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1.
ACS Omega ; 9(24): 25748-25755, 2024 Jun 18.
Article in English | MEDLINE | ID: mdl-38911812

ABSTRACT

Water electrolysis for clean hydrogen production requires high-activity, high-stability, and low-cost catalysts for its particularly sluggish half-reaction, the oxygen evolution reaction (OER). Currently, the most promising of such catalysts working in alkaline conditions is a core-shell nanostructure, NiFe@NC, whose Fe-doped Ni (NiFe) nanoparticles are encapsulated and interconnected by N-doped graphitic carbon (NC) layers, but the exact OER mechanism of these catalysts is still unclear, and even the location of the OER active site, either on the core side or on the shell side, is still debated. Therefore, we herein derive a plausible active-site model for each side based on various experimental evidence and density functional theory calculations and then build OER free-energy diagrams on both sides to determine the active-site location. The core-side model is an FeO4-type (rather than NiO4-type) active site where an Fe atom sits on Ni oxide layers grown on top of the core surface during catalyst activation, whose facile dissolution provides an explanation for the activity loss of such catalysts directly exposed to the electrolyte. The shell-side model is a NiN4-type (rather than FeN4-type) active site where a Ni atom is intercalated into the porphyrin-like N4C site of the NC shell during catalyst synthesis. Their OER free-energy diagrams indicate that both sites require similar amounts of overpotentials, despite a complete shift in their potential-determining steps, i.e., the final O2 evolution from the oxophilic Fe on the core and the initial OH adsorption to the hydrophobic shell. We conclude that the major active sites are located on the core, but the NC shell not only protects the vulnerable FeO4 active sites on the core from the electrolyte but also provides independent active sites, owing to the N doping.

2.
ACS Appl Mater Interfaces ; 15(23): 28093-28105, 2023 Jun 14.
Article in English | MEDLINE | ID: mdl-37276489

ABSTRACT

When the polymer electrolyte membrane fuel cell (PEMFC) is operated under low humidity, the proton conductivity decreases due to membrane dehydration, causing adverse effects on fuel cell performance. Introducing appropriate additives to the membrane and catalyst layer to prevent membrane degradation at low humidity brings significant performance improvements to proton exchange membrane fuel cells. We developed a perovskite-structured multi-metal oxide Ce0.667Zr0.05Ti0.95O3-δ (CZTO) with high radical scavenging properties and good structural stability. The nanostructured ceramic CZTO is introduced into the membrane and cathode catalyst layer to improve the durability of the membrane electrode assembly. The Nafion-CZTO membrane exhibited maximum power densities of 1298 and 519 mW cm-2 at 100 and 20% relative humidity, respectively. The improved performance of Nafion-CZTO membranes over commercial Nafion membranes is due to the high proton conductivity and better radical scavenging properties of the CZTO additive. In addition, the expected positive effects of applying CZTO additives to the catalyst layer are verified by low charge transfer resistance and high electrochemical surface activity of the CZTO catalyst through electrochemical impedance spectroscopy and electrochemical surface area analyses.

3.
Adv Sci (Weinh) ; 9(29): e2201410, 2022 Oct.
Article in English | MEDLINE | ID: mdl-35981872

ABSTRACT

Transition metals have been recognized as excellent and efficient catalysts for the electrochemical nitric oxide reduction reaction (NORR) to value-added chemicals. In this work, a class of core-shell electrocatalysts that utilize nickel nanoparticles in the core and nitrogen-doped porous carbon architecture in the shell (Ni@NC) for the efficient electroreduction of NO to ammonia (NH3 ) is reported. In Ni@NC, the NC prevents the dissolution of Ni nanoparticles and ensures the long-term stability of the catalyst. The Ni nanoparticles involve in the catalytic reduction of NO to NH3 during electrolysis. As a result, the Ni@NC achieves a faradaic efficiency (FE) of 72.3% at 0.16 VRHE . The full-cell electrolyzer is constructed by coupling Ni@NC as cathode for NORR and RuO2 as an anode for oxygen evolution reaction (OER), which delivers a stable performance over 20 cycles at 1.5 V. While integrating this setup with a PV-electrolyzer cell, and it demonstrates an appreciable FE of >50%. Thus, the results exemplify that the core-shell catalyst based electrolyzer is a promising approach for the stable NO to NH3 electroconversion.

