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1.
J Colloid Interface Sci ; 671: 394-409, 2024 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-38815375

RESUMO

Addressing the challenges of enhancing water-splitting efficiency necessitates the exploration and rational design of high-performance and durable electrocatalysts with appealing nanoarchitectures. In this study, we present the design and fabrication of conjugated cMOF/LDH hetero-nano petals decorated with monodispersed Metal-N sites, which are uniformly shelled over tungsten oxynitride (WNO) nanowire arrays to form a unique core-shell architecture. For this rational engineering, WNO nanowire arrays were grown on carbon cloth. Then, a thin-layered Ru-Co-Fe layered double hydroxide (RuCoFe/LDH) was deposited around these wires, resulting in a highly porous three-dimensional array of hierarchical hetero RuCoFe-LDHs@WNO-NWs core-shell nanowires (RuCoFe-NSs@WNO-NWs). Subsequently, the linkers coordinated with the RuCoFe-LDH nanosheets and transformed them in-situ into the RuCoFe-cMOF nano petals (RuCoFe-NPs@WNO-NWs). Notably, the linker's amino groups functioned as hooks for precisely anchoring and stabilizing metal sites, forming the metal nitride (M-N) moieties. Interestingly, the designed bi-functional catalyst exhibited superior catalytic activities for both OER (230 mV @ 10 mAcm-2) and HER (49 mV @ 10 mAcm-2) in an alkaline medium. Additionally, an electrolyzer cell employing Ru-CoFe-NPs@WNO-NWs as a bi-functional electrocatalyst required 1.49V to reach a current density of 10 mA cm-2. These remarkable catalytic performances can be attributed to several key factors, including opulent exposed active sites, an efficient charge/mass transport pathway, an optimized electronic structure, and an interfacial synergy effect. Hence, this study provides a new perspective for the design of efficient bi-functional electrocatalysts for use in the energy related electrochemical devices.

2.
J Colloid Interface Sci ; 666: 307-321, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38603874

RESUMO

The pursuit of efficient and sustainable hydrogen production through water splitting has led to intensive research in the field of electrocatalysis. However, the impediment posed by sluggish reaction kinetics has served as a significant barrier. This challenge has inspired the development of electrocatalysts characterized by high activity, abundance in earth's resources, and long-term stability. In addressing this obstacle, it is imperative to meticulously fine-tune the structure, morphology, and electronic state of electrocatalysts. By systematically manipulating these key parameters, the full potential of electrocatalysts can unleash, enhancing their catalytic activity and overall performance. Hence in this study, a novel heterostructure is designed, showcasing core-shell architectures achieved by covering W2N-WC nanowire arrays with tri-metallic Nickel-Cobalt-Iron layered triple hydroxide nanosheets on carbon felt support (NiCoFe-LTH/W2N-WC/CF). By integrating the different virtue such as binder free electrode design, synergistic effect between different components, core-shell structural advantages, high exposed active sites, high electrical conductivity and heterostructure design, NiCoFe-LTH/W2N-WC/CF demonstrates striking catalytic performances under alkaline conditions. The substantiation of all the mentioned advantages has been validated through electrochemical data in this study. According to these results NiCoFe-LTH/W2N-WC/CF achieves a current density of 10 mA cm-2 needs overpotential values of 101 mV for HER and 206 mV for OER, respectively. Moreover, as a bi-functional electrocatalyst for overall water splitting, a two-electrode device needs a voltage of 1.543 V and 1.569 V to reach a current density of 10 mA cm-2 for alkaline water and alkaline seawater electrolysis, respectively. Briefly, this research with attempting to combination of different factors try to present a promising stride towards advancing bi-functional catalytic activity with tailored architectures for practical green hydrogen production via electrochemical water splitting process.

3.
Sci Rep ; 14(1): 6045, 2024 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-38472427

RESUMO

Metal-organic frameworks, as a kind of advanced nanoporous materials with metal centers and organic linkers, have been applied as promising electrode materials in energy storage devices. In this study, we are successfully prepared cobalt sulfide nanosheets (CoS) derived from the metal-organic framework on nickel foam (NF). The prepared electrodes are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, Brunauer-Emmett-Teller and Barrett-Joyner-Halenda and electrochemical methods like voltammetry, galvanostatic charge-discharge curve and electrochemical impedance spectroscopy. The CoS/NF electrode demonstrates a high specific capacity of 377.5 mA h g-1 (1359 C g-1) at the current density of 2 A g-1, considerable rate performance and excellent durability (89.4% after 4000 cycles). A hybrid supercapacitor is assembled using CoS/NF as the positive electrode and activated carbon as the negative electrode, it shows a high energy density of 57.4 W h kg-1 at a power density of 405.2 W kg-1. The electrochemical results suggest that the CoS nanosheet arrays would possess excellent potential for applications in energy storage devices.

