The following materials are used for preparing GO using improved Hummer’s Method in order to get the high C/O ratio.

· Graphite flakes—(Luba Cheme, extra pure 99.5%, 50 µm average sizes, bulk density 20 - 30 gm/100 ml).

· Sulphuric Acid (H₂SO₄)—(MERCK, 98% concentration, density 1.84 Kg/L).

· Phosphoric Acid (H₃PO₄)—(MERCK, 88% concentration, density 1.75 Kg/L).

· Potassium Permanganate (KMnO₄)—(MERCK, 99% purity).

· Hydrogen Peroxide (H₂O₂)—(MERCK, 30% concentration).

· Hydrochloric Acid (HCl)—(MERCK-35% concentration, density 1.18 Kg/L).

· Ethanol (C₂H₅OH)—(MERCK, 99.9% purity, density 0.79 Kg/L).

· Distilled water.

The steps involved in this method are:

· 360 ml H₂SO₄ (98%) and 40 ml H₃PO₄ (88%) were taken in a beaker (Volume ratio of 9:1).

· Graphite powder was added into the acid mixture and stirred for 15 minutes with the help of a hot plate having rpm of 600 - 650.

· After that 18 gm KMnO₄ was added very slowly (time ≈ 5 minutes) to the above mixture by stirring. This reaction is exothermic in nature so the temperature was seen to increase abruptly to 60˚C. So addition of KMnO₄ was done very cautiously.

· The above mixture was stirred for 15 min and temperature was noted. When temperature decreased to 50˚C, a hot plate was used to maintain the mixture temperature 55˚C - 60˚C for 7 - 8 hours.

· The said temperature should be maintained throughout the reaction, after completion of reaction 400 ml cold water (10˚C - 15˚C) was added into the mixture.

· Then 6 ml H₂O₂ (30%) was added and the mixture was kept on ice bath overnight.

· Next day yellowish coloured GO was precipitated. The clear solvent was discarded slowly by siphon.

· In order to wash the GO slurry, 400 ml HCl solution (35%) was added and the mixture was allowed for GO to precipitate.

· After 3 hours GO further precipitated, and was separated by siphon.

· After successive stages of washing with HCl solution, 200 ml of ethanol was added for the coagulation of the material.

· After 4 hours the clear liquid was separated and thick GO slurry was taken.

· Then GO slurry was filtered by filter paper.

· The wet GO was scraped from filter paper and dried in a vacuum oven at 90˚C for 4 hours.

· Thus the dried GO was cooled and kept in sample bottle.

The steps involved during the preparation of GO-Pd nanocomposite by Birch method are listed out bellow

· In a beaker 35 mg GO was taken, after that 40 ml distilled water was added to it. Then the mixture was sonicated for 1 hour.

· After that K₂PdCl₄ (20 mg) was taken in a small beaker and 10 ml distilled water was added to it. The mixture was added to the previous mixture and sonicated for 1 - 1.5 hour.

· 1 ml NH₄OH was added drop wise to the mixture and stirred for 30 minutes.

· Then the solution was put into a 50 ml teflon autoclave at a temperature of 140˚C for 24 hour to form dry GO-Pd nanocomposite.

· Hydrogenation of GO-Pd was carried out by using Benkeser reaction [21]. The reaction was carried out under argon atmosphere.

· Sixty milligrams GO-Pd and 80 ml ethylene diamine (C₂H₈N₂, 99% purity) were mixed in a flask. The mixture was stirred for 20 min under argon atmosphere in a closed flask.

· Then, 200 mg lithium (Luba Chemical, 99% purity) pieces were added to it, and the colour changed to blue. After that, 5 ml, tert-Butanol (98% purity) was added drop wise to the mixture and stirred for 6 hour at room temperature.

· The resulting dark solution was diluted by adding 60 ml ethanol. Then, it was filtered by Whatman filter paper.

· Filtered hydrogenated GO-Pd (H-GO-Pd) was washed with ethanol, acetone, and deionized water. The product was dried in a vacuum oven at 80˚C overnight to obtain hydrogen functionalized GO-Pd composite.