4.
ACS Appl Mater Interfaces ; 13(15): 17699-17706, 2021 Apr 21.
Article in English | MEDLINE | ID: mdl-33825457

ABSTRACT

Li-O2 batteries are attracting considerable attention as a promising power source for electric vehicles as they have the highest theoretical energy density among reported rechargeable batteries. However, the low energy density and efficiency of Li-O2 batteries still act as limiting factors in real cell implementations. This study proposes the cathode structure engineering strategy by tuning the thickness of a catalyst layer to enhance the Li-O2 battery performance. The construction of the Li-O2 battery with a thinner porous cathode leads less parasitic reactions at the solid electrolyte interface, maximization of the catalyst utilization, and facile transport of oxygen gas into the cathode. A remarkably high specific capacity of 33,009 mAh g-1 and the extended electrochemical stability for 75 cycles at a 1000 mAh g-1 limited capacity and 100 mA g-1 were achieved when using the porous Co/CeO1.88-nitrogen-doped carbon nanorod cathode. Further, a high discharge capacity of 20,279 mAh g-1 was also achieved at a relatively higher current density of 300 mA g-1. This work suggests the ideal cathode structure and the feasibility of the Co/CeO1.88-nitrogen-doped carbon nanorod as the cathode material, which can minimize the areal cathode catalyst loading and maximize the gravimetric energy density.

5.
ACS Appl Mater Interfaces ; 12(48): 53719-53730, 2020 Dec 02.
Article in English | MEDLINE | ID: mdl-33206495

ABSTRACT

Development and fabrication of electrodes with favorable electrocatalytic activity, low-cost, and excellent electrocatalytic durability are one of the most important issues in the hydrogen production area using the electrochemical water splitting process. We use the pulse electrodeposition method as a versatile and cost-effective approach to synthesize three-dimensional Ni-Fe-P electrocatalysts on nickel nanostructures under various applied frequencies and duration times, in which nanostructures exhibit excellent intrinsic electrocatalytic activity. Benefiting from the three-dimensional structure, as well as the simultaneous presence of the three elements nickel, iron, and phosphorus, the electrode fabricated at the optimal conditions has indicated outstanding electrocatalytic activity with a η10 of 66 and 198 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in a 1.0 M KOH solution. Also, the water electrolysis cell constructed with this electrode and tested as a bifunctional electrode exhibited 1.508 V for 10 mA cm-2 in overall water splitting. In addition, the lowest amount of potential change in 100 mA cm-2 was observed for HER and OER, indicating excellent electrocatalytic stability. This study proposes a binder-free and economical technique for the synthesis of three-dimensional electrocatalysts.

