Synthesis and Hydrogen Storage in Single-walled Carbon Nanotubes

Single-walled carbon nanotubes (SWNTs) were synthesized by a hydrogen arc discharge method. A high yield of gram quantity of SWNTs per hour was achieved. Tow kinds of SWNT products: web-like substance and thin films in large slices were obtained. Results of resonant Raman scattering measurements indicate that the SWNTs prepared have a wider diameter distribution and a larger mean diameter. Hydrogen uptake measurements of the two kinds of SWNT samples (both as prepared and pretreated) were carried out using a high pressure volumetric method, respectively. And a hydrogen storage capacity of 4 wt pct could be repeatedly achieved for the suitably pretreated SWNTs, which indicates that SWNTs may be a promising hydrogen storage material.

Synthesis and Evaluation on Performance of Hydrogen Storage of Multi-Walled Carbon Nanotubes Decorated with Platinum

By means of chemical reduction,nanoparticles of platinum were deposited on the surface of multi walled carbon nanotubes (MWCNTs).The performance of hydrogen storage of as prepared MWCNTs decorated with platinum was investigated.The results indicate that:(1) Hydrogen uptake is more quick and intense for decorated MWCNTs than that for not decorated ones at 10.931MPa and room temperature.The saturation of hydrogen uptake of the former only lasts about 30min,while the latter needs about 150 min;(2) The amount of hydrogen uptake of decorated MWCNTs is about 1.13wt%, which is larger than that of not decorated ones(about 0.54wt%);(3) However,more than 37% hydrogen absorbed by decorated MWCNTs is chemisorbed.

In situ formation of multiple catalysts for enhancing the hydrogen storage of MgH_(2) by adding porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres

MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).

Synthesis of Carbon Nanotubes by Catalytic Chemical Vapor Deposition Using Hydrogen Storage Alloy as A Catalyst

Carbon nanotubes (CNTs) were synthesized by catalytic chemical vapor deposition and using the alkali-reducing pretreated hydrogen storage alloy (MlNi(4.0)Co(0.6)Al(0.4)) powder as a catalyst. It was found that the surface modification of the alloy was effective to provide the catalytic active sires for CNTs growth. The Ni- and Go-clusters on the surface of the treated alloy were dominant for the growth of CNTs. The composite of CNTs with the hydrogen storage alloy has the potential to be used as a new type of hydrogen storage material without further purification.

Binary molten salt in situ synthesis of sandwich-structure hybrids of hollowβ-Mo2C nanotubes and N-doped carbon nanosheets for hydrogen evolution reaction

Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.

Vermiform Ni@CNT derived from one-pot calcination of Ni-MOF precursor for improving hydrogen storage of MgH_(2)

The Ni-coated carbon nanotubes(Ni@CNT)composite was synthesized by the facile“filtration+calcination”of Ni-based metal−organic framework(MOF)precursor and the obtained composite was used as a catalyst for MgH_(2).MgH_(2)was mixed evenly with different amounts of Ni@CNT(2.5,5.0 and 7.5,wt.%)through ball milling.The MgH_(2)−5wt.%Ni@CNT can absorb 5.2 wt.%H_(2)at 423 K in 200 s and release about 3.75 wt.%H_(2)at 573 K in 1000 s.And its dehydrogenation and rehydrogenation activation energies are reduced to 87.63 and 45.28 kJ/mol(H_(2)).The in-situ generated Mg_(2)Ni/Mg_(2)NiH4 exhibits a good catalytic effect due to the provided more diffusion channels that can be used as“hydrogen pump”.And the presence of carbon nanotubes improves the properties of MgH_(2)to some extent.

Enhanced hydrogen evolution reaction over molybdenum carbide nanoparticles confined inside single-walled carbon nanotubes

Carbon nanotubes(CNTs) have shown as unique nanoreactors to tune the catalytic activity of confined nano-catalysts. Here we report that the catalytic performance of molybdenum carbide nanoparticles(MoC_x NPs) for the hydrogen evolution reaction(HER) process can be enhanced by encapsulation within single-walled carbon nanotubes(SWNTs) with a diameter of 1–2 nm. The catalyst with MoC_x NPs located on the interior surface of SWNTs(MoCx@SWNTs) exhibits a lower onset over-potential and a smaller Tafel slope than the one with MoC_x NPs attached on the exterior surface(MoCx/SWNTs). This is likely attributed to the much smaller particle size and the more reduced states of the confined MoC_x NPs, as well as the larger specific surface area of MoCx@SWNTs compared with Mo Cx/SWNTs. In addition, the electronic structure of the confined MoC_x NPs might be modified by the confinement effects of SWNTs, and hence the adsorption free energy of H atoms on the confined MoC_x NPs, which could also contribute to their higher performance. These results suggest that the SWNTs can be further explored for constructing novel catalysts with beneficial catalytic performance.

