Advances in materials process and separation mechanism of the membrane towards hydrogen separation

The increased demand for a reliable and sustainable renewable energy source encourages the hydrogen-based economy. For the same, membrane separation approaches were reviewed as an advantageous process over contemporary techniques due to the environmentally friendly nature, economically viable pathway, and easily adaptable technology. A comprehensive assessment for the advancements in the type of membranes namely, polymeric and mixed matrix membranes (MMMs) has been delineated in the present article with the fabrication methodologies and associated mechanism for hydrogen separation. In hydrogen separation mechanism of the membrane, depends on the morphology of the membrane (dense or porous). The existence of pores in membranes offers various gas transport mechanisms such as Knudsen diffusion, surface diffusion, capillary condensation, molecular sieving mechanisms were observed, depending on the pore size of membranes and in dense membrane gas transport through the solution-diffusion mechanism. In polymer membrane, hydrogen separation occurs mainly due to solubility and diffusivity of gases. The hydrogen separation mechanism in MMMs is very complex due to the combining effect of polymer and inorganic fillers. So, the gas separation performance of MMMs was evaluated using the modified Maxwell model. Moreover, adequate polymeric material and inorganic fillers have been summarised for MMMs synthesis and highlighting the mechanism for gas transport phenomena in the process. Several types of materials implemented with polymeric matrix examined in the literature, amongst these functionally aligned CNTs with Pd-nanoparticles dispersed in polymer matrix were observed to reveal the best outcome for the hydrogen separation membrane due to the uniform distribution of inorganic material in the matrix. Henceforth, the agglomeration gets reduced promoting hydrogen separation.     

Sorption properties of hydrogen-selective PDMS/zeolite 4A mixed matrix membrane

The present study explores the fundamental science of estimating sorption of gases in membranes comprised of inorganic porous fillers within a polymer matrix with a novel semi-empirical correlation. The sorption properties of H₂, C₃H₈, CO₂ and CH₄ were determined in polydimethylsiloxane (PDMS)/zeolite 4A mixed matrix membranes (MMMs) to assess the viability of these membranes for hydrogen purification and natural gas sweetening. Zeolite filling in MMMs results an increase in solubility over neat PDMS membrane. In addition, incorporation of zeolite 4A to PDMS membrane improved H₂ permeation and H₂/CH₄ selectivity. The results confirmed that zeolite 4A can significantly improve the separation properties of poorly H₂-selective PDMS membrane from 0.7 up to 11 and this overcomes the Robeson upper-bound limitation. This improvement was explained referring the Flory–Huggins interaction parameter within MMMs.     

Selective storage and evolution of hydrogen on nafion/NaCl/graphene quantum dot mixed matrix using tensammetry as power electrochemical technique

Hydrogen storage/evolution behavior of nafion/NaCl/graphene quantum dot (GQD) mixed matrix as selective hydrogen capacitor (power source) was evaluated in detail through an electrochemical process at two independent potential ranges. For this purpose, a three-electrode system included Pt disk as counter electrode, Ag/AgCl as reference electrode and GQD-based mixed matrix-modified Pt disk as working electrode. For hydrogen storage, the deposition potential and time were evaluated to ?1.0 V (vs. Ag/AgCl) and 120 s, respectively under high basic solution generated using NaOH (1.0 M) solution, followed by evolution of hydrogen at +0.8 V (vs. Ag/AgCl) during formation of hydrogen bubbles. The main advantage of this system was the occurrence of hydrogen storage and evolution at two independent potential windows. Both mass transfer and adsorption processes were estimated for the tensammetric peak during the evolution step. The mechanism of hydrogen storage and evolution was obeyed from diffusion and tensammetry, respectively. According to Randles–Sevcik equation using 1.0 mM ${{\text{Fe}\left(\text{CN}\right)}_6}^{3?/4?}$, the active surface area of nafion/NaCl/GQD mixed matrix was ～1906 m²g^?1. Based on the CHN analyses, pressure-concentration temperature as well as hydrogen temperature-programmed desorption, the capacity of the synthesized GQDs for hydrogen storage and evolution was estimated to at least 10.1 and 8.6 wt%, respectively. The stability of the electrode was also estimated during 7000s by chronoamperometry during applying at least 40 cycles in the range from ?1.0 to +1.3 V with reproducible tensammetric peak current (relative standard deviation: 2.54%).     

