Role of Annealing Temperature on Improving the Hydrogen Storage Capacity of Copper Nano-Particles Decorated Carbon Nano Materials Synthesized from Sugarcane Bagasse

Abstract

This study focuses on improving hydrogen storage capacity of Carbon Nano Materials (CNMs) by investigating the role of annealing temperature for the synthesis of Copper Nano-Particles (CuNPs) decorated CNMs synthesized from sugarcane bagasse (SCB). SCB was pyrolyzed at around 750°C in an inert medium. Pyrolyzed carbon thus obtained was activated by alkali. These activated carbons were then decorated with CuNPs by annealing at different temperatures in CO2 atmosphere. The CNMs thus synthesized were characterized using XRD and Raman spectroscopic analysis to elucidate the structural intervention with particle size and defects respectively, while EDAX and ICP-AES were utilized to quantify the amount of copper deposited. SEM analysis depicts the porous morphology being decorated with spherical copper nanoparticles. Hydrogen Storage capacity was explored using Sievert’s apparatus. Pore volumes of CNMs synthesized at different annealing temperature were determined from adsorption isotherm co-relating it with hydrogen adsorption observation from Sievert’s apparatus for evaluating better hydrogen storage.

Introduction

I. INTRODUCTION

Non-renewable fossil fuel source like Petroleum and petrochemicals are depleting day by day generating hazardous emission that adversely affect environment [1]. Multitude of research work is under way to generate sustainable and environment friendly fuel sources that can be generated at competitive costs to current petroleum sources [2] [3].

Hydrogen being one of the most abundant elements on the planet proves to be a sustainable and promising alternative fuel, generating significant energy and water as an emission products [4]. Hydrogen has a unique capability of either driving the IC engines, thus utilising the existing established machinery to be used with minor modifications [5], or being able to generate electricity through the hydrogen fuel cells [6], both generating energy in most desired form without generating hazardous wastes [7]. This makes hydrogen a safe, versatile, and convenient fuel source [8].

The bottle neck in utilizing hydrogen as a fuel lies in its storage [9]. Hydrogen being gas, it must be compressed and stored under pressure cylinders to achieve desired energy density. It is unsafe to use high pressure containers for utilising hydrogen as mobility fuel [10], considering it’s spontaneous and highly exothermic oxidation reaction with abundantly available atmospheric oxygen.

Gas adsorption can control the dispersion of gas, thus limiting the threat of chain reaction and making the explosive gas safe to handle. Chemisorption and physisorption are the two possible means that can serve better hydrogen storage in various materials. Physisorption holds the multiple layers of gas with week Van der wall forces that can be easily reversed to generate hydrogen in less energy expense on demand. Hence it is desirous to generate the micro-porous materials with higher affinity for hydrogen physisorption [11].

Carbon nano material (CNM) provides good mechanical strength and is known to adsorb hydrogen in multiple layers. However, the cost of materials for hydrogen storage may surpass the benefits of usage of hydrogen as fuel considering economics. Hence it is desirous to generate CNMs from the renewable and inexpensive sources that have good multilayer hydrogen physisorption properties and excellent mechanical strength to withstand harsh conditions and store sufficient amount of hydrogen under pressurised conditions [12].

The hydrogen storage capacity of Nano-material of 6.5 wt% for its commercialisation as energy source is proposed by US-DOE (Department of energy). The US-DOE has directed the researcher in this field to target its vehicle storage capacity as 5.5 wt% in 2020 [13].

The current research work is motivated to generate the CNMs from plant waste, sugarcane bagasse (SCB) and its further modification for greater hydrogen physisorption for hydrogen storage. SCB was subjected to pyrolysis at elevated temperatures of 750°C to generate porous CNMs with excellent mechanical strength which was decorated with CuNPs to enhance hydrogen storage capacity of the CNM thus developed.

II. EXPERIMENTAL TECHNIQUE

A. Synthesis of CuNPs Decorated CNM

SCB was pyrolyzed in Lindberg horizontal tube furnace at 750? in an inert atmosphere. The as-obtained carbon was further activated by treating it with alkali solutions. The activated carbon was then loaded with copper particles and annealed in the presence of carbon dioxide (CO2) to get highly porous carbon nanomaterial which was studied for hydrogen adsorption properties using the Sievert’s apparatus [16][17].

