Welding Metallophthalocyanines into Bimetallic Molecular Meshes for

Dec 31, 2018 - (b) PCA for arrays of NiPc-Ni (green), NiPc-Cu (blue), NiNPc-Ni (red) and NiNPc-Cu (yellow) sensors (each type of symbol represents sin...
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Article

Welding Metallophthalocyanines into Bimetallic Molecular Meshes for Ultra-Sensitive, Low-Power Chemiresistive Detection of Gases Zheng Meng, Aylin Aykanat, and Katherine A Mirica J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b11257 • Publication Date (Web): 31 Dec 2018 Downloaded from http://pubs.acs.org on December 31, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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Journal of the American Chemical Society

Welding Metallophthalocyanines into Bimetallic Molecular Meshes for Ultra-Sensitive, Low-Power Chemiresistive Detection of Gases



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Page 3 of 9 NH3

50

20

5 2

40

0 0

10

20

(d) 50

30 40 t/min

0 50

60

0

70

10

100

40

20 10

40 80

0 0

10

20

30 40 t/min

70

60

0 -50 -100 -150 -200 -250 -300 -350 -400 -450

0.2 (ppm)

0

10

20

30 40 t/min

50

60

−



0

70

10 20 30 40 50 60 70 t/min

(f)

0.5

0 60

50

1

20

50

(ppb)

-700

2

40

10 5 2 (ppm)

10

-600

5

60

20

20

30 40 t/min

1000

-500

40,80

−ΔG/G0 (%)

40

30

20

(e)

80

-400

1 0.5 0.2 (ppm)

10 (ppm)

500

-300

2

30 20

10

-200

−ΔG/G0 (%)

−ΔG/G0 (%)

10

50

20 40 80 200

-100

80 40 20 10 5

60

20

30

(c) 0

70

40

N2

N2

(b) 80

80

40

N2

N2

−ΔG/G0 (%)

(a)

NO

H2S

N2

20 40

80 200

−ΔG/G0 (%)

N2

−ΔG/G0 (%)

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500

1000

(ppb)

0

10 20 30 40 50 60 70 t/min

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(b)

NH3

30

y = 0.64x + 5.61 R² = 0.97

−ΔG/G0 (%)

y = 0.37x + 1.90 R² = 0.97

20 10

y = 0.17x + 1.67 R² = 0.95

y = 77.98x + 2.34 R² = 0.98

80

y = 4.39x + 4.17 R² = 0.98

40 20

0

20

(d) 30

40 60 [NH3]/ppm

80

100

initial rate of response

25

y = 0.36x + 0.31 R² = 0.99

20 15 10 5

y = 0.16x + 0.88 R² = 0.97

0

5

10 15 [H2S]/ppm

20

40 60 [NH3]/ppm

80

100

-500 y = -630.65x - 33.93 R² = 0.99

0

20

(f)

H2S y = 4.47x + 8.01 R² = 0.96

150 100

y = 1.09x + 0.81 R² = 0.99

50

0.2

0.4 0.6 0.8 [NO]/ppm

1

1.2

0 NO

-10 -20

y = -34.66x - 0.78 R² = 0.99

-30

y = -37.51x + 0.29 R² = 0.99

-40

0 0

-400

-700 0

(e) 200

NH3

y = -332.48x - 75.41 R² = 0.98

-300

-600

y = 1.51x + 0.42 R² = 0.99

0

0

NO y = -34.13x - 2.42 R² = 0.98 y = -43.89x - 1.75 R² = 0.98

-200

y = 20.19x + 3.12 R² = 0.97

60

0

-100

initial rate of response

−ΔG/G0 (%)

40

y = 0.97x + 11.41 R² = 0.97

(c)

H2 S

100

−ΔG/G0 (%)

50

(a)

initial rate of response

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0

10

20 30 [H2S]/ppm

40

50

0

0.2

0.4 0.6 0.8 [NO]/ppm





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60

(a) −∆G/G0 (%)

NiNPc-Cu

40 ppm NH3

50 NiPc-Ni

40

NiPc-Cu

30

NiNPc-Ni

20 10 0

(b) 120

40 ppm H2S

−∆G/G0 (%)

100 80 60



40 20

0 0

(c) −∆G/G0 (%)

-200 -400 -600 1 ppm NO

-800 (d) 2 1.5

40 ppm NH3

1 PC2

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0.5

1 ppm NO

0 -0.5

ASSOCIATED CONTENT

-1

Supporting Information 40 ppm H2S

-1.5 -4

-2

0 PC1

2

4

AUTHOR INFORMATION Corresponding Author

ACKNOWLEDGMENT ACS Paragon Plus Environment

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REFERENCES

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