X-ray diffraction (XRD, BRUKER D8 Advance) spectras were obtained by using Cu-Kα radiation (l 1/4 1.5418˚A) in the range of 5˚ - 90˚ with a scanning speed of 5 min⁻¹. Scanning Electron microscopy (SEM) images were obtained using A JEOL JEM 2100 (JEOL KOREA LTD., Seoul, Korea) at voltage of 200 kV. Fourier transformation infrared spectra were recorded on an IR Affinity-1 and IR Prestige-21 FTIR Spectrometer (Shimadzu, Chiyoda-Ku, Tokyo, Japan). The samples were compressed into a pellet with KBr. The surface structure parameters were calculated from the N₂ adsorption/desorption isotherms, which were obtained using an automated surface area analyser [5]. A standard BET sample holder was used to hold the GO-Pd and hydrogenated GO-Pd nanocomposites. Total weight of the sample during analysis was 0.04 gm. The samples were first out gassed at 150˚C for 2.5 hours under vacuum and then the isotherm is measured over the relative pressure (P/P₀). Thermogravimetric analyses (TGA) were carried out on Pyris Diamond TG/ DTA (Perkin Elmer, Singapore). The sample was heated from 32˚C to 1000˚C with a rate of heating 15˚C/min under nitrogen atmosphere (circulation rate 150 ml/min). Platinum crucible was used with alpha alumina powder as reference.

The crystalline structure of synthesized GO, GO-Pd, and hydrogenated GO-Pd were studied by analysing XRD patterns. The synthesized GO has a sharp intensity peak at 2θ value of 10.4˚ corresponding to (001) plane as shown in Figure 3. The broadness of peak at 2θ value of 26.8˚ for both GO-Pd and hydrogenated GO-Pd in Figure 4 and Figure 5 is due to the increased disorder of the layers

present in the graphene oxide. In GO, GO-Pd and hydrogenated GO-Pd samples, the above-mentioned peaks are preserved in the same manner along with the prominent Pd peaks. This is an indication of the successful immobilization of Pd nanoparticles over GO-Pd matrix. The diffraction pattern of GO-Pd exhibited strong crystalline peak at 2θ value of 40.3, 46.7, 68.2 and 83.75˚ corresponding to the (111), (200), (220) and (311) planes of a face centred cubic structure of crystalline Pd and is in good agreement with the available literature [40]. Peak at 40.3˚ (111) for both Figure 4 and Figure 5 clearly indicates the nanostructured nature of the palladium particles. XRD pattern of hydrogenated GO-Pd is shown in Figure 5 and the peak at around 10.5˚ (001) confirms the presence of GO on the nanoparticles. The peak at 22.5˚ (111) shows the presence of lithium. The strongest peak appeared at 2θ = 40.44˚, showing that the Pd nanoparticles were embedded into the graphene sheets in the dominant (111) oriented plane. As evident from the XRD profile the peaks are gradually shortened as compared to the XRD profile of GO-Pd nanoparticles. So it shows the Pd particles are adsorbed on the surface of GO.

The decoration of the surface of the graphene sheets by palladium nanoparticles was discussed by FTIR spectroscopy and also FTIR gives the idea about the chemical bonding of the samples. Figure 6 shows the FTIR spectra of GO-Pd and hydrogenated GO-Pd. It clearly shows the attachment of different functional groups to the GO-Pd nanoparticles after hydrogenation. FTIR spectrum revealed that the GO-Pd nanoparticles contain several functional groups like; −OH bending at 3436 cm⁻¹, C=C (1370 cm⁻¹) and C=O carbonyl stretching at 1630 cm⁻¹ [41]. Therefore it has a strong tendency to readily interact with metal ions by hydroxyl and carboxyl group. A peak can be seen around at 3436 cm⁻¹ which shows the stretching mode of O-H, the peak at wave number 3600 cm⁻¹ on hydrogenated GO-Pd as described as the O-H stretching of hydroxyl group that may come from the adsorbed solvents like ethanol and water. On GO-Pd the peaks at 2923 cm⁻¹ and 2859 cm⁻¹ are due to asymmetric and symmetric stretching of C-H bonds. The peak at 1631cm⁻¹ in H-GO-Pd can be attributed to stretching modes of −CO group, the peaks at the wave numbers 1395 cm⁻¹ and 1475 cm⁻¹ indicate the aromatic C=C stretching. Fourier transformation infrared

