Armoring the Pt/C Catalyst with Fine Atomic-Scale Tungsten Species to Increase Tolerance against Thermal and Fuel Cell Stresses

Author(s):  
Liang-Chen Lin ◽  
Yun-Sheng Cheng ◽  
Chun-Han Kuo ◽  
Ying-Cheng Chen ◽  
Wei-Chieh Liao ◽  
...  
2021 ◽  
Author(s):  
Quanchen Feng ◽  
Xingli Wang ◽  
Malte Klingenhof ◽  
Marc Heggen ◽  
Peter Strasser

Abstract Carbon-supported platinum-nickel (Pt-Ni) alloy nanoparticles (NPs) emerge as the electrocatalysts of choice for deployment in polymer electrolyte membrane fuel cell (PEMFC) cathodes. To date, viable PtNi nanoalloy catalysts are characterized by large Pt weight loading of up to 50 wt%. To a large extent, their preparation processes often involve the use of expensive or even hazardous organometallic metal precursors, solvents and capping agents, substantially limiting their synthetic scalability and sustainability. Here, we report a novel synthetic strategy toward highly active low-Pt loaded PtNi nanoalloy Oxygen Reduction Reaction (ORR) catalysts. The synthesis involves the Pyrolysis and Leaching of Ni-organic polymers, subsequent Pt nanoparticle Deposition followed by thermal Alloying (referred to as PLDA) to prepare single Ni atom site (NiNC)-supported bimetallic PtNi nanoalloy electrocatalysts with very low Pt weight contents of 3–5 wt% Pt loading. We demonstrate that despite this low Pt weight loading, the catalysts exhibit more favorable Pt-mass activities compared to conventional, carbon-supported 20–30 wt%Pt Pt-loaded benchmark PtNi alloy catalysts. Using in situ transmission electron microscopy, cyclic voltammetry, and surface CO stripping techniques, we track and unravel the key stages of the formation process of the PtNi nanoparticle catalysts directly at the atomic scale. By carefully chosen reference experiments, we find that carbon-encapsulated Ni NPs, rather than NiNx single sites, serve exclusively as the Ni atom source for PtNi alloy formation during thermal treatments. Our materials concepts offer a pathway to further decrease the overall Pt content of PEM fuel cell devices.


ChemCatChem ◽  
2016 ◽  
Vol 8 (8) ◽  
pp. 1575-1582 ◽  
Author(s):  
Elena Willinger ◽  
Youngmi Yi ◽  
Andrey Tarasov ◽  
Raoul Blume ◽  
Cyriac Massué ◽  
...  

Author(s):  
John F. Cooper

A direct carbon fuel cell (DCFC) using a carbon-rich derivative of coal would maximize the conversion efficiency of this vast energy resource by avoiding the efficiency limitations of heat engines. A total conversion efficiency of 80% (based on heat of combustion of carbon) has been achieved at 30–120 mA/cm2 using carbon materials extracted from coal and other fossil resources. High experimental efficiency is grounded in two favorable aspects of the reaction thermodynamics. The net fuel cell reaction (C + O2 = CO2) has a nearly zero entropy change and therefore a theoretical efficiency of 100%. The fixed chemical potentials of carbon reactant and CO2 product make possible the full utilization of fuel in a single pass through the cell. The pure CO2 product can be used directly in enhanced oil and gas recovery, or sequestered. Historically, the development of carbon fuel cells have been limited by low anode rates, accumulation of impurities in the electrolyte, logistics of refueling, and lack of suitable cathodes. These problems are being addressed by recent developments of highly reactive carbon materials, low-cost techniques for separation of coal from ash, the possibility of pneumatic distribution of solid particulate fuel to the cells, and availability of cathodes from the molten carbonate fuel cell technology. Rate depends on atomic scale disorder and accessibility of reactive sites, but not on purity. Sources of suitable anode fuel include thermally decomposed products of (1) mechanical and chemical coal/ash separation or (2) solvent extraction. With current understanding of the cell basics, the next steps are demonstration of an engineering scale fuel cell stack (∼1 kW), supported by development of coal-to-carbon processes and techniques of electrolyte management. Successful development of a direct conversion fuel cell for coal (or coal-derived carbon) has extraordinary implications in extending the energy reserves of coal-producing nations, easing the control of regulated emissions at the plant, and expanding the use the earth’s greatest fossil resource while decreasing emissions of greenhouse gas.


2011 ◽  
Vol 17 (S2) ◽  
pp. 1620-1621
Author(s):  
H Xin ◽  
D Wang ◽  
H Abruña ◽  
D Muller

Extended abstract of a paper presented at Microscopy and Microanalysis 2011 in Nashville, Tennessee, USA, August 7–August 11, 2011.


Author(s):  
H. Hashimoto ◽  
Y. Sugimoto ◽  
Y. Takai ◽  
H. Endoh

As was demonstrated by the present authors that atomic structure of simple crystal can be photographed by the conventional 100 kV electron microscope adjusted at “aberration free focus (AFF)” condition. In order to operate the microscope at AFF condition effectively, highly stabilized electron beams with small energy spread and small beam divergence are necessary. In the present observation, a 120 kV electron microscope with LaB6 electron gun was used. The most of the images were taken with the direct electron optical magnification of 1.3 million times and then magnified photographically.1. Twist boundary of ZnSFig. 1 is the image of wurtzite single crystal with twist boundary grown on the surface of zinc crystal by the reaction of sulphur vapour of 1540 Torr at 500°C. Crystal surface is parallel to (00.1) plane and electron beam is incident along the axis normal to the crystal surface. In the twist boundary there is a dislocation net work between two perfect crystals with a certain rotation angle.


Author(s):  
R. J. Wilson ◽  
D. D. Chambliss ◽  
S. Chiang ◽  
V. M. Hallmark

Scanning tunneling microscopy (STM) has been used for many atomic scale observations of metal and semiconductor surfaces. The fundamental principle of the microscope involves the tunneling of evanescent electrons through a 10Å gap between a sharp tip and a reasonably conductive sample at energies in the eV range. Lateral and vertical resolution are used to define the minimum detectable width and height of observed features. Theoretical analyses first discussed lateral resolution in idealized cases, and recent work includes more general considerations. In all cases it is concluded that lateral resolution in STM depends upon the spatial profile of electronic states of both the sample and tip at energies near the Fermi level. Vertical resolution is typically limited by mechanical and electronic noise.


Author(s):  
Alexis T. Bell

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.


Author(s):  
A. K. Datye ◽  
D. S. Kalakkad ◽  
L. F. Allard ◽  
E. Völkl

The active phase in heterogeneous catalysts consists of nanometer-sized metal or oxide particles dispersed within the tortuous pore structure of a high surface area matrix. Such catalysts are extensively used for controlling emissions from automobile exhausts or in industrial processes such as the refining of crude oil to produce gasoline. The morphology of these nano-particles is of great interest to catalytic chemists since it affects the activity and selectivity for a class of reactions known as structure-sensitive reactions. In this paper, we describe some of the challenges in the study of heterogeneous catalysts, and provide examples of how electron holography can help in extracting details of particle structure and morphology on an atomic scale.Conventional high-resolution TEM imaging methods permit the image intensity to be recorded, but the phase information in the complex image wave is lost. However, it is the phase information which is sensitive at the atomic scale to changes in specimen thickness and composition, and thus analysis of the phase image can yield important information on morphological details at the nanometer level.


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