Mechanism for electrochemical hydrogen insertion in carbonaceous materials

The mechanism for safe and reversible storage of hydrogen in porous carbonaceous materials by electrochemical decomposition of water in alkaline electrolyte is proposed. Atomic H was found to be inserted into the microdomains of defective graphene layers. Hydrogen storage capacity increases with increasing interlayer distance between carbon sheets. Hydrogen insertion in carbonaceous materials occurs at ambient conditions. Static potential acts as an electrochemical valve which can retain the hydrogen in the carbon structure, thus preventing leakage during storage.     

Solar gasification of carbonaceous materials

Charcoal, wood and paper have been gasified in a packed-bed reactor using steam and solar energy. The steam was generated by spraying water directly on to the surface of the fuel and, at the same time, heating the fuel at the focus of a solar furnace. Half of the steam reacted with carbon and 30 per cent of the incident solar energy was stored as chemical enthalpy.

The performance of a fluidized-bed reactor was compared to that of a packed-bed reactor using charcoal and CO₂. The fraction of the incident solar energy utilized to produce CO (stored) was 10 per cent in the case of the fluidized-bed reactor and 40 per cent for the packed-bed reactor.

The fuel value of the gas produced from the steam-gasification of wood and paper was 65 kcal/mole (320 Btu/lb). On an ash free basis the volume yield of the gas was 1 ± 0.1 m³/kg.     

Studies on the mechanism and capacity of hydrogen uptake by physisorption-based materials

Nanostructure carbons are the most important physisorption-based hydrogen carriers. The mechanism of hydrogen uptake was studied based on the adsorption isotherms collected for a wide range of temperature and pressure. It was concluded that the hydrogen adsorbed is arranged on carbon surface monolayerly; therefore, the storage capacity depends only on the specific surface area of the carbon. This rule applies also for other organic/inorganic materials if the interaction between hydrogen and the solid surface remains the Van der Waals force. Carbon nanotubes cannot be good carriers of hydrogen due to the small surface area, but superactivated carbon is of great potential and a storage capacity over 10 wt% was proven for the condition of 77 K and 6 MPa.     

Concise dynamic model to accurately calculate the hydrogen yield during the reaction process

Estimation of hydrogen production rate and the total amount hydrogen during any reaction process require an accurate and concise dynamic model to describe the variation of hydrogen production rate with reaction time. There must be two comprehensive features of such model, the first one is that the hydrogen production rate calculated by this model is zero at the initial time is zero and the second one is that the integration of this model over time result in an explicit function. In this paper, we present a comprehensive model which meets above two requirements via amendments to the shifted logistic model. The model is validated against measured results through comparison of 25 experimental and theoretical hydrogen production rate. The experimentally validated model is used to calculate the total amount hydrogen during each reaction process. The impact of some experimental conditions on the total hydrogen production was mathematically explained for the first time, and this result reveal the excellent predictive ability of framework suggested in this paper. In addition, that is for an experimental condition history, predictions are achieved by developing a set of “secondary models” that describe some experimental conditions dependence of the “primary models” parameters. The method to obtain the parameters in “secondary models” described in this paper indicated that another major departure from the conventional models is the notion that the “secondary models” do not need to follow any preconceived formula and that they can be derived solely from the observed growth patterns. The presented framework can help the hydrogen production industry.     

谈如何合理地确定内燃机车检修周期

我国铁路作为中国运输业的大动脉,在整个运输业当中起着举足轻重的作用.作为铁路运输的牵引动力--机车,更是重中之重,是运输线的重要保障,只有机车质量提高了,才能保证整个铁路运输的安全、正点、高效.     

