High-performance bimetallic alloy catalyst using Ni and N co-doped composite carbon for the oxygen electro-reduction.

PubMed

Jung, Won Suk

2018-03-15

In this study, a novel synthesis method for the bimetallic alloy catalyst is reported, which is subsequently used as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells (PEMFCs). The support prepared from the Ni-chelate complex shows a mesoporous structure with a specific surface area of ca. 400 m 2  g -1 indicating the suitable support for PEMFC applications. Ethylenediamine is converted to the nitrogen and carbon layers to protect the Ni particles which will diffuse into the Pt lattice at 800 °C. The PtNi/NCC catalyst with PtNi cores and Pt-rich shells is successfully formed when acid-treated as evidenced by line scan profiles. The catalyst particles thus synthesized are well-dispersed on the N-doped carbon support, while the average particle size is ca. 3 nm. In the PEMFC test, the maximum power density of the PtNi/NCC catalyst shows approximately 25% higher than that of the commercial Pt/C catalyst. The mass activity of the PtNi/NCC catalyst showed approximately 3-fold higher than that of the commercial Pt/C catalyst. The mass activity strongly depends on the ratio of Pt to Ni since the strain effect can be strong for catalysts due to the mismatch of lattice parameters of the Ni and Pt. Copyright © 2017 Elsevier Inc. All rights reserved.

Fabrication of High Performing PEMFC Catalyst-Coated Membranes with a Low Cost Air-Assisted Cylindrical Liquid Jets Spraying System

DOE PAGES

Peng, Xiong; Omasta, Travis; Rigdon, William; ...

2016-11-15

In this paper, a low cost air-assisted cylindrical liquid jets spraying (ACLJS) system was developed to prepare high-performance catalyst-coated membranes (CCMs) for proton exchange membrane fuel cells (PEMFCs). The catalyst ink was flowed from a cylindrical orifice and was atomized by an air stream fed from a coaxial slit and sprayed directly onto the membrane, which was suctioned to a heated aluminum vacuum plate. The CCM pore architecture including size, distribution and volume can be controlled using various flow parameters, and the impact of spraying conditions on electrode structure and PEMFC performance was investigated. CCMs fabricated in the fiber-type break-upmore » regime by ACLJS achieved very high performance during PEMFC testing, with the top-performing cells having a current density greater than 1900 mA/cm 2 at 0.7 V under H 2/O 2 flows and 700 mA/cm 2 under H 2/Air at 1.5 bar(absolute) pressure and 60% gas RH, and 80°C cell temperature.« less

Fabrication of High Performing PEMFC Catalyst-Coated Membranes with a Low Cost Air-Assisted Cylindrical Liquid Jets Spraying System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Xiong; Omasta, Travis; Rigdon, William

In this paper, a low cost air-assisted cylindrical liquid jets spraying (ACLJS) system was developed to prepare high-performance catalyst-coated membranes (CCMs) for proton exchange membrane fuel cells (PEMFCs). The catalyst ink was flowed from a cylindrical orifice and was atomized by an air stream fed from a coaxial slit and sprayed directly onto the membrane, which was suctioned to a heated aluminum vacuum plate. The CCM pore architecture including size, distribution and volume can be controlled using various flow parameters, and the impact of spraying conditions on electrode structure and PEMFC performance was investigated. CCMs fabricated in the fiber-type break-upmore » regime by ACLJS achieved very high performance during PEMFC testing, with the top-performing cells having a current density greater than 1900 mA/cm 2 at 0.7 V under H 2/O 2 flows and 700 mA/cm 2 under H 2/Air at 1.5 bar(absolute) pressure and 60% gas RH, and 80°C cell temperature.« less

The PEMFC-integrated CO oxidation — a novel method of simplifying the fuel cell plant

NASA Astrophysics Data System (ADS)

Rohland, Bernd; Plzak, Vojtech

Natural gas and methanol are the most economical fuels for residential fuel cell power generators as well as for mobile PEM-fuel cells. However, they have to be reformed with steam into hydrogen, which is to be cleaned from CO by shift-reaction and by partial oxidation to a level of no more than 30 ppm CO. This level is set by the Pt/Ru-C-anode of the PEMFC. A higher partial oxidation reaction rate for CO than those of Pt/Ru-C can be achieved in an oxidic Au-catalyst system. In the Fe 2O 3-Au system, a reaction rate of 2·10 -3 mol CO/s g Au at 1000 ppm CO and 5% "air bleed" at 80°C is achieved. This high rate allows to construct a catalyst-sheet for each cell within a PEMFC-stack. Practical and theoretical current/voltage characteristics of PEMFCs with catalyst-sheet are presented at 1000 ppm CO in hydrogen with 5% "air bleed". This gives the possibility of simplifying the gas processor of the plant.

Graphitized Carbon: A Promising Stable Cathode Catalyst Support Material for Long Term PEMFC Applications.

PubMed

Mohanta, Paritosh Kumar; Regnet, Fabian; Jörissen, Ludwig

2018-05-28

Stability of cathode catalyst support material is one of the big challenges of polymer electrolyte membrane fuel cells (PEMFC) for long term applications. Traditional carbon black (CB) supports are not stable enough to prevent oxidation to CO₂ under fuel cell operating conditions. The feasibility of a graphitized carbon (GC) as a cathode catalyst support for low temperature PEMFC is investigated herein. GC and CB supported Pt electrocatalysts were prepared via an already developed polyol process. The physical characterization of the prepared catalysts was performed using transmission electron microscope (TEM), X-ray Powder Diffraction (XRD) and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis, and their electrochemical characterizations were conducted via cyclic voltammetry(CV), rotating disk electrode (RDE) and potential cycling, and eventually, the catalysts were processed using membrane electrode assemblies (MEA) for single cell performance tests. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SEM) have been used as MEA diagonostic tools. GC showed superior stability over CB in acid electrolyte under potential conditions. Single cell MEA performance of the GC-supported catalyst is comparable with the CB-supported catalyst. A correlation of MEA performance of the supported catalysts of different Brunauer⁻Emmett⁻Teller (BET) surface areas with the ionomer content was also established. GC was identified as a promising candidate for catalyst support in terms of both of the stability and the performance of fuel cell.

Hierarchical nanostructured hollow spherical carbon with mesoporous shell as a unique cathode catalyst support in proton exchange membrane fuel cell.

PubMed

Fang, Baizeng; Kim, Jung Ho; Kim, Minsik; Kim, Minwoo; Yu, Jong-Sung

2009-03-07

Hierarchical nanostructured spherical carbon with hollow macroporous core in combination with mesoporous shell has been explored to support Pt cathode catalyst with high metal loading in proton exchange membrane fuel cell (PEMFC). The hollow core-mesoporous shell carbon (HCMSC) has unique structural characteristics such as large specific surface area and mesoporous volume, ensuring uniform dispersion of the supported high loading (60 wt%) Pt nanoparticles with small particle size, and well-developed three-dimensionally interconnected hierarchical porosity network, facilitating fast mass transport. The HCMSC-supported Pt(60 wt%) cathode catalyst has demonstrated markedly enhanced catalytic activity toward oxygen reduction and greatly improved PEMFC polarization performance compared with carbon black Vulcan XC-72 (VC)-supported ones. Furthermore, the HCMSC-supported Pt(40 wt%) or Pt(60 wt%) outperforms the HCMSC-supported Pt(20 wt%) even at a low catalyst loading of 0.2 mg Pt cm(-2) in the cathode, which is completely different from the VC-supported Pt catalysts. The capability of supporting high loading Pt is supposed to accelerate the commercialization of PEMFC due to the anticipated significant reduction in the amount of catalyst support required, diffusion layer thickness and fabricating cost of the supported Pt catalyst electrode.

Charting the relationship between phase type-surface area-interactions between the constituent atoms and oxygen reduction activity of Pd–Cu nanocatalysts inside fuel cells by in operando high-energy X-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maswadeh, Yazan; Shan, Shiyao; Prasai, Binay

The activity and stability of nanoalloy catalysts for chemical reactions driving devices for clean energy conversion, in particular the oxygen reduction reaction (ORR), depend critically on optimizing major structural characteristics of the nanoalloys, such as the phase composition, surface area and bonding interactions between the constituent atoms, for the harsh operating conditions inside the devices. The effort requires good knowledge of the potential effect of changes in these characteristics on the catalytic functionality of the nanoalloys and, hence, on the devices' performance. We present the results from an in operando high-energy X-ray diffraction (HE-XRD) study on the concurrent changes inmore » the structural characteristics and ORR activity of Pd–Cu nanoalloy catalysts as they function at the cathode of a proton exchange membrane fuel cell (PEMFC). We find that the as-prepared Pd–Cu nanoalloys with a chemical composition close to Pd1Cu1 are better ORR catalysts in comparison with Pd1Cu2, i.e. Pd-poor, and Pd3Cu1, i.e. Pd-rich, nanoalloys. Under operating conditions though, the former suffers a big loss in ORR activity appearing as a slow-mode oscillation in the current output of the PEMFC. Losses in ORR activity suffered by the latter also exhibit sudden drops and rises during the PEMFC operation. Through atomic pair distribution function (PDF) analysis of the in operando HE-XRD data, we identify the structural changes of Pd–Cu alloy NPs that are behind the peculiar decay of their ORR activity. The results uncover the instant link between the ever-adapting structural state of ORR nanocatalysts inside an operating PEMFC and the performance of the PEMFC. Besides, our results indicate that, among others, taking control over the intra-particle diffusion of metallic species in nanoalloy catalysts may improve the performance of PEMFCs significantly and, furthermore, in operando HE-XRD can be an effective tool to guide the effort. Finally, we argue that, though showing less optimal ORR activity in the as-prepared state, monophase Pd–Cu alloy catalysts with a composition ranging between Pd1Cu1 and Pd3Cu1 may deliver optimal performance inside operating PEMFCs.« less

Enhanced MEA Performance for PEMFCs under Low Relative Humidity and Low Oxygen Content Conditions via Catalyst Functionalization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xin, Le; Yang, Fan; Xie, Jian

2017-01-01

This work demonstrates that functionalizing annealed-Pt/Ketjen black EC300j (a-Pt/KB) and dealloyed-PtNi/Ketjen black EC300j (d-PtNi/KB) catalysts using p-phenyl sulfonic acid can effectively enhance performance in the membrane electrode assemblies (MEAs) of proton exchange membrane fuel cells (PEMFCs). The functionalization increased the size of both Pt and PtNi catalyst particles and resulted in the further leaching of Ni from the PtNi catalyst while promoting the formation of nanoporous PtNi nanoparticles. The size of the SO3H-Pt/KB and SO3H-PtNi/KB carbon-based aggregates decreased dramatically, leading to the formation of catalyst layers with narrower pore size distributions.MEA tests highlighted the benefits of the surface functionalization, inmore » which the cells with SO3H-Pt/KB and SO3H-PtNi/KB cathode catalysts showed superior high current density performance under reduced RH conditions, in comparison with cells containing annealed Pt/KB (a-Pt/KB) and de-alloyed PtNi/KB (d-PtNi/KB) catalysts. The performance improvement was particularly evident when using reactant gases with low relative humidity, indicating that the hydrophilic functional groups on the carbon improved the water retention in the cathode catalyst layer. These results show a new avenue for enhancing catalyst performance for the next generation of catalytic materials for PEMFCs.« less

Eliminating micro-porous layer from gas diffusion electrode for use in high temperature polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Su, Huaneng; Xu, Qian; Chong, Junjie; Li, Huaming; Sita, Cordellia; Pasupathi, Sivakumar

2017-02-01

In this work, we report a simple strategy to improve the performance of high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) by eliminating the micro-porous layer (MPL) from its gas diffusion electrodes (GDEs). Due to the absence of liquid water and the general use of high amount of catalyst, the MPL in a HT-PEMFC system works limitedly. Contrarily, the elimination of the MPL leads to an interlaced micropore/macropore composited structure in the catalyst layer (CL), which favors gas transport and catalyst utilization, resulting in a greatly improved single cell performance. At the normal working voltage (0.6 V), the current density of the GDE eliminated MPL reaches 0.29 A cm-2, and a maximum power density of 0.54 W cm-2 at 0.36 V is obtained, which are comparable to the best results yet reported for the HT-PEMFCs with similar Pt loading and operated using air. Furthermore, the MPL-free GDE maintains an excellent durability during a preliminary 1400 h HT-PEMFC operation, owing to its structure advantages, indicating the feasibility of this electrode for practical applications.

Nitrogen-doped three-dimensional graphene-supported platinum catalysts for polymer electrolyte membrane fuel cells application

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Li, Xingxing; Yuan, Wensen; Zhu, Huanhuan; Qin, Yong; Zhang, Shuai; Yuan, Ningyi; Lin, Bencai; Ding, Jianning

Catalysts are a key component of polymer electrolyte membrane fuel cells (PEMFCs). In this work, nitrogen-doped three-dimensional graphene-supported platinum (Pt-3DNG) catalysts are successfully prepared and characterized. SEM and TEM images show the Pt nanoparticles are uniformly dispersed in the sheets of nitrogen-doped 3DNG. Compared with that of the commercial Pt/C catalysts, Pt-3DNG show much better oxygen reduction reaction (ORR) activity and cycling stability, and the reduction in limit current density after 1000 cycles is only about 1.6% for the Pt-3DNG catalysts, whereas 7.2% for the commercial Pt/C catalysts. The single cell using Pt-3DNG catalysts in both the anode and the cathode show a higher peak power density (21.47mW cm-2) than that using commercial Pt/C catalysts (20.17mW cm-2) under the same conditions. These properties make this type of catalyst suitable for the application in PEMFCs.

Metallofullerenes as fuel cell electrocatalysts: a theoretical investigation of adsorbates on C59Pt.

PubMed

Gabriel, Margaret A; Genovese, Luigi; Krosnicki, Guillaume; Lemaire, Olivier; Deutsch, Thierry; Franco, Alejandro A

2010-08-28

Nano-structured electrode degradation in state-of-the-art polymer electrolyte membrane fuel cells (PEMFCs) is one of the main shortcomings that limit the large-scale development and commercialization of this technology. During normal operating conditions of the fuel cell, the PEMFC lifetime tends to be limited by coarsening of the cathode's Pt-based catalyst and by corrosion of the cathode's carbon black support. Because of their chemical properties, metallofullerenes such as C(59)Pt may be more electrochemically stable than the Pt/C mixture. In this paper we investigate, by theoretical methods, the stability of oxygen reduction reaction (ORR) adsorbates on the metallofullerene C(59)Pt and evaluate its potential as a PEMFC fuel cell catalyst.

Electrocatalysts by atomic layer deposition for fuel cell applications

DOE PAGES

Cheng, Niancai; Shao, Yuyan; Liu, Jun; ...

2016-01-22

Here, fuel cells are a promising technology solution for reliable and clean energy because they offer high energy conversion efficiency and low emission of pollutants. However, high cost and insufficient durability are considerable challenges for widespread adoption of polymer electrolyte membrane fuel cells (PEMFCs) in practical applications. Current PEMFCs catalysts have been identified as major contributors to both the high cost and limited durability. Atomic layer deposition (ALD) is emerging as a powerful technique for solving these problems due to its exclusive advantages over other methods. In this review, we summarize recent developments of ALD in PEMFCs with a focusmore » on design of materials for improved catalyst activity and durability. New research directions and future trends have also been discussed.« less

Performance improvement in PEMFC using aligned carbon nanotubes as electrode catalyst support.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, D. J.; Yang, J.; Kariuki, N.

2008-01-01

A novel membrane electrode assembly (MEA) using aligned carbon nanotubes (ACNT) as the electrocatalyst support was developed for proton exchange membrane fuel cell (PEMFC) application. A multiple-step process of preparing ACNT-PEMFC including ACNT layer growth and catalyzing, MEA fabrication, and single cell packaging is reported. Single cell polarization studies demonstrated improved fuel utilization and higher power density in comparison with the conventional, ink based MEA.

Analysis of Deactivation Mechanism on a Multi-Component Sulfur-Tolerant Steam Reforming Catalyst

DTIC Science & Technology

2010-08-01

Alkaline Fuel Cells (AFC) .............................................................................. 4 1.1.2. Proton Exchange Membrane Fuel Cells ( PEMFC ...temperature fuel cells. Alkaline Fuel Cell (AFC), Proton Exchange Membrane Fuel Cell ( PEMFC ), DMFC and Phosphoric Acid Fuel Cell (PAFC) are low...1960s. 1.1.2. Proton Exchange Membrane Fuel Cells ( PEMFC ) Proton exchange membrane fuel cells are said to be the best type of fuel cells to replace

Durability Improvement of Pt/RGO Catalysts for PEMFC by Low-Temperature Self-Catalyzed Reduction.

PubMed

Sun, Kang Gyu; Chung, Jin Suk; Hur, Seung Hyun

2015-12-01

Pt/C catalyst used for polymer electrolyte membrane fuel cells (PEMFCs) displays excellent initial performance, but it does not last long because of the lack of durability. In this study, a Pt/reduced graphene oxide (RGO) catalyst was synthesized by the polyol method using ethylene glycol (EG) as the reducing agent, and then low-temperature hydrogen bubbling (LTHB) treatment was introduced to enhance the durability of the Pt/RGO catalyst. The cyclic voltammetry (CV), oxygen reduction reaction (ORR) analysis, and transmittance electron microscopy (TEM) results suggested that the loss of the oxygen functional groups, because of the hydrogen spillover and self-catalyzed dehydration reaction during LTHB, reduced the carbon corrosion and Pt agglomeration and thus enhanced the durability of the electrocatalyst.

Characterization of the Ternary Compound Pd5Pt3Ni2 for PEMFC Cathode Electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jarvis, Karalee; Zhao, J; Allard Jr, Lawrence Frederick

2010-01-01

Research on proton exchange membrane fuel cells (PEMFC) has increased over the last decade due to an increasing demand for alternative energy solutions. Most PEMFCs use Pt on carbon support as electrocatalysts for oxygen reduction reactions (ORR) [1]. Due to the high cost of Pt, there is a strong drive to develop less expensive catalysts that meet or exceed the performance of Pt. Binary and ternary Pt alloys with less expensive metals are a possible route [1]. In this work, a ternary alloy with composition Pd5Pt3Ni2 was studied as a potential cathode material. Preliminary results showed similar catalytic performance tomore » pure Pt in single-cell tests. However, to enhance its performance, it is necessary to understand how this ternary catalyst behaves during fuel cell operation. Various electron microscopy techniques were used to characterize the ternary Pd5Pt3Ni2 catalysts within the membrane-electrode assembly (MEA) both before and after fuel cell operation.« less

Gram-level synthesis of core-shell structured catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Luo, Mingchuan; Wei, Lingli; Wang, Fanghui; Han, Kefei; Zhu, Hong

2014-12-01

Over the past decade, Pt based core-shell structured alloys have been studied extensively as oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) because of their distinctive electrochemical performance and low Pt loading. In this paper, a facile route based on microwave-assisted polyol method and chemical dealloying process is proposed to synthesize carbon supported core-shell structured nanoparticles (NPs) in gram-level for ORR electrocatalysis in PEMFCs. The obtained samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). These physical characterization indicate that the final synthesized NPs are highly dispersed on the carbon support, and in a core-shell structure with CuPt alloy as the core and Pt as the shell. Electrochemical measurements, conducted by cyclic voltammetry (CV) and rotating disk electrode (RDE) tests, show the core-shell structured catalyst exhibit a 3× increase in mass activity and a 2× increase in specific activity over the commercial Pt/C catalyst, respectively. These results demonstrate that this route can be a reliable way to synthesize low-Pt catalyst in large-scale for PEMFCs.

Effect of Nitrogen Post-Doping on a Commercial Platinum-Ruthenium/Carbon Anode Catalyst

DTIC Science & Technology

2014-02-15

polymer electrolyte membrane fuel cells ( PEMFCs ) closer to commercial viability. However, further improvements in fuel cell durability, particularly...have recently led to significant improvements [3e5]. The genesis of interest in modified carbon support materials for PEMFCs and DMFCs originated in

Synthesis and Characterization of CO-and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shamsuddin Ilias

2005-12-22

The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary,more » ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. During this reporting period we synthesized four Pt-based electrocatalysts catalysts (Pt/Ru/Mo/Se, Pt/Ru/Mo/Ir, Pt/Ru/Mo/W, Ptr/Ru/Mo/Co) on Vulcan XG72 Carbon support by both conventional and ultra-sonication method. From current-voltage performance study, the catalytic activity was found in the increasing order of Pt/Ru/Mo/Ir > Pt/Ru/Mo/W > Pt/Ru/Mo/Co > Pt/Ru/MO/Se. Sonication method appears to provide better dispersion of catalysts on carbon support.« less

New Fluorinated and Sulfonated Block Copolymers Final Report

DTIC Science & Technology

2009-04-23

use polymers namely, Polymer Electrolyte Membrane Fuel Cells ( PEMFC ) and Direct Methanol Fuel Cells (DMFC) The DMFC can be seen as a variant of...the PEMFC . The membranes are typically the same; however, the feed for DMFC is methanol in an aqueous 1-2 M solution or in its vapor form. This fuel...the existing liquid fuels infrastructure can be used for methanol. Catalysts, as well as operating temperature ranges, are very similar to the PEMFC

Operando Raman Micro Spectroscopy of Polymer Electrolyte Fuel Cells

DTIC Science & Technology

2016-01-16

understanding of the processes such as oxygen reduc- tion reaction (ORR), carbon corrosion, and catalysis process of ORR in PEMFCs catalyzed by Pt or...Journal of Membrane Science, 392, 88 (2012). 46. F. Jaouen, F. Charreteur, and J. P. Dodelet, “Fe-based catalysts for oxygen reduction in PEMFCs

Carbon nanocages: a new support material for Pt catalyst with remarkably high durability.

PubMed

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-03-24

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for "real world" application.

Durable electrocatalytic-activity of Pt-Au/C cathode in PEMFCs.

PubMed

Selvaganesh, S Vinod; Selvarani, G; Sridhar, P; Pitchumani, S; Shukla, A K

2011-07-21

Longevity remains as one of the central issues in the successful commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and primarily hinges on the durability of the cathode. Incorporation of gold (Au) to platinum (Pt) is known to ameliorate both the electrocatalytic activity and stability of cathode in relation to pristine Pt-cathodes that are currently being used in PEMFCs. In this study, an accelerated stress test (AST) is conducted to simulate prolonged fuel-cell operating conditions by potential cycling the carbon-supported Pt-Au (Pt-Au/C) cathode. The loss in performance of PEMFC with Pt-Au/C cathode is found to be ∼10% after 7000 accelerated potential-cycles as against ∼60% for Pt/C cathode under similar conditions. These data are in conformity with the electrochemical surface-area values. PEMFC with Pt-Au/C cathode can withstand >10,000 potential cycles with very little effect on its performance. X-ray diffraction and transmission electron microscopy studies on the catalyst before and after AST suggest that incorporating Au with Pt helps mitigate aggregation of Pt particles during prolonged fuel-cell operations while X-ray photoelectron spectroscopy reflects that the metallic nature of Pt is retained in the Pt-Au catalyst during AST in comparison to Pt/C that shows a major portion of Pt to be present as oxidic platinum. Field-emission scanning electron microscopy conducted on the membrane electrode assembly before and after AST suggests that incorporating Au with Pt helps mitigating deformations in the catalyst layer. This journal is © the Owner Societies 2011

Molybdenum Carbide Synthesis Using Plasmas for Fuel Cells

DTIC Science & Technology

2013-06-01

S. A. Hong, I. H. Oh, and S. J. Shin, “Performance and life time analysis of the kW-class PEMFC stack,” Journal of Power Sources, vol. 106, pp. 295...pp. 591–596, 1998. [25] M. Gotz and H. Wendt, “Binary and ternary anode catalyst formulations including the elements W, Sn and Mo for PEMFCs ...and R. C. Urian, “Electrocatalysis of CO Tolerance by Carbon-Supported PtMo Electrocatalysts in PEMFCs ,” Journal of Electrochemical Society, vol

Durability and performance optimization of cathode materials for fuel cells

NASA Astrophysics Data System (ADS)

Colon-Mercado, Hector Rafael

The primary objective of this dissertation is to develop an accelerated durability test (ADT) for the evaluation of cathode materials for fuel cells. The work has been divided in two main categories, namely high temperature fuel cells with emphasis on the Molten Carbonate Fuel Cell (MCFC) cathode current collector corrosion problems and low temperature fuel cells in particular Polymer Electrolyte Fuel Cell (PEMFC) cathode catalyst corrosion. The high operating temperature of MCFC has given it benefits over other fuel cells. These include higher efficiencies (>50%), faster electrode kinetics, etc. At 650°C, the theoretical open circuit voltage is established, providing low electrode overpotentials without requiring any noble metal catalysts and permitting high electrochemical efficiency. The waste heat is generated at sufficiently high temperatures to make it useful as a co-product. However, in order to commercialize the MCFC, a lifetime of 40,000 hours of operation must be achieved. The major limiting factor in the MCFC is the corrosion of cathode materials, which include cathode electrode and cathode current collector. In the first part of this dissertation the corrosion characteristics of bare, heat-treated and cobalt coated titanium alloys were studied using an ADT and compared with that of state of the art current collector material, SS 316. PEMFCs are the best choice for a wide range of portable, stationary and automotive applications because of their high power density and relatively low-temperature operation. However, a major impediment in the commercialization of the fuel cell technology is the cost involved due to the large amount of platinum electrocatalyst used in the cathode catalyst. In an effort to increase the power and decrease the cathode cost in polymer electrolyte fuel cell (PEMFC) systems, Pt-alloy catalysts were developed to increase its activity and stability. Extensive research has been conducted in the area of new alloy development and understanding the mechanisms of ORR. However, a relatively small number of publications are related to the durability of Pt alloys in the PEMFC environment. In the second part of this dissertation an ADT is developed for the evaluation of PEMFC cathode catalysts in a time and cost effective way.

High-performance hydrogen fuel cell using nitrate reduction reaction on a non-precious catalyst.

PubMed

Han, Sang-Beom; Song, You-Jung; Lee, Young-Woo; Ko, A-Ra; Oh, Jae-Kyung; Park, Kyung-Won

2011-03-28

The H(2)-NO(3)(-) electrochemical cell using nitrate reduction on a non-precious cathode catalyst shows much improved efficiency despite ∼75% reduction of Pt metal loading as compared to typical PEMFCs using typical ORR on precious catalysts.

Polybenzimidazole (PBI) functionalized nanographene as highly stable catalyst support for polymer Electrolyte membrane fuel cells (PEMFCs)

DOE PAGES

Xin, Le; Yang, Fan; Qiu, Yang; ...

2016-08-25

Nanoscale graphenes were used as cathode catalyst supports in proton exchange membrane fuel cells (PEMFCs). Surface-initiated polymerization that covalently bonds polybenzimidazole (PBI) polymer on the surface of graphene supports enables the uniform distribution of the Pt nanoparticles, as well as allows the sealing of the unterminated carbon bonds usually present on the edge of graphene from the chemical reduction of graphene oxide. The nanographene effectively shortens the length of channels and pores for O 2 diffusion/water dissipation and significantly increases the primary pore volume. Further addition of p-phenyl sulfonic functional graphitic carbon particles as spacers, increases the specific volume ofmore » the secondary pores and greatly improves O 2 mass transport within the catalyst layers. The developed composite cathode catalyst of Pt/PBI-nanographene (50 wt%) + SO 3H-graphitic carbon black demonstrates a higher beginning of life (BOL) PEMFC performance as compared to both Pt/PBI-nanographene (50 wt%) and Pt/PBI-graphene (50 wt%) + SO 3H-graphitic carbon black (GCB). Accelerated stress tests show excellent support durability compared to that of traditional Pt/Vulcan XC72 catalysts, when subjected to 10,000 cycles from 1.0 V to 1.5 V. As a result, this study suggests the promise of using PBI-nanographene + SO 3H-GCB hybrid supports in fuel cells to achieve the 2020 DOE targets for transportation applications.« less

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode.

PubMed

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-05-23

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

Effect of hydrophobic additive on oxygen transport in catalyst layer of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Wang, Shunzhong; Li, Xiaohui; Wan, Zhaohui; Chen, Yanan; Tan, Jinting; Pan, Mu

2018-03-01

Oxygen transport resistance (OTR) is a critical factor influencing the performance of proton exchange membrane fuel cells (PEMFCs). In this paper, an effective method to reduce the OTR of catalyst layers (CLs) by introducing a hydrophobic additive into traditional CLs is proposed. A low-molecular-weight polytetrafluoroethylene (PTFE) is selected for its feasibility to prepare an emulsion, which is mixed with a traditional catalyst ink to successfully fabricate the CL with PTFE of 10 wt%. The PTFE film exists in the mesopores between the carbon particles. The limiting current of the hydrophobic CL was almost 4000 mA/cm2, which is 500 mA/cm2 higher than that of the traditional CL. PTFE reduces the OTR of the CL in the dry region by as much as 24 s/m compared to the traditional CL and expands the dry region from 2000 mA/cm2 in the traditional CL to 2500 mA/cm2. Furthermore, the CL with the hydrophobic agent can improve the oxygen transport in the wet region (>2000 mA/cm2) more effectively than that in the dry region. All these results indicate that the CL with the hydrophobic agent shows a superior performance in terms of optimizing water management and effectively reduces the OTR in PEMFCs.

Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells.

PubMed

Setzler, Brian P; Zhuang, Zhongbin; Wittkopf, Jarrid A; Yan, Yushan

2016-12-06

Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW -1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

2016-12-01

Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies.

PubMed

Speder, Jozsef; Altmann, Lena; Roefzaad, Melanie; Bäumer, Marcus; Kirkensgaard, Jacob J K; Mortensen, Kell; Arenz, Matthias

2013-03-14

A colloidal synthesis approach is presented that allows systematic studies of the properties of supported proton exchange membrane fuel cell (PEMFC) catalysts. The applied synthesis route is based on the preparation of monodisperse nanoparticles in the absence of strong binding organic stabilizing agents. No temperature post-treatment of the catalyst is required rendering the synthesis route ideally suitable for comparative studies. We report work concerning a series of catalysts based on the same colloidal Pt nanoparticle (NP) suspension, but with different high surface area (HSA) carbon supports. It is shown that for the prepared catalysts the carbon support has no catalytic co-function, but carbon pre-treatment leads to enhanced sticking of the Pt NPs on the support. An unwanted side effect, however, is NP agglomeration during synthesis. By contrast, enhanced NP sticking without agglomeration can be accomplished by the addition of an ionomer to the NP suspension. The catalytic activity of the prepared catalysts for the oxygen reduction reaction is comparable to industrial catalysts and no influence of the particle size is found in the range of 2-5 nm.

Carbon nanocages: A new support material for Pt catalyst with remarkably high durability

PubMed Central

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-01-01

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for “real world” application. PMID:24658614

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

PubMed Central

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-01-01

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance. PMID:27210793

A concise guide to sustainable PEMFCs: recent advances in improving both oxygen reduction catalysts and proton exchange membranes.

PubMed

Scofield, Megan E; Liu, Haiqing; Wong, Stanislaus S

2015-08-21

The rising interest in fuel cell vehicle technology (FCV) has engendered a growing need and realization to develop rational chemical strategies to create highly efficient, durable, and cost-effective fuel cells. Specifically, technical limitations associated with the major constituent components of the basic proton exchange membrane fuel cell (PEMFC), namely the cathode catalyst and the proton exchange membrane (PEM), have proven to be particularly demanding to overcome. Therefore, research trends within the community in recent years have focused on (i) accelerating the sluggish kinetics of the catalyst at the cathode and (ii) minimizing overall Pt content, while simultaneously (a) maximizing activity and durability as well as (b) increasing membrane proton conductivity without causing any concomitant loss in either stability or as a result of damage due to flooding. In this light, as an example, high temperature PEMFCs offer a promising avenue to improve the overall efficiency and marketability of fuel cell technology. In this Critical Review, recent advances in optimizing both cathode materials and PEMs as well as the future and peculiar challenges associated with each of these systems will be discussed.

Lifecycle Cost Assessment of Fuel Cell Technologies for Soldier Power System Applications. Paper and Presentation for the 43rd Power Sources Conference held 8-9 July 2008, Philadelphia, PA

DTIC Science & Technology

2008-07-09

PEMFC in Federal Markets,” 2007 Fuel Cell Seminar, San Antonio, TX, 17 October 2007. 7. Fok, K., “Metal Hydride Fuel Cells: Increases in Power...Lauderdale, FL, March 17-20, 2008. 10. Zhao J., et al, “Reclaim/recycle of Pt/C catalysts for PEMFC ,” Energy Conversion and Management, vol. 48...hydrogen PEMFC or SOFC systems – Baratto et al, Journal of Power Sources – Citigroup, Dist. Telecom Backup – Battelle, Fuel Cell Seminar 2007 • Fuel

Novel carbon nanostructures as catalyst support for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Natarajan, Sadesh Kumar

Polymer electrolyte membrane fuel cell (PEMFC) technology has advanced rapidly in recent years, with one of active area focused on improving the long-term performance of carbon supported catalysts, which has been recognized as one of the most important issues to be addressed for the commercialization of PEMFCs. The central part of a PEMFC is the membrane electrode assembly (MEA) which consists of two electrodes (anode and cathode) and a cation exchange membrane. These electrodes are commonly made of carbon black (most often, Vulcan XC-72) supported on carbon paper or carbon cloth backings. It is the primary objective of this thesis to prepare and investigate carbon nanostructures (CNS, licensed to Hydrogen Research Institute -- IRH, Quebec, Canada), the carbon material with more graphite component like carbon nanotubes (CNTs) for use as catalyst support in PEMFCs. High energy ball-milling of activated carbon along with transition metal catalysts under hydrogen atmosphere, followed by heat-treatment leads to nanocrystalline structures of carbon called CNS. However, CNS formed in the quartz tube after heat-treatment is inevitably accompanied by many impurities such as metal particles, amorphous carbon and other carbon nanoparticules. Such impurities are a serious impediment to detailed characterization of the properties of nanostructures. In addition, since the surface of CNS is itself rather inert, it is difficult to control the homogeneity and size distribution of Pt nanoparticules. In this thesis work, we demonstrated a novel mean to purify and functionalize CNS via acid-oxidation under reflux conditions. To investigate and quantify these nanostructures X-ray diffraction, electrical conductivity measurements, specific surface area measurements, thermogravimetric analysis, X-ray photoelectron spectroscopy and transmission electron microscopy studies were used. Cyclic voltammetry studies were performed on different samples to derive estimates for the relationship between the composition of the acid mixture and their influence in producing high density of surface functional groups. Such surface functionalization on CNS enhances the reactivity, improves the specificity and provides an avenue for Pt deposition. It was also shown that a 1:1 mixture of 7.5 M sulphuric acid and 15 M nitric acid have generated higher composition of non-acidic functional groups over other acid compositions discussed in this thesis. In this thesis, we also demonstrated a novel method to deposit and disperse platinum clusters on carbon nanotubes via a chemically specific nucleation mechanism. To investigate and quantify these platinized CNS X-ray diffraction, thermogravimetric analysis, atomic adsorption spectroscopy and high resolution transmission electron microscopy were used. An average Pt cluster size of 4 nm was dispersed homogeneously on CNS that was functionalized with the method described above. The corrosive nature of carbon support material is a crucial issue for the commercialization of PEMFC systems. Therefore, electrochemical oxidations of Pt/CNS compared with Pt/C were studied in this thesis with the aim to understand their durability as catalyst support in PEMFCs. The surface oxidation of the catalyst materials has been compared following potentiostatic treatments up to 200 h under condition simulating the PEMFC cathode environment (80°C, nitrogen purged 0.5 M sulphuric acid, and a constant potential of 1.2 V). The degradation of Pt catalysts and the carbon support was also evaluated by measuring the cell voltage at constant load after different oxidation intervals at 1.2 V. The agglomeration of Pt catalyst particles and the changes in surface functional groups of the carbon material at different intervals of electrochemical oxidation was evaluated using X-ray diffraction and thermogravimetric studies. The subsequent electrochemical characterization at different treatment time intervals by both the above methods suggests that CNS is electrochemically more stable than Vulcan XC-72 with less surface oxide formation and Pt surface area loss without sacrificing catalytic activity. (Abstract shortened by UMI.)

Dispersion of Rod-like Particles of Nafion in Salt-Free Water/1-Propanol and Water/Ethanol Solutions.

PubMed

Yamaguchi, Makoto; Matsunaga, Takuro; Amemiya, Kazuki; Ohira, Akihiro; Hasegawa, Naoki; Shinohara, Kazuhiko; Ando, Masaki; Yoshida, Toshihiko

2014-12-26

The dispersion of perfluorinated sulfonic acid ionomers in catalyst inks is an important factor controlling the performance of catalyst layers in membrane electrode assemblies of proton exchange membrane fuel cells (PEMFCs). The effect of water/alcohol composition on the dispersion of H-Nafion in water/1-propanol and water/ethanol solutions was studied by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and (19)F nuclear magnetic resonance ((19)F NMR) spectroscopy. Hydrodynamic radii calculated from DLS decay profiles and the radii and interparticle distance of rod-like particles derived from SAXS profiles showed almost the same dependence on alcohol concentration. 1-Propanol was more effective than ethanol to induce changes in the characteristic lengths of the rod-like particles. The motional narrowing in the (19)F NMR spectra by addition of 1-propanol indicates selective solvation of the rod-like particles. We suppose this might have decreased their radii and induced their elongation, which eventually led to extension of the ordered regions as observed in the hydrodynamic radii. Our study helps to clarify the dispersion of Nafion in aqueous alcohol solutions, which has implications for the performance of PEMFCs.

Enhancement of Electrode Stability Using Platinum-Cobalt Nanocrystals on a Novel Composite SiCTiC Support.

PubMed

Millán, María; Zamora, Héctor; Rodrigo, Manuel A; Lobato, Justo

2017-02-22

PtCo alloy catalysts for high temperature PEMFCs (protonic exchange membrane fuel cells) were synthesized on a novel noncarbonaceous support (SiCTiC) using the impregnation method with NaBH 4 as the reducing agent at different synthesis temperatures to evaluate the effect of this variable on their physicochemical and electrochemical properties. The catalysts were characterized by inductively coupled plasma optical emission spectrometry, scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscope-energy dispersive X-ray,and temperature-programmed reduction. In addition, the electrochemical characterization (i.e., cyclic voltammetry, oxygen reduction reaction, and chronoamperometry) was carried out with a rotating disk electrode. For the cyclic voltammetry investigation, 400 cycles were performed in hot phosphoric acid and a half-cell to evaluate the stability of the synthesized catalysts. The catalyst synthesized on SiCTiC exhibited excellent durability compared to the catalyst synthesized on a Vulcan support. In addition, all synthesized catalysts exhibited better catalytic activity than that of the PtCo/C catalysts. The best results were observed for the catalyst synthesized at 80 °C due to its shorter Pt-Pt nearest-neighbor and higher alloy degree. Finally, a preliminary stability test was conducted in an HT-PEMFC, and promising results in terms of stability and performance were observed.

Proton exchange membrane fuel cell model for aging predictions: Simulated equivalent active surface area loss and comparisons with durability tests

NASA Astrophysics Data System (ADS)

Robin, C.; Gérard, M.; Quinaud, M.; d'Arbigny, J.; Bultel, Y.

2016-09-01

The prediction of Proton Exchange Membrane Fuel Cell (PEMFC) lifetime is one of the major challenges to optimize both material properties and dynamic control of the fuel cell system. In this study, by a multiscale modeling approach, a mechanistic catalyst dissolution model is coupled to a dynamic PEMFC cell model to predict the performance loss of the PEMFC. Results are compared to two 2000-h experimental aging tests. More precisely, an original approach is introduced to estimate the loss of an equivalent active surface area during an aging test. Indeed, when the computed Electrochemical Catalyst Surface Area profile is fitted on the experimental measures from Cyclic Voltammetry, the computed performance loss of the PEMFC is underestimated. To be able to predict the performance loss measured by polarization curves during the aging test, an equivalent active surface area is obtained by a model inversion. This methodology enables to successfully find back the experimental cell voltage decay during time. The model parameters are fitted from the polarization curves so that they include the global degradation. Moreover, the model captures the aging heterogeneities along the surface of the cell observed experimentally. Finally, a second 2000-h durability test in dynamic operating conditions validates the approach.

Fabrication of a nanosize-Pt-embedded membrane electrode assembly to enhance the utilization of Pt in proton exchange membrane fuel cells.

PubMed

Choe, Junseok; Kim, Doyoung; Shim, Jinyong; Lee, Inhae; Tak, Yongsug

2011-08-01

A procedure to locate the Pt nanostructure inside the hydrophilic channel of a Nafion membrane was developed in order to enhance Pt utilization in PEMFCs. Nanosize Pt-embedded MEA was constructed by Cu electroless plating and subsequent Pt electrodeposition inside the hydrophilic channels of the Nafion membrane. The metallic Pt nanostructure fabricated inside the membrane was employed as an oxygen reduction catalyst for a PEMFC and facilitated effective use of the hydrophilic channels inside the membrane. Compared to the conventional MEA, a Pt-embedded MEA with only 68% Pt loading showed better PEMFC performance.

Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiberg, Gustav K. H., E-mail: gustav.wiberg@gmail.com, E-mail: m.arenz@chem.ku.dk; Fleige, Michael; Arenz, Matthias, E-mail: gustav.wiberg@gmail.com, E-mail: m.arenz@chem.ku.dk

2015-02-15

We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allowsmore » an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.« less

Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

NASA Astrophysics Data System (ADS)

Wiberg, Gustav K. H.; Fleige, Michael; Arenz, Matthias

2015-02-01

We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allows an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.

Effect of Particle Size and Operating Conditions on Pt 3Co PEMFC Cathode Catalyst Durability

DOE PAGES

Gummalla, Mallika; Ball, Sarah; Condit, David; ...

2015-05-29

The initial performance and decay trends of polymer electrolyte membrane fuel cells (PEMFC) cathodes with Pt 3Co catalysts of three mean particle sizes (4.9 nm, 8.1 nm, and 14.8 nm) with identical Pt loadings are compared. Even though the cathode based on 4.9 nm catalyst exhibited the highest initial electrochemical surface area (ECA) and mass activity, the cathode based on 8.1 nm catalyst showed better initial performance at high currents. Owing to the low mass activity of the large particles, the initial performance of the 14.8 nm Pt3Co-based electrode was the lowest. The performance decay rate of the electrodes withmore » the smallest Pt 3Co particle size was the highest and that of the largest Pt 3Co particle size was lowest. Interestingly, with increasing number of decay cycles (0.6 to 1.0 V, 50 mV/s), the relative improvement in performance of the cathode based on 8.1 nm Pt 3Co over the 4.9 nm Pt 3Co increased, owing to better stability of the 8.1 nm catalyst. The electron microprobe analysis (EMPA) of the decayed membrane-electrode assembly (MEA) showed that the amount of Co in the membrane was lower for the larger particles, and the platinum loss into the membrane also decreased with increasing particle size. This suggests that the higher initial performance at high currents with 8.1 nm Pt 3Co could be due to lower contamination of the ionomer in the electrode. Furthermore, lower loss of Co from the catalyst with increased particle size could be one of the factors contributing to the stability of ECA and mass activity of electrodes with larger cathode catalyst particles. To delineate the impact of particle size and alloy effects, these results are compared with prior work from our research group on size effects of pure platinum catalysts. The impact of PEMFC operating conditions, including upper potential, relative humidity, and temperature on the alloy catalyst decay trends, along with the EMPA analysis of the decayed MEAs, are reported.« less

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells.

PubMed

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab; Nedellec, Yannig; Cosnier, Serge; Shaw, Wendy J; Artero, Vincent; Le Goff, Alan

2017-02-06

A biomimetic nickel bis-diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H 2 /2 H + interconversion from pH 0 to 9, with catalytic preference for H 2 oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio-inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni-based PEMFC reaches 14 mW cm -2 , only six-times-less as compared to full-Pt conventional PEMFC. The Pt-free enzyme-based fuel cell delivers ≈2 mW cm -2 , a new efficiency record for a hydrogen biofuel cell with base metal catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-organic frameworks derived platinum-cobalt bimetallic nanoparticles in nitrogen-doped hollow porous carbon capsules as a highly active and durable catalyst for oxygen reduction reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ying, Jie; Li, Jing; Jiang, Gaopeng

Pt-based nanomaterials are regarded as the most efficient electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, widespread adoption of PEMFCs requires solutions to major challenges encountered with ORR catalysts, namely high cost, sluggish kinetics, and low durability. In this paper, a new efficient method utilizing Co-based metal-organic frameworks is developed to produce PtCo bimetallic nanoparticles embedded in unique nitrogen-doped hollow porous carbon capsules. The obtained catalyst demonstrates an outstanding ORR performance, with a mass activity that is 5.5 and 13.5 times greater than that of commercial Pt/C and Pt black, respectively. Most importantly,more » the product exhibits dramatically improved durability in terms of both electrochemically active surface area (ECAS) and mass activity compared to commercial Pt/C and Pt black catalysts. Finally, the remarkable ORR performance demonstrated here can be attributed to the structural features of the catalyst (its alloy structure, high dispersion and fine particle size) and the carbon support (its nitrogen dopant, large surface area and hollow porous structure).« less

Metal-organic frameworks derived platinum-cobalt bimetallic nanoparticles in nitrogen-doped hollow porous carbon capsules as a highly active and durable catalyst for oxygen reduction reaction

DOE PAGES

Ying, Jie; Li, Jing; Jiang, Gaopeng; ...

2017-11-29

Pt-based nanomaterials are regarded as the most efficient electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, widespread adoption of PEMFCs requires solutions to major challenges encountered with ORR catalysts, namely high cost, sluggish kinetics, and low durability. In this paper, a new efficient method utilizing Co-based metal-organic frameworks is developed to produce PtCo bimetallic nanoparticles embedded in unique nitrogen-doped hollow porous carbon capsules. The obtained catalyst demonstrates an outstanding ORR performance, with a mass activity that is 5.5 and 13.5 times greater than that of commercial Pt/C and Pt black, respectively. Most importantly,more » the product exhibits dramatically improved durability in terms of both electrochemically active surface area (ECAS) and mass activity compared to commercial Pt/C and Pt black catalysts. Finally, the remarkable ORR performance demonstrated here can be attributed to the structural features of the catalyst (its alloy structure, high dispersion and fine particle size) and the carbon support (its nitrogen dopant, large surface area and hollow porous structure).« less

Unraveling micro- and nanoscale degradation processes during operation of high-temperature polymer-electrolyte-membrane fuel cells

NASA Astrophysics Data System (ADS)

Hengge, K.; Heinzl, C.; Perchthaler, M.; Varley, D.; Lochner, T.; Scheu, C.

2017-10-01

The work in hand presents an electron microscopy based in-depth study of micro- and nanoscale degradation processes that take place during the operation of high-temperature polymer-electrolyte-membrane fuel cells (HT-PEMFCs). Carbon supported Pt particles were used as cathodic catalyst material and the bimetallic, carbon supported Pt/Ru system was applied as anode. As membrane, cross-linked polybenzimidazole was used. Scanning electron microscopy analysis of cross-sections of as-prepared and long-term operated membrane-electrode-assemblies revealed insight into micrometer scale degradation processes: operation-caused catalyst redistribution and thinning of the membrane and electrodes. Transmission electron microscopy investigations were performed to unravel the nanometer scale phenomena: a band of Pt and Pt/Ru nanoparticles was detected in the membrane adjacent to the cathode catalyst layer. Quantification of the elemental composition of several individual nanoparticles and the overall band area revealed that they stem from both anode and cathode catalyst layers. The results presented do not demonstrate any catastrophic failure but rather intermediate states during fuel cell operation and indications to proceed with targeted HT-PEMFC optimization.

Self-Supported Mesostructured Pt-Based Bimetallic Nanospheres Containing an Intermetallic Phase as Ultrastable Oxygen Reduction Electrocatalysts.

PubMed

Kim, Ho Young; Cho, Seonghun; Sa, Young Jin; Hwang, Sun-Mi; Park, Gu-Gon; Shin, Tae Joo; Jeong, Hu Young; Yim, Sung-Dae; Joo, Sang Hoon

2016-10-01

Developing highly active and stable cathode catalysts is of pivotal importance for proton exchange membrane fuel cells (PEMFCs). While carbon-supported nanostructured Pt-based catalysts have so far been the most active cathode catalysts, their durability and single-cell performance are yet to be improved. Herein, self-supported mesostructured Pt-based bimetallic (Meso-PtM; M = Ni, Fe, Co, Cu) nanospheres containing an intermetallic phase are reported, which can combine the beneficial effects of transition metals (M), an intermetallic phase, a 3D interconnected framework, and a mesoporous structure. Meso-PtM nanospheres show enhanced oxygen reduction reaction (ORR) activity, compared to Pt black and Pt/C catalysts. Notably, Meso-PtNi containing an intermetallic phase exhibits ultrahigh stability, showing enhanced ORR activity even after 50 000 potential cycles, whereas Pt black and Pt/C undergo dramatic degradation. Importantly, Meso-PtNi with an intermetallic phase also demonstrated superior activity and durability when used in a PEMFC single-cell, with record-high initial mass and specific activities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First Principle Calculation : Investigation on interaction of Pt/Graphene as Catalyst

NASA Astrophysics Data System (ADS)

Anugrah Putri Namari, Nuning; Suprijadi

2017-07-01

The increasing in energy needs and the lack of non-renewable energy sources becomes a challenge for the human being to be able to use renewable energy sources. One of the devices to process renewable energy is Polymer Electrolyte Membrane Fuel Cell (PEMFC) . PEMFC use hydrogen and Oxygen as an energy sources . The most important reaction in fuel cell is Oxidation and reduction process. Therefore, a catalyst is needed to help the OR process. Study of catalyst shows that the most effective fuel cell for now is Platinum. Many fuel cell have use platinum as the catalyst. However, Platinum is a rare and expensive element. Therefore, to reduce the cost of fuel cell fabrication, we need to increase the activity of platinum. In this research, we use graphene as a support material. Then, we will study about the interaction of platinum on graphene and analyze its morphological change and electronic properties.The research conduct using Density Functional Theory (DFT). The calculation result shows that Pt/graphene can break H2 into H+ and the binding between Pt cluster is stronger than binding with the substrate.

Iridium-decorated palladium-platinum core-shell catalysts for oxygen reduction reaction in proton exchange membrane fuel cell.

PubMed

Wang, Chen-Hao; Hsu, Hsin-Cheng; Wang, Kai-Ching

2014-08-01

Carbon-supported Pt, Pd, Pd-Pt core-shell (Pt(shell)-Pd(core)/C) and Ir-decorated Pd-Pt core-shell (Ir-decorated Pt(shell)-Pd(core)/C) catalysts were synthesized, and their physical properties, electrochemical behaviors, oxygen reduction reaction (ORR) characteristics and proton exchange membrane fuel cell (PEMFC) performances were investigated herein. From the XRD patterns and TEM images, Ir-decorated Pt(shell)-Pd(core)/C has been confirmed that Pt was deposited on the Pd nanoparticle which had the core-shell structure. Ir-decorated Pt(shell)-Pd(core)/C has more positive OH reduction peak than Pt/C, which is beneficial to weaken the binding energy of Pt-OH during the ORR. Thus, Ir-decorated Pt(shell)-Pd(core)/C has higher ORR activity than Pt/C. The maximum power density of H2-O2 PEMFC using Ir-decorated Pt(shell)-Pd(core)/C is 792.2 mW cm(-2) at 70°C, which is 24% higher than that using Pt/C. The single-cell accelerated degradation test of PEMFC using Ir-decorated Pt(shell)-Pd(core)/C shows good durability by the potential cycling of 40,000 cycles. This study concludes that Ir-decorated Pt(shell)-Pd(core)/C has the low Pt content, but it can facilitate the low-cost and high-efficient PEMFC. Copyright © 2013 Elsevier Inc. All rights reserved.

Nanostructure-based proton exchange membrane for fuel cell applications at high temperature.

PubMed

Li, Junsheng; Wang, Zhengbang; Li, Junrui; Pan, Mu; Tang, Haolin

2014-02-01

As a clean and highly efficient energy source, the proton exchange membrane fuel cell (PEMFC) has been considered an ideal alternative to traditional fossil energy sources. Great efforts have been devoted to realizing the commercialization of the PEMFC in the past decade. To eliminate some technical problems that are associated with the low-temperature operation (such as catalyst poisoning and poor water management), PEMFCs are usually operated at elevated temperatures (e.g., > 100 degrees C). However, traditional proton exchange membrane (PEM) shows poor performance at elevated temperature. To achieve a high-performance PEM for high temperature fuel cell applications, novel PEMs, which are based on nanostructures, have been developed recently. In this review, we discuss and summarize the methods for fabricating the nanostructure-based PEMs for PEMFC operated at elevated temperatures and the high temperature performance of these PEMs. We also give an outlook on the rational design and development of the nanostructure-based PEMs.

