Electronic Supplementary Information

Keggin-type polyoxometalates molecularly loaded in Zr-ferrocene

metal organic framework nanosheets for solar-driven CO2

cycloaddition

Zhou Fanga, Zheng Dengb, Xinyi Wana, Zhuoyi Lia, Xu Maa, Shabab Hussaina, Zhizhen
Yea, Xinsheng Penga,*

a
State Key Laboratory of Silicon Materials, School of Materials Science and
Engineering, Zhejiang University, Hangzhou 310027, P.R. China

b
Institute of Functional Nano & Soft Materials (FUNSOM), Collaborative Innovation
Center of Suzhou Nano Science and Technology, Soochow University, Suzhou,
215123, China

a,*
Email: pengxinsheng@zju.edu.cn
Table S1 Zeta potential of PMo12 (Entry 1-3), Zr-Fc (Entry 4-6) and 10.26 wt% PMo12@Zr-Fc

(Entry7-9).

Solution with Zeta potential Average zeta

Entry
equal concentration (mV) potential (mV)
1 -7.36
2 PMo12 -8.24 -7.74
3 -7.62
4 5.63
5 Zr-Fc 5.78 5.61
6 5.41
7 -24.1
8 10.26 wt% PMo12@Zr-Fc -22.5 -22.67
9 -21.4
Fig. S1 Zeta potential of PMo12 salt solution, Zr-Fc and 10.26 wt% PMo12@Zr-Fc.
Fig. S2 XRD patterns of PMo12@Zr-Fc MOF nanosheets synthesized with different weight ratio
of PMo12. (a) 1.29 wt%; (b) 2.11 wt% (c) 4.37 wt% (d) 10.26 wt%; (e) 14.68 wt%.

Fig. S3 SEM images of PMo12@Zr-Fc MOF nanosheets: (a) prestine Zr-Fc; (b) 1.29 wt%; (c) 2.11
wt%; (d) 4.37 wt%; (e) 10.26 wt%; (f) 14.68 wt%.
Fig. S4 SEM images of PMo12@Zr-Fc MOF: (a) Zr-Fc; (b) 4.37 wt% PMo 12@ Zr-Fc; (c) 14.68 wt
% PMo12@ Zr-Fc.
Fig. S5 (a) AFM image of Zr-Fc MOF; (b) Thickness of Zr-Fc along the white line measured by
Nano scope analysis; (c) AFM image of PMo 12@ Zr-Fc MOF; (d) Thickness of PMo12@ Zr-Fc
MOF along the white line measured by Nano scope analysis.
 Fig. S6 CO2 adsorption isotherms for Zr-Fc and PMo12@Zr-Fc at 298 K.

(g)
(g)
(f)
(f)
Transmittance

Intensity (a.u.)

(e) (e)
(d) (d)
(c) (c)

(b) (b)

(a) (a)

4000 3500 3000 2500 2000 1500 1000 500 1200 1000 800 600
Wavenumber (cm-1) Wavenumber (cm-1)

Fig. S7 FTIR spectra of (a) Na3PMo12O40; (b) Zr-Fc; (c) 1.29 wt% PMo12@Zr-Fc; (d) 2.11 wt%
PMo12@Zr-Fc; (e) 4.37 wt% PMo12@Zr-Fc; (f) 10.26 wt% PMo12@Zr-Fc; (g) 14.68 wt%
PMo12@Zr-Fc. The right chart manifested details of FTIR spectra from 1300~500cm -1.
Table S2 The ratio of Fe(Ⅱ)/Fe(Ⅲ) and Mo(Ⅳ)/Mo(Ⅵ) in the Zr-Fc and 10.26 wt% PMo 12@Zr-
Fc MOF nanosheets

Fe(Ⅱ) Fe(Ⅲ)
Catalysts 1 3 1
2p 2p 2p 2p3
location (eV) 720.5 708.0 721.2 708.7
Zr-Fc
peak area 1253.2 2506.3 314.3 628.7
10.26 wt% location (eV) 720.5 708.0 721.2 708.7
PMo12@Zr-Fc peak area 2354.3 4708.6 1008.0 2016.1
Mo(Ⅳ) Mo(Ⅵ)
3 5 3
3d 3d 3d 3d5
location (eV) / / 235.7 232.6
Zr-Fc
peak area / / 893.6 1340.4
10.26 wt% location (eV) 235.1 232.0 235.7 232.6
PMo12@Zr-Fc peak area 184.4 276.6 656.6 984.9
 Table S3 ICP-AES analysisa of catalysts for cycloaddition with CO2 and styrene oxide

