Green synthesized N-doped graphitic carbon sheets coated carbon cloth as efficient metal free electrocatalyst for hydrogen evolution reaction

Jebakumar Immanuel Edison, Thomas Nesakumar,Atchudan, Raji,Karthik, Namachivayam,Lee, Yong Rok Elsevier 2017 INTERNATIONAL JOURNAL OF HYDROGEN ENERGY - Vol.42 No.21

<P><B>Abstract</B></P> <P>Heteroatom doped carbon structures received a great attention owing to its applications in catalysis, energy and optics. In this work, a simple hydrothermal approach for the synthesis of nitrogen doped graphitic carbon sheets (N-GCSs) is reported. <I>Rubus parvifolius</I> (<I>R. parvifolius</I>) fruit juice and aqueous ammonia are used as carbon precursor and nitrogen dopant, respectively. The synthesized N-GCSs are characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, high resolution transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM) coupled with energy dispersive spectrum (EDS). The presence of hydroxyl and carbonyl functionalities in the synthesized N-GCSs are confirmed by the FT-IR analysis. The doping of nitrogen in N-GCSs is revealed through the XPS spectrum. The XRD and Raman studies imply that the synthesized N-GCSs are moderate graphitic nature. The FE-SEM and HR-TEM images of N-GCSs exposed its sheet like porous morphology. The electrocatalytic activity of N-GCSs coated carbon cloth (N-GCSs/CC) are examined towards hydrogen evolution reaction (HER) in 0.50 M H<SUB>2</SUB>SO<SUB>4</SUB> using linear sweep voltammetry (LSV), Tafel and electrochemical impedance spectroscopy (EIS) studies. The onset potential of synthesized N-GCSs/CC is about −0.25 V<SUB>RHE</SUB>, which is lower than that of bare carbon cloth (CC) −0.75 V<SUB>RHE</SUB>. The Tafel slope of N-GCSs/CC is smaller (198 mV dec<SUP>−1</SUP>) than that of bare CC (253 mV dec<SUP>−1</SUP>), suggested fast kinetics of N-GCSs. Moreover, the N-GCSs/CC is attained −10 mA cm<SUP>−2</SUP> of current density at very low over potential of −0.320 V<SUB>RHE</SUB>. The EIS studies also proved the excellent catalytic activity of N-GCSs/CC towards HER. Thus, the <I>R. parvifolius</I> derived N-GCSs is a better candidate for HER in acidic medium.</P> <P><B>Highlights</B></P> <P> <UL> <LI> N-doped graphitic carbon sheets (N-GCSs) were prepared by <I>Rubus parvifolius</I> fruit. </LI> <LI> N-GCSs coated carbon cloth (CC) shows good electrocatalytic activity towards HER. </LI> <LI> The onset potential of N-GCSs/CC is about −0.25 V<SUB>RHE</SUB>. </LI> <LI> Tafel slope of N-GCSs/CC is smaller (198 mV dec<SUP>−1</SUP>) than bare CC. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Ultrasonic synthesis, characterization and energy applications of Ni–B alloy nanorods

Edison, Thomas Nesakumar Jebakumar Immanuel,Atchudan, Raji,Karthik, Namachivayam,Sethuraman, Mathur Gopalakrishnan,Lee, Yong Rok Elsevier 2017 Journal of the Taiwan Institute of Chemical Engine Vol.80 No.-

<P><B>Abstract</B></P> <P>Alloy nanostructures had received much attention for their applications in energy, catalysis, and optics. This paper described a facile ultrasonic approach for the synthesis of Ni–B alloy nanorods (Ni–B NRs). The crystallinity, chemical state, surface area and surface morphology of Ni–B NRs were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N<SUB>2</SUB> adsorption–desorption isotherms and high-resolution transmission electron microscopy (HR–TEM) analyses, respectively. The electrocatalytic behavior of Ni–B NRs toward the oxygen evolution reaction (OER) was studied by linear sweep voltammetry (LSV) and Tafel polarization methods in 0.1 M aqueous KOH. The LSV results of Ni–B NRs showed very low OER onset potential of 1.44 V<SUB>RHE</SUB> with an overpotential of 212 mV<SUB>RHE</SUB>. The Ni–B NRs attained 10 mA/cm<SUP>2</SUP> of current density at a very low potential of 1.61 V<SUB>RHE</SUB> than bare SS (1.87 V<SUB>RHE</SUB>) and bare Pt (2.50 V<SUB>RHE</SUB>). Further, Ni–B NRs showed a low Tafel slope of 45 mV/dec when compared to other standard materials, revealed the fast OER kinetics. The calculated specific capacitance of synthesized Ni–B NRs was 581 F/g, from the results of cyclic voltammetry at a scan rate of 2 mV/s. The electrocatalytic and supercapacitor studies exposed that the synthesized Ni–B NRs can be used as an electrocatalyst for OER as well as pseudocapacitor for commercial electric vehicles.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Amorphous Ni–B alloy nanorods (Ni–B NRs) are synthesized by ultrasonic method. </LI> <LI> Ni–B NRs shows excellent electrocatalytic activity toward OER than Ru and Ir. </LI> <LI> Ni–B NRs exhibit good pseudocapacitor behavior in aqueous KOH. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Direct electro-synthesis of MnO₂ nanoparticles over nickel foam from spent alkaline battery cathode and its supercapacitor performance

