advances.sciencemag.org/cgi/content/full/3/7/e1700101/DC1

Supplementary Materials for

Finely controlled multimetallic nanocluster catalysts for solvent-free

aerobic oxidation of hydrocarbons

Masaki Takahashi, Hiromu Koizumi, Wang-Jae Chun, Makoto Kori, Takane Imaoka, Kimihisa Yamamoto

Published 26 July 2017, Sci. Adv. 3, e1700101 (2017)

DOI: 10.1126/sciadv.1700101

This PDF file includes:

fig. S1. UV-vis spectral titration of TPM-DPA G4 on the addition of AuCl3,

PtCl4, and CuCl2.

fig. S2. Durability of Cu32Pt16Au12@TPM-DPA G4/GMC catalysts.

fig. S3. Confirmation of coexistence of Cu, Pt, and Au atoms by STEM-EDX

chemical mappings in Cu32Pt16Au12@TPM-DPA G4/GMC.

fig. S4. Confirmation of coexistence of Cu, Pt, and Au atoms by STEM-EDX

analysis in Cu32Pt16Au12@TPM-DPA G4/GMC.

fig. S5. XPS analysis of various NCs at Cu 2p region.

fig. S6. XPS analysis of various NCs at Pt 4f region.

fig. S7. XPS analysis of various NCs at Au 4f region.

fig. S8. XPS analysis of Cu NCs at Cu 2p region.

fig. S9. XPS analysis of Pt NCs at Pt 4f region.

fig. S10. XPS analysis of Au NCs at Au 4f region.

fig. S11. XAFS analysis for Cu atoms on MNCs.

fig. S12. XAFS analysis for Pt atoms on MNCs.

fig. S13. XAFS analysis for Au atoms on MNCs.

fig. S14. Products ratio of the aerobic oxidation reactions using various NC

catalysts.

fig. S15. Aerobic oxidation of tetralin using a commercially available Pt on

carbon catalyst or MNCs.

fig. S16. The effects of Cu-Pt ratio on catalytic activities of oxidation reaction.

scheme S1. Schematic representation of complexation of TPM-DPA G4 with

AuCl3, PtCl4, and CuCl2.

table S1. Oxidation resistance of Cu and Cu-M alloy NCs in air.

table S2. Curve fitting results of Cu32Pt16Au12@TPM-DPA G4/GMC for Cu K-

edge, Pt L3 and Au L3-edge EXAFS spectra.

table S3. Substrate generality in the aerobic oxidation using MNC catalyst.

fig. S1. UV-vis spectral titration of TPM-DPA G4 on the addition of AuCl3, PtCl4, and CuCl2.

Inset: enlargement of isosbestic points on the addition of AuCl3, PtCl4 and CuCl2.

scheme S1. Schematic representation of complexation of TPM-DPA G4 with AuCl3, PtCl4,

and CuCl2.

fig. S2. Durability of Cu32Pt16Au12@TPM-DPA G4/GMC catalysts.

HAADF-STEM images of Cu32Pt16Au12@TPM-DPA G4 species present on GMC were at different

times (0, 2, 3, and 6 hour) of oxidation reaction under 90 oC and O2 (1 atm).

fig. S3. Confirmation of coexistence of Cu, Pt, and Au atoms by STEM-EDX chemical

mappings in Cu32Pt16Au12@TPM-DPA G4/GMC.

The chemical mappings of Au, Pt, and Cu were measured in the different views of a same

sample.

fig. S4. Confirmation of coexistence of Cu, Pt, and Au atoms by STEM-EDX analysis in

Cu32Pt16Au12@TPM-DPA G4/GMC.

EDX analysis of red square regions in right STEM image.

fig. S5. XPS analysis of various NCs at Cu 2p region.

XPS of Cu60@TPM-DPA G4, Cu32Au28@TPM-DPA G4 Cu32Pt28@TPM-DPA G4 and

Cu32Pt16Au12@TPM-DPA G4 at Cu 2p region. Reference: C1s = 284.5 eV (GC: Glassy carbon).

table S1. Oxidation resistance of Cu and Cu-M alloy NCs in air.

The peak area ratio between Cu (II) and [Cu (0) + Cu (I)] (peak area of [Cu (0) + Cu (I)]/peak

area of Cu(II) in XPS at Cu 2p region.

Cluster [Cu (0) + Cu (I)] / Cu (II)

Cu60 0.36

Cu32Au28 0.59

Cu32Pt28 0.81

Cu32Pt16Au12 2.17

fig. S6. XPS analysis of various NCs at Pt 4f region.

