Supporting Information

An Ultrasensitive Colorimetric Chromium

Chemosensor Based on Dye Color Switching
under the Cr(VI)-Stimulated Au NPs Catalytic
Activity

Yu-Ting Zhuang†, Shuai Chen‡, Rui Jiang†, Yong-Liang Yu†,* and Jian-Hua Wang†

†Research Center for Analytical Sciences, Department of Chemistry, College of

Sciences, Northeastern University, Box 332, Shenyang 110819, P. R., China

‡College of Life and Health Science, Northeastern University, Shenyang 110169, P. R.,

China

*E-mail: yuyl@mail.neu.edu.cn

Phone: +86 24 83688944. Fax: +86 24 83676698

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 Table of contents

Materials………………….…………………….……………………….……………S4

Optimization of experimental parameters……………………………….…………...S6

Figure S1 UV-vis spectra of Au NPs with different particle

sizes……….…….…….S7

Figure S2 Color changes of the detection solution in the presence of 10, 15, 30, and

50 nm Au NPs…………………………………...………………………..………….S8

Figure S3 (A) UV-vis spectra of Au NPs capped with different amounts of GA; (B)

FT-IR spectra of Au NPs, GA, GA-Au NPs and GA-Au NPs +

Cr(VI)…...….….….S9

Figure S4 Effect of reaction temperature on catalytic reduction of MB.…….……..S10

Figure S5 Time-dependent UV-vis absorption spectra for the catalytic reduction of

MB by NaBH4 in the presence of GA-Au NPs..……………………………………S11

Figure S6 Smartphone-based colorimeter for the determination of Cr(VI)…......….S12

Figure S7 (A) TEM and (B) HRTEM images of GA-Au NPs after Cr(VI)

detection…………………………………………………………………………….S13

Figure S8 (A) XPS survey spectrum of GA-Au NPs in the presence of Cr(VI); (B) Cr

2p spectrum of GA-Au NPs in the presence of Cr(VI) …………………………….S14

Figure S9 Two-electron oxidation of gallic acid to corresponding quinone form….S15

Figure S10 Solid UV-vis spectra of filter paper, GA-Au NPs filter paper, MB filter

paper and GA-Au NPs/MB filter paper…………………………………………….S16

Figure S11 SEM images of (A) filter paper and (B) GA-Au NPs filter paper…..….S17

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Figure S12 SEM images of GA-Au NPs filter paper and corresponding element

mapping images of C, O, and Au…………………………………………………...S18

Figure S13 The colorimetric images of MB/GA-Au NPs filter paper in the presence of

Cr(VI) at different pH values……………………………………………………….S19

Figure S14 The colorimetric images of MB/GA-Au NPs filter paper in the presence of

different metal ions…………….…………………………………………………...S20

Figure S15 Photo image of the colorimetric filter paper on the addition of different

concentrations of Cr(VI) and GBW08608………………………………………….S21

Table S1 Comparisons of analytical performances of the MB/GA-Au NPs

chemosensor to other approaches for the detection of Cr(VI) ……………………..S22

Table S2 Determination results for total Cr in solution by MB/GA-Au NPs

chemosensor…………………………………………………………………..…….S23

Table S3 Leachability testing of filter paper using the Toxicity Characteristic

Leaching Procedure and Synthetic Precipitation Leaching Procedure………….….S24

References……………………………………………………………………….….S25

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Materials. The following chemicals are purchased from Sinopharm Chemical

Reagent Co., Ltd., China: methylene blue (MB), tetrachloroauric(III) acid hydrate

