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1.
Nano Lett ; 24(18): 5578-5584, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38682925

RESUMO

The lattice parameter of platinum-based intermetallic compounds (IMCs), which correlates with the intrinsic activity of the oxygen reduction reaction (ORR), can be modulated by crystal phase engineering. However, the controlled preparation of IMCs with unconventional crystal structures remains highly challenging. Here, we demonstrate the synthesis of carbon-supported PtCu-based IMC catalysts with an unconventional L10 structure by a composition-regulated strategy. Experiment and machine learning reveal that the thermodynamically favorable structure changes from L11 to L10 when slight Cu atoms are substituted with Co. Benefiting from crystal-phase-induced strain enhancement, the prepared L10-type PtCu0.8Co0.2 catalyst exhibits much-enhanced mass and specific activities of 1.82 A mgPt-1 and 3.27 mA cmPt-2, which are 1.91 and 1.73 times higher than those of the L11-type PtCu catalyst, respectively. Our work highlights the important role of crystal phase in determining the surface strain of IMCs, and opens a promising avenue for the rational preparation of IMCs with different crystal phases by doping.

2.
Nano Lett ; 24(13): 3994-4001, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38518181

RESUMO

Transforming the Pt-M alloy into an ordered intermetallic is an effective strategy to improve the electrocatalytic activity and stability toward the oxygen reduction reaction (ORR). However, the synthesis of nanosized intermetallics remains challenging. Herein, we report an efficient ORR electrocatalyst, consisting of a monodisperse nanosized PtCu intermetallic on hollow mesoporous carbon spheres (HMCS). As predicted by theoretical calculations, PtCu intermetallics exhibit beneficial electronic structure, with a low theoretical overpotential of 0.33 V and enhanced Cu stability. Resulting from the multiscale modulation of catalyst structure, the O-PtCu/HMCS catalyst delivers a high mass activity of 2.73 A cm-2Pt at 0.9 V and remarkable stability. Identical location transmission electron microscopy (IL-TEM) investigations demonstrate that the rate of carbon corrosion is alleviated on HMCS, which contributes to the long-term durability. This work provides a promising design strategy for an ORR electrocatalyst, and the IL-TEM investigations offer new perspectives for the performance enhancement mechanism.

3.
Mikrochim Acta ; 191(3): 126, 2024 02 08.
Artigo em Inglês | MEDLINE | ID: mdl-38332145

RESUMO

An ultrasensitive sandwich-type electrochemical immunosensor for pro-gastrin-releasing peptide (ProGRP) detection was constructed based on PtCu nanodendrites functionalized Au/polyaniline nanospheres (Au/PANI@PtCu). The prepared Au/PANI@PtCu nanocomposites not only possessed excellent electro-catalytic activity of H2O2 reduction due to the synergistic effect between the Au/PANI and PtCu NDs but also provided large specific surface area for detection of antibodies (Ab2) immobilization. In addition, Au nanoparticles encapsulated multi-wall carbon nanotubes (AuNPs@MWCNTs) were also applied to modify the glassy carbon electrode interface for loading numerous capture antibodies (Ab1). In the presence of target ProGRP, a sandwich-type electrochemical immunosensor showed a strong current response from the electro-catalysis of Au/PANI@PtCu toward H2O2 reduction. Benefiting from the exceptional electro-catalytic performance of Au/PANI@PtCu and the high conductivity of AuNPs@MWCNTs, the sandwich-type immunoassay exhibited remarkable sensitivity in detection. The linear range extended from 100 fg/mL to 10 ng/mL, while achieving an impressively low limit of detection of 77.62 fg/mL.