Robust Platinum-Based Electrocatalysts for Fuel Cell Applications

NASA Astrophysics Data System (ADS)

Coleman, Eric James

Polymer electrolyte fuel cells (PEMFCs) are energy conversion devices that exploit the energetics of the reaction between hydrogen fuel and O 2 to generate electricity with water as the only byproduct. PEMFCs have attracted substantial attention due to their high conversion efficiency, high energy density, and low carbon footprint. However, PEMFC performance is hindered by the high activation barrier and slow reaction rates at the cathode where O2 undergoes an overall 4-electron reduction to water. The most efficient oxygen reduction reaction (ORR) catalyst materials to date are Pt group metals due to their high catalytic activity and stability in a wide range of operating conditions. Before fuel cells can become economically viable, efforts must be taken to decrease Pt content while maintaining a high level of ORR activity. This work describes the design and synthesis of a Pt-Cu electrocatalyst with ORR activity exceeding that of polycrystalline Pt. Production of this novel catalyst is quite simple and begins with synthesis of a porous Cu substrate, formed by etching Al from a Cu-Al alloy. The porous Cu substrate is then coated with a Pt layer via a spontaneous electrochemical process known as galvanic replacement. The Pt layer enhances the ORR activity (as measured by a rotating ring-disk electrode (RRDE)) and acts as a barrier towards corrosion of the Cu understructure. Growth of the Pt layer can be manipulated by time, temperature, concentration of Pt precursor, and convection rate during galvanic replacement. Data from analytical and electrochemical techniques confirm multiple Pt loadings have been achieved via the galvanic replacement process. The boost in ORR activity for the PtCu catalyst was determined to be a result of its lower affinity towards (site-blocking) OH adsorption. A unique catalyst degradation study explains the mechanism of initial catalyst ORR deactivation for both monometallic and bimetallic Pt-based catalysts. Finally, a rigorous and pioneering examination of how Pt surface passivation affects ORR dynamics is presented.

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

DOE PAGES

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin; ...

2018-01-24

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Xiao Xia; Cullen, David A; Pan, Yung-Tin; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Wang, Jingyun; Engelhard, Mark H; Zhang, Hanguang; He, Yanghua; Shao, Yuyan; Su, Dong; More, Karren L; Spendelow, Jacob S; Wu, Gang

2018-03-01

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Erythrocyte-like hollow carbon capsules and their application in proton exchange membrane fuel cells.

PubMed

Kim, Jung Ho; Yu, Jong-Sung

2010-12-14

Hierarchical nanostructured erythrocyte-like hollow carbon (EHC) with a hollow hemispherical macroporous core of ca. 230 nm in diameter and 30-40 nm thick mesoporous shell was synthesized and explored as a cathode catalyst support in a proton exchange membrane fuel cell (PEMFC). The morphology control of EHC was successfully achieved using solid core/mesoporous shell (SCMS) silica template and different styrene/furfuryl alcohol mixture compositions by a nanocasting method. The EHC-supported Pt (20 wt%) cathodes prepared have demonstrated markedly enhanced catalytic activity towards oxygen reduction reactions (ORRs) and greatly improved PEMFC polarization performance compared to carbon black Vulcan XC-72 (VC)-supported ones, probably due to the superb structural characteristics of the EHC such as uniform size, well-developed porosity, large specific surface area and pore volume. In particular, Pt/EHC cathodes exhibited ca. 30-60% higher ORR activity than a commercial Johnson Matthey Pt catalyst at a low catalyst loading of 0.2 mg Pt cm(-2).

Highly efficient and durable TiN nanofiber electrocatalyst supports.

PubMed

Kim, Hyun; Cho, Min Kyung; Kwon, Jeong An; Jeong, Yeon Hun; Lee, Kyung Jin; Kim, Na Young; Kim, Min Jung; Yoo, Sung Jong; Jang, Jong Hyun; Kim, Hyoung-Juhn; Nam, Suk Woo; Lim, Dong-Hee; Cho, EunAe; Lee, Kwan-Young; Kim, Jin Young

2015-11-28

To date, carbon-based materials including various carbon nanostructured materials have been extensively used as an electrocatalyst support for proton exchange membrane fuel cell (PEMFC) applications due to their practical nature. However, carbon dissolution or corrosion caused by high electrode potential in the presence of O2 and/or water has been identified as one of the main failure modes for the device operation. Here, we report the first TiN nanofiber (TNF)-based nonwoven structured materials to be constructed via electrospinning and subsequent two-step thermal treatment processes as a support for the PEMFC catalyst. Pt catalyst nanoparticles (NPs) deposited on the TNFs (Pt/TNFs) were electrochemically characterized with respect to oxygen reduction reaction (ORR) activity and durability in an acidic medium. From the electrochemical tests, the TNF-supported Pt catalyst was better and more stable in terms of its catalytic performance compared to a commercially available carbon-supported Pt catalyst. For example, the initial oxygen reduction performance was comparable for both cases, while the Pt/TNF showed much higher durability from an accelerated degradation test (ADT) configuration. It is understood that the improved catalytic roles of TNFs on the supported Pt NPs for ORR are due to the high electrical conductivity arising from the extended connectivity, high inertness to the electrochemical environment and strong catalyst-support interactions.

Heterogeneous Electrocatalyst of Palladium-Cobalt-Phosphorus on Carbon Support for Oxygen Reduction Reaction in High Temperature Proton Exchange Membrane Fuel Cells.

PubMed

You, Dae Jong; Pak, Chanho; Jin, Seon-Ah; Lee, Kang Hee; Kwon, Kyungjung; Choi, Kyoung Hwan; Heo, Pil Won; Jang, Hongchul; Kim, Jun Young; Kim, Ji Man

2016-05-01

Palladium-cobalt-phosphorus (PdCoP) catalysts supported on carbon (Ketjen Black) were investigated as a cathode catalyst for oxygen reduction reaction (ORR) in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The PdCoP catalyst was synthesized via a modified polyol process in teflon-sealed reactor by microwave-heating. From X-ray diffraction and transmission electron microscopic analysis, the PdCoP catalyst exhibits a face-centered cubic structure, similar to palladium (Pd), which is attributed to form a good solid solution of Co atoms and P atoms in the Pd lattice. The PdCoP nanoparticles with average diameter of 2.3 nm were uniformly distributed on the carbon support. The electrochemical surface area (ECSA) and ORR activity of PdP, PdCo and PdCoP catalysts were measured using a rotating disk electrode technique with cyclic voltammetry and the linear sweep method. The PdCoP catalysts showed the highest performances for ECSA and ORR, which might be attributed both to formation of small nanoparticle by phosphorus atom and to change in lattice constant of Pd by cobalt atom. Furthermore, The HT-PEMFCs single cell performance employing PdCoP catalyst exhibited an enhanced cell performance compared to a single cell using the PdP and PdCo catalysts. This result indicates the importance of electric and geometric control of Pd alloy nanoparticles that can improve the catalytic activity. This synergistic combination of Co and P with Pd could provide the direction of development of non-Pt catalyst for fuel cell system.

Pt-Ni/WC Alloy Nanorods Arrays as ORR Catalyst for PEM Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Begum, Mahbuba; Yurukcu, Mesut; Yurtsever, Fatma

Polymer electrolyte membrane fuel cells (PEMFCs) among the other types of fuel cell technology are attractive power sources, especially for electric vehicle applications. While significant progress and plausible prospects of PEMFCs have been achieved, there are still some challenges related to the performance, durability, and cost that need to be overcome to make them economically viable for widespread commercialization. Our strategy is to develop thin films of high-active and stable catalyst coated on vertically aligned nanorod arrays of conductive and stable support. In this work, we fabricated tungsten carbide (WC) nanorods as support and coated them with a platinum-nickel (Pt-Ni)more » alloy shell denoted as Pt-Ni/WC catalysts. The Pt- Ni/WC nanorods were deposited on glassy carbon disks as well as on silicon substrates for evaluation of their electrocatalytic oxygen reduction reaction (ORR) activity and physical properties. Cyclic voltammetry experiments using rotating disk electrode were performed in perchloric acid (0.1 M HClO4) electrolyte at room temperature to characterize the ORR activity and stability of Pt-Ni/WC nanorods catalysts. Scanning electron microscopy and X-ray diffraction techniques were utilized to study the morphology and crystallographic properties, respectively.« less

Development of a Stochastically-driven, Forward Predictive Performance Model for PEMFCs

NASA Astrophysics Data System (ADS)

Harvey, David Benjamin Paul

A one-dimensional multi-scale coupled, transient, and mechanistic performance model for a PEMFC membrane electrode assembly has been developed. The model explicitly includes each of the 5 layers within a membrane electrode assembly and solves for the transport of charge, heat, mass, species, dissolved water, and liquid water. Key features of the model include the use of a multi-step implementation of the HOR reaction on the anode, agglomerate catalyst sub-models for both the anode and cathode catalyst layers, a unique approach that links the composition of the catalyst layer to key properties within the agglomerate model and the implementation of a stochastic input-based approach for component material properties. The model employs a new methodology for validation using statistically varying input parameters and statistically-based experimental performance data; this model represents the first stochastic input driven unit cell performance model. The stochastic input driven performance model was used to identify optimal ionomer content within the cathode catalyst layer, demonstrate the role of material variation in potential low performing MEA materials, provide explanation for the performance of low-Pt loaded MEAs, and investigate the validity of transient-sweep experimental diagnostic methods.

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts.

PubMed

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-04-06

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production-which far exceeds that of previously reported low-temperature APRM catalysts-to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Characterizing automotive fuel cell materials by soft x-ray scanning transmission x-ray microscopy

NASA Astrophysics Data System (ADS)

Hitchcock, A. P.; Lee, V.; Wu, J.; West, M. M.; Cooper, G.; Berejnov, V.; Soboleva, T.; Susac, D.; Stumper, J.

2016-01-01

Proton-Exchange Membrane Fuel Cell (PEM-FC) based engines are being developed rapidly for near-term implementation in hydrogen fueled, mass production, personal automobiles. Research is focused on understanding and controlling various degradation processes (carbon corrosion, Pt migration, cold start), and reducing cost by reducing or eliminating Pt catalyst. We are using soft X-ray scanning transmission X-ray microscopy (STXM) at the S 2p, C 1s, O 1s and F 1s edges to study a variety of issues related to optimization of PEM-FC materials for automotive applications. A method to efficiently and accurately measure perfluorosulfonic acid distributions was developed and is being used to better understand how different loadings and preparation methods affect the ionomer distribution in the cathode. Progress towards an environmental cell capable of controlling the temperature and humidity of a PEM-FC sample in the STXM is described. Methods for studying the 3D chemical structure of PEM-FC are outlined.

Characterizing automotive fuel cell materials by soft x-ray scanning transmission x-ray microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hitchcock, A. P., E-mail: aph@mcmaster.ca; Lee, V.; Wu, J.

Proton-Exchange Membrane Fuel Cell (PEM-FC) based engines are being developed rapidly for near-term implementation in hydrogen fueled, mass production, personal automobiles. Research is focused on understanding and controlling various degradation processes (carbon corrosion, Pt migration, cold start), and reducing cost by reducing or eliminating Pt catalyst. We are using soft X-ray scanning transmission X-ray microscopy (STXM) at the S 2p, C 1s, O 1s and F 1s edges to study a variety of issues related to optimization of PEM-FC materials for automotive applications. A method to efficiently and accurately measure perfluorosulfonic acid distributions was developed and is being used tomore » better understand how different loadings and preparation methods affect the ionomer distribution in the cathode. Progress towards an environmental cell capable of controlling the temperature and humidity of a PEM-FC sample in the STXM is described. Methods for studying the 3D chemical structure of PEM-FC are outlined.« less

Highly Dispersed Alloy Catalyst for Durability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vivek S. Murthi; Izzo, Elise; Bi, Wu

2013-01-08

Achieving DOE's stated 5000-hr durability goal for light-duty vehicles by 2015 will require MEAs with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of PEMFC stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them withmore » existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.« less

DFT study on bimetallic Pt/Cu(1 1 1) as efficient catalyst for H2 dissociation

NASA Astrophysics Data System (ADS)

Liu, Ji; Fan, Xiaofeng; Sun, Chang Q.; Zhu, Weiguang

2018-05-01

To design a catalyst for the dissociation of H2 with better CO-tolerance performance is very important for proton exchange membrane fuel cells (PEMFCs) towards high efficiency. With slab model, the catalytic properties of overlayer Pt on Cu substrate (Pt/Cu) are analyzed by first-principle calculations. The CO saturation coverage (40%) on Pt2/Cu is found to be lower than that of pure Pt (about 75%). The dissociation barrier from H2 to H is less than 0.4 eV under the saturation coverage of CO. On the basis of kinetics of proton formation, the CO-tolerance ability on double-layer Pt with Cu is found to be greatly improved compared with that on pure Pt. It is expected that Pt overlayer on Cu(1 1 1) is a potential anode material with lower cost for PEMFCs.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports.

PubMed

Sneed, Brian T; Cullen, David A; Reeves, Kimberly S; Dyck, Ondrej E; Langlois, David A; Mukundan, Rangachary; Borup, Rodney L; More, Karren L

2017-09-06

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of the cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Furthermore, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

DOE PAGES

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.; ...

2017-08-15

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

pH matters: The influence of the catalyst ink on the oxygen reduction activity determined in thin film rotating disk electrode measurements

NASA Astrophysics Data System (ADS)

Inaba, Masanori; Quinson, Jonathan; Arenz, Matthias

2017-06-01

We investigated the influence of the ink properties of proton exchange membrane fuel cell (PEMFC) catalysts on the oxygen reduction reaction (ORR) activity determined in thin film rotating disk electrode (TF-RDE) measurements. It was found that the adaption of a previously reported ink recipe to home-made catalysts does not lead to satisfying results, although reported work could be reproduced using commercial catalyst samples. It is demonstrated that the pH of the catalyst ink, which has not been addressed in previous TF-RDE studies, is an important parameter that needs to be carefully controlled to determine the intrinsic ORR activity of high surface area catalysts.

The Solid-Phase Synthesis of an Fe-N-C Electrocatalyst for High-Power Proton-Exchange Membrane Fuel Cells.

PubMed

Liu, Qingtao; Liu, Xiaofang; Zheng, Lirong; Shui, Jianglan

2018-01-26

The environmentally friendly synthesis of highly active Fe-N-C electrocatalysts for proton-exchange membrane fuel cells (PEMFCs) is desirable but remains challenging. A simple and scalable method is presented to fabricate Fe II -doped ZIF-8, which can be further pyrolyzed into Fe-N-C with 3 wt % of Fe exclusively in Fe-N 4 active moieties. Significantly, this Fe-N-C derived acidic PEMFC exhibits an unprecedented current density of 1.65 A cm -2 at 0.6 V and the highest power density of 1.14 W cm -2 compared with previously reported NPMCs. The excellent PEMFC performance can be attributed to the densely and atomically dispersed Fe-N 4 active moieties on the small and uniform catalyst nanoparticles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High Temperature Polymers for use in Fuel Cells

NASA Technical Reports Server (NTRS)

Peplowski, Katherine M.

2004-01-01

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require highly efficient power density for lowering emissions and meeting increasing consumer demands. Many of the solutions can be provided by proton exchange membrane fuel cells and lithium batteries. NASA Glenn Research Center has recognized this need, and is presently engaged in a solution. The goals for the summer include mastering synthesis techniques, understanding the reactions occurring during the synthesis, and characterizing the resulting polymer membranes using NMR, DSC, and TGA for the PEMFC and lithium batteries.

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Branko N. Popov

2009-03-03

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Branko N. Popov

2009-02-20

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Narayan, Sri R. (Inventor); Hays, Charles C. (Inventor)

2015-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Hays, Charles C. (Inventor); Narayan, Sri R. (Inventor)

2013-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Stability of High-Performance Pt-Based Catalysts for Oxygen Reduction Reactions.

PubMed

Lin, Rui; Cai, Xin; Zeng, Hao; Yu, Zhuoping

2018-04-01

Due to their environmental sustainability and high efficiency, proton-exchange-membrane fuel cells (PEMFCs) are expected to be an essential type of energy source for electric vehicles, energy generation, and the space industry in the coming decades. Here, the recent developments regarding shape-controlled nanostructure catalysts are reviewed, with a focus on the stability of high-performance Pt-based catalysts and related mechanisms. The catalysts, which possess great activity, are still far from meeting the requirements of their applications, due to stability issues, especially in membrane electrode assemblies (MEAs). Thus, solutions toward the comprehensive performance of Pt-based catalysts are discussed here. The research trends and related theories that can promote the application of Pt-based catalysts are also provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of PEMFC Electrodes from Milligram-Amounts of Catalyst Powder

DOE PAGES

Yarlagadda, Venkata; McKinney, Samuel E.; Keary, Cristin L.; ...

2017-06-03

Development of electrocatalysts with higher activity and stability is one of the highest priorities in enabling cost-competitive hydrogen-air fuel cells. Although the rotating disk electrode (RDE) technique is widely used to study new catalyst materials, it has been often shown to be an unreliable predictor of catalyst performance in actual fuel cell operation. Fabrication of membrane electrode assemblies (MEA) for evaluation which are more representative of actual fuel cells generally requires relatively large amounts (>1 g) of catalyst material which are often not readily available in early stages of development. In this study, we present two MEA preparation techniques usingmore » as little as 30 mg of catalyst material, providing methods to conduct more meaningful MEA-based tests using research-level catalysts amounts.« less

Conductivity in zeolite-polymer composite membranes for PEMFCs

NASA Astrophysics Data System (ADS)

Sancho, T.; Soler, J.; Pina, M. P.

Structured materials, such as zeolites can be candidates to be used as electrolytes in proton exchange membrane fuel cells (PEMFC) to substitute polymeric membranes, taking advantage of their higher chemical and thermal stability and their specific adsorption properties. The possibility to work at temperatures of nearly 150 °C would make easy the selection of the fuel, decreasing the influence of CO in the catalyst poisoning, and it would also improve the kinetics of the electrochemical reactions involved. In this work, four zeolites and related materials have been studied: mordenite, NaA zeolite, umbite and ETS-10. In special, the influence of relative humidity and temperature have been carefully explored. A conductivity cell was designed and built to measure in cross direction, by using the electrochemical impedance spectroscopy. The experimental system was validated using Nafion ® as a reference material by comparing the results with bibliography data. Samples were prepared by pressing the zeolite powders, with size of 1 μm on average, using polymer PVDF (10 wt.%) as a binder. The results here obtained, in spite of not reaching the absolute values of the Nafion ® ones, show a lower effect of the dehydration phenomenon on the conduction performance in the temperature range studied (from room temperature to 150 °C). This increase of the operation temperature range would give important advantages to the PEMFC. ETS-10 sample shows the best behaviour with respect to conductivity exhibiting an activation energy value comparable with reported for Nafion ® membrane.

Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

PubMed

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Nogami, Masayuki; Ohtaki, Michitaka

2013-07-01

In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next PEMFCs, and DMFCs.

Nonlinear predictive control for durability enhancement and efficiency improvement in a fuel cell power system

NASA Astrophysics Data System (ADS)

Luna, Julio; Jemei, Samir; Yousfi-Steiner, Nadia; Husar, Attila; Serra, Maria; Hissel, Daniel

2016-10-01

In this work, a nonlinear model predictive control (NMPC) strategy is proposed to improve the efficiency and enhance the durability of a proton exchange membrane fuel cell (PEMFC) power system. The PEMFC controller is based on a distributed parameters model that describes the nonlinear dynamics of the system, considering spatial variations along the gas channels. Parasitic power from different system auxiliaries is considered, including the main parasitic losses which are those of the compressor. A nonlinear observer is implemented, based on the discretised model of the PEMFC, to estimate the internal states. This information is included in the cost function of the controller to enhance the durability of the system by means of avoiding local starvation and inappropriate water vapour concentrations. Simulation results are presented to show the performance of the proposed controller over a given case study in an automotive application (New European Driving Cycle). With the aim of representing the most relevant phenomena that affects the PEMFC voltage, the simulation model includes a two-phase water model and the effects of liquid water on the catalyst active area. The control model is a simplified version that does not consider two-phase water dynamics.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

PubMed

Principi, Emiliano; Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

2009-11-21

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

Fabrication of polymer electrolyte membrane fuel cell MEAs utilizing inkjet print technology

NASA Astrophysics Data System (ADS)

Towne, Silas; Viswanathan, Vish; Holbery, James; Rieke, Peter

Utilizing drop-on-demand technology, we have successfully fabricated hydrogen-air polymer electrolyte membrane fuel cells (PEMFC), demonstrated some of the processing advantages of this technology and have demonstrated that the performance is comparable to conventionally fabricated membrane electrode assemblies (MEAs). Commercial desktop inkjet printers were used to deposit the active catalyst electrode layer directly from print cartridges onto Nafion ® polymer membranes in the hydrogen form. The layers were well-adhered and withstood simple tape peel, bending and abrasion tests and did so without any post-deposition hot press step. The elimination of this processing step suggests that inkjet-based fabrication or similar processing technologies may provide a route to less expensive large-scale fabrication of PEMFCs. When tested in our experimental apparatus, open circuit voltages up to 0.87 V and power densities of up to 155 mW cm -2 were obtained with a catalyst loading of 0.20 mg Pt cm -2. A commercially available membrane under identical, albeit not optimized test conditions, showed about 7% greater power density. The objective of this work was to demonstrate some of the processing advantages of drop-on-demand technology for fabrication of MEAs. It remains to be determined if inkjet fabrication offers performance advantages or leads to more efficient utilization of expensive catalyst materials.

New catalyst supports prepared by surface modification of graphene- and carbon nanotube structures with nitrogen containing carbon coatings

NASA Astrophysics Data System (ADS)

Oh, Eun-Jin; Hempelmann, Rolf; Nica, Valentin; Radev, Ivan; Natter, Harald

2017-02-01

We present a new and facile method for preparation of nitrogen containing carbon coatings (NCC) on the surface of graphene- and carbon nanotubes (CNT), which has an increased electronic conductivity. The modified carbon system can be used as catalyst support for electrocatalytic applications, especially for polymer electrolyte membrane fuel cells (PEMFC). The surface modification is performed by impregnating carbon structures with a nitrogen containing ionic liquid (IL) with a defined C:N ratio, followed by a thermal treatment under ambient conditions. We investigate the influence of the main experimental parameters (IL amount, temperature, substrate morphology) on the formation of the NCC. Additionally, the structure and the chemical composition of the resulting products are analyzed by electron microscopic techniques (SEM, TEM), energy disperse X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS) and hot extraction analysis. The modified surface has a nitrogen content of 29 wt% which decreases strongly at temperatures above 600 °C. The new catalyst supports are used for the preparation of PEMFC anodes which are characterized by polarization measurements and electrochemical impedance spectroscopy (EIS). Compared to unmodified graphene and CNT samples the electronic conductivity of the modified systems is increased by a factor of 2 and shows improved mass transport properties.

Develop high activity, low cost non-PGM fuel cell electrocatalyst and stable supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Colon-Mercado, H. R.; Elvington, M. C.; Garcia-Diaz, B. L.

2016-09-28

A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFC. Iron based functionalities have been engineered into Metallic Organic Framework (MOF) catalysts to evaluate their impact on activity for the ORR. A series of FePhen@MOF catalysts have been synthesized with varying [Fe] to investigate the effect on electrochemical and electrocatalytic properties. The magnitude of the Fe II/III redox couple and the electrochemical surface area are analyzed to determine if there is a correlation between [Fe] and the ORR onset potential and/or the relative number of active sites.

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts

NASA Astrophysics Data System (ADS)

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-03-01

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production—which far exceeds that of previously reported low-temperature APRM catalysts—to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Platinum-TM (TM = Fe, Co) alloy nanoparticles dispersed nitrogen doped (reduced graphene oxide-multiwalled carbon nanotube) hybrid structure cathode electrocatalysts for high performance PEMFC applications.

PubMed

Vinayan, B P; Ramaprabhu, S

2013-06-07

The efforts to push proton exchange membrane fuel cells (PEMFC) for commercial applications are being undertaken globally. In PEMFC, the sluggish kinetics of oxygen reduction reactions (ORR) at the cathode can be improved by the alloying of platinum with 3d-transition metals (TM = Fe, Co, etc.) and with nitrogen doping, and in the present work we have combined both of these aspects. We describe a facile method for the synthesis of a nitrogen doped (reduced graphene oxide (rGO)-multiwalled carbon nanotubes (MWNTs)) hybrid structure (N-(G-MWNTs)) by the uniform coating of a nitrogen containing polymer over the surface of the hybrid structure (positively surface charged rGO-negatively surface charged MWNTs) followed by the pyrolysis of these (rGO-MWNTs) hybrid structure-polymer composites. The N-(G-MWNTs) hybrid structure is used as a catalyst support for the dispersion of platinum (Pt), platinum-iron (Pt3Fe) and platinum-cobalt (Pt3Co) alloy nanoparticles. The PEMFC performances of Pt-TM alloy nanoparticle dispersed N-(G-MWNTs) hybrid structure electrocatalysts are 5.0 times higher than that of commercial Pt-C electrocatalysts along with very good stability under acidic environment conditions. This work demonstrates a considerable improvement in performance compared to existing cathode electrocatalysts being used in PEMFC and can be extended to the synthesis of metal, metal oxides or metal alloy nanoparticle decorated nitrogen doped carbon nanostructures for various electrochemical energy applications.

Pt monolayer shell on nitrided alloy core — A path to highly stable oxygen reduction catalyst

DOE PAGES

Hu, Jue; Kuttiyiel, Kurian A.; Sasaki, Kotaro; ...

2015-07-22

The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC). Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared Pt MLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability ofmore » the Pt MLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.« less

The Experimental Measurement of Local and Bulk Oxygen Transport Resistances in the Catalyst Layer of Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Chao; Cheng, Xiaojing; Lu, Jiabin; Shen, Shuiyun; Yan, Xiaohui; Yin, Jiewei; Wei, Guanghua; Zhang, Junliang

2017-12-07

Remarkable progress has been made in reducing the cathodic Pt loading of PEMFCs; however, a huge performance loss appears at high current densities, indicating the existence of a large oxygen transport resistance associated with the ultralow Pt loading catalyst layer. To reduce the Pt loading without sacrificing cell performance, it is essential to illuminate the oxygen transport mechanism in the catalyst layer. Toward this goal, an experimental approach to measure the oxygen transport resistance in catalyst layers is proposed and realized for the first time in this study. The measuring approach involves a dual-layer catalyst layer design, which consists of a dummy catalyst layer and a practical catalyst layer, followed by changing the thickness of dummy layer to respectively quantify the local and bulk resistances via limiting current measurements combined with linear extrapolation. The experimental results clearly reveal that the local resistance dominates the total resistance in the catalyst layer.

Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abroshan, Hadi; Bothra, Pallavi; Back, Seoin

Here, the oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal–air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated bymore » the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoN RS(100) and CoN ZB(110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.« less

Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction

DOE PAGES

Abroshan, Hadi; Bothra, Pallavi; Back, Seoin; ...

2018-02-12

Here, the oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal–air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated bymore » the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoN RS(100) and CoN ZB(110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.« less

Sol-Gel Synthesis, Electrochemical Characterization, and Stability Testing of Ti0.7W0.3O2 Nanoparticles for Catalyst Support Applications in Proton-Exchange Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subban, Chinmayee V.; Zhou, Qin; Hu, Anthony

2010-11-19

The materials currently used in proton-exchange membrane fuel cells (PEMFCs) require complex control of operating conditions to make them sufficiently durable to permit commercial deployment. One of the major materials challenges to allow simplification of fuel cell operating strategies is the discovery of catalyst supports that are much more stable to oxidative decomposition than currently used carbon blacks. Here we report the synthesis and characterization of Ti 0.7W 0.3O 2 nanoparticles (approximately 50 nm diameter), a promising doped metal oxide that is a candidate for such a durable catalyst support. The synthesized nanoparticles were platinized, characterized by electrochemical testing, andmore » evaluated for stability under PEMFC and other oxidizing acidic conditions. Ti 0.7W 0.3O 2 nanoparticles show no evidence of decomposition when heated in a Nafion solution for 3 weeks at 80 °C. In contrast, when heated in sulfuric, nitric, perchloric, or hydrochloric acid, the oxide reacts to form salts such as titanylsulfatehydrate from sulfuric acid. Electrochemical tests show that rates of hydrogen oxidation and oxygen reduction by platinum nanoparticles supported on Ti 0.7W 0.3O 2 are comparable to those of commercial Pt on carbon black.« less

Can CO-tolerant Anodes be Economically Viable for PEMFC Applications with Reformates?

DOE PAGES

He, P.; Zhang, Y.; Ye., S.; ...

2014-10-05

Several years ago, the answer to this question was negative based on the criteria for an anode with <0.1 mg cm-2 of platinum group metals to perform similarly without and with 50 ppm CO in hydrogen proton exchange membrane fuel cells (PEMFCs). Now, with the amount of CO impurities reduced to 10 ppm in reformates, a <1% performance loss with a 1.5% air-bleed has become a reasonable target. The CO-tolerant catalyst also needs to be dissolution resistant up to 0.93 V, viz., the potential experienced at the anode during startup and shutdown of the fuel cells. We recently demonstrated ourmore » ability to simultaneously enhance activity and stability by using single crystalline Ru@Pt core-shell nanocatalysts. Here, we report that the performance target with reformates was met using bilayer-thick Ru@Pt core-shell nanocatalysts with 0.047 mg cm-2 Pt and 0.024 mg cm-2 Ru loading, supporting a positive prognosis for the economically viable use of reformates in PEMFC applications.« less

Functionalized Single-Walled Carbon Nanotube-Based Fuel Cell Benchmarked Against US DOE 2017 Technical Targets

PubMed Central

Jha, Neetu; Ramesh, Palanisamy; Bekyarova, Elena; Tian, Xiaojuan; Wang, Feihu; Itkis, Mikhail E.; Haddon, Robert C.

2013-01-01

Chemically modified single-walled carbon nanotubes (SWNTs) with varying degrees of functionalization were utilized for the fabrication of SWNT thin film catalyst support layers (CSLs) in polymer electrolyte membrane fuel cells (PEMFCs), which were suitable for benchmarking against the US DOE 2017 targets. Use of the optimum level of SWNT -COOH functionality allowed the construction of a prototype SWNT-based PEMFC with total Pt loading of 0.06 mgPt/cm2 - well below the value of 0.125 mgPt/cm2 set as the US DOE 2017 technical target for total Pt group metals (PGM) loading. This prototype PEMFC also approaches the technical target for the total Pt content per kW of power (<0.125 gPGM/kW) at cell potential 0.65 V: a value of 0.15 gPt/kW was achieved at 80°C/22 psig testing conditions, which was further reduced to 0.12 gPt/kW at 35 psig back pressure. PMID:23877112

Experimental dissection of oxygen transport resistance in the components of a polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Oh, Hwanyeong; Lee, Yoo il; Lee, Guesang; Min, Kyoungdoug; Yi, Jung S.

2017-03-01

Oxygen transport resistance is a major obstacle for obtaining high performance in a polymer electrolyte membrane fuel cell (PEMFC). To distinguish the major components that inhibit oxygen transport, an experimental method is established to dissect the oxygen transport resistance of the components of the PEMFC, such as the substrate, micro-porous layer (MPL), catalyst layer, and ionomer film. The Knudsen numbers are calculated to determine the types of diffusion mechanisms at each layer by measuring the pore sizes with either mercury porosimetry or BET analysis. At the under-saturated condition where condensation is mostly absent, the molecular diffusion resistance is dissected by changing the type of inert gas, and ionomer film permeation is separated by varying the inlet gas humidity. Moreover, the presence of the MPL and the variability of the substrate thickness allow the oxygen transport resistance at each component of a PEMFC to be dissected. At a low relative humidity of 50% and lower, an ionomer film had the largest resistance, while the contribution of the MPL was largest for the other humidification conditions.

Functionalized single-walled carbon nanotube-based fuel cell benchmarked against US DOE 2017 technical targets.

PubMed

Jha, Neetu; Ramesh, Palanisamy; Bekyarova, Elena; Tian, Xiaojuan; Wang, Feihu; Itkis, Mikhail E; Haddon, Robert C

2013-01-01

Chemically modified single-walled carbon nanotubes (SWNTs) with varying degrees of functionalization were utilized for the fabrication of SWNT thin film catalyst support layers (CSLs) in polymer electrolyte membrane fuel cells (PEMFCs), which were suitable for benchmarking against the US DOE 2017 targets. Use of the optimum level of SWNT -COOH functionality allowed the construction of a prototype SWNT-based PEMFC with total Pt loading of 0.06 mg(Pt)/cm²--well below the value of 0.125 mg(Pt)/cm² set as the US DOE 2017 technical target for total Pt group metals (PGM) loading. This prototype PEMFC also approaches the technical target for the total Pt content per kW of power (<0.125 g(PGM)/kW) at cell potential 0.65 V: a value of 0.15 g(Pt)/kW was achieved at 80°C/22 psig testing conditions, which was further reduced to 0.12 g(Pt)/kW at 35 psig back pressure.

Remarkable support effect on the reactivity of Pt/In2O3/MOx catalysts for methanol steam reforming

NASA Astrophysics Data System (ADS)

Liu, Xin; Men, Yong; Wang, Jinguo; He, Rong; Wang, Yuanqiang

2017-10-01

Effects of supports over Pt/In2O3/MOx catalysts with extremely low loading of Pt (1 wt%) and In2O3 loadings (3 wt%) are investigated for the hydrogen production of methanol steam reforming (MSR) in the temperature range of 250-400 °C. Under practical conditions without the pre-reduction, the 1Pt/3In2O3/CeO2 catalyst shows the highly efficient catalytic performance, achieving almost complete methanol conversion (98.7%) and very low CO selectivity of 2.6% at 325 °C. The supported Pt/In2O3 catalysts are characterized by means of Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), high-resolution transmission microscopy (HRTEM), temperature programmed reduction with hydrogen (H2-TPR), CO pulse chemisorption, temperature programmed desorption of methanol and water (CH3OH-TPD and H2O-TPD). These demonstrate that the nature of catalyst support of Pt/In2O3/MOx plays crucial roles in the Pt dispersion associated by the strong interaction among Pt, In2O3 and supporting materials and the surface redox properties at low temperature, and thus affects their capability to activate the reactants and determines the catalytic activity of methanol steam reforming. The superior 1Pt/3In2O3/CeO2 catalyst, exhibiting a remarkable reactivity and stability for 32 h on stream, demonstrates its potential for efficient hydrogen production of methanol steam reforming in mobile and de-centralized H2-fueled PEMFC systems.

Dynamic response performance of proton exchange membrane fuel cell stack with Pt/C-RuO2·xH2O electrode

NASA Astrophysics Data System (ADS)

Lu, Lu; Xu, Hongfeng; Zhao, Hong; Sun, Xin; Dong, Yiming; Ren, Ruiming

2013-11-01

The dynamic response performance of a proton exchange membrane fuel cell (PEMFC) significantly affects its durability and reliability. Thus, the improvement of the dynamic performance of PEMFC has become the key for prolonging the PEMFC life in fuel cell vehicle applications. In this study, RuO2·xH2O is prepared by sol-gel method, and then sprayed onto catalyst layers to promote PEMFC dynamic response performance. The prepared RuO2·xH2O is characterized by TEM, which shows that the average particle size of RuO2·xH2O is 8 nm and that the particulates are uniformly distributed. A 10-cell stack is assembled using membrane electrode assembly (MEA) with and without RuO2·xH2O. This stack is studied under various loading cycles and operating conditions, including different air stoichiometries, relative humidities, and loading degrees. Results show that the steady-state performance of the MEA with RuO2·xH2O is better than that in the MEA without RuO2·xH2O with a decreasing relative humidity from 80% to 20%. A slower and more unstable dynamic response of the MEA without RuO2·xH2O is observed as air stoichiometry and relative humidity decrease as well as the loading increase. Thus, RuO2·xH2O improves the dynamic response performance, indicating that RuO2·xH2O can buffer the voltage undershoot, improve the stability, and prolong the lifetime of the PEMFC stack.

Structure-to-property relationships in fuel cell catalyst supports: Correlation of surface chemistry and morphology with oxidation resistance of carbon blacks

NASA Astrophysics Data System (ADS)

Artyushkova, Kateryna; Pylypenko, Svitlana; Dowlapalli, Madhu; Atanassov, Plamen

2012-09-01

Linking durability of carbon blacks, expressed as their oxidation resistance, used in PEMFCs as catalyst supports, with their chemistry and morphology is an important task towards designing carbon blacks with desired properties. Structure-to-property relationship between surface chemistry determined by X-ray photoelectron spectroscopy (XPS), morphological structure determined by digital image processing of scanning electron microscopy (SEM) images, physical properties, and electrochemical corrosion behavior determined in an air-breathing gas-diffusion electrode is studied for several un-altered and several modified carbon blacks. We are showing that surface chemistry, graphitic content and certain physical characteristics such as Brunauer-Emmett-Teller (BET) surface area and pore volume, determined by nitrogen adsorptions are not sufficient to explain high corrosion instability of types of carbon blacks. Inclusion of morphological characteristics, such as roughness, texture and shape parameters provide for more inclusive description and therefore more complete structure-to-property correlations of corrosion behavior of carbon blacks. This paper presents the first direct statistically-derived structure-to-property relationship, developed by multivariate analysis (MVA) that links chemical and physical structural properties of the carbon blacks to their critical properties as supports for PEMFC catalysts. We have found that balance between electrocatalytic activity and high resistance towards oxidation and corrosion is achieved by balance between amount of graphitic content and surface oxide coverage, smaller overall roughness and, finally, larger amount of big elongated and loose, and, hypothetically, more hydrophobic pores.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles ismore » tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). We report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunablemore » through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. In using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe 3+ to Fe 2+) likely bonded with pyridinic N (FeN 4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H 2SO 4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μg Pt/cm 2). Finally, enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O 2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

DOE PAGES

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; ...

2017-09-13

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). We report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunablemore » through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. In using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe 3+ to Fe 2+) likely bonded with pyridinic N (FeN 4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H 2SO 4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μg Pt/cm 2). Finally, enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O 2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

DOE PAGES

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.; ...

2017-05-02

Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for the imminentmore » commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo - TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. Furthermore, the ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.

Abstract Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for themore » imminent commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo—TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. The ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.

Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for the imminentmore » commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo - TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. Furthermore, the ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Durability test with fuel starvation using a Pt/CNF catalyst in PEMFC.

PubMed

Jung, Juhae; Park, Byungil; Kim, Junbom

2012-01-05

In this study, a catalyst was synthesized on carbon nanofibers [CNFs] with a herringbone-type morphology. The Pt/CNF catalyst exhibited low hydrophilicity, low surface area, high dispersion, and high graphitic behavior on physical analysis. Electrodes (5 cm2) were prepared by a spray method, and the durability of the Pt/CNF was evaluated by fuel starvation. The performance was compared with a commercial catalyst before and after accelerated tests. The fuel starvation caused carbon corrosion with a reverse voltage drop. The polarization curve, EIS, and cyclic voltammetry were analyzed in order to characterize the electrochemical properties of the Pt/CNF. The performance of a membrane electrode assembly fabricated from the Pt/CNF was maintained, and the electrochemical surface area and cell resistance showed the same trend. Therefore, CNFs are expected to be a good support in polymer electrolyte membrane fuel cells.

Durability test with fuel starvation using a Pt/CNF catalyst in PEMFC

PubMed Central

2012-01-01

In this study, a catalyst was synthesized on carbon nanofibers [CNFs] with a herringbone-type morphology. The Pt/CNF catalyst exhibited low hydrophilicity, low surface area, high dispersion, and high graphitic behavior on physical analysis. Electrodes (5 cm2) were prepared by a spray method, and the durability of the Pt/CNF was evaluated by fuel starvation. The performance was compared with a commercial catalyst before and after accelerated tests. The fuel starvation caused carbon corrosion with a reverse voltage drop. The polarization curve, EIS, and cyclic voltammetry were analyzed in order to characterize the electrochemical properties of the Pt/CNF. The performance of a membrane electrode assembly fabricated from the Pt/CNF was maintained, and the electrochemical surface area and cell resistance showed the same trend. Therefore, CNFs are expected to be a good support in polymer electrolyte membrane fuel cells. PMID:22221426

Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

NASA Astrophysics Data System (ADS)

Lubers, Alia Marie

Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most successful hydrogen pumping catalysts, comparable to a commercial Pt/C catalyst. Synthesized Pt/C materials were also used as PEMFC catalysts. We found the ALD catalysts with lower platinum loading to be competitive with a commercial fuel cell catalyst, especially when exhibiting similar platinum particle characteristics. The functionalized carbon helped produce smaller and more dispersed platinum particles; however, it encouraged carbon corrosion within an electrode, severing electrical connections and lowering energy production. The most suitable chemistry for competitive Pt/C catalysts was produced by platinum ALD on unmodified carbon using hydrogen as a reactant. ALD is a promising method for fabricating electrocatalysts, which could help fuel cells become an economically viable alternative to fossil fuels.

TiO2 and Al2O3 promoted Pt/C nanocomposites as low temperature fuel cell catalysts for electro oxidation of methanol in acidic media

NASA Astrophysics Data System (ADS)

Naeem, Rabia; Ahmed, Riaz; Shahid Ansari, Muhammad

2014-06-01

Carbon corrosion and platinum dissolution are the two major catalyst layer degradation problems in polymer electrolyte membrane fuel cells (PEMFC). Ceramic addition can reduce the corrosion of carbon and increase the stability of catalysts. Pt/TiO2, Pt/TiO2-C, Pt/Al2O3 and Pt/Al2O3-C catalysts were synthesized and characterized. Electrochemical surface area of Pt/TiO2-C and Pt/Al2O3-C nanocomposite catalysts was much higher than the Pt/TiO2 and Pt/Al2O3 catalysts. Peak current, specific activity and mass activity of the catalysts was also determined by cyclic voltammetry and were much higher for the carbon nanocomposites. Exchange current densities were determined from Tafel plots. Heterogeneous rates of reaction of electro oxidation of methanol were determined for all the catalysts and were substantially higher for titania catalysts as compared to alumina added catalysts. Mass activity of Pt/TiO2-C was much higher than mass activity of Pt/Al2O3-C. Stability studies showed that addition of ceramics have increased the catalytic activity and durability of the catalysts considerably.

Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

NASA Astrophysics Data System (ADS)

Dade, William N.

Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

Study of superhydrophobic electrosprayed catalyst layers using a localized reference electrode technique

NASA Astrophysics Data System (ADS)

Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Brightman, E.; Hinds, G.

2016-09-01

The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of <50 mV, compared with 79 mV for the conventional gas diffusion cathode. Higher performance and homogeneity of cell response is attributed to the superhydrophobic nature of the macroporous electrosprayed catalyst layer structure, which enhances the rate of expulsion of liquid water from the cathode. On the other hand, at low current densities (<0.5 A cm-2), the electrosprayed layers exhibit more heterogeneous distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

Performance and durability of carbon black-supported Pd catalyst covered with silica layers in membrane-electrode assemblies of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Fujii, Keitaro; Ito, Mizuki; Sato, Yasushi; Takenaka, Sakae; Kishida, Masahiro

2015-04-01

Pd metal particles supported on a high surface area carbon black (Pd/CB) were covered with silica layers to improve the durability under severe cathode condition of proton exchange membrane fuel cells (PEMFCs). The performance and the durability of the silica-coated Pd/CB (SiO2/Pd/CB) were investigated by rotating disk electrode (RDE) in aqueous HClO4 and single cell test of the membrane-electrode assemblies (MEAs). SiO2/Pd/CB showed excellent durability exceeding Pt/CB during potential cycle in single cell test as well as in RDE measurement while Pd/CB significantly degraded. Furthermore, the MEA using SiO2/Pd/CB as the cathode catalyst showed higher performance than that using Pd/CB even in the initial state. The catalytic activity of SiO2/Pd/CB was higher than that of Pd/CB, and the drop of the cell performances due to the inhibition of electron conduction, proton conduction, and oxygen diffusion by the silica layer was not significant. It has been shown that the silica-coating is a very practical technique that can stabilize metal species originally unstable in the cathode condition of PEMFCs without a decrease in the cell performance.

Insights into PEMFC Performance Degradation from HCl in Air

DOE Office of Scientific and Technical Information (OSTI.GOV)

O Baturina; A Epshteyn; P Northrup

2011-12-31

The performance degradation of a proton exchange membrane fuel cell (PEMFC) is studied in the presence of HCl in the air stream. The cathode employing carbon-supported platinum nanoparticles (Pt/C) was exposed to 4 ppm HCl in air while the cell voltage was held at 0.6 V. The HCl poisoning results in generation of chloride and chloroplatinate ions on the surface of Pt/C catalyst as determined by a combination of electrochemical tests and ex-situ chlorine K-edge X-Ray absorption near-edge structure (XANES) spectroscopy. The chloride ions inhibit the oxygen reduction reaction (ORR) and likely affect the wetting properties of diffusion media/catalyst layer,more » while the chloroplatinate ions are responsible for enhanced platinum particle growth most likely due to platinum dissolution-redeposition. The chloride ions can cause corrosion of the Pt nanoparticles in the presence of aqueous HCl in air even if no potential is applied. Although the majority of chloride ions are desorbed from the Pt surface by hydrogen treatment of the cathode, they partially remain in the system and re-adsorb on platinum at cell voltages of 0.5-0.9 V. Chloride ions are removed from the system and fuel cell performance at 0.5-0.7 V is restored by multiple exposures to low potentials.« less

4D imaging of polymer electrolyte membrane fuel cell catalyst layers by soft X-ray spectro-tomography

NASA Astrophysics Data System (ADS)

Wu, Juan; Melo, Lis G. A.; Zhu, Xiaohui; West, Marcia M.; Berejnov, Viatcheslav; Susac, Darija; Stumper, Juergen; Hitchcock, Adam P.

2018-03-01

4D imaging - the three-dimensional distributions of chemical species determined using multi-energy X-ray tomography - of cathode catalyst layers of polymer electrolyte membrane fuel cells (PEM-FC) has been measured by scanning transmission x-ray microscopy (STXM) spectro-tomography at the C 1s and F 1s edges. In order to monitor the effects of radiation damage on the composition and 3D structure of the perfluorosulfonic acid (PFSA) ionomer, the same volume was measured 3 times sequentially, with spectral characterization of that same volume at several time points during the measurements. The changes in the average F 1s spectrum of the ionomer in the cathode as the measurements progressed gave insights into the degree of chemical modification, fluorine mass loss, and changes in the 3D distributions of ionomer that accompanied the spectro-tomographic measurement. The PFSA ionomer-in-cathode is modified both chemically and physically by radiation damage. The 3D volume decreases anisotropically. By reducing the incident flux, partial defocusing (50 nm spot size), limiting the number of tilt angles to 14, and using compressed sensing reconstruction, we show it is possible to reproducibly measure the 3D structure of ionomer in PEM-FC cathodes at ambient temperature while causing minimal radiation damage.

Development of membrane electrode assembly for high temperature proton exchange membrane fuel cell by catalyst coating membrane method

NASA Astrophysics Data System (ADS)

Liang, Huagen; Su, Huaneng; Pollet, Bruno G.; Pasupathi, Sivakumar

2015-08-01

Membrane electrode assembly (MEA), which contains cathode and anode catalytic layer, gas diffusion layers (GDL) and electrolyte membrane, is the key unit of a PEMFC. An attempt to develop MEA for ABPBI membrane based high temperature (HT) PEMFC is conducted in this work by catalyst coating membrane (CCM) method. The structure and performance of the MEA are examined by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and I-V curve. Effects of the CCM preparation method, Pt loading and binder type are investigated for the optimization of the single cell performance. Under 160 °C and atmospheric pressure, the peak power density of the MEA, with Pt loading of 0.5 mg cm-2 and 0.3 mg cm-2 for the cathode and the anode, can reach 277 mW cm-2, while a current density of 620 A cm-2 is delivered at the working voltage of 0.4 V. The MEA prepared by CCM method shows good stability operating in a short term durability test: the cell voltage maintained at ∼0.45 V without obvious drop when operated at a constant current density of 300 mA cm-2 and 160 °C under ambient pressure for 140 h.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reshetenko, T. V.; Bender, G.; Bethune, K.

The overall current density that is measured in a proton exchange membrane fuel cell (PEMFC) represents the average of the local reaction rates. The overall and local PEMFC performances are determined by several primary loss mechanisms, namely activation, ohmic, and mass transfer. Spatial performance and loss variabilities are significant and depend on the cell design and operating conditions. A segmented cell system was used to quantify different loss distributions along the gas channel to understand the effects of gas humidification. A reduction in the reactant stream humidification decreased cell performance and resulted in non-uniform distributions of overpotentials and performance alongmore » the flow field. Activation and ohmic overpotentials increased with a relative humidity decrease due to insufficient membrane and catalyst layer hydration. The relative humidity of the cathode had a strong impact on the mass transfer overpotential due to a lower oxygen permeability through the dry Nafion film covering the catalyst surface. The mass transfer loss distribution was non-uniform, and the mass transfer overpotential increased for the outlet segments due to the oxygen consumption at the inlet segments, which reduced the oxygen concentration downstream, and a progressive water accumulation from upstream segments. Electrochemical impedance spectroscopy (EIS) and an equivalent electric circuit (EEC) facilitated the analysis and interpretation of the segmented cell data.« less

Microwave decoration of Pt nanoparticles on entangled 3D carbon nanotube architectures as PEM fuel cell cathode.

PubMed

Sherrell, Peter C; Zhang, Weimin; Zhao, Jie; Wallace, Gordon G; Chen, Jun; Minett, Andrew I

2012-07-01

Proton-exchange membrane fuel cells (PEMFCs) are expected to provide a complementary power supply to fossil fuels in the near future. The current reliance of fuel cells on platinum catalysts is undesirable. However, even the best-performing non-noble metal catalysts are not as efficient. To drive commercial viability of fuel cells forward in the short term, increased utilization of Pt catalysts is paramount. We have demonstrated improved power and energy densities in a single PEMFC using a designed cathode with a Pt loading of 0.1 mg cm(-2) on a mesoporous conductive entangled carbon nanotube (CNT)-based architecture. This electrode allows for rapid transfer of both fuel and waste to and from the electrode, respectively. Pt particles are bound tightly, directly to CNT sidewalls by a microwave-reduction technique, which provided increased charge transport at this interface. The Pt entangled CNT cathode, in combination with an E-TEK 0.2 mg cm(-2) anode, has a maximum power and energy density of 940 mW cm(-2) and 2700 mA cm(-2), respectively, and a power and energy density of 4.01 W mg(Pt)(-1) and 6.35 A mg(Pt)(-1) at 0.65 V. These power densities correspond to a specific mass activity of 0.81 g Pt per kW for the combined mass of both anode and cathode electrodes, approaching the current US Department of Energy efficiency target. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

U.S. DOE Progress Towards Developing Low-Cost, High Performance, Durable Polymer Electrolyte Membranes for Fuel Cell Applications.

PubMed

Houchins, Cassidy; Kleen, Greg J; Spendelow, Jacob S; Kopasz, John; Peterson, David; Garland, Nancy L; Ho, Donna Lee; Marcinkoski, Jason; Martin, Kathi Epping; Tyler, Reginald; Papageorgopoulos, Dimitrios C

2012-12-18

Low cost, durable, and selective membranes with high ionic conductivity are a priority need for wide-spread adoption of polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). Electrolyte membranes are a major cost component of PEMFC stacks at low production volumes. PEMFC membranes also impose limitations on fuel cell system operating conditions that add system complexity and cost. Reactant gas and fuel permeation through the membrane leads to decreased fuel cell performance, loss of efficiency, and reduced durability in both PEMFCs and DMFCs. To address these challenges, the U.S. Department of Energy (DOE) Fuel Cell Technologies Program, in the Office of Energy Efficiency and Renewable Energy, supports research and development aimed at improving ion exchange membranes for fuel cells. For PEMFCs, efforts are primarily focused on developing materials for higher temperature operation (up to 120 °C) in automotive applications. For DMFCs, efforts are focused on developing membranes with reduced methanol permeability. In this paper, the recently revised DOE membrane targets, strategies, and highlights of DOE-funded projects to develop new, inexpensive membranes that have good performance in hot and dry conditions (PEMFC) and that reduce methanol crossover (DMFC) will be discussed.

Microwave-assisted synthesis of Pt/CNT nanocomposite electrocatalysts for PEM fuel cells.

PubMed

Zhang, Weimin; Chen, Jun; Swiegers, Gerhard F; Ma, Zi-Feng; Wallace, Gordon G

2010-02-01

Microwave-assisted heating of functionalized, single-wall carbon nanotubes (FCNTs) in ethylene glycol solution containing H(2)PtCl(6), led to the reductive deposition of Pt nanoparticles (2.5-4 nm) over the FCNTs, yielding an active catalyst for proton-exchange membrane fuel cells (PEMFCs). In single-cell testing, the Pt/FCNT composites displayed a catalytic performance that was superior to Pt nanoparticles supported by raw (unfunctionalized) CNTs (RCNTs) or by carbon black (C), prepared under identical conditions. The supporting single-wall carbon nanotubes (SWNTs), functionalized with carboxyl groups, were studied by thermogravimetric analysis (TGA), cyclic voltammetry (CV), and Raman spectroscopy. The loading level, morphology, and crystallinity of the Pt/SWNT catalysts were determined using TGA, SEM, and XRD. The electrochemically active catalytic surface area of the Pt/FCNT catalysts was 72.9 m(2)/g-Pt.

Theoretical studies of Pt-Ti nanoparticles for potential use as PEMFC electrocatalysts.

PubMed

Jennings, Paul C; Pollet, Bruno G; Johnston, Roy L

2012-03-07

A theoretical investigation is presented of alloying platinum with titanium to form binary Pt-Ti nanoalloys as an alternative to the expensive pure platinum catalysts commonly used for Proton Exchange Membrane Fuel Cell cathode electrocatalysts. Density Functional Theory calculations are performed to investigate compositional effects on structural properties as well as Oxygen Reduction Reaction kinetics and poisoning effects. High symmetry A(32)-B(6) clusters are studied to investigate structural properties. From these structures binding energies of hydroxyl and carbon monoxide are studied on a range of sites on the surface of the clusters. Promising results are obtained suggesting that the bimetallic Pt-Ti nanoalloys may exhibit enhanced properties compared to pure platinum catalysts.

The contamination mechanism and behavior of amide bond containing organic contaminant on PEMFC

DOE PAGES

Cho, Hyun -Seok; Das, Mayukhee; Wang, Heli; ...