m(PMo ):
12
Zr Fe Mo
Entry Catalyst m(catalyst) (wt
(mg/L) (mg/L) (mg/L)
%)
1 Zr-Fc 2.438 1.867 / /
2 1-PMo12@Zr-Fc 2.524 1.885 0.0378 1.29
3 2-PMo12@Zr-Fc 2.191 1.658 0.0509 2.11
4 3-PMo12@Zr-Fc 2.072 1.711 0.116 4.37
5 4-PMo12@Zr-Fc 2.875 2.154 0.339 10.26
6 5-PMo12@Zr-Fc 3.450 2.568 0.503 14.68
7 UiO-66 3.623 / / /
8 4-PMo12@Zr-Fcb 2.729 1.863 0.278 8.32
9 4-PMo12@Zr-Fcc 2.403 1.789 0.291 10.59
 a
The ICP samples were prepared by immersed in isovolumic aqua regia and dilute in suitable
concentration, and the results of elements contents were averaged by three times experiments
b
The catalyst was recycled after six times cyclic reactions
c
The catalyst was obtained by regenerated and activated by repeatedly immersion

Fig. S8 NH3-TPD plot of Zr-Fc and PMo12@Zr-Fc MOF nanosheets. The peaks at around 100℃
and 360℃ represent the weak and moderate active acid sites. The peak at 400 ℃ is considered as
the NH3 desorption temperature. The TGA plot also improve that Zr-Fc have been destroyed at
above 400 ℃.
Fig. S9 (a) GC/MS curves of solutions taken after cycloaddition catalysis reaction. (b)-(d) GC/MS
analysis of peak 1 to 3, respectively. Reaction condition: 5 mg PMo 12@Zr-Fc, 0.25 mmol co-
catalyst TBAB, CO2 1 atm, 900 rpm, 80 ℃, 4 h. There are three peaks on the plots of GC/MS
analysis. Peak 1 and peak 2 matched well with styrene oxide and dodecane, and peak 3 matched
well with styrene carbonate, demonstrating successful composite of cyclic product with no by-
product of cycloaddition.
Fig. S10 GC curves of solutions taken after cycloaddition reaction with different amount of PMo 12
@SZr-Fc MOF catalysts: (a) Zr-Fc; (b) 1.29 wt% PMo 12@Zr-Fc; (c) 2.11 wt% PMo12@Zr-Fc; (d)
4.37 wt% PMo12@Zr-Fc; (e) 10.26 wt% PMo12@Zr-Fc; (f) 14.68 wt% PMo12@Zr-Fc.
Fig. S11 (a) GC curves of solution taken after cycloaddition reaction with different reaction time.
The samples for GC test were taken out every 2 hour.(a) 2 h; (b) 4 h; (c) 6 h; (d) 8 h; (e) 10 h; (f)
12 h; (b) The yield in the cycloaddition reaction with different reaction time. The samples for GC
test were taken from cycloaddition reactor every 2 hours to investigate the time influence on yield
of styrene carbonate. Reaction condition: 12.5 mmol styrene oxide, 5 mg catalyst (10.26 wt
%PMo12@Zr-Fc), 0.25 mmol co-catalyst TBAB, CO2 1 atm, 900 rpm, 80 ℃, 8 h. The yield was
determined by GC.
Fig. S12 XRD patterns of (a) initial 10.26 wt% PMo 12@Zr-Fc MOF nanosheet; (b) 10.26 wt%
PMo12@Zr-Fc after six cyclic cycloaddition reactions with same reaction conditions: 12.5 mmol
styrene oxide, 5 mg catalyst, 0.25 mmol co-catalyst TBAB, 80 ℃, 1 atm CO2, 900 rpm.
Table S4 Catalytic properties of different catalysts for cycloaddition with CO2 and styrene oxide

Reaction conditions Yield TOF

Catalyst TON Ref.
P(bar)/T(℃)/t(h) (%) (h-1)
(I-)Meim-UiO-66 1/80/24 46 88 3.7 [1]

FJI-C10 1/80/12 48 136 11.3 [2]

PCN-900(Eu)-CoTCPP
1/50/20 81 675 33.8 [3]
-CoBPYDC
[(CH3)2NH2]6·[Cd3L
1/50/12 74 1850 154.2 [4]
(H2O)2]·12H2O

Zn8C63H27N3O26 1/60/12 91 4 0.3 [5]

MOF-5 1/50/15 92 42 2.8 [6]

1·Mn 1/80/4 30 60 15.0 [7]

