Supporting Information

Facile “green” aqueous synthesis of mono- and bimetallic trimesate metal-

organic frameworks
Anna Nowacka,a Pol Briantais,b Carmelo Prestipinob,* and Francesc X. Llabrés i Xamenaa,*
a Instituto de Tecnología Química, Universitat Politècnica de València, Consejo Superior de
Investigaciones Científicas, Avda. de los Naranjos, s/n, 46022 Valencia, Spain
bInstitut Sciences Chimiques de Rennes, UMR-CNRS 6226, Campus de Beaulieu, Université de
Rennes 1, 35042 Rennes Cedex, France

Table S1. Solutions mixture ratio used in the synthesis of Co-Ni bimetallic trimesate single crystals
Preparation of Ni/Co solution
Na3BTC solution
Ni/Co-BTC Ni 0,1M Co 0,1M Ni/Co solution
H2O (0.0125 M)
solution solution
Ni-BTC 1.9 mL 0 mL 8.1 mL 6 mL 6 mL
Co10Ni-BTC 1.71 mL 0.19 mL 8.1 mL 6 mL 6 mL
Co20Ni-BTC 1.52 mL 0.38 mL 8.1 mL 6 mL 6 mL
Co30Ni-BTC 1.33 mL 0.57 mL 8.1 mL 6 mL 6 mL
Co40Ni-BTC 1.14 mL 0.76 mL 8.1 mL 6 mL 6 mL
Co50Ni-BTC 0.95 mL 0.95 mL 8.1 mL 6 mL 6 mL
Co60Ni-BTC 0.76 mL 1.14 mL 8.1 mL 6 mL 6 mL
Co70Ni-BTC 0.57 mL 1.33 mL 8.1 mL 6 mL 6 mL
Co80Ni-BTC 0.38 mL 1.52 mL 8.1 mL 6 mL 6 mL
Co90Ni-BTC 0.19 mL 1.71 mL 8.1 mL 6 mL 6 mL
Co-BTC 0 mL 1.9 mL 8.1 mL 6 mL 6 mL
 10 20 30 40 50 60

Diffraction angle (2)

Figure S1. XRD diffraction pattern (Cu K radiation) of Co-BTC (top) and Mn-BTC (bottom).
 100 Co-BTC 100
Ni-BTC
90 90

80 80

70 70
Weight (%)

Weight (%)
60 60

50 50

40 40

30 30

20 20
100 200 300 400 500 600 700 100 200 300 400 500 600 700
o o
Temerature ( C) Temperature ( C)

100 100
Cu-BTC Zn-BTC
90 90

80 80

70 70
Weight (%)

Weight (%)
60 60

50 50

40 40

30 30

20 20
100 200 300 400 500 600 700 100 200 300 400 500 600 700
o o
Temperature ( C) Temperature ( C)

Figure S2. TGA curves of monometallic M-BTC materials (M = Co, Ni, Cu, Zn)

Table S2. Measured weight losses for each step in the TGA curves in Fig. S2, and calculated
molecular formula of the MOF (assuming that the solid residue corresponds to the respective
metal oxide)
Weight loss (%)
MOF FORMULA
STEP I STEP II RESIDUE
Theoretical 26,7 45,5 27,8
Co-BTC Co3BTC1,8 ·11,3H2O
Experimental 26,9 43,0 30,1
Theoretical 26,7 45,5 27,8
Ni-BTC Ni3BTC1,9 ·11,2H2O
Experimental 25,6 45,7 28,7
Theoretical 26,3 44,6 29,1
Cu-BTC Cu3BTC2,1 ·12H2O
Experimental 25,9 45,5 28,6
Theoretical 26,1 44,3 29,6
Zn-BTC Zn3BTC2 ·12,2H2O
Experimental 25,6 44,7 29,7
Figure S3. Detailed view of M3(BTC)2·12 H2O showing hydrogen bonds. Atoms in the lower layer
are colored as a function of atomic type while the atoms in the upper layer are all colored green.

45000

40000

35000

Ni 29 30
30000
Co
25000
Counts

20000

15000 35 36

10000

5000

20 40 60 80
2(°)

Figure S4. XRD diffraction patterns (Cu K radiation) of the CoxNi-BTC samples. The insets
show expanded view of some selected peaks, in which peak discrimination is clearly observed.
Table S3. Total metal content and percentage of Ni and Co of the various CoxNi-BTC samples,
as determined by ICP analysis.
MOF Co molar % Ni molar% Total metal content %
NiBTC 0 100 23,6
Co10Ni-BTC 10,6 89,4 24,4
Co20Ni-BTC 19,6 80,4 24,4
Co30Ni-BTC 30,9 69,1 24,7
Co40Ni-BTC 41,3 58,7 24,4
Co50Ni-BTC 50,9 49,1 24,1
Co60Ni-BTC 60,6 39,4 24,6
Co70Ni-BTC 71,0 29,0 25,3
Co80Ni-BTC 80,1 19,9 25,4
Co90Ni-BTC 89,9 10,1 24,5
CoBTC 100 0 24,4

Figure S5. Aspect of the CoxNiy-BTC samples: (from left to right) Ni-BTC, Co10Ni-BTC,
Co20Ni-BTC, Co30Ni-BTC, Co50Ni-BTC, Co60Ni-BTC, Co70Ni-BTC, Co80Ni-BTC and Co-
BTC.
 100

90 Co-BTC
0

80 Co-BTC + Ni-BTC

70
Mass loss (%)

Co30Ni-BTC
-20

DTG (%)
60
Co-BTC
50

40 -40

30

20
-60
50 100 150 200 250 300 350 400 450 500
100 200 300 400 500
o
Temperature ( C) o
Temperature ( C)

Figure S6. TGA (left) and derivative curves (right) of pure Co-BTC and Ni-BTC, a bimetallic
Co30Ni-BTC sample, and a physical mixture of 30% Co-BTC and 70% Ni-BTC.

16000
CoBTC
14000 ZnBTC

12000
Intensity (counts)

10000

8000

6000

4000

2000

0
15 20 25 30 35 40 45 50 55 60
2(°)

Figure S7. XRD diffraction patterns (Cu K radiation) of the CoxZn-BTC samples.
 Mn-BTC
Mn90Ni-BTC
Mn80Ni-BTC
Mn70Ni-BTC
Mn60Ni-BTC
Mn50Ni-BTC
Mn40Ni-BTC
Mn30Ni-BTC
Mn20Ni-BTC
Mn10Ni-BTC
Ni-BTC
5 10 15 20 25 30 35
o
Diffraction angle 2( )

Figure S8. XRD diffraction patterns (Cu K radiation) of the MnxZn-BTC samples.