Synthesis and characterization of transition metal mixed oxide doped graphene embedded durable electrocatalyst for hydrogen evolution reaction

A promising electrocatalyst containing variable percentage of V₂O₅–TiO₂ mixed oxide in graphene oxide support was prepared by embedding the catalyst on Cu substrate through facile electroless Ni–Co–P plating for hydrogen evolution reaction. The solvothermal decomposition method was opted for tuning the crystalline characteristics of prepared material. The optimized mixed oxide was well characterized, active sites centres were identified and explained by X-ray diffraction, high resolution tunnelling electron microscopy, scanning electron microscopy coupled with energy dispersive X-ray and X-ray photon spectroscopy analysis. The structural and electronic characteristics of material was done by fourier transform infrared spectroscopy and the electrochemical behaviour of the prepared material was evaluated by using Tafel plot, electrochemical impedance analysis, linear sweep voltammetry, open circuit analysis and chronoamperometry measurements. The results show the enhanced catalytic activity of Ni–Co–P than pure Ni–P plate, due to synergic effect. Moreover, the prepared mixed oxide incorporated Ni–Co–P plate has a high activity towards HER with low over potential of 101 mV, low Tafel slope of 36 mVdec^?1, high exchange current density of 9.90 × 10^?2 Acm^?2.     

Graphene oxide modified non-noble metal electrode for alkaline anion exchange membrane water electrolyzers

This paper reports the performance of a graphene oxide modified non noble metal based electrode in alkaline anion exchange water electrolyzer. The electrolytic cell was fabricated using a polystyrene based anion exchange membrane and a ternary alloy electrode of Ni as cathode and oxidized Ni electrode coated with graphene oxide as anode. The electrochemical activity of the graphene oxide modified electrode was higher than the uncoated electrode. The anion exchange membrane water electrolyzer (AEMWE) with the modified electrode gave 50% higher current density at 30 °C with deionised water compared to that of an uncoated electrode at 2 V. Performance was found to increase with increase in temperature and with the use of alkaline solutions. The results of the solid state water electrolysis cell are promising method of producing low cost hydrogen.     

Experimental and theoretical studies of hydrogen generation by binary metal (oxide)-graphene oxide composite materials

Theoretical and experimental studies with focuse on hydrogen generation through the hydrolysis of graphene oxide (GO) functionalized with magnesium (GOMg), titanium (GOTi), and niobium (GONb) were performed. Thermogravimetric (TGA) results reveal variable thermal decomposition profiles for the composites, in agreement with the decomposition of the labile oxygenated groups of GO. X-ray photoelectron spectroscopy (XPS) results show variable oxygen content (%) for the composites and the formation of MgO, TiO₂, and NbO₂ layers on the GO surface. The hydrogen generation studies suggest that the formation of a Mg(OH)₂ layer on the GO surface is a critical limiting factor for the hydrolysis of GOMg, whereas TiO₂ and NbO₂ catalyze the hydrolysis of GONb and GOTi. The hydrogen generation results reveal that GONb produced the highest H₂ yield of 2 L in 2 h compared to 1.5 L for GOTi and 1.3 L for GOMg. The results support the claim that the hydrolysis of GO functionalized with niobium and titanium are promising candidates for on-board H₂ generation applications.     

