Enhanced reversible hydrogen storage properties of wrinkled graphene microflowers confined LiBH_(4) system with high volumetric hydrogen storage capacity

LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.

Ti-doped nano-porous graphene： A material for hydrogen storage and sensor

Clustering of Ti on carbon nanostructures has proved to be an obstacle in their use as hydrogen storage materials. Using density functional theory we show that Ti atoms will not cluster at moderate concentrations when doped into nanoporous graphene. Since each Ti atom can bind up to three hydrogen molecules with an average binding energy of 0.54 eV/H2, this material can be ideal for storing hydrogen under ambient thermodynamic conditions. In addition, nanoporous graphene is magnetic with or without Ti doping, but when it is fully saturated with hydrogen, the magnetism disappears. This novel feature suggests that nanoporous graphene cannot only be used for storing hydrogen, but also as a hydrogen sensor.

Characteristics of MOF, MWCNT and graphene containing materials for hydrogen storage: A review

Hydrogen is a generally abundant, safe, clean and environmentally apt alternative fuel, which replenishes the void generated by depleting fossil fuel reserves. The adoption of hydrogen as an energy source has been restricted to low levels due to the complications associated with its viable storage and usage. Existing technologies, such as storage of hydrogen in compressed and liquefied forms are not adequate to meet the broad on-board applications. The gravimetric energy density(120 MJ/kg) of hydrogen is three times higher than that of gasoline products, so solid-state hydrogen storage is advantageous.Metal-organic frameworks(MOFs), multi-walled carbon nanotubes(MWCNTs) and graphene are solid adsorbents majorly employed for efficient H_2 storage. The prominent features of MOFs such as permanent porosity, structural rigidity, and surface area are attractive and ideal for hydrogen storage. In addition,nanostructured carbon materials(MWCNTs and graphene) and their composites have demonstrated significant hydrogen storage capacities. Some important parameters for the success of the hydrogen economy include high storage density, adsorption/desorption temperature and cycling time. Cryo-hydrogen storage was achieved in MOFs and their composites with carbon structures, but storage at ambient temperature and acceptable pressures is a major hurdle. This review discusses various strategies and mechanisms in the design of adsorbents explored to improve H_2 storage capacities and afford opportunities to develop new sustainable hydrogen technologies to meet energy targets.

Nitrogen Doped Graphene as Potential Material for Hydrogen Storage

The nitrogen doped graphene was synthesized by hydrothermal route utilizing 2-Chloroethylamine hydrochloride as nitrogen precursor in the presence of graphene oxide (GO). Nitrogen-doped graphene material is developed for its application in hydrogen storage at room temperature. Nitrogen doped graphene layered material shows ~1.5 wt% hydrogen storage capacity achieved at room temperature and 90 bar pressure.

Heteroatom Doped Multi-Layered Graphene Material for Hydrogen Storage Application

A variety of distinctive techniques have been developed to produce graphene sheets and their functionalized subsidiaries or composites. The production of graphene sheets by oxidative exfoliation of graphite can be a suitable route for the preparation of high volumes of graphene derivatives. P-substituted graphene material is developed for its application in hydrogen sorption in room temperature. Phosphorous doped graphene material with multi-layers of graphene shows a nearly ~2.2 wt% hydrogen sorption capacity at 298 K and 100 bar. This value is higher than that for reduced graphene oxide (RGO without phosphorous).