Edison, Thomas Nesakumar Jebakumar Immanuel,Atchudan, Raji,Karthik, Namachivayam,Xiong, Dangsheng,Lee, Yong Rok Elsevier 2019 JOURNAL- TAIWAN INSTITUTE OF CHEMICAL ENGINEERS Vol.97 No.-

<P><B>Abstract</B></P> <P>This work reports the recovery of manganese ions from spent primary alkaline battery (PAB) cathode, subsequent anodic electro-synthesis of MnO<SUB>2</SUB> nanoparticles on Ni foam (MnO<SUB>2</SUB> NPs/Ni foam) for supercapacitors. The as-fabricated MnO<SUB>2</SUB> NPs/Ni foam is characterized by common optical and surface analytical techniques. The X-ray diffraction (XRD) of MnO<SUB>2</SUB> NPs/Ni foam matches well with γ-MnO<SUB>2</SUB> NPs pattern and hence the synthesized MnO<SUB>2</SUB> NPs mainly exist in γ-phase. The synthesized MnO<SUB>2</SUB> NPs are mostly in spherical cluster shape with an average size of 15 nm, inferred from the scanning electron microscopic (SEM) images. The X-ray photoelectron spectroscopy (XPS) result reveals that, synthesized MnO<SUB>2</SUB> NPs embraces with two different oxidation states such as 4<SUP>+</SUP> (MnO<SUB>2</SUB>) and 3<SUP>+</SUP> (MnOOH). The MnO<SUB>2</SUB> NPs/Ni foam delivers a maximum specific capacity of 549 F/g at the scan rate of 5 mV/s in three electrodes aqueous K<SUB>2</SUB>SO<SUB>4</SUB> system. Further, the two electrode asymmetric supercapacitor device is constructed with MnO<SUB>2</SUB> NPs/Ni foam as a positive and commercial graphene nanoplatelets coated Ni foam (GNP/Ni foam) as a negative electrode. The assembled supercapacitor device yields a maximum specific capacitance of 105 F/g at 5 mV/s, which achieves a maximum energy density of 14.7 Wh/kg at the power density of 748.9 W/kg between 0 and 1.5 V of working potential. This effort may pave the way for recovery and utilization of spent PAB cathode materials for energy storage devices.</P> <P><B>Highlights</B></P> <P> <UL> <LI> This work presents simple method for the recovery and utilization of Mn<SUP>2+</SUP> from spent alkaline battery cathode. </LI> <LI> The average size of the MnO<SUB>2</SUB> NPs was about 15 nm with spherical cluster shape. </LI> <LI> The electro-synthesized MnO<SUB>2</SUB> NPs revealed good electrochemical performance in K<SUB>2</SUB>SO<SUB>4</SUB>. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Corrosion inhibition performance of spermidine on mild steel in acid media

Edison, Thomas Nesakumar Jebakumar Immanuel,Atchudan, Raji,Pugazhendhi, Arivalagan,Lee, Yong Rok,Sethuraman, Mathur Gopalakrishnan Elsevier 2018 Journal of molecular liquids Vol.264 No.-

