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1.
Adv Colloid Interface Sci ; 333: 103298, 2024 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-39243484

RESUMO

This review paper focuses on group IVB transition metal nitrides (TMNs) such as titanium nitride (TiN), zirconium nitride (ZrN), and hafnium nitride (HfN) and as alternative plasmonic materials to noble metals like gold and silver. It delves into the fabrication methods of these TMNs, particularly emphasizing thin film fabrication techniques like magnetron sputtering and atomic layer deposition, as well as nanostructure fabrication processes applied to these thin films. Overcoming the current fabrication and application-related challenges requires a deep understanding of the material properties, deposition techniques, and application requirements. Here, we discuss the impact of fabrication parameters on the properties of resulting films, highlighting the importance of aligning fabrication methods with practical application requirements for optimal performance. Additionally, we summarize and tabulate the most recent plasmonic applications of these TMNs in fields like biosensing, photovoltaic energy, and photocatalysis, contributing significantly to the current literature by consolidating knowledge on TMNs.

2.
ACS Nano ; 18(35): 24469-24483, 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39172806

RESUMO

Bacterial infections claim millions of lives every year, with the escalating menace of microbial antibiotic resistance compounding this global crisis. Nanozymes, poised as prospective substitutes for antibiotics, present a significant frontier in antibacterial therapy, yet their precise enzymatic origins remain elusive. With the continuous development of nanozymes, the applications of elemental N-modulated nanozymes have spanned multiple fields, including sensing and detection, infection therapy, cancer treatment, and pollutant degradation. The introduction of nitrogen into nanozymes not only broadens their application range but also holds significant importance for the design of catalysts in biomedical research. The synergistic interplay between W and N induces pivotal alterations in electronic configurations, endowing tungsten nitride (WN) with a peroxidase-like functionality. Furthermore, the introduction of N vacancies augments the nanozyme activity, thus amplifying the catalytic potential of WN nanostructures. Rigorous theoretical modeling and empirical validation corroborate the genesis of the enzyme activity. The meticulously engineered WN nanoflower architecture exhibits an exceptional ability in traversing bacterial surfaces, exerting potent bactericidal effects through direct physical interactions. Additionally, the topological intricacies of these nanostructures facilitate precise targeting of generated radicals on bacterial surfaces, culminating in exceptional bactericidal efficacy against both Gram-negative and Gram-positive bacterial strains along with notable inhibition of bacterial biofilm formation. Importantly, assessments using a skin infection model underscore the proficiency of WN nanoflowers in effectively clearing bacterial infections and fostering wound healing. This pioneering research illuminates the realm of pseudoenzyme activity and bacterial capture-killing strategies, promising a fertile ground for the development of innovative, high-performance artificial peroxidases.


Assuntos
Antibacterianos , Nitrogênio , Antibacterianos/farmacologia , Antibacterianos/química , Nitrogênio/química , Testes de Sensibilidade Microbiana , Compostos de Tungstênio/química , Compostos de Tungstênio/farmacologia , Peroxidase/metabolismo , Peroxidase/química , Animais , Tungstênio/química , Tungstênio/farmacologia , Materiais Biomiméticos/química , Materiais Biomiméticos/farmacologia , Infecções Bacterianas/tratamento farmacológico , Camundongos , Catálise , Nanoestruturas/química , Escherichia coli/efeitos dos fármacos , Humanos
3.
Materials (Basel) ; 17(14)2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39063821

RESUMO

Supercapacitor electrode materials play a decisive role in charge storage and significantly affect the cost and capacitive performance of the final device. Engineering of the heterostructure of metal-organic framework (MOF)-derived transition metal nitrides (TMNs) can be conducive to excellent electrochemical performance owing to the synergistic effect, optimized charge transport/mass transfer properties, and high electrical conductivity. In this study, a Co4N/CoN heterostructure was incorporated into a nitrogen-doped support by radio-frequency (RF) plasma after simple pyrolysis of Co-based formate frameworks (Co-MFFs), with the framework structure well retained. Plasma engineering can effectively increase the ratio of Co4N in the Co4N/CoN heterostructure, accelerating the electron transfer rate and resulting in a rough surface due to the reduction effect of high-energy electrons and the etching effect of ions. Benefiting from the plasma modification, the obtained electrode material Co4N/CoN@C-P exhibits a high specific capacitance of 346.2 F·g-1 at a current density of 1 A·g-1, approximately 1.7 times that of CoN/Co4N@C prepared by pyrolysis. The specific capacitance of Co4N/CoN@C-P reaches 335.6 F·g-1 at 10 A·g-1, approximately 96.9% of that at 1 A·g-1, indicating remarkable rate capability. Additionally, the capacitance retention remains at 100% even after 1000 cycles, suggesting excellent cycling stability. The rational design and plasma engineering of the TMN heterostructures at the nanoscale are responsible for the excellent electrochemical performance of this novel composite material.