6.
ACS Appl Mater Interfaces ; 12(49): 54524-54536, 2020 Dec 09.
Article in English | MEDLINE | ID: mdl-33236633

ABSTRACT

Metal oxynitrides have been considered recently as emerging electrode materials for supercapacitors. Herein, we converted titanate nanotubes into a series of titanium oxynitride (TiON) nanorods at nitridation temperatures of 800, 900, and 1000 °C in ammonia gas and tested them as supercapacitor electrodes. TiON-800, TiON-900, and TiON-1000 showed capacities of 60, 140, and 71 F g-1, respectively, at a current density of 1 A g-1. However, because of TiON's low capacity, a heterostructure (TiON-900/MnCo2O4) was designed based on the optimized TiON with MnCo2O4 (MCO). The heterostructure TiON-900-MCO and MCO electrode materials showed specific capacities of 515 and 381 F g-1, respectively, at a current density of 1 A g-1. The cycling stability retention of TiON-900 and MCO were 75 and 68%, respectively; moreover, the heterostructure of TiON-900-MCO reached 78% at a current density of 5 A g-1 over 5000 cycles. The increased capacity and sustained cycling stability retention are attributable to the synergistic effect of TiON-900 and MCO. A coin cell (CC)-type symmetric supercapacitor prototype of TiON-900-MCO was fabricated and tested in the voltage range of 0.0-2.0 V in 1 M LiClO4 in propylene carbonate/dimethyl carbonate electrolyte, and a 79% cycling retention capacity of TiON-900-MCO-CC was achieved over 10 000 cycles at a current density of 250 mA g-1. We demonstrated a prototypical single cell of TiON-900-MCO-CC as a sustained energy output by powering a red-light emitting diode that indicated TiON-900-MCo electrode materials' potential application in commercial supercapacitor devices.

7.
Nanoscale ; 12(34): 17858-17869, 2020 Sep 14.
Article in English | MEDLINE | ID: mdl-32840553

ABSTRACT

The development of affordable electrocatalysts for both oxygen reduction and evolution reactions (ORR/OER) has received great interest due to their importance in metal-air batteries and regenerative fuel cells. We developed a high-performance bifunctional oxygen electrocatalyst based on Pd nanoparticles supported on cobalt hydroxide nanoplatelets (Pd/Co(OH)2) as an air cathode for metal-air batteries. The Pd/Co(OH)2 shows remarkably higher electrocatalytic activity in comparison with commercial catalysts (Pt/C, IrO2), including an ORR half-wave potential (E1/2) of 0.87 V vs. RHE and an OER overpotential of 0.39 V at 10 mA cm-2 in aqueous alkaline medium. The Zn-air battery constructed with Pd/Co(OH)2 presents stable charge/discharge voltage (ΔEOER-ORR = 0.69 V), along with durable cycling stability for over 30 h. Also, this cathode exhibits a maximum discharge capacity of 17 698 mA h g-1, and stable battery operation over 50 cycles at a fixed capacity of 1000 mA h g-1, as an efficient air electrode for Li-O2 batteries, indicating that Pd/Co(OH)2 can be a potential candidate for both aqueous and non-aqueous metal-air batteries.

8.
Nanoscale ; 11(35): 16621-16634, 2019 Sep 21.
Article in English | MEDLINE | ID: mdl-31460535

ABSTRACT

The development of a bi-functional active and stable catalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is an important challenge in overall electrochemical water splitting. In this study, firstly, nickel nanocones (NNCs) were formed using electrochemical deposition, and then Ni-Co-Fe based mixed sulfide ultrathin nanosheets were obtained by directly depositing on the surface of the nanocones using the CV method. With a hierarchical structure of Ni-Fe-Co-S nanosheets, not only was a high active surface area created, but also the electron transfer and mass transfer were enhanced. This structure also led to the faster release of hydrogen bubbles from the surface. An overpotential value of 106 mV was required on the surface of this electrode to generate a current density of 10 mA cm-2 in the HER, whereas, for the OER, 207 mV overpotential was needed to generate a current density of 10 mA cm-2. Furthermore, this electrode required 1.54 V potential to generate a current density of 10 mA cm-2 in the total electrochemical water splitting. The resulting electrode also exhibited reasonable electrocatalytic stability, and after 10 hours of electrolysis in the overall water splitting reaction, the voltage change was negligible. This study introduces a simple, efficient, reasonable and cost-effective method of creating an effective catalyst for the overall water splitting process.

9.
Chem Sci ; 9(31): 6532-6539, 2018 Aug 21.
Article in English | MEDLINE | ID: mdl-30310584

ABSTRACT

A family of Al-rich ZSM-5 zeolites with Si/Al = 8 ± 0.5 was prepared according to a biomass-mediated supramolecular approach. A combination of advanced characterisation techniques and periodic density functional theory (DFT) calculations unraveled the purity and stability of un-expected Al-enriched ZSM-5 structures, hence allowing to cross the frontier of Si/Al lower limit. In addition, these Al-rich ZSM-5 zeolites demonstrated high catalytic activity in n-hexane cracking and methanol conversion into hydrocarbons, being in line with the presence of numerous Brønsted acid sites.

