composite, grand canonical Monte Carlo (GCMC) simulation is executed for Cu-BTC/GA composites with different numbers of graphene oxide (GO) layers. It is demonstrated that the increased hydrogen uptake in Cu-BTC/GA composites is mainly ascribed to the hydrogen uptake in the interface region between Cu-BTC and GA. Additionally, the hydrogen uptake of the Cu-BTC/GA composites decreases as the number of GO layers increases, implicating that fewer GO layers or thinner GA is favorable for hydrogen adsorption of Cu-BTC/GA composites.     

Improved hydrogen storage performance of defected carbon nanotubes with Pd spillover catalysts dispersed using supercritical CO2 fluid

Hydrogen storage properties of carbon nanotubes (CNTs) modified by oxidative etching and decoration of Pd spillover catalysts are investigated. A mixed H₂SO₄/H₂O₂ solution containing ferrous ions (Fe²⁺) is useful to open the caps, to shorten the length, and to generate defects on CNTs. The Pd catalysts are deposited on the CNTs with the aid of supercritical carbon dioxide (scCO₂); as a result, a highly dispersed Pd nanoparticles and an intimate connection between Pd and carbon surface can be obtained. Combination of the two approaches can optimize a hydrogen spillover reaction on CNTs, resulting in a superior hydrogen storage capacity of 1.54 wt% (at 25 °C and 6.89 MPa), which corresponds to an enhancement factor of ∼4.5 as compared to that of pristine CNTs.     

Electroless deposition of Ni nanoparticles on carbon nanotubes with the aid of supercritical CO2 fluid and a synergistic hydrogen storage property of the composite

A hybrid synthesis protocol that combines electroless plating and the supercritical CO₂ (scCO₂) technique is developed for the first time to decorate multi-walled carbon nanotubes (CNTs) with Ni nanoparticles. The scCO₂ fluid, which is immiscible with aqueous plating solution, renders a heterogeneous Ni deposition reaction and suppresses the lateral growth of Ni, which leads to the formation of nanoparticles. A uniform dispersion of tightly anchored particles, a few nanometers in diameter, on CNTs can be achieved. Since the electroless deposition process can be easily manipulated, large-scale production should be realizable. The constructed CNT/Ni nano-composite exhibits a synergistic property in hydrogen storage performance, which is evaluated using a high-pressure microbalance. The deposited nanoparticles enhance the hydrogen spillover reaction on CNTs, tripling the hydrogen storage amount at room temperature as compared to pristine CNTs.     

Effect of carbon allotropes on the structure and hydrogen sorption during reactive ball-milling of Mg–C powder mixtures

Hydrogen sorption by magnesium–carbon composites during reactive high-energy ball milling under hydrogen was investigated. Mg-based composites absorb up to 5 wt.% of hydrogen during milling. It was found that reactive ball milling of magnesium with the different carbon allotropes (graphite, ultrafine diamonds, carbon nanotubes and amorphous carbon powder produced by electric breakdown of organic liquids) leads to a significant increase of hydrogen sorption rate. Morphology and phase composition of the synthesized Mg–C composites have been studied by TEM and XRD. Special attention was focused on the study of structural changes in the carbon additives. The hydrogenation rate of magnesium-carbon composites during reactive ball milling is strongly affected by the nature of carbon additives and their dispersion in an initial state.     

Mg-based composites for enhanced hydrogen storage performance

Hydrogen storage in solids of hydrides is advantageous in comparison to gaseous or liquid storage. Magnesium based materials are being studies for solid-state hydrogen storage due to their advantages of high volumetric and gravimetric hydrogen storage capacity. However, unfavorable thermodynamic and kinetic barriers hinder its practical application. In this work, we presented that kinetics of Mg-based composites were significantly improved during high energy ball milling in presence of various types of carbon, including plasma carbon produced by plasma-reforming of hydrocarbons, activated carbon, and carbon nanotubes. The improvement of the kinetics and de-/re-hydrogenation performance of MgH₂ and TiC-catalysed MgH₂ by introduction of carbon are strongly dependent on the milling time, amount of carbon and carbon structure. The lowest dehydrogenation temperature was observed at 180 °C by the plasma carbon–modified MgH₂/TiC. We found that nanoconfinement of carbon structures stabilised Mg-based nanocomposites and hinders the nanoparticles growth and agglomeration. Plasma carbon was found to show better effects than the other two carbon structures because the plasma carbon contained both few layer graphene sheets that served as an active dispersion matrix and amorphous activated carbons that promoted the spill-over effect of TiC catalysed MgH₂. The strategy in enhancing the kinetics and thermodynamics of Mg-based composites is leading to a better design of metal hydride composites for hydrogen storage.     

