Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 18 de 18
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
ChemSusChem ; 15(8): e202200027, 2022 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-35263034

RESUMO

As highlighted by the recent roadmaps from the European Union and the United States, water electrolysis is the most valuable high-intensity technology for producing green hydrogen. Currently, two commercial low-temperature water electrolyzer technologies exist: alkaline water electrolyzer (A-WE) and proton-exchange membrane water electrolyzer (PEM-WE). However, both have major drawbacks. A-WE shows low productivity and efficiency, while PEM-WE uses a significant amount of critical raw materials. Lately, the use of anion-exchange membrane water electrolyzers (AEM-WE) has been proposed to overcome the limitations of the current commercial systems. AEM-WE could become the cornerstone to achieve an intense, safe, and resilient green hydrogen production to fulfill the hydrogen targets to achieve the 2050 decarbonization goals. Here, the status of AEM-WE development is discussed, with a focus on the most critical aspects for research and highlighting the potential routes for overcoming the remaining issues. The Review closes with the future perspective on the AEM-WE research indicating the targets to be achieved.


Assuntos
Membranas Artificiais , Água , Ânions , Eletrólise , Hidrogênio
2.
ACS Appl Mater Interfaces ; 13(49): 58532-58538, 2021 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-34870405

RESUMO

The development of precious group metal-free (PGM-free) catalysts for the oxygen reduction reaction is considered as the main thrust for the cost reduction of fuel cell technologies and their mass production. Within the PGM-free category, molecular catalysts offer an advantage over other heat-treated PGM-free catalysts owing to their well-defined structure, which enables further design of more active, selective, and durable catalysts. Even though non-heat-treated molecular catalysts with exceptional performance have been reported in the past, they were rarely tested in a fuel cell. Herein, we report on a molecular catalyst under alkaline conditions: fluorinated iron phthalocyanine (FeFPc) supported on cheap and commercially available high-surface area carbon─BP2000 (FeFPc@BP2000). It exhibits the highest activity ever reported for molecular catalysts under alkaline conditions in half-cells and fuel cells.

3.
ChemSusChem ; 14(7): 1737-1746, 2021 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-33561301

RESUMO

Trimetallic double hydroxide NiFeCo-OH is prepared by coprecipitation, from which three different catalysts are fabricated by different heat treatments, all at 350 °C maximum temperature. Among the prepared catalysts, the one prepared at a heating and cooling rate of 2 °C min-1 in N2 atmosphere (designated NiFeCo-N2 -2 °C) displays the best catalytic properties after stability testing, exhibiting a high current density (9.06 mA cm-2 at 320 mV), low Tafel slope (72.9 mV dec-1 ), good stability (over 20 h), high turnover frequency (0.304 s-1 ), and high mass activity (46.52 A g-1 at 320 mV). Stability tests reveal that the hydroxide phase is less suitable for long-term use than catalysts with an oxide phase. Two causes are identified for the loss of stability in the hydroxide phase: a) Modeling of the distribution function of relaxation times (DFRT) reveals the increase in resistance contributed by various relaxation processes; b) density functional theory (DFT) surface energy calculations reveal that the higher surface energy of the hydroxide-phase catalyst impairs the stability. These findings represent a new strategy to optimize catalysts for water splitting.

4.
ACS Appl Mater Interfaces ; 13(7): 8315-8323, 2021 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-33587602

RESUMO

In an effort to develop durable, corrosion-resistant catalyst support materials for polymer electrolyte fuel cells, modified polymer-assisted deposition method was used to synthesize tungsten carbide (WC, WC1-x), which was later used as a support material for Pt-based oxygen reduction reaction catalyst, as an alternative for the corrosion-susceptible, carbon supports. The Pt-deposited tungsten carbide's corrosion-resistance, oxygen reduction reaction electrocatalysis, and durability were studied and compared to that of Pt/C. Bulk free carbon was found to be absent from the ceramic matrix which had particle size in the range of 2-25 nm. Tungsten carbide support appears to enhance the oxygen reduction activity on Pt, showing an increase in mass activity (nearly 2-fold at 0.85 V vs RHE) and specific activity (more than 7 times higher), alongside decrease in overpotential, in comparison to Pt/C. A significant increase in durability was also observed with the tungsten carbide-based system.

