Supporting Information

Mechanism and Kinetics of Hydrogen Peroxide

Decomposition on Platinum Nanocatalysts

Rui Serra-MaiaƗ, Marion BellierƗ, Stephen Chastka Ɨ, Kevin

TranhuuƗ, Andrew SubowoƗ, J. Donald Rimstidt Ɨ, Pavel M. Usov¥,

Amanda J. Morris¥, F. Marc MichelƗ*

Ɨ
Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg VA
24061 USA
¥
Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg VA 24061
USA

*
Corresponding author: mfrede2@vt.edu

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Figure S1. Oxygen reduction reaction mechanisms (reproduced with permission from reference 1. Copyright
1
2012 Royal Society of Chemistry) .

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 a

Figure S2. Transmission electron microscopy

image of a small cluster of Pt nanopowder (a) and
Pt black (b). Each cluster is formed by a few
nanocrystals loosely attached.

S-3
 Table S1. Rate measurements for Pt nanopowder and Pt black at different conditions of
 , pH and

temperature.

Catalyst Temp.,   pH
 ( ∙  ) log
 R,  .  .  log R


-06
Pt nanopowder 275 0.00363 9.17 0.0001 -4.00 1.8⨯10 -5.74
-06
Pt nanopowder 293 0.00341 9.25 0.0001 -4.00 4.52⨯10 -5.35
-06
Pt nanopowder 275 0.00363 7.87 0.0003 -3.52 5.99⨯10 -5.22
-05
Pt nanopowder 274 0.00365 4.82 0.001 -3.00 1.45⨯10 -4.84
-06
Pt nanopowder 275 0.00363 3.7 0.0001 -4.00 2.21⨯10 -5.66
-06
Pt nanopowder 293 0.00341 3.02 0.0001 -4.00 3.76⨯10 -5.42
-06
Pt nanopowder 293 0.00341 9.3 0.0001 -4.00 9.43⨯10 -5.03
-05
Pt nanopowder 293 0.00341 6.68 0.0001 -4.00 1.06⨯10 -4.98
-04
Pt nanopowder 293 0.00341 9.25 0.001 -3.00 1.02⨯10 -3.99
-05
Pt nanopowder 293 0.00341 3.06 0.001 -3.00 1.97⨯10 -4.71
-05
Pt nanopowder 275 0.00363 3.24 0.001 -3.00 1.39⨯10 -4.86
-06
Pt nanopowder 275 0.00363 9.65 0.0001 -4.00 5.28⨯10 -5.28
-05
Pt nanopowder 293 0.00341 4.44 0.0005 -3.30 1.74⨯10 -4.76
-05
Pt nanopowder 293 0.00341 6 0.0005 -3.30 3.61⨯10 -4.44
-06
Pt nanopowder 293 0.00341 3.8 0.0001 -4.00 4.88⨯10 -5.31
-06
Pt nanopowder 293 0.00341 8.5 0.0001 -4.00 8.41⨯10 -5.08
-04
Pt nanopowder 293 0.00341 8.36 0.001 -3.00 1.08⨯10 -3.97
-05
Pt nanopowder 293 0.00341 6.26 0.001 -3.00 5.00⨯10 -4.3
-05
Pt nanopowder 293 0.00341 5.14 0.001 -3.00 4.67⨯10 -4.33
-05
Pt nanopowder 293 0.00341 6.77 0.00025 -3.60 1.77⨯10 -4.75
-05
Pt nanopowder 293 0.00341 3.94 0.00025 -3.60 1.44⨯10 -4.84
-06
Pt nanopowder 274 0.00365 7.96 0.0001 -4.00 8.64⨯10 -5.06
-06
Pt nanopowder 276 0.00362 3.11 0.0001 -4.00 3.61⨯10 -5.44
-05
Pt nanopowder 275 0.00364 3.33 0.001 -3.00 2.58⨯10 -4.59
-05
Pt nanopowder 276 0.00363 8.49 0.001 -3.00 5.37⨯10 -4.27
-06
Pt nanopowder 275 0.00363 3.05 0.0001 -4.00 1.13⨯10 -5.95
-05
Pt nanopowder 278 0.0036 8.2 0.001 -3.00 3.01⨯10 -4.52
-05
Pt nanopowder 327 0.00306 3.48 0.0001 -4.00 1.13⨯10 -4.95
-05
Pt nanopowder 318 0.00314 5.91 0.0003 -3.52 3.71⨯10 -4.43
-04
Pt nanopowder 323 0.0031 3.5 0.001 -3.00 1.01⨯10 -4
-04
Pt nanopowder 316 0.00317 8.6 0.001 -3.00 1.42⨯10 -3.85
-04
Pt nanopowder 318 0.00315 5.94 0.001 -3.00 1.04⨯10 -3.98
-05
Pt nanopowder 323 0.0031 6 0.0003 -3.52 3.64⨯10 -4.44
-05
Pt nanopowder 317 0.00316 3.44 0.0003 -3.52 3.60⨯10 -4.44
-05
Pt nanopowder 316 0.00317 8.58 0.0003 -3.52 3.89⨯10 -4.41
-07
Pt black 293 0.00341 3.07 0.0001 -4.00 4.14⨯10 -6.38
-06
Pt black 293 0.00341 5.39 0.0001 -4.00 1.17⨯10 -5.93
-06
Pt black 293 0.00341 8.7 0.0001 -4.00 1.02⨯10 -5.99
-06
Pt black 293 0.00341 2.91 0.0005 -3.30 3.29⨯10 -5.48

