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Article ; Online: Covalent Triazine Framework C 6 N 6 as an Electrochemical Sensor for Hydrogen-Containing Industrial Pollutants. A DFT Study

Hassan H. Hammud / Muhammad Yar / Imene Bayach / Khurshid Ayub

Nanomaterials, Vol 13, Iss 1121, p

2023 Volume 1121

Abstract: Industrial pollutants pose a serious threat to ecosystems. Hence, there is a need to search for new efficient sensor materials for the detection of pollutants. In the current study, we explored the electrochemical sensing potential of a C 6 N 6 sheet for ...

Abstract	Industrial pollutants pose a serious threat to ecosystems. Hence, there is a need to search for new efficient sensor materials for the detection of pollutants. In the current study, we explored the electrochemical sensing potential of a C 6 N 6 sheet for H-containing industrial pollutants (HCN, H 2 S, NH 3 and PH 3 ) through DFT simulations. The adsorption of industrial pollutants over C 6 N 6 occurs through physisorption, with adsorption energies ranging from −9.36 kcal/mol to −16.46 kcal/mol. The non-covalent interactions of analyte@C 6 N 6 complexes are quantified by symmetry adapted perturbation theory (SAPT0), quantum theory of atoms in molecules (QTAIM) and non-covalent interaction (NCI) analyses. SAPT0 analyses show that electrostatic and dispersion forces play a dominant role in the stabilization of analytes over C 6 N 6 sheets. Similarly, NCI and QTAIM analyses also verified the results of SAPT0 and interaction energy analyses. The electronic properties of analyte@C 6 N 6 complexes are investigated by electron density difference (EDD), natural bond orbital analyses (NBO) and frontier molecular orbital analyses (FMO). Charge is transferred from the C 6 N 6 sheet to HCN, H 2 S, NH 3 and PH 3 . The highest exchange of charge is noted for H 2 S (−0.026 e − ). The results of FMO analyses show that the interaction of all analytes results in changes in the E H-L gap of the C 6 N 6 sheet. However, the highest decrease in the E H-L gap (2.58 eV) is observed for the NH 3 @C 6 N 6 complex among all studied analyte@C 6 N 6 complexes. The orbital density pattern shows that the HOMO density is completely concentrated on NH 3 , while the LUMO density is centred on the C 6 N 6 surface. Such a type of electronic transition results in a significant change in the E H-L gap. Thus, it is concluded that C 6 N 6 is highly selective towards NH 3 compared to the other studied analytes.
Keywords	industrial pollutants ; covalent triazine framework C 6 N 6 ; density functional theory ; QTAIM analysis ; Chemistry ; QD1-999
Subject code	290
Language	English
Publishing date	2023-03-01T00:00:00Z
Publisher	MDPI AG
Document type	Article ; Online
Database	BASE - Bielefeld Academic Search Engine (life sciences selection)

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Article ; Online: Corrosion Inhibition Using Harmal Leaf Extract as an Eco-Friendly Corrosion Inhibitor

Nasreen Al Otaibi / Hassan H. Hammud

Molecules, Vol 26, Iss 7024, p

2021 Volume 7024

Abstract: Extract of natural plants is one of the most important metallic corrosion inhibitors. They are readily available, nontoxic, environmentally friendly, biodegradable, highly efficient, and renewable. The present project focuses on the corrosion inhibition ... ...