10.
ACS Omega ; 3(8): 8621-8630, 2018 Aug 31.
Article in English | MEDLINE | ID: mdl-31458992

ABSTRACT

A unique three-dimensional (3D) structure consisting of a hierarchical nickel-cobalt dichalcogenide spinel nanostructure is investigated for its electrocatalytic properties at benign neutral and alkaline pH and applied as an air cathode for practical zinc-air batteries. The results show a high oxygen evolution reaction catalytic activity of nickel-cobalt sulfide nanosheet arrays grown on carbon cloth (NiCo2S4 NS/CC) over the commercial benchmarking catalyst under both pH conditions. In particular, the NiCo2S4 NS/CC air cathode shows high discharge capacity, a narrow potential gap between discharge and charge, and superior cycle durability with reversibility, which exceeds that of commercial precious metal-based electrodes. The excellent performance of NiCo2S4 NS/CC in water electrolyzers and zinc-air batteries is mainly due to highly exposed electroactive sites with a rough surface, morphology-based advantages of nanosheet arrays, good adhesion between NiCo2S4 and the conducting carbon cloth, and the active layer formed of nickel-cobalt (oxy)hydroxides during water splitting. These results suggest that NiCo2S4 NS/CC could be a promising candidate as an efficient electrode for high-performance water electrolyzers and rechargeable zinc-air batteries.

11.
Chem Commun (Camb) ; 53(55): 7836-7839, 2017 Jul 06.
Article in English | MEDLINE | ID: mdl-28653704

ABSTRACT

Chrysanthemum flower-like NiCo2O4-nitrogen doped graphene oxide composite material has been explored as a bifunctional cathode electrocatalyst for aqueous zinc-air and non-aqueous lithium-oxygen batteries. This cathode exhibits maximum discharge capacities of 712 and 15 046 mA h g-1 for zinc-air and lithium-oxygen batteries, respectively, with stable cycling over 50 cycles.

12.
Chem Commun (Camb) ; 53(22): 3277-3280, 2017 Mar 18.
Article in English | MEDLINE | ID: mdl-28261726

ABSTRACT

In this communication, we present a new synthesis method for the fabrication of hybrid metal-Cu2S (M = Pt, FePt) nanocrystals (HNs). The metal-Cu2S HNs were investigated in photocatalytic hydrogen generation as effective co-catalysts on TiO2. The Pt-Cu2S/TiO2 catalyst showed a higher hydrogen generation rate compared with a pure TiO2 catalyst. This enhancement is attributed to the synergistic effects between Cu2S and Pt, which significantly improve the light absorption ability and the charge separation activity.

13.
ACS Appl Mater Interfaces ; 9(14): 12416-12426, 2017 Apr 12.
Article in English | MEDLINE | ID: mdl-28337912

ABSTRACT

One of the important challenges in alkaline water electrolysis is to utilize a bifunctional catalyst for both hydrogen evolution (HER) and oxygen evolution (OER) reactions to increase the efficiency of water splitting devices for the long durable operations. Herein, nickel-cobalt-titanium (NCT) alloy is directly grown on a high corrosion resistance titanium foil by a simple, single, and rapid electrochemical deposition at room temperature. The electrocatalytic activity of NCT alloy electrodes is evaluated for both HER and OER in aqueous electrolyte. Our NCT electrocatalyst exhibits low overpotentials around 125 and 331 mV for HER and OER, respectively, in 1 M KOH. In addition to this outstanding activity, the bifunctional catalyst also exhibits excellent OER and HER electrode stability up to 150 h of continuous operation with a minimal loss in activity. Further, the NCT alloy directly grown on titanium foil is used to directly construct membrane electrode assembly (MEA) for alkaline electrolyte membrane (AEM) water electrolyzer, which make the practical applicability. This single-step electrodeposition reveals NCT on titanium foil with high activity and excellent electrode stability suitable for replacing alternative commercial viable catalyst for the alkaline water splitting.

