A Solid-Solution Approach for Redox Active Metal-Organic Frameworks with Tunable Redox Conductivity

Article abstract of DOI:10.1021/jacs.9b10639

Systematically tuning the conductivity of metal-organic frameworks (MOFs) is key to synergizing their attractive synthetic control and porosity with electrochemical attributes useful in energy and sensing technologies. A priori control of charge transfer

Full text of DOI:10.1021/jacs.9b10639

Subscriber access provided by University of Glasgow Library
Communication
A solid-solution approach for redox active metal
organic frameworks with tunable redox conductivity
Gavin S. Mohammad-Pour, Kendrich O. Hatfield, David C. Fairchild, Kenneth
Hernandez-Burgos, Joaquín Rodríguez-López, and Fernando J. Uribe-Romo
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 01 Dec 2019
Downloaded from pubs.acs.org on December 2, 2019
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.

Page 1 of 11
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
A solid-solution approach for redox active metal organic
frameworks with tunable redox conductivity
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 11
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
퐷푒 = 16 푘푒푡푟푁푁
2
ACS Paragon Plus Environment

Page 3 of 11
Journal of the American Chemical Society
푁푁−푟0)/훿
푘푒푡 = 푘′푒−(푟
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Å
ASSOCIATED CONTENT
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 11
Supporting Information
1
2
3
4
5
6
7
8
9
AUTHOR INFORMATION
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Corresponding Author
Author Contributions
Notes
ACKNOWLEDGMENT
REFERENCES
ACS Paragon Plus Environment

Page 5 of 11
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 11
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
6
ACS Paragon Plus Environment

Page 7 of 11
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
165x89mm (300 x 300 DPI)
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 11
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 1. (a) Depiction of a MOF thin film electrode containing varied amounts of redox active links that
enable fast redox conductivity via redox hopping. (b) Synthesis of MOF thin film electrodes with finely tunes
substitutional solid solution amounts of redox active links.
286x309mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 9 of 11
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 2. MOF film characterization. (a) Plot of the SSS input-output mol% ratio of the Fc link incorporated
in the thin film MOFs as deter-mined by EDXS, evidencing 1:1 input-output incorporation. (b) GIXD of MOF
thin films grown on FTO substrates. Stars denote peaks corresponding to FTO.
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 10 of 11
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 3. Cyclic voltammetry data of Fc containing MOF electrodes. (a) Cyclic voltammograms at various Fc
link content (scan rate of 20 mV s-1, in 0.1 M LiBF4 in MeCN and Pt counter electrode). (b) Peak current of
the 100% Fc MOF electrode as a function of the square root of scan rate. (c) Peak currents of the MOF
electrodes as a function of their ferrocene content (scan rate of 20 mV s-1).
625x189mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 11 of 11
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 4. Charge transport in redox-active MOF films. (a) UV-visible absorption spectra of 100 mol% Fc MOF
thin film before (orange trace) and after oxidation (blue trace), evidencing the formation of ferricenium ion.
(b) Absorbance of ferricenium as a function of Fc content in the MOF thin films. (c) Diffusion coefficient of
electron transfer derived from Anson plots as function of Fc content (orange symbols), compared to modeled
De from Eqs. (1) and (2) (blue line). (d) Cyclic voltammetry of a 100% Fc electrode in 0.1 M H2SO4 (aq)
over 1500 cycles.
ACS Paragon Plus Environment