Abstract	Extract of natural plants is one of the most important metallic corrosion inhibitors. They are readily available, nontoxic, environmentally friendly, biodegradable, highly efficient, and renewable. The present project focuses on the corrosion inhibition effects of Peganum Harmala leaf extract. The equivalent circuit with two time constants with film and charge transfer components gave the best fitting of impedance data. Extraction of active species by sonication proved to be an effective new method to extract the inhibitors. High percent inhibition efficacy IE% of 98% for 283.4 ppm solutions was attained using impedance spectroscopy EIS measurements. The values of charge transfer R ct increases while the double layer capacitance C dl values decrease with increasing Harmal extract concentration. This indicates the formation of protective film. The polarization curves show that the Harmal extract acts as a cathodic-type inhibitor. It is found that the adsorption of Harmal molecules onto the steel surface followed Langmuir isotherm. Fourier-transform infrared spectroscopy FTIR was used to determine the electron-rich functional groups in Harmal extract, which contribute to corrosion inhibition effect. Scanning electron microscopy SEM measurement of a steel surface clearly proves the anticorrosion effect of Harmal leaves.
Keywords	Harmal leaves ; anticorrosion ; equivalent electrical circuit ; EIS ; Tafel ; Organic chemistry ; QD241-441
Subject code	621
Language	English
Publishing date	2021-11-01T00:00:00Z
Publisher	MDPI AG
Document type	Article ; Online
Database	BASE - Bielefeld Academic Search Engine (life sciences selection)

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Article ; Online: An Integrated Experimental and Theoretical Studies on the Corrosion Inhibition of Carbon Steel by Harmal Extracts

Hassan H. Hammud / Sarah A. Maache / Nasreen Al Otaibi / Nadeem S. Sheikh

Molecules, Vol 27, Iss 7250, p

2022 Volume 7250

Abstract: The corrosion inhibition effect of the three extracts from Harmal roots (HRE), leaves (HLE), and flowers (HFE) were studied for carbon steel corrosion inhibition in 0.25 M H 2 SO 4 solution. The electrochemical impedance study indicated that the three ... ...

Abstract	The corrosion inhibition effect of the three extracts from Harmal roots (HRE), leaves (HLE), and flowers (HFE) were studied for carbon steel corrosion inhibition in 0.25 M H 2 SO 4 solution. The electrochemical impedance study indicated that the three types of extracts decreased corrosion effectively through a charge transfer mechanism. Harmal roots and leaf extracts showed inhibition values of 94.1% and 94.2%, while it was 88.7% for Harmal flower extract at the inhibitor concentration of 82.6 ppm. Potentiodynamic polarization data revealed that Harmal extracts acted through predominant cathodic type inhibition. Both the corrosion current density and corrosion rate decreased significantly in the presence of Harmal extracts compared to blank solution. The corrosion rate (mpy) value was 63.3, 86.1, and 180.7 for HRE, HLE, and HFE, respectively. The adsorption-free energy change Δ G ads (kJ·mol −1 ) values calculated from the Langmuir adsorption isotherm plots were for HRE (−35.08), HLE (−33.17), and HFE (−33.12). Thus, corrosion inhibition occurred due to the adsorption of Harmal extract on the carbon steel surface via the chemisorption mechanism. Moreover, a computational investigation using B3LYP/6-311G++(d,p) basis set in both gaseous and aqueous phases was performed for the major alkaloids (1–8) present in the Harmal extract.
Keywords	harmal extract ; electrochemical studies ; anti-corrosion ; DFT calculations ; Organic chemistry ; QD241-441
Subject code	669
Language	English
Publishing date	2022-10-01T00:00:00Z
Publisher	MDPI AG
Document type	Article ; Online
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Article ; Online: Hierarchical Graphitic Carbon-Encapsulating Cobalt Nanoparticles for Catalytic Hydrogenation of 2,4-Dinitrophenol

Hassan H. Hammud / Hassan Traboulsi / Ranjith Kumar Karnati / Syed Ghazanfar Hussain / Esam M. Bakir

Catalysts, Vol 12, Iss 39, p

2022 Volume 39

Abstract: Cobalt hierarchical graphitic carbon nanoparticles (Co@HGC) ( 1 ), ( 2 ), and ( 3 ) were prepared by simple pyrolysis of a cobalt phenanthroline complex in the presence of anthracene at different temperatures and heating times, under a nitrogen ... ...