4.
Chemosphere ; 352: 141340, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38301836

RESUMO

Nanoarchitectured design of the metal sulfides with highly available surface and abundant electroactive centers and using them as electrocatalyst for fabricate the electrochemical sensors for the detection of hydrazine (N2H4) and hydrogen peroxide (H2O2) is challenging and desirable. Herein, Cu2O nanospheres powder is firstly prepared using chemical reduction of copper chloride and then drop-casted on the glassy carbon electrode (GCE) surface. In the next step, CoFeS nanoflakes are electrodeposited on Cu2O nanospheres by cyclic voltammetry method to form CoFeS/Cu2O nanocomposite as a detection platform for measuring N2H4 and H2O2. Accordingly, Cu2O nanospheres are not only used as substrate, but also guided the CoFeS nanoflakes to adhere to the electrode surface without need to any binder or conductive additive, which enhances the electrical conductivity of the sensing active materials. As the hydrazine sensor, the CoFeS/Cu2O/GCE displayed wide linear ranges (0.0001-0.021 mM and 0.021-1.771 mM), low detection limit (0.12 µM), very high sensitivities (103.33 and 21.23 mA mM-1 cm-2), and excellent selectivity. The as-made nanocomposite also exhibited low detection limit of 1.26 µM for H2O2 sensing with very high sensitivities (12.31 and 3.96 mA mM-1 cm-2) for linear ranges of 0.001-0.03 mM and 0.03-2.03 mM, respectively, and negligible response against interfering substances. The superior analytical performance of the CoFeS/Cu2O for N2H4 electro-oxidation and H2O2 electro-reduction can be attributed to structure stability, high electroactive surface area, and good availability to analyte species and electrolyte diffusion. Moreover, to examine the potency of the prepared nanocomposite in real applications, the seawater sample was analyzed and results display that the CoFeS/Cu2O/GCE can be utilized as a reliable and applicable platform for measuring N2H4 and H2O2.


Assuntos
Peróxido de Hidrogênio , Nanosferas , Peróxido de Hidrogênio/química , Cobre/química , Galvanoplastia , Carbono/química , Eletrodos , Técnicas Eletroquímicas/métodos
5.
ACS Appl Mater Interfaces ; 15(36): 42568-42584, 2023 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-37665661

RESUMO

In parallel to the depletion of potable water reservoirs, novel technologies have been developed for seawater softening, as it is the most abundant source for generating deionized water. Although salt removal at subosmotic pressures and ambient temperatures by applying low-operating potentials with high energy efficiency made capacitive deionization (CDI) an advantageous water-softening process, its practical application is limited by insufficient ion removal capacity and low concentration influent. The performance of a CDI system is in progress with engineering the electrode active materials, also facilitating the advance design in highly saline- and seawater study. Herein, an innovative strategy was developed to provide high-performance CDI systems based on efficient and electrochemical ion-uptake active materials with a simple initial preparation. Nitrogen-doped porous carbons (N-pCs) received benefits from a high specific surface area and good surface wettability. The N-pCs were modified with molybdenum oxide/sulfide intercalative array and developed as CDI electrode active materials for desalination of both low/medium saline- and seawater. The MoS2/S,N-pC electrode materials exhibited perfect optimized salt adsorption capacity (SACs) of 47.9 mg g-1 when compared to N-pC (37.9 mg g-1) and MoO3/N-pC (39.6 mg g-1) counterparts at 1.4 V in a 750 ppm NaCl solution. In addition, the assembled CDI cells exhibited reasonable cycle stability and retained 96.7% of their initial SAC in continuous CDI cycles for 128,000 s. The fabricated CDI cell rendered an excellent salt removal efficiency (SRE, %) of 13.34% from the real seawater sample at 1.2 V. In detail, the SRE % of the NaCl, KCl, MgCl2, and CaCl2 soluble salts with respect to seawater sample exhibited a remarkable SRE % of 30.8%, 36%, 32.6%, and 19.3%, respectively. These SRE % values (>13.34%) provide convincing evidence on the reasonable ion uptake capability of the fabricated CDI cells for removing Na+, K+, Mg2+, and Ca2+ ions compared to other soluble component. The advanced cell design parallel to the promising outcomes provided herein makes these CDI systems immensely propitious for efficient water softening.

