Solid-state ECL sensors -固态电化学发光传感器

-5 -5
Log(ECL Intensity)
4000
[Glucose]/mol L
-6
-1
3.7 3.6 3.5 3.4 3.3 -7
1
0.02
0 0.0

-1/2
0.03
/ rpm
-1/2
0.04
0.05
0.6
1.2
2000
Potential / V vs SCE
4.0x10 -5 8.0x10 -4 1.0x10 -4 4.0x10 -4 8.0x10 -3 1.0x10
(I)、Laponite-Ru(bpy)32+固态电化学发光
350 B a b 15 12 9 6 3 0 5 10 15 20 25 30 laponite loading / mg 35
ECL intensity (a.u)
300 250 200 150 100 50 0
Peak current ( m A)
Electrochem. Commun. 12 (2010) 905–908
（II）、联吡啶钌（II）-吡咯衍生物的固态电化学 发光 I
CurreA
100
100
b
ECL Intensity / A.U.
ECL Intensity / A.U.
Current / mA
Log(ECL Intensity/A.U.)
4000
2000
3.30
ECL Intensity / A.U.
40
a b
a
3.15
a b c d
1
ECL intensity / A.U.
Current / mA
3.00
20
2000
b
0 0.0 0.4 0.8 1.2
1000
Log(Cglucose/mM)
微纳材料发光研究及传感应用
丁收年 教授/博导
东南大学化学化工学院
2013-12-8 南京
主要内容
基于三联吡啶合钌（ＩＩ）及其衍生物的固态电化学发 光
Laponite-Ru(bpy)32+ Ru(bpy)32+- pyrrole derivative Ru(bpy)32+- pyrene derivative
Current / mA
120
Peak current / mA
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光
240
300 150 0 0.0 0.4
0

