Flocculates of Au nanoparticles in catalysis

NMSL – nanoAu and catalysis

04/21/23 B. Y. Wang, J. H. Chen 1

Nanoparticle ： AuNS-L-Pd

• Goal– Catalytic reaction within nanoparticle

flocculates

• Experiment– Cyclotrimerization of 3-hexyne in chloroform

at r.t.

04/21/23B. Y. Wang, J. H. Chen 2

Dispersed in DMSO

Dispersed in CHCl3 + DMSO靜置

取出上

層

Sub-micron Flocculates Sub-micron Flocculates

Results

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(A)

(B)

(A)(A)

157±23 nm

300 400 500 600 700 800 900 1000 11000.00

0.05

0.10

(A) (B) (C)

Wavelength (nm)

Absorb

ance (A

U)

0.0

0.1

0.2

0.3

Dispersed in DMSO

Dispersed in CHCl3 + DMSOAging

Upper Soln

(C) (A) (B)(D)

(D)

Results

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(A) (B)

300 400 500 600 700 800 900 1000 11000.00

0.05

0.10

(A) (B) (C)

Wavelength (nm)

Absorb

ance (A

U)

0.0

0.1

0.2

0.3

(C)

(C)

(A)

(B)

Dispersed in DMSO

Dispersed in CHCl3 + DMSO

(C) (A) (B)(D)Aging

Upper Soln

Types Diagrams TEM images

A

B

C

Catalysis of different types

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Catalytic results

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Types Pd molParticle

weight (mg)Reaction time (hr)

Yield (%)

B 3x10-6 - 0.5 >99

A 3.92x10-7 1 0.5 11.52

B 3.92x10-7 1 0.5 14.47

C 4.02x10-7 1.7 0.5 0

A 0.92x10-7 0.6 1.5 2.69

B 0.92x10-7 0.6 1.5 5.19

C 1.07x10-7 2.2 1.5 0

1 c.c. CDCl3; 0.075 mmol reactant; R.T. ; Stir rate: 300 rpm

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樣品 Cat. M Cat. mol% 觸媒重量(mg)

反應時間 (min)

產率 (%)

RS/ L-Pd:

轉速(rpm)

備註

A 3x10-3 4 - 30 >99 - - A.林玉雲學姐的論文B.3.92x10-7 mol Pd/mgC.1.54x10-7 mol Pd/mgD.3,22x10-7 mol Pd/mgE.1.67x10-7 mol Pd/mgF.2.60x10-7 mol Pd/mg G.2.21x10-7 mol Pd/mgH.3.35x10-7 mol Pd/mg

CDCl3:1 ml ; 反應物 :0.075 mmol ;

*CDCl3:686 l反應物 :0.05 mmol

＃ CDCl3:500 l反應物 :0.0375 mmol

B(13) 3.92x10-4 0.52 1 30 14 - 300

C 0.92x10-4 0.12 0.6 90 5.2 1.1 300

D 1.6x10-4 0.21 0.50 1200 0 1.6 600

D 1.19x10-3 1.58 3.7 600 3.2 1.6 1200

E 1.67x10-4 0.22 1 780 0 - 600

F 6.24x10-4 0.83 2.40 720 0 1.4 600

F* 3.00x10-3 4.13 7.86 30 0 1.4 990

G 3.01x10-3 4.01 13.7 50 7.5 1 1200

G# 6.10x10-3 8.13 13.9 120 74 1 1200

H#(13)

6.10x10-3 8.13 9.1 60 53 0.8 1200

1(Liquid)

6.08x10-3 8.10 16.5 120 0 1.8 12001. 1.84x10-7 mol Pd/mg

04/21/23 B. Y. Wang, J. H. Chen 8

LL+L-Pd

L+L-Pd+thiol

L-Pd L-Pd8.28.6

507-Pd毒化實驗

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攪拌前攪拌後

8.28.6

Sample 1 攪拌前後光譜變化

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樣品 Cat MCat. mol

% 觸媒重量

(mg)

反應時間 (hr)

產率 (%)

RS/ L-Pd:

轉速(rpm)

備註

CyclotrimerizationG.2.21x10-7 mol

Pd/mgF. 1.84x10-7 mol Pd/mg

G 6.10x10-3 8.13 13.9 2 74 1 1200

1 6.08x10-3 8.10 16.5 2 0 1.8 1200

Heck reaction

G 1.33x10-7 0.00133 0.6 1.5 95 1 600

1 1.29x10-7 0.00129 0.7 1.5 85 1.8 600

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Sample G

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Sample 1

反應系統• Heck reaction

• Reaction condition ： 115 oC for 1.5 hr

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O

O

I

O

O

10 mmol0.278 ml

Bp: 182 oC; MW: 203; D: 1.823 g/ml

10 mmol0.355 ml

Bp: 160 oC; MW: 128; D: 0.899 g/ml

Pd: 0.001 mol%

NEt3

0.375 mlBp: 88.8 oC;

0.25 ml DMSO

Need Pd 1x10-7 mol

反應系統• Cyclotrimerization

• Reaction condition ： r.t. for 0.5 hr

04/21/23 Richard Wang 14

Et Et EtEt

Et Et

EtEt

0.075 mmol8.52 l

Bp: 81 oC; MW: 82.14; D: 0.723 g/ml

1 ml CHCl3 、 THF

Pd: 4 mol%

Need Pd 3x10-6 mol

RAW DATA

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A-1

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B-1

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A-2

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B-2

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C. AuNS-L-Pd

D. AuNS-L

D. AuNS-L-Pd

F. AuNS-L

F. AuNS-L-Pd

G. AuNS-L-Pd

H. AuNS-L

H. AuNS-L-Pd

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1. L-AuNS-L-Pd