(HAuCl4·4H2O), potassium dichromate (K2Cr2O7), sodium acetate (CH3COONa),

zinc acetate (Zn(CH3COO)2), cupric acetate monohydrate (Cu(CH3COO)2·H2O),

aluminum nitrate (Al(NO3)3·9H2O), cadmium acetate (Cd(CH3CO2)2), nickel(II)

acetate tetrahydrate (Ni(CH3COO)2·4H2O), chromium chloride hexahydrate

(CrCl3·6H2O), lithium acetate (CH3COOLi), cobalt(II) acetate (C4H6CoO4), lead

acetate (CH3COO)2Pb), calcium chloride (CaCl2), barium chloride (BaCl2),

manganese(II) chloride (MnCl2·4H2O), iron(II) chloride tetrahydrate (FeCl2·4H2O),

iron(III) chloride (FeCl3·6H2O), magnesium chloride hexahydrate (MgCl2·6H2O),

sodium hydroxide (NaOH), sodium citrate (C6H5Na3O7), sodium borohydride

(NaBH4), sodium phosphate (Na3PO4), potassium acetate (C2H3KO2), sodium sulfide

(Na2S), sodium fluoride (NaF), sodium pyrophosphate anhydrous (Na4P2O7), sodium

iodide (NaI), sodium perchlorate monohydrate (NaClO4·H2O), sodium sulfide

(Na2S·9H2O), sodium acetate trihydrate (C2H3NaO2·3H2O), sodium hydrogen sulfite

(NaHSO3+Na2S2O5), potassium iodate (KIO3), potassium thiocyanate (KSCN),

sodium tetraborate decahydrate (Na2B4O7·10H2O), sodium hydrogen carbonate

(NaHCO3), sodium bromide (NaBr), sodium chloride (NaCl), sodium phosphate

dodecahydrate (Na3PO4·12H2O), sodium phosphate (Na3PO4), sodium nitrate (NaNO3)

and 5,5-dimethyl-1-pyrroline N-oxide (DMPO). p-hydroxybenzoic acid (p-HBA),

3-hydroxybenzoic acid (3-HBA), 3, 5-dihydroxybenzoic acid (3, 5-DHBA), 3,

4-dihydroxybenzoic acid (PCA) and gallic acid (GA) were purchased from J&K

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Chemical Ltd. (Beijing, China). All chemicals are at last of analytical grade unless

specified otherwise and used without further purification. China. Deionized water of

18 MΩ·cm is used throughout the experiments.

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Optimization of Experimental Parameters. To achieve the high sensitivity and

specificity for Cr(VI) detection, some experimental parameters including solution pH,

Au NPs size, GA concentration, reaction temperature and time are investigated in

detail. To avoid the decomposition of NaBH4 under acidic condition and aggregation

of Au NPs under alkaline condition, neutral condition at pH 7.0 is suitable for Cr(VI)

detection. The different Au NPs sizes (10, 15, 30, and 50 nm) are chosen to assess the

catalytic ability toward the reduction of MB. The results indicate that 15-nm Au NPs

present the best catalytic performance (Figure S1, S2). Figure S3A is the UV-vis

spectra of Au NPs capped with different amounts of GA. With increasing the amount

of GA, the absorption bands of gallic acid are enhanced in UV region at 214 and 264

nm,1 in good agreement with the FT-IR spectra (Figure S3B). Taking into

consideration the aggregation of Au NPs, the concentration ratio of Au NPs to GA is

fixed at 1: 1. The catalytic activity of GA-Au NPs is assessed at three different

temperatures (25, 30 and 45°C) after incubation for 2 min by measuring the

absorbance value of MB (Figure S4). The results indicate that the fastest reduction of

MB is achieved at 25°C. Figure S5 is the time-dependent UV-vis absorption spectra

for the catalytic reduction of MB by NaBH4 in the presence of GA-Au NPs and

Cr(VI). It is found that the present chemosensor can give a rapid signal response in 2

min.

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 10 nm Au NPs

Absorbance (a.u.)
15 nm Au NPs
30 nm Au NPs
1.5
50 nm Au NPs

50 30 15 10

1.0

0.5

0.0
400 500 600 700 800
Wavelength (nm)

Figure S1. UV-vis spectra of Au NPs with different particle sizes.

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 0s

30 s

60 s

90 s

150 s

10 nm 15 nm 30 nm 50 nm

Figure S2. Color changes of the detection solution in the presence of 10, 15, 30, and

50 nm Au NPs, respectively.

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 A 1.5 GA
Au NPs
B
Absorbance (a.u.)