Molecular Simulation of Hydrogen Adsorption Density in Single-Walled Carbon Nanotubes and Multilayer Adsorption Mechanism

The adsorption of hydrogen onto single-walled carbon nanotubes (SWCNTs) was studied by molecular dynamics (MD) sim'lation. It was found that the hydrogen molecules distribute regularly inside and outside of the tube. Density distribution was computed for H2 molecule. Theoretical analysis of the result showed the multilayer adsorption mechanism of SWCNTs. The storage of H2 in SWCNTs is computed, which provides essential theoretical reference for further study of hydrogen adsorption in SWCNTs.

Effects of carbon nanotubes on hydrogen storage property of Mg-based nanocomposites

Mg-based hydrogen storage nanocomposites added with carbon nanotubes(CNTs) were prepared by mechanical milling under the atmosphere of hydrogen. The results show that because of their own excellent heat conductivity and good hydrogen storage ability, the carbon nanotubes improve the mass transfer and heat transfer properties of the Mg-based nanocomponents, thus enhancing the kinetic property of hydrogen absorption and desorption of the hydrogen storage nanocomposites, and raising the hydrogen storage capacity. Due to the addition of the carbon nanotubes, the milling stress in the process of preparing the Mg-based nanocomposites is reduced, the components can be closely bonded easily, and the additives can play better catalytic roles.

Performance of hydrogen storage of carbon nanotubes decorated with palladium

Carbon nanotubes（CNTs） decorated with palladium were synthesized and applied to hydrogen storage of gas phase. The results show that the amount of hydrogen storage of the decorated CNTs is up to 3.9%（mass fraction）, of which, almost 85% H2 can be desorbed at ambient temperature and pressure, while the non-decorated CNTs has a poor performance of hydrogen storage（only about 0.5%H2, mass fraction）. These indicate that it is feasible to enhance the performance of hydrogen storage of CNTs by further decoration with hydrogen-storing metals or alloys.

Synthesis of Single-Walled Carbon Nanotubes by Induction Thermal Plasma

The production of high quality single-walled carbon nanotubes(SWCNTs)on a bulk scale has been an issue of considerable interest.Recently,it has been demonstrated that high quality SWCNTs can be continuously synthesized on large scale by using induction thermal plasma technology.In this process,the high energy density of the thermal plasma is employed to generate dense vapor-phase precursors for the synthesis of SWCNTs.With the current reactor system,a carbon soot product which contains approximately 40 wt%of SWCNTs can be continuously synthesized at the high production rate of~100 g/h.In this article,our recent research efforts to achieve major advances in this technology are presented.Firstly,the processing parameters involved are examined systematically in order to evaluate their individual inuences on the SWCNT synthesis.Based on these results,the appropriate operating conditions of the induction thermal plasma process for an effective synthesis of SWCNTs are discussed.A characterization study has also been performed on the SWCNTs produced under the optimum processing conditions.Finally,a mathematical model of the process currently under development is described.The model will help us to better understand the synthesis of SWCNTs in the induction plasma process.

Plasma-assisted ammonia synthesis under mild conditions for hydrogen and electricity storage:Mechanisms,pathways,and application prospects

Ammonia,with its high hydrogen storage density of 17.7 wt.%(mass fraction),cleanliness,efficiency,and renewability,presents itself as a promising zero-carbon fuel.However,the traditional Haber−Bosch(H−B)process for ammonia synthesis necessitates high temperature and pressure,resulting in over 420 million tons of carbon dioxide emissions annually,and relies on fossil fuel consumption.In contrast,dielectric barrier discharge(DBD)plasma-assisted ammonia synthesis operates at low temperatures and atmospheric pressures,utilizing nitrogen and hydrogen radicals excited by energetic electrons,offering a potential alternative to the H−B process.This method can be effectively coupled with renewable energy sources(such as solar and wind)for environmentally friendly,distributed,and efficient ammonia production.This review delves into a comprehensive analysis of the low-temperature DBD plasma-assisted ammonia synthesis technology at atmospheric pressure,covering the reaction pathway,mechanism,and catalyst system involved in plasma nitrogen fixation.Drawing from current research,it evaluates the economic feasibility of the DBD plasmaassisted ammonia synthesis technology,analyzes existing dilemmas and challenges,and provides insights and recommendations for the future of nonthermal plasma ammonia processes.