spectroscopy of hydrogenated GO-Pd shows different aromatic sp³ (C−H) stretching at ortho, meta and para positions. Peak at 824 cm⁻¹ wave number is responsible for C−H stretching for para position, peak at 1002 cm⁻¹ designates C−H bond in ortho position and 729 cm⁻¹ peak is the signature of C−H stretching in meta position. It can be observed from FTIR analysis that hydrogen adsorption occurred at all the ortho, meta, and para positions of aromatic graphene. A peak at 621 cm⁻¹ was signified the formation of Pd-O bond. It is well recognized that the GO-Pd bonding can be formed through some physical/chemical interactions such as Vander Waals force, H-bonding and other bonds. Pd atoms may possibly react with the −OH and −COOH groups on the functionalized GO and thus the bonding C−O−Pd or O=C−O−Pd might form through a dehydration reaction.

Surface areas are commonly reported as BET surface areas and pore size distribution of GO-Pd and hydrogenated GO-Pd samples are obtained by applying the theory of Brunauer, Emmett, and Teller. Nitrogen adsorption isotherms measured at 77˚ K are shown in the Figure 7. Nitrogen at 77˚ K is considered to be a standard adsorbent for surface area and pore size analysis. The isotherms shown in Figure 7 follows type-IV curve which indicates the presence of mesoporous material in these samples. This type of isotherm was observed for all of the samples and at approximately P/P₀ ~ 0.65, there is a hysteresis occurred that indicates the presence of small mesopores in the prepared nanocomposites [42]. The “C” parameter is a measure of the strength of the interaction of the adsorbate (N₂) with the surface and the higher the C parameter, the sharper the “knee point” in the early part of the isotherm at low P/P₀ [43] [44]. The value of

C for Nitrogen adsorption at 77˚ K for hydrogenated GO-Pd is 128.502.

The BET plot of GO-Pd and hydrogenated GO-Pd are shown in the Figure 8 and Figure 9 and the distribution indicates the presence of mesopores (2 - 50 nm), which makes the material as a unique gas adsorbing medium. GO-Pd sample has less mesopores and smaller pore volume, because some mesopores were blocked with Pd or other chemical reactions in the process of Pd-NPs decoration and the subsequent reduction. Because of this reason, the BET surface area of hydrogenated GO-Pd is 14.037 m²/g and it is less compared to GO-Pd surface

area which is 27.136 m²/g. In Figure 10 and Figure 11 which is the pore size distribution of GO-Pd and hydrogenated GO-Pd, we have found from Barrett-Joyner-Halenda (BJH) analysis that the pore volume of GO-Pd is 0.023 cc/g as compared to 0.009 cc/g for hydrogenated GO-Pd. This contraction of pore volume indicates that hydrogen is filled in the pore after hydrogenation of GO-Pd nanoparticles. Hydrogen isotherms at 77˚ K show that capacities at very low temperature are associated with the surface area of the materials [45]. The activity of the palladium at 77˚ K is very weak because the kinetics of the adsorption process is extremely slow, and thus, the total capacity is mainly due to the

physical adsorption. The adsorption of hydrogen in the palladium structure is a quite complicated process that involves, first, dissolution of hydrogen in palladium and, second, formation of the palladium hydride [9] [45]. As the temperature increases, physical adsorption becomes weaker and the activity of palladium increases because the accommodation of hydrogen in the palladium crystalline network becomes faster.

For analysing the morphological characteristics of the composite we have done SEM characterization of samples. Figure 12 shows SEM images of GO-Pd and hydrogenated GO-Pd. The quality of dispersion of Pd particles in the graphene matrix significantly influences the hydrogen storage in the nanocomposite [46]. We optimized the distribution of particles, and Figure 12 exhibits the morphologies of the Pd/graphene oxide nanocomposites. Figure 12 shows uniform distribution of palladium particles on graphene oxide sheets and it signifies that palladium is uniformly mixed and spread across the graphene oxide. But after hydrogenation the morphology of GO-Pd nanoparticles are changed and the distribution of palladium is not uniform on the surface of graphene oxide sheet because palladium forms a cluster form with graphene oxide. The significant decrease of the Pd particle size in the nanocomposite could be related to an enhanced dispersion and lower mobility of Pd particles in the graphene substrate [21] [37] [46]. The particles could have bonded to the edges, defects, and functional groups on the surface of graphene. This interaction may have further stabilized the Pd nanoparticles and effectively prevented the particle aggregation on the graphene surface.