2015-02-03

In this paper, a study is presented of the effects of an organic contaminant containing an amide bond (-CONH-), ε-caprolactam, on polymer electrolyte membrane fuel cells (PEMFCs). The ε-caprolactam has been detected in leachates from polyphthalamide materials that are being considered for use as balance-of-plant structural materials for PEMFCs. Contamination effects from ε-caprolactam in Nafion membranes are shown to be controlled by temperature. A possible explanation of the temperature effect is the endothermic ring-opening reaction of the amide bond (-NHCO-) of the cyclic ε-caprolactam. UV-vis and ATR-IR spectroscopy studies confirmed the presence of open ring structure of ε-caprolactam in membranes.more » The ECSA and kinetic current for the ORR of the Pt/C catalyst were also investigated and were observed to decrease upon contamination by the ε-caprolactam. By comparison of the CVs of ammonia and acetic acid, we confirmed the adsorption of carboxylic acid (-COOH) or carboxylate anion (-COO-) onto the surface of the Pt. In conclusion, a comparison of in situ voltage losses at 80°C and 50°C also revealed temperature effects, especially in the membrane, as a result of the dramatic increase in the HFR.« less

Investigation of electrolyte leaching in the performance degradation of phosphoric acid-doped polybenzimidazole membrane-based high temperature fuel cells

NASA Astrophysics Data System (ADS)

Jeong, Yeon Hun; Oh, Kyeongmin; Ahn, Sungha; Kim, Na Young; Byeon, Ayeong; Park, Hee-Young; Lee, So Young; Park, Hyun S.; Yoo, Sung Jong; Jang, Jong Hyun; Kim, Hyoung-Juhn; Ju, Hyunchul; Kim, Jin Young

2017-09-01

Precise monitoring of electrolyte leaching in high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) devices during lifetime tests is helpful in making a diagnosis of their quality changes and analyzing their electrochemical performance degradation. Here, we investigate electrolyte leaching in the performance degradation of phosphoric acid (PA)-doped polybenzimidazole (PBI) membrane-based HT-PEMFCs. We first perform quantitative analyses to measure PA leakage during cell operation by spectrophotometric means, and a higher PA leakage rate is detected when the current density is elevated in the cell. Second, long-term degradation tests under various current densities of the cells and electrochemical impedance spectroscopy (EIS) analysis are performed to examine the influence of PA loss on the membrane and electrodes during cell performance degradation. The combined results indicate that PA leakage affect cell performance durability, mostly due to an increase in charge transfer resistance and a decrease in the electrochemical surface area (ECSA) of the electrodes. Additionally, a three-dimensional (3-D) HT-PEMFC model is applied to a real-scale experimental cell, and is successfully validated against the polarization curves measured during various long-term experiments. The simulation results highlight that the PA loss from the cathode catalyst layer (CL) is a significant contributor to overall performance degradation.

Performance of gas diffusion layer from coconut waste for proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Widodo, H.; Destyorini, F.; Insiyanda, D. R.; Subhan, A.

2017-04-01

The performance of Gas Diffusion Layer (GDL) synthesized from coconut waste. Gas Diffusion Layer (GDL), produced from coconut waste, as a part of Proton Exchange Membrane Fuel Cell (PEMFC) component, has been characterized. In order to know the performance, the commercial products were used as the remaining parts of PEMFC. The proposed GDL possesses 69% porosity for diffusion of Hydrogen fuel and Oxygen, as well as for transporting electron. With the electrical conductivity of 500 mS.cm-1, it also has hydrophobic properties, which is important to avoid the reaction with water, with the contact angle of 139°. The 5 × 5 cm2 GDL paper was co-assembled with the catalyst, Nafion membrane, bipolar plate, current collector, end plate to obtain single Stack PEMFC. The performance was examined by flowing fuel and gas with the flow rate of 500 and 1000 ml.min-1, respectively, and analyse the I-V polarization curve. The measurements were carried out at 30, 35, and 40°C for 5 cycles to ensure the repeatability. The results shows that the current density and the maximum power density reaches 203 mA.cm-2 and 143 mW.cm-2, respectively, with a given voltage 0.6 V, at 40°C.

Investigations on the corrosion resistance of metallic bipolar plates (BPP) in proton exchange membrane fuel cells (PEMFC) - understanding the effects of material, coating and manufacturing

NASA Astrophysics Data System (ADS)

Dur, Ender

Polymer Electrolyte Membrane Fuel Cell (PEMFC) systems are promising technology for contributing to meet the deficiency of world`s clean and sustainable energy requirements in the near future. Metallic bipolar plate (BPP) as one of the most significant components of PEMFC device accounts for the largest part of the fuel cell`s stack. Corrosion for metallic bipolar plates is a critical issue, which influences the performance and durability of PEMFC. Corrosion causes adverse impacts on the PEMFC`s performance jeopardizing commercialization. This research is aimed at determining the corrosion resistance of metallic BPPs, particularly stainless steels, used in PEMFC from different aspects. Material selection, coating selection, manufacturing process development and cost considerations need to be addressed in terms of the corrosion behavior to justify the use of stainless steels as a BPP material in PEMFC and to make them commercially feasible in industrial applications. In this study, Ti, Ni, SS304, SS316L, and SS 430 blanks, and BPPs comprised of SS304 and SS316L were examined in terms of the corrosion behavior. SS316L plates were coated to investigate the effect of coatings on the corrosion resistance performance. Stamping and hydroforming as manufacturing processes, and three different coatings (TiN, CrN, ZrN) applied via the Physical Vapor Deposition (PVD) method in three different thicknesses were selected to observe the effects of manufacturing processes, coating types and coating thicknesses on the corrosion resistance of BPP, respectively. Uncoated-coated blank and formed BPP were subjected to two different corrosion tests: potentiostatic and potentiodynamic. Some of the substantial results: 1- Manufacturing processes have an adverse impact on the corrosion resistance. 2- Hydroformed plates have slightly higher corrosion resistance than stamped samples. 3- BPPs with higher channel size showed better corrosion resistance. 4- Since none of the uncoated samples meet the 2015 target of the U.S. Department of Energy, surface coating is required. 5- ZrN and CrN coated BPPs exhibited higher corrosion resistance meeting DOE target while TiN coated samples had the lowest corrosion resistance. Higher coating thicknesses improved the corrosion resistance of the BPPs. 6- Process sequence between coating and manufacturing is not significant for hydroforming case (ZrN and CrN) and stamping case (CrN) in terms of the corrosion resistance. In other words, coating the BPP`s substrate material before manufacturing process does not always decrease the corrosion resistance of the BPPs.

Percolation in a Proton Exchange Membrane Fuel Cell Catalyst Layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stacy, Stephen; Allen, Jeffrey

Water management in the catalyst layers of proton exchange membrane fuel cells (PEMFC) is confronted by two issues, flooding and dry out, both of which result in improper functioning of the fuel cell and lead to poor performance and degradation. At the present time, the data that has been reported about water percolation and wettability within a fuel cell catalyst layer is limited. A method and apparatus for measuring the percolation pressure in the catalyst layer has been developed based upon an experimental apparatus used to test water percolation in porous transport layers (PTL). The experimental setup uses a pseudomore » Hele-Shaw type testing where samples are compressed and a fluid is injected into the sample. Testing the samples gives percolation pressure plots which show trends in increasing percolation pressure with an increase in flow rate. A decrease in pressure was seen as percolation occurred in one sample, however the pressure only had a rising effect in the other sample.« less

Evaluation of PEMFC System Contaminants on the Performance of Pt Catalyst via Cyclic Voltammetry: Preprint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Macomber, C.; Dinh, H. N.

2012-07-01

Using electrochemical cyclic voltammetry as a quick ex-situ screening tool, the impact of the extracted solution and the individual leachable constituents from prospective BOP component materials on the performance and recoverability of the platinum catalyst were evaluated. Taking an extract from Zytel{trademark} HTN51G35HSLR (PPA) as an example, the major leachable organic components are caprolactam and 1,6 hexanediol. While these organic compounds by themselves do poison the Pt catalyst to some extent, such influence is mostly recoverable by means of potential holding and potential cycling. The extracted solution, however, shows a more drastic poisoning effect and it was not recoverable. Thereforemore » the non-recoverable poisoning effect observed for the extracted solution is not from the two organic species studied. This demonstrates the complexity of such a contaminant study. Inorganic compounds that are known poisons like sulfur even in very low concentrations, may have a more dominant effect on the Pt catalyst and the recoverability.« less

Critical advancements in achieving high power and stable nonprecious metal catalyst–based MEAs for real-world proton exchange membrane fuel cell applications

PubMed Central

Zhou, Yingjie; Bai, Kyoung

2018-01-01

Despite great progress in the development of nonprecious metal catalysts (NPMCs) over the past several decades, the performance and stability of these promising catalysts have not yet achieved commercial readiness for proton exchange membrane fuel cells (PEMFCs). Through rational design of the cathode catalyst layer (CCL), we demonstrate the highest reported performance for an NPMC-based membrane electrode assembly (MEA), achieving a peak power of 570 mW/cm2 under air. This record performance is achieved using a precommercial catalyst for which nearly all pores are <3 nm in diameter, challenging previous beliefs regarding the need for larger catalyst pores to achieve high current densities. This advance is achieved at industrially relevant scales (50 cm2 MEA) using a precommercial NPMC. In situ electrochemical analysis of the CCLs is also used to help gain insight into the degradation mechanism observed during galvanostatic testing. Overall, the performance of this NPMC-based MEA has achieved commercial readiness and will be introduced into an NPMC-based product for portable power applications. PMID:29582018

U.S. DOE Progress Towards Developing Low-Cost, High Performance, Durable Polymer Electrolyte Membranes for Fuel Cell Applications

PubMed Central

Houchins, Cassidy; Kleen, Greg J.; Spendelow, Jacob S.; Kopasz, John; Peterson, David; Garland, Nancy L.; Ho, Donna Lee; Marcinkoski, Jason; Martin, Kathi Epping; Tyler, Reginald; Papageorgopoulos, Dimitrios C.

2012-01-01

Low cost, durable, and selective membranes with high ionic conductivity are a priority need for wide-spread adoption of polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). Electrolyte membranes are a major cost component of PEMFC stacks at low production volumes. PEMFC membranes also impose limitations on fuel cell system operating conditions that add system complexity and cost. Reactant gas and fuel permeation through the membrane leads to decreased fuel cell performance, loss of efficiency, and reduced durability in both PEMFCs and DMFCs. To address these challenges, the U.S. Department of Energy (DOE) Fuel Cell Technologies Program, in the Office of Energy Efficiency and Renewable Energy, supports research and development aimed at improving ion exchange membranes for fuel cells. For PEMFCs, efforts are primarily focused on developing materials for higher temperature operation (up to 120 °C) in automotive applications. For DMFCs, efforts are focused on developing membranes with reduced methanol permeability. In this paper, the recently revised DOE membrane targets, strategies, and highlights of DOE-funded projects to develop new, inexpensive membranes that have good performance in hot and dry conditions (PEMFC) and that reduce methanol crossover (DMFC) will be discussed. PMID:24958432

Statistical Simulation of the Performance and Degradation of a PEMFC Membrane Electrode Assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harvey, David; Bellemare-Davis, Alexander; Karan, Kunal

2012-07-01

A 1-D MEA Performance model was developed that considered transport of liquid water, agglomerate catalyst structure, and the statistical variation of the MEA characteristic parameters. The model was validated against a low surface area carbon supported catalyst across various platinum loadings and operational conditions. The statistical variation was found to play a significant role in creating noise in the validation data and that there was a coupling effect between movement in material properties with liquid water transport. Further, in studying the low platinum loaded catalyst layers it was found that liquid water played a significant role in the increasing themore » overall transport losses. The model was then further applied to study platinum dissolution via potential cycling accelerated stress tests, in which the platinum was found to dissolve nearest the membrane effectively resulting in reaction distribution shifts within the layer.« less

Degradation Study by Start-Up/Shut-Down Cycling of Superhydrophobic Electrosprayed Catalyst Layers Using a Localized Reference Electrode Technique.

PubMed

Ferreira-Aparicio, Paloma; Chaparro, Antonio M; Folgado, M Antonia; Conde, Julio J; Brightman, Edward; Hinds, Gareth

2017-03-29

Degradation of a polymer electrolyte membrane fuel cell (PEMFC) with electrosprayed cathode catalyst layers is investigated during cyclic start-up and shut-down events. The study is carried out within a single cell incorporating an array of reference electrodes that enables measurement of cell current as a function of local cathode potential (localized polarization curves). Accelerated degradation of the cell by start-up/shut-down cycling gives rise to inhomogeneous performance loss, which is more severe close to the gas outlet and occurs predominantly during start-up. The degradation consists primarily of loss of cathode catalyst activity and increase in cell internal resistance, which is attributed to carbon corrosion and Pt aggregation in both anode and cathode. Cells with an electrosprayed cathode catalyst layer show lower degradation rates during the first 100 cycles, compared with those of a conventional gas diffusion electrode. This difference in behavior is attributed to the high hydrophobicity of the electrosprayed catalyst layer microstructure, which retards the kinetics of corrosion of the carbon support. In the long term, however, the degradation rate is dominated by the Pt/C ratio in the cathode catalyst layer.

Pt Catalyst Degradation in Aqueous and Fuel Cell Environments studied via In-Operando Anomalous Small-Angle X-ray Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gilbert, James A.; Kariuki, Nancy N.; Wang, Xiaoping

2015-08-01

The evolution of Pt nanoparticle cathode electrocatalyst size distribution in a polymer electrolyte membrane fuel cell (PEMFC) was followed during accelerated stress tests using in-operando anomalous small-angle X-ray scattering (ASAXS). This evolution was compared to that observed in an aqueous electrolyte environment using stagnant electrolyte, flowing electrolyte, and flowing electrolyte at elevated temperature to reveal the different degradation trends in the PEMFC and aqueous environments and to determine the relevance of aqueous measurements to the stability of Pt nanoparticle catalyst in the fuel cell environment. The observed changes in the particle size distributions (PSDs) were analyzed to elucidate the extentmore » and mechanisms of particle growth and corresponding mass and active surface area losses in the different environments. These losses indicate a Pt nanoparticle surface area loss mechanism controlled by Pt dissolution, the particle size dependence of Pt dissolution, the loss of dissolved Pt into the membrane and electrolyte, and, to a lesser extent, the re-deposition of dissolved Pt onto larger particles. Based on the geometric surface area loss, mass loss, and mean particle size increase trends, the aqueous environment best reflecting the fuel cell environment was found to be one in which the electrolyte is flowing rather than stagnant. Pt nanoparticle surface area loss resulting from potential cycling can be inhibited by reducing the number of particles smaller than a critical particle diameter (CPD), which was found to be similar to 3.5 to similar to 4 nm, with the CPD dependent on both the cycling protocol (square wave vs triangle wave) and the catalyst environment (fuel cell, aqueous stagnant, aqueous flowing electrolyte, or elevated temperature flowing electrolyte)« less

Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

NASA Astrophysics Data System (ADS)

Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

2017-10-01

Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

PubMed Central

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-01-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8–1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study. PMID:25491655

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell.

PubMed

Lei, M; Wang, Z B; Li, J S; Tang, H L; Liu, W J; Wang, Y G

2014-12-10

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-12-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

Fabrication of three-dimensional buckypaper catalyst layer with Pt nanoparticles supported on polyelectrolyte functionalized carbon nanotubes for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Shiyao; Zheng, Junsheng; Huang, Jun; Dai, Ningning; Li, Ping; Zheng, Jim P.

2018-07-01

Polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA) functionalized carbon nanotubes (CNTs) supported Pt electrocatalyst was synthesized as a substitute for commonly used Pt/C and Pt/CNTs (modified by harsh acid-oxidation treatment) catalysts. In addition, this catalyst was fabricated as the cathode catalyst layer (CL) with a unique double-layered structure for proton exchange membrane fuel cells (PEMFCs). Thermogravimetric analysis shows an enhanced thermal stability of Pt/PDDA-CNTs. The Pt/PDDA-CNTs catalyst with an average Pt particle size of ∼3.1 nm exhibits the best electrocatalytic activity and a significantly enhanced electrochemical stability. Scanning electron microscope, energy dispersive spectrometer and mercury intrusion porosimetry results demonstrate the gradient distribution of Pt content and pore size along the thickness of buckypaper catalyst layer (BPCL). The accelerated degradation test results of BPCLs indicate that this gradient structure can ensure a high Pt utilization in the BPCLs (up to 90%) and further improve the catalyst durability. In addition, the membrane electrode assembly (MEA) fabricated with cathode BPCL-PDDA shows the best single cell performance and long-term stability, and a reduction of Pt loading can be achieved. The feasibility of BPCL for improving the Pt utilization is also demonstrated by the cathode cyclic voltammetry in MEA.

Low cost iodine intercalated graphene for fuel cells electrodes

NASA Astrophysics Data System (ADS)

Marinoiu, Adriana; Raceanu, Mircea; Carcadea, Elena; Varlam, Mihai; Stefanescu, Ioan

2017-12-01

On the theoretical predictions, we report the synthesis of iodine intercalated graphene for proton exchange membrane fuel cells (PEMFCs) applications. The structure and morphology of the samples were characterized by X-ray photoelectron spectroscopy (XPS) analysis, specific surface area by BET method, Raman investigations. The presence of elemental iodine in the form of triiodide and pentaiodide was validated, suggesting that iodine was trapped between graphene layers, leading to interactions with C atoms. The electrochemical performances of iodinated graphenes were tested and compared with a typical PEMFC configuration, containing different Pt/C loading (0.4 and 0.2 mg cm-2). If iodinated graphene is included as microporous layer, the electrochemical performances of the fuel cell are higher in terms of power density than the typical fuel cell. Iodine-doped graphenes have been successfully obtained by simple and cost effective synthetic strategy and demonstrated new insights for designing of a high performance metal-free ORR catalyst by a scalable technique.

Bromomethane Contamination in the Cathode of Proton Exchange Membrane Fuel Cells.

PubMed

Zhai, Yunfeng; Baturina, Olga; Ramaker, David E; Farquhar, Erik; St-Pierre, Jean; Swider-Lyons, Karen E

2016-09-20

The effects of bromomethane (BrCH 3 ), an airborne contaminant, on the performance of a single PEMFC are compared with that of another halocarbon, chlorobenzene. Under a constant current of 1 A cm -2 and at 45 °C, 20 ppm bromomethane causes approximately 30% cell voltage loss in approximately 30 h, as opposed to much more rapid performance degradation observed with chlorobenzene. Electrochemical impedance spectroscopy, cyclic voltammetry, linear scanning voltammetry, and polarization measurements are applied to characterize the temporary electrochemical reaction effect and permanent performance effects. X-ray absorption spectroscopy is used to confirm that Br is adsorbed on the Pt electrocatalyst surface. We conclude that airborne bromomethane poisons a PEMFC in a different way from chlorobenzene because it is largely hydrolyzed to bromide, Br - , which is then excluded from the Pt catalyst by the negatively charged Nafion ionomer. The little Br - and bromomethane that adsorbs on the Pt surface can be partially removed by cycling but causes some irreversible surface area loss.

Bromomethane Contamination in the Cathode of Proton Exchange Membrane Fuel Cells

PubMed Central

Baturina, Olga; Ramaker, David E.; Farquhar, Erik; St-Pierre, Jean; Swider-Lyons, Karen E.

2016-01-01

The effects of bromomethane (BrCH3), an airborne contaminant, on the performance of a single PEMFC are compared with that of another halocarbon, chlorobenzene. Under a constant current of 1 A cm−2 and at 45 °C, 20 ppm bromomethane causes approximately 30% cell voltage loss in approximately 30 h, as opposed to much more rapid performance degradation observed with chlorobenzene. Electrochemical impedance spectroscopy, cyclic voltammetry, linear scanning voltammetry, and polarization measurements are applied to characterize the temporary electrochemical reaction effect and permanent performance effects. X-ray absorption spectroscopy is used to confirm that Br is adsorbed on the Pt electrocatalyst surface. We conclude that airborne bromomethane poisons a PEMFC in a different way from chlorobenzene because it is largely hydrolyzed to bromide, Br−, which is then excluded from the Pt catalyst by the negatively charged Nafion ionomer. The little Br− and bromomethane that adsorbs on the Pt surface can be partially removed by cycling but causes some irreversible surface area loss. PMID:27695133

Nanoscale current imaging of the conducting channels in proton exchange membrane fuel cells.

PubMed

Bussian, David A; O'Dea, James R; Metiu, Horia; Buratto, Steven K

2007-02-01

The electrochemically active area of a proton exchange membrane fuel cell (PEMFC) is investigated using conductive probe atomic force microscopy (CP-AFM). A platinum-coated AFM tip is used as a nanoscale cathode in an operating PEMFC. We present results that show highly inhomogeneous distributions of conductive surface domains at several length scales. At length scales on the order of the aqueous domains of the membrane, approximately 50 nm, we observe single channel electrochemistry. I-V curves for single conducting channels are obtained, which yield insight into the nature of conductive regions across the PEM. In addition, we demonstrate a new characterization technique, phase current correlation microscopy, which gives a direct measure of the electrochemical activity for each aqueous domain. This shows that a large number ( approximately 60%) of the aqueous domains present at the surface of an operating Nafion membrane are inactive. We attribute this to a combination of limited aqueous domain connectivity and catalyst accessibility.

A multiscale approach to accelerate pore-scale simulation of porous electrodes

NASA Astrophysics Data System (ADS)

Zheng, Weibo; Kim, Seung Hyun

2017-04-01

A new method to accelerate pore-scale simulation of porous electrodes is presented. The method combines the macroscopic approach with pore-scale simulation by decomposing a physical quantity into macroscopic and local variations. The multiscale method is applied to the potential equation in pore-scale simulation of a Proton Exchange Membrane Fuel Cell (PEMFC) catalyst layer, and validated with the conventional approach for pore-scale simulation. Results show that the multiscale scheme substantially reduces the computational cost without sacrificing accuracy.

New Method to Synthesize Highly Active and Durable Chemically Ordered fct-PtCo Cathode Catalyst for PEMFCs.

PubMed

Jung, Won Suk; Popov, Branko N

2017-07-19

In the bottom-up synthesis strategy performed in this study, the Co-catalyzed pyrolysis of chelate-complex and activated carbon black at high temperatures triggers the graphitization reaction which introduces Co particles in the N-doped graphitic carbon matrix and immobilizes N-modified active sites for the oxygen reduction reaction (ORR) on the carbon surface. In this study, the Co particles encapsulated within the N-doped graphitic carbon shell diffuse up to the Pt surface under the polymer protective layer and forms a chemically ordered face-centered tetragonal (fct) Pt-Co catalyst PtCo/CCCS catalyst as evidenced by structural and compositional studies. The fct-structured PtCo/CCCS at low-Pt loading (0.1 mg Pt cm -2 ) shows 6% higher power density than that of the state-of-the-art commercial Pt/C catalyst. After the MEA durability test of 30 000 potential cycles, the performance loss of the catalyst is negligible. The electrochemical surface area loss is less than 40%, while that of commercial Pt/C is nearly 80%. After the accelerated stress test, the uniform catalyst distribution is retained and the mean particle size increases approximate 1 nm. The results obtained in this study indicated that highly stable compositional and structural properties of chemically ordered PtCo/CCCS catalyst contribute to its exceptional catalyst durability.

Carbon Corrosion in PEM Fuel Cells and the Development of Accelerated Stress Tests

DOE PAGES

Macauley, Natalia; Papadias, Dennis D.; Fairweather, Joseph; ...

2018-03-15

Here, carbon corrosion is an important degradation mechanism that can impair PEMFC performance through the destruction of catalyst connectivity, collapse of the electrode pore structure, loss of hydrophobic character, and an increase of the catalyst particle size. In this study, carbon corrosion was quantified in situ by measurement of carbon dioxide in the fuel cell exhaust gases through non-dispersive infrared spectroscopy during simulated drive cycle operations consisting of potential cycling with varying upper and lower potential limits. These studies were conducted for three different types of carbon supports. A reduction in the catalyst layer thickness was observed during a simulatedmore » drive cycle operation with a concomitant decrease in catalyst layer porosity, which led to performance losses due to increased mass transport limitations. The observed thickness reduction was primarily due to compaction of the catalyst layer, with the actual mass of carbon oxidation (loss) contributing only a small fraction (< 20%). The dynamics of carbon corrosion are presented along with a model that simulates the transient and dynamic corrosion rates observed in our experiments. Accelerated carbon corrosion stress tests are presented and their effects are compared to those observed for the drive cycle test.« less

Carbon Corrosion in PEM Fuel Cells and the Development of Accelerated Stress Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Macauley, Natalia; Papadias, Dennis D.; Fairweather, Joseph

Here, carbon corrosion is an important degradation mechanism that can impair PEMFC performance through the destruction of catalyst connectivity, collapse of the electrode pore structure, loss of hydrophobic character, and an increase of the catalyst particle size. In this study, carbon corrosion was quantified in situ by measurement of carbon dioxide in the fuel cell exhaust gases through non-dispersive infrared spectroscopy during simulated drive cycle operations consisting of potential cycling with varying upper and lower potential limits. These studies were conducted for three different types of carbon supports. A reduction in the catalyst layer thickness was observed during a simulatedmore » drive cycle operation with a concomitant decrease in catalyst layer porosity, which led to performance losses due to increased mass transport limitations. The observed thickness reduction was primarily due to compaction of the catalyst layer, with the actual mass of carbon oxidation (loss) contributing only a small fraction (< 20%). The dynamics of carbon corrosion are presented along with a model that simulates the transient and dynamic corrosion rates observed in our experiments. Accelerated carbon corrosion stress tests are presented and their effects are compared to those observed for the drive cycle test.« less

Investigation of water droplet dynamics in PEM fuel cell gas channels

NASA Astrophysics Data System (ADS)

Gopalan, Preethi

Water management in Proton Exchange Membrane Fuel Cell (PEMFC) has remained one of the most important issues that need to be addressed before its commercialization in automotive applications. Accumulation of water on the gas diffusion layer (GDL) surface in a PEMFC introduces a barrier for transport of reactant gases through the GDL to the catalyst layer. Despite the fact that the channel geometry is one of the key design parameters of a fluidic system, very limited research is available to study the effect of microchannel geometry on the two-phase flow structure. In this study, the droplet-wall dynamics and two-phase pressure drop across the water droplet present in a typical PEMFC channel, were examined in auto-competitive gas channel designs (0.4 x 0.7 mm channel cross section). The liquid water flow pattern inside the gas channel was analyzed for different air velocities. Experimental data was analyzed using the Concus-Finn condition to determine the wettability characteristics in the corner region. It was confirmed that the channel angle along with the air velocity and the channel material influences the water distribution and holdup within the channel. Dynamic contact angle emerged as an important parameter in controlling the droplet-wall interaction. Experiments were also performed to understand how the inlet location of the liquid droplet on the GDL surface affects the droplet dynamic behavior in the system. It was found that droplets emerging near the channel wall or under the land lead to corner filling of the channel. Improvements in the channel design has been proposed based on the artificial channel roughness created to act as capillary grooves to transport the liquid water away from the land area. For droplets emerging near the center of the channel, beside the filling and no-filling behavior reported in the literature, a new droplet jumping behavior was observed. As droplets grew and touched the sidewalls, they jumped off to the sidewall leaving the whole GDL exposed for gases to diffuse to the catalyst layer. A theoretical model was developed and a criterion was proposed to predict the droplet jumping behavior in the gas channel. A theoretical force balance model was proposed to predict the pressure force and air velocity required to remove the droplet from the channel to avoid complete channel blockage. The overall goal of this work was to identify the gas channel configuration that provides efficient water removal with a lower pressure drop in the system efficiency while meeting the US Department of Energy's specifications for a PEMFC for automotive application.

New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

PubMed

Ferreira-Aparicio, Paloma

2009-09-01

The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

Highly active non-PGM catalysts prepared from metal organic frameworks

DOE PAGES

Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; ...

2015-06-11

Finding inexpensive alternatives to platinum group metals (PGMs) is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs). Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/N x/C) prepared from iron doped zeolitic imidazolate frameworks (ZIFs) are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/N x/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR) electrocatalytic activity mustmore » be demonstrated in membrane-electrode assemblies (MEAs) of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.« less

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

NASA Astrophysics Data System (ADS)

Kim, Minjoong; Kwon, Chorong; Eom, Kwangsup; Kim, Jihyun; Cho, Eunae

2017-03-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability.

PubMed

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-03-14

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO 2 (Nb-TiO 2 ) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO 2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb 0.25 Ti 0.75 O 2 ). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO 2 -nanofibers (Pt/Nb-TiO 2 ) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO 2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO 2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO 2 nanofiber catalyst can be attributed to high corrosion resistance of TiO 2 and strong interaction between Pt and TiO 2 .

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

PubMed Central

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-01-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2. PMID:28290503

Proton-Exchange-Membrane Fuel Cell Powerplants Developed and Tested for Exploration Missions

NASA Technical Reports Server (NTRS)

Hoberecht, Mark A.; Pham, Nang T.

2005-01-01

Proton-exchange-membrane fuel cell (PEMFC) technology has received major attention for terrestrial applications, such as the automotive and residential markets, for the past 20 years. This attention has significantly advanced the maturity of the technology, resulting in ever more compact, efficient, reliable, and inexpensive PEMFC designs. In comparison to the terrestrial operating environment, the space operating environment is much more demanding. Microgravity to high-gravity loads and the need to use pure oxygen (rather than air) as the fuel cell oxidizer place more stringent demands on PEMFC technology. NASA and its partners from industry are leveraging terrestrial PEMFC advancements by conducting parallel space technology development for future exploration missions. A team from the NASA Glenn Research Center, NASA Johnson Space Center, and NASA Kennedy Space Center recently completed the first phase of a PEMFC powerplant development effort for exploration missions. The industry partners for this phase of the development effort were ElectroChem, Inc., and Teledyne Energy Systems, Inc. Under contract to Glenn, both of these industry partners successfully designed, fabricated, and tested a breadboard PEMFC powerplant in the 1- to 5-kW power range. These powerplants were based on existing company-proprietary fuel cell stack designs, combined with off-the-shelf components, which formed the balance of the powerplant design. Subsequent to the contractor development efforts, both powerplants were independently tested at Johnson to verify operational and performance characteristics, and to determine suitability for further technology development in the second phase of the NASA-led effort. Following the independent NASA testing, Teledyne Energy Systems, Inc., was selected to develop an engineering model PEMFC powerplant. This effort was initiated by the 2nd Generation Reusable Launch Vehicle (RLV) Program Office in 2001; it transitioned to the Next Generation Launch Technologies (NGLT) Program Office in 2003. The effort is now being funded by the Exploration Program Office. We plan to summarize the results from the ongoing engineering model PEMFC powerplant development in a future Research & Technology article.

Proton-Exchange-Membrane Fuel Cell Powerplants Developed and Tested for Exploration Missions

NASA Astrophysics Data System (ADS)

Hoberecht, Mark A.; Pham, Nang T.

2005-06-01

Proton-exchange-membrane fuel cell (PEMFC) technology has received major attention for terrestrial applications, such as the automotive and residential markets, for the past 20 years. This attention has significantly advanced the maturity of the technology, resulting in ever more compact, efficient, reliable, and inexpensive PEMFC designs. In comparison to the terrestrial operating environment, the space operating environment is much more demanding. Microgravity to high-gravity loads and the need to use pure oxygen (rather than air) as the fuel cell oxidizer place more stringent demands on PEMFC technology. NASA and its partners from industry are leveraging terrestrial PEMFC advancements by conducting parallel space technology development for future exploration missions. A team from the NASA Glenn Research Center, NASA Johnson Space Center, and NASA Kennedy Space Center recently completed the first phase of a PEMFC powerplant development effort for exploration missions. The industry partners for this phase of the development effort were ElectroChem, Inc., and Teledyne Energy Systems, Inc. Under contract to Glenn, both of these industry partners successfully designed, fabricated, and tested a breadboard PEMFC powerplant in the 1- to 5-kW power range. These powerplants were based on existing company-proprietary fuel cell stack designs, combined with off-the-shelf components, which formed the balance of the powerplant design. Subsequent to the contractor development efforts, both powerplants were independently tested at Johnson to verify operational and performance characteristics, and to determine suitability for further technology development in the second phase of the NASA-led effort. Following the independent NASA testing, Teledyne Energy Systems, Inc., was selected to develop an engineering model PEMFC powerplant. This effort was initiated by the 2nd Generation Reusable Launch Vehicle (RLV) Program Office in 2001; it transitioned to the Next Generation Launch Technologies (NGLT) Program Office in 2003. The effort is now being funded by the Exploration Program Office. We plan to summarize the results from the ongoing engineering model PEMFC powerplant development in a future Research & Technology article.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

On the Preparation and Testing of Fuel Cell Catalysts Using the Thin Film Rotating Disk Electrode Method.

PubMed

Inaba, Masanori; Quinson, Jonathan; Bucher, Jan Rudolf; Arenz, Matthias

2018-03-16

We present a step-by-step tutorial to prepare proton exchange membrane fuel cell (PEMFC) catalysts, consisting of Pt nanoparticles (NPs) supported on a high surface area carbon, and to test their performance in thin film rotating disk electrode (TF-RDE) measurements. The TF-RDE methodology is widely used for catalyst screening; nevertheless, the measured performance sometimes considerably differs among research groups. These uncertainties impede the advancement of new catalyst materials and, consequently, several authors discussed possible best practice methods and the importance of benchmarking. The visual tutorial highlights possible pitfalls in the TF-RDE testing of Pt/C catalysts. A synthesis and testing protocol to assess standard Pt/C catalysts is introduced that can be used together with polycrystalline Pt disks as benchmark catalysts. In particular, this study highlights how the properties of the catalyst film on the glassy carbon (GC) electrode influence the measured performance in TF-RDE testing. To obtain thin, homogeneous catalyst films, not only the catalyst preparation, but also the ink deposition and drying procedures are essential. It is demonstrated that an adjustment of the ink's pH might be necessary, and how simple control measurements can be used to check film quality. Once reproducible TF-RDE measurements are obtained, determining the Pt loading on the catalyst support (expressed as Pt wt%) and the electrochemical surface area is necessary to normalize the determined reaction rates to either surface area or Pt mass. For the surface area determination, so-called CO stripping, or the determination of the hydrogen underpotential deposition (Hupd) charge, are standard. For the determination of the Pt loading, a straightforward and cheap procedure using digestion in aqua regia with subsequent conversion of Pt(IV) to Pt(II) and UV-vis measurements is introduced.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

PubMed

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

On the Preparation and Testing of Fuel Cell Catalysts Using the Thin Film Rotating Disk Electrode Method

PubMed Central

Inaba, Masanori; Quinson, Jonathan; Bucher, Jan Rudolf; Arenz, Matthias

2018-01-01

We present a step-by-step tutorial to prepare proton exchange membrane fuel cell (PEMFC) catalysts, consisting of Pt nanoparticles (NPs) supported on a high surface area carbon, and to test their performance in thin film rotating disk electrode (TF-RDE) measurements. The TF-RDE methodology is widely used for catalyst screening; nevertheless, the measured performance sometimes considerably differs among research groups. These uncertainties impede the advancement of new catalyst materials and, consequently, several authors discussed possible best practice methods and the importance of benchmarking. The visual tutorial highlights possible pitfalls in the TF-RDE testing of Pt/C catalysts. A synthesis and testing protocol to assess standard Pt/C catalysts is introduced that can be used together with polycrystalline Pt disks as benchmark catalysts. In particular, this study highlights how the properties of the catalyst film on the glassy carbon (GC) electrode influence the measured performance in TF-RDE testing. To obtain thin, homogeneous catalyst films, not only the catalyst preparation, but also the ink deposition and drying procedures are essential. It is demonstrated that an adjustment of the ink's pH might be necessary, and how simple control measurements can be used to check film quality. Once reproducible TF-RDE measurements are obtained, determining the Pt loading on the catalyst support (expressed as Pt wt%) and the electrochemical surface area is necessary to normalize the determined reaction rates to either surface area or Pt mass. For the surface area determination, so-called CO stripping, or the determination of the hydrogen underpotential deposition (Hupd) charge, are standard. For the determination of the Pt loading, a straightforward and cheap procedure using digestion in aqua regia with subsequent conversion of Pt(IV) to Pt(II) and UV-vis measurements is introduced. PMID:29608166

Pt/glassy carbon model catalysts prepared from PS-b-P2VP micellar templates.

PubMed

Gu, Yunlong; St-Pierre, Jean; Ploehn, Harry J

2008-11-04

Poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer was used as a micellar template to fabricate arrays of Pt nanoparticles on mica and glassy carbon (GC) supports. Polymer micellar deposition yields Pt nanoparticles with tunable particle size and surface number density on both mica and GC. After deposition of precursor-loaded micelles onto GC, oxygen plasma etching removes the polymer shell, followed by thermal treatment with H2 gas to reduce the Pt. Etching conditions were optimized to maximize removal of the polymer while minimizing damage to the GC. Arrays of Pt nanoparticles with controlled size and surface number density can be prepared on mica (for particle size characterization) and GC to make Pt/GC model catalysts. These model catalysts were characterized by tapping mode atomic force microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry to measure activity for oxidation of carbon monoxide or methanol. Cyclic voltammetry results demonstrate the existence of a correlation between Pt particle size and electrocatalytic properties including onset potential, tolerance of carbonaceous adsorbates, and intrinsic activity (based on active Pt area from CO stripping voltammetry). Results obtained with Pt/GC model catalysts duplicate prior results obtained with Pt/porous carbon catalysts therefore validating the synthesis approach and offering a new, tunable platform to study catalyst structure and other effects such as aging on proton exchange membrane fuel cell (PEMFC) reactions.

A novel (ex situ) method to quantify oxygen diffusion coefficient of polymer fuel cells backing and catalyst layers

NASA Astrophysics Data System (ADS)

Baricci, Andrea; Casalegno, Andrea

2016-09-01

Limiting current density of oxygen reduction reaction in polymer electrolyte fuel cells is determined by several mass transport resistances that lower the concentration of oxygen on the catalyst active site. Among them, diffusion across porous media plays a significant role. Despite the extensive experimental activity documented in PEMFC literature, only few efforts have been dedicated to the measurement of the effective transport properties in porous layers. In the present work, a methodology for ex situ measurement of the effective diffusion coefficient and Knudsen radius of porous layers for polymer electrolyte fuel cells (gas diffusion layer, micro porous layer and catalyst layer) is described and applied to high temperature polymer fuel cells State of Art materials. Regression of the measured quantities by means of a quasi 2D physical model is performed to quantify the Knudsen effect, which is reported to account, respectively, for 30% and 50% of the mass transport resistance in micro porous layer and catalyst layer. On the other side, the model reveals that pressure gradient consequent to permeation in porous layers of high temperature polymer fuel cells has a negligible effect on oxygen concentration in relevant operating conditions.

Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

PubMed

Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

2018-06-26

It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

New insights into non-precious metal catalyst layer designs for proton exchange membrane fuel cells: Improving performance and stability

NASA Astrophysics Data System (ADS)

Banham, Dustin; Kishimoto, Takeaki; Sato, Tetsutaro; Kobayashi, Yoshikazu; Narizuka, Kumi; Ozaki, Jun-ichi; Zhou, Yingjie; Marquez, Emil; Bai, Kyoung; Ye, Siyu

2017-03-01

The activity of non-precious metal catalysts (NPMCs) has now reached a stage at which they can be considered as possible alternatives to Pt for some proton exchange membrane fuel cell (PEMFC) applications. However, despite significant efforts over the past 50 years on catalyst development, only limited studies have been performed on NPMC-based cathode catalyst layer (CCL) designs. In this work, an extensive ionomer study is performed to investigate the impact of ionomer equivalent weight on performance, which has uncovered two crucial findings. Firstly, it is demonstrated that beyond a critical CCL conductance, no further improvement in performance is observed. The procedure used to determine this critical conductance can be used by other researchers in this field to aid in their design of high performing NPMC-based CCLs. Secondly, it is shown that the stability of NPMC-based CCLs can be improved through the use of low equivalent weight ionomers. This represents a completely unexplored pathway for further stability improvements, and also provides new insights into the possible degradation mechanisms occurring in NPMC-based CCLs. These findings have broad implications on all future NPMC-based CCL designs.

Electrochemical behavior of platinum nanoparticles on a carbon xerogel support modified with a [(trifluoromethyl)-benzenesulfonyl]imide electrolyte.

PubMed

Liu, Bing; Mei, Hua; DesMarteau, Darryl; Creager, Stephen E

2014-12-11

A monoprotic [(trifluoromethyl)benzenesulfonyl]imide (SI) superacid electrolyte was used to covalently modify a mesoporous carbon xerogel (CX) support via reaction of the corresponding trifluoromethyl aryl sulfonimide diazonium zwitterion with the carbon surface. Electrolyte attachment was demonstrated by elemental analysis, acid-base titration, and thermogravimetric analysis. The ion-exchange capacity of the fluoroalkyl-aryl-sulfonimide-grafted carbon xerogel (SI-CX) was ∼0.18 mequiv g(-1), as indicated by acid-base titration. Platinum nanoparticles were deposited onto the SI-grafted carbon xerogel samples by the impregnation and reduction method, and these materials were employed to fabricate polyelectrolyte membrane fuel-cell (PEMFC) electrodes by the decal transfer method. The SI-grafted carbon-xerogel-supported platinum (Pt/SI-CX) was characterized by X-ray diffraction and transmission electron microscopy to determine platinum nanoparticle size and distribution, and the findings are compared with CX-supported platinum catalyst without the grafted SI electrolyte (Pt/CX). Platinum nanoparticle sizes are consistently larger on Pt/SI-CX than on Pt/CX. The electrochemically active surface area (ESA) of platinum catalyst on the Pt/SI-CX and Pt/CX samples was measured with ex situ cyclic voltammetry (CV) using both hydrogen adsorption/desorption and carbon monoxide stripping methods and by in situ CV within membrane electrode assemblies (MEAs). The ESA values for Pt/SI-CX are consistently lower than those for Pt/CX. Some possible reasons for the behavior of samples with and without grafted SI layers and implications for the possible use of SI-grafted carbon layers in PEMFC devices are discussed.

Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: I. Impact of Impurities, Measurement Protocols and Applied Corrections

DOE PAGES

Shinozaki, Kazuma; Zack, Jason W.; Richards, Ryan M.; ...

2015-07-22

The rotating disk electrode (RDE) technique is being extensively used as a screening tool to estimate the activity of novel PEMFC electrocatalysts synthesized in lab-scale (mg) quantities. Discrepancies in measured activity attributable to glassware and electrolyte impurity levels, as well as conditioning, protocols and corrections are prevalent in the literature. Moreover, the electrochemical response to a broad spectrum of commercially sourced perchloric acid and the effect of acid molarity on impurity levels and solution resistance were also assessed. Our findings reveal that an area specific activity (SA) exceeding 2.0 mA/cm 2 (20 mV/s, 25°C, 100 kPa, 0.1 M HClO 4)more » for polished poly-Pt is an indicator of impurity levels that do not impede the accurate measurement of the ORR activity of Pt based catalysts. After exploring various conditioning protocols to approach maximum utilization of the electrochemical area (ECA) and peak ORR activity without introducing catalyst degradation, an investigation of measurement protocols for ECA and ORR activity was conducted. Down-selected protocols were based on the criteria of reproducibility, duration of experiments, impurity effects and magnitude of pseudo-capacitive background correction. In sum, statistical reproducibility of ORR activity for poly-Pt and Pt supported on high surface area carbon was demonstrated.« less

A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells.

PubMed

Miller, Hamish A; Lavacchi, Alessandro; Vizza, Francesco; Marelli, Marcello; Di Benedetto, Francesco; D'Acapito, Francesco; Paska, Yair; Page, Miles; Dekel, Dario R

2016-05-10

One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM-FCs). The anion exchange membrane fuel cell (AEM-FC) has long been proposed as a solution as non-Pt metals may be employed. Despite this, few examples of Pt-free AEM-FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt-free AEM-FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt-free AEM-FC that employs a mixed carbon-CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM-FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anion exchange membrane fuel cells: Current status and remaining challenges

NASA Astrophysics Data System (ADS)

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; Bae, Chulsung; Yan, Yushan; Zelenay, Piotr; Kim, Yu Seung

2018-01-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. In this perspective article, we describe the current status of AEMFCs as having reached beginning of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. These perspectives may provide useful insights for the development of next-generation of AEMFCs.

Anion exchange membrane fuel cells: Current status and remaining challenges

DOE PAGES

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; ...

2017-09-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

A noble metal-free proton-exchange membrane fuel cell based on bio-inspired molecular catalysts.

PubMed

Tran, P D; Morozan, A; Archambault, S; Heidkamp, J; Chenevier, P; Dau, H; Fontecave, M; Martinent, A; Jousselme, B; Artero, V

2015-03-01

Hydrogen is a promising energy vector for storing renewable energies: obtained from water-splitting, in electrolysers or photoelectrochemical cells, it can be turned back to electricity on demand in fuel cells (FCs). Proton exchange membrane (PEM) devices with low internal resistance, high compactness and stability are an attractive technology optimized over decades, affording fast start-up times and low operating temperatures. However, they rely on the powerful catalytic properties of noble metals such as platinum, while lower cost, more abundant materials would be needed for economic viability. Replacing these noble metals at both electrodes has long proven to be a difficult task, so far incompatible with PEM technologies. Here we take advantage of newly developed bio-inspired molecular H 2 oxidation catalysts and noble metal-free O 2 -reducing materials, to fabricate a noble metal-free PEMFC, with an 0.74 V open circuit voltage and a 23 μW cm -2 output power under technologically relevant conditions. X-ray absorption spectroscopy measurements confirm that the catalysts are stable and retain their structure during turnover.

Flexible and Lightweight Fuel Cell with High Specific Power Density.

PubMed

Ning, Fandi; He, Xudong; Shen, Yangbin; Jin, Hehua; Li, Qingwen; Li, Da; Li, Shuping; Zhan, Yulu; Du, Ying; Jiang, Jingjing; Yang, Hui; Zhou, Xiaochun

2017-06-27

Flexible devices have been attracting great attention recently due to their numerous advantages. But the energy densities of current energy sources are still not high enough to support flexible devices for a satisfactory length of time. Although proton exchange membrane fuel cells (PEMFCs) do have a high-energy density, traditional PEMFCs are usually too heavy, rigid, and bulky to be used in flexible devices. In this research, we successfully invented a light and flexible air-breathing PEMFC by using a new design of PEMFC and a flexible composite electrode. The flexible air-breathing PEMFC with 1 × 1 cm 2 working area can be as light as 0.065 g and as thin as 0.22 mm. This new PEMFC exhibits an amazing specific volume power density as high as 5190 W L -1 , which is much higher than traditional (air-breathing) PEMFCs. Also outstanding is that the flexible PEMFC retains 89.1% of its original performance after being bent 600 times, and it retains its original performance after being dropped five times from a height of 30 m. Moreover, the research has demonstrated that when stacked, the flexible PEMFCs are also useful in mobile applications such as mobile phones. Therefore, our research shows that PEMFCs can be made light, flexible, and suitable for applications in flexible devices. These innovative flexible PEMFCs may also notably advance the progress in the PEMFC field, because flexible PEMFCs can achieve high specific power density with small size, small volume, low weight, and much lower cost; they are also much easier to mass produce.

Modelling and validation of Proton exchange membrane fuel cell (PEMFC)

NASA Astrophysics Data System (ADS)

Mohiuddin, A. K. M.; Basran, N.; Khan, A. A.

2018-01-01

This paper is the outcome of a small scale fuel cell project. Fuel cell is an electrochemical device that converts energy from chemical reaction to electrical work. Proton Exchange Membrane Fuel Cell (PEMFC) is one of the different types of fuel cell, which is more efficient, having low operational temperature and fast start up capability results in high energy density. In this study, a mathematical model of 1.2 W PEMFC is developed and simulated using MATLAB software. This model describes the PEMFC behaviour under steady-state condition. This mathematical modeling of PEMFC determines the polarization curve, power generated, and the efficiency of the fuel cell. Simulation results were validated by comparing with experimental results obtained from the test of a single PEMFC with a 3 V motor. The performance of experimental PEMFC is little lower compared to simulated PEMFC, however both results were found in good agreement. Experiments on hydrogen flow rate also been conducted to obtain the amount of hydrogen consumed to produce electrical work on PEMFC.

Analysis performance of proton exchange membrane fuel cell (PEMFC)

NASA Astrophysics Data System (ADS)

Mubin, A. N. A.; Bahrom, M. H.; Azri, M.; Ibrahim, Z.; Rahim, N. A.; Raihan, S. R. S.

2017-06-01

Recently, the proton exchange membrane fuel cell (PEMFC) has gained much attention to the technology of renewable energy due to its mechanically ideal and zero emission power source. PEMFC performance reflects from the surroundings such as temperature and pressure. This paper presents an analysis of the performance of the PEMFC by developing the mathematical thermodynamic modelling using Matlab/Simulink. Apart from that, the differential equation of the thermodynamic model of the PEMFC is used to explain the contribution of heat to the performance of the output voltage of the PEMFC. On the other hand, the partial pressure equation of the hydrogen is included in the PEMFC mathematical modeling to study the PEMFC voltage behaviour related to the input variable input hydrogen pressure. The efficiency of the model is 33.8% which calculated by applying the energy conversion device equations on the thermal efficiency. PEMFC’s voltage output performance is increased by increasing the hydrogen input pressure and temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Hyun -Seok; Das, Mayukhee; Wang, Heli

In this paper, a study is presented of the effects of an organic contaminant containing an amide bond (-CONH-), ε-caprolactam, on polymer electrolyte membrane fuel cells (PEMFCs). The ε-caprolactam has been detected in leachates from polyphthalamide materials that are being considered for use as balance-of-plant structural materials for PEMFCs. Contamination effects from ε-caprolactam in Nafion membranes are shown to be controlled by temperature. A possible explanation of the temperature effect is the endothermic ring-opening reaction of the amide bond (-NHCO-) of the cyclic ε-caprolactam. UV-vis and ATR-IR spectroscopy studies confirmed the presence of open ring structure of ε-caprolactam in membranes.more » The ECSA and kinetic current for the ORR of the Pt/C catalyst were also investigated and were observed to decrease upon contamination by the ε-caprolactam. By comparison of the CVs of ammonia and acetic acid, we confirmed the adsorption of carboxylic acid (-COOH) or carboxylate anion (-COO-) onto the surface of the Pt. In conclusion, a comparison of in situ voltage losses at 80°C and 50°C also revealed temperature effects, especially in the membrane, as a result of the dramatic increase in the HFR.« less

Degradation forecast for PEMFC cathode-catalysts under cyclic loads

NASA Astrophysics Data System (ADS)

Moein-Jahromi, M.; Kermani, M. J.; Movahed, S.

2017-08-01

Degradation of Fuel Cell (FC) components under cyclic loads is one of the biggest bottlenecks in FC commercialization. In this paper, a novel experimental based algorithm is presented to predict the Catalyst Layer (CL) performance loss during cyclic load. The algorithm consists of two models namely Models 1 and 2. The Model 1 calculates the Electro-Chemical Surface Area (ECSA) and agglomerate size (e.g. agglomerate radius, rt,agg) for the catalyst layer under cyclic load. The Model 2 is the already-existing model from our earlier studies that computes catalyst performance with fixed structural parameters. Combinations of these two Models predict the CL performance under an arbitrary cyclic load. A set of parametric/sensitivity studies is performed to investigate the effects of operating parameters on the percentage of Voltage Degradation Rate (VDR%) with rank 1 for the most influential one. Amongst the considered parameters (such as: temperature, relative humidity, pressure, minimum and maximum voltage of the cyclic load), the results show that temperature and pressure have the most and the least influences on the VDR%, respectively. So that, increase of temperature from 60 °C to 80 °C leads to over 20% VDR intensification, the VDR will also reduce 1.41% by increasing pressure from 2 atm to 4 atm.

Purifier-integrated methanol reformer for fuel cell vehicles

NASA Astrophysics Data System (ADS)

Han, Jaesung; Kim, Il-soo; Choi, Keun-Sup

We developed a compact, 3-kW, purifier-integrated modular reformer which becomes the building block of full-scale 30-kW or 50-kW methanol fuel processors for fuel cell vehicles. Our proprietary technologies regarding hydrogen purification by composite metal membrane and catalytic combustion by washcoated wire-mesh catalyst were combined with the conventional methanol steam-reforming technology, resulting in higher conversion, excellent quality of product hydrogen, and better thermal efficiency than any other systems using preferential oxidation. In this system, steam reforming, hydrogen purification, and catalytic combustion all take place in a single reactor so that the whole system is compact and easy to operate. Hydrogen from the module is ultrahigh pure (99.9999% or better), hence there is no power degradation of PEMFC stack due to contamination by CO. Also, since only pure hydrogen is supplied to the anode of the PEMFC stack, 100% hydrogen utilization is possible in the stack. The module produces 2.3 Nm 3/h of hydrogen, which is equivalent to 3 kW when PEMFC has 43% efficiency. Thermal efficiency (HHV of product H 2/HHV of MeOH in) of the module is 89% and the power density of the module is 0.77 kW/l. This work was conducted in cooperation with Hyundai Motor Company in the form of a Korean national project. Currently the module is under test with an actual fuel cell stack in order to verify its performance. Sooner or later a full-scale 30-kW system will be constructed by connecting these modules in series and parallel and will serve as the fuel processor for the Korean first fuel cell hybrid vehicle.

Multiphase transport in polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Gauthier, Eric D.