4.
Nanomaterials (Basel) ; 14(14)2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-39057890

RESUMO

Titanium nitride (TiN) is a candidate material for several plasmonic applications, and pulsed laser ablation in liquids (PLAL) represents a rapid, scalable, and environmentally friendly approach for the large-scale production of nanomaterials with customized properties. In this work, the nanosecond PLAL process is developed, and we provide a concise understanding of the process parameters, such as the solvent and the laser fluence and pulse wavelength, to the size and structure of the produced TiN nanoparticles (NPs). TiN films of a 0.6 µm thickness developed by direct-current (DC) magnetron sputtering were used as the ablation targets. All laser process parameters lead to the fabrication of spherical NPs, while the laser pulse fluence was used to control the NPs' size. High laser pulse fluence values result in larger TiN NPs (diameter around 42 nm for 5 mJ and 25 nm for 1 mJ), as measured from scanning electron microscopy (SEM). On the other hand, the wavelength of the laser pulse does not affect the mean size of the TiN NPs (24, 26, and 25 nm for 355, 532, and 1064 nm wavelengths, respectively). However, the wavelength plays a vital role in the quality of the produced TiN NPs. Shorter wavelengths result in NPs with fewer defects, as indicated by Raman spectra and XPS analysis. The solvent type also significantly affects the size of the NPs. In aqueous solutions, strong oxidation of the NPs is evident, while organic solvents such as acetone, carbides, and oxides cover the TiN NPs.

5.
Nano Lett ; 24(21): 6233-6239, 2024 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-38758973

RESUMO

We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11̅00) surface. To this end, ScN is grown on freestanding GaN(11̅00) substrates and self-assembled GaN nanowires exhibiting (11̅00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]∥GaN(11̅00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11̅00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.

6.
Chem Asian J ; 19(16): e202400220, 2024 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-38654594

RESUMO

The advancement of a sustainable and scalable catalyst for hydrogen production is crucial for the future of the hydrogen economy. Electrochemical water splitting stands out as a promising pathway for sustainable hydrogen production. However, the development of Pt-free electrocatalysts that match the energy efficiency of Pt while remaining economical poses a significant challenge. This review addresses this challenge by highlighting latest breakthroughs in Pt-free catalysts for the hydrogen evolution reaction (HER). Specifically, we delve into the catalytic performance of various transition metal phosphides, metal carbides, metal sulphides, and metal nitrides toward HER. Our discussion emphasizes strategies for enhancing catalytic performance and explores the relationship between structural composition and the performance of different electrocatalysts. Through this comprehensive review, we aim to provide insights into the ongoing efforts to overcome barriers to scalable hydrogen production and pave the way for a sustainable hydrogen economy.

7.
Small ; 20(30): e2310535, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38420898

RESUMO

The exploiting electrocatalysts for water/seawater electrolysis with remarkable activity and outstanding durability at industrial grade current density remains a huge challenge. Herein, CoMoNx and Fe-doped CoMoNx nanosheet arrays are in-situ grown on Ni foam, which possess plentiful holes, multilevel heterostructure, and lavish Co5.47N/MoN@NF and Fe-Co5.47N/MoN@NF interfaces. They require low overpotentials of 213 and 296 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under alkaline media to achieve current density of 800 mA cm-2, respectively, and both possess low Tafel slopes (51.1 and 49.1 mV dec-1) and undiminished stability over 80 h. Moreover, the coupled Co5.47N/MoN@NF and Fe-Co5.47N/MoN@NF electrolyzer requires low voltages of 1.735 V to yield 500 mA cm-2 in alkaline water. Notably, they also exhibit exceptional electrocatalytic properties in alkaline seawater (1.833 V@500 mA cm-2). The experimental studies and theoretical calculations verify that Fe doping does reduce the energy barrier from OH* to O* intermediates during OER process after catalyst reconstruction, and the non-metallic N site from MoN exhibits the lowest theoretical overpotential. The splendid catalytic performance is attributed to the optimized local electron configuration and porous structure. This discovery provides a new design method toward low-cost and excellent catalysts for water/seawater splitting to produce hydrogen.