First Principles Calculations of Hydrogen Storage on Calcium-Decorated, Boron-Doped Bilayer Graphene

In this paper, the adsorption and storage of hydrogen on calcium-decorated, boron-doped bilayer graphene was investigated using first principles calculation. The calcium-decorated bilayer graphene was investigated and it was shown that the binding energy of H2 molecule adsorbed on the calcium-decorated bilayer graphene is −0.02 eV and the energy does not belong to reversible usage range of −0.2 - −0.6 eV. Substitutional boron doping can improve the adsorption energy of Ca to bilayer graphene with the empty pz orbital of boron atoms. Our calculations show that calcium atoms can be solidly adsorbed on the interlayer (Ca/B/Graphene) and outerlayer (2Ca/B/Graphene and 3Ca/B/Graphene) of B-doped bilayer graphene. Hydrogen molecule binds with Ca/B/Graphene, 2Ca/B/Graphene and 3Ca/B/Graphene system with an energy that belongs to reversible usage range of −0.2 - −0.6 eV. The overlap between Ca 3d and H2σ orbitals just below the Fermi energy demonstrates the charge transfer between the Ca atom and the H atom and the role of hybridization of the 3d orbita of Ca with the σ orbitals of H2 in efficient adsorption of hydrogen molecules. The charge from hydrogen bonding orbital transfers to empty 3d orbitals of the Ca atom, and then from the 3d orbitals of the Ca atom donated to H2σ* antibonding orbital. Hydrogen moleculars can be adsorbed on the interlayer and outerlayer of Ca-decorated B-doped bilayer graphene.

First Principles DFT Study of Hydrogen Storage on Graphene with La Decoration

The properties of hydrogen storage on graphene with La decoration are investigated using a first-principles plane-wave pseudopotential method based on the density functional theory in this paper. The clustering problem of La decorated graphene is considered and B doping can solve it effectively in theory. We obtain the stable geometrical configuration of the modified system and the properties of hydrogen storage are excellent. It can absorb up to 6 H2 molecules with an average adsorption energy range of?–0.529 to –0.655 eV/H2, which meets the ideal range between the physisorbed and chemisorbed states for hydrogen storage. Furthermore, it is proved that the existence of La atom alters the charge distribution of H2 molecules and graphene sheet based on the calculation and analysis about the electronic density of states and charge density difference of the modified system. La atom interacts with hydrogen molecules through Kubas interaction. Thereby, it improves the performance of graphene sheet for hydrogen storage. The modified system exhibits the excellent potential to become one of the most suitable candidates for hydrogen storage medium at near ambient conditions with molecule state.

Effect of Nitrogen and Sulfur Co‑Doped Graphene on the Electrochemical Hydrogen Storage Performance of Co_(0.9)Cu_(0.1)Si Alloy

Co_(0.9)Cu_(0.1)Si alloy was prepared by mechanical alloying method.Nitrogen-doped graphene(NG)and nitrogen–sulfur codoped graphene(NSG)were prepared by hydrothermal method.5 wt%graphene oxide,NG and NSG were doped into Co_(0.9)Cu_(0.1)Si alloy,respectively,by ball milling to improve the electrochemical hydrogen storage performance of the composite material.X-ray diffraction and scanning electron microscopy were used to characterize the structure and morphology of the composite material,and the LAND battery test system and three-electrode battery system were used to test the electrochemical performance of the composite material.The composite material showed better discharge capacity and better cycle stability than the pristine alloy.In addition,in order to study the optimal ratio of NSG,3%,5%,7%and 10%of NSG were doped into Co_(0.9)Cu_(0.1)Si alloy,respectively.Co_(0.9)Cu_(0.1)Si alloy doped with 5%NSG had the best performance among all the samples.The best discharge capacity was 580.1 mAh/g,and its highest capacity retention rate was 64.1%.The improvement in electrochemical hydrogen storage performance can be attributed to two aspects.On the one hand,the electrocatalytic performance of graphene is improved by co-doping nitrogen and sulfur,on the other hand,graphene has excellent electrical conductivity.