14.
ChemSusChem ; 10(7): 1554-1562, 2017 04 10.
Article in English | MEDLINE | ID: mdl-28145092

ABSTRACT

Cost-effective dual heteroatom-doped 3D carbon nanofoam-wrapped FeS nanoparticles (NPs), FeS-C, act as efficient bifunctional catalysts for Li-O2 batteries. This cathode exhibits a maximum deep discharge capacity of 14 777.5 mA h g-1 with a 98.1 % columbic efficiency at 0.1 mA cm-2 . The controlled capacity (500 mA h g-1 ) test of this cathode delivers a minimum polarization gap of 0.73 V at 0.1 mA cm-2 and is sustained for 100 cycles with an energy efficiency of approximately 64 % (1st cycle) and 52 % (100th cycle) at 0.3 mA cm-2 , under the potential window of 2.0-4.5 V. X-ray photoelectron spectroscopy reveals the substantial reversible formation and complete decomposition of Li2 O2 . The excellent recharging ability, high rate performance, and cycle stability of this catalyst is attributed to the synergistic effect of FeS catalytic behavior and textural properties of heteroatom-doped carbon nanostructures.


Subject(s)
Electric Power Supplies , Ferrous Compounds/chemistry , Lithium/chemistry , Nanoparticles/chemistry , Oxygen/chemistry , Catalysis , Chemical Phenomena , Electrodes
15.
Chem Commun (Camb) ; 53(5): 917-920, 2017 Jan 10.
Article in English | MEDLINE | ID: mdl-28008439

ABSTRACT

A highly ion-selective membrane for vanadium redox flow batteries (VRBs) consisting of sulfonated poly(arylene ether ketone) (SPAEK) and polyoxometalate coupled with a graphene oxide was designed and fabricated. The SPAEK/PW-mGO composite membrane showed an effectively low self-discharge rate and excellent Coulombic efficiency (98.73%) in VRBs.

16.
Bioelectrochemistry ; 110: 79-90, 2016 Aug.
Article in English | MEDLINE | ID: mdl-27100467

ABSTRACT

This manuscript reports a new approach for the synthesis of one dimensional gold nanostructure (AuNs) and its application in the development of cholesterol biosensor. Au nanostructures have been synthesized by exploiting ß-diphenylalanine (ß-FF) as an sacrificial template, whereas the Au nanoparticles (AuNPs) were synthesized by ultrasound irradiation. X-ray diffractometer (XRD), scanning electron microscope (SEM) and energy dispersive analysis of X-rays (EDAX) have been employed to characterize the morphology and composition of the prepared samples. With the aim to develop a highly sensitive cholesterol biosensor, cholesterol oxidase (ChOx) was immobilized on AuNs which were appended on the graphite (Gr) electrode via chemisorption onto thiol-functionalized graphene oxide (GO-SH). This Gr/GO-SH/AuNs/ChOx biosensor has been characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy and chronoamperometry. CV results indicated a direct electron transfer between the enzyme and the electrode surface. A new potentiostat intermitant titration technique (PITT) has been studied to determine the diffusion coefficient and maxima potential value. The proposed biosensor showed rapid response, high sensitivity, wide linear range and low detection limit. Furthermore, our AuNs modified electrode showed excellent selectivity, repeatability, reproducibility and long term stability. The proposed electrode has also been used successfully to determine cholesterol in serum samples.