Hydrogen-induced phase transition of MgZrTiFe0.5Co0.5Ni0.5 high entropy alloy

In this study, the MgZrTiFe_0.5Co_0.5Ni_0.5 high entropy alloy was processed by high-energy ball milling under both argon and hydrogen atmospheres. The hydrogen storage behavior of the samples was evaluated by combination of thermal analyses and in-situ synchrotron powder X-ray diffraction. It is shown that this alloy forms a body-centered cubic (BCC) structure when milled under argon pressure. The BCC phase is capable to absorb up to 1.2%wt. of hydrogen and during absorption it undergoes a phase transition forming a face-centered cubic (FCC) high entropy hydride. This FCC hydride can be directly synthesized by high-energy ball milling under hydrogen pressure.     

Carbon-based nanocomposites in solid-state hydrogen storage technology: An overview

Hydrogen fuel is becoming a hot topic among the scientific community as an alternative energy source. Hydrogen is eco-friendly, renewable, and green. The synthesis and development of materials with great potential for hydrogen storage is still a challenge in research and needs to be addressed to store hydrogen economically and efficiently. Various solid-state materials have been fabricated for hydrogen energy storage; however, carbon-based nanocomposites have gained more attention because of its high surface area, low processing cost, and light weight nature. Carbon materials are easy to modify with various metals, metal oxides (MOs), and other organometallic frameworks because of the functional groups available on the surface and edges that increase the storage capacity of hydrogen. In addition, chemisorption is another way to enhance the hydrogen storage capacity of carbon-based nanocomposites. In this review, we discuss the success achieved thus far and the challenges that remain for the physical and chemical storage of hydrogen in various carbon-based nanocomposites. Various compositions of catalysts (eg, metal, MOs, alloy, metal organic frameworks) and carbon materials are designed for hydrogen storage. Superior energy storage in hybrids and composites as compared with pristine materials (catalysts or carbon nanotubes) is governed by the interaction, activation, and hydrogen adsorption/absorption mechanism of materials in the reaction profile. (Nano)composites comprising carbon material with metals, MOs, or alloys are important in this field, not only because of their potential for hydrogen sorption but also their significant cyclic stability and high efficiency upon successive adsorption-desorption cycles.     

Nanostructured hydrogen storage materials prepared by high-energy reactive ball milling of magnesium and ferrovanadium

Hydrogen storage nanocomposites prepared by high energy reactive ball milling of magnesium and vanadium alloys in hydrogen (HRBM) are characterised by exceptionally fast hydrogenation rates and a significantly decreased hydride decomposition temperature. Replacement of vanadium in these materials with vanadium-rich Ferrovanadium (FeV, V80Fe20) is very cost efficient and is suggested as a durable way towards large scale applications of Mg-based hydrogen storage materials. The current work presents the results of the experimental study of Mg–(FeV) hydrogen storage nanocomposites prepared by HRBM of Mg powder and FeV (0–50 mol.%). The additives of FeV were shown to improve hydrogen sorption performance of Mg including facilitation of the hydrogenation during the HRBM and improvements of the dehydrogenation/re-hydrogenation kinetics. The improvements resemble the behaviour of pure vanadium metal, and the Mg–(FeV) nanocomposites exhibited a good stability of the hydrogen sorption performance during hydrogen absorption – desorption cycling at T = 350 °C caused by a stability of the cycling performance of the nanostructured FeV acting as a catalyst. Further improvement of the cycle stability including the increase of the reversible hydrogen storage capacity and acceleration of H₂ absorption kinetics during the cycling was observed for the composites containing carbon additives (activated carbon, graphite or multi-walled carbon nanotubes; 5 wt%), with the best performance achieved for activated carbon.     

Correlation between electrochemical properties of the CNTs/AB5 composite hydrogen storage alloys and their catalytic properties for KBH4

Searching for non-precious metal anode catalysts with high catalytic activity and capable of inhibiting hydrolysis side reactions is very important for direct borohydride fuel cell (DBFC). In this work, the as-cast AB₅ alloy powders are firstly mixed with CNTs in a ratio of 1:9. Then the mixture of AB₅ alloy and CNTs is ball milled in different milling time. Finally, the CNTs/AB₅ composite alloys are obtained. Not only the catalytic properties of the CNTs/AB₅ composite alloys used as anode catalysts in DBFC, but also the electrochemical properties of the alloys have been investigated in detail. The research results indicate that, as the ball milling time is extended, the electrochemical properties and catalytic properties on ΒΗ₄⁻ of the CNTs/AB₅ composite alloys become better first and then worsen. The CNTs/AB₅ alloy milled 2 h exhibits the best electrochemical properties and catalytic properties. Furthermore, we predict that the electrochemical properties of the composite alloy are positively correlated with the catalytic properties as anode catalyst for DBFC.