A critical review on improving hydrogen storage properties of metal hydride via nanostructuring and integrating carbonaceous materials

Hydrogen-based economy has a great potential for addressing the world's environmental concerns by using hydrogen as its future energy carrier. Hydrogen can be stored in gaseous, liquid and solid-state form, but among all solid-state hydrogen storage materials (metal hydrides) have the highest energy density. However, hydrogen accessibility is a challenging step in metal hydride-based materials. To improve the hydrogen storage kinetics, effects of functionalized catalysts/dopants on metal atoms have been extensively studied. The nanostructuring of metal hydrides is a new focus and has enhanced hydrogen storage properties by allowing higher surface area and thus reversibility, hydrogen storage density, faster and tunable kinetics, lower absorption and desorption temperatures, and durability. The effect of incorporating nanoparticles of carbon-based materials (graphene, C60, carbon nanotubes (CNTs), carbon black, and carbon aerogel) showed improved hydrogen storage characteristics of metal hydrides. In this critical review, the effects of various carbon-based materials, catalysts, and dopants are summarized in terms of hydrogen-storage capacity and kinetics. This review also highlights the effects of carbon nanomaterials on metal hydrides along with advanced synthesis routes, and analysis techniques to explore the effects of encapsulated metal hydrides and carbon particles. In addition, effects of carbon composites in polymeric composites for improved hydrogen storage properties in solid-state forms, and new characterization techniques are also discussed. As is known, the nanomaterials have extremely higher surface area (100–1000 time more surface area in m²/g) when compared to the bulk scale materials; thus, hydrogen absorption and desorption can be tuned in nanoscale structures for various industrial applications. The nanoscale tailoring of metal hydrides with carbon materials is a promising strategy for the next generation of solid-state hydrogen storage systems for different industries.     

Solar-driven pyrolysis and gasification of low-grade carbonaceous materials

Three low-grade carbonaceous materials from biomass (Scenedesmus algae and wheat straw) and waste treatment (sewage sludge) have been selected as feedstock for solar-driven thermochemical processes. Solar-driven pyrolysis and gasification measurements were conducted directly irradiating the samples in a 7 kW_e high flux solar simulator and the released gases H₂, CO, CO₂ and CH₄ and the sample temperature were continuously monitored.Solar-driven experiments showed that H₂ and CO evolved as important product gases demonstrating the high quality of syngas production for the three feedstocks. Straw is the more suitable feedstock for solar-driven processes due to the high gas production yields. Comparing the solar-driven experiments, gasification generates higher percentage of syngas (mix of CO and H₂) respect to total gas produced (sum of H₂, CO, CO₂ and CH₄) than pyrolysis. Thus, solar-driven gasification generates better quality of syngas production than pyrolysis.     

Cryogenic hydrogen uptake of high surface area porous carbon materials activated by potassium hydroxide

A porous carbon material with specific surface area of 894 m²/g and pore volume of 0.47 cm³/g has been easily synthesized by pyrolysis of a gel containing nickel chloride. Transmission electron microscopy reveals a texture of evenly spreading spherical mesopores and well dispersed micropores. Potassium hydroxide treatment results in a surface area and pore volume of the pristine materials of up to 2930 m²/g and 1.52 cm³/g, respectively. Cryogenic hydrogen uptake capacities were measured and the highest capacity of 6.24 wt% was obtained at 77 K under 2 MPa.     

A simple method for the production of highly ordered porous carbon materials with increased hydrogen uptake capacities

The synthesis, characterization and hydrogen uptake of porous carbons generated by heat treatment was investigated using various zeolites and mesoporous silicas as hard templates. The effect of heat treatment on the structural order, textural properties and hydrogen uptake capacities of porous carbons templated from the model zeolite EMC-2 in a temperature range of 600–800 °C during chemical vapour deposition were studied in details. The heat treatment improved the structural order of replicated microporous carbons, significantly increased both total and microporous surface area and pore volume, and remarkably increased the hydrogen uptake capacity. The optimized heat treatment conditions were at 900 °C for 3 h. The heat treatment at high temperatures was found to be a simple and general approach to synthesize well-ordered microporous carbons from different zeolite templates, using various carbon precursors and through different synthesis methods. The microporous carbons possessed a high surface area and pore volume with increased microporosity and therefore exhibited improved hydrogen storage capacities up to 5.85 wt% at 20 bar and −196 °C. The heat treatment, however, has no obvious effect on the textural properties and hydrogen uptake capacities for mesoporous carbons templated from mesoporous silicas.     