Assuntos
Técnicas Biossensoriais , Nanopartículas Metálicas , Nanotubos de Carbono , Peptídeo Liberador de Gastrina , Ouro , Peróxido de Hidrogênio , Anticorpos Imobilizados , Imunoensaio , Anticorpos
4.
Small ; : e2307970, 2023 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-38054785

RESUMO

Surface engineering offers opportunities for the design and synthesis of Pt-based alloyed electrocatalysts with high mass activity and resistance to CO poisoning, which is of great significance for methanol electrooxidation. Surface curvature regulation may endow electrocatalysts with enhanced atomic utilization and abundance of unsaturated atoms; however, a reliable synthetic route for controlled construction of tailorable curved surface is still lacking. Here, a colloidal-chemical method to synthesize two types of PtCu branched-structured electrocatalysts, where the concave curvature can be customized is reported. These studies show that, among various synthesis parameters, the concentration of CuCl2 ·2H2 O precursor is the key factor in manipulating the reaction kinetics and determining the concave surface curvature. Significantly, PtCu branched nanocrystals with long and sharp arms (PtCu BNCs-L), featuring a high concave surface curvature, exhibit remarkable activity and stability toward MOR, which is mainly attributed to advanced features of a highly concave surface and the synergistically bifunctional effect from introduced oxophilic Cu metal. In situ Raman spectroscopy and CO stripping test demonstrates weakened CO adsorption and accelerated CO removal on PtCu BNCs-L. This work highlights the importance of surface curvature, opening up an appealing route for the design and synthesis of advanced electrocatalysts with well-defined surface configurations.

5.
Small ; 18(29): e2202782, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35754168

RESUMO

The precise and comprehensive manipulation of the component, size, and geometric nano-architecture of platinum-based electrocatalysts into porous and hollow structure can effectively impart the catalysts with substantially improved electrochemical performance, yet remain formidably challenging. Herein, a straightforward fabrication of porous platinum-copper alloyed nanobowls (abbreviated as Pt3 Cu NBs hereafter) assembled by ultrafine nanoparticles (≈2.9 nm) via a one-pot hydrothermal approach with the assistance of a structure-directing agent of N,N'-methylenebisacrylamide (MBAA) is reported. The involvement of MBAA plays a decisive role in the formation of Pt-MBAA complex solid nanospheres, which serve as the self-sacrificial reactive template for the deposition/growth of Pt3 Cu nanoparticles and the eventual formation of the asymmetric open-shelled nanobowls. Benefitting from the 3D sufficient accessibility of exterior/interior surfaces, high atom-utilization efficiency, and PtCu bimetallic alloy synergy, the self-supported Pt3 Cu NBs demonstrate remarkably enhanced activity, better anti-poisoning capability, and reinforced robustness for the methanol oxidation reaction (MOR) as compared with the commercial Pt black benchmark, exhibiting great application promises in practical fuel cell systems. It is envisaged that the innovative self-templated synthetic strategy outlined here may provide a perspective to design a range of porous bowl-shaped high-performance nanocatalysts.

6.
Mikrochim Acta ; 187(9): 530, 2020 08 29.
Artigo em Inglês | MEDLINE | ID: mdl-32860548

RESUMO

A paper-based electrochemiluminescence (ECL) biosensor characterized by the signal amplification of reticular DNA-functionalized PtCu nanoframes (DNA-PtCuTNFs) and analyte-triggered DNA walker was developed for sensitive streptavidin assay. Silver microflower functionalized paper-based sensing platform was prepared to fix the hairpin strand (S1). With addition of the streptavidin, plenty of DNA walkers consisting of the walking strands (S2) labeled with biotin and streptavidin were established, which protected S2 from digestion via the terminal protection mechanism. The sequential introduction of the DNA walker and capture probe initiated the hairpin structure opening of S1 and strand displacement reaction (SDR) happening, causing the S2 release. Subsequently, S1 hybridized with S3. The free S2 further hybridized with adjacent S1 to trigger the next cycle. After multiple cycles, the DNA-PtCuTNFs, the fire-new signal enhancer, with remarkable peroxidase activity, were successfully attached onto the paper electrode via metal-catalyst-free click chemistry. Based on the SDR of the DNA walker and the catalysis of DNA-PtCuTNFs, a significantly boosted ECL signal of luminol was obtained. Under the optimal conditions, the developed sensor for streptavidin assay exhibited a low detection limit of 33.4 fM with a linear range from 0.1 pM to 0.1 µM. Graphical abstract.