5.
ChemSusChem ; 14(8): 1886-1892, 2021 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-33629811

RESUMO

In the search for replacement of the platinum-based catalysts for fuel cells, MN4 molecular catalysts based on abundant transition metals play a crucial role in modeling and investigation of the influence of the environment near the active site in platinum-group metal-free (PGM-free) oxygen reduction reaction (ORR) catalysts. To understand how the ORR activity of molecular catalysts can be controlled by the active site structure through modification by the pH and substituent functional groups, the change of the ORR onset potential and the electron number in a broad pH range was examined for three different metallocorroles. Experiments revealed a switch between two different ORR mechanisms and a change from 2e- to 4e- pathway in the pH range of 3.5-6. This phenomenon was shown by density functional theory (DFT) calculations to be related to the protonation of the nitrogen atoms and carboxylic acid groups on the corroles indicated by the pKa values of the protonation sites in the vicinity of the ORR active sites. Control of the electron-withdrawing nature of these groups characterized by the pKa values could switch the ORR from the H+ to e- rate-determining step mechanisms and from 2e- to 4e- ORR pathways and also controlled the durability of the corrole catalysts. The results suggest that protonation of the nitrogen atoms plays a vital role in both the ORR activity and durability for these materials and that pKa of the N atoms at the active sites can be used as a descriptor for the design of high-performance, durable PGM-free catalysts.

6.
Nanoscale ; 13(8): 4576-4584, 2021 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-33600541

RESUMO

In order to solely rely on renewable and efficient energy sources, reliable energy storage and production systems are required. Hydrogen is considered an ideal solution as it can be produced electrochemically by water electrolysis and renewably while no pollutants are released when consumed. The most common catalysts in electrolyzers are composed of rare and expensive precious group metals. Replacing these materials with Earth-abundant materials is important to make these devices economically viable. Metal organic frameworks are one possible solution. Herein we demonstrate the synthesis and characterization studies of metal benzene-tri-carboxylic acid-based metal-organic frameworks embedded in activated carbon. The conductive composite material was found to be electrocatalytically active for both the oxygen evolution reaction and the hydrogen evolution reaction. Furthermore, several metal organic frameworks sharing the same ligand but with different first-row transition metals (M = Co, Cu, Fe, Mn) were compared, and the trend of their activity is discussed. Cobalt was found to have the highest activity among the studied metal centers, and therefore has the best potential to serve as a bifunctional catalyst for alkaline electrolyzers.

7.
Chem Commun (Camb) ; 56(61): 8627-8630, 2020 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-32601628

RESUMO

Molecular oxygen reduction reaction catalysts based on metallo-corrole with the smallest meso-substituent reported to-date, Co(iii)CF3-corrole, was synthesized and compared to the well-studied Co(iii)tpfcorrole when adsorbed on a high surface area carbon support. This study shows the improved electrocatalytic performance with the new corrole, attributed to its unique compact structure, which enables surface interactions in favor of lowering the reaction overpotential by 70 mV.

8.
Angew Chem Int Ed Engl ; 59(6): 2483-2489, 2020 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-31774933

RESUMO

Aerogels are fascinating materials that can be used for a wide range of applications, one of which is electrocatalysis of the important oxygen reduction reaction. In their inorganic form, aerogels can have ultrahigh catalytic site density, high surface area, and tunable physical properties and chemical structures-important features in heterogeneous catalysis. Herein, we report on the synthesis and electrocatalytic properties of an iron-porphyrin aerogel. 5,10,15,20-(Tetra-4-aminophenyl)porphyrin (H2 TAPP) and FeII were used as building blocks of the aerogel, which was later heat-treated at 600 °C to enhance electronic conductivity and catalytic activity, while preserving its macrostructure. The resulting material has a very high concentration of atomically dispersed catalytic sites (9.7×1020  sites g-1 ) capable of catalyzing the oxygen reduction reaction in alkaline solution (Eonset =0.92 V vs. RHE, TOF=0.25 e- site-1 s-1 at 0.80 V vs. RHE).