6.
Talanta ; 257: 124375, 2023 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-36821966

RESUMO

Having a prime significance in diagonsing and predicting the dangerous symptoms of chronic diseases in the early stages, special attention has been drawn by wearable glucose-sensing platforms in recent years. Herein, modified commercial cotton fabrics, decorated with binary Ni-Co metal-organic frameworks (NC-MOFs) through a one-pot scalable hydrothermal route, were directly utilized as flexible electrodes for non-enzymatic glucose amperometric sensing. Glucose sensitivities of 105.2 µA mM-1 cm-2 and 23 µA mM-1 cm-2 were acheived within two distinct linear dynamic ranges of 0.04-3.13 mM and 3.63-8.28 mM, respectively. Receiving benefits from a remarkable glucose sensitivity behavior in co-existence of iso-structures and interferences, rapid response (4.2 s), and remarkable reproducibility and repeatability, NC-MOF-modified cotton fabric electrodes are imensilly promising for developing high-performance wearable glucose sensing platfroms. The sensing performance of fabricated electrodes was further investigated in human blood serum and saliva.


Assuntos
Estruturas Metalorgânicas , Dispositivos Eletrônicos Vestíveis , Humanos , Estruturas Metalorgânicas/química , Níquel/química , Cobalto/química , Reprodutibilidade dos Testes , Glucose/química , Eletrodos
7.
Inorg Chem ; 62(3): 1178-1191, 2023 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-36607645

RESUMO

Increasing demands for pollution-free energy resources have stimulated intense research on the design and fabrication of highly efficient, inexpensive, and stable non-noble earth-abundant metal catalysts with remarkable catalytic activity for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Morphology control of the catalysts is widely implemented as an effective strategy to change the surface atomic coordination and increase the catalytic behavior of the catalysts. In this study, we have designed a series of Mn-Co catalyts with different morphologies on the graphite paper substrate to enhance OER and HER activities in alkaline media. The prepared catalysts with different morphologies were successfully obtained by adjusting the amount of ammonium fluoride (NH4F) in the hydrothermal process. The electrochemical tests display that the cubic-like Mn-Co catalyst with pyramids on the faces at a concentration of 0.21 M NH4F exhibits the best activity toward both OER and HER. The cubic-like Mn-Co catalyst with pyramids on the faces showed overpotentials of 240 and 82 mV at a current density of 10 mA cm-2 for OER and HER, respectively. Also, the cubic-like Mn-Co catalyst with pyramids on the faces required overpotentials of 319 and 216 mV to reach the current density of 100 mA cm-2 for OER and HER, respectively. The current density of this catalyst at η = 0.32 V was 701.05 mA cm-2 for OER, and for HER, the current density of the catalyst was 422.89 mA cm-2 at η = 0.23 V. The Tafel slopes of the Mn-Co catalyst with cubic-like structures with pyramids on the faces were 78 and 121 mV dec-1 for OER and HER, respectively. A two-electrode overall water electrolysis system using this bifunctional Mn-Co catalyst exhibited low cell voltages of 1.60 in the alkaline electrolyte at the standard current density of 10 mA cm-2 with appropriate stability. These electrochemical merits exhibit the considerable potential of the cubic-like Mn-Co catalyst with pyramids on the faces for bifunctional OER and HER applications.


Assuntos
Fluoretos , Água , Manganês , Hidróxidos , Cobalto , Carbonatos , Eletrólise , Hidrogênio , Oxigênio
8.
J Colloid Interface Sci ; 626: 1070-1084, 2022 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-35839676

