on-preparation-testing-fuel-cell-catalysts-using-thin-film-rotating

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

We present a step-by-step tutorial to prepare proton exchange membrane fuel cell (PEMFC) catalysts, consisting of Pt nanoparticles (NPs) supported on a ...

University of Copenhagen

University of Bern

The influence of particle size on the oxygen reduction reaction (ORR) activity of Pt was examined in three different electrolytes: two acidic solutions, with varying anionic adsorption strength (HClO(4) < H(2)SO(4)); and an alkaline solution (KOH). The experiments show that the absolute ORR rate is dependent on the supporting electrolyte; however, the relationship between activity and particle size is rather independent of the supporting electrolyte. The specific activity (SA) toward the ORR rapidly decreases in the order of polycrystalline Pt > unsupported Pt black particles (~30 nm) > high surface area (HSA) carbon supported Pt nanoparticle catalysts (of various size between 1 and 5 nm). In contrast to previous work, it is highlighted that the difference in SA between the individual HSA carbon supported catalysts (1 to 5 nm) is rather trivial and that the main challenge is to understand the significant differences in SA between the polycrystalline Pt, unsupported Pt particles, and HSA carbon supported Pt catalysts. Finally, a comparison between measured and modeled activities (based on the distribution of surface planes and their SAs) for different particle sizes indicates that such simple models do not capture all aspects of the behavior of HSA carbon supported catalysts.

The particle size effect on the oxygen reduction reaction activity of Pt catalysts: influence of electrolyte and relation to single crystal models.

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.

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

The diminished surface-area-normalized catalytic activity of highly dispersed Pt nanoparticles compared with bulk Pt is particularly intricate, and not yet understood. Here we report on the oxygen reduction reaction (ORR) activity of well-defined, size-selected Pt nanoclusters; a unique approach that allows precise control of both the cluster size and coverage, independently. Our investigations reveal that size-selected Pt nanoclusters can reach extraordinarily high ORR activities, especially in terms of mass-normalized activity, if deposited at high coverage on a glassy carbon substrate. It is observed that the Pt cluster coverage, and hence the interparticle distance, decisively influence the observed catalytic activity and that closely packed assemblies of Pt clusters approach the surface activity of bulk Pt. Our results open up new strategies for the design of catalyst materials that circumvent the detrimental dispersion effect, and may eventually allow the full electrocatalytic potential of Pt nanoclusters to be realized.

The effect of particle proximity on the oxygen reduction rate of size-selected platinum clusters.

We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

We present a detailed description of the construction and testing of an electrochemical cell allowing measurements at elevated temperature and pressure. The cell consists of a stainless steel pressure vessel containing the electrochemical glass cell exhibiting a three electrode configuration. The design of the working electrode is inspired by conventional rotating disk electrode setups. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on polycrystalline platinum and also high surface area type electrocatalysts.

Design and test of a flexible electrochemical setup for measurements in aqueous electrolyte solutions at elevated temperature and pressure.

Platinum bimetallic alloys are well-known for their ability to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Pt(x)Co(1-x) colloidal nanoparticles were synthesized with varying initial Pt : Co ratios, but constant size to investigate how the initial metal composition affects their electrocatalytic performance. The results show that upon contact with acid environment the Co leaches out of the particles leading to almost identical compositions, independent of the initial differences. Surprisingly the data show a clear trend in ORR activity, although the Pt(x)Co(1-x) nanoparticles almost completely de-alloy during acid leaching, i.e. under reaction conditions in a fuel cell. To scrutinize the resulting particle structure after de-alloying we used pair distribution function (PDF) analysis and X-ray diffraction (XRD) gaining insight into the structural disorder and its dependence on the initial metal composition. Our results suggest that not only the ORR activity, but also the corrosion resistance of the synthesized NPs, are dependent on the structural disorder resulting from the de-alloying process.

Structural disordering of de-alloyed Pt bimetallic nanocatalysts: the effect on oxygen reduction reaction activity and stability.