XPS of Pt60@ TPM-DPA G4, Pt32Au28@ TPM-DPA G4, Cu32Pt28@ TPM-DPA G4, Cu32Pt16Au12@

TPM-DPA G4 and Pt foil at Pt 4f region. Reference: C1s = 284.5 eV (GC: Glassy carbon).

fig. S7. XPS analysis of various NCs at Au 4f region.

XPS of Au60@ TPM-DPA G4, Pt32Au28@ TPM-DPA G4, Cu32Au28@ TPM-DPA G4, Cu32Pt16Au12@

TPM-DPA G4 and Au powder at Au 4f region. Reference: C1s = 284.5 eV (GC: Glassy carbon).

fig. S8. XPS analysis of Cu NCs at Cu 2p region.

XPS of CuCl2, Cu60@ TPM-DPA G4, and Cu2O (bulk) at Cu 2p region. Reference: C1s = 284.5

eV (GC: Glassy carbon).

fig. S9. XPS analysis of Pt NCs at Pt 4f region.

XPS of PtCl4, Pt60@TPM-DPA G4 and Pt foil at Pt 4f region. Reference: C1s = 284.5 eV (GC:

Glassy carbon).

fig. S10. XPS analysis of Au NCs at Au 4f region.

XPS of AuCl3, Au60@ TPM-DPA G4 and Au powder at Au 4f region. Reference: C1s = 284.5 eV

(GC: Glassy carbon).

(a)

(b)

No

rma

lize

d a

bso

rption

/ a

rb.

un

its

90409020900089808960

Photon energy / eV

Cu foil Cu32Pt16Au12

CuO Cu2O

Cu K-edge

-30

-20

-10

0

10

20

30

k3(k

)

1210864

k / Å -1

Cu foil Cu32Pt16Au12

CuO Cu2O

(c)

fig. S11. XAFS analysis for Cu atoms on MNCs.

XAFS spectra of Cu atom on Cu32Pt16Au12@TPM-DPA G4/GMC, CuO, Cu2O, and Cu foil as a

reference. (a) Cu K-edge XANES spectra, (b) k3-weighted Cu K-edge EXAFS spectra, (c)

Fourier-transformed k3-weighted Cu K-edge EXAFS spectra for Cu32Pt16Au12@ TPM-DPA G4/GMC, CuO,

Cu2O, and Cu foil as a reference. *Fourier transform was limited where k = 3.0 ~ 11.5 Å-1 in EXAFS

spectra.

30

25

20

15

10

5

0

|FT

| of

k3(k

) /

arb

. unit

6543210

r / Å

Cu foil Cu32Pt16Au12

CuO Cu2O

(a)

(b)

No

rma

lize

d a

bso

rption

/ a

rb.

un

its

116201160011580115601154011520

Photon energy / eV

Pt foil Cu32Pt16Au12

Pt L3-edge

-20

-10

0

10

20

k3(k

)

1210864

k / Å -1

Pt foil Cu32Pt16Au12

(c)

fig. S12. XAFS analysis for Pt atoms on MNCs.

Pt L3-edge XANES spectra, (b) k3-weighted Pt L3-edge EXAFS spectra, (c) Fourier-transformed k3-weighted

Pt L3-edge EXAFS spectra for Cu32Pt16Au12@ TPM-DPA G4/GMC and Pt foil as a reference. *Fourier

transform was limited where k = 3.0 ~ 9 Å-1 in EXAFS spectra.

10

8

6

4

2

0

|FT

| of

k3(k

) /

arb

. unit

6543210

r / Å

Pt foil Cu32Pt16Au12

(a)

(b)

No

rma

lize

d a

bso

rption

/ a

rb.

un

its

1198011960119401192011900

Photon energy / eV

Au foil Cu32Pt16Au12

Au L3-edge

-10

-5

0

5

10

k3(k

)

1210864

k / Å -1

Au foil Cu32Pt16Au12

(c)

fig. S13. XAFS analysis for Au atoms on MNCs.

(a) Au L3-edge XANES spectra, (b) k3-weighted Au L3-edge EXAFS spectra, (c) Fourier-transformed

k3-weighted Au L3-edge EXAFS spectra for Cu32Pt16Au12@ TPM-DPA G4/GMC and Au foil as a

reference. *Fourier transform was limited where k = 3.0 ~ 11.5 Å-1 in EXAFS spectra.

10

8

6

4

2

0

|FT

| of

k3(k

) /

arb

. unit

6543210

r / Å

Au foil Cu32Pt16Au12

table S2. Curve fitting results of Cu32Pt16Au12@TPM-DPA G4/GMC for Cu K-edge, Pt L3 and

Au L3-edge EXAFS spectra.