Assuntos
Técnicas Biossensoriais/métodos , DNA/química , Nanoestruturas/química , Papel , Estreptavidina/sangue , Técnicas Biossensoriais/instrumentação , Biotina/química , Catálise , Cobre/química , DNA/genética , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Ácidos Nucleicos Imobilizados/química , Ácidos Nucleicos Imobilizados/genética , Limite de Detecção , Medições Luminescentes/instrumentação , Medições Luminescentes/métodos , Hibridização de Ácido Nucleico , Platina/química , Reprodutibilidade dos Testes , Prata/química , Estreptavidina/química
7.
Mikrochim Acta ; 187(9): 538, 2020 09 02.
Artigo em Inglês | MEDLINE | ID: mdl-32876849

RESUMO

A molybdenum disulfide based graphite phase carbon nitride (MoS2/g-C3N4) which is supported by a platinum-copper nanoparticle (PtCu) Z-type catalyst was created in this study. The catalyst exploits optoelectronic synergistic effect with large surface area, good catalysis, and biocompatibility to amplify the signal. The electrode impedance of the synthesized MoS2/g-C3N4-PtCu was reduced five times in visible light compared with dark conditions, thereby improving the detection of carcinoembryonic antigen (CEA). At a voltage of - 0.4 V, the immunoprobe constructed with this material is used for CEA detection. A linear relationship between 100 fg mL-1 and 80 ng mL-1 concentrations was achieved with a minimum detection limit of 33 fg mL-1 (S/N = 3). The recovery rate was 103-104%, and the relative standard deviation was 2.9-3.8%. This implies that the sandwich immunosensors have good reproducibility, selectivity, and stability and can be used in various applications. Graphical Abstract.


Assuntos
Técnicas Biossensoriais/métodos , Antígeno Carcinoembrionário/metabolismo , Cobre/química , Dissulfetos/química , Grafite/química , Nanopartículas Metálicas/química , Molibdênio/química , Compostos de Nitrogênio/química , Platina/química , Humanos
8.
Small ; 15(10): e1804407, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30724461

RESUMO

Developing electrocatalysts with ultrathin nanostructures and high mesoporosity is a relevant high-priority research direction toward enhancing the performance of noble metals. Herein, mesoporous, highly excavated octahedral PtCu3 nanostructures are prepared by a facile one-pot synthesis. The mesoporous, highly excavated octahedral PtCu3 nanostructures are built with mutually perpendicular interlaced mesoporous nanosheets with a thickness of ≈4.5 nm. Benefiting from its mesoporous features, three-dimensional (3D) open surfaces, ultrathin nanosheets, and a Cu-rich surface, PtCu3 exhibits excellent electrocatalytic performance and high antipoisoning activity toward the methanol oxidation reaction.

9.
Artigo em Inglês | MEDLINE | ID: mdl-31099294

RESUMO

Many metal nanoparticles are reported to have intrinsic enzyme-like activities and offer great potential in chemical and biomedical applications. In this study, PtCu alloy nanoparticles (NPs), synthesized through hydrothermal treatment of Cu2+ and Pt2+ in an aqueous solution, were evaluated for ferroxidase-like and antibacterial activity. Electron spin resonance (ESR) spectroscopy and colorimetric methods were used to demonstrate that PtCu NPs exhibited strong ferroxidase-like activity in a weakly acidic environment and that this activity was not affected by the presence of most other ions, except silver. Based on the color reaction of salicylic acid in the presence of Fe3+, we tested the ferroxidase-like activity of PtCu NPs to specifically detect Fe2+ in a solution of an oral iron supplement and compared these results with data acquired from atomic absorption spectroscopy and the phenanthroline colorimetric method. The results showed that the newly developed PtCu NPs detection method was equivalent to or better than the other two methods used for Fe2+ detection. The antibacterial experiments showed that PtCu NPs have strong antibacterial activity against Staphylococcus aureus and Escherichia coli. Herein, we demonstrate that the peroxidase-like activity of PtCu NPs can catalyze H2O2 and generate hydroxyl radicals, which may elucidate the antibacterial activity of the PtCu NPs against S. aureus and E. coli. These results showed that PtCu NPs exhibited both ferroxidase- and peroxidase-like activity and that they may serve as convenient and efficient NPs for the detection of Fe2+ and for antibacterial applications.


