Plasma-assisted synthesis and characterization

of Au-manganese oxide nanostructures 6

Au/Mn2O3

as electrocatalysts for oxygen evolution 5

4
Mn2O3
Au/MnO2

j (mA/cm )
MnO2

2
3

Davide Barreca*,a, Chiara Maccatob, Alberto Gasparottob, Lorenzo Bigianib, Teresa Andreuc,d, 1

0
Johan Verbeecke, Cinzia Sadaf, Evgeny Moding, Oleg I. Lebedevh, Juan Ramón Morantec,d 100 nm
1.40 1.45 1.50 1.55 1.60 1.65
EWE (V) vs RHE

* davide.barreca@unipd.it
a
CNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, Italy; b Department of Chemical Sciences, Padova University and INSTM,
35131 Padova, Italy; c Catalonia Institute for Energy Research - IREC, Sant Adrià de Besòs, 08930 Barcelona, Spain; d Universitat de Barcelona (UB), 08028 Barcelona, Spain;
e EMAT and NANOlab Center of Excellence, University of Antwerp, 2020 Antwerpen, Belgium; f Department of Physics and Astronomy, Padova University and INSTM, 35131

Padova, Italy; g CIC nanoGUNE BRTA, 20018 Donostia - San Sebastian, Spain; h Laboratoire CRISMAT, UMR 6508 CNRS/ENSICAEN/UCBN, 14050 Caen Cedex 4, France

Plasma-assisted chemical vapor deposition (PA-CVD) + radio frequency (RF)-sputtering

 Fabrication of
Aim of the work supported
MnO2 and Mn2O3 Ar, 5 W, 0.3 mbar 500°C, 1 h
 Development nanostructures 60°C, 1 h

of cost-effective and and

eco-friendly functionalization
electrocatalysts with Au
for the nanoparticles
oxygen evolution (NPs) to enhance Ar-O2
20 W, 1 mbar
reaction (OER) OER activity 300°C, 1 h FTO = F-doped tin oxide

(critical issue in water

FE-SEM  elongated lamellar
splitting for the production of green hydrogen, CO2 TEM + EDXS Au/Mn2O3
structures
reduction, metal-air batteries) MnO2
20 nm width = 25 nm
(b) BF-TEM HR
length = 250 nm
 annealing in air:
XRD -MnO2 (tetragonal)  dendrites with a high
* β-MnO2 •
β-Mn2O3
• • •  annealing in Ar: active area
• FTO
-Mn2O3 (cubic)
100 nm 100 nm
 reduced charge carrier
Intensity (a.u.)

Au/Mn2O3

 No variations after Au Au/MnO2 transport distances

Mn2O3 20 nm
deposition (c)
* * Au/MnO2
  Uniform decoration by
MnO2
high dispersion & low dispersed Au NPs
content of Au ( = 10 nm) HAADF-STEM
20 25 30 35 40 45 50 nanoparticles (NPs)
2 (°)
100 nm 100 nm mostly in near-surface
regions, but even in MnO2 Au/MnO2

 Effective dispersion of Mn2O3

20 nm inner ones (see SIMS)
XPS Au NPs nm
nm

120
(Au/Mn atomic ratio = 0.20)  Intimate Au/Mn oxide150
40

 annealing contact & strong 50

2.5 2.5 2.5
Au/Mn2O3 in air: MnO2 interaction (see XPS) 2.5 2.0 2.0 2.0 2.0
1.5 1.5 1.5
μm 1.5 1.0
Mn2O3 BE(Mn2p3/2) 642.5 eV 100 nm 100 nm 0.5 0.5
1.0 μm μm 1.0
0.5 0.5
1.0 μm

Mn3s multiplet MnO2 Au/MnO2

Au/MnO2 MnO2 Au/MnO
Au/MnO
Mn Au/Mn
Au/Mn O2O3
2O3 22
splitting (MS) 4.7 eV Au/Mn2O3 20 nm 5 5
tapping
2 3

MnO2 10 O
Sn
10
AFM O mode
Sn
SIMS yield (cps)
SIMS yield (cps)

4 4
10 nm
 annealing in Ar: 10
nm
nm nm
3 3 120
Mn2O3 10 10 80 120
150  Similar surface 40
Mn2p Mn3s BE(Mn2p3/2) 641.8 eV 2 2
40
20
10 50 10 texture Au
Intensity (a.u.)

Mn3s MS 5.3 eV
Intensity (a.u.)

2.5 2.5 2.5 2.5 2.5

2.5 2.5 2.0
2.0
100 nm 100
10nm
1 Mn  RMS roughness =
2.5
102.0
1
Mn2.0
1.5
2.0
1.5 1.5
2.0 2.0
1.5
1.5
2.0
1.5
1.5 μm 1.5 1.0 1.0 μm μm 1.0 1.0 μm
μm 1.0 μm
0.525 nm
μm 1.0 0.5 1.0 μm
 O1s: 10
0
10
0 1.0
0.5
0.5
0.5 0.5
0.5 0.5

Mn-O-Mn (I @ 529.9 eV) 0 100 200 300 400 0 100 200 300
Mn2O3
400
Au/Mn2O3
Depth (nm)
Thickness (nm) Depth (nm)
Thickness (nm)
O defects (II @ 531.8 eV) Cs+, 14.5 keV, 25 nA
SIMS beamMnO
blanking
2
Au/MnO
Au/MnO
Mn2O3 22 Au/Mn
Au/Mn22O3 Conclusions
660 650 640 95 90 85 80 75 10
6 nm106 nm
(-) secondary ions
BE (eV) BE (eV)
10%  after Au introduction: 10
5
O 510
5
O O 80 5 120 ✓ Supported MnO2 and Mn2O3-based
10 10 O
Sn Sn 40
electrocatalysts by an original vapor-
[C]< 10 ppm Sn
SIMS yield (cps)
SIMS yield (cps)
SIMS yield (cps)
SIMS yield (cps)

O1s II I Au4f  high purity

4 4 20 Sn
Au-oxide interaction and 10
10
410
10
4
Intensity (a.u.)

phase route (PA-CVD + Au sputtering +

Intensity (a.u.)