Transmittance (%)
5:1 GA: Au NPs Au NPs
1:1 GA: Au NPs
1.0 1:5 GA: Au NPs
1:10 GA: Au NPs GA

0.5
GA-Au NPs

0.0 GA-Au NPs+Cr(VI)

200 300 400 500 600 700 800 4000 3200 2400 1600 800
Wavelength (nm) Wavenumbers (cm-1)

Figure S3. (A) UV-vis spectra of Au NPs capped with different amounts of GA; (B)

FT-IR spectra of Au NPs, GA, GA-Au NPs and GA-Au NPs + Cr(VI).

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 1.25

Absorbance (a.u.)
1.00

0.75

0.50

0.25

0.00
15 20 25 30 35 40
o
Temperature ( C)
Figure S4. Effect of reaction temperature on catalytic reduction of MB. Conditions:

MB concentration: 0.020 mM, 1 mL; GA-Au NPs concentration: 40 nM, 9 μL;

NaBH4 concentration: 0.04 M, 40 μL; Cr(VI) concentration: 100 nM, 10 μL.

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 1.5

Absorbance (a.u.)
1.0

0.5

0.0
0 5 10 15 20 25 30
Time (min)

Figure S5. Time-dependent UV-vis absorption spectra for the catalytic reduction of

MB by NaBH4 in the presence of GA-Au NPs. Conditions: MB concentration: 0.020

mM, 1 mL; GA-Au NPs concentration: 40 nM, 9 μL; NaBH4 concentration: 0.04 M,

40 μL; Cr(VI) concentration: 100 nM, 10 μL; temperature: 25°C.

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 A 1.0 B 1.0

0.8
y=0.3732x+0.241
0.8
1 10 20 30 40 50 80 100 R2=0.9911
R/B ratio

R/B ratio
0.6
Cr(VI) (nM)
0.6
0.4

0.2 0.4
y=0.0094x+0.0146
0.0 R2=0.9965
0.2
0 20 40 60 80 100 0.0 0.5 1.0 1.5 2.0
Cr(VI) concentration (nM) Cr(VI) concentration (μM)

Figure S6. Smartphone-based colorimeter for the determination of Cr(VI). Condition:

(A) Volume of Cr(VI) solution: 10 μL; MB concentration: 0.020 mM, 1 mL; GA-Au

NP concentration: 40 nM, 9 μL; NaBH4 concentration: 0.04 M, 40 μL; temperature:

25°C ; (B) Volume of Cr(VI) solution: 10 μL; NaBH4 concentration: 0.04 M, 20 μL;

temperature: 25°C.

The RGB color intensity is acquired by smartphone camera. The intensity ratio

of R/B versus the concentration of Cr(VI) is plotted for calibration curve.

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Figure S7. (A) TEM and (B) HRTEM images of GA-Au NPs after Cr(VI) detection.

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 A O1s B Cr 2p
Cr 2p 3/2
Cr 2p 1/2
C1s

Intensity (a.u.)
Intensity (a.u.)

Cr 2p

Au 4f Au 4d

0 150 300 450 600 750 570 575 580 585 590 595 600
Binding Energy (eV) Binding Energy (eV)

Figure S8. (A) XPS survey spectrum of GA-Au NPs in the presence of Cr(VI); (B) Cr

2p spectrum of GA-Au NPs in the presence of Cr(VI).

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 + 2e- + 2H+

Figure S9. Two-electron oxidation of gallic acid to corresponding quinone form.

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 Filter paper
1.0

Absorbance (a.u.)
GA-Au NPs filter paper
MB filter paper
GA-Au NPs+MB filter paper
0.8

0.6

0.4

0.2

0.0
400 500 600 700 800
Wavelength (nm)

Figure S10. Solid UV-vis spectra of filter paper, GA-Au NPs filter paper, MB filter

paper and MB/GA-Au NPs filter paper.

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Figure S11. SEM images of (A) filter paper and (B) GA-Au NPs filter paper.