8.
Small ; 20(16): e2307246, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38039499

RESUMO

Perovskite solar cells (PSCs) with a booming high power conversion efficiency (PCE) are on their road toward industrialization. A proper design of the counter electrode (CE) with low cost, high conductivity, chemical stability, and good interface contact with the other functional layer atop the perovskite layer is vital for the overall performance of PSCs. Herein, the application of titanium nitride (TiN) is reported as a conductive medium for the printable CE in hole-conductor-free mesoscopic PSCs. TiN improves the conductivity of the CE and reduces the resistivity from 20 to 10 mΩ∙cm. TiN also improves the wettability of the CE with perovskite and enhances the back interface contact, which promotes charge collection. On the other hand, TiN is chemically stable during processing and undergoes no distinguishable chemical reaction with halide perovskite. Devices with TiN as the conductive media in the CE deliver a champion PCE of 19.01%. This work supplies a considerable choice for the CE design of PSCs toward industrial applications.

9.
Chemistry ; 29(54): e202301207, 2023 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-37434541

RESUMO

Azidoporphinatoiron(III) ([1]) is an archetypal model complex for the photochemical generation of nitridoiron(V) complexes via cleavage of dinitrogen. So far, this process has only been studied with continuous irradiation in thin films under cryogenic conditions or in frozen solutions. In addition, the photooxidation from iron(III) to iron(V) competes with photoreduction to iron(II) via cleavage of an azidyl radical. The quantum yields of both pathways remained hitherto undisclosed. Here, we investigated the photolysis of this model complex in room temperature liquid solution using stationary and time-resolved infrared spectroscopy. The two reaction pathways are unambiguously identified in quenching studies and their quantum yields are accurately determined. Nitridoporphinatoiron(V) ([2]) exhibits N-atom-2-electron-transfer reactivity toward tert-butyl isonitrile and forms a carbodiimido species. In the presence of tert-butyl isonitrile, the two products of the photoreduction pathway react to cationic diisonitriloporphinatoiron(III) and azide anions, which in turn combine to reform [1] and the quencher.

10.
Nanotechnology ; 34(37)2023 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-37311438

RESUMO

The self-assembly of heteroepitaxial GaN nanowires using either molecular beam epitaxy (MBE) or metal-organic vapor phase epitaxy (MOVPE) mostly results in wafer-scale ensembles with ultrahigh (>10µm-2) or ultralow (<1µm-2) densities, respectively. A simple means to tune the density of well-developed nanowire ensembles between these two extremes is generally lacking. Here, we examine the self-assembly of SiNxpatches on TiN(111) substrates which are eventually acting as seeds for the growth of GaN nanowires. We first found that if prepared by reactive sputtering, the TiN surface is characterized by {100} facets for which the GaN incubation time is extremely long. Fast GaN nucleation is only obtained after deposition of a sub-monolayer of SiNxatoms prior to the GaN growth. By varying the amount of pre-deposited SiNx, the GaN nanowire density could be tuned by three orders of magnitude with excellent uniformity over the entire wafer, bridging the density regimes conventionally attainable by direct self-assembly with MBE or MOVPE. The analysis of the nanowire morphology agrees with a nucleation of the GaN nanowires on nanometric SiNxpatches. The photoluminescence analysis of single freestanding GaN nanowires reveals a band edge luminescence dominated by excitonic transitions that are broad and blue shifted compared to bulk GaN, an effect that is related to the small nanowire diameter and to the presence of a thick native oxide. The approach developed here can be principally used for tuning the density of most III-V semiconductors nucleus grown on inert surfaces like 2D materials.