Tuning microstructures of Mg-Ce-Ni hydrogen storage alloys via Cu and carbon nanotube additions

Mg-based alloys are regarded as highly promising materials for hydrogen storage.Despite significant improvements of the properties for Mg-based alloys,challenges such as slow hydrogen absorption/desorption kinetics and high thermodynamic stability continue to limit their practical application.In this study,to assess hydrogen storage alloys with enhanced properties,incorporating both internal microstructure modulation through the preparation of amorphous/nanocrystalline structures and surface property enhancement with the addition of Cu and carbon nanotubes(CNTs),the kinetic properties of activation and hydrogenation,thermodynamic properties,and dehydrogenation kinetics are tested.The results reveal a complementary interaction between the added Cu and CNTs,contributing to the superior hydrogen storage performance observed in sample 7A-2Cu-1CNTs with an amorphous/nanocrystalline structure compared to the other experimental samples.Additionally,the samples are fully activated after the initial hydrogen absorption and desorption cycle,demonstrating outstanding hydrogenation kinetics under both high and low temperature experimental conditions.Particularly noteworthy is that the hydrogen absorption exceeds 1.8 wt.% within one hour at 333 K.Furthermore,the activation energy for dehydrogenation is decreased to 64.71 kJ·mol^(–1).This research may offer novel insights for the design of new-type Mg-based hydrogen storage alloys,which possess milder conditions for hydrogen absorption and desorption.

Study on Highly Active Catalysts and a Once-Through Process for Methanol Synthesis from Syngas

Highly active CNT-promoted co-precipitated Cu-ZnO-Al_2O_3 catalysts,symbolized as Cu_iZn_jAl_k-x%CNTs, were prepared, and their catalytic activity for once-throughmethanol synthesis from syngas was investigated. The results illustrated that, under the reactionconditions (at 493 K, 5.0 MPa, the volume ratio of H_2/CO/CO_2/N_2= 62/30/5/3, GHSV= 4000 h^(-1),the observed single-pass CO-conversion and methanol-STY over a Cu_6Zn_3Al_1-12.5%CNTs catalystreached 64% and 1210 mg/(h-g), which was about 68% and 66% higher than those (38% and 730 mg/(h·g))over the corresponding CNT-free catalyst, Cu-6Zn_3Al_1, respectively. The characteristic studies ofthe catalysts revealed that appropriate incorporation of a minor amount of the CNTs into theCu_iZn_jAl_k brought about little change in the apparent activation energy of the methanol synthesisreaction, however, led to a considerable increase in the catalyst's active Cu surface area andpronouncedly enhanced the stationary-state concentration of active hydrogen-adspecies on the surfaceof the functioning catalyst, which would be favorable to increasing the rate of the COhydro-genation reactions. Moreover, the operation temperature for methanol synthesis over theCNT-promoted catalysts can be 10-20 degrees lower than that over the corresponding CNT-free contrastsystem, which would contribute considerably to an increase in equilibrium CO-conversion andCH_3OH-yield.

Effects of structure and sur-face properties on carbon nanotubes' hydrogen storage characteristics

Hydrogen adsorption experiments were carried out in special stainless steel vessels at room temperature (298K) and under 10 MPa using self-synthesized multi-walled carbon nanotubes. In the experiments, carbon nanotubessynthesized by the seeded catalyst method were pretreatedby being soaked in chemical reagents or annealed at hightemperature before they were used to adsorb hydrogen, but their capacity for hydrogen storage was still poor. Carbonnanotubes synthesized by the floating catalyst method were found to be able to adsorb more hydrogen. They have ahydrogen storage capacity of over 4% after they wereannealed at high temperatures, which suggested that theycould be used as a promising material for hydrogen storage.