Assuntos
Antibacterianos/toxicidade , Ceruloplasmina/toxicidade , Nanopartículas Metálicas/toxicidade , Ligas/toxicidade , Testes de Sensibilidade Microbiana , Staphylococcus aureus/efeitos dos fármacos
10.
Food Chem ; 443: 138459, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38306911

RESUMO

Nowadays, the widespread use of organophosphorus pesticides (OPs) in agricultural production leads to varying degrees of residues in crops, which pose a potential threat to human health. Conventional methods used in national standard for the detection of OPs in fruits and vegetables require expensive instruments or cumbersome sample pretreatment steps for the analysis. To address these challenges, in this work, we took advantage of the peroxidase-like activity of PtCu3 alloy nanocrystals (NCs) for a colorimetric and smartphone assisted sensitive detection of OPs. With the assist of a smartphone, the concentration of OPs on the peel of fruits could be obtained by comparing the B/RG value (the brightness value of blue divided by those of red and green) of a test strip with a calibration curve. This work not only provides a facile and cost-effective method to detect pesticides but also makes a positive contribution to food safety warning.


Assuntos
Técnicas Biossensoriais , Praguicidas , Humanos , Praguicidas/análise , Compostos Organofosforados/análise , Colorimetria , Frutas/química , Smartphone , Acetilcolinesterase/química , Técnicas Biossensoriais/métodos
11.
Talanta ; 279: 126576, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-39018952

RESUMO

Herein, we developed a platinum-copper nano-enzyme-linked immunosorbent assay (NLISA) based split diagnostic platform for the ultrasensitive detection of cardiac troponin I (cTnI). The PtCu nanozyme synthesized by one-pot synthesis exhibited ultra-high peroxidase-like activity (35.17 U mg-1), which was about 4.5 times higher than that of the unmodified Pt nanozyme (8.83 U mg-1). Due to the efficient peroxidase-like activity of the copper-platinum complexed nanozyme, transduction and sequential amplification of cTnI biological signals were achieved in combination with a liposome-embedded amplification strategy. The encapsulation efficiency was calculated by introducing a liposomal bilayer model, which showed that the introduction of a single liposomal molecule could amplify the signal up to 870-fold, thus promising a high sensitivity test. Notably, the dynamic response of cTnI was in the range of 0.1-5000 pg mL-1 with an ultra-low detection limit (0.048 pg mL-1). The developed NLISA analysis system provides a new way to discover efficient and sensitive alternatives to ELISA kits, which can meet the practical needs of community healthcare testing conditions and rapid testing in hospitals.

12.
ACS Appl Mater Interfaces ; 16(11): 13893-13902, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38462697

RESUMO

It is challenging to synthesize oxygen reduction reaction (ORR) electrocatalysts that are highly efficient, affordable, and stable for use in proton exchange membrane fuel cells. To address this challenge, we developed a low platinum-loading (only 6.68% wt) ORR catalyst (PtCu1-NC), comprising CuPt nanoparticles (average size: 1.51 nm) supported on the N-doped carbon substrates. PtCu1-NC possesses a high specific surface area of 662 m2 g-1 and a hierarchical porous structure, facilitating efficient mass transfer. The synergistic effect from introduced copper and the electron effect from nitrogen modify the electronic structure of platinum, effectively accelerating the ORR reaction and enhancing stability. Density functional theory calculations demonstrate the catalytic mechanism and further verify the synergistic effect. Electrochemical assessments indicate that PtCu1-NC exhibits specific activity and mass activity 5.3 and 5.6 times higher, respectively, than commercial Pt/C. The half-wave potential is 27 mV more positive than that of commercial Pt/C. The electrochemical active surface area value is 104.3 m2 g-1, surpassing that of Pt/C. Approximately 78% of current is retained after 10,000 s chronoamperometry measurement. These results highlight the effectiveness of alloying in improving the catalyst performance.