Subject(s)
Biosensing Techniques/methods , Cholesterol/analysis , Gold/chemistry , Graphite/chemistry , Metal Nanoparticles/chemistry , Nanotechnology , Oxides/chemistry , Chemistry Techniques, Synthetic , Cholesterol Oxidase/chemistry , Cholesterol Oxidase/metabolism , Electrochemistry , Electrodes , Ferricyanides/chemistry , Hydrogen-Ion Concentration , Temperature
17.
ACS Appl Mater Interfaces ; 8(9): 6019-31, 2016 Mar 09.
Article in English | MEDLINE | ID: mdl-26887571

ABSTRACT

Perovskites have emerged as promising earth-abundant alternatives to precious metals for catalyzing the oxygen evolution reaction (OER). Herein, we report the synthesis of a series of porous perovskite nanostructures, LaCo0.97O3-δ, with systematic Ni substitution in Co octahedral sites. Their electrocatalytic activity during the water oxidation reaction was studied in alkaline electrolytes. The electrocatalytic OER activity and stability of the perovskite nanostructure was evaluated using the rotating disk electrode technique. We show that the progressive replacement of Co by Ni in the LaCo0.97O3-δ perovskite structure greatly altered the electrocatalytic activity and that the La(Co0.71Ni0.25)0.96O3-δ composition exhibited the lowest OER overpotential of 324 and 265 mV at 10 mA cm(-2) in 0.1 M KOH and 1 M KOH, respectively. This value was much lower than that of the noble metal catalysts, IrO2, Ru/C, and Pt/C. Furthermore, the La(Co0.71Ni0.25)0.96O3-δ nanostructure showed outstanding electrode stability, with no observable decrease in performance up to 114th cycle in the auxiliary linear sweep voltammetry that lasted for 10 h in chronoamperometry studies. The excellent oxygen evolution activity of the La(Co0.71Ni0.25)0.96O3-δ perovskite nanostructure can be attributed to its intrinsic structure, interconnected particle arrangement, and unique redox characteristics. The enhanced intrinsic electrocatalytic activity of the La(Co0.71Ni0.25)0.96O3-δ catalyst was correlated with several parameters, such as the electrochemical surface area, the roughness factor, and the turnover frequency, with respect to variation in the transition metals of the perovskite structure. Subsequently, La(Co0.71Ni0.25)0.96O3-δ was utilized as the air cathode in a zinc-air battery application.

18.
ACS Appl Mater Interfaces ; 7(29): 15716-25, 2015 Jul 29.
Article in English | MEDLINE | ID: mdl-26125300

ABSTRACT

Micro-/nanoscale noble metal (Ag, Au, and Pt) particle-decorated 3D porous nickel electrodes for hydrogen evolution reaction (HER) in alkaline electrolyte are fabricated via galvanostatic electrodeposition technique. The developed electrodes are characterized by field emission scanning electron microscopy and electrochemical measurements including Tafel polarization curves, cyclic voltammetry, and electrochemical impedance spectroscopy. It is clearly shown that the enlarged real surface area caused by 3D highly porous dendritic structure has greatly reinforced the electrocatalytic activity toward HER. Comparative analysis of electrodeposited Ag, Au, and Pt particle-decorated porous nickel electrodes for HER indicates that both intrinsic property and size of the noble metal particles can lead to distinct catalytic activities. Both nanoscale Au and Pt particles have further reinforcement effect toward HER, whereas microscale Ag particles exhibit the reverse effect. As an effective 3D hydrogen evolution cathode, the nanoscale Pt-particle-decorated 3D porous nickel electrode demonstrates the highest catalytic activity with an extremely low overpotential of -0.045 V for hydrogen production, a considerable exchange current density of 9.47 mA cm(-2) at 25 °C, and high durability in long-term electrolysis, all of which are attributed to the intrinsic catalytic property and the extremely small size of Pt particles.