10.
Inorg Chem ; 58(14): 8995-9003, 2019 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-31247811

RESUMO

Recently, we reported on a series of aminomethylene-phosphonate (AMP) analogues, bearing one or two heterocyclic groups on the aminomethylene moiety, as promising Zn(II) chelators. Given the strong Zn(II) binding properties of these compounds, they may find useful applications in metal chelation therapy. With a goal of inhibiting the devastating oxidative damage caused by prion protein in prion diseases, we explored the most promising ligand, {bis[(1H-imidazol-4-yl)methyl]amino}methylphosphonic acid, AMP-(Im)2, 4, as an inhibitor of the oxidative reactivity associated with the Cu(II) complex of prion peptide fragment 84-114. Specifically, we first characterized the Cu(II) complex with AMP-(Im)2 by ultraviolet-visible spectroscopy and electrochemical measurements that indicated the high chemical and electrochemical stability of the complex. Potentiometric pH titration provided evidence of the formation of a stable 1:1 [Cu(II)-AMP-(Im)2]+ complex (ML), with successive binding of a second AMP-(Im)2 molecule yielding ML2 complex [Cu(II)-(AMP-(Im)2)2]+ (log K' = 15.55), and log ß' = 19.84 for ML2 complex. The CuN3O1 ML complex was demonstrated by X-ray crystallography, indicating the thermodynamically stable square pyramidal complex. Chelation of Cu(II) by 4 significantly reduced the oxidation potential of the former. CuCl2 and the 1:2 Cu:AMP-(Im)2 complex showed one-electron redox of Cu(II)/Cu(I) at 0.13 and -0.35 V, respectively. Indeed, 4 was found to be a potent antioxidant that at a 1:1:1 AMP-(Im)2:Cu(II)-PrP84-114 molar ratio almost totally inhibited the oxidation reaction of 4-methylcatechol. Circular dichroism data suggest that this antioxidant activity is due to formation of a ternary, redox inactive Cu(II)-Prp84-114-[AMP-(Im)2] complex. Future studies in prion disease animal models are warranted to assess the potential of 4 to inhibit the devastating oxidative damage caused by PrP.


Assuntos
Cobre/química , Isoxazóis/química , Príons/química , Tetrazóis/química , Modelos Moleculares , Oxirredução , Conformação Proteica
11.
Data Brief ; 19: 281-287, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29892647

RESUMO

In this article, we collected the most significant and recent data in brief in the field of metal organic frameworks oxygen reduction reaction catalysts, obtained from some of the most recent research papers in the field. We present lists of materials and their key parameters that are relevant to the cathode catalysts in polymer electrolyte membrane fuel cells. All the materials listed in this paper are composed of metal organic frameworks, zeolitic imidazolate frameworks, or their derivatives. These are divided into two main groups: pristine MOFs and MOF-derived materials. The data in this article is a summary of more extensive review (Gonen and Elbaz, 2018) [1].

12.
J Phys Chem Lett ; 9(9): 2229-2234, 2018 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-29649872

RESUMO

We use first-principles calculations to study the formation of Pt nanorafts and their oxygen reduction reaction (ORR) catalytic activity on Mo2C. Due to the high Pt binding energy on C atoms, Pt forms sheet-like structures on the Mo2C surface instead of agglomerating into particles. We find that the disordered Mo2C surface carbon arrangement limits the Pt sheet growth, leading to the formation of 4-6 atom Pt nanorafts. The O-O repulsion between the O atoms on the Mo2C and O adsorbate enhances the ORR activity by weakening the O adsorption energy. We find a significant change from the usual scaling of the energies of the intermediates in the ORR pathway and a strong interaction between the nanoraft and water that lead to a high activity of the Pt nanorafts. Fundamentally, our work demonstrates that the activity of metal catalysts can be strongly affected by manipulation of the atomic arrangement of the supporting carbide surface.

13.
Adv Mater ; 30(41): e1800406, 2018 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-29682822

RESUMO

One of the most important chemical reactions for renewable energy technologies such as fuel cells and metal-air batteries today is oxygen reduction. Due to the relatively sluggish reaction kinetics, catalysts are necessary to generate high power output. The most common catalyst for this reaction is platinum, but its scarcity and derived high price have raised the search for abundant nonprecious metal catalysts. Inspired from enzymatic processes which are known to catalyze oxygen reduction reaction efficiently, employing transition metal complexes as their catalytic centers, many are working on the development of bioinspired and biomimetic catalysts of this class. This research news article gives a glimpse of the recent progress on the development of bioinspired molecular catalyst for oxygen reduction, highlighting the importance of the molecular structure of the catalysts, from advancements in porphyrins and phthalocyanines to the most recent work on corroles, and 3D networks such as metal-organic frameworks and polymeric networks, all with nonpyrolyzed, well-defined molecular catalysts for oxygen reduction reaction.


Assuntos
Materiais Biomiméticos/química , Fontes de Energia Elétrica , Catálise , Oxirredução
14.
Chem Commun (Camb) ; 53(96): 12942-12945, 2017 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-29155903

RESUMO

Four ß-pyrrole-substituted cobalt(iii) corroles were studied as electrocatalysts for the oxygen reduction reaction. The results disclose high dependence of the corrole's performance on its substituents, but once adsorbed on a high surface area carbon, this effect vanishes, resulting in a better catalytic performance than most well-defined molecular electrocatalysts for this reaction.