Effect of titanium based complex catalyst and carbon nanotubes on hydrogen storage performance of magnesium

Mg （MgH2）-based composites, using carbon nanotubes （CNTs） and pre-synthesized titanium based complex （TCat） as the cat- alysts, were prepared by high energy ball milling technique. The use of both catalysts demonstrated markedly improved the hydrogen storage performance, e.g. a significant increase of hydrogen release rate and decrease of desorption temperature. The synthesized composites can absorb almost 6 wt% of hydrogen within 3 min at 200 ~C and desorb 6 wt% hydrogen in 10 min at 310 ~C. The influence of CNTs and TCat on desorption temperature was also investigated by using temperature programmed desorption （TPD）. The TPD results reveal that the peak desorption temperature and the onset temperature can be lowered by 109 ~C and 155 ~C, respectively, compared to the non-catalyzed MgH2. The reaction enthalpy and entropy of hydrogen de- sorption for the synthesized MgH2-based composites are calculated by the van＇t Hoff analysis to be 73.1 kJ/mol H2 and 130.2 J/mol H2 K, respectively.

Tailoring the Diameter of Single-Walled Carbon Nanotubes for Optical Applications

Single-walled carbon nanotubes （SWCNTs） with specific diameters are required for various applications particularly in electronics and photonics, since the diameter is an essential characteristic determining their electronic and optical properties. In this work, the selective growth of SWCNTs with a certain mean diameter is achieved by the addition of appropriate amounts of CO2 mixed with the carbon source （CO） into the aerosol （floating catalyst） chemical vapor deposition reactor. The noticeable shift of the peaks in the absorption spectra reveals that the mean diameters of the as-deposited SWCNTs are efficiently altered from 1.2 to 1.9 nm with increasing CO2 concentration. It is believed that CO2 acts as an etching agent and can selectively etch small diameter tubes due to their highly curved carbon surfaces. Polymer-free as-deposited SWCNT films with the desired diameters are used as saturable absorbers after stamping onto a highly reflecting Ag-mirror using a simple dry-transfer technique. Sub-picosecond mode-locked fiber laser operations at -1.56μm and -2 μm are demonstrated, showing improvements in the performance after the optimization of the SWCNT properties.

Electrochemical hydrogen storage of aligned multi-walled carbon nanotubes

Hydrogen storage of aligned multi-walled car-bon nanotubes (a-MWNTs), non-aligned MWNTs (n- MWNTs) and graphite electrodes are studied by the electro-chemical measurements. The electrodes are prepared by mixing carbon nanotubes (CNTs), copper powder and PTFE binder in a weight ratio of 1︰5︰3 and compressing the mixture into porous nickel collector. The results show that the electrochemical hydrogen storage capacity of the a-MWNT electrode is up to 1625 mAh/g, corresponding to a high hydrogen storage of 5.7 wt%, which is 10 times that of graphite electrode and is 13 times that of n-MWNT electrode, suggesting that a-MWNTs are promising materials for electrochemical hydrogen storage.

Improvement in growth yield of single-walled carbon nanotubes with narrow chirality distribution by pulse plasma CVD

A pulse plasma chemical vapor deposition (CVD) technique was developed for improving the growth yield of single-walled carbon nanotubes (SWNTs) with a narrow chirality distribution. The growth yield of the SWNTs could be improved by repetitive short duration pulse plasma CVD, while maintaining the initial narrow chirality distribution. Detailed growth dynamics is discussed based on a systematic investigation by changing the pulse parameters. The growth of SWNTs with a narrow chirality distribution could be controlled by the difference in the nucleation time required using catalysts comprising relatively small or large particles as the key factor. The nucleation can be controlled by adjusting the pulse on/ofF time ratio and the total processing time.

Interaction of hydrogen molecules on Ni-doped single-walled carbon nanotube

Adsorption of hydrogen molecules on an Ni-doped （8,0） single-walled carbon nanotube （SWNT） is investigated by using first-principles density functional calculations. The result shows that a single Ni atom adsorbed on the bridge site of the tube could cannot dissociate the H2, however it can chemisorb three H2 at most, with the average binding energy per H2 suitable for the hydrogen storage at the room temperature. More H2 would physisorb around an Ni atom weakly. As for the SWNT with an Ni dimer adsorbed, we find that when the H2 approaches the Ni Ni bond, it dissociates without overcoming any barrier and makes bonds with Ni atom.