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 1 μm
C

O Au

Figure S12. SEM images of GA-Au NPs filter paper and corresponding element

mapping images of C, O, and Au.

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 1 2 3 4 5 6 7 8 9 10 11 12

pH

Figure S13. The colorimetric images of MB/GA-Au NPs filter paper in the presence

of Cr(VI) at different pH values. Condition: Cr(VI) concentration: 0.5 μM, 10 μL;

NaBH4 concentration: 0.04 M, 20 μL; temperature: 25°C.

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Blank Cr(VI) Li+ Na+ K+ Ag+ Pb2+ Zn2+ Cd2+ Ca2+ Co2+ Ba2+ Fe 2+ Hg2+ Mn2+ Mg2+ Ni2+ Cu2+ Cr3+ Al3+ Fe 3+ Mix

Blank Cr(VI) F- Cl- Br- I- Ac- NO3- IO3- HCO3- HSO3- ClO4- SCN- MnO4- S2- CO32- P2O72- B4O72-PO43- Mix

Figure S14. The colorimetric images of MB/GA-Au NPs filter paper in the presence

of different metal ions. Condition: Cr(VI) concentration: 2 μM, 10 μL; Ag(I)

concentration: 5 μM, 10 μL; Cu(II) concentration: 5 μM, 10 μL; other ions

concentration: 10 μM, 10 μL; NaBH4 concentration: 0.04 M, 20 μL; temperature:

25°C.

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 Blank 0.1 0.2 0.4 0.6 0.8 1.0 2.0 μM

GBW08608

Figure S15. Photo image of the colorimetric filter paper on the addition of different

concentrations of Cr(VI) and GBW08608. Condition: volume of sample solution: 10

μL; NaBH4 concentration: 0.04 M, 20 μL; temperature: 25°C.

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Table S1. Comparisons of analytical performances of the MB/GA-Au NPs

chemosensor to other approaches for the detection of Cr(VI)

Sensing/recognition Linear LOD

Method Time Ref
material range (nM) (nM)

SERS TiO2@Ag NPs 20 min 10-2000 1.45 2

Alizarin red S-sensitized

SERS — 600-1×104 600 3
TiO2NPs
Methylene blue/Au
CV — 100-5×104 100 4
electrode

PEC Graphitic carbon nitride 10 min 0.19-19 0.1 5

Chemiresistor rGO with DTT-Au NPs — 0.9-800 0.9 6

MOF[Eu7(mtb)5(H2O)16]·N
Luminescence 24 h 0-770 10.8 7
O3·8DMA·18H2O

Colorimetry N-T/gold nanoparticle 25 min 500-2500 70 8

Colorimetry Au NPs — 1-9 0.4 9

This
Colorimetry MB/GA-Au NPs 2 min 0.05-100 0.05
work

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Table S2. Determination results for total Cr in solution by MB/GA-Au NPs

chemosensor

Chemosensor ICP-MS
Cr(VI) Cr(III) Total Cr
(nmol L-1) (nmol L-1) (nmol L-1) Found Recovery Found Recovery
(nmol L-1) (%) (nmol L-1) (%)
0.50 0.10 0.60 0.60±0.03 100 0.6056±0.0140 101
0.20 0.70 0.71±0.02 101 0.6930±0.0207 99
0.30 0.80 0.79±0.03 99 0.8026±0.0148 100
10.0 10.0 20.0 19.9±0.2 100 20.879±0.385 104
20.0 30.0 30.0±0.3 100 30.929±1.232 103
40.0 50.0 50.1±0.5 100 50.849±0.304 102

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 Table S3. Leachability testing of filter paper using the Toxicity Characteristic

Leaching Procedure (TCLP) and Synthetic Precipitation Leaching Procedure (SPLP)

Adsorbed Cr(VI) Loaded Au Leached Cr(VI) Leached Au US-EPA limits for Cr

Method
(mg L-1) (ng) (mg L-1) (ng) (mg L-1)
TCLP 50 7.1 0.0015 N.D.a 5
SPLP 50 7.1 0.002 N.D.a 0.1
a Not detected.

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