Assuntos
Gálio , Nanofios , Nanofios/química , Estanho , Gálio/química , Luminescência , Óxidos
11.
ACS Appl Mater Interfaces ; 15(3): 4733-4742, 2023 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-36625508

RESUMO

Epitaxial titanium nitride (TiN) and titanium oxynitride (TiON) thin films have been grown on sapphire substrates using a pulsed laser deposition (PLD) method in high-vacuum conditions (base pressure <3 × 10-6 T). This vacuum contains enough residual oxygen to allow a time-independent gas phase oxidation of the ablated species as well as a time-dependent regulated surface oxidation of TiN to TiON films. The time-dependent surface oxidation is controlled by means of film deposition time that, in turn, is controlled by changing the number of laser pulses impinging on the polycrystalline TiN target at a constant repetition rate. By changing the number of laser pulses from 150 to 5000, unoxidized (or negligibly oxidized) and oxidized TiN films have been obtained with the thickness in the range of four unit cells to 70 unit cells of TiN/TiON. X-ray photoelectron spectroscopy (XPS) investigations reveal higher oxygen content in TiON films prepared with a larger number of laser pulses. The oxidation of TiN films is achieved by precisely controlling the time of deposition, which affects the surface diffusion of oxygen to the TiN film lattice. The lattice constants of the TiON films obtained by x-ray diffraction (XRD) increase with the oxygen content in the film, as predicted by molecular dynamics (MD) simulations. The lattice constant increase is explained based on a larger electrostatic repulsive force due to unbalanced local charges in the vicinity of Ti vacancies and substitutional O. The bandgap of TiN and TiON films, measured using UV-visible spectroscopy, has an asymmetric V-shaped variation as a function of the number of pulses. The bandgap variation following the lower number of laser pulses (150-750) of the V-shaped curve is explained using the quantum confinement effect, while the bandgap variation following the higher number of laser pulses (1000-5000) is associated with the modification in the band structure due to hybridization of O2p and N2p energy levels.

12.
Adv Mater ; 35(5): e2207757, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36538726

RESUMO

The large and rapidly growing family of 2D early transition metal carbides, nitrides, and carbonitrides (MXenes) raises significant interest in the materials science and chemistry of materials communities. Discovered a little more than a decade ago, MXenes have already demonstrated outstanding potential in various applications ranging from energy storage to biology and medicine. The past two years have witnessed increased experimental and theoretical efforts toward studying MXenes' mechanical and tribological properties when used as lubricant additives, reinforcement phases in composites, or solid lubricant coatings. Although research on the understanding of the friction and wear performance of MXenes under dry and lubricated conditions is still in its early stages, it has experienced rapid growth due to the excellent mechanical properties and chemical reactivities offered by MXenes that make them adaptable to being combined with other materials, thus boosting their tribological performance. In this perspective, the most promising results in the area of MXene tribology are summarized, future important problems to be pursued further are outlined, and methodological recommendations that could be useful for experts as well as newcomers to MXenes research, in particular, to the emerging area of MXene tribology, are provided.

13.
Front Chem ; 10: 1073175, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36531324

RESUMO

Hydrogen (H2) has been considered an ideal alternative energy source for solving energy supply security and greenhouse gas reduction. Although platinum group metal (PGM) catalysts have excellent performance in hydrogen electrocatalysis, their scarcity and high cost limit their industrial application. Therefore, it is necessary to develop low-cost and efficient non-PGM catalysts. Transition metal nitrides (TMNs) have attracted much attention because of their excellent catalytic performance in hydrogen electrochemistry, including hydrogen evolution reaction (HER)/hydrogen oxidation reaction (HOR). In this paper, we review and discuss the mechanism of HER/HOR in alkaline media. We compare and evaluate electrocatalytic performance for the HER/HOR TMN catalysts recently reported. Finally, we propose the prospects and research trends in sustainable alkaline hydrogen electrocatalysis.

14.
ACS Appl Mater Interfaces ; 14(41): 46708-46715, 2022 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-36195562

RESUMO

Harnessing solar energy by employing concentrated solar power (CSP) systems requires materials with high electrical conductivity and optical reflectivity. Silver, with its excellent optical reflectance, is traditionally used as a reflective layer in solar mirrors for CSP technologies. However, silver is soft and expensive, quickly tarnishes, and requires a protective layer of glass for practical applications. Moreover, supply-side constraints and high-temperature instability of silver have led to the search for alternative materials that exhibit high solar and infrared reflectance. Transition metal nitrides, such as titanium nitride, have emerged as alternative plasmonic materials to gold starting from a spectral range of ∼500 nm. However, to achieve high solar reflection (∼320-2500 nm), materials with epsilon-near-zero starting from the near-ultraviolet (UV) spectral region are required. Here, we show the development of refractory epitaxial hafnium nitride (HfN) and zirconium nitride (ZrN) thin films as excellent mirrors with a solar reflectivity of ∼90.3% and an infrared reflectivity of ∼95%. Low-loss and high-quality epsilon-near-zero resonance at near-UV (∼340-380 nm) spectral regions are achieved in HfN and ZrN by carefully controlling the stoichiometry, leading to a sharp increase in the reflection edge that is on par with silver. Temperature-dependent reflectivity and dielectric constants are further measured to demonstrate their high-temperature suitability. The development of refractory epitaxial HfN and ZrN thin films with high solar and infrared reflectance makes them excellent alternative plasmonic materials to silver and would pave their applications in CSP, daytime radiative cooling, and others.