In the presented work, the electrochemical stability of platinized silicon carbide is studied. Postmortem transmission electron microscopy and X-ray photoelectron spectroscopy were used to document the change in the morphology and structure upon potential cycling of Pt/SiC catalysts. Two different potential cycle aging tests were used in order to accelerate the support corrosion, simulating start-up/shutdown and load cycling. On the basis of the results, we draw two main conclusions. First, platinized silicon carbide exhibits improved electrochemical stability over platinized active carbons. Second, silicon carbide undergoes at least mild oxidation if not even silicon leaching.

Electrochemical stability and postmortem studies of Pt/SiC catalysts for polymer electrolyte membrane fuel cells.

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.

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

A protocol for the bottom-up self-assembly of nanogaps is developed through molecular linking of gold nanoparticles (AuNPs). Two π-conjugated oligo(phenylene ethynylene) molecules (OPE) with dithiocarbamate anchoring groups are used as ligands for the AuNPs. OPE-4S with a dithiocarbamate in each end of the molecule and a reference molecule OPE-2S with only a single dithiocarbamate end group. The linking mechanism of OPE-4S is investigated by using a combination of TEM, UV-Vis absorption and surface enhanced Raman spectroscopy (SERS) as well as studying the effect of varying the OPE-4S to AuNP concentration ratio. UV-Vis absorption confirms the formation of AuNP aggregates by the appearance of an extended plasmon band (EPB) for which the red shift and intensity depend on the OPE-4S:AuNP ratio. SERS confirms the presence of OPE-4S and shows a gradual increase of the signal intensity with increasing OPE-4S:AuNP ratios up to a ratio of about 4000, after which the SERS intensity does not increase significantly. For OPE-2S, no linking is observed below full coverage of the AuNPs indicating that the observed aggregate formation at high OPE-2S:AuNP ratios, above full AuNP coverage, is most likely of a physical nature (van der Waals forces or π-π interactions).

Gold nanoparticles assembled with dithiocarbamate-anchored molecular wires.

The oxygen reduction reaction (ORR) is one of the key processes in electrocatalysis. In this communication, the ORR is studied using a rotating disk electrode (RDE). In conventional work, this method limits the potential region where kinetic (mass transport free) reaction rates can be determined to a narrow range. Here, we applied a new approach, which allows us to analyze the ORR rates in the diffusion-limited potential region of high mass transport. Thus, for the first time, the effect of anion adsorption on the ORR can be studied at such potentials.

Article	Year
The particle size effect on the oxygen reduction reaction activity of Pt catalysts: influence of electrolyte and relation to single crystal models. Journal of the American Chemical Society\| PubMed ID: 21950956	2011
Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies. Physical chemistry chemical physics : PCCP\| PubMed ID: 23381718	2013
The effect of particle proximity on the oxygen reduction rate of size-selected platinum clusters. Nature materials\| PubMed ID: 23872730	2013
Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electroche... The Review of scientific instruments\| PubMed ID: 23902087	2013
Design and test of a flexible electrochemical setup for measurements in aqueous electrolyte solutions at elevated temperature and pressure. The Review of scientific instruments\| PubMed ID: 25173310	2014
Structural disordering of de-alloyed Pt bimetallic nanocatalysts: the effect on oxygen reduction reaction activity and stability. Physical chemistry chemical physics : PCCP\| PubMed ID: 25537262	2015
Electrochemical stability and postmortem studies of Pt/SiC catalysts for polymer electrolyte membrane fuel cells. ACS applied materials & interfaces\| PubMed ID: 25719513	2015
Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures. The Review of scientific instruments\| PubMed ID: 25725862	2015
Gold nanoparticles assembled with dithiocarbamate-anchored molecular wires. Scientific reports\| PubMed ID: 26471461	2015
Accessing the Inaccessible: Analyzing the Oxygen Reduction Reaction in the Diffusion Limit. ACS applied materials & interfaces\| PubMed ID: 29063766	2017

Matthias Arenz

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