13.
ACS Appl Mater Interfaces ; 16(12): 14694-14703, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38477616

RESUMO

Improving the N2 selectivity is always a great challenge for the selective catalytic oxidation of ammonia (NH3-SCO) over noble-metal-based (especially Pt) catalysts. In this work, Cu as an efficient promoter was introduced into the Pt/SSZ-13 catalyst to significantly improve the N2 selectivity of the NH3-SCO reaction. A PtCu alloy was formed in the PtCu/SSZ-13 catalyst, as confirmed by X-ray diffraction, transmission electron microscopy, energy dispersive spectrometry mapping, and X-ray absorption spectroscopy results. As indicated by the X-ray photoelectron spectroscopy analysis, the Pt species in the alloyed PtCu nanoparticle was mainly present in the electron-rich state on PtCu/SSZ-13, while the electron-deficient Cu and isolated Cu2+ species were both present on the surface of PtCu/SSZ-13. Due to such a unique alloyed structure with an altered oxidation state, the N2 selectivity of NH3-SCO on the PtCu/SSZ-13 catalyst was remarkably improved, while the NH3-SCO activity was kept comparable to that on Pt/SSZ-13. The reaction path was changed from the NH mechanism on Pt/SSZ-13 to both NH and internal selective catalytic reduction mechanisms on the PtCu/SSZ-13 catalyst, which was considered the main reason for the enhanced N2 selectivity. This work provides a new route to synthesize efficient alloy catalysts for optimizing the N2 selectivity of NH3-SCO for NH3 slip control in diesel exhaust purification.

14.
J Colloid Interface Sci ; 652(Pt A): 1006-1015, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37639923

RESUMO

Designing Pt-skin on the catalyst surface is critical to developing efficient and stable electrocatalysts toward oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. In this paper, an acidic reductant is proposed to synchronously manipulate in-situ growth of Pt-skin on the surface of alloyed Pt-Cu nanospheres (PtCuNSs) by a facile one-pot synthesis in an aqueous solution. Ascorbic acid can create a Pt-skin of three atomic layers to make the typical PtCu-alloy@Pt-skin core/shell nanostructure rather than the uniform alloys generated by using alkaline reductants. Surfactant as soft-template can make the alloyed PtCuNSs with a three-dimensional porous network structure. Multiple characterizations of XRD, XPS and XAFS are used to confirm Pt-alloying with Cu and formation of core/shell structure of such a catalyst. This PtCuNSs/C exhibits a half-wave potential of 0.913 V (vs. RHE), with mass activity and specific activity about 3.5 and 6.4 times higher than those of Pt/C, respectively. Fuel cell tests verify the excellent activity of PtCuNSs/C catalyst with a maximum power density of about 1.2 W cm-2. Moreover, this catalyst shows excellent stability, achieving a long-term operation of 40,000 cycles. Furthermore, theoretical calculations reveal the enhancement effect of characteristic PtCu-alloy@Pt-skin nanostructure on both catalytic ORR activity and stability.