A key technology to improve the cyclic performances of carbonaceous materials for lithium secondary battery anodes

Any carbonaceous material does not necessarily provide a favorable surface fora smooth electrochemical lithium doping/undoping reaction because the carbon surface is covered with a very thin inhibiting surface layer. Especially, carbonaceous materials prepared at lower temperatures exhibit very poor charge/discharge cycleability. Removing such a surface layer was found quite effective to provide very favorable electrode surfaces for the doping/undoping reaction. Simple heating of the pristine sample in vacuum was effective, but a more effective and versatile method was a mild oxidation treatment at a moderate temperature only for several minutes. Upon being treated with the mild oxidation, the cycleability as well as high rate capacity of carbonaceous materials were improved to a great extent. A trace amount of water contained in nonaqueous electrolyte was also found to deteriorate the electrochemical properties, which was ascribed to the formation of retarding surface film such as LiOH through the reduction reaction with lithium cation and water during charging.     

On the application of standard isotherms to hydrogen adsorption in microporous materials

A mathematical framework for simulating equilibrium hydrogen adsorption isotherms in porous materials and estimating the values of key parameters associated with the adsorption process is developed. Explicit expressions for the excess, adsorbed, compressed and absolute masses, for any model isotherm, are derived. The modelling framework is used in combination with five standard equilibrium isotherm models to simulateexperimental data for Prussian blue analogues, nitropussides and metal-organic frameworks via nonlinear regression. The surface areas, the affinity and heterogeneity factors, and the pressure-dependent adsorption volumes are calculatedand compared to values available in the literature and the sensitivity of the results to the number of data points is quantified. The consistency of the results using different isotherm models is evaluated.     

Review on the interface engineering in the carbonaceous titania for the improved photocatalytic hydrogen production

Hydrogen is the prime source of energy with enormous attention in the current research development process as it is safe, clean, eco-friendly, and can be produced from renewable resources through simple catalytic reactions. Scalable production of hydrogen through photocatalysis has been achieved using carbon-modified semiconductors since 2009. In this direction, this review delivers comprehensive understandings into the interface and structural interactions between TiO₂ and carbonaceous materials such as carbon, carbon nanotubes, graphene, activated carbon, graphitic carbon nitride, carbon quantum dots, etc., and their influences toward improving the hydrogen generation activity of these systems. Besides, recently developed carbonaceous materials such as 3-D graphene, carbon nanohorns, and carbon nanocones have also been discussed on their character in the photocatalytic water splitting procedure. In general, the observed improvements in this carbon-modified TiO₂ attributed to the synergetic effects, which offer the active migration of charge carriers and reduced recombination rates in the photocatalyst. Finally, highlighting the future perspectives of the carbonaceous materials in photocatalytic applications are concluded.     

氢能知识系列讲座(3)如何把氢储存起来?

氢能体系主要包括氢的生产、储存和运输、应用三个环节。而氢能的储存是关键，也是目前氢能应用的主要技术障碍。大家知道，所有元素中氢的重量最轻，在标准状态下，它的密度为0．0899g／L，为水的密度的万分之一。在-252．7℃时，可成为液体，密度为70g／L，仅为水的十五分之一。所以，氢气可以储存，但是很难高密度地储存。     

On thermodynamics of methane + carbonaceous materials adsorption

This study presents the theoretical frameworks for the thermodynamic quantities namely the heat of adsorption, specific heat capacity, entropy, and enthalpy for the adsorption of methane onto various carbonaceous materials. The proposed theoretical frameworks are developed from the rigor of thermodynamic property surfaces of a single component adsorbate–adsorbent system and by incorporating the micropore filling theory approach, where the effect of adsorbed phase volume is considered. The abovementioned thermodynamic properties are quantitatively evaluated from the experimental uptake data for methane adsorption onto activated carbons such as Maxsorb III at temperatures ranging from 120 to 350 K and pressures up to 25 bar. Employing the proposed thermodynamic approaches, this paper shows the thermodynamic maps of the charge and discharge processes of adsorbed natural gas (ANG) storage system for understanding the behaviors of natural gas in ANG vessel.     