2.5
charge redistribution 3 3 2.5
2.0
2.5
2.0 2.0
2.5
 in-depth
10 dispersion 10
310 3
10 1.5
μm 1.0
1.5
2.0Au
1.5
thermal treatments)
1.5
1.0 μm μm 1.0 1.0 μm
2 2
BE(Au4f7/2) 84.5 eV of Au NPs
10 in Mn oxides 10 10
2
Au 10
2 0.5 0.5 0.5 0.5

(Mn oxide porosity + Mn ✓ Dendritic MnO2/Mn2O3 morphology

[>  0.5 eV than bulk Au(0)] 10
1
10 10
1 1
Mn 10
1 Mn
RF-sputtering infiltration) and high O vacancy content
Au NPs → Mn oxide 0
10 10 10
0 0
10
0

540 535 530 525 92 88 84 80

electron transfer  intimate Au/Mn
0 oxide200
100 contact
300 400 0 0 100
100 200200 300300 400
400 0 100 200 300 ✓ Even decoration with highly
BE (eV) BE (eV) Depth (nm)
Thickness (nm) Depth
Depth
Thickness (nm)
(nm)
(nm)
Thickness (nm) Depth (nm)
Thickness (nm) dispersed, low-sized Au nanoparticles

10
6
Mn2O3
10
6
Au/Mn2O3
✓ Tailored OER performances ( for
0.5 M KOH, 3 electrode set-up  current density ∝ EWE Mn2O3-based systems, enhanced by Au
  < 800 nm: OER performances 5
O counterelectrode;
10(Pt mesh 10
5
O
Optical absorption Sn functionalization)
SIMS yield (cps)
SIMS yield (cps)

interband Hg/HgO
4 reference electrode) 4
Sn
10 10  catalytic activity increase in the order
transitions 6 3 3
MnO2 < Au/MnO
Au 2 <<< Mn2O3 < Au/Mn2O3
(direct, allowed) 10 10
Perspectives
5 1.6 2 2
in Mn oxides 10 10
✓ Improvement of metal oxide OER
EWE (V) vs RHE

4 1 Mn 1  MnMn
2O3 more active than MnO2
j (mA/cm )

1.5 10 10
2

MnO2 performances trough controllable

Absorbance (a.u.)

 Tauc plots: 3 Au/MnO2 0 0 ( catalytic activity)

10 10 plasma processing
EG = 2.00 eV Mn2O3
1.4 MnO2400 0
 Au 200
100
NPs 300
enhance OER performances
2 Au/Mn2O3 0 100 200 300
for MnO2-based Depth (nm)
Thickness Au/MnO2
(nm)
Mn2O3
Depth (nm)
Thickness (nm) ✓ Contribution towards commercially
systems 1 1.3
Au/Mn2O3 Au donation to Mn sites and  O vacancies viable water (photo)eletrolysis for a
EG = 2.15 eV 0
at the Au/Mn oxide interfaces (see XPS) sustainable hydrogen fuel production
Au/MnO2
MnO2 for Mn2O3-based 1.40 1.45 1.50 1.55 1.60 1.65 0.1 1
2
ones EWE (V) vs RHE j (mA/cm )
600 800 1000 1200
Wavelength (nm)
 Tail towards j @ 1.65 V vs. RHE η @ 1 mA/cm2 Tafel slope [1] L. Bigiani, A. Gasparotto, T. Andreu, J. Verbeeck, C. Sada, E. Modin, O.I. Lebedev, J.R.
(mA/cm2) (mV) (mV/decade)
the IR region → Morante, D. Barreca, C. Maccato, Adv. Sustain. Systems, 2021,
O vacancies → MnO2 1.57± 396± 66 https://doi.org/10.1002/adsu.202000177.
Absorbance (a.u.)

sub-band Au/MnO2 1.90± 386± 64 [2] L. Bigiani, T. Andreu, C. Maccato, E. Fois, A. Gasparotto, C. Sada, G. Tabacchi, D. Krishnan,
gap states J. Verbeeck, J.R. Morante, D. Barreca, J. Mater. Chem. A, 2020, 8, 16902.
Mn2O3 4.31± 312± 84
(see XPS) [3] L. Bigiani, A. Gasparotto, C. Maccato, C. Sada, J. Verbeeck, T. Andreu, J.R. Morante, D.
favorably Au/Mn2O3 4.97± 309 82 Barreca, ChemCatChem, 2020, 12, 5984.
affecting [4] L. Bigiani, C. Maccato, T. Andreu, A. Gasparotto, C. Sada, E. Modin, O.I. Lebedev, J.R.
Au/Mn2O3
Mn2O3 electrocatalytic  Performances compare favorably with previous Mn oxides Morante, D. Barreca, ACS Appl. Nano Mater., 2020, 3, 9889.
performances  Tafel slopes > for Mn2O3-based systems that perform better..?.. [5] L. Bigiani, D. Barreca, A. Gasparotto, T. Andreu, J. Verbeeck, C. Sada, E. Modin, O.I.
400 600 800 1000 1200
Wavelength (nm) ≠ reaction mechanism, or  coverage of MnO2 Lebedev, J.R. Morante, C. Maccato, Appl. Catal., B, 2021, 284, 119684.
materials by surface intermediates