15.
Angew Chem Int Ed Engl ; 61(46): e202213041, 2022 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-36148482

RESUMO

Recent interest in skeletal editing necessitates the continued development of reagent classes with the ability to transfer single atoms. Terminal transition metal nitrides hold immense promise for single-atom transfer, though their use in organic synthesis has so far been limited. Here we demonstrate a synthetic cycle with associated detailed mechanistic studies that primes the development of terminal transition metal nitrides as valuable single-atom transfer reagents. Specifically, we show [cis-terpyOsNCl2 ]PF6 inserts nitrogen into indenes to afford isoquinolines. Mechanistic studies for each step (insertion, aromatization, product release, and nitride regeneration) are reported, including crystallographic characterization of diverted intermediates, kinetics, and computational studies. The mechanistic foundation set by this synthetic cycle opens the door to the further development of nitrogen insertion heteroarene syntheses promoted by late transition metal nitrides.

16.
Nanomaterials (Basel) ; 12(15)2022 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-35957091

RESUMO

The energy crisis and environmental issues are becoming more severe due to the long-term consumption of fossil fuels. Therefore, novel energy-conversion devices with high energy density and environmental friendliness are expected to provide reliable alternatives to traditional fossil-based energy systems. However, because of the inevitable use of costly precious metals as the electrode catalysts for such devices, their popularization is seriously hindered. Transition metal nitrides (TMNs) exhibit similar surface and adsorption properties to noble metals because the atomic distance between metal atoms increases and the d-band center of metal atoms downshifts after nitrogen atoms enter the metal lattice. TMNs have become one of the best electrode materials to replace noble metal-based electrocatalysts in next-generation energy-storage and energy-conversion devices. In this review, the recent developments in the electrocatalytic application of TMNs are covered. First, we discuss the structure and activity origin of TMNs and introduce the common synthesis methods for the preparation of TMNs. Subsequently, we illustrate the applications of mono-metallic TMNs and multi-metallic TMNs in oxygen-reduction reaction, oxygen-evolution reaction, and bifunctional oxygen reduction and evolution reactions. Finally, we summarize the challenges of TMNs encountered at the present stage, and expect their future development.

17.
Biosensors (Basel) ; 12(7)2022 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-35884257

RESUMO

The last decade witnessed the emergence of a new family of 2D transition metal carbides and nitrides named MXenes, which quickly gained momentum due to their exceptional electrical, mechanical, optical, and tunable functionalities. These outstanding properties also rendered them attractive materials for biomedical and biosensing applications, including drug delivery systems, antimicrobial applications, tissue engineering, sensor probes, auxiliary agents for photothermal therapy and hyperthermia applications, etc. The hydrophilic nature of MXenes with rich surface functional groups is advantageous for biomedical applications over hydrophobic nanoparticles that may require complicated surface modifications. As an emerging 2D material with numerous phases and endless possible combinations with other 2D materials, 1D materials, nanoparticles, macromolecules, polymers, etc., MXenes opened a vast terra incognita for diverse biomedical applications. Recently, MXene research picked up the pace and resulted in a flood of literature reports with significant advancements in the biomedical field. In this context, this review will discuss the recent advancements, design principles, and working mechanisms of some interesting MXene-based biomedical applications. It also includes major progress, as well as key challenges of various types of MXenes and functional MXenes in conjugation with drug molecules, metallic nanoparticles, polymeric substrates, and other macromolecules. Finally, the future possibilities and challenges of this magnificent material are discussed in detail.


