Accurate determination of catalyst loading on glassy NANO

18–20 JULY, 2018

carbon disk and its impact on thin film rotating disk ENERGY
electrode for oxygen reduction reaction.
5th International Conference on
Nanotechnology, Nanomaterials &
Thin Films for Energy Applications

Muralidhar G. Chourashiya$, R. Sharma and Shuang Ma Andersen*

Department of Chemical Engineering, Biotechnology and Environmental Technology, University of Southern Denmark (SDU), Denmark.

ABSTRACT
 Thin film-rotating disc electrode (TF- RDE) experiments  Our approach:
• Fast research platform for screening of NEWLY developed  Estimated the amount Pt loadings (of commercial electrocatalyst)
electrocatalysts for oxygen reduction reaction (ORR) activity,  using literature based (conventional) scheme and the proposed, X-ray
• Estimates ORR performance parameters – quick performance check fluorescent (XRF) based scheme
• Helpful as quality check before testing catalyst in actual fuel cells.  Defined 'Catalyst-Density-of-the-Ink’ parameter suggests
 Problem: Errors in estimation of amount of active catalyst on RDE  the actual loading varies with the ink-conditions, which is considered
• Might lead to erroneous estimation of performance values constant in the conventional scheme.
 We present an approach to resolve the issue and present the proof-of-  The XRF based scheme,
concept (though it has been used in some labs, it is not well documented)  Simple and direct, improves the experimental reproducibility.

General ORR catalysts evaluation scheme
Pt based electrocatalysts 

Synthesized Commercial

TGA Specified or based on precursor

Alcohol Pt loading (wt%)

mQ water Ionomer

Ultrasonication Electrochemical 
Ink formulation Catalyst  techniques with TF‐RDE
weight  ORR surface specific 
LSV

Drop of precise  on RDE activity (SSA) 

Ink drop casting 

volume
Electrochemical 
on RDE

CV

Drop volume by  surface area (ESA)
drop weight
Mass specific 
LSV

Drying activity (MSA)

The defining parameters and IDs of inks studied in this investigation:

XRF analyzer
Precursor wt% Supplied by Manufacturer TGA wt% (residue)

ID Electro‐catalysts Ink age #of ink Condition(s)

Stock 

Ink stock solvent

Cat / 
Catalyst on support

Suprt
soln

BASF _O1 Three  #O1 Aged ink – re‐dispersed 

XRF reading
Inomer Alcohol Water Catalyst Support
BASF 
Water (mQ/DD)

Density (g/cc)

Density (g/cc)
Density (g/cc)

Density (g/cc)

Density (g/cc)

Density (g/cc)

Density (g/cc)
BASF _O2 months old #O2 Ink of #O1 + 1h on mixer
Ionomer %

Support %
Catalyst %
Alcohol %

catalyst 
Ionomer

Water %

Support
Catalyst
Alcohol

BASF _F1 Freshly  #F1 immediately after high‐energy ultrasonication

(20wt.%Pt/C)
BASF _F2 prepared #F2 Ink of #F1 + 1h on mixer
Drop casting for thin film RDE expt. Ink 
HiSpec _O1 Three  #O1 Aged ink – re‐dispersed XRF reading of 
Ink
Drop wt. (mg) Or
Drop volume (µl)

Drop cast Substrate Loading calculations formulation

HiSpec9100  coated RDE
wt of catalyst in 

wt of catatalyst  

HiSpec _O2 months old #O2 Ink of #O1 + 1h on mixer 

Cast area (cm2)

Catlyst wt (mg)

Density (g/cc)
Stock Sol (ml)
Drop wt (mg)

Drop vol (ul)

catalyst 
in cast (mg)

RDE
(µg/cm²)
Loading 

HiSpec _F1 Freshly  #F1 immediately after high‐energy ultrasonication

Ink (mg)

Conversion using
Cast on

(55%Pt/C) caliberation curve

HiSpec _F2 prepared #F2 Ink of #F1 + 1h on mixer
Loading (µg/cm²) Platinum wt. (mg) on RDE Platinum wt. (mg) on RDE
 Commercial catalyst: BASF catalyst 20 wt.% Pt/C and 55 wt.% Pt/C and HiSpec9100 catalyst (Johnson Matthey, 55.5 – 57.8 wt.% Pt/C)
 Ink recipe: 10 mg of the catalyst + 5 mL stock solution (mix of isopropyl alcohol, 5 wt% Nafion and mQ water in 20: 0.4: 79.6 proportion) Conventional scheme XRF based scheme

TEM of BASF

TEM of HiSpec
Variation of loading/drop wt. (i.e. ‘catalyst‐density‐of‐ink’ 
defined as estimated loading (mg/cm2) divided by measured 
drop weight (mg)) for the XRF based scheme and conventional 
(Conv.) scheme, where loading is estimated using 
Calculated ESA (m2/g) values (, red triangles), MSA (A/mg) values (●, blue circles) and SSA 
manufacturer provided data.  Loading values for HiSpec9100  (mA/cm2) values (, magenta star) of investigated inks, based on Pt loading estimated using (a) 
Potential vs RHE (V) catalysts are divided by a factor of 2.75 (55/20 = 2.75, i.e. ratio  conventional scheme and (b) XRF based scheme. The plot also includes respective loading/drop 
Comparison of cyclic voltammograms of inks under investigation.  Pt wt.%) to compensate stretching of Y‐axis. wt. (■, black squares) for reference. 

Summary and conclusions: 
• TF-RDE experiments–fast screening technique for newly developed ORR electrocatalysts.
• Accurate performance parameters estimation is must to avoid the wastage of resources

• Study shows the importance of correct Pt weight used in TF-RDE experiments.

• Actual Pt loading varies with the ink-conditions and cause irreproducibility
• Catalyst-density-of-the-ink (ratio of estimated loadings & drop wt.) for a specific ink
• Varied when estimated using XRF based scheme with mixing time while
• It is considered constant when estimated using conventional scheme.
• XRF based scheme is simple, direct and allows post-mortem analysis
XRF scheme enables post‐mortem analysis by the virtue of direct loading estimation. • Useful in electrocatalysis investigation & reaction mechanism understanding

Acknowledgment:  Authors thank Innovation Fund Denmark (IFD) for a financial support through project 
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$ Muralidhar G. Chourashiya: chourashiya@gmail.com ORCID: 0000‐0001‐9248‐0029 https://chourashiya.blogspot.com  https://www.linkedin.com/in/chourashiya/