15.
J Colloid Interface Sci ; 629(Pt A): 53-62, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36049329

RESUMO

Regulating catalyst composition is one of the efficient approaches to boost intrinsic activity of electrocatalysts for water splitting. Herein, four different hollow porous platinum-copper (PtCu) nanotubes (NTs) with controllable compositions were precisely fabricated by a facile wet-chemistry method. Importantly, Pt5Cu2 NTs display the best hydrogen evolution reaction (HER) performance in all pH conditions compared to other samples, which just require overpotentials of 34 ± 2, 32 ± 2, and 284 ± 2 mV at 10 mA cm-2 in basic, acidic, and neutral solutions, respectively. Moreover, Pt5Cu2 NTs also exhibit outstanding stability and corrosion resistance in all pH ranges. Then, mechanism analysis reveals that the electronic structure of Pt sites is regulated by changing the ratio of Pt and Cu, which directly optimizes the binding energy of reaction intermediates and promotes electron transfer during the HER process. In addition, a porous nanotube structure with countless nanoparticles on the surface provides a large number of active sites, enhancing the adsorption/desorption of reactants. This work emphasizes the importance of catalyst composition and provides a highly active potential HER catalyst for practical hydrogen production.

16.
Anal Chim Acta ; 1260: 341212, 2023 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-37121659

RESUMO

Adenosine, as an endogenous nucleoside modulator, plays an important role in heart rate regulation, neurotransmission, and control of the respiratory system and thus it is significantly important to realize its sensitive detection. Herein, a highly sensitive electrochemical aptasensor for adenosine detection was proposed by using multi-walled carbon nanotubes (MWCNTs) as support matrix loading PtCu nanoparticles (PtCu-MWCNTs) to amplify signal. On one hand, disposable screen-printing gold electrodes (SPGEs) were used as superb sensing base to ensure the stable connection of aptamers 1 (ssDNA1). On the other hand, the PtCu-MWCNTs complex was synthesized through a one-pot method, which not only can precisely control the proportion of metal mass in the product but also exhibited superior electrocatalytic activity towards H2O2. The recognition reactions were achieved by stepwise incubation of ssDNA1, ssDNA2-PtCu-MWCNTs (denoted as ssDNA2-label), and adenosine on the SPGEs. As a result, the constructed electrochemical aptasensor exhibited a wide linear range from 10 nM to 1.0 µM with a low detection limit of 1.0 nM (S/N = 3) for adenosine detection. The aptasensor also successfully realized the adenosine detection in human serum samples, which means that the proposed aptasensor holds a potential application in point-of-care detection.


Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Nanopartículas Metálicas , Nanotubos de Carbono , Humanos , Adenosina , Técnicas Biossensoriais/métodos , Técnicas Eletroquímicas/métodos , Eletrodos , Ouro , Peróxido de Hidrogênio , Limite de Detecção , Platina/química , Cobre/química
17.
J Hazard Mater ; 442: 130000, 2023 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-36137886

RESUMO

Rational tailoring of hollow and porous bimetallic structures with excellent electrocatalytic performance is appealing yet challenging. Further, combining independent bimetallic nanoparticles with flexible two-dimensional substrate by forming stable heterocomplex is still highly desired for electrocatalysis. Herein, hierarchical PtCu alloy octahedrons with hollow interiors and nanosheet-assembled nanoshells were synthesized by a facile and efficient chemical transformation strategy using Cu2O as sacrificial templates. Such octahedral PtCu nanocages displayed significantly enhanced electrocatalytic activity owing to their unique hollow and porous architectures which provided easy access for analytes to the catalyst surface. Thereafter, introduction of Ti3C2Tx MXene was realized via simple incubation of Ti3C2Tx in solution containing the 3-aminopropyltriethoxysilane-capped PtCu, and their electrostatic interaction guaranteed the firm adsorption of PtCu nanocages on Ti3C2Tx nanosheets. It turned out that the sensitivity of the hybrid sensor was remarkably improved for electrochemical monitoring of endocrine disrupting pollutants in water, exhibiting ultrawide linear ranges and sub-nanomole detection limits. The eminent electrode performance is attributed to the high specific area, fast electrochemical kinetics, decent electrical catalytic ability, and the synergistic effect between Pt, Cu, and MXene.