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 -06
Pt black 293 0.00341 6.23 0.0005 -3.30 4.62⨯10 -5.34
-06
Pt black 293 0.00341 7.57 0.0005 -3.30 4.02⨯10 -5.4
-06
Pt black 293 0.00341 9.17 0.0005 -3.30 2.87⨯10 -5.54
-06
Pt black 293 0.00341 3.06 0.001 -3.00 4.86⨯10 -5.31
-06
Pt black 293 0.00341 5.39 0.001 -3.00 6.50⨯10 -5.19
-06
Pt black 293 0.00341 8.87 0.001 -3.00 7.05⨯10 -5.15
-06
Pt black 293 0.00341 6.84 0.001 -3.00 5.63⨯10 -5.25
-07
Pt black 293 0.00341 3.8 0.0001 -4.00 6.69⨯10 -6.17
-07
Pt black 293 0.00341 7.6 0.0001 -4.00 5.16⨯10 -6.29
-07
Pt black 293 0.00341 4.09 0.00025 -3.60 7.34⨯10 -6.13
-07
Pt black 293 0.00341 6.45 0.00025 -3.60 8.22⨯10 -6.09
-07
Pt black 274 0.00365 2.91 0.0001 -4.00 1.61⨯10 -6.79
-07
Pt black 274 0.00365 9.3 0.0001 -4.00 2.47⨯10 -6.61
-06
Pt black 277 0.00361 8.01 0.001 -3.00 2.97⨯10 -5.53
-06
Pt black 277 0.00361 3.34 0.001 -3.00 1.63⨯10 -5.79
-07
Pt black 275 0.00363 3.29 0.0003 -3.52 6.97⨯10 -6.16
-07
Pt black 280 0.00357 7.7 0.0003 -3.52 6.37⨯10 -6.2
-06
Pt black 311 0.00322 5.5 0.0001 -4.00 1.28⨯10 -5.89
-06
Pt black 324 0.00309 8.75 0.0001 -4.00 2.41⨯10 -5.62
-06
Pt black 319 0.00314 3.48 0.0001 -4.00 1.00⨯10 -6.00
-06
Pt black 320 0.00313 3.49 0.0003 -3.52 5.20⨯10 -5.28
-06
Pt black 315 0.00318 8.82 0.0003 -3.52 5.33⨯10 -5.27
-05
Pt black 319 0.00313 5.78 0.001 -3.00 1.47⨯10 -4.83
-05
Pt black 320 0.00313 3.48 0.001 -3.00 1.60⨯10 -4.8
-05
Pt black 317 0.00316 8.55 0.001 -3.00 1.31⨯10 -4.88
-06
Pt black 316 0.00317 5.85 0.0003 -3.52 4.25⨯10 -5.37
-07
Pt-Liu-3nm 293 0.00341 1.12 0.0025 -2.60 7.52⨯10 -6.12
-06
Pt-Liu-3nm 293 0.00341 1.12 0.005 -2.30 1.75⨯10 -5.75
-06
Pt-Liu-3nm 293 0.00341 7.27 0.0025 -2.60 1.77⨯10 -5.75
-06
Pt-Liu-3nm 293 0.00341 7.27 0.005 -2.30 3.40⨯10 -4.47
-06
Pt-Liu-3nm 293 0.00341 10.96 0.0025 -2.60 2.00⨯10 -5.70
-06
Pt-Liu-3nm 293 0.00341 10.96 0.005 -2.30 4.21⨯10 -5.38

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 o
Table S2. Rate measurements for Pt nanopowder and Pt black heated at 240 C for 24h at different
condition of
 , pH and temperature.