Gas sorption in H2-selective mixed matrix membranes: Experimental and neural network modeling

Robust artificial neural network (ANN) was developed to forecast sorption of gases in membranes comprised of porous nanoparticles dispersed homogenously within polymer matrix. The main purpose of this study was to predict sorption of light gases (H₂, CH₄, CO₂) within mixed matrix membranes (MMMs) as function of critical temperature, nanoparticles loading and upstream pressure. Collected data were distributed into three portions of training (70%), validation (19%), and testing (11%). The optimum network structure was determined by trial-error method (4:6:2:1) and was applied for modeling the gas sorption. The prediction results were remarkably agreed with the experimental data with MSE of 0.00005 and correlation coefficient of 0.9994.     

Study of deep oxidation and sulfonation of graphene oxide as low-temperature fuel cell electrolyte

In order improve the fuel cell performance of a free-standing graphene oxide (GO) membrane, the impacts of both the additional oxidation of GO and the modification with vinilsulfonic acid were investigated. The modification with vinilsulfonic acid was conducted with and without adding potassium persulfate, K₂S₂O₈, which is a radical initiator for the polymerization of vinylsulfonate. A total of six types of free-standing GO membranes with and without the oxidation and/or the modification were prepared. The oxidation and the modification additively increased the proton conductivity, and the oxidation significantly improved the durability of the fuel cell performance at 30 °C. The membrane of GOhvsi, of which GO was oxidized and modified with the initiator, showed very high in-plane proton conductivities at 30 °C, i.e., 0.54 S cm^?1 at RH 100%. The H₂–O₂ fuel cell using GOhvsi showed maximum power densities as high as 136 mW cm^?2 and 184 mW cm^?2 at 30 °C and 50 °C, respectively. The performance at 30 °C was stable for more than 20 h. The improved durability by the oxidation was attributed to the increased defects of carbon based on an XPS analysis. The TPD-MS analysis suggested that the oxygenated functional groups at the defects would increase the binding strength.     

The evaluation of methane mixed reforming reaction in an industrial membrane reformer for hydrogen production

In this work, the performance of an industrial dense PdAg membrane reformer for hydrogen production with methane mixed reforming reaction was evaluated. The rate parameters of mixed reforming reaction on a Ni based catalyst optimized by using the experimental results. One-dimensional models have been considered to model the steam reforming industrial membrane reformer (SRIMR) and mixed reforming industrial membrane reformer (MRIMR). The models are validated by experimental data.The proficiency of MRIMR and SRIMR at similar conditions used as a basis of comparison in terms of temperature, methane conversion, hydrogen yield, syngas production rate and CO₂ flow rate. Results revealed that the methane conversion, hydrogen yield and syngas production rate in MRIMR is considerably higher than SRIMR. Furthermore, the operation temperature of MRIMR could be 195 °C lower than that for SRIMR. This would contribute to a major decrease in process costs as well as a reduction in catalyst sintering. On the other hand, although MRIMR consumes CO₂, the exited CO₂ flow rate at the SRIMR is three times more than that of at the MRIMR, which is a main advantage of MRIMR from the environmental issues point of view.     

Ru–Ni/GA-MMO composites as highly active catalysts for CO selective methanation in H2-rich gases

CO selective methanation (CO-SMET) is as an ideal H₂-rich gases purification measurement for proton exchange membrane fuel cell system. Herein, the graphene aerogel-mixed metal oxide (GA-MMO) supported Ru–Ni bimetallic catalysts are exploited for CO-SMET in H₂-rich gases. The results reveal that a three-dimensional network structure GA-MMO aerogel with higher specific surface area, better thermal stability and more defects or structural disorders is formed when MMO:GO mass ratio is in the range of 1–4. After loading of Ru, more NiO are reduced to metallic Ni by hydrogen spillover effect, and thus obviously enhances the reactivity. The GA-MMO supported Ru–Ni catalyst exhibits more excellent metal dispersion, reducibility, stronger CO adsorption and activation than the MMO supported Ru–Ni catalyst, thereby resulting in better catalytic performance and stability. This work offers new insights into the construction of highly active catalyst for the efficient generation of high-quality H₂ from H₂-rich gases.