<P><B>Abstract</B></P> <P>The corrosion inhibition and adsorption behavior of spermidine on mild steel (MS) in 1 M sulfuric and 0.50 M hydrochloric acid have been investigated at room temperature by electrochemical methods viz., electrochemical impedance spectroscopy (EIS) and Tafel polarization techniques. The adsorption of spermidine on MS is studied by Langmuir adsorption isotherm, Fourier transform infrared (FT-IR) spectroscopy and density functional theory (DFT) analysis. The Tafel results imply that, spermidine behaves mixed mode inhibitor and the corrosion inhibition efficiency increases with increasing of spermidine concentration. The EIS results exposed that, the formation of adsorptive layer of spermidine increase the charge transfer resistance and subsequent drop in the double layer capacitance of MS in acids. The calculated free energy of adsorption (ΔG) for spermidine in HCl and H<SUB>2</SUB>SO<SUB>4</SUB> are −31.92 and −30.48 kJ mol<SUP>−1</SUP> which suggested the physical along with chemical mode of adsorption of inhibitor. The formation of inhibitive protection layer on MS is confirmed by FT-IR spectroscopy. The correlation of corrosion inhibition performance and molecular structure of spermidine is discussed by DFT method. All the results showed that spermidine is an excellent corrosion inhibitor for MS in both H<SUB>2</SUB>SO<SUB>4</SUB> and HCl acids.</P> <P><B>Highlights</B></P> <P> <UL> <LI> The acid corrosion inhibition performance of spermidine on mild steel was evaluated. </LI> <LI> The spermidine act as mixed mode inhibitor revealed by Tafel studies. </LI> <LI> Spermidine adsorbed on mild steel and effectively retards corrosion. </LI> </UL> </P>

Facile synthesis of carbon encapsulated RuO₂ nanorods for supercapacitor and electrocatalytic hydrogen evolution reaction

Jebakumar Immanuel Edison, Thomas Nesakumar,Atchudan, Raji,Lee, Yong Rok Elsevier 2019 INTERNATIONAL JOURNAL OF HYDROGEN ENERGY - Vol.44 No.4

<P><B>Abstract</B></P> <P>In this work, carbon encapsulated RuO<SUB>2</SUB> nanorods (RuO<SUB>2</SUB> NRs/C) has been synthesized by thermolysis of ruthenium chloride and <I>Punica granatum</I> (<I>P. granatum</I>) peel under N<SUB>2</SUB> atmosphere. The synthesized RuO<SUB>2</SUB> NRs/C was characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction method (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM) with energy dispersive spectroscopy (EDS) analyses. The FT-IR results suggested that the organic constituents of <I>P. granatum</I> have been carbonized and encapsulated over RuO<SUB>2</SUB> nanorods (RuO<SUB>2</SUB> NRs). The XRD pattern of RuO<SUB>2</SUB> NRs/C revealed its crystalline nature and carbon encapsulation. The synthesized RuO<SUB>2</SUB> NRs/C has been well dispersed with the average width of 20 nm, exposed from the FE-SEM and HR-TEM images. The EDS results of RuO<SUB>2</SUB> NRs/C showed the existence of three elements viz., Ru, O and C. Further, the supercapacitor and electrocatalytic hydrogen evolution reaction (HER) activities of RuO<SUB>2</SUB> NRs/C were studied using standard electrochemical methods. The synthesized RuO<SUB>2</SUB> NRs/C offered a maximum specific capacitance of 151.3 F g<SUP>−1</SUP> at a scan rate of 5 mV s<SUP>−1</SUP>, obtained from the cyclic voltammetry results. The onset over potential and Tafel slope of synthesized RuO<SUB>2</SUB> NRs/C for HER were −0.099 V<SUB>RHE</SUB> and −99.4 mV dec<SUP>−1</SUP>, respectively. The present study revealed that RuO<SUB>2</SUB> NRs/C as a better candidate for supercapacitor and HER.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Carbon encapsulated RuO<SUB>2</SUB> nanorods (RuO<SUB>2</SUB> NRs/C) were synthesized by simple thermolysis. </LI> <LI> RuO<SUB>2</SUB> NRs/C shows good supercapacitor and electrocatalytic HER activity. </LI> <LI> RuO<SUB>2</SUB> NRs/C offered a maximum specific capacitance of 151.3 F g<SUP>−1</SUP> at 5 mV s<SUP>−1</SUP>. </LI> <LI> The onset potential and Tafel slope of RuO<SUB>2</SUB> NRs/C for HER were −0.099 V<SUB>RHE</SUB> and −99.4 mV dec<SUP>−1</SUP>. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Biogenic Synthesis of Silver Nanoparticles Using Cnidium officinale Extract and Their Catalytic Reduction of 4-Nitroaniline

Edison, Thomas Nesakumar Jebakumar Immanuel,Baral, Ek Raj,Lee, Yong Rok,Kim, Sung Hong Springer-Verlag 2016 Journal of cluster science Vol.27 No.1