Abstract	Cobalt hierarchical graphitic carbon nanoparticles (Co@HGC) ( 1 ), ( 2 ), and ( 3 ) were prepared by simple pyrolysis of a cobalt phenanthroline complex in the presence of anthracene at different temperatures and heating times, under a nitrogen atmosphere. The samples were used for the catalytic hydrogenation of 2,4-dinitrophenol. Samples ( 1 ) and ( 3 ) were prepared by heating at 600 °C and 800 °C respectively, while ( 2 ) was prepared by heating at 600 °C with an additional intermediate stage at 300 °C. This work revealed that graphitization was catalyzed by cobalt nanoparticles and occurred readily at temperatures of 600 °C and above. The nanocatalysts were characterized by Scanning Electron Microscopy SEM, energy dispersive X-ray analysis EDX, Raman, Xrd, and XPS. The analysis revealed the presence of cobalt and cobalt oxide species as well as graphitized carbon, while TEM analysis indicated that the nanocatalyst contains mainly cobalt nanoparticles of 3–20 nm in size embedded in a lighter graphitic web. Some bamboo-like multiwall carbon nanotubes and graphitic onion-like nanostructures were observed in ( 3 ). The structures and chemical properties of the three catalysts were correlated with their catalytic activities. The apparent rate constants k app (min −1 ) of the 2,4-dinitrophenol reductions were 0.34 for ( 2 ), 0.17 for ( 3 ), 0.04 for ( 1 ), 0.005 (no catalyst). Among the three studied catalysts, the highest rate constant was obtained for ( 2 ), while the highest conversion yield was achieved by ( 3 ). Our data show that an increase in agglomeration of the cobalt species reduces the catalytic activity, while an increase in pyrolysis temperature improves the conversion yield. The nanocatalyst enhances hydrogen generation in the presence of sodium borohydride and reduces 2,4-dinitrophenol to p-diamino phenol. The best nanocatalyst ( 3 ) was prepared at 800 °C. It consisted of uniformly distributed cobalt nanoparticles sheltered by hierarchical graphitic carbon. The nanocatalyst is easily separated and recycled from the reaction system and proved to be degradation resistant, to have robust stability, and high activity towards the reduction reaction of nitrophenols.
Keywords	cobalt nanocarbon ; 2,4-dinitrophenol ; catalytic hydrogenation ; pyrolysis ; cobalt phenanthroline complex ; Chemical technology ; TP1-1185 ; Chemistry ; QD1-999
Subject code	540
Language	English
Publishing date	2022-12-01T00:00:00Z
Publisher	MDPI AG
Document type	Article ; Online
Database	BASE - Bielefeld Academic Search Engine (life sciences selection)

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Article ; Online: Removal of Malachite Green Using Hydrochar from PALM Leaves

Hassan H. Hammud / Mohamad H. Hammoud / Aqeel A. Hussein / Youssef B. Fawaz / Malai Haniti Sheikh Abdul Hamid / Nadeem S. Sheikh

Sustainability, Vol 15, Iss 8939, p

2023 Volume 8939

Abstract: Biochar was prepared by the hydrothermal carbonization (HTC) of palm leaves, characterized, and utilized as an adsorbent for Malachite Green dye (MG). The Higher Heating Value (HHV) of biochar depends on the carbonization temperature and has a maximum ... ...