RESUMO

Exploring bi-functional electrocatalysts with excellent activity, good durability, and cost-effectiveness for electrochemical hydrogen and oxygen evolution reactions (HER and OER) in the same electrolyte is a critical step towards a sustainable hydrogen economy. Three main features such as high density of active sites, improved charge transfer, and optimized electronic configuration have positive effects on the electrocatalyst activity. In this context, understanding structure-composition-property relationships and catalyst activity is very important and highly desirable. Herein, for the first time, we present the design and fabrication of novel MOF-derived ultra-small Ru/RuO2 nanoparticles doped in copper/cobalt nitride (CuCoN) encapsulated in nitrogen-doped nanoporous carbon framework (NC) (Ru/RuO2/CuCoN@NC). For the synthesize of this nanocomposite, firstly bimetallic Cu-Co/MOF hollow nanospheres are prepared via a facile emulsion-based interfacial reaction method and used as the template for Ru ion doping (Ru-doped Cu-Co/MOF). Then, Ru-doped Cu-Co/MOF precursor during the carbonization/nitridation/cooling process converted to the Ru/RuO2/CuCoN@NC nanocomposite. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, Ru/RuO2/CuCoN@NC hollow nanosphere electrocatalyst demonstrates striking catalytic performances under alkaline conditions with a current density of 10 mA cm-2at low overpotentials of 41 mV for HER and 231 mV for OER, respectively. Moreover, as a bifunctional electrocatalyst for overall water splitting, a two-electrode device needs a voltage of 1.51 V to reach a current density of 10 mA cm-2. Comprehensive electrochemical studies show that the excellent electrocatalytic performance of the Ru/RuO2/CuCoN@NC hollow nanosphere could be attributed to the improved physical and chemical properties such as desirable compositional, catalysts uniform dispersion, structural advantages of more exposed active sites, optimized electronic structure, high electrical conductivity, and interfacial synergy effect. This work paves a novel avenue for constructing robust bifunctional electrocatalyst for overall water splitting.

9.
Nanoscale ; 14(25): 9150-9168, 2022 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-35723639

RESUMO

The increasing energy demand for next-generation portable and miniaturized electronics has drawn tremendous attention to develop microscale energy storage and conversion devices with light weight and flexible characteristics. Herein, we report the preparation of flower-like cobalt vanadium selenide/nickel copper selenide (CoVSe/NiCuSe) microspheres with three-dimensional hierarchical structure of micropore growth on copper wire for a flexible fiber microsupercapacitor (microSC) and overall water splitting. The CoV-LDH microspheres are anchored on the dendrite-like NiCu nanostructured Cu wire using a hydrothermal method (CoV-LDH/NiCu@CW). The sulfidation and selenization of CoV-LDH/NiCu was carried out through the ion-exchange reaction of OH- with sulfide and selenide ions to obtain CoVS/NiCuS@CW and CoVSe/NiCuSe@CW electrodes, respectively. Benefitting from the unique structure, the flower-like CoVSe/NiCuSe@CW microspheres exhibit better electrochemical performance compared with other as-prepared fiber-shaped electrodes. As an electrode active material for microSC, CoVSe/NiCuSe microspheres exhibit a specific capacitance of 35.40 F cm-3 at 4 mA cm-2, and maintain 281.25 F cm-3 even at a high current density of 83 mA cm-2, indicating outstanding charge storage capacitance and excellent rate capability. Moreover, the assembled flexible solid-state asymmetric microSCs based on flower-like CoVSe/NiCuSe microspheres-coated Cu wire as the positive electrode and polypyrrole/reduced graphene oxide-coated carbon fiber as the negative electrode manifests a maximum energy density of 20.17 mW h cm-3 at a power density of 624.32 mW cm-3 and remarkable cycling stability (96.7% after 5000 cycles) with good mechanical stability. As an electrocatalyst for oxygen and hydrogen evolution reactions in alkaline medium, the CoVSe/NiCuSe electrode delivers an overpotential of 297 mV and 165 mV at 100 mA cm-2. Furthermore, the CoVSe/NiCuSe-based electrolysis cell for overall water splitting presents a low cell voltage (1.7 V at 50 mA cm-2) as well as high durability.