(a) Cu K-edge EXAFS

sample bond N r / Å E0 / eV 2/ 10-3Å2 Rf / %

Cu foil* Cu-Cu 12 2.55 n/a n/a n/a

Cu32Pt16Au12 Cu-O 1.4 ± 0.4 1.94 ± 0.02 5.8 ± 4.2 2.5 ± 1.8 0.5

Cu-Au 4.3 ± 1.7 2.66 ± 0.02 0.5 ± 3.6 12.5 ± 0.8

sample bond N r / Å E0 / eV 2/ 10-3Å2 Rf / %

Cu32Pt16Au12 Cu-O 1.3 ± 0.3 1.94 ± 0.02 5.3 ± 4.2 2.4 ± 1.8 0.5

Cu-Pt 4.0 ± 1.7 2.65 ± 0.02 0.06 ± 4.1 12.5 ± 0.8

**Fourier transform and Fourier filtering region were limited where k = 3.0 ~ 11.5 Å-1 and r = 1.1 ~ 3.0 Å,

respectively.

(b) Pt L3-edge EXAFS

sample bond N r / Å E0 / eV 2/ 10-3Å2 Rf / %

Pt foil* Pt-Pt 12 2.77 n/a n/a n/a

Cu32Pt16Au12 Pt-Pt/Au 7.3 ± 3.8 2.68 ± 0.04 2.7 ± 4.7 12.3 ± 1.8 0.08

Pt-Cu 2.8 ± 1.5 (2.65) 5.9 ± 4.3 (12.5)

**Fourier transform and Fourier filtering region were limited where k = 3.0 ~ 9.0 Å-1 and r = 1.6 ~ 3.6 Å,

respectively.

(c) Au L3-edge EXAFS

sample bond N r / Å E0 / eV 2/ 10-3Å2 Rf / %

Au foil* Au-Au 12 2.89 n/a n/a n/a

Cu32Pt16Au12 Au-Au/Pt 7.3 ± 3.1 2.77 ± 0.02 4.9 ± 2.8 10.6 ± 0.6 0.7

Au-Cu 1.7 ± 0.9 (2.66) 6.7 ± 4.7 (12.5)

**Fourier transform and Fourier filtering region were limited where k = 3.0 ~ 11.5 Å-1 and r = 1.4 ~ 3.2 Å,

respectively.

*Crystallographic data.

***Values in parentheses were fixed.

Notations: N, coordination number; r, bond distance between absorber and backscatter atoms; 2, the

Debye-Waller factor (DW); E0, the inner potential correction accounts for the difference in the inner

potential between the sample and the reference; Rf (R-factor), a goodness of curve fit.

fig. S14. Products ratio of the aerobic oxidation reactions using various NC catalysts.

Comparison of the catalytic activity of various metal nanoclusters on the TOF (turnover

frequency) based on the transformation from indan to three products of indanone, indanol and

indan hydroperoxide. The turnover frequencies [(Cu+Pt+Au) atom-1 h-1] were normalized by

the total molar amount of the metal content and were determined by 1H NMR analysis using

anisole as an internal standard. Reaction condition: catalysts (0.0056 mol%), 90 oC, O2 (1 atm),

6 h.

fig. S15. Aerobic oxidation of tetralin using a commercially available Pt on carbon catalyst

or MNCs.

TOFs of 1,2,3,4-tetrahydronaphthalene oxidation catalyzed by Cu32Pt16Au12@ TPM-DPA

G4/GMC and Pt/C (aldrich, 10 wt%). The turnover frequencies [(Cu+Pt+Au) atom-1 h-1] were

normalized by the total molar amount of the metal content and were determined by 1H NMR

analysis using anisole as an internal standard. Reaction condition: catalysts (0.0056 mol%), 90

oC, air or O2 (1 atm), 6 h.

table S3. Substrate generality in the aerobic oxidation using MNC catalyst.

Oxidation of hydrocarbons catalysed by Cu32Pt16Au12 catalysts under air or O2 (1 atm)a.

aThe turnover frequencies [(Cu+Pt+Au) atom-1 h-1] were normalized by the total molar amount

of the metal content and were determined by 1H NMR analysis using anisole as an internal

standard.

fig. S16. The effects of Cu-Pt ratio on catalytic activities of oxidation reaction.

Comparison of catalytic activities of alloy nanoclusters with different composition ratio of Cu

and Pt atom. The turnover frequencies [(Cu+Pt) atom-1 h-1] were normalized by the total molar

amount of the metal content and were determined by 1H NMR analysis using anisole as an

internal standard. Reaction condition: catalysts (0.0056 mol%), 90 oC, air, 6 h.