Abstract	Biochar was prepared by the hydrothermal carbonization (HTC) of palm leaves, characterized, and utilized as an adsorbent for Malachite Green dye (MG). The Higher Heating Value (HHV) of biochar depends on the carbonization temperature and has a maximum value of 24.81 MJ/kg. Activation using H 2 O 2 oxidation of HTC biochar prepared at 208 °C produced AHTC with improved capacity. The optimum pH was found to be in the range 7–8. Freundlich, Langmuir, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to study MG adsorption data. The Langmuir isotherm provided the best fit for experimental data. Experiments conducted using activated biochar AHTC at 25 °C resulted in an adsorption capacity of 62.80 mg/g, far greater than what was observed for HTC biochar (45.59 mg/g). The maximum adsorption capacity was 88% when the concentration of MG solution was 66 ppm. The free energy change in adsorption DG° indicated that the adsorption process was spontaneous. Adsorption followed pseudo-second-order kinetics. Fixed-column adsorptions models, namely, Thomas, Yan et al. and Yoon–Nelson models, were investigated for AHTC. The column adsorption capacity determined by the Thomas model was 33.57 mg/g. In addition, a computational investigation has been carried out to determine the structural and electronic features, as well as the quantum chemical parameters of HTC and MG. Moreover, the interaction between the HTC and MG is investigated, which is further elaborated by performing non-covalent interaction (NCI) through the reduced density gradient (RDG) analysis. Thus, the easily prepared hydrochar from abundant waste palm leaves can be used as a high-value biocoal and efficient adsorbent of the cationic dye malachite green.
Keywords	biochar ; hydrothermal ; higher heating value ; adsorption ; activation ; kinetics ; Environmental effects of industries and plants ; TD194-195 ; Renewable energy sources ; TJ807-830 ; Environmental sciences ; GE1-350
Subject code	660
Language	English
Publishing date	2023-06-01T00:00:00Z
Publisher	MDPI AG
Document type	Article ; Online
Database	BASE - Bielefeld Academic Search Engine (life sciences selection)

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Article ; Online: Electrocatalytic Properties of 3D Hierarchical Graphitic Carbon–Cobalt Nanoparticles for Urea Oxidation

Nusaybah Alotaibi / Hassan H. Hammud / Nasreen Al Otaibi / Thirumurugan Prakasam

ACS Omega, Vol 5, Iss 40, Pp 26038-

2020 Volume 26048

Keywords	Chemistry ; QD1-999
Language	English
Publishing date	2020-09-01T00:00:00Z
Publisher	American Chemical Society
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Article ; Online: Cobalt–Carbon Nanoparticles with Silica Support for Uptake of Cationic and Anionic Dyes from Polluted Water

Hassan H. Hammud / Ranjith Kumar Karnati / Nusaybah Alotaibi / Syed Ghazanfar Hussain / Thirumurugan Prakasam

Molecules, Vol 26, Iss 7489, p

2021 Volume 7489

Abstract: Silica-supported hierarchical graphitic carbon sheltering cobalt nanoparticles Co-HGC@SiO 2 (1) were prepared by pyrolysis at 850 °C of [Co(phen)(H 2 O) 4 ]SO 4 ·2H 2 O complex with silica in the presence of pyrene as a carbon source under nitrogen ... ...

Abstract	Silica-supported hierarchical graphitic carbon sheltering cobalt nanoparticles Co-HGC@SiO 2 (1) were prepared by pyrolysis at 850 °C of [Co(phen)(H 2 O) 4 ]SO 4 ·2H 2 O complex with silica in the presence of pyrene as a carbon source under nitrogen atmosphere. Nanocomposites (2) and (3) were obtained by acid treatment of (1) with HCl and HF acid, respectively. The nanocomposites showed rough hierarchical carbon microstructures over silica support decorated with irregular cobalt nanospheres and nanorods 50 to 200 nm in diameter. The nanoparticles consist of graphitic shells and cobalt cores. SEM, EDAX and TEM elemental mapping indicate a noticeable loss of cobalt in the case of (2) and loss of cobalt and silica in the case of (3) with an increase in porosity. Nanocomposite (3) showed the highest BET surface area 217.5 m 2 g −1 . Raman spectrum shows defect D-band and graphitic G-band as expected in carbon nanostructures. PXRD reveals the presence of cobalt(0) nanoparticles. XPS indicates the presence of Co(II) oxides and the successful doping of nitrogen in the nanocomposites. Moreover, TEM elemental mapping provides information about the abundance of Si, Co, C, N and S elements in zones. Nanocomposite (1) showed maximum uptake capacity of 192.3 and 224.5 mg/g for crystal violet CV and methyl orange MO dyes, respectively. Nanocomposite (2) showed a capacity of 94.1 and 225.5 mg/g for CV and MO dyes, respectively. Nanocomposite (4) obtained after treatment of (1) with crystal violet proved successful adsorption of CV. Co-HGC (5) prepared without addition of silica has a capacity for CV equal to 192 mg/g, while it is 769.2 mg/g with MO. Electrostatics and π–π interactions of graphite and cobalt species in the nanocomposites with aromatic rings of cationic and anionic dyes are responsible for the adsorption. Yan et al. was the best model to describe column kinetics. The thomas column adsorption model showed that the maximum uptake capacity of (1) was 44.42 mg/g for CV and 32.62 mg/g for MO. for a column packed with ...
Keywords	pyrolysis ; cobalt ; nanocarbon ; silica ; surface analysis ; adsorption ; Organic chemistry ; QD241-441
Subject code	333
Language	English
Publishing date	2021-12-01T00:00:00Z
Publisher	MDPI AG
Document type	Article ; Online
Database	BASE - Bielefeld Academic Search Engine (life sciences selection)