10.
Nanoscale ; 13(41): 17576-17591, 2021 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-34661211

RESUMO

Although important advances have been acquired in the field of electrocatalysis, the design and fabrication of highly efficient and stable non-noble earth-abundant metal catalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remain a significant challenge. In this study, we have designed a superior bifunctional catalyst for OER and HER in alkaline media based on the Co-Mo-P/Zn-Co-S multicomponent heterostructure. The as-prepared multicomponent heterostructure was successfully obtained via a simple three-step hydrothermal-sulfidation-electrodeposition process consisting of star-like Co-Zn-S covered with Co-Mo-P. The structure and morphology evaluation of the prepared catalysts were performed via Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, and elemental mapping techniques. The electrochemical tests show that Co-Mo-P/Co-Zn-S exhibits outstanding activity toward both OER and HER with OER overpotentials of 273 mV and 312 mV to drive the benchmark current densities of 10 and 50 mA cm-2, respectively, with a Tafel slope of 41 mV dec-1. In addition, the HER overpotentials of 120 mV and 165 mV were required to reach the benchmark current densities of 10 and 50 mA cm-2, respectively, with a Tafel slope of 61.7 mV dec-1 that outperforms most other state-of-the-art catalysts. In the case of HER, the prepared catalyst required an overpotential of 202 mV to reach the current density of 200 mA cm-2 that was much lower than the overpotential of Pt/C (286 mV) to achieve the same current density. Co-Mo-P/Co-Zn-S also exhibits a suitable stability length of 10 h for OER and HER during the chronoamperometric tests. The superior performance of the Co-Mo-P/Co-Zn-S multicomponent heterostructure toward OER and HER may be related to the large specific surface area, accelerated mass and electron transport, and synergistic effect of multiple hybrid materials. These merits suggest that Co-Mo-P/Co-Zn-S can be considered as a promising catalyst for bi-functional OER and HER, and can be offered a great promise for future applications.

11.
J Colloid Interface Sci ; 604: 832-843, 2021 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-34303176

RESUMO

Increasing energy demands for pollution-free and renewable energy technologies have stimulated intense research on the development of inexpensive, highly efficient, and stable non-noble metal electrocatalysts for oxygen evolution reaction (OER). In this study, a superior OER performance was achieved using a tri-metallic (Zn, Co, Ni) high-performance electrocatalyst. We successfully fabricated a peony-flower-like hierarchical ZnCo2O4 through an additive-free hydrothermal reaction followed by heat treatment. Then NiCo-LDH (layered double hydroxides) nano-flakes was electrodeposited on the ZnCo2O4/GCE surface to prepare NiCo-LDH/ZnCo2O4/GCE which was used as electrode for OER. The structure and morphology of the catalysts were characterized by several techniques including Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, elemental mapping and Brunauer-Emmett-Teller method. The NiCo-LDH/ZnCo2O4 catalyst provided high catalytic activity toward OER under alkaline condition (1.0 M KOH) with a low overpotential of 260 mV to drive the benchmark current density of 10 mA cm-2 and Tafel slope of 62 mV dec-1, as well as long-term stability and high turnover frequency of 0.0641 s-1 at overpotential of 340 mV. The NiCo-LDH/ZnCo2O4 catalyst was found to perform significantly better than NiCo-LDH, ZnCo2O4, NiCo-LDH/Co3O4, Co3O4, and commercial RuO2 catalysts. The outstanding OER performance of NiCo-LDH/ZnCo2O4 catalyst, which may be attributed to the large specific surface area, accelerated mass and electron transport, and synergistic effect of multiple hybrid materials, makes it a promising catalyst for OER.

12.
J Colloid Interface Sci ; 593: 182-195, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33744529

RESUMO

To attain superior energy density concurrently with high power density, high-performance supercapacitors have been developed. Herein an innovative strategy has been adopted to fabricate unique binder-free electrodes composed of a unique porous structure of binary metal carbonate hydroxide nanomace-decorated hydrothermal porous carbon spheres (PCSs). Hierarchical nickel-cobalt carbonate hydroxide (NiCOCH) nanomaces, directly grown on PCSs, are used as positive electrodes for supercapacitors fabrication. Furthermore, Fe2O3@PCS composites, having benefits of highly reversible redox reaction in the negative potential window and highly porous structure, are employed as the negative electrode in the fabrication of the asymmetric supercapacitors (ASCs). The assembled NiCoCH@PCS// Fe2O3@PCS asymmetric devices with a wide electrochemical potential window not only have the merit of high energy and power densities but also receive benefits from remarkable cycle stability. These encouraging outcomes that are mutually beneficial, make these fabricated ASCs significantly ideal for high-performance electronics.