15.
ChemSusChem ; 10(15): 3069-3074, 2017 08 10.
Artigo em Inglês | MEDLINE | ID: mdl-28627139

RESUMO

A new platinum-copper alloy electrocatalyst for the direct electro-oxidation of dimethyl ether (DME) has been synthesized in an easy and low-cost approach and studied by using an array of techniques, including X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, and elemental analysis. Structural characterization revealed that the synthesized PtCu nanoparticles (3 nm on average) formed homogeneous nanochains without aggregation of metallic platinum or copper. The catalyst's activity towards electro-oxidation of DME was tested using cyclic voltammetry (CV) and in membrane-electrode assembly (MEA) in a full cell and was found to be promising. The direct DME fuel cell (DDMEFC) studied in this work has relatively high energy density, of 13.5 mW cm-1 and thus shows great potential as fuel for low power fuel cells. The newly synthesized PtCu catalyst exhibited almost double the performance of commercial PtRu in electrocatalytic DME oxidation.


Assuntos
Cobre/química , Nanopartículas Metálicas/química , Éteres Metílicos/química , Platina/química , Catálise , Eletroquímica , Oxirredução
16.
Langmuir ; 32(44): 11672-11680, 2016 11 08.
Artigo em Inglês | MEDLINE | ID: mdl-27728764

RESUMO

The oxidation level and properties of reduced graphene oxides (rGOs) were fine-tuned using temperature-programmed reductive annealing. rGOs were annealed at different temperatures (from 500 to 1000 °C) in hydrogen to modulate their oxidation levels. The surface of the rGOs was fully characterized using electron paramagnetic resonance backed by Raman, X-ray diffraction, and chemical analysis measurements. These experiments were used to study the changes in the surface of the rGO, its surface functionalities, and its defects as a function of the reduction temperature. In addition, electrochemical measurements to quantify the oxidation level of the rGOs offer a simple tool to correlate the properties of rGOs with their structure. Finally, we explored the effect of different levels of reduction on conductivity, capacitance, and surface reactivity. This research offers simple methodological techniques and routes to control and characterize the oxidation level of bulk quantities of rGO.

17.
Angew Chem Int Ed Engl ; 54(47): 14080-4, 2015 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-26429211

RESUMO

The future of affordable fuel cells strongly relies on the design of earth-abundant (non-platinum) catalysts for the electrochemical oxygen reduction reaction (ORR). However, the bottleneck in the overall process occurs therein. We have examined herein trivalent Mn, Fe, Co, Ni, and Cu complexes of ß-pyrrole-brominated corrole as ORR catalysts. The adsorption of these complexes on a high-surface-area carbon powder (BP2000) created a unique composite material, used for electrochemical measurements in acidic aqueous solutions. These experiments disclosed a clear dependence of the catalytic activity on the metal center of the complexes, in the order of Co>Fe>Ni>Mn>Cu. The best catalytic performance was obtained for the Co(III) corrole, whose onset potential was as positive as 0.81 V versus the reversible hydrogen electrode (RHE). Insight into the properties of these systems was gained by spectroscopic and computational characterization of the reduced and oxidized forms of the metallocorroles.

18.
Inorg Chem ; 51(8): 4694-706, 2012 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-22458367

RESUMO

A series of divalent first row triflate complexes supported by the ligand tris(2-pyridylmethyl)amine (TPA) have been investigated as oxygen reduction catalysts for fuel cell applications. [(TPA)M(2+)](n+) (M = Mn, Fe, Co, Ni, and Cu) derivatives were synthesized and characterized by X-ray crystallography, cyclic voltammetry, NMR spectroscopy, magnetic susceptibility, IR spectroscopy, and conductance measurements. The stoichiometric and electrochemical O(2) reactivities of the series were examined. Rotating-ring disk electrode (RRDE) voltammetry was used to examine the catalytic activity of the complexes on a carbon support in acidic media, emulating fuel cell performance. The iron complex displayed a selectivity of 89% for four-electron conversion and demonstrated the fastest reaction kinetics, as determined by a kinetic current of 7.6 mA. Additionally, the Mn, Co, and Cu complexes all showed selective four-electron oxygen reduction (<28% H(2)O(2)) at onset potentials (~0.44 V vs RHE) comparable to state of the art molecular catalysts, while being straightforward to access synthetically and derived from nonprecious metals.


Assuntos
Fontes de Energia Elétrica , Compostos Organometálicos/química , Oxigênio/química , Piridinas/química , Elementos de Transição/química , Carbono/química , Eletroquímica , Polímeros de Fluorcarboneto/química
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...