Catalyst Temp.,  pH
 log R, log R


 ( ∙  )
     .  . 
-06
Pt nanopowder 295 0.00339 5.85 0.0001 -4.00 7.34⨯10 -5.13
-06
Pt nanopowder 315 0.00318 5.8 0.0001 -4.00 9.69⨯10 -5.01
-05
Pt nanopowder 296 0.00338 5.85 0.001 -3.00 8.26⨯10 -4.08
-04
Pt nanopowder 314 0.00318 5.87 0.001 -3.00 1.40⨯10 -3.85
-05
Pt nanopowder 322 0.00310 5.88 0.0003 -3.52 3.02⨯10 -4.52
-05
Pt nanopowder 296 0.00338 5.91 0.0003 -3.52 1.86⨯10 -4.73
-06
Pt black 295 0.00339 5.9 0.0001 -4.00 1.71⨯10 -5.77
-05
Pt black 295 0.00338 5.83 0.001 -3.00 1.26⨯10 -4.90
-05
Pt black 320 0.00312 5.8 0.001 -3.00 3.02⨯10 -4.52
-06
Pt black 322 0.00310 5.8 0.0001 -4.00 4.23⨯10 -5.37
-06
Pt black 295 0.00338 5.77 0.0003 -3.52 3.64⨯10 -5.44
-05
Pt black 323 0.00309 5.8 0.0003 -3.52 1.07⨯10 4.97

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Section A. Evaluation of •HO in solution during the
decomposition of H2O2 by Pt black
The presence of •OH in solution was evaluated for the catalyzed decomposition of H2O2 at

  = 100 μ and   = 1000 μ on Pt black. Absorbance measurements at 420 nm

following the protocol described in section 3.4 resulted in an absorbance of 0.004 and 0.002 for

the decomposition of H2O2 at each of the studied concentrations. The concentrations of •OH

calculated from the determined absorbance values were negative. This result indicates that the

amount of •OH species formed and released into solution during the decomposition of H2O2 on

Pt black was negligible and below the limit of detection of this method for both tested  

conditions.

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 Cyclic voltammetry of Pt nanopowder and Pt black
Cyclic voltammetry analysis performed in 0.5 M H2SO4/H2O electrolyte showed that Pt black

and Pt nanopowder oxidize from Pt to Pt(O) at 0.54 V vs Ag/AgCl and reduce from Pt(O) to Pt at

0.19 V vs Ag/AgCl. These processes occur at similar potentials for both materials. A significant

reduction peak is observed in the first cycle for both catalysts, indicating that the surface of both

catalysts is partially oxidized in the original state. Comparison of the voltammograms obtained in

neutral electrolyte (0.1 M Na2SO4/H2O) shows that the reduction peak shifts to more negative

potentials, -0.27 and –0.32 V vs Ag/AgCl for Pt black and Pt nanopowder, respectively. The

potential of Pt oxidation, however, remained unchanged. This result indicates that while the

mechanism of reduction of Pt(O) is pH-dependent the mechanism of Pt oxidation is not.

Figure S3. Cyclic voltammogram for Pt nanopowder (red) and Pt black (black).

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 Figure S4. Example of the initial rate method. The initial rate of H2O2 decomposition was determined by
the derivative of the quadratic regression extrapolated to t=0. For a quadratic regression, that value is the
coefficient of the term with power of 1. In the example of the figure the initial rate of H2O2 decomposition is
  
64.0 .
∙

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 Table S3. Rate measurements for Pt nanopowder and Pt black submitted to H2O2 pre-treatment exposure.
The conditions of
 , pH and temperature were maintained constant for all runs.

Catalyst Temp.,  pH
 log !" log r, log r


   #$%
 ( ∙  )
       .  . 
-06
Pt nanopowder 295 0.00338 5.84 0.0001 -4.00 0.98 -0.01 9.07⨯10 -5.04
-06
Pt nanopowder 295 0.00338 5.87 0.0001 --4.00 0.0098 -1.01 9.13⨯10 -5.04
-06
Pt nanopowder 295 0.00338 5.82 0.0001 -4.00 0.00098 -2.01 9.88⨯10 -5.00
-05
Pt nanopowder 295 0.00338 5.91 0.0001 -4.00 0.000098 -3.01 1.08⨯10 -4.96
-06
Pt black 295 0.00338 5.99 0.0001 -4.00 0.98 -0.01 3.05⨯10 -5.51
-06
Pt black 294 0.00340 6.02 0.0001 -4.00 0.0098 -1.01 3.17⨯10 -5.49
-06
Pt black 294 0.00340 6.07 0.0001 -4.00 0.00098 -2.01 2.50⨯10 -5.60
-06
Pt black 294 0.00340 6.1 0.0001 -4.00 0.000098 -3.01 2.36⨯10 -5.62

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 References

1. Katsounaros, I.; Schneider, W. B.; Meier, J. C.; Benedikt, U.; Biedermann, P. U.; Auer,
A. A.; Mayrhofer, K. J., Hydrogen Peroxide Electrochemistry on Platinum: Towards
Understanding the Oxygen Reduction Reaction Mechanism. Phys. Chem. Chem. Phys 2012,
14, 7384-7391.

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