1/2
0.8
/ (V s )
-1 1/2
1.2
SEM
-120
A
0.4 0.8 1.2
A
30000
Potential / V vs SCE
b
2000
ECL intensity / a.u.
150
Peak current / mA
1500
a
1000
100
Current / mA
50
50th cycle
0
50 500 0 10 20 30 40 50 60 70
-2
A
Surface coverage / nmol cm
-50 0.4 0.8
(I)、Laponite-Ru(bpy)32+固态电化学发光
Electrochem. Commun. 12 (2010) 227-230
(I)、Laponite-Ru(bpy)32+固态电化学发光
24 a' 20
320 280
a
ECL intensity (a.u.)
16
Current (mA)
2
3
e f
Potential / V vs. SCE
0 0.0
0
0.4 0.8 1.2
0
10
20
Potential / V vs. SCE
Time / s
ECL quenching by nanogold
Determination of glucose
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光-乙醇生物传感器
Peak current ( m A)
b
12 18 24 Immersion time (h)
30
(I)、Laponite-Ru(bpy)32+固态电化学发光
400
ECL Intensity / A. U.
A
A
200
0 0.0
6000
0.5 1.0 Potential / V vs SCE
1.5
ECL Intensity / A. U.
A
III
0
a
50 a 0 0.0
200
ECL Intensity / A.U.
-50 0.0
Potential / V vs. 10 mM Ag
0.4
0.8
+
1.2
50
100
Potential / V vs. SCE
0.4
0.8
1.2
300 200 100 0
ECL intensity (A.U.)
A
N N
N Ru N
B
N
2+
(PF6)2
N
O
O
Chem. Eur. J. 2012, 18, 11564 – 11568
（III）、联吡啶钌-芘/SWCNTs复合物电化学 发光
A
B A
SWCNTs
Ru-pyrene/SWCNTs
（III）、联吡啶钌-芘/SWCNTs复合物电化学 发光
20
1st cycle
纳米金生长
葡萄糖生物ECL传感器 GOD: 葡萄糖氧化酶 hv: 电化学发光
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光
Electropolymeric film
Nanogold/Electropolymeric film
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光-葡萄糖生物传感器
+
Peak Current / mA
Potential / V vs. 10 mM Ag
+
Consecutive CV curves
EC property of Ru-pyrene/SWCNTs composite
（III）、联吡啶钌-芘/SWCNTs复合物电化学 发光
200 150
2400
ECL intensity / A.U.
250
ECL intensity (a.u)
200 150 100 50
A
ECL intensity (a.u)
0 0.1 0.2 0.3 0.6 1 2+ Ru(bpy)3 loading (CEC)
350 300 250 200 150 100 50 0 0 6 a
C
24 20 16 12 8 4 0
Counts / A. U.
In organic solution
Counts / A. U.
1.0
1.0
II
In aqueous solution
0.5
0.0 400
Wavelength / nm
600
800
0.5
0.0
560
600
640
Wavelength / nm
ECL and PL spectra
+1mM H2O2 +10mM H2O2 +100 mM H2O2
400
a b c
4 c b a
2000
+1mM H2O2
0 0 50 100 150
Current / mA
Time / s
200
103 ilim-1 / mA-1
3
ECL Intensity / A. U.
2
1.0x10
1.0x10
Ru(II)
N N N
a
0 0.0 0.4 0.8 1.2
(PF6)2
Potential / V vs. SCE
1200
N
ECL intensity / A.U.
600
0 1 2 3 4 5
-2
6
J.Electroanal.Chem. 692 (2013) 60-65
Surface Coverage / nmol cm
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光
4000
1200
40
b a
b
ECL intensity / A.U.
ECL intensity / A.U.
Current / mA
20
2000
600
0 0.0
Potential / V vs. SCE
0.4
0.8
1.2
a
0 0.0
0
0.4
0.8
B
B
4000
2000
0 0.0
0.5
1.0
1.5
Potential / V vs SCE
RSC Adv. 2 (2012) 10813-10816
(I)、Laponite-Ru(bpy)32+固态电化学发光
6000
Original 1mM Glucose
ECL Intensity / A.U.
4000
b
A
4000
B b
Current / mA
800
Current / m
ECL intensity / A.U.
1600
300
100 50 0
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光-乙醇传感器
SEM and AFM images of Laponite film (A) and Laponite-ADH film (B).
（II）、联吡啶钌（II）-吡咯衍生物的固态电化 学发光-乙醇生物传感器
（III）、联吡啶钌-芘/SWCNTs复合物电化学 发光
1.2
0
200
400
600
Potential / V vs. SCE
Time / s
Enhanced ECL in H2O/CH3CN
Stability
固态电化学发光生物传感器-1
合成半导体纳晶 滴涂 hv
合成联吡啶钌（II）吡咯衍生物
电聚合
固态电化学发光界面 吸附5nm纳米金
hv
纳米金活化的电化学发光界面 葡萄糖 hv GOD+ AuCl4-温育
B
B
50
100
0
2
4
6
8
10
-2
0
Surface Coverage / nm ol cm
0 0.0
0 0.0
Surface Coverage (nmol cm )
0
1
2
3
4 -2
0.4
0.8
1.2
0.4
0.8
+
1.2
Potential / V vs. SCE
Potential / V vs. 10 mM Ag
Log(ECL Intensity/A.U)
4000 [NADH] mM
2 1 0.5 0.05 0.01
4
ECL Intensity / A.U
3
2 -2 -1 0 1
2000
Log (CNADH/mM)
0 0 10 20 30
Time / s
Electroanalysis 25( 2013) 697–702
基于半导体纳晶的固态电化学发光
F-SnO2 ECL ECL and ECR of CdS ECL of CdTe/TiO2 TiO2 ECL C-dots-nanoAg ECL to detect S2- ions
基于金属簇的荧光传感器
Au@Ag PL to detect S2- ions Au NCs PL to detect PO43- ions
20 15 10 5 0 50 -1 100 Scan rate / mV s
120
60
5th cycle
Current / mA
0.8 1.2
Current /mA
2nd cycle
10 0
0 0.0 0.4
-10 0.0 0.3 0.6 0.9 1.2
Potential / V vs10mM Ag
-6
Log(Cglucose / M)
-5
-4
-3
-2
Rotating-disk electrode voltammograms
0
0
5
10
15
20
25
Time / s
（II）、联吡啶钌（II）-吡咯衍生物的固态电化学 发光
(BF4)2
N N N N N
Ru2+
N N N
CV and ECL curve
Potential / V vs SCE
0.4
0.8
1.2
C
Potential / V vs SCE
0.4 0.8 1.2
Electroanalysis 23 (2011) 1306-1310
0.0
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光
200
100 1st cycle 25th cycle
1.2V -1.2V -1.2V 1.2V -1.2V
20000
Counts
10000
0
B
0 5 10 15 20 25
Time / s
150
2500
b a
FL imaging
ECL intensity / a.u.
2000 1500 1000 500 0 0.0
100
Current / mA
B
50 0 -50
240 200 160 120 80 40 0 -40 0.0 0.4 0.8 1.2 Potential (V) vs.SCE 1.6 b
12 a 8 4 0 -4 -8 0.0 0.2 0.4 0.6 0.8 Potential (V) vs. SCE 1.0 1.2 b b'
CV curve
ECL-Potential curve
0 80
B
1.2
Potential / V vs SCE
Stability
（II）、联吡啶钌（II）-吡咯衍生物的固态电 化学发光
1000
40
b
b
ECL Intensity / A.U.
Current / mA
20
N
500
a
0 0.0 0.4 0.8 1.2
N N
N N
Potential / V vs. SCE