<P>Silver nanoparticles (AgNPs) with two different morphologies were synthesized using aqueous extract of Cnidium officinale rhizomes under different reaction conditions and applied to the facile aqueous phase reduction of 4-nitroaniline (4-NA) as catalysts. The synthesized AgNPs are characterized by UV-Visible spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) method and high resolution transmission electron microscopy (HR-TEM) with energy dispersive X-ray spectroscopy (EDS) analysis. HR-TEM showed that the synthesized AgNPs had two different morphological forms; truncated triangular prism shapes with a mean size of similar to 35 nm and spherical shapes with a mean size of similar to 9 nm. The HR-TEM and XRD results are consistent with the standard values. The catalytic activities of both AgNPs were compared on the reduction of 4-NA in water by NaBH4 as a reducing agent. The reduction of 4-NA was monitored using UV-Visible spectroscopy. The similar to 9 nm (spherical) sized AgNPs showed superior catalytic activity than the larger AgNPs. The calculated rate constant (k) for the catalytic reduction of 4-nitroanilie by spherical AgNPs was 11.16 x 10(-3) s(-1).</P>

Optical Sensor for Dissolved Ammonia Through the Green Synthesis of Silver Nanoparticles by Fruit Extract of Terminalia chebula

Edison, Thomas Nesakumar Jebakumar Immanuel,Atchudan, Raji,Lee, Yong Rok Springer-Verlag 2016 Journal of cluster science Vol.27 No.2

<P>In this work we reported an optical sensor for the detection of dissolved ammonia through the green synthesis of silver nanoparticles (AgNPs) using aqueous fruit extract of Terminalia chebula. The formation of AgNPs was monitored by visual observation and the detection of Surface Plasmon Resonance (SPR) peak using UV-Vis spectrophotometer. The naked eye visual inspection revealed the rate of formation of AgNPs in control reaction (absence of ammonia) is slower than that of other ammonia contained solutions which was confirmed from the UV-Vis spectroscopic results. The absorbance intensity of AgNPs was linearly (R-2 = 0.9850) correlated with the concentration of dissolved ammonia from 0 to 100 ppm. The formation of diamine silver complex and ammonium phenolate ion increases the SPR absorbance intensity of AgNPs. The blue shift of SPR peak, while increasing concentration of ammonia is due to the size decreasing of AgNPs, which was confirmed from the HR-TEM analysis.</P>

Binder-free electro-synthesis of highly ordered nickel oxide nanoparticles and its electrochemical performance

Edison, Thomas Nesakumar Jebakumar Immanuel,Atchudan, Raji,Lee, Yong Rok Elsevier 2018 ELECTROCHIMICA ACTA Vol.283 No.-

<P><B>Abstract</B></P> <P>In this work, highly ordered nickel oxide nanoparticles were electrochemically synthesized on nickel foam (NiO<SUB>x</SUB> NPs/Ni foam) via the formation and subsequent heat treatment of nickel hydroxide. The synthesized NiO<SUB>x</SUB> NPs were characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) with elemental analysis and high resolution transmission electron microscopy (HR-TEM). The XRD results revealed the presence of two different oxide phases with high crystallinity. The synthesized NiO<SUB>x</SUB> NPs were highly ordered spherical morphology with average size of 7 nm, identified from the FE-SEM images. Further, the electrochemical performance of synthesized NiO<SUB>x</SUB> NPs/Ni foam was evaluated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge discharge (GCD) methods. The calculated specific capacity of NiO<SUB>x</SUB> NPs/Ni foam was found to be 219 C/g (60.7 mAh/g) at scan rate of 5 mV/s. This present work implies that the electro-synthesized NiO<SUB>x</SUB> NPs/Ni foam as a good binder-free, highly stable battery-type material and it can be used as a positive electrode for hybrid-capacitors.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Highly ordered NiO<SUB>x</SUB> nanoparticles were synthesized on Ni foam by cathodic electrodeposition. </LI> <LI> The average size of the NiO<SUB>x</SUB> NPs was about 7 nm with spherical shape. </LI> <LI> The electro-synthesized NiO<SUB>x</SUB> NPs shows good electrochemical performance in 2 M aqueous KOH. </LI> <LI> The NiO<SUB>x</SUB> NPs showed a maximum specific capacity of 219 C/g (60.7 mAh/g) at 5 mV/s. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Green synthesis of nitrogen-doped carbon nanograss for supercapacitors