B. Hydrogen Adsorption by Sievert’s Apparatus

Adsorption of hydrogen was studied by Sievert’s apparatus at a pressure of 60 bars at ambient temperature using Van der Waals real gas equation [18]. 5g of CNM samples were loaded in a sample holder of Sievert’s apparatus whose observations are tabulated in below Table I.

TABLE I: HYDROGEN ADSORPTION BY CNMS ANNEALED AT DIFFERENT TEMPERATURE

III. RESULTS AND DISCUSSIONS

A.  XRD Analysis of CNMs

The CNMs were subjected to X-Rays Diffraction (XRD) analysis using Malvern Panalytical's Empyrean diffractometer having X-ray tube with Cu target of wavelength as Cu Kα-1.54184 Å and X-ray generator of 45kV & 40mA. XRD diffraction peaks were obtained in continuous scanning mode with a scanning range of Diffraction angle (2θ) as 10–90°.

TABLE II: PEAK TABLE OF XRD ANALYSIS OF CNMs

The results are depicted in Fig. I and Fig. II and Table II. The observed values of diffraction angles are in good agreement with standard values of CuNPs in JCPDS file. No. 04-0836. Reflection Planes observed from diffraction spectra as mentioned in the Table II indicate FCC structure of copper particles [19]. From the ICDD card No. 00-056-0159, The broad humps in the spectra in the lower range at 22.18° & 21.76° diffraction angle of D6 & D9 respectively indicate amorphous phase due to reduced Graphene Oxide (rGO) with further confirmation of broad and week intensity peak at 43° diffraction angle which are deconvulated from CuNPs merging peak in both carbon material [18][19][20].

Further, Full width at half maximum (FWHM) of peak was used to calculate particle size of CuNPs for both materials using Debye Scherer’s equation [18]. Particle size of CuNPs in D6 is in the range of 12.2 to 14.3 nm and that of D9 is 8.7 to 9.8 nm. It was observed that as the annealing temperature increases from 600°C to 700°C particle size of CuNPs decorated on CNMs decreases showing the annealing temperature effect. Thus XRD confirms Nano structure of the material which is further explored in SEM analysis.

B. SEM Analysis of CNMs

Scanning Electron Microscopy (SEM) provides crucial information regarding the morphology of the microstructures of the CNMs. These CNMs synthesised from SCB were subjected to SEM analysis using FEI Quanta 200 FEG SEM for elucidating the surface morphology and its correlation to annealing temperature. Fig. III shows spherical beads of CuNPs of size of 30-40 nm range decorated over the porous structure of CNMs in D6 sample while that of D9 in Fig. IV, the particle size of 20-30 nm observed thus showing the temperature effect.

Raman spectroscopic analysis results of both the material in above Fig. VII, Fig. VIII and Table IV elucidates two peaks at around 1329cm-1 and 1585cm-1 as D-band and G-band belonging to mixture of Distorted and graphitic sp2 carbon whose intensity and area ratio calculated as 0.81 for D6 and 0.84 for D9 confirms that the distorted sp2 carbon increases with the increase in annealing temperature during synthesis of CNMs from SCB [13][22]. Less intense Peak at 2334cm-1 and 2335cm-1 in D6 & D9 spectra respectively represents 2D band as a overtones of D band of sp2 graphitic carbon [23].

IV. ACKNOWLEDGEMENT

We sincerely express our gratitude to ICON LAB (Mumbai), SAIF (IIT Bombay) and SMART Instrument LAB (Thane) for carrying out the analysis and characterization of synthesized CNMs.

Conclusion

From all the above analysis, it can be concluded that with the increase in annealing temperature, ID/IG ratio of Raman spectra increases, indicating the increase in the defects in graphitic carbon while copper deposition on the porous carbon decreases along with the decrease of copper particle size. Pore Volume of CNM too decreases and hence hydrogen adsorption capacity decreases with increase in annealing temperature for the synthesis of CNMs from SCB. Decrease in hydrogen adsorption with decrease in copper deposition co-relates with the spill over effect of CuNPs [24] [25].

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Copyright

Copyright © 2023 Bholanath T. Mukherjee, Manoj D. Basutkar, Suyash S. Prasad. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.