Thermodynamic Aspects of the Graphene/Graphane/Hydrogen Systems: Relevance to the Hydrogen On-Board Storage Problem

The present analytical review is devoted to the current problem of thermodynamic stability and related thermodynamic characteristics of the following graphene layers systems: 1) double-side hydrogenated graphene of composition CH (theoretical graphane) (Sofo et al. 2007) and experimental graphane (Elias et al. 2009);2) theoretical single-side hydrogenated graphene of composition CH;3) theoretical single-side hydrogenated graphene of composition C2H (graphone);4) experimental hydrogenated epitaxial graphene, bilayer graphene and a few layers of graphene on SiO2 or other substrates;5) experimental and theoretical single-external side hydrogenated single-walled carbon nanotubes, and experimental hydrofullerene C60H36;6) experimental single-internal side hydrogenated (up to C2H or CH composition) graphene nanoblisters with intercalated high pressure H2 gas inside them, formed on a surface of highly oriented pyrolytic graphite or epitaxial graphene under the atomic hydrogen treatment;and 7) experimental hydrogenated graphite nanofibers-multigraphene with intercalated solid H2 nano-regions of high density inside them, relevant to solving the problem of hydrogen on-board storage (Nechaev 2011-2012).

La内嵌graphene/MoS_(2)层的储氢性能研究

运用密度泛函理论研究了La内嵌graphene/MoS_(2)层的储氢性能.由于La的内嵌graphene/MoS_(2)异质结的层间距被拉大.详细研究了氢气分子在La内嵌的graphene/MoS_(2)结构上的吸附行为.结果表明,一个La原子最多可以吸附六个氢气分子,采用GGA/PBE泛函计算得到氢气分子的平均吸附能为0.198 eV.合适的吸附能使得设计材料能够在温和条件下实现可逆存储.重要的是,La原子能够分散地内嵌在graphene/MoS_(2)异质结中,这将为氢气分子提供更多吸附位.研究表明理论上预测La内嵌graphene/MoS_(2)材料是一种潜在的储氢材料.

First-principles study of hydrogen adsorption on titanium-decorated single-layer and bilayer graphenes

The adsorption of hydrogen molecules on titanium-decorated （Ti-decorated） single-layer and bilayer graphenes is studied using density functional theory （DFT） with the relativistic effect. Both the local density approximation （LDA） and the generalized gradient approximation （GGA） are used for obtaining the region of the adsorption energy of H2 molecules on Ti-decorated graphene. We find that a graphene layer with titanium （Ti） atoms adsorbed on both sides can store hydrogen up to 9.51 wt% with average adsorption energy in a range from -0.170 eV to 0.518 eV. Based on the adsorption energy criterion, we find that chemisorption is predominant for H2 molecules when the concentration of H2 molecules absorbed is low while physisorption is predominant when the concentration is high. The computation results for the bilayer graphene decorated with Ti atoms show that the lower carbon layer makes no contribution to hydrogen adsorption.

MgH_2-graphene复合储氢材料吸放氢性能

通过球磨制备MgH2,MgH2-G和MgH2-graphene储氢材料,研究石墨烯添加对MgH2吸放氢性能的影响。结果表明,石墨和石墨烯对球磨过程中MgH2的细化有促进作用;石墨和石墨烯的添加对MgH2的吸放氢动力学有良好的改善作用;特别是MgH2-graphene储氢材料有优良的吸放氢性能,在573 K下于5,2 min内放氢和再吸氢质量分数都为7.0%,且其放氢起始温度较MgH2的低50 K。

三明治结构graphene-2Li-graphene的储氢性能

本文使用密度泛函理论中的广义梯度近似对扩展三明治结构graphene-2Li-graphene的几何结构、电子性质和储氢性能进行计算研究.计算得知:位于单层石墨烯中六元环面心位上方的单个Li原子与基底之间的结合能最大(1.19 eV),但小于固体Li的实验内聚能(1.63 eV),然而,在双层石墨烯之间的单个Li原子与基底的结合能增加到3.41 eV,远大于固体Li的实验内聚能,因此位于双层石墨烯之间的多个Li原子不会成簇,有利于进一步储氢.扩展三明治结构graphene-2Li-graphene中每个Li原子最多可以吸附3个H_2分子,储氢密度高达10.20 wt.%,超过美国能源部制定的5.5 wt.%的目标.该体系对1—3个H_2分子的平均吸附能分别为0.37,0.17和0.12 eV,介于物理吸附和化学吸附(0.1—0.8 eV)之间,因此该体系可以实现常温常压下对H_2的可逆吸附.通过对态密度分析可知,每个Li原子主要通过电场极化作用吸附多个H_2分子.动力学和巨配分函数计算表明graphene-2Li-graphene结构对H_2分子具有良好的可逆吸附性能.该研究可以为开发良好的储氢材料提供一个好的研究思路,为实验工作提供理论依据.