Atchudan, Raji,Edison, Thomas Nesakumar Jebakumar Immanuel,Perumal, Suguna,Thirukumaran, Periyasamy,Vinodh, Rajangam,Lee, Yong Rok Elsevier 2019 Journal of the Taiwan Institute of Chemical Engine Vol.102 No.-

<P><B>Abstract</B></P> <P>In the present study, a novel N-doped carbon nanograss (NCNG) were synthesized from the used baby-diaper absorbent via carbonization under the argon atmosphere and has been applied as an electroactive material for flexible supercapacitor. The synthesized NCNG display a grass-like morphology with an acceptable degree of graphitization. The surface areas and average pore size of NCNG were 183 m<SUP>2</SUP> g<SUP>−1</SUP> and 3.3 nm, respectively. On the basis of good structural ordering with reasonable surface area, the NCNG was coated on a carbon cloth and studied their electrochemical performance toward the supercapacitors. The obtained quasi-rectangular shaped cyclic voltammetry curves indicate good capacitive behavior of the NCNG. The galvanostatic charge-discharge experimental results showed that the specific capacitance of NCNG was 81 F g<SUP>−1</SUP> at a current density of 0.5 A g<SUP>−1</SUP> with capacitance retention of 95% after 10,000 cycles of charge-discharge. The slow decrements of specific capacitance with the increment of current density indicate superior rate capability of synthesized NCNG. These excellent electrochemical performances of the synthesized NCNG from used (waste) baby-diaper extend their potential applications in various nanoelectronics field. To the best of authors knowledge, first time the NCNG synthesized from the garbage-waste and can extend their synthesis in large-scale.</P> <P><B>Highlights</B></P> <P> <UL> <LI> The first time, N-doped carbon nanograss was synthesized using used baby-diaper. </LI> <LI> The synthesized NCNG is good structural ordering with a reasonable surface area. </LI> <LI> NCNG delivered a high specific capacitance with good capacitance retention. </LI> <LI> In addition, NCNG from used baby-diaper extend their synthesis in large-scale. </LI> <LI> Importantly, the waste diaper derived energy storage is alternative clean energy. </LI> </UL> </P>

Electrocatalytic and energy storage performance of bio-derived sulphur-nitrogen-doped carbon

Atchudan, Raji,Edison, Thomas Nesakumar Jebakumar Immanuel,Perumal, Suguna,Parveen, Asrafali Shakila,Lee, Yong Rok Elsevier 2019 Journal of Electroanalytical Chemistry Vol.833 No.-

<P><B>Abstract</B></P> <P>Sulphur and nitrogen-rich carbon layers (S/N-CLs) have been derived successfully <I>via</I> a simple calcination for high energy applications including supercapacitor and electrocatalytic hydrogen evolution reaction (HER). The flexible working electrode was fabricated using thoroughly analyzed S/N-CLs composite as an active electrode energy material for supercapacitor and HER. The S/N-CLs composite shows a higher specific capacitance of 266Fg<SUP>−1</SUP> at a current density of 0.5Ag<SUP>−1</SUP> and a satisfied cycling stability with 84% capacitance retention even after 5000cycles of galvanostatic charge-discharge. On the other hand, the synthesized S/N-CLs composite was used as an electrocatalyst for HER and it exhibits an excellent HER performance with an onset overpotential of −75mV, and a Tafel slope of 73mVdec<SUP>−1</SUP> in 0.5M H<SUB>2</SUB>SO<SUB>4</SUB> aqueous electrolyte. Also, the S/N-CLs composite displayed good stability and strong durability. The high electrocatalytic activity and stability of S/N-CLs composite toward HER due to the active site of a compound which may originate from the heteroatom-functional groups including N and S in the carbon structure. Overall, the high-performance supercapacitors and enhancing HER based on heteroatom-doped carbon structures could be promising in replacing traditional supercapacitors for many electronic devices and electrocatalyst for HER.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Conversion of <I>Magnolia liliiflora</I> into S/N-CLs composite by a simple carbonization </LI> <LI> S/N-CLs delivered a higher C<SUB>s</SUB> of 266Fg<SUP>−1</SUP> at 0.5Ag<SUP>−1</SUP> with a satisfied stability. </LI> <LI> S/N-CLs exhibits an excellent HER performance with a Tafel slope of 73mVdec<SUP>−1</SUP>. </LI> <LI> This is the first attempt in synthesis of S/N-CLs using <I>Magnolia liliiflora</I> flower. </LI> <LI> S/N-CLs will be an alternative for traditional energy storage material and electrocatalyst. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>