Assuntos
Poluentes Ambientais , Cobre/química , Eletrodos , Ligas/química , Água
18.
J Hazard Mater ; 439: 129612, 2022 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-35872456

RESUMO

The elimination of volatile organic compounds (VOCs) emitted from the process of industry production is of great significance to improve the atmospheric environment. Herein the catalytic oxidation of the toluene and iso-hexane mixture, as the typical components from furniture paint industry, and the enhancement in the catalytic stability for toluene oxidation were investigated in detail. The formation rate of active oxygen species was very important for the development of the catalyst with high catalytic stability. Compared with the Pt/M catalyst, the Pt-Cu/M catalyst owned stronger ability of VOCs adsorption and gaseous oxygen activation by introducing additional sites for activating O2. The Langmuir-Hinshelwood (adsorbed oxygen) and Mars-van Krevelen (lattice oxygen) mechanism existed in toluene oxidation over the present Pt/M and Pt-Cu/M catalysts, respectively. The change in the involved active oxygen species during toluene oxidation was resulted from the Pt-Cu alloy structure. In addition to the adsorption of O2, a part of active lattice oxygen species can also be replenished by the migration of bulk lattice oxygen over Pt-Cu/M. With a rise in the reaction temperature, weakly adsorbed iso-hexane could be timely reacted with the more active lattice oxygen species to keep the catalytic stability over the Pt/M and Pt-Cu/M catalysts. Generally, we not only prepared a promising material for the catalytic removal of VOCs from the furniture paint industry, but also provided a new strategy for the generation of active oxygen species, making the catalyst exhibit high catalytic oxidation stability.

19.
ACS Appl Mater Interfaces ; 14(9): 11457-11464, 2022 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-35201741

RESUMO

The excellent performance and safety of direct formic acid fuel cells (DFAFCs) promote them as potential power sources for portable electronic devices. However, their real application is still highly challenging due to the poor power performance and high complexity in the fabrication of catalyst electrodes. In this work, we demonstrate a new gas diffusion electrode (GDE) with ultrathin PtCu alloy nanowire (NW) arrays in situ grown on the carbon paper gas diffusion layer surface. The growing process is achieved by a facile template- and surfactant-free self-growth assisted reduction method at room temperature. A finely controlled ion reduction process tunes the nucleation and crystal growth of Pt and Cu leading to the formation of alloy nanowires with an average diameter of about 4 nm. The GDE is directly used as the anode for DFAFCs. The results in the half-cell GDE measurement indicate that the introduction of Cu in PtCu NWs boosts the direct oxidation pathway for formic acid. The Pt3Cu1 NW GDE shows a 2.4-fold higher power density compared to the Pt NW GDE in the membrane electrode assembly test in single cells.

20.
Adv Sci (Weinh) ; 9(14): e2104927, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35266308

RESUMO

Structure-controlled Pt-based nanocrystals have the great potential to provide a flexible strategy for improving the catalysis of the oxygen reduction reaction (ORR). Here, a new synthetic approach is developed to tune the 3D structure of Pt-based alloys, and switch a synthetic reaction which produces solid PtCu octahedral stars (OSs) to produce PtCu nested skeleton cubes (NSCs) by simple addition of Ni(acac)2 . In particular, Ni2+ -guided anisotropic growth is observed to generate the nested skeleton structure in PtCu NSCs. Ni2+ , though absent from the nanoalloys, not only endows faster Cu reduction kinetics but also acts as a structure-directing agent. Moreover, it is shown that acetic acid treatment of PtCu NSCs/C exposes Pt-rich surface with a fine-tuned Pt d-band center energy and the reduced Cu leaching, resulting in strikingly high activity and stability. Acid-treated PtCu NSCs/C shows a remarkable ORR mass activity of 5.13 A mgPt -1 , about 26 times higher than commercial Pt/C catalyst. This catalyst also exhibits excellent stability with a lower activity decay of 11.5% and the negligible variation in structure after 10 000 cycles.

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