Electrochemical hydrogen-storage capacity of graphene can achieve a carbon-hydrogen atomic ratio of 1:1

As a promising hydrogen-storage material,graphene is expected to have a theoretical capacity of 7.7 wt%,which means a carbon-hydrogen atomic ratio of 1:1.However,it has not been demonstrated yet by experiment,and the aim of the U.S.Department of Energy is to achieve 5.5 wt%in 2025.We designed a spatially-confined electrochemical system and found that the storage capacity of hydrogen adatoms on single layer graphene(SLG)is as high as 7.3 wt%,which indicates a carbon-hydrogen atomic ratio of 1:1 by considering the sp^(3) defects of SLG.First,SLG was deposited on a large-area polycrystalline platinum(Pt)foil by chemical vapor deposition(CVD);then,a micropipette with reference electrode,counter electrode and electrolyte solution inside was impacted on the SLG/Pt foil(the working electrode)to construct the spatially-confined electrochemical system.The SLG-uncovered Pt atoms act as the catalytic sites to convert protons(H^(+))to hydrogen adatoms(H_(ad)),which then spill over and are chemically adsorbed on SLG through surface diffusion during the cathodic scan.Because the electrode processes are reversible,the H_(ad) amount can be measured by the anodic stripping charge.This is the first experimental evidence for the theoretically expected hydrogen-storage capacity on graphene at ambient environment,especially by using H+rather than hydrogen gas(H_(2))as the hydrogen source,which is of significance for the practical utilization of hydrogen energy.

Nd–Mg–Ni alloy electrodes modified by reduced graphene oxide with improved electrochemical kinetics

To improve the electrochemical kinetics of Nd–Mg–Ni alloy electrodes, the alloy surface was modified with highly conductive reduced graphene oxide(rGO) via a chemical reduction process. Results indicated that rGO sheets uniformly coated on the alloy surface, yielding a threedimensional network layer. The coated surfaces contained numerous hydrophilic functional groups, leading to better wettability of the alloy in aqueous alkaline media. This, in turn, increased the concentration of electro-active species at the interface between the electrode and the electrolyte, improving the electrochemical kinetics and the rate discharge of the electrodes. The high rate dischargeability at 1500 mA·g^(–1) increased from 53.2% to 83.9% after modification. In addition, the modification layer remained stable and introduced a dense metal oxide layer to the alloy surface after a long cycling process. Therefore, the protective layer prevented the discharge capacity from quickly decreasing and improved cycling stability.

Fundamental Open Questions on Engineering of “Super” Hydrogen Sorption in Graphite Nanofibers: Relevance for Clean Energy Applications

Herein, some fundamental open questions on engineering of “super” hydrogen sorption (storage) in carbonaceous nanomaterials are considered, namely: 1) on thermodynamic stability and related characteristics of some hydrogenated graphene layers nanostructures: relevance to the hydrogen storage problem;2) determination of thermodynamic characteristics of graphene hydrides;3) a treatment and interpretation of some recent STM, STS, HREELS/LEED, PES, ARPS and Raman spectroscopy data on hydrogensorbtion with epitaxial graphenes;4) on the physics of intercalation of hydrogen into surface graphene-like nanoblisters in pyrolytic graphite and epitaxial graphenes;5) on the physics of the elastic and plastic deformation of graphene walls in hydrogenated graphite nanofibers;6) on the physics of engineering of “super” hydrogen sorption (storage) in carbonaceous nanomaterials, in the light of analysis of the Rodriguez-Baker extraordinary data and some others. These fundamental open questions may be solved within several years.