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Article ; Online: Remarkable Single Atom Catalyst of Transition Metal (Fe, Co & Ni) Doped on C 2 N Surface for Hydrogen Dissociation Reaction

Ahmed Bilal Shah / Sehrish Sarfaraz / Muhammad Yar / Nadeem S. Sheikh / Hassan H. Hammud / Khurshid Ayub

Nanomaterials, Vol 13, Iss 1, p

2022 Volume 29

Abstract: Currently, hydrogen is recognized as the best alternative for fossil fuels because of its sustainable nature and environmentally friendly processing. In this study, hydrogen dissociation reaction is studied theoretically on the transition metal doped ... ...

Abstract	Currently, hydrogen is recognized as the best alternative for fossil fuels because of its sustainable nature and environmentally friendly processing. In this study, hydrogen dissociation reaction is studied theoretically on the transition metal doped carbon nitride (C 2 N) surface through single atom catalysis. Each TMs@C 2 N complex is evaluated to obtain the most stable spin state for catalytic reaction. In addition, electronic properties (natural bond orbital NBO & frontier molecular orbital FMO) of the most stable spin state complex are further explored. During dissociation, hydrogen is primarily adsorbed on metal doped C 2 N surface and then dissociated heterolytically between metal and nitrogen atom of C 2 N surface. Results revealed that theFe@C 2 N surface is the most suitable catalyst for H 2 dissociation reaction with activation barrier of 0.36 eV compared with Ni@C 2 N (0.40 eV) and Co@C 2 N (0.45 eV) complexes. The activation barrier for H 2 dissociation reaction is quite low in case of Fe@C 2 N surface, which is comparatively better than already reported noble metal catalysts.
Keywords	hydrogen dissociation reaction ; hydrogen energy ; C 2 N surface ; single atom catalyst ; catalysis ; transition metals ; Chemistry ; QD1-999
Subject code	540
Language	English
Publishing date	2022-12-01T00:00:00Z
Publisher	MDPI AG
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Article ; Online: Novel cobalt–carbon@silica adsorbent

Nusaybah Alotaibi / Hassan H. Hammud / Nasreen Al Otaibi / Syed Ghazanfar Hussain / Thirumurugan Prakasam

Scientific Reports, Vol 10, Iss 1, Pp 1-

2020 Volume 17

Abstract: Abstract Recently, carbon nanostructures are of high importance due to their unique characteristics and interesting applications. Pyrolysis of anthracene with cobalt complex Co(2,2′-bipy)Cl2 (1), where (2,2′-bipy) is 2,2′-bipyridine, in the absence and ... ...