Thermogravimetric analysis gives the details about this thermal instability of the

chemical bonding. TGA is the useful tool to estimate the amount of functional groups attached to the graphene [21]. Figure 13 shows the TGA curves of GO-Pd and hydrogenated GO-Pd.

In Figure 13 we have shown that the reduction of wt% occurs with increasing temperature. For both GO-Pd and hydrogenated GO-Pd mass reduction occurs from temperature of 20˚C. As boiling point of ammonia solution is 24.7˚C the reduction starts below this temperature for both GO-Pd and hydrogenated GO-Pd. For GO-Pd the plot shows reduction of mass occurs from 20˚C to 200˚C due to the vaporisation of impure solvents which is remaining in the materials such as tert-Butanol having boiling point 83˚C, ethanol having boiling point 78.37˚C, acetone having boiling point 56˚C and hydrogen peroxide having boiling point 150.2˚C. For hydrogenated GO-Pd nanocomposite the reduction of mass is more compared to GO-Pd nanocomposite in the temperature range 20˚C to 200˚C. Here in hydrogenated GO-Pd the reduction of mass occurs at four different steps, 1) from 20˚C to 150˚C as shown. Most of the mass reduced due to the vaporisation of remaining solvents present in the composites such as ethanol, tert-Butanol, ethylene diamine, water, acetone, hydrogen peroxide and ammonia solution, 2) from 150˚C to 200˚C some mass reduction occurs which is also due to the remaining solvent which is adsorbed by palladium nanoparticles as shown in the Figure 13, 3) from 200˚C - 350˚C the weight reduction occurs due to the physically adsorbed hydrogen which is attached to the subsurface Pd atoms in the hydrogenated GO-Pd composites, this physically adsorbed hydrogen which is attached to Pd atoms with a weak Vander Waal’s force is released when the temperature reaches above 200˚C, 4) from 350˚C to 630˚C the weight reduction occurs due to the chemisorption of hydrogen to the GO-Pd

nanocomposites and here in this temperature range C-H bond starts to break as the bond energy of C=C stretching (614 KJ/mol) is more than C−H stretching (413 KJ/mol), more energy (heat or temperature) is required to break the C=C bond than C−H bond [47]. After 630˚C onwards C=C bonds starts to break which is not necessary for our purpose.

For H-GO-Pd at 200˚C weight loss is 68.25% and at 350˚C weight loss is 81.48%, this reduction of weight is the release of physically adsorbed hydrogen which is attached to the palladium surface by weak Vander wall’s force. In between 350˚C to 630˚C the weight changes 18.52% to 14.4% and this reduction of weight is due to the release of hydrogen gas which occurs due to the breakage of C-H covalent bond that is formed during the hydrogenation of GO-Pd nanocomposites.

From TGA analysis we have found that hydrogen is released in the temperature range of 200˚C to 630˚C in two phases. First phase is from 200˚C - 350˚C; which is due to the physiosorption. Second phase is from 350˚C - 630˚C; which is due to chemically adsorbed hydrogen. So the total amount of hydrogen stored in the nanocomposite is 17.35%.

Figure 14 shows a comparative analysis of hydrogen storage (wt %) ability of GO-Pd composite estimated from the present study with the reported values of hydrogen storage in literatures. It is observed that hydrogenation of GO-Pd by employing Benkeser reaction results in considerably higher value of hydrogen storage (17.35%) than the reported values of hydrogen storage on graphene using chemisorption and physiosorption processes. Maximum percent storage reported in the literature employing graphene oxide is 7.7% [21] [27]. This study also reveals that the weight percent hydrogen, chemisorbed on GO-Pd through Benkeser reaction is almost 2.5 times than the weight percent hydrogen adsorbed on graphene oxide under the similar conditions.