球磨对石墨烯纳米片储氢性能的影响

探究了球磨参数(球磨速度、球磨时间和球料比)对石墨烯储氢性能的影响,并利用X射线衍射仪(XRD)对球磨后的石墨烯进行了晶体结构分析。结果表明:采用合适的球磨参数可改善石墨烯的储氢性能,球磨时间过长、球磨速度过快、球料比过大会导致石墨烯团聚。当球磨时间为12h,球料比为320∶1,球磨转速为330r/min时石墨烯储氢性能较优,储氢容量为2.49wt%。

Nitrogen-doped graphene hydrogel-supported NiPt-CeOx nanocomposites and their superior catalysis for hydrogen generation from hydrazine at room temperature

The safe and efficient storage and release of hydrogen is one of the key technological challenges for the fuel cell-based hydrogen economy. Hydrazine monohydrate has attracted considerable attention as a safe and convent chemical hydrogen-storage material. Herein, we report the facile synthesis of NiPt-CeOx nanocomposites supported by three-dimensional nitrogen-doped graphene hydrogels （NGHs） via a simple one-step co-reduction synthesis method. These catalysts were composition-dependent for hydrogen generation from an alkaline solution of hydrazine. （NisPt5）I-（CeOx）0.B/NGH exhibited the highest catalytic activity, with 100% hydrogen selectivity and turnover frequencies of 408 h^-1 at 298 K and 3,064 h^-1 at 323 K. These superior catalytic performances are attributed to the electronic structure of the NiPt centers, which was modified by the electron interaction between NiPt and CeOx and the strong metal-support interaction between NiPt-CeOx and the NGH.

Azobenzene/graphene hybrid for high-density solar thermal storage by optimizing molecular structure

A large capacity storing solar energy as latent heat in a close-cycle is essentially important for solar thermal fuels. This paper presents a solar thermal molecule model of a photo-isomerizable azobenzene(Azo) molecule covalently bound to graphene. The storage capacity of the Azo depending on isomerization enthalpy(ΔH) is calculated based on density functional theory. The result indicates that the ΔH of Azo molecules on the graphene can be tuned by electronic interaction, steric hindrance and molecular hydrogen bonds(H-bonds). Azo with the withdrawing group on the ortho-position of the free benzene shows a relatively high ΔH due to resonance effect. Moreover, the H-bonds on the trans-isomer largely increase ΔH because they stabilize the trans-isomer at a low energy. 2-hydroxy-4-carboxyl-2′,6′,-dimethylamino-Azo/graphene shows the maximum ΔH up to 1.871 e V(107.14 Wh kg^(-1)), which is 125.4% higher than Azo without functional groups. The Azo/graphene model can be used for developing high-density solar thermal storage materials by controlling molecular interaction.

Three-dimensional nitrogen-doped graphene hydrogel supported Co-CeOx nanoclusters as efficient catalysts for hydrogen generation from hydrolysis of ammonia borane

The development of highly active noble-metal-flee catalysts for catalytic hydrolysis of ammonia borane is mandatory for its application in hydrogen storage. Herein, Co-CeOx nanoclusters have been successfully anchored on a three-dimensional nitrogen-doped graphene hydrogel （NGH） by a simple coreduction method and further used as efficient catalysts to catalytic hydrolysis of ammonia borane at room temperature. Thanks to the strong synergistic electronic effect between Co and CeOx, as well as the strong metal-support interaction between Co-CeOx and 3D NGH, the as-synthesized Co-（CeOx）0.91/NGH catalyst exhibits superior catalytic activity toward hydrolysis of ammonia borane, with the turnover frequency （TOF） value of 79.5 min 1, which is almost 13 times higher than that of Co]NGH, and higher than most of the reported noble-metal-free catalysts.