The development of efficient non-platinum group metal (non-PGM) catalysts for oxygen reduction reaction (ORR) is of paramount importance for clean and sustainable energy storage and conversion devices. The major bottleneck in developing Fe-N-C materials as the leading non-PGM catalysts lies in the poor understanding of the nature of active sites and reaction mechanisms. Herein, we report a scalable metal organic framework-derived Fe-N-C catalyst with high ORR activity demonstrated in practical H 2 /air fuel cells, and an unprecedented turnover frequency (TOF) in acid in rotating disk electrode. By characterizing the catalyst under both ex situ and operando conditions using combined microscopic and spectroscopic techniques, we show that the structures of active sites under ex situ and working conditions are drastically different. Resultantly, the active site proposed here, a non-planar ferrous Fe-N 4 moiety embedded in distorted carbon matrix characterized by a high Fe 2+/3+ redox potential, is in contrast with those proposed hitherto derived from ex situ characterizations. This site reversibly switches to an in-plane ferric Fe-N 4 moiety poisoned by oxygen adsorbates during the redox transition, with the population of active sites controlled by the Fe 2+/3+ redox potential. The unprecedented TOF of the active site is correlated to its near-optimal Fe 2+/3+ redox potential, and essentially originated from its favorable biomimetic dynamic nature that balances the site-blocking effect and O 2 dissociation. The porous and disordered carbon matrix of the catalyst plays pivotal roles for its measured high ORR activity by hosting high population of reactant-accessible active sites. 50In situ characterizations reveal that the biomimetic dynamic nature of the Fe-N-C active site with a near-optimal Fe 2+/3+ redox potential formed upon pyrolysis accounts for its high ORR activity by balancing the site-blocking effect and O 2 dissociation.
Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo-PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shape enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable PtNi(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.
Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data, which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.
Many industrial catalysts are composed of metal particles supported on metal oxides (MMO). It is known that the catalytic activity of MMO materials is governed by metal and metal oxide interactions (MMOI), but how to optimize MMO systems via manipulation of MMOI remains unclear, due primarily to the ambiguous nature of MMOI. Herein, we develop a Pt/NbO/C system with tunable structural and electronic properties via a modified arc plasma deposition method. We unravel the nature of MMOI by characterizing this system under reactive conditions utilizing combined electrochemical, microscopy, and in situ spectroscopy. We show that Pt interacts with the Nb in unsaturated NbO owing to the oxygen deficiency in the MMO interface, whereas Pt interacts with the O in nearly saturated NbO, and further interacts with Nb when the oxygen atoms penetrate into the Pt cluster at elevated potentials. While the Pt-Nb interactions do not benefit the inherent activity of Pt toward oxygen reduction reaction (ORR), the Pt-O interactions improve the ORR activity by shortening the Pt-Pt bond distance. Pt donates electrons to NbO in both Pt-Nb and Pt-O cases. The resultant electron eficiency stabilizes low-coordinated Pt sites, hereby stabilizing small Pt particles. This determines the two characteristic features of MMO systems: dispersion of small metal particles and high catalytic durability. These findings contribute to our understandings of MMO catalytic systems.
Special delivery! The title system, composed of a highly magnetic core surrounded by a thin uniform gold shell, has been synthesized and applied to the magnetically facilitated delivery of genetic material (siRNA or plasmid DNA) into neural stem cells (NSCs) for controlling their neural differentiation in a spatiotemporally controlled, biocompatible manner.
High stability, availability of multiple oxidation states, and accessibility within a wide electrochemical window are the prime features of Nb that make it a favorable candidate for electrocatalysis, especially when it is combined with Pt. However, Nb has been used as a support in the form of oxides in all previously reported Pt−Nb electrocatalysts, and no Pt−Nb alloying phase has been demonstrated hitherto. Herein, we report a multifunctional Pt−Nb composite (PtNb/NbO x -C) where Nb exists both as an alloying component with Pt and as an oxide support and is synthesized by means of a simple wet chemical method. In this work, the Pt−Nb alloy phase has been firmly verified with the help of multiple spectroscopic methods. This allows for the experimental evidence of the theoretical prediction that Pt−Nb alloy interactions improve the oxygen reduction reaction (ORR) activity of Pt. In addition, such a combination of multiphase Nb brings up myriad features encompassing increased ORR durability, immunity to phosphate anion poisoning, enhanced hydrogen oxidation reaction (HOR) activity, and oxidative carbon monoxide (CO) stripping, making this electrocatalyst useful in multiple fuel cell systems.
Phosphoric acid fuel cells are successfully used as energy conversion technologies in stationary power applications. However, decreased proton conductivity and lower oxygen permeability of phosphoric-acid-imbibed membranes require prohibitive loadings of the traditional noble-metal-based electrocatalyst, such as platinum supported on carbon. Additionally, specific adsorption of phosphate anions on the catalyst results in a surface poisoning that further reduces electrocatalytic activity. Here we report a nonplatinum group metal (non-PGM) electrocatalyst as an alternative cathode electrocatalyst for oxygen reduction in phosphoric acid fuel cells. The non-PGM was prepared in a one-pot synthesis using a metal organic framework and iron salt precursor. Phosphate anion poisoning was monitored electrochemically and spectroscopically in reference to the current state-of-the-art Pt-based catalyst at room temperature. Unlike Pt-based catalysts that are prone to phosphate poisoning, the non-PGM electrocatalyst exhibits immunity to surface poisoning by phosphate anions at room temperature. Imaging with microscopy reveals that the iron particles are isolated from the electrolyte by graphitic layers, which ultimately protect the iron from phosphate anion adsorption. The non-PGM electrocatalyst represents the highest performance to date in a high-temperature phosphoric acid membrane system, which is likely attributed to its immunity to phosphate adsorption at the harsher fuel cell environments.
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