13.
J Colloid Interface Sci ; 585: 750-763, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33121753

RESUMO

Evolution of renewable energies in the era of the modernized world has been strongly tied up to the incessant development of high-performance energy storage systems benefiting from both high energy and power densities. In the present work, binder-free positive electrodes are fabricated via a facile electrochemical deposition route in which copper oxide nanorods (CuO NRs) directly grown onto the copper foam (CF) are decorated with bimetallic cobalt-zinc sulfide nanoarrays (Co-Zn-S NAs). The fabricated Co-Zn-S@CuO-CFs represent promising specific capacity of 317.03 C.g-1 at 1.76 A.g-1, along with superior cyclic stability (113% retention after 4500 cycles). Negative electrodes were further prepared through a direct deposition of iron sulfide nanosheets (Fe-S NSs) onto the graphene oxide (GO), showing remarkable the specific capacitance of 543.9 F.g-1 at 0.79 A.g-1. Receiving benefits from remarkable energy and power densities (25.71 Wh.kg-1 and 8.73 kW.kg-1) alongside the reasonable life-stability, the fabricated asymmetric supercapacitor (ASC) devices are on merit for developing high-performance energy storage systems.

14.
Nanoscale ; 12(30): 16123-16135, 2020 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-32700712

RESUMO

Over the last few years, substantial efforts have been made to develop earth-abundant bi-functional catalysts for urea oxidation and energy-saving electrolytic hydrogen production due to their low cost and the potential to replace traditional noble-metal-based catalysts. Nevertheless, finding a straightforward and effective route to prepare efficient catalysts with unique structural features and optimal supports still is a big challenge. Among the various candidates, metal-organic framework (MOF)-derived materials show great advantages as new kinds of active non-precious catalysts. On the other hand, the controllable integration of MOFs and carbon-based nanomaterials leads to further enhancement in terms of the stability and electrical conductivity of catalysts. In this communication, we develop an MOF-carbon-based composite to synthesize a transition metal phosphide (TMP) catalyst for the electrocatalytic oxidation of urea. First, poly(pyrrole-co-aniline) (PPCA) hollow nanospheres were fabricated via the in situ emulsion polymerization of a mixture of aniline and pyrrole in the presence of Triton X-100. Then, the simple carbonization treatment of these PPCA hollow spheres led to the carbonized hollow carbon nanospheres (HCNs) with ultrahigh surface areas and uniform nano-morphologies. After that, bimetallic MM'/MOFs (M/M' = Ni, Co) were uniformly grown around the HCNs via a simple hydrothermal reaction (NiCo/MOF@HCNs). During the synthesis process, by adjusting Ni/Co ratios, the MOF morphology can be engineered so that by reducing the Ni/Co ratio, the flower-like structures change into urchin-like structures. Finally, this NiCo/MOF@HCNs precursor with different Ni/Co ratios during the in situ carbonization/phosphorization was chemically converted into Ni-Co mixed-metal phosphides (NixCo2-xP/C@HCNs). Finally, the electrocatalytic activity of the prepared catalysts was tested for the urea oxidation reaction (UOR) and hydrogen evolution reaction (HER).

15.
ACS Appl Mater Interfaces ; 12(14): 16250-16263, 2020 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-32096627

RESUMO

Developing effective and priceless electrocatalysts is an indispensable requirement for advancing the efficiency of water splitting to get clean and sustainable fuels. Herein, we reported a feasible strategy for preparing a trimetallic (NiCoFe) superior electrocatalyst with a novel open-cage/3D frame-like structure for an oxygen evolution reaction (OER). It is prepared by consequent thermal treatments of a CoFe Prussian blue analogue frame/cage-like structure under an argon (CoFeA-TT) atmosphere and then electrochemical deposition of nickel-cobalt sulfide nanosheets as a shell layer on it. The electrochemical measurements demonstrated that the deposition of NiCo-S on CoFeA-TT (NiCo-S@CoFeA-TT) has the best catalytic performance and can drive the benchmark current density of 10 mA cm-2 at a low overpotential of 268 mV with a Tafel slope of 62 mV dec-1 and an excellent long-term catalytic stability in an alkaline medium. Its outstanding electrocatalytic performances are endowed from frame/cage-like structures, highly exposed active sites, accelerated mass and electron transport, and the synergistic effect of multiple hybrid components. The NiCo-S@CoFeA-TT showed a better performance than most advanced nonprecious catalysts and the noble commercial RuO2 catalyst. This study exhibited an effective and efficient procedure to design 3D porous architecture catalysts for the energy-relevant electrocatalysis reaction.