19.
Nanoscale ; 7(17): 7644-50, 2015 May 07.
Article in English | MEDLINE | ID: mdl-25833146

ABSTRACT

Non-precious metal catalysts, such as metal-coordinated to nitrogen doped-carbon, have shown reasonable oxygen reduction reaction (ORR) performances in alkaline fuel cells. In this report, we present the development of a highly active, stable and low-cost non-precious metal ORR catalyst by direct synthesis under autogenic-pressure conditions. Transmission electron microscopy studies show highly porous Fe-N-C and Co-N-C structures, which were further confirmed by Brunauer-Emmett-Teller surface area measurements. The surface areas of the Fe-N-C and Co-N-C catalysts were found to be 377.5 and 369.3 m(2) g(-1), respectively. XPS results show the possible existence of N-C and M-Nx structures, which are generally proposed to be the active sites in non-precious metal catalysts. The Fe-N-C electrocatalyst exhibits an ORR half-wave potential 20 mV higher than the reference Pt/C catalyst. The cycling durability test for Fe-N-C over 5000 cycles shows that the half-wave potential lost only 4 mV, whereas the half-wave potential of the Pt/C catalyst lost about 50 mV. The Fe-N-C catalyst exhibited an improved activity and stability compared to the reference Pt/C catalyst and it possesses a direct 4-electron transfer pathway for the ORR process. Further, the Fe-N-C catalyst produces extremely low HO2(-) content, as confirmed by the rotating ring-disk electrode measurements. In the alkaline fuel single cell tests, maximum power densities of 75 and 80 mW cm(-2) were observed for the Fe-N-C and Pt/C cathodes, respectively. Durability studies (100 h) showed that decay of the fuel cell current was more prominent for the Pt/C cathode catalyst compared to the Fe-N-C cathode catalyst. Therefore, the Fe-N-C catalyst appears to be a promising new class of non-precious metal catalysts prepared by an autogenic synthetic method.

20.
J Biomed Mater Res A ; 103(9): 2875-87, 2015 Sep.
Article in English | MEDLINE | ID: mdl-25691137

ABSTRACT

We synthesized graphitic carbon-coated magnetic nanoparticles (Fe@C NPs) and evaluated their physicochemical properties and mechanism of cytotoxicity in vitro. The structure of these nanocomposites consisted of an iron core encapsulated by a graphitic-carbon shell. The diameter of these Fe@C NPs was 81 ± 14 nm, and the thickness of the carbon layer encapsulating the core was 7.0 ± 0.5 nm. Inhibition of cell proliferation was induced by exposure to Fe@C NPs at doses above 50 µg mL(-1) . The exposed cells did not show increased activation of apoptosis biomarkers such as PARP, caspase-3, caspase-7, and caspase-9, and apoptosis-specific responses such as DNA laddering and annexin V binding to the cell membranes. In addition, the expression levels of autophagy-specific biomarkers such as ATG5 and LC3 after exposure were not enhanced, either. Instead, we observed increased release of lactate dehydrogenase in the culture media and red-fluorescent cell cytosol stained with ethidium homodimer I after the exposure. These results indicated enhanced cell membrane permeability after exposure to Fe@C NPs, probably caused by necrosis. The analysis of the regulatory molecules of cell cycling and proliferation, ERK, p53, and AKT, implied that cell cycle arrest was initiated and the cells were sensitized to necrosis. This necrotic cell death was also observed in carbon shells from Fe@C NPs obtained by removing the metal core. In conclusion, the graphitic carbon-encapsulated magnetic nanoparticles synthesized by one-pot synthesis induced necrotic cell death to human HEK293 cells, which was caused by graphitic carbon surface encapsulating the metal core.


Subject(s)
Cell Death/drug effects , Coated Materials, Biocompatible/toxicity , Graphite/toxicity , Magnetite Nanoparticles/toxicity , Apoptosis/drug effects , Autophagy/drug effects , Biomarkers/metabolism , Cell Membrane Permeability/drug effects , Cell Proliferation/drug effects , Coated Materials, Biocompatible/chemistry , HEK293 Cells , Humans , Magnetite Nanoparticles/ultrastructure , Materials Testing , Nanocomposites/chemistry , Nanocomposites/toxicity , Nanocomposites/ultrastructure , Necrosis , Particle Size
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