Polymer electrolyte membrane fuel cells (PEMFCs) enable efficient conversion of fuels to electricity. They have enormous potential due to the high energy density of the fuels they utilize (hydrogen or alcohols). Power density is a major limitation to wide-scale introduction of PEMFCs. Power density in hydrogen fuel cells is limited by accumulation of water in what is termed fuel cell `flooding.' Flooding may occur in either the gas diffusion layer (GDL) or within the flow channels of the bipolar plate. These components comprise the electrodes of the fuel cell and balance transport of reactants/products with electrical conductivity. This thesis explores the role of electrode materials in the fuel cell and examines the fundamental connection between material properties and multiphase transport processes. Water is generated at the cathode catalyst layer. As liquid water accumulates it will utilize the largest pores in the GDL to go from the catalyst layer to the flow channels. Water collects to large pores via lateral transport at the interface between the GDL and catalyst layer. We have shown that water may be collected in these large pores from several centimeters away, suggesting that we could engineer the GDL to control flooding with careful placement and distribution of large flow-directing pores. Once liquid water is in the flow channels it forms slugs that block gas flow. The slugs are pushed along the channel by a pressure gradient that is dependent on the material wettability. The permeable nature of the GDL also plays a major role in slug growth and allowing bypass of gas between adjacent channels. Direct methanol fuel cells (DMFCs) have analogous multiphase flow issues where carbon dioxide bubbles accumulate, `blinding' regions of the fuel cell. This problem is fundamentally similar to water management in hydrogen fuel cells but with a gas/liquid phase inversion. Gas bubbles move laterally through the porous GDL and emerge to form large bubbles within the flow channel. We have compared the role of GDL materials in liquid drop and gas bubble formation and movement within fuel cells.

Method of fabricating electrode catalyst layers with directionally oriented carbon support for proton exchange membrane fuel cell

DOEpatents

Liu, Di-Jia; Yang, Junbing

2010-07-20

A method of making a membrane electrode assembly (MEA) having an anode and a cathode and a proton conductive membrane there between. A bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated in the nanotubes forms at least one portion of the MEA and is in contact with the membrane. A combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into a first reaction zone maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is transmitted to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes. The nanotubes are in contact with a portion of the MEA at production or being positioned in contact thereafter. Methods of forming a PEMFC are also disclosed.

Gas-liquid two-phase flow behaviors and performance characteristics of proton exchange membrane fuel cells in a short-term microgravity environment

NASA Astrophysics Data System (ADS)

Guo, Hang; Liu, Xuan; Zhao, Jian Fu; Ye, Fang; Ma, Chong Fang

2017-06-01

In this work, proton exchange membrane fuel cells (PEMFCs) with transparent windows are designed to study the gas-liquid two-phase flow behaviors inside flow channels and the performance of a PEMFC with vertical channels and a PEMFC with horizontal channels in a normal gravity environment and a 3.6 s short-term microgravity environment. Experiments are conducted under high external circuit load and low external circuit load at low temperature where is 35 °C. The results of the present experimental work demonstrate that the performance and the gas-liquid two-phase flow behaviors of the PEMFC with vertical channels exhibits obvious changes when the PEMFCs enter the 3.6 s short-term microgravity environment from the normal gravity environment. Meanwhile, the performance of the PEMFC with vertical channels increases after the PEMFC enters the 3.6 s short-term microgravity environment under high external circuit load, while under low external circuit load, the PEMFC with horizontal channels exhibits better performance in both the normal gravity environment and the 3.6 s short-term microgravity environment.

Prognostics of Proton Exchange Membrane Fuel Cells stack using an ensemble of constraints based connectionist networks

NASA Astrophysics Data System (ADS)

Javed, Kamran; Gouriveau, Rafael; Zerhouni, Noureddine; Hissel, Daniel

2016-08-01

Proton Exchange Membrane Fuel Cell (PEMFC) is considered the most versatile among available fuel cell technologies, which qualify for diverse applications. However, the large-scale industrial deployment of PEMFCs is limited due to their short life span and high exploitation costs. Therefore, ensuring fuel cell service for a long duration is of vital importance, which has led to Prognostics and Health Management of fuel cells. More precisely, prognostics of PEMFC is major area of focus nowadays, which aims at identifying degradation of PEMFC stack at early stages and estimating its Remaining Useful Life (RUL) for life cycle management. This paper presents a data-driven approach for prognostics of PEMFC stack using an ensemble of constraint based Summation Wavelet- Extreme Learning Machine (SW-ELM) models. This development aim at improving the robustness and applicability of prognostics of PEMFC for an online application, with limited learning data. The proposed approach is applied to real data from two different PEMFC stacks and compared with ensembles of well known connectionist algorithms. The results comparison on long-term prognostics of both PEMFC stacks validates our proposition.

Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes

NASA Astrophysics Data System (ADS)

Workman, Michael J.; Dzara, Michael; Ngo, Chilan; Pylypenko, Svitlana; Serov, Alexey; McKinney, Sam; Gordon, Jonathan; Atanassov, Plamen; Artyushkova, Kateryna

2017-04-01

Development of platinum group metal free catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) requires understanding of the interactions between surface chemistry and performance, both of which are strongly dependent on synthesis conditions. To elucidate these complex relationships, a set of Fe-N-C catalysts derived from the same set of precursor materials is fabricated by varying several key synthetic parameters under controlled conditions. The results of physicochemical characterization are presented and compared with the results of rotating disk electrode (RDE) analysis and fuel cell testing. We find that electrochemical performance is strongly correlated with three key properties related to catalyst composition: concentrations of 1) atomically dispersed Fe species, 2) species in which N is bound to Fe, and 3) surface oxides. Not only are these factors related to performance, these types of chemical species are shown to correlate with each other. This study provides evidence supporting the role of iron coordinated with nitrogen as an active species for the ORR, and offers synthetic pathways to increase the density of atomically dispersed iron species and surface oxides for optimum performance.

Synthesis of carbon nanofibers by CVD as a catalyst support material using atomically ordered Ni3C nanoparticles

NASA Astrophysics Data System (ADS)

Li, Meifeng; Li, Na; Shao, Wei; Zhou, Chungen

2016-12-01

Atomically ordered nickel carbide (Ni3C) nanoparticles in polygonal shapes were prepared through the reduction of nickelocene. A novel type of carbon nanofiber (CNF) with twisted conformation was synthesized successfully by catalytic chemical vapor deposition (CCVD) using the obtained Ni3C nanoparticles at a relatively low temperature of 350 °C, which is below the lower limit temperature of 400 °C for the growth of CNFs using metal catalysts. The growth mechanism of the twisted CNFs from Ni3C was freshly derived based on the detailed characterizations. Compared with the growth of CNFs from Ni, graphene layers nucleate at monoatomic step edges and grow in a layer-by-layer manner, while the rotation of the polygonal Ni3C nanoparticles fabricates the twisted conformation during the CNF growth. The electrochemical activity and performance of the twisted CNFs loaded with Pt as electrode catalysts for a polymer electrolyte membrane fuel cell (PEMFC) were measured to be better than those of straight CNFs grown from Ni nanoparticles at 500 °C, since the specific surface conformation helps to make the loaded Pt more homogeneous.

Synthesis of carbon nanofibers by CVD as a catalyst support material using atomically ordered Ni3C nanoparticles.

PubMed

Li, Meifeng; Li, Na; Shao, Wei; Zhou, Chungen

2016-11-22

Atomically ordered nickel carbide (Ni 3 C) nanoparticles in polygonal shapes were prepared through the reduction of nickelocene. A novel type of carbon nanofiber (CNF) with twisted conformation was synthesized successfully by catalytic chemical vapor deposition (CCVD) using the obtained Ni 3 C nanoparticles at a relatively low temperature of 350 °C, which is below the lower limit temperature of 400 °C for the growth of CNFs using metal catalysts. The growth mechanism of the twisted CNFs from Ni 3 C was freshly derived based on the detailed characterizations. Compared with the growth of CNFs from Ni, graphene layers nucleate at monoatomic step edges and grow in a layer-by-layer manner, while the rotation of the polygonal Ni 3 C nanoparticles fabricates the twisted conformation during the CNF growth. The electrochemical activity and performance of the twisted CNFs loaded with Pt as electrode catalysts for a polymer electrolyte membrane fuel cell (PEMFC) were measured to be better than those of straight CNFs grown from Ni nanoparticles at 500 °C, since the specific surface conformation helps to make the loaded Pt more homogeneous.

Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1

NASA Astrophysics Data System (ADS)

Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

2015-02-01

Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

Stereochemistry-Dependent Proton Conduction in Proton Exchange Membrane Fuel Cells.

PubMed

Thimmappa, Ravikumar; Devendrachari, Mruthyunjayachari Chattanahalli; Kottaichamy, Alagar Raja; Tiwari, Omshanker; Gaikwad, Pramod; Paswan, Bhuneshwar; Thotiyl, Musthafa Ottakam

2016-01-12

Graphene oxide (GO) is impermeable to H2 and O2 fuels while permitting H(+) shuttling, making it a potential candidate for proton exchange membrane fuel cells (PEMFC), albeit with a large anisotropy in their proton transport having a dominant in plane (σIP) contribution over the through plane (σTP). If GO-based membranes are ever to succeed in PEMFC, it inevitably should have a dominant through-plane proton shuttling capability (σTP), as it is the direction in which proton gets transported in a real fuel-cell configuration. Here we show that anisotropy in proton conduction in GO-based fuel cell membranes can be brought down by selectively tuning the geometric arrangement of functional groups around the dopant molecules. The results show that cis isomer causes a selective amplification of through-plane proton transport, σTP, pointing to a very strong geometry angle in ionic conduction. Intercalation of cis isomer causes significant expansion of GO (001) planes involved in σTP transport due to their mutual H-bonding interaction and efficient bridging of individual GO planes, bringing down the activation energy required for σTP, suggesting the dominance of a Grotthuss-type mechanism. This isomer-governed amplification of through-plane proton shuttling resulted in the overall boosting of fuel-cell performance, and it underlines that geometrical factors should be given prime consideration while selecting dopant molecules for bringing down the anisotropy in proton conduction and enhancing the fuel-cell performance in GO-based PEMFC.

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells

PubMed Central

Liu, Xiaoteng; Christensen, Paul A.; Kelly, Stephen M.; Rocher, Vincent; Scott, Keith

2013-01-01

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved. PMID:24957065

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells.

PubMed

Liu, Xiaoteng; Christensen, Paul A; Kelly, Stephen M; Rocher, Vincent; Scott, Keith

2013-12-05

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved.

Microfluidic Synthesis Enables Dense and Uniform Loading of Surfactant-Free PtSn Nanocrystals on Carbon Supports for Enhanced Ethanol Oxidation.

PubMed

Wu, Fuxiang; Zhang, Dongtang; Peng, Manhua; Yu, Zhihui; Wang, Xiayan; Guo, Guangsheng; Sun, Yugang

2016-04-11

Developing new synthetic methods for carbon supported catalysts with improved performance is of fundamental importance in advancing proton exchange membrane fuel cell (PEMFC) technology. Continuous-flow, microfluidic reactions in capillary tube reactors are described, which are capable of synthesizing surfactant-free, ultrafine PtSn alloyed nanoparticles (NPs) on various carbon supports (for example, commercial carbon black particles, carbon nanotubes, and graphene sheets). The PtSn NPs are highly crystalline with sizes smaller than 2 nm, and they are highly dispersed on the carbon supports with high loadings up to 33 wt%. These characteristics make the as-synthesized carbon-supported PtSn NPs more efficient than state of the art commercial Pt/C catalysts applied to the ethanol oxidation reaction (EOR). Significantly enhanced mass catalytic activity (two-times that of Pt/C) and improved stability are obtained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Correlation between theoretical descriptor and catalytic oxygen reduction activity of graphene supported palladium and palladium alloy electrocatalysts

NASA Astrophysics Data System (ADS)

Seo, Min Ho; Choi, Sung Mook; Lee, Dong Un; Kim, Won Bae; Chen, Zhongwei

2015-12-01

The oxygen reduction reaction, ORR, performances of graphene-supported palladium (Pd) and palladium alloys (Pd3X: X = Ag, Co and Fe) catalysts with highly dispersed catalyst particles are investigated in acidic and alkaline conditions using a rotating disk electrode, RDE. Graphene nanosheet, GNS, supported Pd based catalysts are fabricated without surfactant through the impregnation of Pd and 2nd metal precursors on GNS, leading to small and uniformly dispersed nanoparticles, even when high metal loading of up to 60 wt.% are deposited on supports. The ab-initio density functional theory, DFT, calculations, which are based on the d-band center theory, have been applied to correlate with the results of the ORR performances obtained by half-cell tests. Additionally, the cohesive energy, Ecoh, and dissolution potential, Um, for the Pd nanoparticles have been calculated to understand thermodynamic stability. To elucidate the d-band center shift, the Pd 3d5/2 core-level binding energies for Pd/GNS, Pd3Ag/GNS, Pd3Fe/GNS and Pd3Co/GNS have been investigated by X-ray photoelectron spectroscopy, XPS. The GNS-supported Pd, or Pd-based alloy-nanoparticle catalyst shows good ORR activity under acidic and alkaline conditions, suggesting it may offer potential replacement for Pt for use in cathode electrodes of anion-exchange membrane fuel cell, AEMFC, and acid based polymer electrolyte fuel cell, PEMFC.

Investigation of carbon supported PtW catalysts as CO tolerant anodes at high temperature in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Hassan, Ayaz; Paganin, Valdecir A.; Ticianelli, Edson A.

2016-09-01

The CO tolerance mechanism and the stability of carbon supported PtW electrocatalysts are evaluated in the anode of a proton exchange membrane fuel cell (PEMFC) at two different temperatures. The electrocatalysts are characterized by energy dispersive spectroscopy, X-ray diffraction, and transmission electron spectroscopy. Employed electrochemical techniques include cyclic voltammetry, CO stripping, fuel cell polarization, and online mass spectrometry. At a cell temperature of 85 °C, the PtW/C catalyst shows higher CO tolerance compared to Pt/C due an electronic effect of WOx in the Pt 5d band, which reduces the CO adsorption. An increase in hydrogen oxidation activity in the presence of CO is observed for both the catalysts at a higher temperature, due to the decrease of the Pt-CO coverage. A reduction in the current densities occurs for the PtW/C catalyst in both polarization curves and cyclic voltammograms after 5000 cycles of the anode in the range of 0.1-0.7 V vs. RHE at 50 mVs-1. This decrease in performance is assigned to the dissolution of W, with a consequent increase in the membrane resistivity. However, the observed decline of performance is small either in the presence of pure H2 or in the presence of H2/CO.

Ultrahigh PEMFC performance of a thin-film, dual-electrode assembly with tailored electrode morphology.

PubMed

Jung, Chi-Young; Kim, Tae-Hyun; Yi, Sung-Chul

2014-02-01

A dual-electrode membrane electrode assembly (MEA) for proton exchange membrane fuel cells with enhanced polarization under zero relative humidity (RH) is fabricated by introducing a phase-separated morphology in an agglomerated catalyst layer of Pt/C (platinum on carbon black) and Nafion. In the catalyst layer, a sufficient level of phase separation is achieved by dispersing the Pt catalyst and the Nafion dispersion in a mixed-solvent system (propane-1,2,3-triol/1-methyl-2-pyrrolidinone).The high polymer chain mobility results in improved water uptake and regular pore-size distribution with small pore diameters. The electrochemical performance of the dual-film electrode assembly with different levels of phase separation is compared to conventional electrode assemblies. As a result, good performance at 0 % RH is obtained because self-humidification is dramatically improved by attaching this dense and phase-separated catalytic overlayer onto the conventional catalyst layer. A MEA prepared using the thin-film, dual-layered electrode exhibits 39-fold increased RH stability and 28-fold improved start-up recovery time during the on-off operation relative to the conventional device. We demonstrate the successful operation of the dual-layered electrode comprised of discriminatively phase-separated agglomerates with an ultrahigh zero RH fuel-cell performance reaching over 95 % performance of a fully humidified MEA. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of cerium and nickel doped titanium nanofibers for hydrolysis of sodium borohydride.

PubMed

Tamboli, Ashif H; Gosavi, S W; Terashima, Chiaki; Fujishima, Akira; Pawar, Atul A; Kim, Hern

2018-07-01

A recyclable titanium nanofibers, doped with cerium and nickel doped was successfully synthesized by using sol-gel and electrospinning method for hydrogen generation from alkali free hydrolysis of NaBH 4 . The resultant nanocomposite was characterized to find out the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy),N 2 adsorption-desorption and BET (Brunauer-Emmett-Teller), etc. The results revealed that cerium and nickel nanoparticles were homogeneously distributed on the surface of the TiO 2 nanofibers due to having similar oxidation state and atomic radium of TiO 2 nanofibers with CeO 2 and NiO for the effective immobilization of metal ions. The NiO doped catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH 4 at room temperature. These catalysts have ability to produce 305 mL of H 2 within the time of 160 min at room temperature. Additionally, reusability test revealed that the catalyst is active even after five runs of hydrolytic reaction, implying the as-prepared NiO doped TiO 2 nanofibers could be considered as a potential candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells). Copyright © 2018 Elsevier Ltd. All rights reserved.

Enhanced Catalytic Activities of NiPt Truncated Octahedral Nanoparticles toward Ethylene Glycol Oxidation and Oxygen Reduction in Alkaline Electrolyte.

PubMed

Xia, Tianyu; Liu, Jialong; Wang, Shouguo; Wang, Chao; Sun, Young; Gu, Lin; Wang, Rongming

2016-05-04

The high cost and poor durability of Pt nanoparticles (NPs) are great limits for the proton exchange membrane fuel cells (PEMFCs) from being scaled-up for commercial applications. Pt-based bimetallic NPs together with a uniform distribution can effectively reduce the usage of expensive Pt while increasing poison resistance of intermediates. In this work, a simple one-pot method was used to successfully synthesize ultrafine (about 7.5 nm) uniform NiPt truncated octahedral nanoparticles (TONPs) in dimethylformamid (DMF) without any seeds or templates. The as-prepared NiPt TONPs with Pt-rich surfaces exhibit greatly improved catalytic activities together with good tolerance and better stability for ethylene glycol oxidation reaction (EGOR) and oxygen reduction reaction (ORR) in comparison with NiPt NPs and commercial Pt/C catalysts in alkaline electrolyte. For example, the value of mass and specific activities for EGOR are 23.2 and 17.6 times higher comparing with those of commercial Pt/C, respectively. Our results demonstrate that the dramatic enhancement is mainly attributed to Pt-rich surface, larger specific surface area, together with coupling between Ni and Pt atoms. This developed method provides a promising pathway for simple preparation of highly efficient electrocatalysts for PEMFCs in the near future.

Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

NASA Astrophysics Data System (ADS)

Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

2016-09-01

We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

Comparing shut-down strategies for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Oyarce, Alejandro; Zakrisson, Erik; Ivity, Matthew; Lagergren, Carina; Ofstad, Axel Baumann; Bodén, Andreas; Lindbergh, Göran

2014-05-01

Application of system strategies for mitigating carbon corrosion of the catalyst support in proton exchange fuel cells (PEMFCs) is a requirement for PEMFC systems, especially in the case of systems for transport application undergoing thousands of start-ups and shut-downs (SU/SD) during its lifetime. This study compares several of the most common shut-down strategies for 1100 cycles SU/SD cycles at 70 °C and 80% RH using commercially available fuel cell components. Each cycle simulates a prolonged shut-down, i.e. finishing each cycle with air filled anode and cathode. Furthermore, all start-ups are unprotected, i.e. introducing the H2 rich gas into an air filled anode. Finally, each cycle also includes normal fuel cell operation at 0.5 A cm-2 using synthetic reformate/air. H2 purge of the cathode and O2 consumption using a load were found to be the most effective strategies. The degradation rate using the H2 purge strategy was 23 μV cycle-1 at 0.86 A cm-2 using H2 and air at the anode and cathode, respectively. This degradation rate may be regarded as a generally low value, especially considering that this value also includes the degradation rate caused by unprotected start-ups.

Hawaii Energy and Environmental Technologies (HEET) Initiative

DTIC Science & Technology

2011-12-01

polymer electrolyte fuel cells ( PEMFCs ) performance. This work was performed to support the DOE manufacturing initiative for PEMFC production. The work...performed by exposing the MEA cathode to 10 ppm SO2 in N2 at certain potential and typical operating conditions of a PEMFC for certain time, then...adsorbate by analyzing the electrochemical reduction and oxidation potential and charge. As for the in-situ SO2 adsorption experiments, a PEMFC under

In-Situ Measurement of High-Temperature Proton Exchange Membrane Fuel Cell Stack Using Flexible Five-in-One Micro-Sensor

PubMed Central

Lee, Chi-Yuan; Weng, Fang-Bor; Kuo, Yzu-Wei; Tsai, Chao-Hsuan; Cheng, Yen-Ting; Cheng, Chih-Kai; Lin, Jyun-Ting

2016-01-01

In the chemical reaction that proceeds in a high-temperature proton exchange membrane fuel cell stack (HT-PEMFC stack), the internal local temperature, voltage, pressure, flow and current nonuniformity may cause poor membrane material durability and nonuniform fuel distribution, thus influencing the performance and lifetime of the fuel cell stack. In this paper micro-electro-mechanical systems (MEMS) are utilized to develop a high-temperature electrochemical environment-resistant five-in-one micro-sensor embedded in the cathode channel plate of an HT-PEMFC stack, and materials and process parameters are appropriately selected to protect the micro-sensor against failure or destruction during long-term operation. In-situ measurement of the local temperature, voltage, pressure, flow and current distributions in the HT-PEMFC stack is carried out. This integrated micro-sensor has five functions, and is favorably characterized by small size, good acid resistance and temperature resistance, quick response, real-time measurement, and the goal is being able to be put in any place for measurement without affecting the performance of the battery. PMID:27763559

In-Situ Measurement of High-Temperature Proton Exchange Membrane Fuel Cell Stack Using Flexible Five-in-One Micro-Sensor.

PubMed

Lee, Chi-Yuan; Weng, Fang-Bor; Kuo, Yzu-Wei; Tsai, Chao-Hsuan; Cheng, Yen-Ting; Cheng, Chih-Kai; Lin, Jyun-Ting

2016-10-18

In the chemical reaction that proceeds in a high-temperature proton exchange membrane fuel cell stack (HT-PEMFC stack), the internal local temperature, voltage, pressure, flow and current nonuniformity may cause poor membrane material durability and nonuniform fuel distribution, thus influencing the performance and lifetime of the fuel cell stack. In this paper micro-electro-mechanical systems (MEMS) are utilized to develop a high-temperature electrochemical environment-resistant five-in-one micro-sensor embedded in the cathode channel plate of an HT-PEMFC stack, and materials and process parameters are appropriately selected to protect the micro-sensor against failure or destruction during long-term operation. In-situ measurement of the local temperature, voltage, pressure, flow and current distributions in the HT-PEMFC stack is carried out. This integrated micro-sensor has five functions, and is favorably characterized by small size, good acid resistance and temperature resistance, quick response, real-time measurement, and the goal is being able to be put in any place for measurement without affecting the performance of the battery.

CERDEC Fuel Cell Team: Military Transitions for Soldier Fuel Cells

DTIC Science & Technology

2008-10-27

Fuel Cell (DMFC) (PEO Soldier) Samsung: 20W DMFC (CRADA) General Atomics & Jadoo: 50W Ammonia Borane Fueled PEMFC Current Fuel Cell Team Efforts...Continued Ardica: 20W Wearable PEMFC operating on Chemical Hydrides Spectrum Brands w/ Rayovac: Hydrogen Generators and Alkaline Fuel Cells for AA...100W Ammonia Borane fueled PEMFC Ultralife: 150W sodium borohydride fueled PEMFC Protonex: 250W RMFC and Power Manager (ARO) NanoDynamics: 250W SOFC

Conclusions and Recommendations Regarding the Deep Sea Hybrid Power Systems Initial Study

DTIC Science & Technology

2010-06-01

proton-exchange membrane fuel cells ( PEMFC ) powered with hydrogen and oxygen, similar to that used on proven subsurface vessels; (2) fuel-cells...AND STORAGE OPTIONS CONSIDERED FOR INITIAL STUDY NO. NOMENCLATURE DESCRIPTION 1 PWR Nuclear Reactor + Battery 2 FC1 PEMFC + Line for surface O2...Wellhead Gas + Reformer + Battery 3 FC2 PEMFC + Stored O2 + Wellhead Gas + Reformer + Battery 4 SV1 PEMFC + Submersible Vehicle for O2 Transport

A review of high-temperature polymer electrolyte membrane fuel-cell (HT-PEMFC)-based auxiliary power units for diesel-powered road vehicles

NASA Astrophysics Data System (ADS)

Liu, Yongfeng; Lehnert, Werner; Janßen, Holger; Samsun, Remzi Can; Stolten, Detlef

2016-04-01

This paper presents an extensive review of research on the development of auxiliary power units with enhanced reformate tolerance for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Developments in diesel reforming for fuel cells as auxiliary power units (APUs), single fuel cells and stacks and systems are outlined in detail and key findings are presented. Summaries of HT-PEMFC APU applications and start-up times for HT-PEMFC systems are then given. A summary of cooling HT-PEMFC stacks using a classic schematic diagram of a 24-cell HT-PEMFC stack, with a cooling plate for every third cell, is also presented as part of a stack analysis. Finally, a summary of CO tolerances for fuel cells is given, along with the effects of different CO volume fractions on polarization curves, the fraction of CO coverage, hydrogen coverage, anode overpotential and cell potential.

Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy.

PubMed

Berejnov, Viatcheslav; Martin, Zulima; West, Marcia; Kundu, Sumit; Bessarabov, Dmitri; Stumper, Jürgen; Susac, Darija; Hitchcock, Adam P

2012-04-14

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.

The use of 1H NMR microscopy to study proton-exchange membrane fuel cells.

PubMed

Feindel, Kirk W; Bergens, Steven H; Wasylishen, Roderick E

2006-01-16

To understand proton-exchange membrane fuel cells (PEMFCs) better, researchers have used several techniques to visualize their internal operation. This Concept outlines the advantages of using 1H NMR microscopy, that is, magnetic resonance imaging, to monitor the distribution of water in a working PEMFC. We describe what a PEMFC is, how it operates, and why monitoring water distribution in a fuel cell is important. We will focus on our experience in constructing PEMFCs, and demonstrate how 1H NMR microscopy is used to observe the water distribution throughout an operating hydrogen PEMFC. Research in this area is briefly reviewed, followed by some comments regarding challenges and anticipated future developments.

Defining the Operational Conditions for High Temperature Polymer Fuel Cells in Naval Environments

DTIC Science & Technology

2008-12-31

benefits of both Proton Exchange Membrane Fuel Cells ( PEMFCs ) and phosphoric acid fuel cell technologies: a solid polymer electrolyte, the PBI...membrane, but with higher temperature (160°C) operation. PBI membrane technology is far less developed than that for PEMFCs , but it is rapidly emerging as...how air contaminants affect the properties of proton exchange membrane fuel cells ( PEMFCs ). PEMFCs operate at 80 °C, and are the present choice of fuel

In-Situ Anomalous Small-Angle X-ray Scattering Studies of Polymer Electrolyte Membrane Fuel Cell Catalyst Degradation

NASA Astrophysics Data System (ADS)

Gilbert, James Andrew

Polymer electrolyte membrane fuel cells (PEMFCs) are a promising high efficiency energy conversion technology, but their cost effective implementation, especially for automotive power, has been hindered by degradation of the electrochemically-active surface area (ECA) of the Pt nanoparticle electrocatalysts. While numerous studies using ex-situ post-mortem techniques have provided insight into the effect of operating conditions on ECA loss, the governing mechanisms and underlying processes are not fully understood. Toward the goal of elucidating the electrocatalyst degradation mechanisms, we have followed particle size distribution (PSD) growth evolutions of Pt and Pt-alloy nanoparticle catalysts during potential cycling in an aqueous acidic environment (with and without flow of electrolyte) and in a fuel cell environment using in-situ anomalous small-angle X-ray scattering (ASAXS). The results of this thesis show a surface area loss mechanism of Pt nanoparticles supported on carbon to be predominantly controlled by Pt dissolution, the particle size dependence of Pt dissolution, the loss of dissolved Pt into the membrane and electrolyte, and, to a lesser extent, the re-deposition of dissolved Pt onto larger particles. The relative extent of these loss mechanisms are shown to be dependent on the environment, the temperature, and the potential cycling conditions. Correlation of ASAXS-determined particle growth with both calculated and voltammetrically-determined oxide coverages demonstrates that the oxide coverage is playing a key role in the dissolution process and in the corresponding growth of the mean Pt nanoparticle size and loss of ECA. This understanding potentially reduces the complex changes in PSDs and ECA resulting from various voltage profiles to the response to a single variable, oxide coverage. A better understanding of the degradation mechanisms of Pt and Pt-alloy nanoparticle distributions could lead to more stable electrocatalysts while simultaneously reducing the cost of the materials, thereby supporting more durable and lower cost PEMFCs.

Microscale X-ray tomographic investigation of the interfacial morphology between the catalyst and micro porous layers in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Prass, Sebastian; Hasanpour, Sadegh; Sow, Pradeep Kumar; Phillion, André B.; Mérida, Walter

2016-07-01

The interfacial morphology between the catalyst layer (CL) and micro porous layer (MPL) influences the performance of proton exchange membrane fuel cells (PEMFCs). Here we report a direct method to investigate the CL-MPL interfacial morphology of stacked and compressed gas diffusion layer (GDL with MPL)-catalyst coated membrane (CCM) assemblies. The area, origin and dimensions of interfacial gaps are studied with high-resolution X-ray micro computed tomography (X-μCT). The projected gap area (fraction of the CL-MPL interface separated by gaps) is higher for GDL-CCM assemblies with large differences in the surface roughness between CL and MPL but reduces with increasing compression and similarity in roughness. Relatively large continuous gaps are found in proximity to cracks in the MPL. These are hypothesized to form due to the presence of large pores on the surface of the GDL. Smaller gaps are induced by the surface roughness features throughout the CL-MPL interface. By modification of the pore sizes on the GDL surface serving as substrate for the MPL, the number and dimension of MPL crack induced gaps can be manipulated. Moreover, adjusting the CL and MPL surface roughness parameters to achieve similar orders of roughness can improve the surface mating characteristics of these two components.

Electron beam induced radiation damage in the catalyst layer of a proton exchange membrane fuel cell.

PubMed

He, Qianping; Chen, Jihua; Keffer, David J; Joy, David C

2014-01-01

Electron microscopy is an essential tool for the evaluation of microstructure and properties of the catalyst layer (CL) of proton exchange membrane fuel cells (PEMFCs). However, electron microscopy has one unavoidable drawback, which is radiation damage. Samples suffer temporary or permanent change of the surface or bulk structure under radiation damage, which can cause ambiguity in the characterization of the sample. To better understand the mechanism of radiation damage of CL samples and to be able to separate the morphological features intrinsic to the material from the consequences of electron radiation damage, a series of experiments based on high-angle annular dark-field-scanning transmission scanning microscope (HAADF-STEM), energy filtering transmission scanning microscope (EFTEM), and electron energy loss spectrum (EELS) are conducted. It is observed that for thin samples (0.3-1 times λ), increasing the incident beam energy can mitigate the radiation damage. Platinum nanoparticles in the CL sample facilitate the radiation damage. The radiation damage of the catalyst sample starts from the interface of Pt/C or defective thin edge and primarily occurs in the form of mass loss accompanied by atomic displacement and edge curl. These results provide important insights on the mechanism of CL radiation damage. Possible strategies of mitigating the radiation damage are provided. © 2013 Wiley Periodicals, Inc.

Fuel cell system with sodium borohydride as hydrogen source for unmanned aerial vehicles

NASA Astrophysics Data System (ADS)

Kim, Kyunghwan; Kim, Taegyu; Lee, Kiseong; Kwon, Sejin

In this study, we design and fabricate a fuel cell system for application as a power source in unmanned aerial vehicles (UAVs). The fuel cell system consists of a fuel cell stack, hydrogen generator, and hybrid power management system. PEMFC stack with an output power of 100 W is prepared and tested to decide the efficient operating conditions; the stack must be operated in the dead-end mode with purge in order to ensure prolonged stack performance. A hydrogen generator is fabricated to supply gaseous hydrogen to the stack. Sodium borohydride (NaBH 4) is used as the hydrogen source in the present study. Co/Al 2O 3 catalyst is prepared for the hydrolysis of the alkaline NaBH 4 solution at room temperature. The fabricated Co catalyst is comparable to the Ru catalyst. The UAV consumes more power in the takeoff mode than in the cruising mode. A hybrid power management system using an auxiliary battery is developed and evaluated for efficient energy management. Hybrid power from both the fuel cell and battery powers takeoff and turning flight operations, while the fuel cell supplies steady power during the cruising flight. The capabilities of the fuel-cell UAVs for long endurance flights are validated by successful flight tests.

Overview and benchmark analysis of fuel cell parameters estimation for energy management purposes

NASA Astrophysics Data System (ADS)

Kandidayeni, M.; Macias, A.; Amamou, A. A.; Boulon, L.; Kelouwani, S.; Chaoui, H.

2018-03-01

Proton exchange membrane fuel cells (PEMFCs) have become the center of attention for energy conversion in many areas such as automotive industry, where they confront a high dynamic behavior resulting in their characteristics variation. In order to ensure appropriate modeling of PEMFCs, accurate parameters estimation is in demand. However, parameter estimation of PEMFC models is highly challenging due to their multivariate, nonlinear, and complex essence. This paper comprehensively reviews PEMFC models parameters estimation methods with a specific view to online identification algorithms, which are considered as the basis of global energy management strategy design, to estimate the linear and nonlinear parameters of a PEMFC model in real time. In this respect, different PEMFC models with different categories and purposes are discussed first. Subsequently, a thorough investigation of PEMFC parameter estimation methods in the literature is conducted in terms of applicability. Three potential algorithms for online applications, Recursive Least Square (RLS), Kalman filter, and extended Kalman filter (EKF), which has escaped the attention in previous works, have been then utilized to identify the parameters of two well-known semi-empirical models in the literature, Squadrito et al. and Amphlett et al. Ultimately, the achieved results and future challenges are discussed.

Synthesis, characterization and optimization of platinum-alloy nanoparticle catalysts in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Srivastava, Ratndeep

Renewable hydrogen-fuelled proton exchange membrane (PEMFC) fuel cells have consistently demonstrated great promise as a future source of energy due to their high conversion efficiency, lower temperature of operation and lack of greenhouse emissions. One of the major impediments in the commercialization of polymer electrolyte membrane fuel cells is the insufficient catalytic reactivity and higher cost of Pt electrocatalysts which are utilized for the electroreduction of oxygen from air. This dissertation focuses primarily on a family of Pt alloy fuel cell electrocatalysts referred to as de-alloyed core-shell electrocatalysts. These materials are bimetallic or multimetallic nanoparticles, mostly supported on conductive supports which were first described in a dissertation by Dr. S. Koh earlier in 2009.1 De-alloyed Pt nanoparticle electrocatalysts are formed from base metal rich binary Pt-M and ternary Pt-M1-M 2 (M, M1, M2 = Cu, Co, Ni, Fe and Cr) alloy nanoparticle precursors. The precursors are transformed and activated by electrochemical selective dissolution of the less noble metal component of the precursors (de-alloying). They have shown exceptional activity for oxygen reduction reaction (ORR) in idealized electrochemical half cell measurements, in particular rotating disk electrode experiments. However, these materials were never tested or implemented in realistic Membrane Electrode Assemblies (MEA) and single PEM fuel cells. The objective of this work was to implement de-alloyed Pt particle catalysts in realistic fuel cell electrode layers as well as a detailed characterization of their behavior and stability. The major challenges of MEA implementation consists of the behavior of the new nanostructured electrocatalysts inside the complex three-phase interface of polymer membrane ionomer, liquid water, metal catalyst, support, and reactant gas. Activity measurements were followed by medium and long-term durability analysis by potential cycling of the membrane electrode assemblies to high potentials. These de-alloyed catalysts show improved resistance to electro-chemical surface area degradation as compared to state of the art available commercial Pt/C catalysts. TEM imaging with combination of electrochemical characterization helps in determining the mechanisms for particle growth and failures. Anomalous small angle x-ray scattering (ASAXS) and x-ray diffraction (XRD) techniques were also used in the characterization of these materials.

Micro Galvanic Cell To Generate PtO and Extend the Triple-Phase Boundary during Self-Assembly of Pt/C and Nafion for Catalyst Layers of PEMFC.

PubMed

Long, Zhi; Gao, Liqin; Li, Yankai; Kang, Baotao; Lee, Jin Yong; Ge, Junjie; Liu, Changpeng; Ma, Shuhua; Jin, Zhao; Ai, Hongqi

2017-11-08

The self-assembly powder (SAP) with varying Nafion content was synthesized and characterized by XRD, XPS, HRTEM, and mapping. It is observed that the oxygen from oxygen functional groups transfers to the surface of Pt and generate PtO during the process of self-assembly with the mechanism of micro galvanic cell, where Pt, carbon black, and Nafion act as the anode, cathode and electrolyte, respectively. The appearance of PtO on the surface of Pt leads to a turnover of Nafion structure, and therefore more hydrophilic sulfonic groups directly contact with Pt, and thus the triple-phase boundary (TPB) has been expanded.

Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Libo; Zhou, Gang, E-mail: gzhou@mail.buct.edu.cn

2016-04-14

The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO{sub 2} is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximatemore » to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs.« less

The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells.

PubMed

Kongkanand, Anusorn; Mathias, Mark F

2016-04-07

Substantial progress has been made in reducing proton-exchange membrane fuel cell (PEMFC) cathode platinum loadings from 0.4-0.8 mgPt/cm(2) to about 0.1 mgPt/cm(2). However, at this level of cathode Pt loading, large performance loss is observed at high-current density (>1 A/cm(2)), preventing a reduction in the overall stack cost. This next developmental step is being limited by the presence of a resistance term exhibited at these lower Pt loadings and apparently due to a phenomenon at or near the catalyst surface. This issue can be addressed through the design of catalysts with high and stable Pt dispersion as well as through development and implementation of ionomers designed to interact with Pt in a way that does not constrain oxygen reduction reaction rates. Extrapolating from progress made in past decades, we are optimistic that the concerted efforts of materials and electrode designers can resolve this issue, thus enabling a large step toward fuel cell vehicles that are affordable for the mass market.

Enhanced performance of polybenzimidazole-based high temperature proton exchange membrane fuel cell with gas diffusion electrodes prepared by automatic catalyst spraying under irradiation technique

NASA Astrophysics Data System (ADS)

Su, Huaneng; Pasupathi, Sivakumar; Bladergroen, Bernard Jan; Linkov, Vladimir; Pollet, Bruno G.

2013-11-01

Gas diffusion electrodes (GDEs) prepared by a novel automatic catalyst spraying under irradiation (ACSUI) technique are investigated for improving the performance of phosphoric acid (PA)-doped polybenzimidazole (PBI) high temperature proton exchange membrane fuel cell (PEMFC). The physical properties of the GDEs are characterized by pore size distribution and scanning electron microscopy (SEM). The electrochemical properties of the membrane electrode assembly (MEA) with the GDEs are evaluated and analyzed by polarization curve, cyclic voltammetry (CV) and electrochemistry impedance spectroscopy (EIS). Effects of PTFE binder content, PA impregnation and heat treatment on the GDEs are investigated to determine the optimum performance of the single cell. At ambient pressure and 160 °C, the maximum power density can reach 0.61 W cm-2, and the current density at 0.6 V is up to 0.38 A cm-2, with H2/air and a platinum loading of 0.5 mg cm-2 on both electrodes. The MEA with the GDEs shows good stability for fuel cell operating in a short term durability test.

Conceptual Design Tool to Analyze Electrochemically-Powered Micro Air Vehicles

DTIC Science & Technology

2011-03-01

technology polarization curve ( PEMFC ) ................................... 103  Figure 50.  Aerodynamic CA results, simulations 1-16...114  Figure 54.  Future technology polarization curve ( PEMFC ...Phosphoric Acid Fuel Cell PEMFC Proton Exchange Membrane or Polymer Electrolyte Membrane QPROP A Motor and Propeller Matching Program RC Radio Controlled

Using Polymer Electrolyte Membrane Fuel Cells in a Hybrid Surface Ship Propulsion Plant to Increase Fuel Efficiency

DTIC Science & Technology

2010-06-01

cell ( PEMFC ), and the phosphoric acid fuel cell (PAFC). 2.3.1 Solid Oxide Fuel Cells (SOFC) The first type of fuel cell considered is the SOFC. This...durability issues for use within a given application. 2.3.2 Polymer Electrolyte Membrane Fuel Cells ( PEMFC ) The PEMFC operates by passing hydrogen that has...cells. Some advantages of PEMFC operating at such low temperatures is that the fuel cell doesn’t require as meticulous of a support system infrastructure

Materials Challenges for Automotive PEM Fuel Cells

NASA Astrophysics Data System (ADS)

Gasteiger, Hubert

2004-03-01

Over the past few years, significant R efforts aimed at meeting the challenging cost and performance targets required for the use of Polymer Electrolyte Membrane (PEM) fuel cells in automotive applications. Besides engineering advances in bipolar plate materials and design, the optimization of membrane-electrode assemblies (MEAs) was an important enabler in reducing the cost and performance gaps towards commercial viability for the automotive market. On the one hand, platinum loadings were reduced from several mgPt/cm2MEA [1] to values of 0.5-0.6 mgPt/cm2MEA in current applications and loadings as low as 0.25 mgPt/cm2MEA have been demonstrated on the research level [2]. On the other hand, implementation of thin membranes (20-30 micrometer) [3, 4] as well as improvements in diffusion medium materials, essentially doubled the achievable power density of MEAs to ca. 0.9 W/cm2MEA (at 0.65 V) [5], thereby not only reducing the size of a PEMFC fuel cell system, but also reducing its overall materials cost (controlled to a large extent by membrane and Pt-catalyst cost). While this demonstrated a clear path towards automotive applications, a renewed focus of R efforts is now required to develop materials and fundamental materials understanding to assure long-term durability of PEM fuel cells. This presentation therefore will discuss the state-of-the-art knowledge of catalyst, catalyst-support, and membrane degradation mechanisms. In the area of Pt-catalysts, experience with phosphoric acid fuel cells (PAFCs) has shown that platinum sintering leads to long-term performance losses [6]. While this is less critical at the lower PEMFC operating temperatures (<100C) compared to PAFCs (>200C), very little is known about the dependence of Pt-sintering on temperature, cell voltage, and catalyst type (i.e., Pt versus Pt-alloys) and will be discussed here. Similarly, carbon-support corrosion can contribute significantly to voltage degradation in PAFCs [7], and even in the PEMFC environment more corrosion-resistant support materials (e.g., graphitized carbons) are desirable. While thin polymer electrolyte membranes (20-30 micrometer) enable high power density operation, the requirements on their chemical and mechanical stability are significantly more demanding compared to the thick membranes (100-200 micrometer) used in the past [1]. While the currently used perfluoro-sulfonicacid (PFSA) membranes are chemically very stable, they are known to degrade in the fuel cell environment [4] via peroxyl-radical attack, strongly enhanced in the presence of iron [8]. While the exact degradation mechanism is actively investigated, its understanding is clearly required to improve the chemical stability of PFSA's. Similarly, very little is known about the mechanical properties of polymer electrolyte membranes and critical issues will be discussed. References: 1. Strasser, K.; ``H2/O2 PEM Fuel Cell Module for an Air-Independent Propulsion System in a Submarine''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 4, chapter 88, 2003, pp. 1201-1214. 2. Gasteiger, H. A.; Panels, J. E.; Yan, S. G.; J. Power Sources in press. 3. Gasteiger, H. A.; Gu, W.; Makharia, R.; Mathias, M. F.; Sompalli, S.; ``Beginning-of-Life MEA Performance: Efficiency Loss Contributions''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 3, chapter 46, 2003, pp. 593-610. 4. Cleghorn, S.; Kolde, J.; Liu, W.; ``Catalyst-Coated Composite Membranes''; in: Handbook of Fuel Cells - Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 3, chapter 44, 2003, pp. 566-575. 5. Mathias, M. F.; Gasteiger, H. A.; Fundamental Research and Development Challenges in Polymer Electrolyte Fuel Cell Technology; in Proceedings of the Proton Conducting Membrane Fuel Cells III Symposium; The Electrochemical Society: 2002, in press. 6. Landsman, D. A.; Luczak, F. J.; ``Catalyst Studies and Coating Technologies''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 4, chapter 60, 2003, pp. 811-831. 7. Kinoshita, K.; Carbon: Electrochemical and Physicochemical Properites; John Wiley & Sons (New York, USA): 1988. 8. LaConti, A. B.; Hamdan, M.; McDonald, R. C.; ``Mechanisms of Chemical Degradation''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 3, chapter 49, 2003, pp. 647-662.

Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

PubMed

Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

2017-06-20

An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

Review of Fuel Cell Technologies for Military Land Vehicles

DTIC Science & Technology

2014-09-01

fuel cell technologies for APUs are Proton Exchange Membrane Fuel Cells ( PEMFC ), direct methanol fuel cells and Solid Oxide Fuel Cells (SOFC). The...6 4.2 Proton Exchange Membrane Fuel Cells ( PEMFC ...OEM Original Equipment Manufacturer PEM Proton Exchange Membrane PEMFC Proton Exchange Membrane Fuel Cell SOFC Solid Oxide Fuel Cell TRL Technical

Engineered Graphene Materials: Synthesis and Applications for Polymer Electrolyte Membrane Fuel Cells.

PubMed

He, Daping; Tang, Haolin; Kou, Zongkui; Pan, Mu; Sun, Xueliang; Zhang, Jiujun; Mu, Shichun

2017-05-01

Engineered graphene materials (EGMs) with unique structures and properties have been incorporated into various components of polymer electrolyte membrane fuel cells (PEMFCs) such as electrode, membrane, and bipolar plates to achieve enhanced performances in terms of electrical conductivity, mechanical durability, corrosion resistance, and electrochemical surface area. This research news article provides an overview of the recent development in EGMs and EGM-based PEMFCs with a focus on the effects of EGMs on PEMFC performance when they are incorporated into different components of PEMFCs. The challenges of EGMs for practical PEMFC applications in terms of production scale, stability, conductivity, and coupling capability with other materials are also discussed and the corresponding measures and future research trends to overcome such challenges are proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured TiOx as a catalyst support material for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Phillips, Richard S.

Recent interest in the development of new catalyst support materials for proton exchange membrane fuel cells (PEMFCs) has stimulated research into the viability of TiO2-based support structures. Specifically, substoichiometric TiO2 (TiOx) has been reported to exhibit a combination of high conductivity, stability, and corrosion resistance. These properties make TiOx-based support materials a promising prospect when considering the inferior corrosion resistance of traditional carbon-based supports. This document presents an investigation into the formation of conductive and stable TiOx thin films employing atomic layer deposition (ALD) and a post deposition oxygen reducing anneal (PDORA). Techniques for manufacturing TiOx-based catalyst support nanostructures by means of ALD in conjunction with carbon black (CB), anodic aluminum oxide (AAO) and silicon nanowires (SiNWs) will also be presented. The composition and thickness of resulting TiOx thin films was determined with the aid of Auger electron spectroscopy (AES), Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM). Film crystal structure was determined with X-ray diffraction (XRD) analysis. Film conductivity was calculated using four-point probe (4-PP) and film thickness measurement data. Resulting thin films show a significant decrease of oxygen in ALD TiOx films corresponding with a great increase in conductivity following the PDORA. The effectiveness of the PDORA was also found to be highly dependent on ALD process parameters. TiOx-based nanostructures were coated with platinum using one of three Pt deposition techniques. First, liquid phase deposition (LPD), which was performed at room temperature, provided equal access to catalyst support material surfaces which were suspended in solution. Second, plasma enhanced atomic layer deposition (PEALD), which was performed at 450°C, provided good Pt particle dispersion and particle size controllability. Third, physical vapor deposition (PVD), which was also performed at room temperature, was used as a low temperature vapor-phase deposition technique for comparison with PEALD Pt coated materials. The temperature of the Pt deposition technique is an important parameter to consider due to the potential adverse effects of the strong metal support interaction (SMSI) which may take place at temperatures above 200°C. Platinum coated nanostructures were analyzed electrochemically using cyclic voltammetry (CV), rotating disk electrode (RDE) and accelerated stress tests (ASTs). CV and RDE results generally show that platinum activity values are initially not as high as those typically observed for platinum on carbon; however, AST results indicate that TiO x-based materials are much more stable long-term and hence their level of activity is likely to overtake traditional platinum on carbon materials in a PEMFC system.

Emission Measurements of Ultracell XX25 Reformed Methanol Fuel Cell System

DTIC Science & Technology

2008-06-01

combination of electrochemical devices such as fuel cell and battery. Polymer electrolyte membrane fuel cells ( PEMFC ) using hydrogen or liquid...communications and computers, sensors and night vision capabilities. High temperature PEMFC offers some advantages such as enhanced electrode kinetics and better...tolerance of carbon monoxide that will poison the conventional PEMFC . Ultracell Corporation, Livermore, California has developed a first

Theoretical Studies in Enhancing the Efficiency of Cathode and Anode Materials in PEMFC (Proton Exchange Membrane Fuel Cells)

DTIC Science & Technology

2011-03-04

efficiency of cathode and anode materials in PEMFC (Proton Exchange Membrane Fuel Cells) 5a. CONTRACT NUMBER FA23861014012 5b. GRANT NUMBER 5c. PROGRAM...Rev. 8-98) Prescribed by ANSI Std Z39-18 Theoretical studies in enhancing the efficiency of cathode and anode materials in PEMFC (Proton Exchange

Advanced Energy Storage and Conversion Devices

DTIC Science & Technology

2008-12-01

determined lithium-ion insertion mechanisms. 3.1 Background and Objectives Polymer electrolyte membrane fuel cells ( PEMFCs ) function by permitting...is one of the most critical components in the polymer electrolyte fuel cells. In recent years, PEMFCs have been identified as promising power...and residual hydrocarbons that are commonly produced by internal combustion engines. PEMFCs , due to their high efficiency and modularity of design

Exploring Alkaline Stable Organic Cations for Polymer Hydroxide Exchange Membranes

DTIC Science & Technology

2015-04-29

1   1.1.2   Proton exchange membrane fuel cells ( PEMFCs ) ......................... 3   1.1.3   Alkaline fuel cells (AFCs...160   xi LIST OF FIGURES Figure 1.1:   Schematic diagram of a PEMFC ...according to the type of electrolyte they use. Nowadays, there are six major types of fuel cells: proton-exchange membrane fuel cells ( PEMFCs ), hydroxide

Development of Novel PEM Membrane and Multiphase CD Modeling of PEM Fuel Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. J. Berry; Susanta Das

2009-12-30

To understand heat and water management phenomena better within an operational proton exchange membrane fuel cell's (PEMFC) conditions, a three-dimensional, two-phase computational fluid dynamic (CFD) flow model has been developed and simulated for a complete PEMFC. Both liquid and gas phases are considered in the model by taking into account the gas flow, diffusion, charge transfer, change of phase, electro-osmosis, and electrochemical reactions to understand the overall dynamic behaviors of species within an operating PEMFC. The CFD model is solved numerically under different parametric conditions in terms of water management issues in order to improve cell performance. The results obtainedmore » from the CFD two-phase flow model simulations show improvement in cell performance as well as water management under PEMFCs operational conditions as compared to the results of a single phase flow model available in the literature. The quantitative information obtained from the two-phase model simulation results helped to develop a CFD control algorithm for low temperature PEM fuel cell stacks which opens up a route in designing improvement of PEMFC for better operational efficiency and performance. To understand heat and water management phenomena better within an operational proton exchange membrane fuel cell's (PEMFC) conditions, a three-dimensional, two-phase computational fluid dynamic (CFD) flow model has been developed and simulated for a complete PEMFC. Both liquid and gas phases are considered in the model by taking into account the gas flow, diffusion, charge transfer, change of phase, electro-osmosis, and electrochemical reactions to understand the overall dynamic behaviors of species within an operating PEMFC. The CFD model is solved numerically under different parametric conditions in terms of water management issues in order to improve cell performance. The results obtained from the CFD two-phase flow model simulations show improvement in cell performance as well as water management under PEMFCs operational conditions as compared to the results of a single phase flow model available in the literature. The quantitative information obtained from the two-phase model simulation results helped to develop a CFD control algorithm for low temperature PEM fuel cell stacks which opens up a route in designing improvement of PEMFC for better operational efficiency and performance.« less

Carbon corrosion of proton exchange membrane fuel cell catalyst layers studied by scanning transmission X-ray microscopy

NASA Astrophysics Data System (ADS)

Hitchcock, Adam P.; Berejnov, Viatcheslav; Lee, Vincent; West, Marcia; Colbow, Vesna; Dutta, Monica; Wessel, Silvia

2014-11-01

Scanning Transmission X-ray Microscopy (STXM) at the C 1s, F 1s and S 2p edges has been used to investigate degradation of proton exchange membrane fuel cell (PEM-FC) membrane electrode assemblies (MEA) subjected to accelerated testing protocols. Quantitative chemical maps of the catalyst, carbon support and ionomer in the cathode layer are reported for beginning-of-test (BOT), and end-of-test (EOT) samples for two types of carbon support, low surface area carbon (LSAC) and medium surface area carbon (MSAC), that were exposed to accelerated stress testing with upper potentials (UPL) of 1.0, 1.2, and 1.3 V. The results are compared in order to characterize catalyst layer degradation in terms of the amounts and spatial distributions of these species. Pt agglomeration, Pt migration and corrosion of the carbon support are all visualized, and contribute to differing degrees in these samples. It is found that there is formation of a distinct Pt-in-membrane (PTIM) band for all EOT samples. The cathode thickness shrinks due to loss of the carbon support for all MSAC samples that were exposed to the different upper potentials, but only for the most aggressive testing protocol for the LSAC support. The amount of ionomer per unit volume significantly increases indicating it is being concentrated in the cathode as the carbon corrosion takes place. S 2p spectra and mapping of the cathode catalyst layer indicates there are still sulfonate groups present, even in the most damaged material.