Abstract	Abstract Recently, carbon nanostructures are of high importance due to their unique characteristics and interesting applications. Pyrolysis of anthracene with cobalt complex Co(2,2′-bipy)Cl2 (1), where (2,2′-bipy) is 2,2′-bipyridine, in the absence and presence of silica gave in high yield cobalt-carbon nanocomposite CoCNC (2) and CoCNC@SiO2 (3) at 600 °C and 850 °C, respectively. They were characterized using SEM, TEM, PXRD, Raman and XPS. (3) and (2) contain core–shell cobalt(0)/cobalt oxide-graphite with or without silica support. PXRD indicates that (2) contains crystalline hexagonal α-Co and cubic β-Co phases while (3) contains only cubic β-Co phase and silica. The structure of (2) is 3D hierarchical carbon architecture wrapping spherical and elliptical cobalt nanoparticles. (3) consists of graphitized structures around cobalt nanoparticles embedded in the silica matrix. XPS reveals that the nanocomposites contain oxygen functional groups that enhance uptake of cationic dyes. CoCNC@SiO2 (3) has higher capacity and thus is better adsorbent of Basic Violet 3 than CoCNC (2). The Langmuir adsorption capacity of (3) is 19.4 mg g−1 while column capacity is 12.55 mg g−1 at 25 °C. Freundlich isotherm and pseudo-second-order kinetic models fit well the adsorption data. Thermodynamics indicate that adsorption(3) is exothermic. Column regeneration was tested for three cycles and Yan et al. was found the best kinetic model.
Keywords	Medicine ; R ; Science ; Q
Language	English
Publishing date	2020-10-01T00:00:00Z
Publisher	Nature Publishing Group
Document type	Article ; Online
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Article ; Online: Synthesis of mesoporous SnO2/NiO nanocomposite using modified sol–gel method and its electrochemical performance as electrode material for supercapacitors

Bhaskar Varshney / M. J. Siddiqui / A. Hakeem Anwer / M. Zain Khan / Faheem Ahmed / Abdullah Aljaafari / Hassan H. Hammud / Ameer Azam

Scientific Reports, Vol 10, Iss 1, Pp 1-

2020 Volume 13

Abstract: Abstract In this research work, SnO2, NiO and SnO2/NiO nanocomposites were synthesized at low temperature by modified sol–gel method using ultrasonication. Prepared samples were investigated for their properties employing various characterization ... ...

Abstract	Abstract In this research work, SnO2, NiO and SnO2/NiO nanocomposites were synthesized at low temperature by modified sol–gel method using ultrasonication. Prepared samples were investigated for their properties employing various characterization techniques. X-ray diffraction (XRD) patterns confirmed the purity and phase of the samples as no secondary phase was detected. The average crystallite size of the nanocomposites was found to decrease from 19.24 to 4.53 nm with the increase in NiO concentration. It was confirmed from SEM micrographs that the material has mesoporous morphology. This mesoporous morphology resulted in the increase of the surface to mass ratio of the material, which in turn increases the specific capacitance of the material. The UV–Visible spectra showed the variation in the band gap of SnO2/NiO at different weight ratio ranging from 3.49 to 3.25 eV on increasing NiO concentration in the samples. These composites with different mass ratio of SnO2 and NiO were also characterized by FT-IR spectroscopy that showed shifting of the peaks centered at 545 cm−1 in the spectra for NiO/SnO2 nanocomposite. The analysis of the electrochemical performance of the material was done with the help of cyclic voltammetry and Galvanostatic charge–discharge. The specific capacitance of the synthesized samples with different concentration of SnO2 and NiO was analyzed at different scan rates of 5 to 100 mV/s. Interestingly, 7:1 mass ratio of NiO and SnO2 (SN7) nanocomposite exhibited a maximum specific capacitance of ~ 464 F/g at a scan rate of 5 mV/s and good capacitance retention of 87.24% after 1,000 cycles. These excellent electrochemical properties suggest that the SnO2/NiO nanocomposite can be used for high energy density supercapacitor electrode material.
Keywords	Medicine ; R ; Science ; Q
Subject code	620
Language	English
Publishing date	2020-07-01T00:00:00Z
Publisher	Nature Publishing Group
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