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Flocculates of Au nanoparticles in catalysis
NMSL – nanoAu and catalysis
04/18/23 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.
04/18/23B. 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
04/18/23 B. Y. Wang, J. H. Chen 3
(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
04/18/23 B. Y. Wang, J. H. Chen 4
(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
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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
04/18/23 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