16.
Talanta ; 210: 120696, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-31987185

RESUMO

In this study, for the first time, we reported a fast and facile three-step in situ strategy for direct controllable growth of the Co3(BTC)2 MOFs thin films on the GCE, through the rapid conversion of the electrodeposited Co(OH)2 nano-flakes on rGO/GCE, to crystalline rectangular bar-shape structures of MOFs. X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy and elemental mapping analysis used to the structural and morphological characterization of the well-synthesized MOFs. The as-prepared Co3(BTC)2 MOFs were used to construct a non-enzymatic sensing platform for determining the glucose in alkaline solution. The designed electrode demonstrated two wide linear dynamic range of 1 µM - 0.33 mM and 0.33 mM-1.38 mM with high sensitivity of 1792 µA mM-1 cm-2 and 1002 µA mM-1 cm-2, respectively, good repeatability and reproducibility, high selectivity against interference species and good poisoning resistance against chloride ions and a low detection limit of 0.33 µM (S/N = 3). Finally, the application of the proposed sensor for the determination of glucose in the human blood serum samples was investigated and results showed excellent recoveries, which confirmed that the fabricated sensor can act as a reliable and sensitive platform for biological and clinical samples analysis.


Assuntos
Técnicas Biossensoriais , Carbono/química , Cobalto/química , Técnicas Eletroquímicas , Glucose/análise , Hidróxidos/química , Estruturas Metalorgânicas/química , Eletrodos , Grafite/síntese química , Grafite/química , Tamanho da Partícula , Propriedades de Superfície
17.
J Colloid Interface Sci ; 563: 241-251, 2020 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-31877421

RESUMO

Growing demands for clean and renewable energy technologies have sparked broad research on the development of highly efficient and stable non-noble metal electrocatalysts for oxygen evolution reaction (OER). In this regard, in the present work a three-dimensional Fe2TiO5/nitrogen-doped graphene (denoted as 3D FTO/NG) hybrid electrocatalyst was synthesized via a facile in-situ process using a hydrothermal method. Structural characterization of the prepared nanocomposite is performed by various techniques e.g. field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) analysis, Fourier transform infrared spectra (FT-IR), X-ray photoelectron spectroscopy spectra (XPS), X-ray diffraction (XRD) and Raman spectroscopic methods. A novel binder-free electrode for OER activity has been prepared by coating a 3D FTO/NG onto nickel foam (NF). In particular, the 3D FTO/NG nanocomposite, which is synthesized with in-situ hydrothermal process, exhibited a remarkable OER performance in alkaline media. The prepared electrocatalyst showed a small overpotential of 0.36 V with a Tafel slope of 0.07 V dec-1 at 100 A m-2 with a long-term stability for OER reaction in 1 M KOH. The outstanding OER performance and durability of 3D FTO/NG can be attributed to the synergistic effects originating from NG and FTO in the prepared electrocatalyst, which helps to enhance the conductivity of the nanocomposite. The presence of conductive NG in the prepared 3D nanocomposite can not only improve the mechanical stability, but also facilitate its electron transport. Also, N atoms and FTO provide abundant electrocatalytic active sites, which accelerate evolution of gas bubbles. This work provides a promising approach for synthesis of inexpensive and efficient OER electrocatalysts.

18.
Anal Chem ; 91(23): 14960-14966, 2019 12 03.
Artigo em Inglês | MEDLINE | ID: mdl-31682108

RESUMO

Finding fast and reliable ways to detect pathogenic bacteria is crucial for addressing serious public health issues in clinical, environmental, and food settings. Here, we present a novel assay based on the conversion of an electrochemical signal into a more convenient optical readout for the visual detection of Escherichia coli. Electropolymerizing polyaniline (PANI) on an indium tin oxide screen-printed electrode (ITO SPE), we achieved not only the desired electrochromic behavior but also a convenient way to modify the electrode surface with antibodies (taking advantage of the many amine groups of PANI). Applying a constant potential to the PANI-modified ITO SPE induces a change in their oxidation state, which in turn generates a color change on the electrode surface. The presence of E. coli on the electrode surface increases the resistance in the circuit affecting the PANI oxidation states, producing a different electrochromic response. Using this electrochromic sensor, we could measure concentrations of E. coli spanning 4 orders of magnitude with a limit of detection of 102 colony forming unit per 1 mL (CFU mL-1) by the naked eye and 101 CFU mL-1 using ImageJ software. In this work we show that merging the sensitivity of electrochemistry with the user-friendliness of an optical readout can generate a new and powerful class of biosensors, with potentially unlimited applications in a variety of fields.