PEMFC for aeronautic applications: A review on the durability aspects

NASA Astrophysics Data System (ADS)

Dyantyi, Noluntu; Parsons, Adrian; Sita, Cordellia; Pasupathi, Sivakumar

2017-11-01

Proton exchange membrane fuel cells (PEMFC) not only offer more efficient electrical energy conversion, relative to on-ground/backup turbines but generate by-products useful in aircraft such as heat for ice prevention, deoxygenated air for fire retardation and drinkable water for use on-board. Consequently, several projects (e.g. DLR-H2 Antares and RAPID2000) have successfully tested PEMFC-powered auxiliary unit (APU) for manned/unmanned aircraft. Despite the progress from flying PEMFC-powered small aircraft with 20 kW power output as high as 1 000 m at 100 km/h to 33 kW at 2 558 m, 176 km/h [1, 2, 3], durability and reliability remain key challenges. This review reports on the inadequate understanding of behaviour of PEMFC under aeronautic conditions and the lack of predictive methods conducive for aircraft that provide real-time information on the State of Health of PEMFCs. -To minimize performance loss due to high altitude and inclination by adjusting cathode stoichiometric ratio. -To improve quality of oxygen-depleted air by controlling operating temperature and stoichiometric ratio. -Need to devise real time prediction methods conducive for determining PEMFC SoH in aircraft.

Polyarylenethioethersulfone Membranes for Fuel Cells (Postprint)

DTIC Science & Technology

2010-01-01

The Electrochemical SocietyProton exchange membrane fuel cells PEMFCs are an attrac- tive power source due to their energy efficiency and...standard in PEMFC technology.3,4 Nafion membranes have a polytetrafluoro- ethylene PTFE backbone, which provides thermal and chemical stability, and...diffusion layers to fabricate MEAs. Single-cell test (H- PEMFC ).— MEAs were positioned in a single-cell fixture with graphite blocks as current

Hawaii Energy and Environmental Technologies (HEET) Initiative

DTIC Science & Technology

2010-08-01

segmented cell system for investigation of PEMFC performance distribution using both cyclic voltammetry (CV) and linear sweep voltammetry (LSV). In...mitigation strategies. Under prior work it was shown that SO2 contamination in the cathode of a PEMFC resulted in a two-stage degradation of cell...emission rate in a PEMFC is an important parameter for monitoring the Nafion degradation. Generally, the Nafion electrolyte degradation is

Determining Water Content and Distribution in PEMFCs to Predict Aging While in Storage

DOE PAGES

Stariha, Sarah; Wilson, Mahlon Scott; LaManna, Jacob M.; ...

2017-08-24

Proton membrane exchange fuel cells (PEMFCs) have the potential to be long term backup power sources with a startup time on the order of seconds. Water management is the key issue in being able to successfully store PEMFCs for extended periods of time. In this work custom made PEMFCs were humidified at various relative humidities (%RH) and subsequently stored for different lengths of time. The fuel cell’s water content was then imaged at the National Institute of Standards and Technology (NIST) neutron imaging facility. In conclusion, the cells’ startup performances were measured simulating quick startup conditions to define the effectmore » of different water distributions.« less

Determining Water Content and Distribution in PEMFCs to Predict Aging While in Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stariha, Sarah; Wilson, Mahlon Scott; LaManna, Jacob M.

Proton membrane exchange fuel cells (PEMFCs) have the potential to be long term backup power sources with a startup time on the order of seconds. Water management is the key issue in being able to successfully store PEMFCs for extended periods of time. In this work custom made PEMFCs were humidified at various relative humidities (%RH) and subsequently stored for different lengths of time. The fuel cell’s water content was then imaged at the National Institute of Standards and Technology (NIST) neutron imaging facility. In conclusion, the cells’ startup performances were measured simulating quick startup conditions to define the effectmore » of different water distributions.« less

Carbon composite bipolar plate for high-temperature proton exchange membrane fuel cells (HT-PEMFCs)

NASA Astrophysics Data System (ADS)

Lee, Dongyoung; Lee, Dai Gil

2016-09-01

A carbon/epoxy composite bipolar plate is an ideal substitute for the brittle graphite bipolar plate for lightweight proton exchange membrane fuel cells (PEMFCs) because of its high specific strength and stiffness. However, conventional carbon/epoxy composite bipolar plates are not applicable for high-temperature PEMFCs (HT-PEMFCs) because these systems are operated at higher temperatures than the glass transition temperatures of conventional epoxies. Therefore, in this study, a cyanate ester-modified epoxy is adopted for the development of a carbon composite bipolar plate for HT-PEMFCs. The composite bipolar plate with exposed surface carbon fibers is produced without any surface treatments or coatings to increase the productivity and is integrated with a silicone gasket to reduce the assembly cost. The developed carbon composite bipolar plate exhibits not only superior electrical properties but also high thermo-mechanical properties. In addition, a unit cell test is performed, and the results are compared with those of the conventional graphite bipolar plate.

Block Copolymers for Alkaline Fuel Cell Membrane Materials

DTIC Science & Technology

2014-07-30

temperature fuel cells including proton exchange membrane fuel cell ( PEMFC ) and alkaline fuel cell (AFC) with operation temperature usually lower than 120...advantages over proton exchange membrane fuel cells ( PEMFCs ) resulting in the popularity of AFCs in the US space program.[8-11] The primary benefit AFC...offered over PEMFC is better electrochemical kinetics on the anode and cathode under the alkaline environment, which results in the ability to use

COLLABORATIVE RESEARCH AND DEVELOPMENT (CR&D) Delivery Order 0067: Molecular Simulations for Hydrated Polymer Fuel Membranes

DTIC Science & Technology

2007-11-01

proton transfer. 1. INTRODUCTION While polymer electrolyte membrane fuel cells ( PEMFCs ) hold out the possibility for providing several important...Among the broader aims of the research is to develop PEMFC systems which can operate at higher temperatures than presently achievable while still...efforts have provided insight into the mechanisms which enable proton conduction in PEMFCs . Hydrated membranes are two-phase systems, an

Cationic Polymers Developed for Alkaline Fuel Cell Applications

DTIC Science & Technology

2015-01-20

into five categories: proton exchange membrane fuel cell ( PEMFC ), alkaline fuel cell (AFC), molten carbonate fuel cell (MCFC), solid oxide fuel...SOFC and PAFC belong to high temperature fuel cell, which can be applied in stationary power generation. PEMFC and AFC belong to low temperature fuel...function of the polymer electrolyte is to serve as electrolyte to transport ions between electrodes. PEMFC uses a polymer as electrolyte and works

Hawaii Energy and Environmental Technologies (HEET) Initiative

DTIC Science & Technology

2009-05-01

current density measured in a PEM fuel cell ( PEMFC ) represents the average of the local reaction rates. Depending on cell design and operating...loss mechanisms determine the spatial and overall performance of a PEMFC : activation, concentration, ohmic, and mass transfer losses. Activation losses...distribution of these various losses in a PEMFC using a six-channel serpentine flow-field. Voltage losses were attributed to each of the mechanisms at each

Development of the anode bipolar plate/membrane assembly unit for air breathing PEMFC stack using silicone adhesive bonding

NASA Astrophysics Data System (ADS)

Kim, Minkook; Lee, Dai Gil

2016-05-01

Polymer electrolyte membrane fuel cells (PEMFC) exhibit a wide power range, low operating temperature, high energy density and long life time. These advantages favor PEMFC for applications such as vehicle power sources, portable power, and backup power applications. With the push towards the commercialization of PEMFC, especially for portable power applications, the overall balance of plants (BOPs) of the systems should be minimized. To reduce the mass and complexity of the systems, air-breathing PEMFC stack design with open cathode channel configuration is being developed. However, the open cathode channel configuration incurs hydrogen leakage problem. In this study, the bonding strength of a silicon adhesive between the Nafion membrane and the carbon fiber/epoxy composite bipolar plate was measured. Then, an anode bipolar plate/membrane assembly unit which was bonded with the silicone adhesive was developed to solve the hydrogen leakage problem. The reliability of the anode bipolar plate/membrane assembly unit was estimated under the internal pressure of hydrogen by the FE analysis. Additionally, the gas sealability of the developed air breathing PEMFC unit cell was experimentally measured. Finally, unit cell performance of the developed anode bipolar plate/membrane assembly unit was tested and verified under operating conditions without humidity and temperature control.

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Chhina, H.; Campbell, S.; Kesler, O.

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H 2SO 4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Lulu; Su, Dong; Zhu, Shangqian

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

A noble metal-free proton-exchange membrane fuel cell based on bio-inspired molecular catalysts† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03774j Click here for additional data file.

PubMed Central

Tran, P. D.; Morozan, A.; Archambault, S.; Heidkamp, J.; Chenevier, P.; Dau, H.; Fontecave, M.

2015-01-01

Hydrogen is a promising energy vector for storing renewable energies: obtained from water-splitting, in electrolysers or photoelectrochemical cells, it can be turned back to electricity on demand in fuel cells (FCs). Proton exchange membrane (PEM) devices with low internal resistance, high compactness and stability are an attractive technology optimized over decades, affording fast start-up times and low operating temperatures. However, they rely on the powerful catalytic properties of noble metals such as platinum, while lower cost, more abundant materials would be needed for economic viability. Replacing these noble metals at both electrodes has long proven to be a difficult task, so far incompatible with PEM technologies. Here we take advantage of newly developed bio-inspired molecular H2 oxidation catalysts and noble metal-free O2-reducing materials, to fabricate a noble metal-free PEMFC, with an 0.74 V open circuit voltage and a 23 μW cm–2 output power under technologically relevant conditions. X-ray absorption spectroscopy measurements confirm that the catalysts are stable and retain their structure during turnover. PMID:29142673

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

DOE PAGES

Zhang, Lulu; Su, Dong; Zhu, Shangqian; ...

2016-04-26

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Quantitative Biofractal Feedback Part II ’Devices, Scalability & Robust Control’

DTIC Science & Technology

2008-05-01

in the modelling of proton exchange membrane fuel cells ( PEMFC ) may work as a powerful tool in the development and widespread testing of alternative...energy sources in the next decade [9], where biofractal controllers will be used to control these complex systems. The dynamic model of PEMFC , is...dynamic response of the PEMFC . In the Iftukhar model, the fuel cell is represented by an equivalent circuit, whose components are identified with

A Hybrid Approach to Tactical Vehicles

DTIC Science & Technology

2011-09-01

membrane fuel cell ( PEMFC ), molten carbonate fuel cell (MCFC), solid oxide fuel cell (SOFC), phosphoric acid fuel cell (PAFC), alkaline fuel cell (AFC...and the direct methanol fuel cell (DMFC) (Ehsani, Gao, & Emadi, 2010). Of the six major types of fuel cells; the PEMFC , SOFC, and AFC are... PEMFC (21st Century Truck Program, 2000). There are a number of advantages of using a fuel cell as the primary power source for a vehicle. All fuel

Cooling System Design for PEM Fuel Cell Powered Air Vehicles

DTIC Science & Technology

2010-06-18

Research Laboratory (NRL) has developed a proton exchange membrane fuel cell ( PEMFC ) powered unmanned air vehicle (UAV) called the Ion Tiger. The Ion Tiger...to design a cooling system for the Ion Tiger and investigate cooling approaches that may be suitable for future PEMFC powered air vehicles. The...modifications) to other PEMFC systems utilizing a CHE for cooling. 18-06-2010 Memorandum Report Unmanned Air Vehicle UAV Fuel cell PEM Cooling Radiator January

Modeling and Optimization of Renewable and Hybrid Fuel Cell Systems for Space Power and Propulsion

DTIC Science & Technology

2010-11-14

For that the project achieved: the optimization of SOFC and PEMFC internal structure and external shape under a volume constraint; an initial set of...subcomponent models for regenerative, renewable fuel cell system (RFC); the integration of PEMFC into RFC systems were developed; power electronic...with the same objectives and goals but using a PEMFC regenerative system instead. This research group studied and published on the optimization and

Polyarylenethioethersulfone Membranes for Fuel Cells (Postprint)

DTIC Science & Technology

2007-09-01

2007. 0013-4651/2007/1549/B960/9/$20.00 © The Electrochemical SocietyProton exchange membrane fuel cells PEMFCs are an attrac- tive power source...DuPont have become the commercially available standard in PEMFC technology.3,4 Nafion membranes have a polytetrafluoro- ethylene PTFE backbone, which...Inc. were used as anode and cathode gas diffusion layers to fabricate MEAs. Single-cell test (H- PEMFC ).— MEAs were positioned in a single-cell fixture

Preliminary Design of an Autonomous Underwater Vehicle Using Multi-Objective Optimization

DTIC Science & Technology

2014-03-01

fuel cell PC propulsive coefficient PEMFC proton exchange membrane fuel cell PHP propulsive horsepower PO Pareto optimal PSO particle swarm...membrane fuel cell ( PEMFC ), molten carbonate fuel cell (MCFC), solid oxide fuel cell (SOFC) and direct and indirect methanol fuel cell (DMFC). Figure...of fuel cells in depth, I will note that PEMFCs are smaller and have a lower operating temperature compared to the other types. Those are the main

Electrochemically Promoted Organic Isomerization Reactions at Polymer Electrolyte Fuel Cell Cathodes

DTIC Science & Technology

2011-01-04

fuel cells ( PEMFCs ) incorporate an ionomer membrane (e.g., Nafion 117) for support of electro- catalytic layers and proton conduction between the...central to PEMFC electrocatalysis. For example, a spin coated Nafion layer on polycrystalline Pt enhances electrocatalysis.7,8 Little is known about...CO Poisoning Effect in PEMFCs Operational at Temperatures up to 200°C. Journal of the Electrochemical Society, 2003. 150(12): p. A1599-A1605. 21

Performance comparison of two fuel cell hybrid buses with different powertrain and energy management strategies

NASA Astrophysics Data System (ADS)

Ouyang, Minggao; Xu, Liangfei; Li, Jianqiu; Lu, Languang; Gao, Dawei; Xie, Qicheng

In order to assess the influences of different powertrain structures and energy management strategies on the performance of hybrid fuel cell buses (FCB), two buses (FCB A and FCB B) were constructed with a "energy hybrid structure" and "power hybrid structure", respectively. Different energy management strategies were investigated based on analysis of the two systems. And the two buses were compared with each other in a bus cycle and constant speed testing. The Polymer Electrolyte Membrane Fuel Cell (PEMFC) in FCB A showed an advantage in fuel economy for it worked usually in the high efficient range of the PEMFC engine. The hydrogen consumption rate in the cycle testing was 7.9 kg/100 km and 9.8 kg/100 km for FCB A and FCB B, and in the 40 kmph constant speed testing it was 3.3 kg/100 km and 4.0 kg/100 km, respectively. The fuel economy could be improved when the hydrogen and air supply subsystems are optimized and controlled with an advanced algorithm. It could also benefit from a braking energy regeneration system. Compared with FCB A, the PEMFC in FCB B worked under unfavorable operation conditions because its working range was comparatively wide, and the power changing rate was relatively large from a statistical point of view, which resulted in performance recession of the PEMFC in FCB B. After a mileage of 7000 km, the output power of the PEMFC in FCB B was reduced by 10%, compared with 2.4% in FCB A. An advanced energy management strategy is necessary to split the power between the PEMFC and a battery suitable for long durability of a PEMFC.

TechSolutions 11: An Introduction to Power and Energy

DTIC Science & Technology

2009-01-01

facilitate ionic conduction under hydrated conditions. The operating temperature for PEMFCs is relatively cool (70°C). The reactions on the anode and...cathode side of the FC are the same as those shown for PAFCs. Direct methanol fuel cells (DMFCs) are a subset of PEMFCs . These FCs utilize the same...an electrically E58 The AMMTIAC Quarterly, Volume 4, Number 1 Figure 7. Diagram of a PEMFC .[47] 1 Hydrogen fuel is channeled through field flow

Conceptual Design Tool for Fuel-Cell Powered Micro Air Vehicles

DTIC Science & Technology

2010-03-01

Electrolyte Membrane PEMFC PEM Fuel Cell RAM Rapid Aircraft Modeler R/C Radio Controlled RMFC Reformed Methanol Fuel Cell SBIR Small Business...of rechargeable batteries, the Proton Exchange Membrane Fuel Cell ( PEMFC ) is only limited by the amount of hydrogen it can store, and can be...of fuel cells within MAVs through the creation of the Hornet. This slightly heavier, 380 g MAV integrated a 10 W PEMFC into the wing surface for a

Durability and Performance of Polystyrene-b-Poly(vinylbenzyl trimethylammonium) Diblock Copolymer and Equivalent Blend Anion Exchange Membranes

DTIC Science & Technology

2015-01-01

requiring circulation of the electrolyte to filter out the carbonate solids. The superior power density of proton exchange membrane fuel cells ( PEMFC ...without requir- ing a CO2 free oxidant stream, prevented commercial develop- ment of the liquid AFC, allowing PEMFCs to dominate low temperature fuel...cell research and development. PEMFCs employ a solid acidic polymer to transport protons from anode to cathode. PEMs have been researched heavily the

Synthesis and Structure-Conductivity Relationship of Polystyrene-block-Poly(vinyl benzyl trimethylammonium) for Alkaline Anion Exchange Membrane Fuel Cells

DTIC Science & Technology

2012-01-01

Proton exchange membrane fuel cells ( PEMFCs ), which convert chemical energy to electrical energy through redox reactions, have been developed as...platinum)-based electrocata- lysts, the commercialization of PEMFCs is still limited. Addi- tionally, oxygen reduction and fuel (hydrogen or alcohol) oxi...These are serious obstacles to the extensive adoption of PEMFCs as energy devices.4 An alkaline fuel cell (AFC) uses potassium hydroxide as a liq- uid

A High Performance H2-Cl2 Fuel Cell for Space Power Applications

NASA Technical Reports Server (NTRS)

Anderson, Everett B.; Taylor, E. Jennings; Wilemski, Gerald; Gelb, Alan

1993-01-01

NASA has numerous airborne/spaceborne applications for which high power and energy density power sources are needed. The proton exchange membrane fuel cell (PEMFC) is an attractive candidate for such a power source. PEMFC's offer many advantages for airborne/spaceborne applications. They have high power and energy densities, convert fuel to electrical power with high efficiency at both part and full load, and can rapidly startup and shutdown. In addition, PEMFC's are lightweight and operate silently. A significant impediment to the attainment of very high power and energy densities by PEMFC's is their current exclusive reliance on oxygen as the oxidant. Conventional PEMFC's oxidize hydrogen at the anode and reduce oxygen at the cathode. The electrode kinetics of oxygen reduction are known to be highly irreversible, incurring large overpotential losses. In addition, the modest open circuit potential of 1.2V for the H2-O2 fuel cell is unattainable due to mixed potential effects at the oxygen electrode. Because of the high overpotential losses, cells using H2 and O2 are capable of achieving high current densities only at very low cell voltages, greatly curtailing their power output. Based on experimental work on chlorine reduction in a gas diffusion electrode, we believe significant increases in both the energy and power densities of PEMFC systems can be achieved by employing chlorine as an alternative oxidant.

Experimental and numerical studies of micro PEM fuel cell

NASA Astrophysics Data System (ADS)

Peng, Rong-Gui; Chung, Chen-Chung; Chen, Chiun-Hsun

2011-10-01

A single micro proton exchange membrane fuel cell (PEMFC) has been produced using Micro-electromechanical systems (MEMS) technology with the active area of 2.5 cm2 and channel depth of about 500 µm. A theoretical analysis is performed in this study for a novel MEMS-based design of amicro PEMFC. Themodel consists of the conservation equations of mass, momentum, species and electric current in a fully integrated finite-volume solver using the CFD-ACE+ commercial code. The polarization curves of simulation are well correlated with experimental data. Three-dimensional simulations are carried out to treat prediction and analysis of micro PEMFC temperature, current density and water distributions in two different fuel flow rates (15 cm3/min and 40 cm3/min). Simulation results show that temperature distribution within the micro PEMFC is affected by water distribution in the membrane and indicate that low and uniform temperature distribution in the membrane at low fuel flow rates leads to increased membrane water distribution and obtains superior micro PEMFC current density distribution under 0.4V operating voltage. Model predictions are well within those known for experimental mechanism phenomena.

Pumpless thermal management of water-cooled high-temperature proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Song, Tae-Won; Choi, Kyoung-Hwan; Kim, Ji-Rae; Yi, Jung S.

2011-05-01

Proton exchange membrane fuel cells (PEMFCs) have been considered for combined heat and power (CHP) applications, but cost reduction has remained an issue for commercialization. Among various types of PEMFC, the high-temperature (HT) PEMFC is gaining more attention due to the simplicity of the system, that will make the total system cost lower. A pumpless cooling concept is introduced to reduce the number of components of a HT PEMFC system even further and also decrease the parasitic power required for operating the system. In this concept, water is used as the coolant, and the buoyancy force caused by the density difference between vapour and liquid when operated above boiling temperate is utilized to circulate the coolant between the stack and the cooling device. In this study, the basic parameters required to design the cooling device are discussed, and the stable operation of the HT PEMFC stack in both the steady-state and during transient periods is demonstrated. It found that the pumpless cooling method provides more uniform temperature distribution within the stack, regardless of the direction of coolant flow.

Alkaline sodium borohydride gel as a hydrogen source for PEMFC or an energy carrier for NaBH 4-air battery

NASA Astrophysics Data System (ADS)

Liu, B. H.; Li, Z. P.; Chen, L. L.

In this preliminary study, we tried to use sodium polyacrylate as the super absorbent polymer to form alkaline NaBH 4 gel and explored its possibilities for borohydride hydrolysis and borohydride electro-oxidation. It was found that the absorption capacity of sodium polyacrylate decreased with increasing NaBH 4 concentration. The formed gel was rather stable in the sealed vessel but tended to slowly decompose in open air. Hydrogen generation from the gel was carried out using CoCl 2 catalyst precursor solutions. Hydrogen generation rate from the alkaline NaBH 4 gel was found to be higher and impurities in hydrogen were less than that from the alkaline NaBH 4 solution. The NaBH 4 gel also successfully powered a NaBH 4-air battery.

Separation Method for Oxygen Mass Transport Coefficient in Two Phase Porous Air Electrodes - Transport in Gas and Solid Polymer or Liquid Electrolyte Phases

DTIC Science & Technology

2013-08-06

of the problem studied Proton exchange membrane fuel cells ( PEMFCs ) are the most promising candidate systems for alternative electricity...characteristic. The limiting current can be used as a tool to study mass transport phenomena in PEMFC because it can provide experimental data for the...coefficient for PEMFCs under in situ conditions based on the galvanostatic discharge of a cell with an interrupted reactant supply. The results indicated

Energy Conversion Efficiency Potential for Forward-Deployed Generation Using Direct Carbon Fuel Cells

DTIC Science & Technology

2012-05-01

fuel cells vs. DCFCs. PEMFC PAFC MCFC SOFC DCFC Electrolyte Polymer Phosphoric acid Molten car- bonate salt Ceramic Fused KNO3 Operating...air O2/air CO2/O2/air O2/air Humidified air Efficiency (Higher Heating Value [HHV]) 30–35% 40–50% 50–60% 45–55% 80% PEMFC : Proton Exchange... PEMFC proton-exchange membrane fuel cell SOFC solid oxide fuel cell SRI Statistical Research, Inc. TR technical report TRL technology readiness level

Design of Conventional Submarines with Advanced Air Independent Propulsion Systems and Determination of Corresponding Theater-Level Impacts

DTIC Science & Technology

2010-01-01

rescue vehicle e: Error term ft: Feet HDW: Howaldtswerke- Deutsche Werft GmbH PEMFC : Proton exchange membrane fuel cells IR: Indiscretion rate/ratio...engines &Rankine cycle power plants &Closed cycle engines A PEMFC AIP system is fitted in the 212 class of submarines that German shipbuilders How...bines a conventional system consisting of a diesel engine and a lead acid battery, with the PEMFC AIP system used for slow, silent cruising. The AIP

Proton exchange membrane fuel cells for space and electric vehicle applications: From basic research to technology development

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Mukerjee, Sanjeev; Parthasarathy, A.; CesarFerreira, A.; Wakizoe, Masanobu; Rho, Yong Woo; Kim, Junbom; Mosdale, Renaut A.; Paetzold, Ronald F.; Lee, James

1994-01-01

The proton exchange membrane fuel cell (PEMFC) is one of the most promising electrochemical power sources for space and electric vehicle applications. The wide spectrum of R&D activities on PEMFC's, carried out in our Center from 1988 to date, is as follows (1) Electrode Kinetic and Electrocatalysis of Oxygen Reduction; (2) Optimization of Structures of Electrodes and of Membrane and Electrode Assemblies; (3) Selection and Evaluation of Advanced Proton Conducting Membranes and of Operating Conditions to Attain High Energy Efficiency; (4) Modeling Analysis of Fuel Cell Performance and of Thermal and Water Management; and (5) Engineering Design and Development of Multicell Stacks. The accomplishments on these tasks may be summarized as follows: (1) A microelectrode technique was developed to determine the electrode kinetic parameters for the fuel cell reactions and mass transport parameters for the H2 and O2 reactants in the proton conducting membrane. (2) High energy efficiencies and high power densities were demonstrated in PEMFCs with low platinum loading electrodes (0.4 mg/cm(exp 2) or less), advanced membranes and optimized structures of membrane and electrode assemblies, as well as operating conditions. (3) The modeling analyses revealed methods to minimize mass transport limitations, particularly with air as the cathodic reactant; and for efficient thermal and water management. (4) Work is in progress to develop multi-kilowatt stacks with the electrodes containing low platinum loadings.

Fuel Cell Stack Testing and Durability in Support of Ion Tiger UAV

DTIC Science & Technology

2010-06-02

N00173-08-2-C008 specified. In June 2008, the first M250 stack 242503 data were incorporated into the PEMFC system model as a look-up data table...control and operational model which implements the operational strategy by controlling the power from the PEMFC systems and battery pack for a total...Outputs PEMFC System Outputs <~~>*<*,yrx**i~yc*r»>r-’+**^^ FCS_P«wi_Dwn«l (W) 10 15 20 25 BfOfumon PCM« Cwnind Wi ) 5 10 15

Wavelet-Transform-Based Power Management of Hybrid Vehicles with Multiple On-board Energy Sources Including Fuel Cell, Battery and Ultracapacitor

DTIC Science & Technology

2008-09-12

considered to be promising for application as distributed generation sources due to high efficiency and compactness [1-2], [21-24]. The PEMFC is...also a primary candidate for environment-friendly vehicles. The nomenclatures of the PEMFC are as follows: B , C : Constants to calculate the...0 O H H-O H-O 1 2 N I q q r r FU = (10) The block diagram of the PEMFC model based on the above equations is shown in Fig

New, efficient and viable system for ethanol fuel utilization on combined electric/internal combustion engine vehicles

NASA Astrophysics Data System (ADS)

Sato, André G.; Silva, Gabriel C. D.; Paganin, Valdecir A.; Biancolli, Ana L. G.; Ticianelli, Edson A.

2015-10-01

Although ethanol can be directly employed as fuel on polymer-electrolyte fuel cells (PEMFC), its low oxidation kinetics in the anode and the crossover to the cathode lead to a substantial reduction of energy conversion efficiency. However, when fuel cell driven vehicles are considered, the system may include an on board steam reformer for converting ethanol into hydrogen, but the hydrogen produced contains carbon monoxide, which limits applications in PEMFCs. Here, we present a system consisting of an ethanol dehydrogenation catalytic reactor for producing hydrogen, which is supplied to a PEMFC to generate electricity for electric motors. A liquid by-product effluent from the reactor can be used as fuel for an integrated internal combustion engine, or catalytically recycled to extract more hydrogen molecules. Power densities comparable to those of a PEMFC operating with pure hydrogen are attained by using the hydrogen rich stream produced by the ethanol dehydrogenation reactor.

Study and performances analysis of fuel cell assisted vector control variable speed drive system used for electric vehicles

NASA Astrophysics Data System (ADS)

Pachauri, Rupendra Kumar; Chauhan, Yogesh K.

2017-02-01

This paper is a novel attempt to combine two important aspects of fuel cell (FC). First, it presents investigations on FC technology and its applications. A description of FC operating principles is followed by the comparative analysis of the present FC technologies together with the issues concerning various fuels. Second, this paper also proposes a model for the simulation and performances evaluation of a proton exchange membrane fuel cell (PEMFC) generation system. Furthermore, a MATLAB/Simulink-based dynamic model of PEMFC is developed and parameters of FC are so adjusted to emulate a commercially available PEMFC. The system results are obtained for the PEMFC-driven adjusted speed induction motor drive (ASIMD) system, normally used in electric vehicles and analysis is carried out for different operating conditions of FC and ASIMD system. The obtained results prove the validation of system concept and modelling.

Nanotechnology for environmentally sustainable electromobility

NASA Astrophysics Data System (ADS)

Ellingsen, Linda Ager-Wick; Hung, Christine Roxanne; Majeau-Bettez, Guillaume; Singh, Bhawna; Chen, Zhongwei; Whittingham, M. Stanley; Strømman, Anders Hammer

2016-12-01

Electric vehicles (EVs) powered by lithium-ion batteries (LIBs) or proton exchange membrane hydrogen fuel cells (PEMFCs) offer important potential climate change mitigation effects when combined with clean energy sources. The development of novel nanomaterials may bring about the next wave of technical improvements for LIBs and PEMFCs. If the next generation of EVs is to lead to not only reduced emissions during use but also environmentally sustainable production chains, the research on nanomaterials for LIBs and PEMFCs should be guided by a life-cycle perspective. In this Analysis, we describe an environmental life-cycle screening framework tailored to assess nanomaterials for electromobility. By applying this framework, we offer an early evaluation of the most promising nanomaterials for LIBs and PEMFCs and their potential contributions to the environmental sustainability of EV life cycles. Potential environmental trade-offs and gaps in nanomaterials research are identified to provide guidance for future nanomaterial developments for electromobility.

Electrochemical reduction of toluene to methylcyclohexane for use as an energy carrier

NASA Astrophysics Data System (ADS)

Matsuoka, Koji; Miyoshi, Kota; Sato, Yasushi

2017-03-01

The electrochemical reduction of liquid toluene to methylcyclohexane (MCH) was investigated using a membrane electrode assembly (MEA) and high active-area catalysts commonly used in proton exchange membrane fuel cells (PEMFC). The current density on Pt/C was higher than on PtRu/C, which was comparable to that of alkaline water electrolysis. The potential of hydrogen evolution was shifted negatively by the presence of toluene and MCH. Therefore, the toluene reduction reaction was almost perfectly separated from the hydrogen evolution reaction. Toluene was perfectly reduced to MCH at around 0 V vs. RHE on PtRu/C and no by-products were detected in the solutions after electrolysis. MCH was produced at a Faradaic efficiency of more than 96% by carefully keeping the potential above -30 mV vs. RHE. Through this electrolytic process, we were able to reduce the concentration of toluene from 100% to 7.6%.

An in situ carbonization-replication method to synthesize mesostructured WO3/C composite as nonprecious-metal anode catalyst in PEMFC.

PubMed

Cui, Xiangzhi; Hua, Zile; Wei, Chenyang; Shu, Zhu; Zhang, Liangxia; Chen, Hangrong; Shi, Jianlin

2013-02-01

A meostructured WO(3)/C composite with crystalline framework and high electric conductivity has been synthesized by a new in situ carbonization-replication route using the block copolymer (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol)) present in situ in the pore channels of mesoporous silica template as carbon source. X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, thermogravimetry differential thermal analysis, and N(2) adsorption techniques were adopted for the structural characterization. Cyclic voltammetry, chronoamperometry, and single-cell test for hydrogen electrochemical oxidation were adopted to characterize the electrochemical activities of the mesoporous WO(3)/C composite. The carbon content and consequent electric conductivity of these high-surface-area (108-130 m(2) g(-1)) mesostructured WO(3)/C composite materials can be tuned by variation of the duration of heat treatment, and the composites exhibited high and stable electrochemical catalytic activity. The single-cell test results indicated that the mesostructured WO(3)/C composites showed clear electrochemical catalytic activity toward hydrogen oxidation at 25 °C, which makes them potential non-precious-metal anode catalysts in proton exchange membrane fuel cell. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low platinum loading for high temperature proton exchange membrane fuel cell developed by ultrasonic spray coating technique

NASA Astrophysics Data System (ADS)

Su, Huaneng; Jao, Ting-Chu; Barron, Olivia; Pollet, Bruno G.; Pasupathi, Sivakumar

2014-12-01

This paper reports use of an ultrasonic-spray for producing low Pt loadings membrane electrode assemblies (MEAs) with the catalyst coated substrate (CCS) fabrication technique. The main MEA sub-components (catalyst, membrane and gas diffusion layer (GDL)) are supplied from commercial manufacturers. In this study, high temperature (HT) MEAs with phosphoric acid (PA)-doped poly(2,5-benzimidazole) (AB-PBI) membrane are fabricated and tested under 160 °C, hydrogen and air feed 100 and 250 cc min-1 and ambient pressure conditions. Four different Pt loadings (from 0.138 to 1.208 mg cm-2) are investigated in this study. The experiment data are determined by in-situ electrochemical methods such as polarization curve, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The high Pt loading MEA exhibits higher performance at high voltage operating conditions but lower performances at peak power due to the poor mass transfer. The Pt loading 0.350 mg cm-2 GDE performs the peak power density and peak cathode mass power to 0.339 W cm-2 and 0.967 W mgPt-1, respectively. This work presents impressive cathode mass power and high fuel cell performance for high temperature proton exchange membrane fuel cells (HT-PEMFCs) with low Pt loadings.

Operando fuel cell spectroscopy

NASA Astrophysics Data System (ADS)

Kendrick, Ian Michael

The active state of a catalyst only exists during catalysis (1) provided the motivation for developing operando spectroscopic techniques. A polymer electrolyte membrane fuel cell (PEMFC) was designed to interface with commercially available instruments for acquisition of infrared spectra of the catalytic surface of the membrane electrode assembly (MEA) during normal operation. This technique has provided insight of the complex processes occurring at the electrode surface. Nafion, the solid electrolyte used in most modern-day polymer electrolyte membrane fuel cells (PEMFC), serves many purposes in fuel cell operation. However, there is little known of the interface between Nafion and the electrode surface. Previous studies of complex Stark tuning curves of carbon monoxide on the surface of a platinum electrode were attributed the co-adsorption of bisulfite ions originating from the 0.5M H2SO4 electrolyte used in the study(2). Similar tuning curves obtained on a fuel cell MEA despite the absence of supplemental electrolytes suggest the adsorption of Nafion onto platinum (3). The correlation of spectra obtained using attenuated total reflectance spectroscopy (ATR) and polarization modulated IR reflection-absorption spectroscopy (PM-IRRAS) to a theoretical spectrum generated using density functional theory (DFT) lead to development of a model of Nafion and platinum interaction which identified participation of the SO3- and CF3 groups in Nafion adsorption. The use of ethanol as a fuel stream in proton exchange membrane fuel cells provides a promising alternative to methanol. Relative to methanol, ethanol has a greater energy density, lower toxicity and can be made from the fermentation of biomass(4). Operando IR spectroscopy was used to study the oxidation pathway of ethanol and Stark tuning behavior of carbon monoxide on Pt, Ru, and PtRu electrodes. Potential dependent products such as acetaldehyde, acetic acid and carbon monoxide are identified as well as previously unobserved peaks corresponding to adsorbed ethanol. A modification to the operando fuel cell design allowed for acquisition of Raman spectra. A confocal Raman microscope enabled characterization of the MEA through depth profiling. The potential dependent peaks of an Fe-N x/C catalyst were identified and compared to the theoretical spectra of the proposed active sites. It was determined that oxygen adsorbed onto iron/iron oxide carbon nanostructures were responsible for the experimentally obtained peaks. This finding was supported by additional Raman studies carried out on a catalyst with these active sites removed through peroxide treatments. 1 Topsoe, H., Developments in operando studies and in situ characterization of heterogeneous catalysts. Journal of Catalysis, 2003. 216(1-2): p. 155-164. 2 Stamenkovic, V., et al., Vibrational properties of CO at the Pt(111)-solution interface: the anomalous stark-tuning slope. Journal of Physical Chemistry B, 2005. 109(2): p. 678-680. 3 Kendrick, I., et al., Elucidating the Ionomer-Electrified Metal Interface. J. Am. Chem. Soc., 2010. 132(49): p. 17611-17616. 4 Lamy, C. and Leger, J.M., FUEL-CELLS - APPLICATION TO ELECTRIC VEHICLES. Journal De Physique Iv, 1994. 4(C1): p. 253-281.

Molten Carbonate Fuel Cell Operation With Dual Fuel Flexibility

DTIC Science & Technology

2007-10-01

electrolyte membrane fuel cell ( PEMFC ). At the higher operating temperature, fuel reforming of natural gas can occur internally, eliminating the need...oxygen PAFC Phosphoric Acid Fuel Cell PEMFC Polymer Electrolyte Membrane Fuel Cell PDS Propane Desulfurization System ppm parts per million psig

Fuel Cells Using the Protic Ionic Liquid and Rotator Phase Solid Electrolyte Principles

DTIC Science & Technology

2008-02-13

Talk “High temperature Polymer Electrolyte Membrane Fuel Cells (HT- PEMFCs ) for Portable Power in Large-Scale Energy Storage Devices”, Paper Number 195...Membrane Fuel Cells (HT- PEMFCs ) for Portable Power in Large-Scale Energy Storage Devices”, Paper Number 195, 212th Meeting of the Electrochemical

History of Fuel Cell R&D at Fort Belvoir, Virginia

DTIC Science & Technology

2008-04-01

PEMFC but BOP is reduced. In many respects it behaves like a PAFC. MOLTEN CARBONATE FUEL CELL (MCFC) The MCFC operates at high temperature...clean up as required by the PEMFC . It can utilize air cooling without concern electrolyte control which greatly eases BOP issues. The PAFC is highly

ElectroCat: DOE's approach to PGM-free catalyst and electrode R&D

DOE PAGES

Thompson, Simon T.; Wilson, Adria R.; Zelenay, Piotr; ...

2018-02-03

The successful development of high-performance, durable platinum group metal-free (PGM-free) electrocatalysts and electrodes for polymer electrolyte membrane fuel cells (PEMFCs) will ultimately improve the cost-competiveness of fuel cells in a wide range of applications. This is considered to be a critical development especially for automotive fuel cell applications in order to bring the system cost of an automotive fuel cell system down to the $30/kW cost target set by the U.S. Department of Energy (DOE). The platinum group metal (PGM) electrocatalysts are a major contributor to the system cost. Addressing the technical challenges to PGM-free electrocatalyst and electrode development, therefore,more » represents one of DOE's most pressing research and development (R&D) priorities. ElectroCat was formed by the DOE as part of the Energy Materials Network (EMN) in early 2016, and shares with other EMN consortia the goal of decreasing the time to market for advanced materials related to clean energy technologies, in the context of increasing U.S. fuel cell electric vehicle (FCEV) manufacturing competitiveness. To accomplish this, the consortium performs core research and development and provides universities and companies streamlined access to the unique, world-class set of tools and expertise relevant to early-stage applied PGM-free catalyst R&D of the member national laboratories. Moreover, ElectroCat fosters a systematic methodology by which prospective catalysts and electrodes are prepared and analyzed rapidly and comprehensively using high-throughput, combinatorial methods. Catalyst discovery is augmented by theory as well as foundational electrocatalysis and materials knowledge at the participating national laboratories. Furthermore, ElectroCat has developed a data sharing framework, requisite of all EMN consortia, for disseminating its findings to the public via a searchable database, to further expedite incorporation of PGM-free electrocatalysts into next-generation fuel cells by advancing the general understanding of the PGM-free electrocatalyst field.« less

ElectroCat: DOE's approach to PGM-free catalyst and electrode R&D

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, Simon T.; Wilson, Adria R.; Zelenay, Piotr

The successful development of high-performance, durable platinum group metal-free (PGM-free) electrocatalysts and electrodes for polymer electrolyte membrane fuel cells (PEMFCs) will ultimately improve the cost-competiveness of fuel cells in a wide range of applications. This is considered to be a critical development especially for automotive fuel cell applications in order to bring the system cost of an automotive fuel cell system down to the $30/kW cost target set by the U.S. Department of Energy (DOE). The platinum group metal (PGM) electrocatalysts are a major contributor to the system cost. Addressing the technical challenges to PGM-free electrocatalyst and electrode development, therefore,more » represents one of DOE's most pressing research and development (R&D) priorities. ElectroCat was formed by the DOE as part of the Energy Materials Network (EMN) in early 2016, and shares with other EMN consortia the goal of decreasing the time to market for advanced materials related to clean energy technologies, in the context of increasing U.S. fuel cell electric vehicle (FCEV) manufacturing competitiveness. To accomplish this, the consortium performs core research and development and provides universities and companies streamlined access to the unique, world-class set of tools and expertise relevant to early-stage applied PGM-free catalyst R&D of the member national laboratories. Moreover, ElectroCat fosters a systematic methodology by which prospective catalysts and electrodes are prepared and analyzed rapidly and comprehensively using high-throughput, combinatorial methods. Catalyst discovery is augmented by theory as well as foundational electrocatalysis and materials knowledge at the participating national laboratories. Furthermore, ElectroCat has developed a data sharing framework, requisite of all EMN consortia, for disseminating its findings to the public via a searchable database, to further expedite incorporation of PGM-free electrocatalysts into next-generation fuel cells by advancing the general understanding of the PGM-free electrocatalyst field.« less

Spontaneous oscillations of cell voltage, power density, and anode exit CO concentration in a PEM fuel cell.

PubMed

Lu, Hui; Rihko-Struckmann, Liisa; Sundmacher, Kai

2011-10-28

The spontaneous oscillations of the cell voltage and output power density of a PEMFC (with PtRu/C anode) using CO-containing H(2) streams as anodic fuels have been observed during galvanostatic operating. It is ascribed to the dynamic coupling of the CO adsorption (poisoning) and the electrochemical CO oxidation (reactivating) processes in the anode chamber of the single PEMFC. Accompanying the cell voltage and power density oscillations, the discrete CO concentration oscillations at the anode outlet of the PEMFC were also detected, which directly confirms the electrochemical CO oxidation taking place in the anode chamber during galvanostatic operating. This journal is © the Owner Societies 2011

A novel method for effective diffusion coefficient measurement in gas diffusion media of polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Yang, Linlin; Sun, Hai; Fu, Xudong; Wang, Suli; Jiang, Luhua; Sun, Gongquan

2014-07-01

A novel method for measuring effective diffusion coefficient of porous materials is developed. The oxygen concentration gradient is established by an air-breathing proton exchange membrane fuel cell (PEMFC). The porous sample is set in a sample holder located in the cathode plate of the PEMFC. At a given oxygen flux, the effective diffusion coefficients are related to the difference of oxygen concentration across the samples, which can be correlated with the differences of the output voltage of the PEMFC with and without inserting the sample in the cathode plate. Compared to the conventional electrical conductivity method, this method is more reliable for measuring non-wetting samples.

3-Dimensional Computational Fluid Dynamics Modeling of Solid Oxide Fuel Cell Using Different Fuels

DTIC Science & Technology

2011-01-01

major types of fuel cells in practice are listed below: Polymer Electrolyte Membrane Fuel Cell ( PEMFC ) Alkaline Fuel cell (AFC) Phosphoric Acid...Material Operating Temperature (oC) Efficiency (%) PEMFC H2, Methanol, Formic Acid Hydrated Organic Polymer < 90 40-50 AFC Pure H2 Aqueous

Neutron Imaging of Lithium Concentration for Validation of Li-Ion Battery State of Charge Estimation

DTIC Science & Technology

2010-12-01

2008: Understanding liq- uid water distribution and removal phenomena in an op- erating pemfc via neutron radiography. Journal of The...2008: Measurement of liq- uid water accumulation in a pemfc with dead-ended an- ode. Journal of The Electrochemical Society, 155 (11), B1168–B1178

Hollow microspheres with a tungsten carbide kernel for PEMFC application.

PubMed

d'Arbigny, Julien Bernard; Taillades, Gilles; Marrony, Mathieu; Jones, Deborah J; Rozière, Jacques

2011-07-28

Tungsten carbide microspheres comprising an outer shell and a compact kernel prepared by a simple hydrothermal method exhibit very high surface area promoting a high dispersion of platinum nanoparticles, and an exceptionally high electrochemically active surface area (EAS) stability compared to the usual Pt/C electrocatalysts used for PEMFC application.

PEMFC catalyst layers: the role of micropores and mesopores on water sorption and fuel cell activity.

PubMed

Soboleva, Tatyana; Malek, Kourosh; Xie, Zhong; Navessin, Titichai; Holdcroft, Steven

2011-06-01

The effects of carbon microstructure and ionomer loading on water vapor sorption and retention in catalyst layers (CLs) of PEM fuel cells are investigated using dynamic vapor sorption. Catalyst layers based on Ketjen Black and Vulcan XC-72 carbon blacks, which possess distinctly different surface areas, pore volumes, and microporosities, are studied. It is found that pores <20 nm diameter facilitate water uptake by capillary condensation in the intermediate range of relative humidities. A broad pore size distribution (PSD) is found to enhance water retention in Ketjen Black-based CLs whereas the narrower mesoporous PSD of Vulcan CLs is shown to have an enhanced water repelling action. Water vapor sorption and retention properties of CLs are correlated to electrochemical properties and fuel cell performance. Water sorption enhances electrochemical properties such as the electrochemically active surface area (ESA), double layer capacitance and proton conductivity, particularly when the ionomer content is very low. The hydrophilic properties of a CL on the anode and the cathode are adjusted by choosing the PSD of carbon and the ionomer content. It is shown that a reduction of ionomer content on either cathode or anode of an MEA does not necessarily have a significant detrimental effect on the MEA performance compared to the standard 30 wt % ionomer MEA. Under operation in air and high relative humidity, a cathode with a narrow pore size distribution and low ionomer content is shown to be beneficial due to its low water retention properties. In dry operating conditions, adequate ionomer content on the cathode is crucial, whereas it can be reduced on the anode without a significant impact on fuel cell performance. © 2011 American Chemical Society

The Effect of K and Acidity of NiW-Loaded HY Zeolite Catalyst for Selective Ring Opening of 1-Methylnaphthalene.

PubMed

Lee, You-Jin; Kim, Eun-Sang; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-05-01

Bi-functional catalysts were prepared using HY zeolites with various SiO2/Al2O3 ratios for acidic function, NiW for metallic function, and K for acidity control. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction was investigated using the prepared bi-functional catalysts with different levels of acidity in a fixed bed reactor system. In NiW/HY catalysts without K addition, the acidity decreased with the SiO2/Al2O3 mole ratio of the HY zeolite. Ni1.1W1.1/HY(12) catalyst showed the highest acidity but slightly lower yields for the selective ring opening than Ni1.1W1.1/HY(30) catalyst. The acidity of the catalyst seemed to play an important role as the active site for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. Catalyst acidity could be controlled between Ni1.1W1.1/HY(12) and Ni1.1W1.1/HY(30) by adding a moderate amount of K to Ni1.1W1.1/HY(12) catalyst. K0.3Ni1.1W1.1/HY(12) catalyst should have the optimum acidity for the selective ring opening. The addition of a moderate amount of K to the NiW/HY catalyst must improve the catalytic performance due to the optimization of catalyst acidity.

Two Catalysts for Selective Oxidation of Contaminant Gases

NASA Technical Reports Server (NTRS)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

Catalyst for selective conversion of synthesis gas and method of making the catalyst

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch (F-T) catalyst, a method of making the catalyst and an F-T process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range. In general, the selective and notably stable catalyst, consists of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of an F-T metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Composite polymer membranes for proton exchange membrane fuel cells operating at elevated temperatures and reduced humidities

NASA Astrophysics Data System (ADS)

Zhang, Tao

Proton Exchange Membrane Fuel Cells (PEMFCs) are the leading candidate in the fuel cell technology due to the high power density, solid electrolyte, and low operational temperature. However, PEMFCs operating in the normal temperature range (60-80°C) face problems including poor carbon monoxide tolerance and heat rejection. The poisoning effect can be significantly relieved by operating the fuel cell at elevated temperature, which also improves the heat rejection and electrochemical kinetics. Low relative humidity (RH) operation is also desirable to simplify the reactant humidification system. However, at elevated temperatures, reduced RH PEMFC performance is seriously impaired due to irreversible water loss from presently employed state-of-the-art polymer membrane, Nafion. This thesis focuses on developing polymer electrolyte membranes with high water retention ability for operation in elevated temperature (110-150°C), reduced humidity (˜50%RH) PEMFCs. One approach is to alter Nafion by adding inorganic particles such as TiO2, SiO2, Zr(HPO 4)2, etc. While the presence of these materials in Nafion has proven beneficial, a reduction or no improvement in the PEMFC performance of Nafion/TiO2 and Nafion/Zr(HPO4)2 membranes is observed with reduced particle sizes or increased particle loadings in Nafion. It is concluded that the PEMFC performance enhancement associated with addition of these inorganic particles was not due to the particle hydrophilicity. Rather, the particle, partially located in the hydrophobic region of the membrane, benefits the cell performance by altering the membrane structure. Water transport properties of some Nafion composite membranes were investigated by NMR methods including pulsed field gradient spin echo diffusion, spin-lattice relaxation, and spectral measurements. Compared to unmodified Nafion, composite membranes materials exhibit longer longitudinal relaxation time constant T1. In addition to the Nafion material, sulfonated styrene-ethylene/butylene-styrene triblock copolymer (sSEBS) was investigated as an alternate membrane candidate. sSEBS was modified through introduction of polymer crosslinks using benzephenone as a photoinitiator and addition of a titania co-phase. A photocrosslinked membrane initially containing 15% benzophenone and 3% titania laminated with a 10 mum Nafion layer was found to produce the best PEMFC performance (120°C, 50%RH).

Cobalt Fischer-Tropsch catalysts having improved selectivity

DOEpatents

Miller, James G.; Rabo, Jule A.

1989-01-01

The promoter(s) Mn oxide or Mn oxide and Zr oxide are added to a cobalt Fischer-Tropsch catalyst combined with the molecular sieve TC-103 or TC-123 such that the resultant catalyst demonstrates improved product selectivity, stability and catalyst life. The improved selectivity is evidenced by lower methane production, higher C5+ yield and increased olefin production.

Neutron Imaging of Lithium Concentration in Battery Pouch Cells

DTIC Science & Technology

2011-06-01

water distribution and removal phenomena in an operating pemfc via neutron radiography,” J. Electrochem. Soc., vol. 155, no. 3, pp. B294–B302, 2008...12] J. B. Siegel, D. A. McKay, A. G. Stefanopoulou, D. S. Hussey, and D. L. Jacobson, “Measurement of liquid water accumulation in a pemfc with dead

A Study on a Prognosis Algorithm for PEMFC Lifetime Prediction based on Durability Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xian; Pisu, Pierluigi; Toops, Todd J

2010-01-01

Of the fuel cells being studied, the proton exchange membrane fuel cell (PEMFC) is viewed as the most promising for transportation. Yet until today, the commercialization of the PEMFC has not been widespread in spite of its large expectation. Poor long term performances or durability, and high production and maintenance costs account for the main reasons. For the final commercialization of fuel cell in transportation field, the durability issue must be addressed, while the costs should be further brought down. In the meantime, health-monitoring and prognosis techniques are of great significance in ensuring the normal operation of the fuel cellmore » and preventing or predicting its likely abrupt and catastrophic failure.« less

A mathematical model for predicting the life of polymer electrolyte fuel cell membranes subjected to hydration cycling

NASA Astrophysics Data System (ADS)

Burlatsky, S. F.; Gummalla, M.; O'Neill, J.; Atrazhev, V. V.; Varyukhin, A. N.; Dmitriev, D. V.; Erikhman, N. S.

2012-10-01

Under typical Polymer Electrolyte Membrane Fuel Cell (PEMFC) fuel cell operating conditions, part of the membrane electrode assembly is subjected to humidity cycling due to variation of inlet gas RH and/or flow rate. Cyclic membrane hydration/dehydration would cause cyclic swelling/shrinking of the unconstrained membrane. In a constrained membrane, it causes cyclic stress resulting in mechanical failure in the area adjacent to the gas inlet. A mathematical modeling framework for prediction of the lifetime of a PEMFC membrane subjected to hydration cycling is developed in this paper. The model predicts membrane lifetime as a function of RH cycling amplitude and membrane mechanical properties. The modeling framework consists of three model components: a fuel cell RH distribution model, a hydration/dehydration induced stress model that predicts stress distribution in the membrane, and a damage accrual model that predicts membrane lifetime. Short descriptions of the model components along with overall framework are presented in the paper. The model was used for lifetime prediction of a GORE-SELECT membrane.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winter, Lea R.; Gomez, Elaine; Yan, Binhang

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Utilizing a Segmented Fuel Cell to Study the Effects of Electrode Coating Irregularities on PEM Fuel Cell Initial Performance

DOE PAGES

Phillips, Adam; Ulsh, Michael; Porter, Jason; ...

2017-04-27

An understanding of the impact of coating irregularities on beginning of life polymer electrolyte fuel cell (PEMFC) performance is essential to develop and establish manufacturing tolerances for its components. Coating irregularities occurring in the fuel cell electrode can either possess acceptable process variations or potentially harmful defects. A segmented fuel cell (SFC) is employed to understand how 100% catalyst reduction irregularities ranging from 0.125 to 1 cm 2 in the cathode electrode of a 50 cm 2 sized cell impact spatial and total cell performance at dry and wet humidification conditions. Here, by analyzing the data in a differential formatmore » the local performance effects of irregularity sizes down to 0.25 cm 2 were detected in the current distribution of the cell. Slight total cell performance impacts, due to irregularity sizes of 0.5 and 1 cm 2, were observed under dry operation and high current densities.« less

Utilizing a Segmented Fuel Cell to Study the Effects of Electrode Coating Irregularities on PEM Fuel Cell Initial Performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, Adam; Ulsh, Michael; Porter, Jason

An understanding of the impact of coating irregularities on beginning of life polymer electrolyte fuel cell (PEMFC) performance is essential to develop and establish manufacturing tolerances for its components. Coating irregularities occurring in the fuel cell electrode can either possess acceptable process variations or potentially harmful defects. A segmented fuel cell (SFC) is employed to understand how 100% catalyst reduction irregularities ranging from 0.125 to 1 cm 2 in the cathode electrode of a 50 cm 2 sized cell impact spatial and total cell performance at dry and wet humidification conditions. Here, by analyzing the data in a differential formatmore » the local performance effects of irregularity sizes down to 0.25 cm 2 were detected in the current distribution of the cell. Slight total cell performance impacts, due to irregularity sizes of 0.5 and 1 cm 2, were observed under dry operation and high current densities.« less

MEMS-based thin-film fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2003-10-28

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Selective Oxidation of n-Hexane by Cu (II) Nanoclusters Supported on Nanocrystalline Zirconia Catalyst.