Assuntos
Pesquisa Biomédica , Sistemas de Liberação de Medicamentos , Antibacterianos/química
18.
Small ; 18(34): e2203042, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35908802

RESUMO

Transition metal nitrides (TMNs) nanostructures possess distinctive electronic, optical, and catalytic properties, showing great promise to apply in clean energy, optoelectronics, and catalysis fields. Nonetheless, phase-regulation of NiFe-bimetallic nitrides nanocrystals or nanohybrid architectures confronts challenges and their electrocatalytic overall water splitting (OWS) performances are underexplored. Herein, novel pure-phase Ni2+ x Fe2- x N nanocrystals armored with amorphous N-doped carbon (NC) nanoparticles nanocubes (NPNCs) are obtained by controllable nitridation of NiFe-Prussian-blue analogues derived oxides/NC NPNCs under Ar/NH3 atmosphere. Such Ni2+ x Fe2- x N/NC NPNCs possess mesoporous structures and show enhanced electrocatalytic activity in 1 m KOH electrolyte with the overpotential of 101 and 270 mV to attain 10 and 50 mA cm-2 current toward hydrogen and oxygen evolution reactions, outperforming their counterparts (mixed-phase NiFe2 O4 /Ni3 FeN/NC and NiFe oxides/NC NPNCs). Remarkably, utilizing them as bifunctional catalysts, the assembled Ni2+ x Fe2- x N/NC||Ni2+ x Fe2- x N/NC electrolyzer only needs 1.51 V cell voltage for driving OWS to approach 10 mA cm-2 water-splitting current, exceeding their counterparts and the-state-of-art reported bifunctional catalysts-based devices, and Pt/C||IrO2 couples. Additionally, the Ni2+ x Fe2- x N/NC||Ni2+ x Fe2- x N/NC manifests excellent durability for OWS. The findings presented here may spur the development of advanced TMNs nanostructures by combining phase, structure engineering, and hybridization strategies and stimulate their applications toward OWS or other clean energy fields.

19.
Small ; 18(4): e2105696, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34837326

RESUMO

The oxygen evolution reaction (OER) plays a key role in many electrochemical energy conversion systems, but it is a kinetically sluggish reaction and requires a large overpotential to deliver appreciable current, especially for the non-noble metal electrocatalysts. In this study, the authors report a surface phase engineering strategy to improve the OER performance of transition metal nitrides (TMNs). The iron-nickel nitrides/alloy nanospheres (FeNi3 -N) wrapped in carbon are synthesized, and the optimized FeNi3 -N catalyst displays dual-phase nitrides on the surface induced by atom migration phenomenon, resulting from the different migration rates of metal atoms during the nitridation process. It shows excellent OER performance in alkaline media with an overpotential of 222 mV at 10 mA cm-2 , a small Tafel slope of 41.53 mV dec-1 , and long-term durability under high current density (>0.5 A cm-2 ) for at least 36 h. Density functional theory (DFT) calculations further reveal that the dual-phase nitrides are favorable to decrease the energy barrier, modulate the d-band center to balance the absorption and desorption of the intermediates, and thus promote the OER electrochemical performance. This strategy may shed light on designing OER and other catalysts based on surface phase engineering.

20.
Mikrochim Acta ; 189(1): 1, 2021 12 02.
Artigo em Inglês | MEDLINE | ID: mdl-34855022

RESUMO

Mo5N6 nanosheets were synthesized by a nickel-induced growth method and were found to possess peroxidase-like activity in acidic condition and catalase-like activity in weak basic condition. In acidic condition, Mo5N6 nanosheets can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to form a blue color product (TMBOX). At the co-existence of 4-aminophenol (4-AP), 4-AP can react with H2O2 and TMBOX, resulting in the decrease of TMBOX and the fading of blue color. Therefore, a facile, sensitive colorimetric method for the quantitative detection of 4-AP was developed. The linear range for 4-AP was 1.0 to 80.0 µmol⋅L‒1 (R2 = 0.999), and the detection limit was 0.56 µmol⋅L‒1 based on 3σ/k. Resorcinol, aniline, humic acid, and common ions and anions in surface water did not interfere the determination of 4-AP. This colorimetric method was applied to measure the 4-AP in real water sample from Wulong River in Fujian Province of China. The relative standard deviation for the determination of 4-AP was ranged from 0.03 to 1.88%, and the recoveries from spiked samples were ranged between 99.2 and 107.6%. The determination results were consistent with those obtained by HPLC.


Assuntos
Aminofenóis/análise , Colorimetria/métodos , Nanoestruturas/química , Poluentes da Água/análise , Aminofenóis/química , Benzidinas/química , Catálise , Compostos Cromogênicos/química , Peróxido de Hidrogênio/química , Limite de Detecção , Oxirredução , Rios/química , Poluentes da Água/química
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