Assuntos
Compostos de Anilina/química , Colorimetria/métodos , Eletroquímica/métodos , Escherichia coli/isolamento & purificação , Colorimetria/normas , Eletrodos , Limite de Detecção , Oxirredução , Polimerização , Software , Compostos de Estanho
19.
J Colloid Interface Sci ; 555: 655-666, 2019 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-31408764

RESUMO

In this work, we present the design and fabrication of a novel nanocomposite based on noble metal and metal oxide nanoparticles dispersed on highly porous carbon obtained via the pyrolysis of an inorganic complex and metal-organic frameworks. This nanocomposite is prepared by a two-step procedure: first, the composite support of nanoporous carbon (NPC) is obtained by the direct carbonization of the Cr-benzene dicarboxylic ligand (BDC) MOF in an Argon atmosphere at 500 °C (Cr2O3-NPC). A mixture containing Cr2O3-NPC and [PtCl(SnCl3)(SMe2)2] is then prepared, and underflow of Argon is heated to 380 °C. Finally, Pt-SnO2 nanoparticles are loaded on the Cr2O3-NPC support, and the obtained nanocomposite was denoted as Pt-SnO2/Cr2O3-NPC. The morphology and crystalline structure of the prepared nanocomposites were characterized using XRD, SEM, EDX, FT-IR, and XPS. In addition, the prepared nanocomposite was examined as a novel electrocatalyst for the ethanol electro-oxidation reaction (EOR). The obtained results demonstrated that, compared with Pt/Cr2O3-NPC, Pt-SnO2/Cr2O3-NPC showed higher electrocatalytic activity, lower onset potential, and a higher level of poisoning tolerance toward of ethanol oxidation in acidic media. The overall results corroborate the predominant role of SnO2 as an excellent catalytic-enhancing agent thorough facilitating the charge transfer process and increasing the CO poisoning oxidation by the spillover of OHads to the Pt surface. Thus, the prepared Pt-SnO2/Cr2O3-NPC catalyst could be considered a promising anode catalyst for direct ethanol fuel cells.

20.
Nanoscale ; 11(26): 12655-12671, 2019 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-31237600

RESUMO

The planned design of nanocomposites combined with manageable production processes, which can offer controllability over the nanomaterial structure, promises the practical applications of functional nanomaterials. Hollow core-shell nanostructure architectures represent an emerging category of advanced functional nanomaterials, whose benefits derived from their notable properties may be hampered by complicated construction processes, especially in the sensing domain. In this regard, we designed a highly porous three-dimensional array of hierarchical hetero Cu(OH)2@CoNi-LDH core-shell nanotubes via a quick, very simple, green, and highly controllable three-step in situ method; they were directly grown on a glassy carbon electrode to fabricate an enzyme-free glucose sensor. By virtue of an open structure containing a hollow conductive core and a highly porous catalytic active shell, which were both synthesized by the in situ method, hierarchical self-standing core-shell nanotubes were obtained. They provided an enlarged active surface area, highly accessible catalytic sites, faster electron transfer, effortless electrolyte ion diffusion pathways, and structural stability, thus leading to improved electrocatalytic performances and durability towards glucose electro-oxidation; this was reflected by the fast sensitive responses of the as-prepared sensor towards glucose and comparable results with the automatic biochemistry analyzer used in hospitals in real sample analysis. Moreover, the commercialization capability of the proposed sensor was evaluated analogously by directly grown hierarchical Cu(OH)2@CoNi-LDH core-shell nanotubes on graphite screen-printed exposable electrodes through a 3-step in situ method. Cu(OH)2@CoNi-LDH NS-NTs/GSPE showed accurate responses towards glucose, lack of any fouling effect of the electrocatalyst layer over a wide range of glucose concentrations and comparable results with that of a commercial glucometer in real sample analysis, which revealed high sensitivity, selectivity, and durability of the low-cost on-site sensor as well as excellent versatility of its fabrication method. Thus, the self-supporting, cost-affordable, facile, and fast electrode fabrication procedure with versatility and meticulous structural controllability presented in this research provides a new architecture for the advancement of high-performance electrochemical sensors and miniaturized detection devices.

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