PubMed

Acharyya, Shankha Shubhra; Ghosh, Shilpi; Adak, Shubhadeep; Singh, Raghuvir; Saran, Sandeep; Bal, Rajaram

2015-08-01

Cu (II) nanoclusters supported on nanocrystalline zirconia catalyst (with size ~15 nm), was prepared by using cationic surfactant cetyltrimethylammonium in a hydrothermal synthesis method. The catalyst was characterized by XRD, XPS, TGA, SEM, TEM, FTIR and ICP-AES. The catalyst was found to be efficient in selective oxidation of n-hexane to 2-hexanol. An n-hexane conversion of 55%, with a 2-hexanol selectivity of 70% was achieved over this catalyst in liquid phase, without the use of any solvent. The catalyst can be reused several times without any significant activity loss.

Tuning Ni-catalyzed CO 2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation

DOE PAGES

Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

2017-10-16

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

A PEMFC hybrid electric vehicle real time control system

NASA Astrophysics Data System (ADS)

Sun, Hongqiao

In recent years, environmental friendly technologies and alternative energy solutions have drawn a lot of public attentions due to global energy crisis and pollution issues. Fuel cell (FC), a technology invented almost at the same time as the internal combustion (IC) engine, is now the focus of the automotive industry again. The fuel cell vehicle (FCV) has zero emission and its efficiency is significantly higher than the conventional IC engine power vehicles. Among a variety of FCV technologies, proton exchange membrane (PEM) FC vehicle appears to be far more attractive and mature. The prototype PEMFC vehicle has been developed and demonstrated to the public by nearly all the major automotive manufacturers in recent years. However, to the interest of the public research, publications and documentations on the PEMFC vehicle technology are rarely available due to its proprietary nature, which essentially makes it a secured technology. This dissertation demonstrates a real world application of a PEMFC hybrid electric vehicle. Through presenting the vehicle design concept, developing the real time control system and generating generic operation principles, this dissertation targets at establishing the public knowledge base on this new technology. A complete PEMFC hybrid electric vehicle design, including vehicle components layout, process flow diagram, real time control system architecture, subsystem structures and control algorithms, is presented in order to help understand the whole vehicle system. The design concept is validated through the vehicle demonstration. Generic operating principles are established along with the validation process, which helps populate this emerging technology. Thereafter, further improvements and future research directions are discussed.

A strain-controlled C2N monolayer membrane for gas separation in PEMFC application

NASA Astrophysics Data System (ADS)

Deng, Shengwei; Hu, Hui; Zhuang, Guilin; Zhong, Xing; Wang, Jianguo

2018-05-01

Ultrathin membranes with controllable pore sizes have great potential to realize high-selectivity gas separation at low energy cost, especially for those mixtures with narrow size distributions. Using a combination of van der Waals-corrected density functional theory (DFT) calculations and molecular dynamics (MD) simulation, we examine the separation ability of biaxial stretched monolayer C2N nanosheets which is applied to the O2 separation from CO/CO2/O2 mixtures in the cathode of proton exchange membrane fuel cells (PEMFC). The DFT calculations show that the diffusion energy barrier for molecules passing through the membrane followed by CO, CO2 and O2 in descending order, and an overall decrease of energy barriers due to the widen the pore size is observed with the increase of applied strains. Furthermore, MD results show that the nanosheet can effectively purify O2 from CO2 and CO with a strain from 8% to 10%. It confirms that the selectivity is determined by the electronic structure related interaction in addition to the kinetic diameter of individual molecules. The O2 permeability is improved progressively with further increase of strain, and small amount of CO2 begins to permeate through the nanosheet at relatively large strain, while the excellent CO isolation is not compromised until the theoretical maximum strain.

High Pt utilization PEMFC electrode obtained by alternative ion-exchange/electrodeposition.

PubMed

Chen, Siguo; Wei, Zidong; Li, Hua; Li, Li

2010-12-14

High Pt utilization PEMFC electrodes were prepared by an alternative ion-exchange/electrodeposition (AIEE) technique. The results demonstrated that the MEA employing an AIEE electrode with a Pt loading of 0.014 mg Pt cm(-2) exhibits performance approximately 2.2 times larger than that employing a conventional Nafion-bonded Pt/C electrode with a same Pt loading.

Design of flexible polyphenylene proton-conducting membrane for next-generation fuel cells.

PubMed

Miyake, Junpei; Taki, Ryunosuke; Mochizuki, Takashi; Shimizu, Ryo; Akiyama, Ryo; Uchida, Makoto; Miyatake, Kenji

2017-10-01

Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in automotive, stationary, and portable applications. Perfluorosulfonic acid (PFSA) ionomers (for example, Nafion) have been the benchmark PEMs; however, several problems, including high gas permeability, low thermal stability, high production cost, and environmental incompatibility, limit the widespread dissemination of PEMFCs. It is believed that fluorine-free PEMs can potentially address all of these issues; however, none of these membranes have simultaneously met the criteria for both high performance (for example, proton conductivity) and durability (for example, mechanical and chemical stability). We present a polyphenylene-based PEM (SPP-QP) that fulfills the required properties for fuel cell applications. The newly designed PEM exhibits very high proton conductivity, excellent membrane flexibility, low gas permeability, and extremely high stability, with negligible degradation even under accelerated degradation conditions, which has never been achieved with existing fluorine-free PEMs. The polyphenylene PEM also exhibits reasonably high fuel cell performance, with excellent durability under practical conditions. This new PEM extends the limits of existing fluorine-free proton-conductive materials and will help to realize the next generation of PEMFCs via cost reduction as well as the performance improvement compared to the present PFSA-based PEMFC systems.

Development of compact fuel processor for 2 kW class residential PEMFCs

NASA Astrophysics Data System (ADS)

Seo, Yu Taek; Seo, Dong Joo; Jeong, Jin Hyeok; Yoon, Wang Lai

Korea Institute of Energy Research (KIER) has been developing a novel fuel processing system to provide hydrogen rich gas to residential polymer electrolyte membrane fuel cells (PEMFCs) cogeneration system. For the effective design of a compact hydrogen production system, the unit processes of steam reforming, high and low temperature water gas shift, steam generator and internal heat exchangers are thermally and physically integrated into a packaged hardware system. Several prototypes are under development and the prototype I fuel processor showed thermal efficiency of 73% as a HHV basis with methane conversion of 81%. Recently tested prototype II has been shown the improved performance of thermal efficiency of 76% with methane conversion of 83%. In both prototypes, two-stage PrOx reactors reduce CO concentration less than 10 ppm, which is the prerequisite CO limit condition of product gas for the PEMFCs stack. After confirming the initial performance of prototype I fuel processor, it is coupled with PEMFC single cell to test the durability and demonstrated that the fuel processor is operated for 3 days successfully without any failure of fuel cell voltage. Prototype II fuel processor also showed stable performance during the durability test.

Z-Selective Ruthenium Metathesis Catalysts: Comparison of Nitrate and Nitrite X-type Ligands

PubMed Central

Pribisko, Melanie A.; Ahmed, Tonia S.; Grubbs, Robert H.

2014-01-01

Two new Ru-based metathesis catalysts, 3 and 4, have been synthesized for the purpose of comparing their catalytic properties to those of their cis-selective nitrate analogues, 1 and 2. Although catalysts 3 and 4 exhibited slower initiation rates than 1 and 2, they maintained high cis-selectivity in homodimerization and ring-opening metathesis polymerization reactions. Furthermore, the nitrite catalysts displayed higher cis-selectivity than 2 for ring-opening metathesis polymerizations, and 4 delivered higher yields of polymer. PMID:25484484

Z-Selective Ruthenium Metathesis Catalysts: Comparison of Nitrate and Nitrite X-type Ligands.

PubMed

Pribisko, Melanie A; Ahmed, Tonia S; Grubbs, Robert H

2014-12-14

Two new Ru-based metathesis catalysts, 3 and 4 , have been synthesized for the purpose of comparing their catalytic properties to those of their cis -selective nitrate analogues, 1 and 2 . Although catalysts 3 and 4 exhibited slower initiation rates than 1 and 2 , they maintained high cis -selectivity in homodimerization and ring-opening metathesis polymerization reactions. Furthermore, the nitrite catalysts displayed higher cis -selectivity than 2 for ring-opening metathesis polymerizations, and 4 delivered higher yields of polymer.

Surface modification by carbon ion implantation for the application of ni-based amorphous alloys as bipolar plate in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Kim, Min-Uk; Kim, Do-Hyang; Han, Seung-hee; Fleury, Eric; Seok, Hyun-Kwang; Cha, Pil-Ryung; Kim, Yu-Chan

2011-04-01

Ni-based amorphous alloys with surface modification by carbon ion implantation are proposed as an alternative bipolar plate material for polymer electrolyte membrane fuel cells (PEMFCs). Both Ni60Nb20Ti10Zr10 alloys with and without carbon ion implantation have corrosion resistance as good as graphite as well as much lower contact resistance than 316L stainless steel in the PEMFC environment. The formation of conductive surface carbide due to carbon ion implantation results in a decrease in the contact resistance to a level comparable to that of graphite. This combination of excellent properties indicates that carbon ion implanted Ni-based amorphous alloys can be potential candidate materials for bipolar plates in PEMFCs.

Carbon dioxide-selective membranes and their applications in hydrogen processing

NASA Astrophysics Data System (ADS)

Zou, Jian

Fuel cells, which are regarded as a promising energy conversion approach in the 21st century, are now receiving increasing attention worldwide. In most cases, hydrogen is the preferred fuel for fuel cells, especially for proton-exchange membrane fuel cells (PEMFCs). One key issue in the development of PEMFC is how to generate hydrogen from the available hydrocarbon fuels. Most feasible strategies consist of a reforming step followed by the water gas shift (WGS) reaction. The resulting synthesis gas (syngas) still consists of 0.5--1.0% CO, which needs to be reduced to less than 10 ppm to meet the requirement of PEMFCs. Therefore, a further CO clean-up step is usually used to decrease CO concentration. In the present work, new CO2-selective membranes were synthesized and their applications for fuel cell fuel processing and synthesis gas purification were investigated. In order to enhance CO2 transport across membranes, the synthesized membranes contained both mobile and fixed site carriers in crosslinked poly(vinyl alcohol). The effects of crosslinking, membrane composition, feed pressure, water content, and temperature on transport properties were investigated. The membranes have shown a high permeability and a good CO 2/H2 selectivity and maintained their separation performance up to 170°C. One type of these membranes showed a permeability of 8000 Barrers (1 Barrer = 10-10 cm3 (STP).cm/(cm 2.s.cm.Hg)) and a CO2/H2 selectivity of 290 at 110°C. This membrane had a permeability of 1200 Barrers and a CO 2/H2 selectivity of 33 even at 170°C. The applications of the synthesized membranes were demonstrated in a CO2-removal experiment, in which the CO2 concentration in retentate was decreased from 17% to less than 10 ppm. With such membranes, there are several options to reduce the CO concentration of syngas. One option is to develop a WGS membrane reactor, in which both the low temperature WGS reaction and the CO2-removal take place. Another option is to use a proposed process consisting of a CO2-removal membrane module followed by a conventional low-temperature WGS reactor. A third option is to use methanation after the CO2-removal, one of the most widely used processes for the CO clean-up step. Experimental results showed that CO concentration was reduced to below 10 ppm with all three approaches. In the membrane reactor, a CO concentration of less than 10 ppm and a H 2 concentration of greater than 50% (on the dry basis) were achieved at various flow rates of a simulated autothermal reformate. In the proposed CO2-removal/WGS process, with more than 99.5 % CO2 removed from the synthesis gas, the reversible WGS was shifted forward so that the CO concentration was decreased from 1.2% to less than 10 ppm (dry), which is the requirement for PEMFC. The WGS reactor had a gas hourly space velocity of 7650 h-1 at 150°C and the H2 concentration in the outlet was more than 54.7% (dry). The applications of the synthesized CO2-selective membranes for high-pressure synthesis gas purification were also studied. Synthesis gas is the primary source for hydrogen as well as an intermediate for a broad range of chemicals. The separation of CO2 from synthesis gas is a critical step to obtain high purity hydrogen in many industrial plants, especially refinery plants. We studied the synthesized polymeric CO2 -selective membranes for synthesis gas purification at feed pressures higher than 200 psia and temperatures ranging from 100 to 150°C. The effects of feed pressure, microporous support, temperature, and permeate pressure were investigated using a simulated synthesis gas containing 20% carbon dioxide and 80% hydrogen. The membranes synthesized showed best CO2 permeability and CO2/H2 selectivity at 110°C. At a feed pressure of 220 psia, the CO2 permeability and CO2/H2 selectivity reached 756 Barrers and 42, respectively, whereas at a feed pressure of 440 psia, the CO2 permeability was 391 Barrers and the CO 2/H2 selectivity was about 25.

Polymers application in proton exchange membranes for fuel cells (PEMFCs)

NASA Astrophysics Data System (ADS)

Walkowiak-Kulikowska, Justyna; Wolska, Joanna; Koroniak, Henryk

2017-07-01

This review presents the most important research on alternative polymer membranes with ionic groups attached, provides examples of materials with a well-defined chemical structure that are described in the literature. Furthermore, it elaborates on the synthetic methods used for preparing PEMs, the current status of fuel cell technology and its application. It also briefly discusses the development of the PEMFC market.

Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural to 5-Formyl-2-furancarboxylic Acid in Water.

PubMed

Ventura, Maria; Aresta, Michele; Dibenedetto, Angela

2016-05-23

A simple, cheap, and selective catalyst based on copper/cerium oxides is described for the oxidation of 5-(hydroxymethyl)furfural (5-HMF) in water. An almost quantitative conversion (99 %) with excellent (90 %) selectivity towards the formation of 5-formyl-2-furancarboxylic acid, a platform molecule for other high value chemicals, is observed. The catalyst does not require any pretreatment or additives, such as bases, to obtain high yield and selectivity in water as solvent and using oxygen as oxidant. When a physical mixture of the oxides is used, low conversion and selectivity are observed. Air can be used instead of oxygen, but a lower conversion rate is observed if the same overall pressure is used, and the selectivity remains high. The catalyst can be recovered almost quantitatively and reused. Deactivation of the catalyst, observed in repeated runs, is due to the deposition of humins on its surface. Upon calcination the catalyst almost completely recovers its activity and selectivity, proving that the catalyst is robust. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

PubMed

Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-02-01

Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Twelve catalyst test runs were made; ten of these runs used catalysts that contained cobalt as the metal component, while the remaining two runs used catalysts that contained iron as the metal component. Five of the ten cobalt catalyst test runs were made with the catalysts containing one of two different shape selective components (UCC-101 and UCC-108) at two different metal component: shape selective component ratios (1:1 and 3:14). The remaining five cobalt catalyst test runs were made with the catalysts containing different additives incorporated into the cobalt. The five cobalt catalyst test runs using catalysts with different additives showedmore » that these additives had pronounced effects on the catalysts' activity, selectivity, and stability. The most outstanding effect was realized with the additive used in the Run 9 catalyst. This additive greatly improved the stability of the catalyst. While having the same initial activity of an additive-free catalyst, its deactivation rate was only one fourth of that of the additive-free catalyst. Futhermore, this additive improved the quality of the hydrocarbon product, which had a high, stable yield of olefins, and, unlike the product of any other cobalt/UCC-101 catalyst, was free of suspended wax. This lack of suspended wax resulted in jet fuel and diesel oil fractions that had substantially lower pour points than did the fractions produced from an additive-free catalyst.« less

Alkaline polymer electrolyte membranes for fuel cell applications.

PubMed

Wang, Yan-Jie; Qiao, Jinli; Baker, Ryan; Zhang, Jiujun

2013-07-07

In this review, we examine the most recent progress and research trends in the area of alkaline polymer electrolyte membrane (PEM) development in terms of material selection, synthesis, characterization, and theoretical approach, as well as their fabrication into alkaline PEM-based membrane electrode assemblies (MEAs) and the corresponding performance/durability in alkaline polymer electrolyte membrane fuel cells (PEMFCs). Respective advantages and challenges are also reviewed. To overcome challenges hindering alkaline PEM technology advancement and commercialization, several research directions are then proposed.

Selective Hydrogenation of Acetylene and Physicochemical Properties of Pd-Fe/Al2O3 Bimetallic Catalysts

NASA Astrophysics Data System (ADS)

Stytsenko, V. D.; Mel'nikov, D. P.; Tkachenko, O. P.; Savel'eva, E. V.; Semenov, A. P.; Kustov, L. M.

2018-05-01

The selective hydrogenation of acetylene on Pd-Fe/Al2O3 catalysts prepared by decomposition of ferrocene on reduced Pd/Al2O3 was studied. The effect of the conditions of treatment of the Pd-ferrocene/ Al2O3 precursor on the catalyst activity and selectivity was investigated, and the optimum conditions were determined at which the Pd-Fe/Al2O3 catalyst has higher selectivity than Pd/Al2O3 without any loss of activity.

A comparison of sodium borohydride as a fuel for proton exchange membrane fuel cells and for direct borohydride fuel cells

NASA Astrophysics Data System (ADS)

Wee, Jung-Ho

Two types of fuel cell systems using NaBH 4 aqueous solution as a fuel are possible: the hydrogen/air proton exchange membrane fuel cell (PEMFC) which uses onsite H 2 generated via the NaBH 4 hydrolysis reaction (B-PEMFC) at the anode and the direct borohydride fuel cell (DBFC) system which directly uses NaBH 4 aqueous solution at the anode and air at the cathode. Recently, research on these two types of fuel cells has begun to attract interest due to the various benefits of this liquid fuel for fuel cell systems for portable applications. It might therefore be relevant at this stage to evaluate the relative competitiveness of the two fuel cells. Considering their current technologies and the high price of NaBH 4, this paper evaluated and analyzed the factors influencing the relative favorability of each type of fuel cell. Their relative competitiveness was strongly dependent on the extent of the NaBH 4 crossover. When considering the crossover in DBFC systems, the total costs of the B-PEMFC system were the most competitive among the fuel cell systems. On the other hand, if the crossover problem were to be completely overcome, the total cost of the DBFC system generating six electrons (6e-DBFC) would be very similar to that of the B-PEMFC system. The DBFC system generating eight electrons (8e-DBFC) became even more competitive if the problem of crossover can be overcome. However, in this case, the volume of NaBH 4 aqueous solution consumed by the DBFC was larger than that consumed by the B-PEMFC.

Supported fischer-tropsch catalyst and method of making the catalyst

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

1987-01-01

A Fischer-Tropsch catalyst and a method of making the catalyst for a Fischer-Tropsch process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas, is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Selective hydrodechlorination of 1,2-dichloroethane catalyzed by trace Pd decorated Ag/Al2O3 catalysts prepared by galvanic replacement

NASA Astrophysics Data System (ADS)

Sun, Jingya; Han, Yuxiang; Fu, Heyun; Wan, Haiqin; Xu, Zhaoyi; Zheng, Shourong

2018-01-01

Ag catalysts decorated by trace Pd supported on γ-Al2O3 with different structure and chemical properties were prepared using a combined impregnation and galvanic replacement method. For comparison, monometallic Ag/γ-Al2O3 and Pd/γ-Al2O3 catalysts were prepared using the impregnation method. Gas-phase catalytic hydrodechlorination of 1,2-dichloroethane to ethylene was investigated on those catalysts. The structures and chemical compositions of bimetallic Pd-Ag particles in the catalysts were controlled by adjusting Pd replacement amount. The as-prepared catalysts were characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and in-situ FTIR spectroscopy of CO adsorption. The results demonstrated that contiguous Pd sites dominated in the monometallic Pd/γ-Al2O3 catalyst, while Pd atoms were separately decorated on the surface of Ag particles in the bimetallic Pd-Ag/γ-Al2O3 catalysts when Pd replacement amount was below 0.30 wt.%. At Pd replacement amount of 0.30 wt.%, Pd ensembles with contiguous Pd sites developed in the bimetallic catalyst. Thus, monometallic Pd/γ-Al2O3 catalyst displayed negligible ethylene selectivity toward the catalytic hydrodechlorination of 1,2-dichloroethane, while bimetallic Pd-Ag/γ-Al2O3 catalyst with a Pd replacement amount of 0.13 wt.% exhibited 94.6% of ethylene selectivity. Furthermore, selectivity to incompletely dechlorinated byproduct chloroethylene decreased with Pd replacement amount, due to the enhanced decoration effect of Pd on large Ag ensembles. Findings in this work provide a promising bimetallic catalyst prepared by galvanic replacement for the selective catalytic hydrodechlorination of 1,2-dichloroethane.

High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

PubMed

Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

2018-02-26

The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

Catalysts for the selective oxidation of hydrogen sulfide to sulfur

DOEpatents

Srinivas, Girish; Bai, Chuansheng

2000-08-08

This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

Feasibility of Renewable Energy Technology at the Afghanistan National Security University: A Site-Specific Study Focused on Potential Renewable Energy Technologies in Northwest Kabul, Afghanistan

DTIC Science & Technology

2011-04-26

70% H2, O2 Proton exchange membrane fuel cell ( PEMFC ) Proton exchange membrane Rm temp to 80 °C 40–60% H2, O2, Air Direct methanol fuel cell...Cell PEMFC Proton Exchange Membrane Fuel Cell PV Photovoltaic SHGC Solar Heat Gain Coefficient SIR savings to investment ratio SOFC Solid Oxide

Nitridation of a Super-Ferritic Stainless Steel for PEMFC Bipolar Plate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Turner, J. A.; Brady, M. P.

2007-01-01

AL29-4C alloy nitrided in pure nitrogen resulted in a nitrogen-modified oxide surface, which is the same as AISI446 nitrided under identical conditions. When the alloy was nitrided 24h at 900 C in N2-4H2, XRD and XPS analysis indicated that the surface layer consisted of a nitride outer layer ({approx}0.20 {micro}m) and an oxide inner layer ({approx} 0.82 {micro}m). According to XPS, the nitride outer layer is composed of CrN and [Cr(N),Fe]2N1-x, with much more Cr2N than Fe2N. Mn is migrated and enriched in the oxide inner layer and combined with chromium oxide.AL29-4C alloy nitrided in N2-4H2 resulted in low ICRmore » and excellent corrosion resistance in simulated PEMFC environments. Current was at ca. -3.0 {micro}A/cm2 in the PEMFC anode environment, and at ca. 0.3 {approx} 0.5 {micro}A/cm2 in the cathode environment. This is considered to be rather stable. After being polarized in a PEMFC environment, the ICR increased slightly compared with the as-nitrided sample, but was still rather low.« less

Experimental study on the optimal purge duration of a proton exchange membrane fuel cell with a dead-ended anode

NASA Astrophysics Data System (ADS)

Lin, Yu-Fen; Chen, Yong-Song

2017-02-01

When a proton exchange membrane fuel cell (PEMFC) is operated with a dead-ended anode, impurities gradually accumulate within the anode, resulting in a performance drop. An anode purge is thereby ultimately required to remove impurities within the anode. A purge strategy comprises purge interval (valve closed) and purge duration (valve is open). A short purge interval causes frequent and unnecessary activation of the valve, whereas a long purge interval leads to excessive impurity accumulation. A short purge duration causes an incomplete performance recovery, whereas a long purge duration results in low hydrogen utilization. In this study, a series of experimental trials was conducted to simultaneously measure the hydrogen supply rate and power generation of a PEMFC at a frequency of 50 Hz for various operating current density levels and purge durations. The effect of purge duration on the cell's energy efficiency was subsequently analyzed and discussed. The results showed that the optimal purge duration for the PEMFC was approximately 0.2 s. Based on the results of this study, a methodical process for determining optimal purge durations was ultimately proposed for widespread application. Purging approximately one-fourth of anode gas can obtain optimal energy efficiency for a PEMFC with a dead-ended anode.

Modeling two-phase flow in three-dimensional complex flow-fields of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Kim, Jinyong; Luo, Gang; Wang, Chao-Yang

2017-10-01

3D fine-mesh flow-fields recently developed by Toyota Mirai improved water management and mass transport in proton exchange membrane (PEM) fuel cell stacks, suggesting their potential value for robust and high-power PEM fuel cell stack performance. In such complex flow-fields, Forchheimer's inertial effect is dominant at high current density. In this work, a two-phase flow model of 3D complex flow-fields of PEMFCs is developed by accounting for Forchheimer's inertial effect, for the first time, to elucidate the underlying mechanism of liquid water behavior and mass transport inside 3D complex flow-fields and their adjacent gas diffusion layers (GDL). It is found that Forchheimer's inertial effect enhances liquid water removal from flow-fields and adds additional flow resistance around baffles, which improves interfacial liquid water and mass transport. As a result, substantial improvements in high current density cell performance and operational stability are expected in PEMFCs with 3D complex flow-fields, compared to PEMFCs with conventional flow-fields. Higher current density operation required to further reduce PEMFC stack cost per kW in the future will necessitate optimizing complex flow-field designs using the present model, in order to efficiently remove a large amount of product water and hence minimize the mass transport voltage loss.

Spatial proton exchange membrane fuel cell performance under bromomethane poisoning

NASA Astrophysics Data System (ADS)

Reshetenko, Tatyana V.; Artyushkova, Kateryna; St-Pierre, Jean

2017-02-01

The poisoning effects of 5 ppm CH3Br in the air on the spatial performance of a proton exchange membrane fuel cell (PEMFC) were studied using a segmented cell system. The presence of CH3Br caused performance loss from 0.650 to 0.335 V at 1 A cm-2 accompanied by local current density redistribution. The observed behavior was explained by possible bromomethane hydrolysis with the formation of Br-. Bromide and bromomethane negatively affected the oxygen reduction efficiency over a wide range of potentials because of their adsorption on Pt, which was confirmed by XPS. Moreover, the PEMFC exposure to CH3Br led to a decrease in the anode and cathode electrochemical surface area (∼52-57%) due to the growth of Pt particles through agglomeration and Ostwald ripening. The PEMFC did not restore its performance after stopping bromomethane introduction to the air stream. However, the H2/N2 purge of the anode/cathode and CV scans almost completely recovered the cell performance. The observed final loss of ∼50 mV was due to an increased activation overpotential. PEMFC exposure to CH3Br should be limited to concentrations much less than 5 ppm due to serious performance loss and lack of self-recovery.

Design of flexible polyphenylene proton-conducting membrane for next-generation fuel cells

PubMed Central

Miyake, Junpei; Taki, Ryunosuke; Mochizuki, Takashi; Shimizu, Ryo; Akiyama, Ryo; Uchida, Makoto; Miyatake, Kenji

2017-01-01

Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in automotive, stationary, and portable applications. Perfluorosulfonic acid (PFSA) ionomers (for example, Nafion) have been the benchmark PEMs; however, several problems, including high gas permeability, low thermal stability, high production cost, and environmental incompatibility, limit the widespread dissemination of PEMFCs. It is believed that fluorine-free PEMs can potentially address all of these issues; however, none of these membranes have simultaneously met the criteria for both high performance (for example, proton conductivity) and durability (for example, mechanical and chemical stability). We present a polyphenylene-based PEM (SPP-QP) that fulfills the required properties for fuel cell applications. The newly designed PEM exhibits very high proton conductivity, excellent membrane flexibility, low gas permeability, and extremely high stability, with negligible degradation even under accelerated degradation conditions, which has never been achieved with existing fluorine-free PEMs. The polyphenylene PEM also exhibits reasonably high fuel cell performance, with excellent durability under practical conditions. This new PEM extends the limits of existing fluorine-free proton-conductive materials and will help to realize the next generation of PEMFCs via cost reduction as well as the performance improvement compared to the present PFSA-based PEMFC systems. PMID:29075671

Study and development of sulfated zirconia based proton exchange fuel cell membranes

NASA Astrophysics Data System (ADS)

Kemp, Brittany Wilson

With the increasing consumption of energy, fuel cells are among the most promising alternatives to fossil fuels, provided some technical challenges are overcome. Proton exchange membrane fuel cells (PEMFCs) have been investigated and improvements have been made, but the problem with NafionRTM, the main membrane for PEMFCs, has not been solved. NafionRTM restricts the membranes from operating at higher temperatures, thus preventing them from working in small electronics. The problem is to develop a novel fuel cell membrane that performs comparably to NafionRTM in PEMFCs. The membranes were fabricated by applying sulfated zirconia, via template wetting, to porous alumina membranes. The fabricated membranes showed a proton conductivity of 0.016 S/cm in comparison to the proton conductivity of Nafion RTM (0.05 S/cm). Both formic acid and methanol had a lower crossover flux through the sulfated zirconia membranes (formic acid- 2.89x10 -7 mols/cm2s and methanol-1.78x10-9 mols/cm2s) than through NafionRTM (formic acid-2.03x10 -8 mols/cm2s methanol-2.42x10-6 mols/cm 2s), indicating that a sulfated zirconia PEMFC may serve as a replacement for NafionRTM.

Medium Effects are as Important as Catalyst Design for Selectivity in Electrocatalytic Oxygen Reduction by Iron-porphyrin Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rigsby, Matthew L.; Wasylenko, Derek J.; Pegis, Michael L.

2015-04-08

Several substituted iron porphyrin com-plexes were evaluated for oxygen reduction reaction (ORR) electrocatalysis in different homogeneous and heterogeneous media. The selectivity for 4-electron re-duction to H2O vs. 2-electron reduction to H2O2 varies substantially from one medium to another for a given catalyst. In many cases, the influence of the medium in which the catalyst is evaluated has a larger effect on the observed selectivity than the factors attributable to chemical modification of the catalyst. For instance, introduction of potential proton relays has variable effects depending on the catalyst medium. Thus, comparisons of ORR selectivity results need to be interpreted withmore » caution, as the catalysis is a property not just of the catalyst, but also of the larger mesoscale environment be-yond the catalyst. Still, in all the direct pairwise comparisons in the same medium, the catalysts with potential proton relays have similar or better selectivity for the preferred 4e– path. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Electropolymerization of camphorsulfonic acid doped conductive polypyrrole anti-corrosive coating for 304SS bipolar plates

NASA Astrophysics Data System (ADS)

Jiang, Li; Syed, Junaid Ali; Gao, Yangzhi; Zhang, Qiuxiang; Zhao, Junfeng; Lu, Hongbin; Meng, Xiangkang

2017-12-01

Conductive polymer coating doped with large molecular organic acid is an alternative method used to protect stainless steel (SS) bipolar plates in proton exchange membrane fuel cells (PEMFCs). However, it is difficult to select the proper doping acid, which improves the corrosion resistance of the coating without affecting its conductivity. In this study, large spatial molecular group camphorsulfonic acid (CSA) doped polypyrrole (PPY) conductive coating was prepared by galvanostatic electropolymerization on 304SS. The electrochemical properties of the coating were evaluated in 0.1 M H2SO4 solution in order to simulate the PEMFC service environment. The results indicate that the coating increased the corrosion potential and shifted Ecorr towards more positive value, particularly the jcorr value of PPY-CSA coated 304SS was dropped from 97.3 to 0.00187 μA cm-2. The long-term immersion tests (660 h) show that the PPY-CSA coating exhibits better corrosion resistance in comparison with the small acid (SO42-) doped PPY-SO42- or PPY/PPY-SO42- coatings. Moreover, the PPY-CSA coating presents low contact resistance and maintains strong corrosion resistance during the prolonged exposure time due to barrier effect and anodic protection.

The effects of clamp torque, humidity, and carbon oxygen poisoning on PEM fuel cell performance

NASA Astrophysics Data System (ADS)

Lee, Woo-Kum

2000-10-01

Proton exchange membrane fuel cell (PEMFC) is attracting much attention as a power source of electric vehicles due to high power density capability. Although there has been much research and development done on PEWC, there are still many problems to be solved. One of the major problems is water management inside the fuel cell. The performance of the fuel cell is strongly influenced by the state of hydration of the membrane. If the membrane is too dry, its conductivity drops resulting in reduced cell performance. An excess of water in the fuel cell can lead to flooding problems, also resulting in performance drop. This dissertation presents experimental data that may be used to verify numerical simulations of a PEM fuel cell. The key to this usefulness is the closure of a water balance in the fuel cell for various operating conditions. The closure results from experimental data showed that the inlet gas streams are not fully saturated with water vapor. Another key to the usefulness of the data is the measurement of the internal compression pressure that is exerted on the gas diffusion layer. Data is presented to show the effect of this compression on the performance of the PEMFC and on the water balance results. Another problem in application of a PEM fuel cell is CO poisoning on the MEA. Gas reformed from methanol or gasoline contains small amount of CO resulting in significant decreasing fuel cell performance. Several recovery techniques were discussed to solve the CO problem. The use of Pt-Ru alloys as anode catalyst has shown that CO is oxidized at more negative potentials as compared to pure Pt. According to the result, an improvement has been achieved at CO level 5 ppm. Another method to prevent CO poisoning has been described by blowing 5% of air into the anode side. The result shows that the performance recovers very quickly as the air is injected during reformate (50 ppm CO).

Impact of ultra-low Pt loadings on the performance of anode/cathode in a proton-exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Billy, E.; Maillard, F.; Morin, A.; Guetaz, L.; Emieux, F.; Thurier, C.; Doppelt, P.; Donet, S.; Mailley, S.

This study focuses on the elaboration of PEMFC electrodes containing ultra-low platinum (Pt) loadings by direct liquid injection metal organic chemical vapor deposition (DLI-MOCVD). DLI-MOCVD offers a large number of advantages for the elaboration of model PEMFC electrodes. First, by using different metal precursors or elaboration temperature, the size of the Pt nanoparticles and thus the intrinsic catalytic activity can easily be tailored in the nanometer range. In this work, Pt nanoparticles (1-5 nm) with remarkable low degree of agglomeration and uniform distribution were deposited onto the microporous side of a commercial gas-diffusion layer (GDL). Second, reduction of the Pt loading is made possible by varying the Pt deposition time and its influence of the cell performance can be extracted without variation of the thickness of the catalytic layer (in previous studies, a decrease of the catalyst utilization was observed when increasing the Pt loading, i.e. the thickness of the catalytic layer (CL)). The electrocatalytic activity of home-made Pt nanoparticles elaborated by DLI-MOCVD was measured in liquid electrolyte or in complete fuel cell operating on H 2/O 2 or H 2/air and compared vs. that of a commercially available electrode containing 500 μg Pt cm -2 (Pt Ref500). At the cathode, the performance of the electrodes containing 104-226 μg of Pt per cm 2 of electrode compares favorably with that of the Pt Ref500 in H 2/O 2 conditions. In H 2/air conditions, additional mass-transport losses are detected in the low-current density region but the high effectiveness of our electrodes improves the performance in the high-current density region. At the anode, the Pt loading can be reduced to 35 μg Pt cm -2 without any voltage loss in agreement with previous observations.

Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols

DOT National Transportation Integrated Search

2010-11-01

The objective of this project is to determine the applicability of metal-based catalysts and optimize the process conditions for thermochemically producing primary alcohols. Metal catalysts were evaluated for their selectivities for producing alcohol...

Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers.

PubMed

Schieweck, Benjamin G; Klankermayer, Jürgen

2017-08-28

Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH 2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Efficient Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over Gold Supported on Zinc Oxide Materials

DOE PAGES

Chen, Hangning; Cullen, David A.; Larese, J. Z.

2015-11-30

We used Au/ZnO catalysts for liquid-phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol and compared with Au/Fe 2O 3 catalysts. To investigate the influence of the support on the hydrogenation activity and selectivity, three different Au/ZnO catalysts were synthesized, including Au/rod-tetrapod ZnO, Au/porous ZnO, and Au/ZnO-CP prepared using a coprecipitation method. Moreover, the influence of calcination temperature was also systematically investigated in this study. The characterization of Au/ZnO catalysts was performed using ICP, N 2 adsorption/desorption isotherms, X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy. Among all the supported Au catalysts prepared in this study, Au/ZnO-CP exhibits bothmore » the highest hydrogenation activity and selectivity. Using a 1.5% Au/ZnO-CP catalyst, 100% selectivity could be achieved with 94.9% conversion. Finally, we find that the Au particle (size and shape), the ZnO support (size and surface texture) and the interaction between Au and ZnO are three important parameters for achieving a highly efficient Au/ZnO catalyst.« less

Promising SiC support for Pd catalyst in selective hydrogenation of acetylene to ethylene

NASA Astrophysics Data System (ADS)

Guo, Zhanglong; Liu, Yuefeng; Liu, Yan; Chu, Wei

2018-06-01

In this study, SiC supported Pd nanoparticles were found to be an efficient catalyst in acetylene selective hydrogenation reaction. The ethylene selectivity can be about 20% higher than that on Pd/TiO2 catalyst at the same acetylene conversion at 90%. Moreover, Pd/SiC catalyst showed a stable catalytic life at 65 °C with 80% ethylene selectivity. With the detailed characterization using temperature-programmed reduction (H2-TPR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, CO-chemisorption and thermo-gravimetric analysis (TGA), it was found that SiC owns a lower surface area (22.9 m2/g) and a broad distribution of meso-/macro-porosity (from 5 to 65 nm), which enhanced the mass transfer during the chemical process at high reaction rate and decreased the residence time of ethylene on catalyst surface. Importantly, SiC support has the high thermal conductivity, which favored the rapid temperature homogenization through the catalyst bed and inhabited the over-hydrogenation of acetylene. The surface electronic density of Pd on Pd/SiC catalyst was higher than that on Pd/TiO2, which could promote desorption of ethylene from surface of the catalyst. TGA results confirmed a much less coke deposition on Pd/SiC catalyst.

Anodic Behaviour of High Nitrogen-Bearing Steel in PEMFC Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Turner, J. A.

2008-02-01

High nitrogen-bearing stainless steels, AISI Type 201 and AL219, were investigated in simulated polymer electrolyte membrane fuel cell (PEMFC) environments to assess the use of these materials in fuel cell bipolar plate applications. Both steels exhibit better corrosion behavior than 316L steel in the same environments. Type 201 steel shows similar but lower interfacial contact resistance (ICR) than 316L, while AL219 steel shows higher ICR than 316L. X-ray photoelectron spectroscopy (XPS) analysis shows that the air-formed films on Type 201 and AL219 are composed of iron oxides, chromium oxide, and manganese oxide. Iron oxides dominate the composition of the air-formedmore » film, specially the outer layer. Chromium oxide dominates passive films. Surface film thicknesses were estimated. The results suggest that high nitrogen-bearing stainless steels are promising materials for PEMFC bipolar plates.« less

Shock and vibration effects on performance reliability and mechanical integrity of proton exchange membrane fuel cells: A critical review and discussion

NASA Astrophysics Data System (ADS)

Haji Hosseinloo, Ashkan; Ehteshami, Mohsen Mousavi

2017-10-01

Performance reliability and mechanical integrity are the main bottlenecks in mass commercialization of PEMFCs for applications with inherent harsh environment such as automotive and aerospace applications. Imparted shock and vibration to the fuel cell in such applications could bring about numerous issues including clamping torque loosening, gas leakage, increased electrical resistance, and structural damage and breakage. Here, we provide a comprehensive review and critique of the literature focusing on the effects of mechanically harsh environment on PEMFCs, and at the end, we suggest two main future directions in FC technology research that need immediate attention: (i) developing a generic and adequately accurate dynamic model of PEMFCs to assess the dynamic response of FC devices, and (ii) designing effective and robust shock and vibration protection systems based on the developed models in (i).

Enhancement of fuel cell performance with less-water dependent composite membranes having polyoxometalate anchored nanofibrous interlayer

NASA Astrophysics Data System (ADS)

Abouzari-lotf, Ebrahim; Jacob, Mohan V.; Ghassemi, Hossein; Ahmad, Arshad; Nasef, Mohamed Mahmoud; Zakeri, Masoumeh; Mehdipour-Ataei, Shahram

2016-09-01

Polyoxometalate immobilized nanofiber was used to fabricate low gas permeable layer for composite membranes designed for proton exchange membrane fuel cell (PEMFC) operating at low relative humidity (RH). The composite membranes revealed enhanced proton conductivity in dry conditions compared with state-of-the-art pristine membrane (Nafion 112, N112). This was coupled with a low fuel crossover inheriting the composite membranes about 100 mV higher OCV than N112 when tested in PEMFC at 60 °C and 40% RH. A maximum power density of up to 930 mW cm-2 was also achieved which is substantially higher than the N112 under similar conditions (577 mW cm-2). Such remarkable performance enhancement along with undetectable leaching of immobilized polyoxometalate, high dimensional stability and low water uptake of the composite membranes suggest a strong potential for PEMFC under low RH operation.

Metal-organic framework catalysts for selective cleavage of aryl-ether bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allendorf, Mark D.; Stavila, Vitalie

The present invention relates to methods of employing a metal-organic framework (MOF) as a catalyst for cleaving chemical bonds. In particular instances, the MOF results in selective bond cleavage that results in hydrogenolyzis. Furthermore, the MOF catalyst can be reused in multiple cycles. Such MOF-based catalysts can be useful, e.g., to convert biomass components.

Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts

DOE PAGES

Ye, Rong; Zhukhovitskiy, Aleksandr V.; Deraedt, Christophe V.; ...

2017-07-13

Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles—some without homogeneous analogues—for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimizemore » and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl 2) or reduced (e.g., with H 2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. Here in this Account, we will briefly introduce metal clusters and describe the synthesis and characterizations of supported DEMCs. We will present the catalysis studies of supported DEMCs in both the batch and flow modes. Lastly, we will summarize the current state of heterogenizing homogeneous catalysis and provide future directions for this area of research.« less

CO 2 hydrogenation over oxide-supported PtCo catalysts: The role of the oxide support in determining the product selectivity

DOE PAGES

Kattel, Shyam; Yu, Weiting; Yang, Xiaofang; ...

2016-05-09

By simply changing the oxide support, the selectivity of a metal–oxide catalysts can be tuned. For the CO 2 hydrogenation over PtCo bimetallic catalysts supported on different reducible oxides (CeO 2, ZrO 2, and TiO 2), replacing a TiO 2 support by CeO 2 or ZrO 2 selectively strengthens the binding of C,O-bound and O-bound species at the PtCo–oxide interface, leading to a different product selectivity. Lastly, these results reveal mechanistic insights into how the catalytic performance of metal–oxide catalysts can be fine-tuned.

Comparison of Two Preparation Methods on Catalytic Activity and Selectivity of Ru-Mo/HZSM5 for Methane Dehydroaromatization

DOE PAGES

Petkovic, Lucia M.; Ginosar, Daniel M.

2014-01-01

Catalytic performance of Mo/HZSM5 and Ru-Mo/HZSM5 catalysts prepared by vaporization-deposition of molybdenum trioxide and impregnation with ammonium heptamolybdate was analyzed in terms of catalyst activity and selectivity, nitrogen physisorption analyses, temperature-programmed oxidation of carbonaceous residues, and temperature-programmed reduction. Vaporization-deposition rendered the catalyst more selective to ethylene and coke than the catalyst prepared by impregnation. This result was assigned to lower interaction of molybdenum carbide with the zeolite acidic sites.

Remarkably selective iridium catalysts for the elaboration of aromatic C-H bonds.

PubMed

Cho, Jian-Yang; Tse, Man Kin; Holmes, Daniel; Maleczka, Robert E; Smith, Milton R

2002-01-11

Arylboron compounds have intriguing properties and are important building blocks for chemical synthesis. A family of Ir catalysts now enables the direct synthesis of arylboron compounds from aromatic hydrocarbons and boranes under "solventless" conditions. The Ir catalysts are highly selective for C-H activation and do not interfere with subsequent in situ transformations, including Pd-mediated cross-couplings with aryl halides. By virtue of their favorable activities and exceptional selectivities, these Ir catalysts impart the synthetic versatility of arylboron reagents to C-H bonds in aromatic and heteroaromatic hydrocarbons.

Attrition Resistant Iron-Based Catalysts For F-T SBCRs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2006-01-31

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+ H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-(FE) based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment; makes the separation of catalyst from the oil/wax product very difficult, if not impossible; and results in a steady loss of catalyst from the reactor. Under a previous Department of Energy (DOE)/University Research Grant (UCR) grant, Hampton University reported, for the first time, the development of demonstrably attrition-resistant Fe F-T synthesis catalysts having good activity, selectivity, and attrition resistance. These catalysts were prepared by spray drying Fe catalysts with potassium (K), copper (Cu), and silica (SiO{sub 2}) as promoters. SiO{sub 2} was also used as a binder for spray drying. These catalysts were tested for activity and selectivity in a laboratory-scale fixed-bed reactor. Fundamental understanding of attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried HPR-43 catalyst having average particle size (aps) of 70 {micro}m with high attrition resistance. This HPR-43 attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5+} selectivity of >78% and methane selectivity of less than 5% at an {alpha} of 0.9. Research is proposed to enable further development and optimization of these catalysts by (1) better understanding the role and interrelationship of various catalyst composition and preparation parameters on attrition resistance, activity, and selectivity of these catalysts, (2) the presence of sulfide ions on a precipitated iron catalyst, and (3) the effect of water on sulfided iron F-T catalysts for its activity, selectivity, and attrition. Catalyst preparations will be based on spray drying. The research employed, among other measurements, attrition testing and F-T synthesis at high pressure. Catalyst activity and selectivity is evaluated using a small fixed-bed reactor and a continuous stirred tank reactor (CSTR). The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1-m-diameter, 2-m-tall spray dryer. The binder silica content was varied from 0 to 20 wt%. The results show that the use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO2 wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than the type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). The two catalysts were also tested at The Center for Applied Energy Research in Lexington, Kentucky of the University of Kentucky. Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5+} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2}).« less

Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

PubMed

Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

2013-01-01

One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Rong; Zhukhovitskiy, Aleksandr V.; Deraedt, Christophe V.

Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles—some without homogeneous analogues—for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimizemore » and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl 2) or reduced (e.g., with H 2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. Here in this Account, we will briefly introduce metal clusters and describe the synthesis and characterizations of supported DEMCs. We will present the catalysis studies of supported DEMCs in both the batch and flow modes. Lastly, we will summarize the current state of heterogenizing homogeneous catalysis and provide future directions for this area of research.« less

Ligand iron catalysts for selective hydrogenation

DOEpatents

Casey, Charles P.; Guan, Hairong

2010-11-16

Disclosed are iron ligand catalysts for selective hydrogenation of aldehydes, ketones and imines. A catalyst such as dicarbonyl iron hydride hydroxycyclopentadiene) complex uses the OH on the five member ring and hydrogen linked to the iron to facilitate hydrogenation reactions, particularly in the presence of hydrogen gas.

Cobalt Fischer-Tropsch catalysts having improved selectivity

DOEpatents

Miller, James G.; Rabo, Jule A.

1989-01-01

A cobalt Fischer-Tropsch catalyst having an improved steam treated, acid extracted LZ-210 support is taught. The new catalyst system demonstrates improved product selectivity at Fischer-Tropsch reaction conditions evidenced by lower methane production, higher C.sub.5.sup.+ yield and increased olefin production.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan , Pellin, Michael J.; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-04-03

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan [Lisle, IL; Pellin, Michael J [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-03-27

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Study of the aromatic hydrocarbons poisoning of platinum cathodes on proton exchange membrane fuel cell spatial performance using a segmented cell system

NASA Astrophysics Data System (ADS)

Reshetenko, Tatyana V.; St-Pierre, Jean

2016-11-01

Aromatic hydrocarbons are produced and used in many industrial processes, which makes them hazardous air pollutants. Currently, air is the most convenient oxidant for proton exchange membrane fuel cells (PEMFCs), and air quality is an important consideration because airborne contaminants can negatively affect fuel cell performance. The effects of exposing the cathode of PEMFCs to benzene and naphthalene were investigated using a segmented cell system. The introduction of 2 ppm C6H6 resulted in moderate performance loss of 40-45 mV at 0.2 A cm-2 and 100-110 mV at 1.0 A cm-2 due to benzene adsorption on Pt and its subsequent electrooxidation to CO2 under operating conditions and cell voltages of 0.5-0.8 V. In contrast, PEMFC poisoning by ∼2 ppm of naphthalene led to a decrease in cell performance from 0.66 to 0.13 V at 1.0 A cm-2, which was caused by the strong adsorption of C10H8 onto Pt at cell voltages of 0.2-1.0 V. Naphthalene desorption and hydrogenation only occurred at potentials below 0.2 V. The PEMFCs' performance loss due to each contaminant was recoverable, and the obtained results demonstrated that the fuel cells' exposure to benzene and naphthalene should be limited to concentrations less than 2 ppm.

Transient studies of low temperature catalysts for methane conversion. Final report, [September 1992--March 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolf, E.E.

1996-09-30

The objective of this project is to use transient techniques to study gas surface interactions during the oxidative conversion of methane. Two groups of catalysts were studied: a double oxide of vanadium and phosphate or VPO, and double oxides of Ni, Co and Rh and lanthana. The objective of the studies involving the VPO catalyst was to understand gas-surface interactions leading to the formation of formaldehyde. In the second group of catalysts, involving metallo-oxides, the main objective was to study the gas-surface interactions that determine the selectivity to C{sub 2} hydrocarbons or synthesis gas. Transient techniques were used to studymore » the methane-surface interactions and the role of lattice oxygen. The selection of the double oxides was made on the hypothesis that the metal oxide would provide an increase interaction with methane whereas the phosphate or lanthanide would provide the sites for oxygen adsorption. The hypothesis behind this selection of catalysts was that increasing the methane interaction with the catalysts would lower the reaction temperature and thus increase the selectivity to the desired products over the total oxidation reaction. In both groups of catalysts the role of Li as a modifier of the selectivity was also studied in detail.« less

Turning Biodiesel Waste Glycerol into 1,3-Propanediol: Catalytic Performance of Sulphuric acid-Activated Montmorillonite Supported Platinum Catalysts in Glycerol Hydrogenolysis.

PubMed

Samudrala, Shanthi Priya; Kandasamy, Shalini; Bhattacharya, Sankar

2018-05-10

Direct C-O hydrogenolysis of bioglycerine to produce 1,3-propanediol selectively is a vital technology that can expand the scope of biodiesel industry and green chemical production from biomass. Herein we report sulphuric acid-activated montmorillonite clay supported platinum nanoparticles as highly effective solid acid catalysts for the selective production of 1,3-propanediol from glycerol. The catalytic performances of the catalysts were investigated in the hydrogenolysis of glycerol with a fixed bed reactor under ambient pressure. The results were found promising and showed that the activation of montmorillonite by sulphuric acid incorporated Brønsted acidity in the catalyst and significantly improved the selectivity to 1,3-propanediol. The catalytic performance of different platinum loaded catalysts was examined and 2 wt% Pt/S-MMT catalyst presented superior activity among others validating 62% 1,3-propanediol selectivity at 94% glycerol conversion. The catalytic activity of 2Pt/S-MMT was systematically investigated under varying reaction parameters including reaction temperature, hydrogen flow rate, glycerol concentration, weight hourly space velocity, and contact time to derive the optimum conditions for the reaction. The catalyst stability, reusability and structure-activity correlation were also elucidated. The high performance of the catalyst could be ascribed to well disperse Pt nanoparticles immobilized on acid-activated montmorillonite, wider pore-structure and appropriate acid sites of the catalyst.

A PdAg bimetallic nanocatalyst for selective reductive amination of nitroarenes.

PubMed

Li, Linsen; Niu, Zhiqiang; Cai, Shuangfei; Zhi, Yun; Li, Hao; Rong, Hongpan; Liu, Lichen; Liu, Lei; He, Wei; Li, Yadong

2013-08-07

Herein we have identified an optimal catalyst, Pd1Ag1.7, for the tandem reductive amination between nitroarenes and aldehydes (selectivity > 93%). Key to the success is the ability to control the compositions of the investigational Pd1-xAgx (x = 0-1) catalysts, as well as the clear composition dependent activity/selectivity trend observed in this study. This catalyst features a wide substrate scope, excellent recyclability, activity and selectivity under ambient conditions.

Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production

DOE PAGES

Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan; ...