Effects of fillers on the hydrogen uptake and volume expansion of acrylonitrile butadiene rubber composites exposed to high pressure hydrogen: -Property of polymeric materials for high pressure hydrogen devices (3)-

To develop sealing materials for high-pressure hydrogen devices, the effects of filler type and amount on the hydrogen uptake and volume expansion of rubber composites were evaluated up to 90 MPa. The amount of hydrogen in the rubber matrix and carbon black was elucidated using nuclear magnetic resonance, and the hydrogen elimination behavior of the composites was analyzed by thermal desorption analyses. As hydrogen physically adsorbed on carbon black, the hydrogen uptake of carbon black-filled composites increased. The hydrogen uptake of the composites filled with nonabsorbent silica was smaller, depending on the weight fraction of silica. The ratio of volume expansion to the amount of hydrogen in the matrix of carbon black-filled composites was suppressed by the reinforcement effect of carbon black, which did not expand with hydrogen uptake. The suppression of silica-filled composites was limited by the volume fraction of silica.     

Electrochemical properties of Mg-based hydrogen storage materials modified with carbonaceous materials prepared by hydriding combustion synthesis and subsequent mechanical milling (HCS + MM)

Mg₂Ni-based hydride was prepared by hydriding combustion synthesis (HCS), and subsequently modified with various carbonaceous materials including graphite, multi-walled carbon nanotubes (MWCNTs), carbon aerogels (CAs) and carbon nanofibers (CNFs) by mechanical milling (MM) for 5 h. The structural properties of the modified hydrides were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). All of the modified hydrides show amorphous or nanocrystalline-like phases. The hydride modified with graphite exhibits the most homogenous distribution of particles and the smallest particle size. The effects of the modifications on electrochemical properties of the hydride were investigated by galvanostatic charge/discharge, linear polarization, Tafel polarization, electrochemical impedance spectroscopy and potentiostatic discharge measurements. The results show that the maximum discharge capacity, the high rate dischargeability (HRD), the exchange current density and the hydrogen diffusion ability of the hydride modified with the carbonaceous materials are all increased. Especially, the hydride modified with graphite possesses the highest discharge capacity of 531 mAh/g and the best electrochemical kinetics property.     

A direct method to determine transfer function parameters in case of hydrogen evolution reaction

Electrochemical impedance spectroscopy is one of the efficient methods for studying reaction mechanisms. In case of hydrogen evolution reaction, the transfer function involved is very complex. It is therefore usually obtained through indirect methods. First, a simple equivalent circuit is usually fitted to the experimental data using complex non-linear least square methods. The circuit parameters thus obtained are then transformed to transfer function parameters. In the present approach, the procedure for obtaining transfer function has been simplified through its piecewise definition in various frequency ranges. A direct method to obtain transfer function using asymptotic analysis has been presented. The method to reduce error involved in the analysis has also been discussed. It has been shown that the approach will also be applicable for other systems.     

Preparation and characterization of carbonaceous materials containing nitrogen as electrochemical capacitor

Carbonaceous materials containing nitrogen (C/N materials) were prepared by a pyrolysis of 2,3,6,7-tetracyano-1,4,5,8-tetraazanaphthalene (CAN). A C/N material prepared by the pyrolysis of CAN at 1070 K (CAN-1070 K) had a C/N atomic ratio of 3.0 and a non-crystalline carbonaceous structure with a BET surface area of 880 m² g⁻¹. The material CAN-1070 K showed large capacitances of 160–180 F g⁻¹ and 110–120 F cm⁻³ in case of current density of 10 mA cm⁻² (2 A g⁻¹) by using three-electrode cell in 1 M H₂SO₄ aqueous solution, in comparison with that of activated carbon (160 F g⁻¹ and 55 F cm⁻³) having BET surface area of 2300 m² g⁻¹. ESCA study indicated that pyridinic and quarternary nitrogen atoms existed in the C/N materials, which could result in producing a pseudo-capacitance in addition to the electric double layer capacitance. Also introduction of nitrogen into the carbonaceous material could enhance the wettability of material, which might also improve the capacitance.