2016-01-31

Synthesis gas (CO + H 2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C 2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H 2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculationsmore » using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate–adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ~6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO 2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO 2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. As a result, this work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.« less

Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan

Synthesis gas (CO + H 2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C 2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H 2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculationsmore » using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate–adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ~6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO 2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO 2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. As a result, this work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.« less

Fabrication of a Flexible Micro CO Sensor for Micro Reformer Applications

PubMed Central

Lee, Chi-Yuan; Chang, Chi-Chung; Lo, Yi-Man

2010-01-01

Integration of a reformer and a proton exchange membrane fuel cell (PEMFC) is problematic due to the presence in the gas from the reforming process of a slight amount of carbon monoxide. Carbon monoxide poisons the catalyst of the proton exchange membrane fuel cell subsequently degrading the fuel cell performance, and necessitating the sublimation of the reaction gas before supplying to fuel cells. Based on the use of micro-electro-mechanical systems (MEMS) technology to manufacture flexible micro CO sensors, this study elucidates the relation between a micro CO sensor and different SnO2 thin film thicknesses. Experimental results indicate that the sensitivity increases at temperatures ranging from 100–300 °C. Additionally, the best sensitivity is obtained at a specific temperature. For instance, the best sensitivity of SnO2 thin film thickness of 100 nm at 300 °C is 59.3%. Moreover, a flexible micro CO sensor is embedded into a micro reformer to determine the CO concentration in each part of a micro reformer in the future, demonstrating the inner reaction of a micro reformer in depth and immediate detection. PMID:22163494

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tong Dongge; Han Xue; Chu Wei

Co-B flowers with mesoporous structure were first prepared via reduction of cobalt acetate by potassium borohydride in the presence of complexing agent ethylenediamine. The as-prepared Co-B flowers were characterized by Fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, N{sub 2} adsorption-desorption, and magnetic performance test. The Co-B flowers exhibited enhanced coercivity, and weakened saturation magnetization and remanet magnetization as compared with the regular Co-B. During the hydrolysis of KBH{sub 4}, the Co-B flowers exhibited higher catalytic activity than the regular Co-B. It is attributed to themore » larger specific surface area and mesoporous channels. During the successive reactions, the conversion of KBH{sub 4} over Co-B flowers was about 97%. The average H{sub 2} generation rate of Co-B flowers was 4620 mL/min/g-catalyst in 1.5 wt% NaOH + 15 wt% KBH{sub 4} solution, which may give a successive H{sub 2} supply for a 748 W polymer electrolyte membrane fuel cell (PEMFC) at 100% H{sub 2} utilization.« less

Solid oxide MEMS-based fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2007-03-13

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Solid polymer MEMS-based fuel cells

DOEpatents

Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Pleasant Hill, CA

2008-04-22

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Site-selective and stereoselective functionalization of non-activated tertiary C-H bonds

NASA Astrophysics Data System (ADS)

Liao, Kuangbiao; Pickel, Thomas C.; Boyarskikh, Vyacheslav; Bacsa, John; Musaev, Djamaladdin G.; Davies, Huw M. L.

2017-11-01

The synthesis of complex organic compounds usually relies on controlling the reactions of the functional groups. In recent years, it has become possible to carry out reactions directly on the C-H bonds, previously considered to be unreactive. One of the major challenges is to control the site-selectivity because most organic compounds have many similar C-H bonds. The most well developed procedures so far rely on the use of substrate control, in which the substrate has one inherently more reactive C-H bond or contains a directing group or the reaction is conducted intramolecularly so that a specific C-H bond is favoured. A more versatile but more challenging approach is to use catalysts to control which site in the substrate is functionalized. p450 enzymes exhibit C-H oxidation site-selectivity, in which the enzyme scaffold causes a specific C-H bond to be functionalized by placing it close to the iron-oxo haem complex. Several studies have aimed to emulate this enzymatic site-selectivity with designed transition-metal catalysts but it is difficult to achieve exceptionally high levels of site-selectivity. Recently, we reported a dirhodium catalyst for the site-selective functionalization of the most accessible non-activated (that is, not next to a functional group) secondary C-H bonds by means of rhodium-carbene-induced C-H insertion. Here we describe another dirhodium catalyst that has a very different reactivity profile. Instead of the secondary C-H bond, the new catalyst is capable of precise site-selectivity at the most accessible tertiary C-H bonds. Using this catalyst, we modify several natural products, including steroids and a vitamin E derivative, indicating the applicability of this method of synthesis to the late-stage functionalization of complex molecules. These studies show it is possible to achieve site-selectivity at different positions within a substrate simply by selecting the appropriate catalyst. We hope that this work will inspire the design of even more sophisticated catalysts, such that catalyst-controlled C-H functionalization becomes a broadly applied strategy for the synthesis of complex molecules.

The selective hydrogenation of crotonaldehyde over bimetallic catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoeb, Ann M.

1997-10-17

The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO 2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO 2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO 2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO 2 catalystsmore » for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO 2, Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.« less

SELECTIVE OXIDATION OF ALCOHOLS OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

EPA Science Inventory

Oxidation of various alcohols is studied in liquid phase under nitrogen atmosphere over vanadium phosphorus oxide catalyst in an environmentally friendly protocol using hydrogen peroxide. The catalyst and the method are found to be suitable for the selective oxidation of a variet...

Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

PubMed

Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi

2018-05-01

A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

Poisoning of a silica supported cobalt catalyst due to the presence of sulfur impurities in syngas during Fischer-Tropsch synthesis: Effect of chelating agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bambal, A.S.; Gardner, T.H.; Kugler, E.L.

2012-01-01

Sulfur compounds that are generally found in syngas derived from coal and biomass are a poison to Fischer-Tropsch (FT) catalysts. The presence of sulfur impurities in the ppm range can limit the life of a FT catalyst to a few hours or a few days. In this study, FT synthesis was carried out in a fixed-bed reactor at 230 °C, 20 bar, and 13,500 Ncm3/h/gcat for 72 h using syngas with H2/CO = 2.0. Cobalt-based catalysts were subjected to poisoning by 10 and 50 ppm sulfur in the syngas. The performance of FT catalyst was compared in context of syngasmore » conversion, product selectivities and yields, during the poisoning as well as post-poisoning stages. At both the impurity concentrations, the sulfur was noted to cause permanent loss in the activity, possibly by adsorbing irreversibly on the surface. The sulfur poison affects the hydrogenation and the chain-propagation ability of the catalysts, and shifts the product selectivity towards short-chain hydrocarbons with higher percentages of olefins. Additional diffusion limitations caused due to sulfur poisoning are thought to alter the product selectivity. The shifts in product selectivities suggest that the sulfur decreases the ability of the catalyst to form C-C bonds to produce longer-chain hydrocarbons. The selective blocking of sulfur is thought to affect the hydrogenation ability on the catalyst, resulting in more olefins in the product after sulfur poisoning. The sulfur poisoning on the cobalt catalyst is expected to cause an increase in the number of sites responsible for WGS or to influence the Boudouard reaction, resulting in a higher CO2 selectivity. Both the sites responsible for CO adsorptions as well as the sites for chain growth are poisoned during the poisoning. Additionally, the performance of a base-case cobalt catalyst is compared with that of catalysts modified by chelating agents (CAs). The superior performance of CA-modified catalysts during sulfur poisoning is attributed to the presence of smaller crystallite sizes and higher dispersions of cobalt on the support. Finally, the sulfur deactivation data is modeled by a simple kinetic expression to determine the deactivation constant, deactivation rates and half-life of the FT catalyst.« less

Platinum-tin catalysts supported on silica highly selective for n-hexane dehydrogenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Llorca, J.; Homs, N.; Sales, J.

Silica-supported Pt-Sn catalysts were prepared by two-step impregnation from [PtCl{sub 2}(PPh{sub 3}){sub 2}] and SnCl{sub 2} solutions of appropriate concentrations to yield Pt/Sn atomic ratios ranging from 0.2 to 5.0. In these systems, the presence of true Pt-Sn alloys was confirmed by X-ray diffraction, transmission electron microscopy, energy dispersive X-ray analysis and electron nanodiffraction. Pt and PtSn alloy phases were found on catalysts with Pt/Sn > 1, PtSn alloy alone on the catalyst with Pt/Sn = 1 and PtSn and PtSn{sub 2} alloys, together with Sn in the catalysts with Pt/Sn < 1. All these catalysts were tested in themore » skeletal reactions of n-hexane at 753 K and atmospheric pressure. The selectivity of Pt changed significantly when alloyed with tin. For Sn-rich compositions a segregation of tin toward the catalyst surface was shown by photoelectron spectroscopy, and high hydrogenolysis selectivity and fast deactivation were observed. In contrast, Pt-rich catalysts, in which a well defined PtSn alloy was observed, were much more stable and exhibited high selectivity to dehydrogenation reaction while maintaining low conversions to benzene and hydrogenolysis products. This selectivity pattern can be interpreted in terms of a change in adsorption properties due to differences in the number of adjacent Pt atoms required for the various reaction pathways. 24 refs., 11 figs., 3 tabs.« less

Complexes of metal chlorides with proton donors — promising polyfunctional catalysts for electrophilic processes

NASA Astrophysics Data System (ADS)

Minsker, Karl S.; Ivanova, S. R.; Biglova, Raisa Z.

1995-05-01

The Bronsted acids formed as a result of the interaction of aluminium chlorides with Group I and II metal chlorides in the presence of proton-donating compounds are promising polyfunctional catalysts for electrophilic processes (polymerisation, depolymerisation and degradation of macromolecules, alkylation, desulfurisation, and hydrogenation). The factor determing the electrophilic activity and selectivity of the action of the catalysts is their acidity. This makes it possible to predict the direction of the changes in the activity and selectivity of the catalyst in specific chemical processes in conformity with the opposite variation rule: with increase in the acidity of the electrophilic catalyst, their activity increases but the selectivity of their action diminishes. The bibliography includes 72 references.

Fischer-Tropsch process

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

1987-01-01

A Fischer-Tropsch process utilizing a product selective and stable catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Development of Molecular Catalysts to Bridge the Gap between Heterogeneous and Homogeneous Catalysts

NASA Astrophysics Data System (ADS)

Ye, Rong

Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g. pi-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g. oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl2) or reduced (e.g., with H2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. While localized surface plasmon resonance (LSPR) provides a powerful platform for nanoparticle catalysis, our studies suggest that in some cases interband transitions should be considered as an alternative mechanism of light-driven nanoparticle catalysis. The benefits already demonstrated by plasmonic nanostructures as catalysts provided the impetus for examining complementary activation modes based on the metal nanoparticle itself. Leveraging these transitions has the potential to provide a means to highly active catalysis modes that would otherwise be challenging to access. For example, for the preparation of highly active metal catalysts on a subnanosized scale is challenging, thus limiting their exploitation and study in catalysis. Our work suggests a novel and facile strategy for the formation of highly active gold nanocluster catalysts by light illumination of the interband transitions in the presence of the appropriate substrate.

Catalytic liquid-phase nitrite reduction: Kinetics and catalyst deactivation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pintar, A.; Bercic, G.; Levec, J.

1998-10-01

Liquid-phase reduction using a solid catalyst provides a potential technique for the removal of nitrites from waters. Activity and selectivity measurements were performed for a wide range of reactant concentrations and reaction conditions in an isothermal semi-batch slurry reactor, which was operated at temperatures below 298 K and atmospheric pressure. The effects of catalyst loading and initial nitrite concentration on the reaction rate were also investigated. The Pd monometallic catalysts were found to be advantageous over the Pd-Cu bimetallic catalyst with respect to either reaction activity or selectivity. Among the catalysts tested, minimum ammonia formation was observed for the Pd(1more » wt.%)/{gamma}-Al{sub 2}O{sub 3} catalyst. The proposed intrinsic rate expression for nitrite disappearance over the most selective catalyst is based on the steady-state adsorption model of Hinshelwood, which accounts for a dissociative hydrogen adsorption step on the catalyst surface and an irreversible surface reaction step between adsorbed hydrogen species and nitrite ions in the Helmholtz layer. Both processes occur at comparable rates. An exponential decay in the activity of Pd(1 wt. %)/{gamma}-Al{sub 2}O{sub 3} catalyst has been observed during the liquid-phase nitrite reduction. This is attributed to the catalyst surface deprotonation, which occurs due to the partial neutralization of stoichiometrically produced hydroxide ions with carbon dioxide.« less

Cu and Boron Doped Carbon Nitride for Highly Selective Oxidation of Toluene to Benzaldehyde.

PubMed

Han, Hongling; Ding, Guodong; Wu, Tianbin; Yang, Dexin; Jiang, Tao; Han, Buxing

2015-07-13

A novel Cu and boron doped graphitic carbon nitride catalyst (Cu-CNB) was synthesized using cheap precursors and systematically characterized. The selective oxidation of toluene proceeded very smoothly over the catalyst at 70 °C using tert-butyl hydroperoxide (TBHP) as the oxidant to exclusively afford benzaldehyde. The catalyst can be used for at least five cycles without decrease in activity and selectivity.

Combinatorial evolution of site- and enantioselective catalysts for polyene epoxidation

NASA Astrophysics Data System (ADS)

Lichtor, Phillip A.; Miller, Scott J.

2012-12-01

Selectivity in the catalytic functionalization of complex molecules is a major challenge in chemical synthesis. The problem is magnified when there are several possible stereochemical outcomes and when similar functional groups occur repeatedly within the same molecule. Selective polyene oxidation provides an archetypical example of this challenge. Historically, enzymatic catalysis has provided the only precedents. Although non-enzymatic catalysts that meet some of these challenges became known, a comprehensive solution has remained elusive. Here, we describe low molecular weight peptide-based catalysts, discovered through a combinatorial synthesis and screening protocol, that exhibit site- and enantioselective oxidation of certain positions of various isoprenols. This diversity-based approach, which exhibits features reminiscent of the directed evolution of enzymes, delivers catalysts that compare favourably to the state-of-the-art for the asymmetric oxidation of these compounds. Moreover, the approach culminated in catalysts that exhibit alternative-site selectivity in comparison to oxidation catalysts previously described.

Effect of potassium promoter on cobalt nano-catalysts for fischer-tropsch reaction

NASA Astrophysics Data System (ADS)

Ali, Sardar; Mohd Zabidi, Noor Asmawati; Subbarao, Duvvuri

2012-09-01

In the present work effect of potassium on cobalt nano-catalysts for Fischer-Tropsch reaction has been presented. The catalysts were prepared using a wet impregnation method and promoted with potassium. Samples were characterized by nitrogen adsorption, H2-TPR, and TEM. The Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor 220 δC, 1 atm, H2/CO = 2 and a velocity (SV) =12 L/g.h. for 5 h. Addition of potassium into Co/CNTs decreased the average size of cobalt nanoparticles and the catalyst reducibility. Potassium-promoted Co catalyst resulted in appreciable increase in the selectivity of C5+ hydrocarbons and suppressed methane formation. The 0.06%KCo/CNTs catalyst enhanced the C5+ hydrocarbons selectivity by a factor of 23.5% and reduced the methane selectivity by a factor of 39.6%

Effects of the Acrylic Polyol Structure and the Selectivity of the Employed Catalyst on the Performance of Two-Component Aqueous Polyurethane Coatings

PubMed Central

Cakic, Suzana; Lacnjevac, Caslav; Stamenkovic, Jakov; Ristic, Nikola; Takic, Ljiljana; Barac, Miroljub; Gligoric, Miladin

2007-01-01

Two kinds of aqueous acrylic polyols (single step and multi step synthesis type) have been investigated for their performance in the two-component aqueous polyurethane application, by using more selective catalysts. The aliphatic polyfunctional isocyanates based on hexamethylen diisocyanates have been employed as suitable hardeners. The complex of zirconium, commercially known as K-KAT®XC-6212, and manganese (III) complexes with mixed ligands based on the derivative of maleic acid have been used as catalysts in this study. Both of the aqueous polyols give good results, in terms of application and hardness, when elevated temperatures and more selective catalysts are applied. A more selective catalyst promotes the reaction between the isocyanate and polyol component. This increases the percentage of urethane bonds and the degree of hardness in the films formed from the two components of aqueous polyurethane lacquers. The polyol based on the single step synthesis route is favourable concerning potlife and hardness. The obtained results show that the performance of the two-component aqueous polyurethane coatings depends on the polymer structure of the polyols as well as on the selectivity of the employed catalyst.

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

DOE PAGES

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme; ...

2017-01-01

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

Bio-oil hydrodeoxygenation catalysts produced using strong electrostatic adsorption

USDA-ARS?s Scientific Manuscript database

We synthesized hydrothermally stable metal catalysts with controlled particle size and distribution, with the goal of determining which catalyst(s) can selectively catalyze the production of aromatics from bio-oil (from pyrolysis of biomass). Both precious and base transition metal catalysts (Ru, Pt...

Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

PubMed

Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

2018-04-13

Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al2O3 supported copper and gold nanoparticles

NASA Astrophysics Data System (ADS)

Ndolomingo, Matumuene Joe; Meijboom, Reinout

2017-03-01

Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al2O3 supported copper and gold nanoparticles. Li2O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N2 absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol is occurring as a function of catalyst and oxidant amounts was investigated, with the apparent rate constant, kapp being proportional to the amount of nano catalyst and oxygen present in the system.

Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design.

PubMed

Madhavan, Nandita; Jones, Christopher W; Weck, Marcus

2008-09-01

Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst site density, and (iv) the nature of the catalyst attachment. Herein, we describe the design of polymer supports tuned to enhance the catalytic activity or decrease, or even eliminate, decomposition pathways of salen-based transition metal catalysts that follow either a monometallic or a bimetallic reaction mechanism. These findings result in the creation of some of the most active and selective salen catalysts in the literature.

Steam Reforming of Ethylene Glycol over MgAl₂O₄ Supported Rh, Ni, and Co Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mei, Donghai; Lebarbier, Vanessa M.; Xing, Rong

Steam reforming of ethylene glycol (EG) over MgAl₂O₄ supported metal (15 wt.% Ni, 5 wt.% Rh, and 15 wt.% Co) catalysts were investigated using combined experimental and theoretical methods. Compared to highly active Rh and Ni catalysts with 100% conversion, the steam reforming activity of EG over the Co catalyst is comparatively lower with only 42% conversion under the same reaction conditions (500°C, 1 atm, 119,000 h⁻¹, S/C=3.3 mol). However, CH₄ selectivity over the Co catalyst is remarkably lower. For example, by varying the gas hour space velocity (GHSV) such that complete conversion is achieved for all the catalysts, CH₄more » selectivity for the Co catalyst is only 8%, which is much lower than the equilibrium CH₄ selectivity of ~ 24% obtained for both the Rh and Ni catalysts. Further studies show that varying H₂O concentration over the Co catalyst has a negligible effect on activity, thus indicating zero-order dependence on H₂O. These experimental results suggest that the supported Co catalyst is a promising EG steam reforming catalyst for high hydrogen production. To gain mechanistic insight for rationalizing the lower CH₃ selectivity observed for the Co catalyst, the initial decomposition reaction steps of ethylene glycol via C-O, O-H, C-H, and C-C bond scissions on the Rh(111), Ni(111) and Co(0001) surfaces were investigated using density functional theory (DFT) calculations. Despite the fact that the bond scission sequence in the EG decomposition on the three metal surfaces varies, which leads to different reaction intermediates, the lower CH₄ selectivity over the Co catalyst, as compared to the Rh and Ni catalysts, is primarily due to the higher barrier for CH₄ formation. The higher S/C ratio enhances the Co catalyst stability, which can be elucidated by the facile water dissociation and an alternative reaction path to remove the CH species as a coking precursor via the HCOH formation. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.« less

Effect of through-plane polytetrafluoroethylene distribution in gas diffusion layers on performance of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Ito, Hiroshi; Iwamura, Takuya; Someya, Satoshi; Munakata, Tetsuo; Nakano, Akihiro; Heo, Yun; Ishida, Masayoshi; Nakajima, Hironori; Kitahara, Tatsumi

2016-02-01

This experimental study identifies the effect of through-plane polytetrafluoroethylene (PTFE) distribution in gas diffusion backing (GDB) on the performance of proton exchange membrane fuel cells (PEMFC). PTFE-drying under vacuum pressure created a relatively uniform PTFE distribution in GDB compared to drying under atmospheric pressure. Carbon paper samples with different PTFE distributions due to the difference in drying conditions were prepared and used for the cathode gas diffusion layer (GDL) of PEMFCs. Also investigated is the effect of MPL application on the performance for those samples. The current density (i) - voltage (V) characteristics of these PEMFCs measured under high relative humidity conditions clearly showed that, with or without MPL, the cell using the GDL with PTFE dried under vacuum condition showed better performance than that dried under atmospheric condition. It is suggested that this improved performance is caused by the efficient transport of liquid water through the GDB due to the uniform distribution of PTFE.

A review of polymer electrolyte membrane fuel cell stack testing

NASA Astrophysics Data System (ADS)

Miller, M.; Bazylak, A.

This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.

NASA's First Year Progress with Fuel Cell Advanced Development in Support of the Exploration Vision

NASA Technical Reports Server (NTRS)

Hoberecht, Mark

2007-01-01

NASA Glenn Research Center (GRC), in collaboration with Johnson Space Center (JSC), the Jet Propulsion Laboratory (JPL), Kennedy Space Center (KSC), and industry partners, is leading a proton-exchange-membrane fuel cell (PEMFC) advanced development effort to support the vision for Exploration. This effort encompasses the fuel cell portion of the Energy Storage Project under the Exploration Technology Development Program, and is directed at multiple power levels for both primary and regenerative fuel cell systems. The major emphasis is the replacement of active mechanical ancillary components with passive components in order to reduce mass and parasitic power requirements, and to improve system reliability. A dual approach directed at both flow-through and non flow-through PEMFC system technologies is underway. A brief overview of the overall PEMFC project and its constituent tasks will be presented, along with in-depth technical accomplishments for the past year. Future potential technology development paths will also be discussed.

Platinum redispersion on metal oxides in low temperature fuel cells.

PubMed

Tripković, Vladimir; Cerri, Isotta; Nagami, Tetsuo; Bligaard, Thomas; Rossmeisl, Jan

2013-03-07

We have analyzed the aptitude of several metal oxide supports (TiO(2), SnO(2), NbO(2), ZrO(2), SiO(2), Ta(2)O(5) and Nb(2)O(5)) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum dissolution at high potentials and the interference of redispersion with normal working potential of the PEMFC cathode. We have calculated the PtO(x) (x = 0, 1, 2) adsorption energies on different metal oxides' surface terminations as well as inside the metal oxides' bulk, and we have concluded that NbO(2) might be a good support for platinum redispersion at PEMFC cathodes.

Chiral catalysts immobilized on achiral polymers: effect of the polymer support on the performance of the catalyst.

PubMed

Altava, Belén; Burguete, M Isabel; García-Verdugo, Eduardo; Luis, Santiago V

2018-04-23

Positive effects of the polymeric support on the performance of supported chiral catalysts, in terms of activity, stability and selectivity-enantioselectivity, have been reported when the support is properly selected and optimized opening the way to the design of more efficient catalytic systems.

Theoretical investigation of the selective dehydration and dehydrogenation of ethanol catalyzed by small molecules.

PubMed

Wang, Yanqun; Tang, Yizhen; Shao, Youxiang

2017-09-01

Catalytic dehydration and dehydrogenation reactions of ethanol have been investigated systematically using the ab initio quantum chemistry methods The catalysts include water, hydrogen peroxide, formic acid, phosphoric acid, hydrogen fluoride, ammonia, and ethanol itself. Moreover, a few clusters of water and ethanol were considered to simulate the catalytic mechanisms in supercritical water and supercritical ethanol. The barriers for both dehydration and dehydrogenation can be reduced significantly in the presence of the catalysts. It is revealed that the selectivity of the catalytic dehydration and dehydrogenation depends on the acidity and basicity of the catalysts and the sizes of the clusters. The acidic catalyst prefers dehydration while the basic catalysts tend to promote dehydrogenation more effectively. The calculated water-dimer catalysis mechanism supports the experimental results of the selective oxidation of ethanol in the supercritical water. It is suggested that the solvent- and catalyst-free self-oxidation of the supercritical ethanol could be an important mechanism for the selective dehydrogenation of ethanol on the theoretical point of view. Copyright © 2017 Elsevier Inc. All rights reserved.

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K.; Yang, Xiaofan

2016-08-02

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K; Yang, Xiaofan

2015-03-24

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Assembly of multiple components in a hybrid microcapsule: designing a magnetically separable Pd catalyst for selective hydrogenation.

PubMed

Amali, Arlin Jose; Sharma, Bikash; Rana, Rohit Kumar

2014-09-15

In analogy to the role of long-chain polyamines in biosilicification, poly-L-lysine facilitates the assembly of nanocomponents to design multifunctional microcapsule structures. The method is demonstrated by the fabrication of a magnetically separable catalyst that accommodates Pd nanoparticles (NPs) as active catalyst, Fe3O4 NPs as magnetic component for easy recovery of the catalyst, and silica NPs to impart stability and selectivity to the catalyst. In addition, polyamines embedded inside the microcapsule prevent the agglomeration of Pd NPs and thus result in efficient catalytic activity in hydrogenation reactions, and the hydrophilic silica surface results in selectivity in reactions depending on the polarity of substrates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

NASA Astrophysics Data System (ADS)

Lohrasbi, Elaheh; Javanbakht, Mehran; Mozaffari, Sayed Ahmad

2017-06-01

The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO3sbnd groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm-2 Pt) reaches to a maximum of 530 mW cm-2 at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

Bacterial nanocellulose/Nafion composite membranes for low temperature polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Jiang, Gao-peng; Zhang, Jing; Qiao, Jin-li; Jiang, Yong-ming; Zarrin, Hadis; Chen, Zhongwei; Hong, Feng

2015-01-01

Novel nanocomposite membranes aimed for both proton-exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC) are presented in this work. The membranes are based on blending bacterial nanocellulose pulp and Nafion (abbreviated as BxNy, where x and y indicates the mass ratio of bacterial cellulose to Nafion). The structure and properties of BxNy membranes are characterized by FTIR, SEM, TG, DMA and EIS, along with water uptake, swelling behavior and methanol permeability tests. It is found that the BxNy composite membranes with reinforced concrete-like structure show excellent mechanical and thermal stability regardless of annealing. The water uptake plus area and volume swelling ratios are all decreased compared to Nafion membranes. The proton conductivities of pristine and annealed B1N9 are 0.071 and 0.056 S cm-1, respectively, at 30 °C and 100% humidity. Specifically, annealed B1N1 exhibited the lowest methanol permeability of 7.21 × 10-7 cm2 s-1. Through the selectivity analysis, pristine and annealed B1N7 are selected to assemble the MEAs. The performances of annealed B1N7 in PEMFC and DMFC show the maximum power densities of 106 and 3.2 mW cm-2, respectively, which are much higher than those of pristine B1N7 at 25 °C. The performances of the pristine and annealed B1N7 reach a level as high as 21.1 and 20.4 mW cm-2 at 80 °C in DMFC, respectively.

Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

DOE PAGES

Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; ...

2016-03-09

The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga

2016-05-01

The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. The use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

Fuel processors for fuel cell APU applications

NASA Astrophysics Data System (ADS)

Aicher, T.; Lenz, B.; Gschnell, F.; Groos, U.; Federici, F.; Caprile, L.; Parodi, L.

The conversion of liquid hydrocarbons to a hydrogen rich product gas is a central process step in fuel processors for auxiliary power units (APUs) for vehicles of all kinds. The selection of the reforming process depends on the fuel and the type of the fuel cell. For vehicle power trains, liquid hydrocarbons like gasoline, kerosene, and diesel are utilized and, therefore, they will also be the fuel for the respective APU systems. The fuel cells commonly envisioned for mobile APU applications are molten carbonate fuel cells (MCFC), solid oxide fuel cells (SOFC), and proton exchange membrane fuel cells (PEMFC). Since high-temperature fuel cells, e.g. MCFCs or SOFCs, can be supplied with a feed gas that contains carbon monoxide (CO) their fuel processor does not require reactors for CO reduction and removal. For PEMFCs on the other hand, CO concentrations in the feed gas must not exceed 50 ppm, better 20 ppm, which requires additional reactors downstream of the reforming reactor. This paper gives an overview of the current state of the fuel processor development for APU applications and APU system developments. Furthermore, it will present the latest developments at Fraunhofer ISE regarding fuel processors for high-temperature fuel cell APU systems on board of ships and aircrafts.

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion

PubMed Central

2017-01-01

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters. PMID:28824820

NiO-PTA supported on ZIF-8 as a highly effective catalyst for hydrocracking of Jatropha oil

PubMed Central

Liu, Jing; He, Jing; Wang, Luying; Li, Rong; Chen, Pan; Rao, Xin; Deng, Lihong; Rong, Long; Lei, Jiandu

2016-01-01

Nickel oxide (NiO) and phosphotungstic acid (PTA) supported on a ZIF-8 (NiO-PTA/ZIF-8) catalyst was first synthesized and it showed high activity and good selectivity for the hydrocracking of Jatropha oil. The catalyst was characterized by SEM, SEM-EDS, TEM, N2 adsorption, FT-IR, XRD and XPS. Compared with the NiO-PTA/Al2O3 catalyst, the selectivity of C15-C18 hydrocarbon increased over 36%, and catalytic efficiency increased 10 times over the NiO-PTA/ZIF-8 catalyst. The prepared NiO-PTA/ZIF-8 catalyst was stable for a reaction time of 104 h and the kinetic behavior was also analyzed. This catalyst was found to bypass the presulfurization process, showing promise as an alternative to sulfided catalysts for green diesel production. PMID:27020579

Catalyst recycling via specific non-covalent adsorption on modified silicas.

PubMed

Kluwer, Alexander M; Simons, Chretien; Knijnenburg, Quinten; van der Vlugt, Jarl Ivar; de Bruin, Bas; Reek, Joost N H

2013-03-14

This article describes a new strategy for the recycling of a homogeneous hydroformylation catalyst, by selective adsorption of the catalyst to tailor-made supports after a batchwise reaction. The separation of the catalyst from the product mixture is based on selective non-covalent supramolecular interactions between a ligand and the support. Changing the solvent releases the active catalyst back into the reactor and allows a subsequent batch reaction with the recycled active catalyst. For this purpose, the bidentate NixantPhos ligand has been equipped with a pyridine group. The corresponding rhodium pre-catalyst [Rh(Nix-py)(acac)] (acac = acetylacetonate) forms a very selective, active and highly stable catalyst, and able to reach a turnover number (TON) of 170 000 in a single run (reaction performed in nearly neat 1-octene, S/C ratio of 200 000, at 140 °C, 20 bars syngas pressure). Various commercially available supports have been explored in binding studies and recycling experiments. The end-capped silica-alumina performs the best so far with respect to ligand-adsorbing properties for the current purpose. Although this system has not been fully optimized, four recycling runs could be performed successfully.

SN-EXCHANGED HYDROTALCITES AS CATALYSTS FOR CLEAN AND SELECTIVE BAEYER-VILLIGER OXIDATION OF KETONES USING HYDROGEN PEROXIDE

EPA Science Inventory

A Sn-doped hydrotalcite (Sn/HT) catalyst prepared by ion-exchange is found to be an active and selective catalyst for the liquid phase Baeyer-Villiger (BV) oxidation of cyclic ketones in acetonitrile using hydrogen peroxide (H2O2) as oxidant. Different reaction perameters such as...

Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

PubMed

Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

2016-12-19

We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane**

PubMed Central

Sattler, Jesper J H B; Gonzalez-Jimenez, Ines D; Luo, Lin; Stears, Brien A; Malek, Andrzej; Barton, David G; Kilos, Beata A; Kaminsky, Mark P; Verhoeven, Tiny W G M; Koers, Eline J; Baldus, Marc; Weckhuysen, Bert M

2014-01-01

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. PMID:24989975

Selective catalytic reduction system and process using a pre-sulfated zirconia binder

DOEpatents

Sobolevskiy, Anatoly; Rossin, Joseph A.

2010-06-29

A selective catalytic reduction (SCR) process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream with a catalyst system, the catalyst system comprising (ZrO.sub.2)SO.sub.4, palladium, and a pre-sulfated zirconia binder. The inclusion of a pre-sulfated zirconia binder substantially increases the durability of a Pd-based SCR catalyst system. A system for implementing the disclosed process is further provided.

Co-Pt core-shell nanostructured catalyst prepared by selective chemical vapor pulse deposition of Pt on Co as a cathode in polymer electrolyte fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seo, Sang-Joon; Chung, Ho-Kyoon; Yoo, Ji-Beom

2014-01-15

A new type of PtCo/C catalyst for use as a cathode in polymer electrolyte fuel cells was prepared by selective chemical vapor pulse deposition (CVPD) of Pt on the surface of Co. The activity of the prepared catalyst for oxygen reduction was higher than that of a catalyst prepared by sequential impregnation (IMP) with the two metallic components. This catalytic activity difference occurs because the former catalyst has smaller Pt crystallites that produce stronger Pt-Co interactions and have a larger Pt surface area. Consequently, the CVPD catalyst has a great number of Co particles that are in close contact withmore » the added Pt. The Pt surface was also electronically modified by interactions with Co, which were stronger in the CVPD catalyst than in the IMP catalyst, as indicated by X-ray diffraction, X-ray photoemission spectroscopy, and cyclic voltammetry measurements of the catalysts.« less

A modified preparation procedure for carbon nanotube-confined Nd/Na heterobimetallic catalyst for anti-selective catalytic asymmetric nitroaldol reactions.

PubMed

Sureshkumar, Devarajulu; Hashimoto, Kazuki; Kumagai, Naoya; Shibasaki, Masakatsu

2013-11-15

A recyclable asymmetric metal-based catalyst is a rare entity among the vast collection of asymmetric catalysts developed so far. Recently we found that the combination of a self-assembling metal-based asymmetric catalyst and multiwalled carbon nanotubes (MWNTs) produced a highly active and recyclable catalyst in which the catalytically active metal complex was dispersed in the MWNT network. Herein we describe an improved preparation procedure and full details of a Nd/Na heterobimetallic complex confined in MWNTs. Facilitated self-assembly of the catalyst with MWNTs avoided the sacrificial use of excess chiral ligand for the formation of the heterobimetallic complex, improving the loading ratio of the catalyst components. Eighty-five percent of the catalyst components were incorporated onto MWNTs to produce the confined catalyst, which was a highly efficient and recyclable catalyst for the anti-selective asymmetric nitroaldol reaction. The requisite precautions for the catalyst preparation to elicit reproducible catalytic performance are summarized. Superior catalytic profiles over the prototype catalyst without MWNTs were revealed in the synthesis of optically active 1,2-nitroalkanols, which are key intermediates for the synthesis of therapeutics.

Highly Selective Deoxydehydration of Tartaric Acid over Supported and Unsupported Rhenium Catalysts with Modified Acidities.

PubMed

Li, Xiukai; Zhang, Yugen

2016-10-06

The deoxydehydration (DODH) of sugar acids to industrially important carboxylic acids is a very attractive topic. Oxorhenium complexes are the most-often employed DODH catalysts. Because of the acidity of the rhenium catalysts, the DODH products of sugar acids were usually in the form of mixture of free carboxylic acids and esters. Herein, we demonstrate strategies for the selective DODH of sugar acids to free carboxylic acids by tuning the Lewis acidity or the Brønsted acidity of the rhenium-based catalysts. Starting from tartaric acid, up to 97 % yield of free maleic acid was achieved. Based on our strategies, functional polymer immobilized heterogeneous rhenium catalysts were also developed for the selective DODH conversion of sugar acids. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation

NASA Astrophysics Data System (ADS)

Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

2014-12-01

Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

Selective Hydrogenation of CO2 to Ethanol over Cobalt Catalysts.

PubMed

Wang, Lingxiang; Wang, Liang; Zhang, Jian; Liu, Xiaolong; Wang, Hai; Zhang, Wei; Yang, Qi; Ma, Jingyuan; Dong, Xue; Yoo, Seung Jo; Kim, Jin-Gyu; Meng, Xiangju; Xiao, Feng-Shou

2018-05-22

Methods for the hydrogenation of CO 2 into valuable chemicals are in great demand but their development is still challenging. Herein, we report the selective hydrogenation of CO 2 into ethanol over non-noble cobalt catalysts (CoAlO x ), presenting a significant advance for the conversion of CO 2 into ethanol as the major product. By adjusting the composition of the catalysts through the use of different prereduction temperatures, the efficiency of CO 2 to ethanol hydrogenation was optimized; the catalyst reduced at 600 ° gave an ethanol selectivity of 92.1 % at 140 °C with an ethanol time yield of 0.444 mmol g -1  h -1 . Operando FT-IR spectroscopy revealed that the high ethanol selectivity over the CoAlO x catalyst might be due to the formation of acetate from formate by insertion of *CH x , a key intermediate in the production of ethanol by CO 2 hydrogenation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous Cu–Al–Co Alloys for Selective Furfural Hydrodeoxygenation to 2-Methylfuran

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hutchings, Gregory S.; Luc, Wesley; Lu, Qi

By finding new catalysts for selective and efficient conversion of biomass-derived products to industrially relevant chemicals and fuels, a transition from fossil fuel feedstocks may be achieved. Furfural (C 5H 4O 2) is a platform chemical which may be converted to multiple heterocyclic and ring-opening products, but to date there have been few catalysts which enable selective hydrodeoxygenation to 2-methylfuran (2-MF, C 5H 6O). Here, we present a self-supported nanoporous Cu–Al–Co ternary alloy catalyst with high furfural HDO activity toward 2-MF, achieving up to 66.0% selectivity and 98.2% overall conversion at 513 K with only a ~5 atomic % Comore » composition. Some further analysis over multiple temperature conditions and nominal Co concentrations was performed to examine optimal conditions and tune catalyst performance, and operando X-ray absorption spectroscopy experiments were conducted to elucidate the structure of the catalyst in the reaction environment.« less

Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Heterogeneous Iron Catalysts.

PubMed

Li, Jiang; Liu, Jun-Ling; Liu, He-Yang; Xu, Guang-Yue; Zhang, Jun-Jie; Liu, Jia-Xing; Zhou, Guang-Lin; Li, Qin; Xu, Zhi-Hao; Fu, Yao

2017-04-10

This work provided the first example of selective hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) over heterogeneous Fe catalysts. A catalyst prepared by the pyrolysis of an Fe-phenanthroline complex on activated carbon at 800 °C was demonstrated to be the most active heterogeneous Fe catalyst. Under the optimal reaction conditions, complete conversion of HMF was achieved with 86.2 % selectivity to DMF. The reaction pathway was investigated thoroughly, and the hydrogenation of the C=O bond in HMF was demonstrated to be the rate-determining step during the hydrodeoxygenation, which could be accelerated greatly by using alcohol solvents as additional H-donors. The excellent stability of the Fe catalyst, which was probably a result of the well-preserved active species and the pore structure of the Fe catalyst in the presence of H 2 , was demonstrated in batch and continuous flow fixed-bed reactors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

DOEpatents

Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

2003-09-23

Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

NASA Astrophysics Data System (ADS)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

Alkene metathesis: the search for better catalysts.

PubMed

Deshmukh, Prashant H; Blechert, Siegfried

2007-06-28

Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

Chemical Posttranslational Modification with Designed Rhodium(II) Catalysts.

PubMed

Martin, S C; Minus, M B; Ball, Z T

2016-01-01

Natural enzymes use molecular recognition to perform exquisitely selective transformations on nucleic acids, proteins, and natural products. Rhodium(II) catalysts mimic this selectivity, using molecular recognition to allow selective modification of proteins with a variety of functionalized diazo reagents. The rhodium catalysts and the diazo reactivity have been successfully applied to a variety of protein folds, the chemistry succeeds in complex environments such as cell lysate, and a simple protein blot method accurately assesses modification efficiency. The studies with rhodium catalysts provide a new tool to study and probe protein-binding events, as well as a new synthetic approach to protein conjugates for medical, biochemical, or materials applications. © 2016 Elsevier Inc. All rights reserved.

Replacing precious metals with carbide catalysts for hydrogenation reactions

DOE PAGES

Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; ...

2015-03-03

Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Nimore » modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.« less

NETL - Fuel Reforming Facilities

ScienceCinema

None

2018-01-26

Research using NETL's Fuel Reforming Facilities explores catalytic issues inherent in fossil-energy related applications, including catalyst synthesis and characterization, reaction kinetics, catalyst activity and selectivity, catalyst deactivation, and stability.

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO₂ Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al₂O₃.

PubMed

Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

2015-12-15

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO₂ and Pt/α-Al₂O₃ catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO₂, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H₂, while H₂ combustion was activated by repeated exposure to H₂ gas during the periodic gas test. Selective CO sensing of the micro-TGS against H₂ was attempted using a double catalyst structure with 0.3-30 wt% Pt/α-Al₂O₃ as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al₂O₃ catalyst, by cancelling out the combustion heat from the AuPtPd/SnO₂ catalyst. In addition, the AuPtPd/SnO₂ and 0.3 wt% Pt/α-Al₂O₃ double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H₂.

Oxidative coupling of methane over supported La{sub 2}O{sub 3} and La-promoted MgO catalysts: Influence of catalyst-support interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, V.R.; Mulla, S.A.R.; Uphade, B.S.

1997-06-01

Methane-to-C{sub 2}-hydrocarbon conversion activity and selectivity (or yield) of MgO and La-promoted MgO catalysts in the oxidative coupling of methane and strong basicity of the catalysts are decreased appreciably when these catalysts are deposited on commonly used commercial low surface area porous catalyst carriers containing Al{sub 2}O{sub 3}, SiO{sub 2}, SiC, or ZrO{sub 2} + HfO{sub 2} as the main components. The decrease in the strong basicity and catalytic activity/selectivity or yield is mostly due to strong chemical interactions between the active catalyst component (viz., MgO and La{sub 2}O{sub 3}) and the reactive components of the catalyst support (viz., Al{submore » 2}O{sub 3} and SiO{sub 2}), resulting in the formation of catalytically inactive binary metal oxides on the support surface. However, the influence of support on the activity/selectivity of La{sub 2}O{sub 3} is relatively very small, and also the chemical interactions of La{sub 2}O{sub 3} with the supports (except that containing a high concentration of SiO{sub 2}) are almost absent. The catalyst-support interactions are thus found to be strongly dependent upon the nature (chemical composition) of both catalyst and support. For developing better supported catalysts for the oxidative coupling of methane, supported La{sub 2}O{sub 3} with some promoters shows high promise.« less

Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

PubMed

Zhang, Jia; Zhang, Jingyi; Xu, Yunfeng; Su, Huimin; Li, Xiaoman; Zhou, Ji Zhi; Qian, Guangren; Li, Li; Xu, Zhi Ping

2014-10-07

Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-doped metal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-doped metal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

ECUT: Energy Conversion and Utilization Technologies program. Heterogeneous catalysis modeling program concept

NASA Technical Reports Server (NTRS)

Voecks, G. E.

1983-01-01

Insufficient theoretical definition of heterogeneous catalysts is the major difficulty confronting industrial suppliers who seek catalyst systems which are more active, selective, and stable than those currently available. In contrast, progress was made in tailoring homogeneous catalysts to specific reactions because more is known about the reaction intermediates promoted and/or stabilized by these catalysts during the course of reaction. However, modeling heterogeneous catalysts on a microscopic scale requires compiling and verifying complex information on reaction intermediates and pathways. This can be achieved by adapting homogeneous catalyzed reaction intermediate species, applying theoretical quantum chemistry and computer technology, and developing a better understanding of heterogeneous catalyst system environments. Research in microscopic reaction modeling is now at a stage where computer modeling, supported by physical experimental verification, could provide information about the dynamics of the reactions that will lead to designing supported catalysts with improved selectivity and stability.

Systematic parameter estimation and sensitivity analysis using a multidimensional PEMFC model coupled with DAKOTA.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chao Yang; Luo, Gang; Jiang, Fangming

2010-05-01

Current computational models for proton exchange membrane fuel cells (PEMFCs) include a large number of parameters such as boundary conditions, material properties, and numerous parameters used in sub-models for membrane transport, two-phase flow and electrochemistry. In order to successfully use a computational PEMFC model in design and optimization, it is important to identify critical parameters under a wide variety of operating conditions, such as relative humidity, current load, temperature, etc. Moreover, when experimental data is available in the form of polarization curves or local distribution of current and reactant/product species (e.g., O2, H2O concentrations), critical parameters can be estimated inmore » order to enable the model to better fit the data. Sensitivity analysis and parameter estimation are typically performed using manual adjustment of parameters, which is also common in parameter studies. We present work to demonstrate a systematic approach based on using a widely available toolkit developed at Sandia called DAKOTA that supports many kinds of design studies, such as sensitivity analysis as well as optimization and uncertainty quantification. In the present work, we couple a multidimensional PEMFC model (which is being developed, tested and later validated in a joint effort by a team from Penn State Univ. and Sandia National Laboratories) with DAKOTA through the mapping of model parameters to system responses. Using this interface, we demonstrate the efficiency of performing simple parameter studies as well as identifying critical parameters using sensitivity analysis. Finally, we show examples of optimization and parameter estimation using the automated capability in DAKOTA.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gottesfeld, S.

The fuel cell is the most efficient device for the conversion of hydrogen fuel to electric power. As such, the fuel cell represents a key element in efforts to demonstrate and implement hydrogen fuel utilization for electric power generation. The low temperature, polymer electrolyte membrane fuel cell (PEMFC) has recently been identified as an attractive option for stationary power generation, based on the relatively simple and benign materials employed, the zero-emission character of the device, and the expected high power density, high reliability and low cost. However, a PEMFC stack fueled by hydrogen with the combined properties of low cost,more » high performance and high reliability has not yet been demonstrated. Demonstration of such a stack will remove a significant barrier to implementation of this advanced technology for electric power generation from hydrogen. Work done in the past at LANL on the development of components and materials, particularly on advanced membrane/electrode assemblies (MEAs), has contributed significantly to the capability to demonstrate in the foreseeable future a PEMFC stack with the combined characteristics described above. A joint effort between LANL and an industrial stack manufacturer will result in the demonstration of such a fuel cell stack for stationary power generation. The stack could operate on hydrogen fuel derived from either natural gas or from renewable sources. The technical plan includes collaboration with a stack manufacturer (CRADA). It stresses the special requirements from a PEMFC in stationary power generation, particularly maximization of the energy conversion efficiency, extension of useful life to the 10 hours time scale and tolerance to impurities from the reforming of natural gas.« less

Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Xinbo; Wang, Danjun; College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an 716000

2014-09-15

Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalystmore » is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.« less

Computational Elucidation of Selectivities and Mechanisms Performed by Organometallic and Bioinorganic Catalysts

NASA Astrophysics Data System (ADS)

Grandner, Jessica Marie

Computational methods were used to determine the mechanisms and selectivities of organometallic-catalyzed reactions. The first half of the dissertation focuses on the study of metathesis catalysts in collaboration with the Grubbs group at CalTech. Chapter 1 describes the studies of the decomposition modes of several ruthenium-based metathesis catalysts. These studies were performed to better understand the decomposition of such catalysts in order to prevent decomposition (Chapter 1.2) or utilize decomposed catalysts for alternative reactions (Chapter 1.1). Chapter 2.1 describes the computational investigation of the origins of stereoretentive metathesis with ruthenium-based metathesis catalysts. These findings were then used to computationally design E-selective metathesis catalysts (Chapter 2.2). While the first half of the dissertation was centered around ruthenium catalysts, the second half of the dissertation pertains to iron-catalyzed reaction, in particular, iron-catalyzed reactions by P450 enzymes. The elements of Chapter 3 concentrate on the stereo- and chemo-selectivity of P450-catalyzed C-H hydroxylations. By combining multiple computational methods, the inherent activity of the iron-oxo catalyst and the influence of the active site on such reactions were illuminated. These discoveries allow for the engineering of new substrates and mutant enzymes for tailored C-H hydroxylation. While the mechanism of C-H hydroxylations catalyzed by P450 enzymes has been well studied, there are several P450-catalyzed transformations for which the mechanism is unknown. The components of Chapter 4 describe the use of computations to determine the mechanisms of complex, multi-step reactions catalyzed by P450s. The determination of these mechanisms elucidates how these enzymes react with various functional groups and substrate architectures and allows for a better understanding of how drug-like compounds may be broken down by human P450s.

UV Light-Assisted Synthesis of Highly Efficient Pd-Based Catalyst over NiO for Hydrogenation of o-Chloronitrobenzene

PubMed Central

Jiang, Weidong; Xu, Bin; Fan, Guangyin; Zhang, Kaiming; Xiang, Zhen; Liu, Xiaoqiang

2018-01-01

Supported Pd-based catalyst over active nickel oxide (NiO) was repared using the impregnation method companying with UV-light irradiation. Moreover, the catalytic performance of the obtained Pd-based catalysts was evaluated towards the hydrogenation of o-chloronitrobenzene (o-CNB). Observations indicate that the as-prepared UV-irradiated Pd/NiO catalyst with a mole fraction 0.2% (0.2%Pd/NiO) has higher activity and selectivity in the o-CNB hydrogenation. Especially, UV-light irradiation played a positive role in the improvement of catalytic activity of 0.2%Pd/NiO catalyst, exhibiting an excess 11-fold activity superiority in contrast with non-UV-irradiated 0.2%Pd/NiO catalyst. In addition, it was investigated that effects of varied factors (i.e., reaction time, temperature, o-CNB/Pd ratio, Pd loading, hydrogen pressure) on the selective hydrogenation of ο-CNB catalyzed by UV-irradiated 0.2%Pd/NiO catalyst. Under the reaction conditions of 60 °C, 0.5 h, 1 MPa H2 pressure, 100% conversion of o-CNB, and 81.1% o-CAN selectivity were obtained, even at high molar ratio (8000:1) of o-CNB to Pd. PMID:29662004

Correlating ultrasonic impulse and addition of ZnO promoter with CO2 conversion and methanol selectivity of CuO/ZrO2 catalysts.

PubMed

Ezeh, Collins I; Yang, Xiaogang; He, Jun; Snape, Colin; Cheng, Xiao Min

2018-04-01

The thermal characteristics of Cu-based catalysts for CO 2 utilization towards the synthesis of methanol were analysed and discussed in this study. The preparation process were varied by adopting ultrasonic irradiation at various impulses for the co-precipitation route and also, by introducing ZnO promoters using the solid-state reaction route. Prepared catalysts were characterised using XRD, TPR, TPD, SEM, BET and TG-DTA-DSC. In addition, the CO 2 conversion and CH 3 OH selectivity of these samples were assessed. Calcination of the catalysts facilitated the interaction of the Cu catalyst with the respective support bolstering the thermal stability of the catalysts. The characterisation analysis clearly reveals that the thermal performance of the catalysts was directly related to the sonication impulse and heating rate. Surface morphology and chemistry was enhanced with the aid of sonication and introduction of promoters. However, the impact of the promoter outweighs that of the sonication process. CO 2 conversion and methanol selectivity showed a significant improvement with a 270% increase in methanol yield. Copyright © 2017 Elsevier B.V. All rights reserved.

Heterogeneous catalysis: Enigmas, illusions, challenges, realities, and emergent strategies of design

NASA Astrophysics Data System (ADS)

Thomas, John Meurig

2008-05-01

Predominantly this article deals with the question of how to design new solid catalysts for a variety of industrial and laboratory-orientated purposes. A generally applicable strategy, illustrated by numerous examples, is made possible based on the use of nanoporous materials on to the (high-area) inner surfaces of which well-defined (experimentally and computationally) active centers are placed in a spatially separated fashion. Such single-site catalysts, which have much in common with metal-centered homogenous catalysts and enzymes, enable a wide range of new catalysts to be designed for a variety of selective oxidations, hydrogenations, hydrations and hydrodewaxing, and other reactions that the "greening" of industrial processes demand. Examples are given of new shape-selective, regio-selective, and enantioselective catalysts, many of which operate under mild, environmentally benign conditions. Also considered are some of the reasons why detailed studies of adsorption and stoichiometric reactions at single-crystal surfaces have, disappointingly, not hitherto paved the way to the design and production of many new heterogenous catalysts. Recent work of a theoretical and high-throughout nature, allied to some experimental studies of well-chosen model systems, holds promise for the identification of new catalysts for simple, but industrially important reactions.

UV Light-Assisted Synthesis of Highly Efficient Pd-Based Catalyst over NiO for Hydrogenation of o-Chloronitrobenzene.

PubMed

Jiang, Weidong; Xu, Bin; Fan, Guangyin; Zhang, Kaiming; Xiang, Zhen; Liu, Xiaoqiang

2018-04-14

Supported Pd-based catalyst over active nickel oxide (NiO) was repared using the impregnation method companying with UV-light irradiation. Moreover, the catalytic performance of the obtained Pd-based catalysts was evaluated towards the hydrogenation of o -chloronitrobenzene ( o -CNB). Observations indicate that the as-prepared UV-irradiated Pd/NiO catalyst with a mole fraction 0.2% (0.2%Pd/NiO) has higher activity and selectivity in the o -CNB hydrogenation. Especially, UV-light irradiation played a positive role in the improvement of catalytic activity of 0.2%Pd/NiO catalyst, exhibiting an excess 11-fold activity superiority in contrast with non-UV-irradiated 0.2%Pd/NiO catalyst. In addition, it was investigated that effects of varied factors (i.e., reaction time, temperature, o -CNB/Pd ratio, Pd loading, hydrogen pressure) on the selective hydrogenation of ο -CNB catalyzed by UV-irradiated 0.2%Pd/NiO catalyst. Under the reaction conditions of 60 °C, 0.5 h, 1 MPa H₂ pressure, 100% conversion of o -CNB, and 81.1% o -CAN selectivity were obtained, even at high molar ratio (8000:1) of o -CNB to Pd.

Stereodivergent catalytic doubly diastereoselective nitroaldol reactions using heterobimetallic complexes.

PubMed

Sohtome, Yoshihiro; Kato, Yuko; Handa, Shinya; Aoyama, Naohiro; Nagawa, Keita; Matsunaga, Shigeki; Shibasaki, Masakatsu

2008-06-05

Stereodivergent construction of three contiguous stereocenters in catalytic doubly diastereoselective nitroaldol reactions of alpha-chiral aldehydes with nitroacetaldehyde dimethyl acetal using two types of heterobimetallic catalysts is described. A La-Li-BINOL (LLB) catalyst afforded anti,syn-nitroaldol products in >20:1-14:1 selectivity, and a Pd/La/Schiff base catalyst afforded complimentary syn,syn-nitroaldol products in 10:1-5:1 selectivity.

Understanding cathode flooding and dry-out for water management in air breathing PEM fuel cells

NASA Astrophysics Data System (ADS)

Paquin, Mathieu; Fréchette, Luc G.

An analysis of water management in air breathing small polymer electrolyte membrane fuel cells (PEMFCs) is presented. Comprehensive understanding of flooding and dry-out limiting phenomena is presented through a combination of analytical modeling and experimental investigations using a small PEMFC prototype. Configurations of the fuel cell with different heat and mass transfer properties are experimentally evaluated to assess the impact of thermal resistance and mass transport resistance on water balance. Manifestation of dry-out and flooding problems, as limiting phenomena, are explained through a ratio between these two resistances. Main conclusions are that decreasing the ratio between thermal and mass transport resistance under a certain point leads to flooding problems in air breathing PEMFC. Increasing this ratio leads to dry-out of the polymer electrolyte membrane. However, too high thermal resistance or too low mass transport resistance reduces the limiting current by pushing forward the dry-out problem. This work provides a framework to achieve the proper balance between thermal rejection and mass transport to optimize the maximum current density of free convection fuel cells.

Degradation of graphene coated copper in simulated proton exchange membrane fuel cell environment: Electrochemical impedance spectroscopy study

NASA Astrophysics Data System (ADS)

Ren, Y. J.; Anisur, M. R.; Qiu, W.; He, J. J.; Al-Saadi, S.; Singh Raman, R. K.

2017-09-01

Metallic materials are most suitable for bipolar plates of proton exchange membrane fuel cell (PEMFC) because they possess the required mechanical strength, durability, gas impermeability, acceptable cost and are suitable for mass production. However, metallic bipolar plates are prone to corrosion or they can passivate under PEMFC environment and interrupt the fuel cell operation. Therefore, it is highly attractive to develop corrosion resistance coating that is also highly conductive. Graphene fits these criteria. Graphene coating is developed on copper by chemical vapor deposition (CVD) with an aim to improving corrosion resistance of copper under PEMFC condition. The Raman Spectroscopy shows the graphene coating to be multilayered. The electrochemical degradation of graphene coated copper is investigated by electrochemical impedance spectroscopy (EIS) in 0.5 M H2SO4 solution at room temperature. After exposure to the electrolyte for up to 720 h, the charge transfer resistance (Rt) of the graphene coated copper is ∼3 times greater than that of the bare copper, indicating graphene coatings could improve the corrosion resistance of copper bipolar plates.

Coordinating IMC-PID and adaptive SMC controllers for a PEMFC.

PubMed

Wang, Guo-Liang; Wang, Yong; Shi, Jun-Hai; Shao, Hui-He

2010-01-01

For a Proton Exchange Membrane Fuel Cell (PEMFC) power plant with a methanol reformer, the process parameters and power output are considered simultaneously to avoid violation of the constraints and to keep the fuel cell power plant safe and effective. In this paper, a novel coordinating scheme is proposed by combining an Internal Model Control (IMC) based PID Control and adaptive Sliding Mode Control (SMC). The IMC-PID controller is designed for the reformer of the fuel flow rate according to the expected first-order dynamic properties. The adaptive SMC controller of the fuel cell current has been designed using the constant plus proportional rate reaching law. The parameters of the SMC controller are adaptively tuned according to the response of the fuel flow rate control system. When the power output controller feeds back the current references to these two controllers, the coordinating controllers system works in a system-wide way. The simulation results of the PEMFC power plant demonstrate the effectiveness of the proposed method. 2009 ISA. Published by Elsevier Ltd. All rights reserved.

Design of an integrated fuel processor for residential PEMFCs applications

NASA Astrophysics Data System (ADS)

Seo, Yu Taek; Seo, Dong Joo; Jeong, Jin Hyeok; Yoon, Wang Lai

KIER has been developing a novel fuel processing system to provide hydrogen rich gas to residential PEMFCs system. For the effective design of a compact hydrogen production system, each unit process for steam reforming and water gas shift, has a steam generator and internal heat exchangers which are thermally and physically integrated into a single packaged hardware system. The newly designed fuel processor (prototype II) showed a thermal efficiency of 78% as a HHV basis with methane conversion of 89%. The preferential oxidation unit with two staged cascade reactors, reduces, the CO concentration to below 10 ppm without complicated temperature control hardware, which is the prerequisite CO limit for the PEMFC stack. After we achieve the initial performance of the fuel processor, partial load operation was carried out to test the performance and reliability of the fuel processor at various loads. The stability of the fuel processor was also demonstrated for three successive days with a stable composition of product gas and thermal efficiency. The CO concentration remained below 10 ppm during the test period and confirmed the stable performance of the two-stage PrOx reactors.

Emission Abatement System

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander

2003-05-13

Emission abatement system. The system includes a source of emissions and a catalyst for receiving the emissions. Suitable catalysts are absorber catalysts and selective catalytic reduction catalysts. A plasma fuel converter generates a reducing gas from a fuel source and is connected to deliver the reducing gas into contact with the absorber catalyst for regenerating the catalyst. A preferred reducing gas is a hydrogen rich gas and a preferred plasma fuel converter is a plasmatron. It is also preferred that the absorber catalyst be adapted for absorbing NO.sub.x.

WaterTransport in PEM Fuel Cells: Advanced Modeling, Material Selection, Testing and Design Optimization

DOE Office of Scientific and Technical Information (OSTI.GOV)

J. Vernon Cole; Abhra Roy; Ashok Damle

2012-10-02

Water management in Proton Exchange Membrane, PEM, Fuel Cells is challenging because of the inherent conflicts between the requirements for efficient low and high power operation. Particularly at low powers, adequate water must be supplied to sufficiently humidify the membrane or protons will not move through it adequately and resistance losses will decrease the cell efficiency. At high power density operation, more water is produced at the cathode than is necessary for membrane hydration. This excess water must be removed effectively or it will accumulate in the Gas Diffusion Layers, GDLs, between the gas channels and catalysts, blocking diffusion pathsmore » for reactants to reach the catalysts and potentially flooding the electrode. As power density of the cells is increased, the challenges arising from water management are expected to become more difficult to overcome simply due to the increased rate of liquid water generation relative to fuel cell volume. Thus, effectively addressing water management based issues is a key challenge in successful application of PEMFC systems. In this project, CFDRC and our partners used a combination of experimental characterization, controlled experimental studies of important processes governing how water moves through the fuel cell materials, and detailed models and simulations to improve understanding of water management in operating hydrogen PEM fuel cells. The characterization studies provided key data that is used as inputs to all state-of-the-art models for commercially important GDL materials. Experimental studies and microscopic scale models of how water moves through the GDLs showed that the water follows preferential paths, not branching like a river, as it moves toward the surface of the material. Experimental studies and detailed models of water and airflow in fuel cells channels demonstrated that such models can be used as an effective design tool to reduce operating pressure drop in the channels and the associated costs and weight of blowers and pumps to force air and hydrogen gas through the fuel cell. Promising improvements to materials structure and surface treatments that can potentially aid in managing the distribution and removal of liquid water were developed; and improved steady-state and freeze-thaw performance was demonstrated for a fuel cell stack under the self-humidified operating conditions that are promising for stationary power generation with reduced operating costs.« less

Tuning Product Selectivity for Aqueous CO2 Reduction with a Mn(bipyridine)-pyrene Catalyst Immobilized on a Carbon Nanotube Electrode

PubMed Central

2017-01-01

The development of high-performance electrocatalytic systems for the controlled reduction of CO2 to value-added chemicals is a key goal in emerging renewable energy technologies. The lack of selective and scalable catalysts in aqueous solution currently hampers the implementation of such a process. Here, the assembly of a [MnBr(2,2′-bipyridine)(CO)3] complex anchored to a carbon nanotube electrode via a pyrene unit is reported. Immobilization of the molecular catalyst allows electrocatalytic reduction of CO2 under fully aqueous conditions with a catalytic onset overpotential of η = 360 mV, and controlled potential electrolysis generated more than 1000 turnovers at η = 550 mV. The product selectivity can be tuned by alteration of the catalyst loading on the nanotube surface. CO was observed as the main product at high catalyst loadings, whereas formate was the dominant CO2 reduction product at low catalyst loadings. Using UV–vis and surface-sensitive IR spectroelectrochemical techniques, two different intermediates were identified as responsible for the change in selectivity of the heterogenized Mn catalyst. The formation of a dimeric Mn0 species at higher surface loading was shown to preferentially lead to CO formation, whereas at lower surface loading the electrochemical generation of a monomeric Mn-hydride is suggested to greatly enhance the production of formate. These results emphasize the advantages of integrating molecular catalysts onto electrode surfaces for enhancing catalytic activity while allowing excellent control and a deeper understanding of the catalytic mechanisms. PMID:28885841

Selective Hydrogenation of Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/SBA-15 Catalyst.

PubMed

Audemar, Maïté; Ciotonea, Carmen; De Oliveira Vigier, Karine; Royer, Sébastien; Ungureanu, Adrian; Dragoi, Brindusa; Dumitriu, Emil; Jérôme, François

2015-06-08

The hydrogenation of furfural to furfuryl alcohol was performed in the presence of a Co/SBA-15 catalyst. High selectivity (96 %) at a conversion higher than 95 % is reported over this catalytic system. As the conversion of furfural to furfuryl alcohol occurs over metallic Co sites, the effect of reduction temperature, H2 pressure, and reaction temperature were studied. Optimum reaction conditions were: 150 °C, 1.5 h, 2.0 MPa of H2 . The catalyst was recyclable, and furfuryl alcohol was recovered with a purity higher than 90 %. The effect of the solvent concentration was also studied. With a minimum of 50 wt % of solvent, the selectivity to furfuryl alcohol and the conversion of furfural remained high (both over 80 %). Likewise, the activity of the catalyst is maintained even in pure furfural, which confirms the real potential of the proposed catalytic system. This catalyst was also used in the hydrogenation of levulinic acid to produce γ-valerolactone selectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CuO/CeO2 catalysts for glycerol selective conversion to lactic acid.

PubMed

Palacio, Ruben; Torres, Sebastian; Royer, Sébastien; Mamede, Anne Sophie; López, Diana; Hernández, Diana

2018-03-26

Ceria supported copper oxide catalysts were produced by a deposition-precipitation method, at a high copper loading (up to >25 wt%). These materials demonstrated excellent properties for glycerol selective conversion to lactic acid, with a conversion reaching up to 87% with a selectivity to lactic acid of 74% (8 h reaction, 220 °C, under N2 pressure). These catalysts also exhibited high stability upon 5 successive reaction cycles. The formation of a crystalline CuO phase was demonstrated in the nanocomposites at a high Cu loading, with elongated shaped particles formed on the cerium oxide surface. Such particles were however, not observed at low Cu loadings. XPS analysis revealed that Cu(ii) was the main Cu species on the fresh catalyst, and that this species was reduced to Cu(i) during the reaction. Complementary characterization over the spent catalyst clearly showed the morphological modifications of the CuO phase, however, did not impact significantly either glycerol conversion or selectivity to lactic acid upon recycling. For instance, apparently, the catalytic activity of CuO largely depends on the Cu(ii) species.

Phosphorylated mesoporous carbon as effective catalyst for the selective fructose dehydration to HMF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villa, Alberto; Schiavoni, Marco; Fulvio, Pasquale F

Phosphorylated mesoporous carbons (PMCs) have been synthesized using an already reported one pot methodology. These materials have been applied as acidic catalysts in the dehydration of fructose to hydroxymethylfurfural (HMF). PMCs showed better selectivity to HMF compared to sulfonated carbon catalyst (SC) despite lower activity. The concentration of P-O groups correlates to the activity/selectivity of the catalysts; the higher the P-O concentration the higher the activity. However, the higher the P-O content the lower the selectivity to HMF. Indeed a lower concentration of the P-O groups (and even the acidic groups) minimized the degradation of HMF to levulinic acid andmore » the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines, water insoluble by-products derived from the dehydration of fructose, blocking the active site of the catalyst. Increasing the amount of P-O groups, higher amount of humines are formed; therefore carbons containing lower amount of phosphorylated groups, such as P/N-0.25, are less prone to deactivation. Keywords: Phosphorylated mesoporous carbons; fructose dehydration; HMF« less

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

PubMed Central

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-01-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system. PMID:25004118

Improving the hydrocarbon production via co-pyrolysis of bagasse with bio-plastic and dual-catalysts layout.

PubMed

Zhang, Huiyan; Likun, Peter Keliona Wani; Xiao, Rui

2018-03-15

Catalytic fast pyrolysis (CFP) of bagasse and bio-plastic (chicken feather keratin) and their mixtures were conducted to produce aromatic hydrocarbons over a HZSM-5, USY, and dual-catalysts layout. The effects of temperature, co-feeding ratios, feed-to-catalyst ratios and dual catalysts on hydrocarbon yields and selectivities were investigated. The results show a general improvement in the aromatic hydrocarbons yields in all cases compared to non-catalytic and pure biomass pyrolysis. The aromatic hydrocarbons increased by 10 fold with the increase of temperature from 400°C to 700°C. The aromatic yields increased 1.5 times at co-feeding, 2.0 greater at feed/HZSM-5 ratio of 1:6, 1.2 times at feed/USY ratio of 1:16, and 2.66 times at USY/HZSM-5 scenario. The selectivities towards benzene increased, at higher co-feeding ratios, while that of toluene shows an opposite trend. Xylenes selectivities were less sensitive to the changes of co-feeding ratios. In contrast, the USY catalyst only produced little amount of toluene and xylenes. The dual catalyst design (USY/HZSM-5) resulted in the highest aromatic yields, than other catalyst design scenarios. The pyrolysis temperature is a significant parameter for hydrocarbon production. Co-feeding bagasse and bio-plastic enhanced biomass conversion to aromatic compounds. For any type of zeolite catalyst, there was an optimum feed-to-catalyst ratio that generated maximum hydrocarbons. Dual catalyst layout shows a new opportunity for efficient conversion of biomass materials into hydrocarbons. Copyright © 2017 Elsevier B.V. All rights reserved.

Catalysts and methods of using the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slowing, Igor Ivan; Kandel, Kapil

2017-02-14

The present invention provides a catalyst including a mesoporous silica nanoparticle and a catalytic material comprising iron. In various embodiments, the present invention provides methods of using and making the catalyst. In some examples, the catalyst can be used to hydrotreat fatty acids or to selectively remove fatty acids from feedstocks.

The effects of battlefield contaminants on PEMFC performance

NASA Astrophysics Data System (ADS)

Moore, Jon M.; Adcock, Paul L.; Lakeman, J. Barry; Mepsted, Gary O.

The effects of contaminants on the performance of an air breathing proton exchange membrane fuel cell (PEMFC) were investigated, by introduction into oxidant air fed to the fuel cell. The impact of the common pollutants sulphur dioxide, nitrogen dioxide, carbon monoxide, propane and benzene and the chemical warfare agents, sarin, sulphur mustard, cyanogen chloride (CNCl) and hydrogen cyanide (HCN) were assessed. At the concentrations studied, the common contaminants had either no effect on performance or caused a reversible depression. The chemical warfare agents all seriously compromised the performance of the fuel cells in an irreversible manner.

Planar array stack design aided by rapid prototyping in development of air-breathing PEMFC

NASA Astrophysics Data System (ADS)

Chen, Chen-Yu; Lai, Wei-Hsiang; Weng, Biing-Jyh; Chuang, Huey-Jan; Hsieh, Ching-Yuan; Kung, Chien-Chih

The polymer electrolyte membrane fuel cell (PEMFC) is one of the most important research topics in the new and clean energy area. The middle or high power PEMFCs can be applied to the transportation or the distributed power system. But for the small power application, it is needed to match the power requirement of the product generally. On the other hand, the direct methanol fuel cell (DMFC) is one of the most common type that researchers are interested in, but recently the miniature or the micro-PEMFCs attract more attention due to their advantages of high open circuit voltage and high power density. The objective of this study is to develop a new air-breathing planar array fuel cell stacked from 10 cells made by rapid prototyping technology which has potential for fast commercial design, low cost manufacturing, and even without converters/inverters for the system. In this paper, the main material of flow field plates is acrylonitrile-butadiene-styrene (ABS) which allows the fuel cell be mass-manufactured by plastic injection molding technology. The rapid prototyping technology is applied to construct the prototype and verify the practicability of the proposed stack design. A 10-cell air-breathing miniature PEMFC stack with a volume of 6 cm × 6 cm × 0.9 cm is developed and tested. Its segmented membrane electrode assembly (MEA) is designed with the active surface area of 1.3 cm × 1.3 cm in each individual MEA. The platinum loading at anode and cathode are 0.2 mg cm -2 and 0.4 mg cm -2, respectively. Results show that the peak power densities of the parallel connected and serial connected stack are 99 mW cm -2 at 0.425 V and 92 mW cm -2 at 4.25 V, respectively under the conditions of 70 °C relative saturated humidity (i.e., dew point temperature), ambient temperature and free convection air. Besides, the stack performance is increased under forced convection. If the cell surface air is blown by an electric fan, the peak power densities of parallel connected and serial connected stack are improved to 123 mW cm -2 at 0.425 V and 105 mW cm -2 at 5.25 V, respectively. The forced convection air can not only increases the oxygen diffusion rate at the air-breathing surface, but also enhance the uniformity of output voltage distribution. The performance obtained in this work reaches to the state-of-the-air of air-breathing planar PEMFC stack comparing to recent literatures. In this study, the different behavior of output performance at water-rich region and water-lean region is also discussed.

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2001-09-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use ofmore » Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University, (ii) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (iii) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to attrition study of the iron-based catalysts. Precipitated silica appeared to decrease attrition resistance of spray-dried iron FT catalysts. It was found that the catalyst with precipitated silica content at around 12wt% showed the lowest attrition resistance. The results of net change in volume moment and catalyst morphology showed supporting evidences to the attrition results. Catalysts with low attrition resistance generated more fines loss, had higher net change in volume moment and showed more breakage of particles. BET surface area and pore volume of this catalyst series fluctuated; therefore no conclusion can be drawn from the data obtained. However, catalyst with no precipitated silica showed the lowest in BET surface area and pore volume, as expected. Addition of precipitated silica to the catalysts had no effect to the phase changes of iron that could have significant influence to catalyst attrition. The presence of precipitated silica is needed for enhancing catalyst surface area; however, the amount of silica added should be compromising with attrition resistance of catalysts.« less

Hydrogenolysis of Glycerol to Propylene Glycol on Nanosized Cu-Zn-Al Catalysts Prepared Using Microwave Process.

PubMed

Kim, Dong Won; Ha, Sang Ho; Moon, Myung Jun; Lim, Kwon Taek; Ryu, Young Bok; Lee, Sun Do; Lee, Man Sig; Hong, Seong-Soo

2015-01-01

Cu-Zn-Al catalysts were prepared using microwave-assisted process and co-precipitation methods. The prepared catalysts were characterized by XRD, BET, XPS and TPD of ammonia and their catalytic activity for the hydrogenolysis of glycerol to propylene glycol was also examined. The XRD patterns of Cu/Zn/Al mixed catalysts show CuO and ZnO crystalline phase regardless of preparation method. The highest glycerol hydrogenolysis conversion is obtained with the catalyst having a Cu/Zn/Al ratio of 2:2:1. Hydrogen pre-reduction of catalysts significantly enhanced both glycerol conversions and selectivity to propylene glycol. The glycerol conversion increased with an increase of reaction temperature. However, the selectivity to propylene glycol increased with an increase of temperature, and then declined to 30.5% at 523 K.

Mn-salen@MIL101(Al): a heterogeneous, enantioselective catalyst synthesized using a 'bottle around the ship' approach.

PubMed

Bogaerts, Thomas; Van Yperen-De Deyne, Andy; Liu, Ying-Ya; Lynen, Frederic; Van Speybroeck, Veronique; Van Der Voort, Pascal

2013-09-21

An enantioselective catalyst, consisting of a chiral Mn(III)salen complex entrapped in the MIL-101 metal organic framework, is reported. For the first time, we assemble a robust MOF-cage around a chiral complex. The heterogeneous catalyst shows the same selectivity as the homogeneous complex and is fully recyclable. Theoretical calculations provide insight into this retention of selectivity.

Development of sustainable Palladium-based catalysts for removal of persistent contaminants from drinking water

NASA Astrophysics Data System (ADS)

Shuai, Danmeng

Pd-based catalytic reduction has emerged as an advanced treatment technology for drinking water decontamination, and a suite of persistent contaminants including oxyanions, N-nitrosoamines, and halogenated compounds are amenable to catalytic reduction. The primary goal of this study is to develop novel Pd-based catalysts with enhanced performance (i.e., activity, selectivity, and sustainability) to remove contaminants from drinking water. The effects of water quality (i.e., co-contaminants in water matrix), catalyst support, and catalyst metal were explored, and they provide insights for preparing catalysts with faster kinetics, higher selectivity, and extended lifetime. Azo dyes are wide-spread contaminants, and they are potentially co-exisiting with target contaminants amenable for catalytic removal. The probe azo dye methyl orange (MO) enhanced catalytic reduction kinetics of a suite of oxyanions (i.e., nitrate, nitrite, bromate, chlorate, and perchlorate) and diatrizoate significantly but not N-nitrosodimethylamine (NDMA) with a variety of Pd-based catalysts. Nitrate was selected as a probe contaminant, and several different azo dyes (i.e., (methyl orange, methyl red, fast yellow AB, metanil yellow, acid orange 7, congo red, eriochrome black T, acid red 27, acid yellow 11, and acid yellow 17) were evaluated for their ability to enhance reduction. A hydrogen atom shuttling mechanism was proposed and a kinetic model was proposed based on Bronsted-Evans-Polanyi (BEP) theory, and they suggest sorbed azo dyes and reduced hydrazo dyes shuttle hydrogen atoms to oxyanions or diatrizoate to enhance their reduction kinetics. Next, vapor-grown carbon nanofiber (CNF) supports were used to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). In order to evaluate the amount of interior versus exterior loading of Pd nanoparticles, a fast and accurate geometric model was developed based on two-dimensional transmission electron microscopy (2D TEM). Results from my method agree adequately with 3D scanning transmission electron microscopy (3D TEM), which is recognized as a convincing method to evaluate interior versus exterior loading. By using Pd CNF catalysts for nitrite reduction, results show that both activity and selectivity are not significantly impacted by Pd interior versus exterior loading. Turnover frequencies (TOFs) among all CNF catalysts are consistent, suggesting faster kinetics are achieved on catalysts with smaller Pd nanoparticles, and suggesting nitrite reduction is neither sensitive to Pd location on CNFs nor Pd structure. However selectivity to dinitrogen is more favorable on larger Pd nanoparticles. Therefore, an optimum Pd nanoparticle size on CNFs balances high reduction kinetics and selectivity to dinitrogen. CNF Pd catalysts perform better than conventional activated or alumina supported Pd catalysts in term of kinetics and selectivity for nitrite reduction, and they maintain consistent activity during multiple reduction cycles. Lastly, the structure-sensitivity of catalytic activity and selectivity for contaminant nitrite, NDMA, and diatrizoate removal were investigated on shape- and size-controlled Pd nanoparticles. Results show that TOFs for nitrite, NDMA, and diatrizoate are dependent on coordination numbers of surface Pd sites at low contaminant concentration, but TOFs for nitrite at high concentration are consistent. Selectivity to ammonia for nitrite reduction decreases with increasing surface Pd sites, i.e., decreasing Pd nanoparticle size irrespective of nitrite concentration, but NDMA reduction is neither shape- nor size-specific, and it exclusively proceeds to ammonia and dimethylamine. Diatrizoate reduction selectivity is also likely to be nonspecific to shape and size, and a series of deiodinated intermediates, 3,5-diacetamidobenzoic acid, and iodide are the produced. Hence, this study suggests that contaminant reduction kinetics and selectivity are Pd shape and size dependent, and the dependence varies by contaminant type and concentration. In summary, Pd-based catalysts can be tailored for enhanced activity, selectivity, and longevity, and catalytic treatment holds the promise for advanced drinking water treatment.

Peptide-templated noble metal catalysts: syntheses and applications

PubMed Central

Wang, Wei; Anderson, Caleb F.; Wang, Zongyuan; Wu, Wei

2017-01-01

Noble metal catalysts have been widely used in many applications because of their high activity and selectivity. However, a controllable preparation of noble metal catalysts still remains as a significant challenge. To overcome this challenge, peptide templates can play a critical role in the controllable syntheses of catalysts owing to their flexible binding with specific metallic surfaces and self-assembly characteristics. By employing peptide templates, the size, shape, facet, structure, and composition of obtained catalysts can all be specifically controlled under the mild synthesis conditions. In addition, catalysts with spherical, nanofiber, and nanofilm structures can all be produced by associating with the self-assembly characteristics of peptide templates. Furthermore, the peptide-templated noble metal catalysts also reveal significantly enhanced catalytic behaviours compared with conventional catalysts because the electron conductivity, metal dispersion, and reactive site exposure can all be improved. In this review, we summarize the research progresses in the syntheses of peptide-templated noble metal catalysts. The applications of the peptide-templated catalysts in organic reactions, photocatalysis, and electrocatalysis are discussed, and the relationship between structure and activity of these catalysts are addressed. Future opportunities, including new catalytic materials designed by using biological principles, are indicated to achieve selective, eco-friendly, and energy neutral synthesis approaches. PMID:28507701

Advanced Materials for PEM-Based Fuel Cell Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

James E. McGrath; Donald G. Baird; Michael von Spakovsky

2005-10-26

Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 degrees C. However, application of these membranes is limited due tomore » their high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in herein.« less

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

PubMed Central

2011-01-01

This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

Ga-Doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction.

PubMed

Lim, JeongHoon; Shin, Hyeyoung; Kim, MinJoong; Lee, Hoin; Lee, Kug-Seung; Kwon, YongKeun; Song, DongHoon; Oh, SeKwon; Kim, Hyungjun; Cho, EunAe

2018-04-11

Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mg Pt -1 ) and a 17.3-fold improvement in the specific activity (2.53 mA cm -2 ) compared to the commercial Pt/C (0.106 A mg Pt -1 and 0.146 mA cm -2 ). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications.

Hydrogen Generation Via Fuel Reforming

NASA Astrophysics Data System (ADS)

Krebs, John F.

2003-07-01

Reforming is the conversion of a hydrocarbon based fuel to a gas mixture that contains hydrogen. The H2 that is produced by reforming can then be used to produce electricity via fuel cells. The realization of H2-based power generation, via reforming, is facilitated by the existence of the liquid fuel and natural gas distribution infrastructures. Coupling these same infrastructures with more portable reforming technology facilitates the realization of fuel cell powered vehicles. The reformer is the first component in a fuel processor. Contaminants in the H2-enriched product stream, such as carbon monoxide (CO) and hydrogen sulfide (H2S), can significantly degrade the performance of current polymer electrolyte membrane fuel cells (PEMFC's). Removal of such contaminants requires extensive processing of the H2-rich product stream prior to utilization by the fuel cell to generate electricity. The remaining components of the fuel processor remove the contaminants in the H2 product stream. For transportation applications the entire fuel processing system must be as small and lightweight as possible to achieve desirable performance requirements. Current efforts at Argonne National Laboratory are focused on catalyst development and reactor engineering of the autothermal processing train for transportation applications.

Degradation of polymer electrolyte membrane fuel cell by siloxane in biogas

NASA Astrophysics Data System (ADS)

Seo, Ji-Sung; Kim, Da-Yeong; Hwang, Sun-Mi; Seo, Min Ho; Seo, Dong-Jun; Yang, Seung Yong; Han, Chan Hui; Jung, Yong-Min; Guim, Hwanuk; Nahm, Kee Suk; Yoon, Young-Gi; Kim, Tae-Young

2016-06-01

We studied the degradation and durability of polymer electrolyte membrane fuel cell (PEMFC) at membrane-electrode-assembly (MEA) level by injection of octamethylcyclotetrasiloxane (D4) as a representative siloxane, which has been found in many industrial and personal products. Specifically, i) GC/MS analysis demonstrated that the ring-opening polymerization of D4 could result in the formation of various linear and cyclic siloxanes in both electrodes of MEA; ii) post-test analysis revealed that the transformed siloxanes were transported from the anode to the cathode via free-volumes in the polymer membrane; iii) RDE measurement and DFT calculation revealed that D4 was not directly responsible for the electrocatalytic activity of Pt; iv) electrochemical analysis demonstrated that the residual methyl groups of siloxane and various siloxanes did not hinder the proton transport in the polymer membrane; and v) siloxanes accumulated in the primary and secondary pores with the exception of an external surface of carbon, causing an increase in the oxygen reactant's resistance and resulting in a decrease of the cell performance. In addition, we confirmed that injection of D4 did not affect the carbon corrosion adversely because the siloxane had little influence on water sorption in the catalyst layer.

Deactivation of Pt/VC proton exchange membrane fuel cell cathodes by SO2, H2S and COS

NASA Astrophysics Data System (ADS)

Gould, Benjamin D.; Baturina, Olga A.; Swider-Lyons, Karen E.

Sulfur contaminants in air pose a threat to the successful operation of proton exchange membrane fuel cells (PEMFCs) via poisoning of the Pt-based cathodes. The deactivation behavior of commercial Pt on Vulcan carbon (Pt/VC) membrane electrode assemblies (MEAs) is determined when exposed to 1 ppm (dry) of SO 2, H 2S, or COS in air for 3, 12, and 24 h while held at a constant potential of 0.6 V. All the three sulfur compounds cause the same deactivation behavior in the fuel cell cathodes, and the polarization curves of the poisoned MEAs have the same decrease in performance. Sulfur coverages after multiple exposure times (3, 12, and 24 h) are determined by cyclic voltammetry (CV). As the exposure time to sulfur contaminants increases from 12 to 24 h, the sulfur coverage of the platinum saturates at 0.45. The sulfur is removed from the cathodes and their activity is partially restored both by cyclic voltammetry, as shown by others, and by successive polarization curves. Complete recovery of fuel cell performance is not achieved with either technique, suggesting that sulfur species permanently affect the surface of the catalyst.

The respective effect of under-rib convection and pressure drop of flow fields on the performance of PEM fuel cells.

PubMed

Wang, Chao; Zhang, Qinglei; Shen, Shuiyun; Yan, Xiaohui; Zhu, Fengjuan; Cheng, Xiaojing; Zhang, Junliang

2017-03-02

The flow field configuration plays an important role on the performance of proton exchange membrane fuel cells (PEMFCs). For instance, channel/rib width and total channel cross-sectional area determine the under-rib convection and pressure drop respectively, both of which directly influence the water removal, in turn affecting the oxygen supply and cathodic oxygen reduction reaction. In this study, effects of under-rib convection and pressure drop on cell performance are investigated experimentally and numerically by adjusting the channel/rib width and channel cross-sectional area of flow fields. The results show that the performance differences with various flow field configurations mainly derive from the oxygen transport resistance which is determined by the water accumulation degree, and the cell performance would benefit from the narrower channels and smaller cross sections. It reveals that at low current densities when water starts to accumulate in GDL at under-rib regions, the under-rib convection plays a more important role in water removal than pressure drop does; in contrast, at high current densities when water starts to accumulate in channels, the pressure drop dominates the water removal to facilitate the oxygen transport to the catalyst layer.

The respective effect of under-rib convection and pressure drop of flow fields on the performance of PEM fuel cells

NASA Astrophysics Data System (ADS)

Wang, Chao; Zhang, Qinglei; Shen, Shuiyun; Yan, Xiaohui; Zhu, Fengjuan; Cheng, Xiaojing; Zhang, Junliang

2017-03-01

The flow field configuration plays an important role on the performance of proton exchange membrane fuel cells (PEMFCs). For instance, channel/rib width and total channel cross-sectional area determine the under-rib convection and pressure drop respectively, both of which directly influence the water removal, in turn affecting the oxygen supply and cathodic oxygen reduction reaction. In this study, effects of under-rib convection and pressure drop on cell performance are investigated experimentally and numerically by adjusting the channel/rib width and channel cross-sectional area of flow fields. The results show that the performance differences with various flow field configurations mainly derive from the oxygen transport resistance which is determined by the water accumulation degree, and the cell performance would benefit from the narrower channels and smaller cross sections. It reveals that at low current densities when water starts to accumulate in GDL at under-rib regions, the under-rib convection plays a more important role in water removal than pressure drop does; in contrast, at high current densities when water starts to accumulate in channels, the pressure drop dominates the water removal to facilitate the oxygen transport to the catalyst layer.

System and method for controlling an engine based on ammonia storage in multiple selective catalytic reduction catalysts

DOEpatents

Sun, MIn; Perry, Kevin L.

2015-11-20

A system according to the principles of the present disclosure includes a storage estimation module and an air/fuel ratio control module. The storage estimation module estimates a first amount of ammonia stored in a first selective catalytic reduction (SCR) catalyst and estimates a second amount of ammonia stored in a second SCR catalyst. The air/fuel ratio control module controls an air/fuel ratio of an engine based on the first amount, the second amount, and a temperature of a substrate disposed in the second SCR catalyst.

Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors

DOE PAGES

Engtrakul, Chaiwat; Mukarakate, Calvin; Starace, Anne K.; ...

2015-11-14

The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO 2-to-Al 2O 3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N 2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form amore » slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew

In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl 2O 4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active andmore » resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H 2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H 2 production. Conversion and selectivity to CH 4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH 4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.« less

System and method for controlling hydrogen elimination during carbon nanotube synthesis from hydrocarbons

DOEpatents

Reilly, Peter T. A.

2010-03-23

A system and method for producing carbon nanotubes by chemical vapor deposition includes a catalyst support having first and second surfaces. The catalyst support is capable of hydrogen transport from the first to the second surface. A catalyst is provided on the first surface of the catalyst support. The catalyst is selected to catalyze the chemical vapor deposition formation of carbon nanotubes. A fuel source is provided for supplying fuel to the catalyst.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1985-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, P.K.; Rabo, J.A.

1985-12-03

Synthesis gas comprising carbon monoxide and hydrogen is converted to C[sub 5][sup +] hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising a SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barroo, Cedric; Janvelyan, Nare; Zugic, Branko

To improve the understanding of catalytic processes, the surface structure and composition of the active materials need to be determined before and after reaction. Morphological changes may occur under reaction conditions and can dramatically influence the reactivity and/or selectivity of a catalyst. Goldbased catalysts with different architectures are currently being developed for selective oxidation reactions at low temperatures. Specifically, nanoporous Au (npAu) with a composition of Au 97-Ag 3 is obtained by dealloying a Ag 70-Au 30 bulk alloy. Recent studies highlight the efficiency of npAu catalysts for methanol oxidation using ozone to activate the catalysts before methanol oxidation. Inmore » this paper, we studied the morphological and compositional changes occurring at the surface of Au-based catalysts in certain conditions.« less

Ce-Sn binary oxide catalyst for the selective catalytic reduction of NOx by NH3

NASA Astrophysics Data System (ADS)

Liu, Zhiming; Feng, Xu; Zhou, Zizheng; Feng, Yongjun; Li, Junhua

2018-01-01

Ce-Sn binary oxide catalysts prepared by the hydrothermal method have been investigated for the selective catalytic reduction (SCR) of NOx with NH3. Compared with pure CeO2 and SnO2, Ce-Sn binary oxide catalyst showed significantly higher NH3-SCR activity. Moreover, Ce-Sn catalyst showed high resistance against H2O and SO2. The high catalytic performance of Ce-Sn binary oxide is attributed to the synergetic effect between Ce and Sn species, which not only enhances the redox property of the catalyst but also increases the Lewis acidity, thus promoting the adsorption and activation of NH3 species, which contributes to improving the NH3-SCR performance.

Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Yongchun; Wang, Yong

Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towardsmore » aromatics.« less

A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

PubMed Central

Hoover, Jessica M.; Stahl, Shannon S.

2011-01-01

Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

Emission abatement system utilizing particulate traps

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander

2004-04-13

Emission abatement system. The system includes a source of emissions and a catalyst for receiving the emissions. Suitable catalysts are absorber catalysts and selective catalytic reduction catalysts. A plasma fuel converter generates a reducing gas from a fuel source and is connected to deliver the reducing gas into contact with the absorber catalyst for regenerating the catalyst. A preferred reducing gas is a hydrogen rich gas and a preferred plasma fuel converter is a plasmatron. It is also preferred that the absorber catalyst be adapted for absorbing NO.sub.x.

Selective synthesis of vitamin K3 over mesoporous NbSBA-15 catalysts synthesized by an efficient hydrothermal method.

PubMed

Selvaraj, M; Park, D-W; Kim, I; Kawi, S; Ha, C S

2012-08-28

Well hexagonally ordered NbSBA-15 catalysts synthesized by an efficient hydrothermal method were used, for the first time, for the selective synthesis of vitamin K(3) by liquid-phase oxidation of 2-methyl-1-naphthol (2MN1-OH) under various reaction conditions. The recyclable NbSBA-15 catalysts were also reused to find their catalytic activities. To investigate the leaching of non-framework niobium species on the surface of silica networks, the results of original and recyclable NbSBA-15 catalysts were correlated and compared. To find an optimum condition for the selective synthesis of vitamin K(3), the washed NbSBA-15(2.2pH) was extensively used in this reaction with various reaction parameters such as temperature, time and ratios of reactant (2M1N-OH to H(2)O(2)), and the obtained results were also demonstrated. Additionally, the liquid-phase oxidation of 2M1N-OH was carried out with different solvents to find the best solvent with a good catalytic activity. Based on the all catalytic studies, the vitamin K(3) selectivity (97.3%) is higher in NbSBA-15(2.2pH) than that of other NbSBA-15 catalysts, and the NbSBA-15(2.2pH) is found to be a highly active and eco-friendly heterogeneous catalyst for the selective synthesis of vitamin K(3).

Effect of catalyst film thickness on carbon nanotube growth by selective area chemical vapor deposition

NASA Astrophysics Data System (ADS)

Wei, Y. Y.; Eres, Gyula; Merkulov, V. I.; Lowndes, D. H.

2001-03-01

The correlation between prepatterned catalyst film thickness and carbon nanotube (CNT) growth by selective area chemical vapor deposition (CVD) was studied using Fe and Ni as catalyst. To eliminate sample-to-sample variations and create a growth environment in which the film thickness is the sole variable, samples with continuously changing catalyst film thickness from 0 to 60 nm were fabricated by electron-gun evaporation. Using thermal CVD CNTs preferentially grow as a dense mat on the thin regions of the catalyst film. Moreover, beyond a certain critical film thickness no tubes were observed. The critical film thickness for CNT growth was found to increase with substrate temperature. There appears to be no strong correlation between the film thickness and the diameter of the tubes. In contrast, using plasma enhanced CVD with Ni as catalyst, vertically oriented CNTs grow in the entire range of catalyst film thickness. The diameter of these CNTs shows a strong correlation with the catalyst film thickness. The significance of these experimental trends is discussed within the framework of the diffusion model for CNT growth.

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process.

PubMed

Guo, Yufang; Liao, Xiaobin; Fu, Mingli; Huang, Haibao; Ye, Daiqi

2015-02-01

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression. Copyright © 2014. Published by Elsevier B.V.

Technology development for iron Fischer-Tropsch catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

O`Brien, R.J.; Raje, A.; Keogh, R.A.

1995-12-31

The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alphamore » iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.« less

Ultrasonic-assisted hydrothermal synthesis and catalytic behavior of a novel SAPO-34/Clinoptilolite nanocomposite catalyst for high propylene demand in MTO process

NASA Astrophysics Data System (ADS)

Moradiyan, Eshagh; Halladj, Rouein; Askari, Sima; Moghimpour Bijani, Parisa

2017-08-01

SAPO-34 as a catalyst has high selectivity and hydrothermal stability, but it is rapidly deactivated by the formation of coke in its micropores. Evaluating the natural Clinoptilolite capability as a binder in nanocomposite catalysts is of interest because of its low cost, and accelerating the reaction. The SAPO-34/Clinoptilolite (S/C) nanocomposite catalysts were synthesized via ultrasonic-assisted hydrothermal method using Clinoptilolite as a binder. Subsequent performance of the catalyst was investigated in the methanol to olefins (MTO) reaction. The structures of synthesized nanocomposite were characterized with several methods such as XRD, XRF, FESEM, TEM, NH3-TPD, FT-IR, and nitrogen adsorption techniques. The modified Clinoptilolite was attained using nitric acid treatment. Although the physicochemical analysis indicated that HNO3-treatment decreases the crystallinity of the Clinoptilolite, the specific surface area of natural zeolite enhances considerably from 20.07 to 187.8 m2/g. The nanocomposite catalysts showed high selectivity toward light olefins with 100% conversion and 90% selectivity to light olefins as desired products at 450 °C. Nanocomposite with the additional diffusion paths for mass transfer provided by binder-filled space ascend to higher catalytic lifetimes in compare with free SAPO-34 catalyst.

Effect of carbon supports on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-methanol

DOE PAGES

Karanjkar, Pranav U.; Burt, Samuel P.; Chen, Xiaoli; ...

2016-09-12

Tetrahydropyran-2-methanol undergoes selective C–O–C hydrogenolysis to produce 1,6-hexanediol using a bifunctional RhRe (reducible metal with an oxophilic promoter) catalyst supported on Vulcan XC-72 carbon (VXC) with >90% selectivity. This RhRe/VXC catalyst is stable over 40 h of reaction in a continuous flow fixed bed reactor. The hydrogenolysis activity of RhRe/VXC is two orders-of-magnitude higher than that of RhRe supported on Norit Darco 12X40 activated carbon (NDC). STEM–EDS analysis reveals that, compared to the RhRe/VXC catalyst, the Re and Rh component metals are segregated on the surface of the low activity RhRe/NDC catalyst, suggesting that Rh and Re in close proximitymore » (“bimetallic” particles) are required for an active hydrogenolysis catalyst. Differences in metal distribution on the carbon surfaces are, in turn, linked to the properties of the carbons: NDC has both a higher surface area and surface oxygen content. Thus, the low areal density of Rh and Re precursors on the high area NDC and/or interactions of the precursors with its O functional groups may interfere with the formation of the bimetallic species required for an active catalyst.« less

Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter

Here, copper electrodes, prepared by reduction of oxidized metallic copper, have been reported to exhibit higher activity for the electrochemical reduction of CO 2 and better selectivity toward C 2 and C 3 (C 2+) products than metallic copper that has not been preoxidized. We report here an investigation of the effects of four different preparations of oxide-derived electrocatalysts on their activity and selectivity for CO 2 reduction, with particular attention given to the selectivity to C 2+ products. All catalysts were tested for CO 2 reduction in 0.1 M KHCO 3 and 0.1 M CsHCO 3 at applied voltagesmore » in the range from –0.7 to –1.0 V vs RHE. The best performing oxide-derived catalysts show up to ~70% selectivity to C 2+ products and only ~3% selectivity to C 1 products at –1.0 V vs RHE when CsHCO 3 is used as the electrolyte. In contrast, the selectivity to C 2+ products decreases to ~56% for the same catalysts tested in KHCO 3. By studying all catalysts under identical conditions, the key factors affecting product selectivity could be discerned. These efforts reveal that the surface area of the oxide-derived layer is a critical parameter affecting selectivity. A high selectivity to C 2+ products is attained at an overpotential of –1 V vs RHE by operating at a current density sufficiently high to achieve a moderately high pH near the catalyst surface but not so high as to cause a significant reduction in the local concentration of CO 2. On the basis of recent theoretical studies, a high pH suppresses the formation of C 1 relative to C 2+ products. At the same time, however, a high local CO 2 concentration is necessary for the formation of C 2+ products.« less

Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction

DOE PAGES

Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter; ...

2017-07-06

Here, copper electrodes, prepared by reduction of oxidized metallic copper, have been reported to exhibit higher activity for the electrochemical reduction of CO 2 and better selectivity toward C 2 and C 3 (C 2+) products than metallic copper that has not been preoxidized. We report here an investigation of the effects of four different preparations of oxide-derived electrocatalysts on their activity and selectivity for CO 2 reduction, with particular attention given to the selectivity to C 2+ products. All catalysts were tested for CO 2 reduction in 0.1 M KHCO 3 and 0.1 M CsHCO 3 at applied voltagesmore » in the range from –0.7 to –1.0 V vs RHE. The best performing oxide-derived catalysts show up to ~70% selectivity to C 2+ products and only ~3% selectivity to C 1 products at –1.0 V vs RHE when CsHCO 3 is used as the electrolyte. In contrast, the selectivity to C 2+ products decreases to ~56% for the same catalysts tested in KHCO 3. By studying all catalysts under identical conditions, the key factors affecting product selectivity could be discerned. These efforts reveal that the surface area of the oxide-derived layer is a critical parameter affecting selectivity. A high selectivity to C 2+ products is attained at an overpotential of –1 V vs RHE by operating at a current density sufficiently high to achieve a moderately high pH near the catalyst surface but not so high as to cause a significant reduction in the local concentration of CO 2. On the basis of recent theoretical studies, a high pH suppresses the formation of C 1 relative to C 2+ products. At the same time, however, a high local CO 2 concentration is necessary for the formation of C 2+ products.« less

Structural dynamics and activity of nanocatalysts inside fuel cells by in operando atomic pair distribution studies.

PubMed

Petkov, Valeri; Prasai, Binay; Shan, Shiyao; Ren, Yang; Wu, Jinfang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian

2016-05-19

Here we present the results from a study aimed at clarifying the relationship between the atomic structure and activity of nanocatalysts for chemical reactions driving fuel cells, such as the oxygen reduction reaction (ORR). In particular, using in operando high-energy X-ray diffraction (HE-XRD) we tracked the evolution of the atomic structure and activity of noble metal-transition metal (NM-TM) nanocatalysts for ORR as they function at the cathode of a fully operational proton exchange membrane fuel cell (PEMFC). Experimental HE-XRD data were analysed in terms of atomic pair distribution functions (PDFs) and compared to the current output of the PEMFC, which was also recorded during the experiments. The comparison revealed that under actual operating conditions, NM-TM nanocatalysts can undergo structural changes that differ significantly in both length-scale and dynamics and so can suffer losses in their ORR activity that differ significantly in both character and magnitude. Therefore we argue that strategies for reducing ORR activity losses should implement steps for achieving control not only over the length but also over the time-scale of the structural changes of NM-TM NPs that indeed occur during PEMFC operation. Moreover, we demonstrate how such a control can be achieved and thereby the performance of PEMFCs improved considerably. Last but not least, we argue that the unique capabilities of in operando HE-XRD coupled to atomic PDF analysis to characterize active nanocatalysts inside operating fuel cells both in a time-resolved manner and with atomic level resolution, i.e. in 4D, can serve well the ongoing search for nanocatalysts that deliver more with less platinum.

ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

James G. Goodwin, Jr.; James J. Spivey; K. Jothimurugesan

1999-03-29

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H2 ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem with themore » use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C5 + selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation. An HPR series of proprietary catalysts was prepared to further improve the attrition resistance. Based on the experience gained, a proprietary HPR-43 catalyst has been successfully spray dried in 500 g quantity. This catalyst showed 95 % CO conversion over 125 h and had less than 4 % methane selectivity. Its attrition resistance was one of the highest among the catalyst tested.« less

In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

PubMed

Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A

2011-09-01

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.

Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene

DOE PAGES

Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.; ...

2016-06-30

There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides aremore » surprisingly resistant to reduction and copper + species remain on the surface during the reaction. Furthermore, our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper + is key for lowering the onset potential and enhancing ethylene selectivity.« less

Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

NASA Astrophysics Data System (ADS)

McManus, Jesse R.; Vohs, John M.

2014-12-01

The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.

CO hydrogenation on PdCo/NaY catalysts: Effect of ion hydration on metal phases and selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuangen Yin; Zongchao Zhang; Sachtler, W.M.H.

1993-02-01

Exposure of calcined PdCo/NaY catalyst precursors to water vapor, prior to reduction, strongly affects the CO hydrogenation activity and selectivity of the reduced bimetal catalysts. With samples that had been exposed to H[sub 2]O before reduction, the formation of hydrocarbons prevails; nonhydrated reference samples of the same overall composition are mainly selective for oxygenates. After 6 h of reaction time PdCo alloy particles of 5.8 nm are detected by XRD in H[sub 2]O-exposed catalysts, but in the reference samples the metal particles are below the limit of detection by XRD. The observed effects are attributed to the formation of mobilemore » aquo-complexes of metal ions; after reduction they are converted to larger alloy particles, richer on Co, than in the reference samples. Results obtained with NaOH-neutralized and Co-free Pd/NaY catalysts are also discussed. 23 refs., 13 figs., 1 tab.« less

Efficient and Highly Selective Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Bucky Nanodiamond.

PubMed

Lin, Yangming; Wu, Kuang-Hsu Tim; Yu, Linhui; Heumann, Saskia; Su, Dang Sheng

2017-09-11

Selective oxidation of alcohols to aldehydes is widely applicable to the synthesis of various green chemicals. The poor chemoselectivity for complicated primary aldehydes over state-of-the-art metal-free or metal-based catalysts represents a major obstacle for industrial application. Bucky nanodiamond is a potential green catalyst that exhibits excellent chemoselectivity and cycling stability for the selective oxidation of primary alcohols in diverse structures (22 examples, including aromatic, substituted aromatic, unsaturated, heterocyclic, and linear chain alcohols) to their corresponding aldehydes. The results are comparable to reported transition-metal catalysts including conventional Pt/C and Ru/C catalysts for certain substrates under solvent-free conditions. The possible activation process of the oxidant and substrates by the surface oxygen groups and defect species are revealed with model catalysts, ex situ electrochemical measurements, and ex situ attenuated total reflectance. The zigzag edges of sp 2 carbon planes are shown to play a key role in these reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Takovite-aluminosilicate-Cr materials prepared by adsorption of Cr3+ from industrial effluents as catalysts for hydrocarbon oxidation reactions.

PubMed

Ciuffi, Katia J; de Faria, Emerson H; Marçal, Liziane; Rocha, Lucas A; Calefi, Paulo S; Nassar, Eduardo J; Pepe, Iuri; da Rocha, Zênis N; Vicente, Miguel A; Trujillano, Raquel; Gil, Antonio; Korili, Sophia A

2012-05-01

The catalytic efficiency of takovite-aluminosilicate-chromium catalysts obtained by adsorption of Cr(3+) ions from aqueous solutions by a takovite-aluminosilicate nanocomposite adsorbent is reported. The adsorbent was synthesized by the coprecipitation method. The catalytic activity of the final Cr-catalysts depended on the amount of adsorbed chromium. (Z)-cyclooctene conversion up to 90% with total selectivity for the epoxide was achieved when the oxidation was carried out with hydrogen peroxide, at room temperature. After five consecutive runs, the catalysts maintained high activity, although after the sixth reuse, the epoxide yields strongly decreased to 35%. The catalysts were also efficient for cyclohexane oxidation, reaching up to 18% conversion, with cyclohexanone/cyclohexanol selectivity close to 1.2. On the whole, their use as catalysts gives a very interesting application for the solids obtained by adsorption of a contaminant cation such as Cr(3+).

Synthesis of Higher Alcohols via Syngas on Cu/Zn/Si Catalysts. Effect of Polyethylene Glycol Content

NASA Astrophysics Data System (ADS)

Cui, Rong-Ji; Yan, Xing; Fan, Jin-Chuan; Huang, Wei

2018-05-01

Cu/Zn/Si catalysts with different polyethylene glycol (PEG) content were prepared by a complete liquid-phase method, and characterized by XRD, H2-TPR, N2-adsorption, and XPS. The influence of PEG content on the higher alcohols synthesis from syngas was investigated. The results showed that addition of PEG can influence the texture and surface properties of the catalysts, and therefore affect their activity and product distribution. With an increase in PEG content, BET surface area, Cu crystallite size and surface active ingredient content of the catalysts first increased and then decreased, the CO conversion had similar variation tendency. However, the pore volume and pore diameter of the catalyst increased, and the binding energy of the active component and the content of Cu2O decreased, which resulted in higher catalyst selectivity towards higher alcohols. The highest C2+OH selectivity in total alcohols was 60.6 wt %.

The Variation of Catalyst and Carrier Gas on Anisole Deoxygenation Reaction

NASA Astrophysics Data System (ADS)

Ariyani, D.; Dwi Nugrahaningtyas, Khoirina; Heraldy, E.

2018-03-01

This research aims to determine the best catalyst and carrier gas in anisole deoxygenation reaction. The reaction was carried out over a flow system with a variation of catalyst CoMo A (CoMo/USY reduction), CoMo B (CoMo/USY oxidation-reduction), and CoMo C (CoMo/ZAA oxidation-reduction). In addition, variation of carrier gas nitrogen and hydrogen was investigated. The result was analyzed using Gas Chromatography-Mass Spectroscopy (GC-MS). The deoxygenation anisole result showed that CoMo A catalyst with hydrogen as the carrier gas has the highest total product yield (50.72 %), intermediate product yield (38.49 % in phenol and 6.99 % in benzaldehyde), and deoxygenation yield (5.24 %). The CoMo C catalyst exhibited the most selective deoxygenation product. The nitrogen carrier gas with the CoMo C catalyst has the best selectivity of benzene product (93.92 %).

Calcium oxide supported gold nanoparticles as catalysts for the selective epoxidation of styrene by t-butyl hydroperoxide.

PubMed

Dumbre, Deepa K; Choudhary, Vasant R; Patil, Nilesh S; Uphade, Balu S; Bhargava, Suresh K

2014-02-01

Gold nanoparticles are deposited on basic CaO supports as catalysts for the selective conversion of styrene into styrene oxide. Synthetic methods, gold loading and calcination temperatures are varied to permit an understanding of their influence on gold nanoparticle size, the presence of cationic gold species and the nature of interaction between the gold nanoparticles and the CaO support. Based on these studies, optimal conditions are designed to make the Au/CaO catalyst efficient for the selective epoxidation of styrene. Copyright © 2013 Elsevier Inc. All rights reserved.

Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

PubMed Central

Oh, Kwang Seok; Woo, Seong Ihl

2011-01-01

A chemiluminescence-based analyzer of NOx gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NOx analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al2O3 substrate was tested for the efficiency of NOx removal using a home-built 64-channel parallel and sequential tubular reactor. The NOx concentrations measured by the NOx analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al2O3. Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NOx analyzer allowed to select Pt-Ce(X) (X=1–3) and Pt–Fe(2) as the optimal catalysts for NOx removal: 73% NOx conversion was achieved with the Pt–Fe(2) alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO. PMID:27877438