C150H204N42O48Zn6 1/100/16 90 148 9.3 [8]

Rh-PMOF-1 1/100/24 88 440 18.3 [9]

PW-SBU Cu-MOF 1/70/10 92 71 7.1 [10]

Cu(Ⅱ)-MOF 1/70/16 90 225 14.1 [8]

Salen-Co(23%)
1/120/12 84 266 22.2 [11]
⊂(Br-)Etim-UiO-66

IL@ZIF-8(Zn/Co) 1/100/24 92 792 33.0 [12]

JLU-Liu21 1/80/48 90 360 7.5 [13]

HKUST-1 1/100/8 28 1132 141.5 [14]

MOF-150 1/100/8 51 2052 256.5 [14]

Cu-NTTA 1/100/8 35 1400 175.0 [14]

This
PMo12@Zr-Fc 1/80/8 87 601 75.1 work
Fig. S13 SEM images of 10.26 wt% PMo12@Zr-Fc MOF nanosheets after cycling 5 times.
Fig. S14 (a) XRD pattern of simulated and experimental UiO-66. (b)SEM images of octahedral
UiO-66.

Fig. S15 Infrared images of cycloaddition reactions with 10.26 wt% PMo 12@Zr-Fc catalyst using
different intensity of simulated sunlight. (a) without external light; (b) 0.1 W/cm 2; (c) 0.2 W/cm2;
(d) 0.3 W/cm2; (e) 0.4 W/cm2; (f) 0.5 W/cm2. The average temperature in the red dotted line frame
was determined by FLIR Tool. (g)-(i) Digital images of plot (a),(d) and (f), intuitively displaying
the change of light intensity.
Fig. S16 The yield of product in the CO 2 cycloaddition reaction driven by different method
(traditional heating method and solar-driven method) under same reaction temperature. Reaction
conditions: 12.5 mmol styrene oxide, 5 mg catalyst (10.26 wt%PMo 12@Zr-Fc), 0.25 mmol co-
catalyst TBAB, CO2 1 atm, 900 rpm, 8 h. The temperatures for heat-driven reaction are the same
as those achieved under different intensity of light showing in the Fig. S15. The yield was
determined by GC.
Fig. S17 Tauc plot obtained by ultraviolet-visible (UV-vis) spectra of (a) PMo 12; (b) Zr-Fc; (c)
PMo12@Zr-Fc.
Fig. S18 (a) Reaction profile of in situ FTIR spectra from 700 cm-1 to 840 cm-1. (b) Reaction
profile of in situ FTIR spectra from 1520 cm-1 to 1570 cm-1.

[1] J. Liang, R.P. Chen, X.Y. Wang, T.T. Liu, X.S. Wang, Y.B. Huang, R. Cao, Postsynthetic
ionization of an imidazole-containing metal-organic framework for the cycloaddition of carbon
dioxide and epoxides, Chem. Sci. 8 (2017) 1570-1575.
[2] J. Liang, Y.Q. Xie, X.S. Wang, Q. Wang, T.T. Liu, Y.B. Huang, R. Cao, An imidazolium-
functionalized mesoporous cationic metal-organic framework for cooperative CO 2 fixation into
cyclic carbonate, Chem. Commun. (Camb) 54 (2018) 342-345.
[3] L. Zhang, S. Yuan, L. Feng, B. Guo, J.S. Qin, B. Xu, C. Lollar, D. Sun, H.C. Zhou, Pore-
environment engineering with multiple metal sites in rare-earth porphyrinic metal-organic
frameworks, Angew. Chem. Int. Ed. Engl. 57 (2018) 5095-5099.
[4] B.B. Lu, W. Jiang, J. Yang, Y.Y. Liu, J.F. Ma, Resorcin[4]arene-based microporous metal-
organic framework as an efficient catalyst for CO 2 cycloaddition with epoxides and highly
selective luminescent sensing of Cr2O72-, ACS Appl. Mater. Interfaces 9 (2017) 39441-39449.
[5] H.F. Zhou, B. Liu, L. Hou, W.Y. Zhang, Y.Y. Wang, Rational construction of a stable Zn 4O-
based MOF for highly efficient CO 2 capture and conversion, Chem. Commun. (Camb) 54 (2018)
456-459.
[6] J. Song, Z. Zhang, S. Hu, T. Wu, T. Jiang, B. Han, MOF-5/n-Bu 4NBr: an efficient catalyst
system for the synthesis of cyclic carbonates from epoxides and CO 2 under mild conditions, Green
Chem. 11 (2009) 1031-1036.
[7] W. Jiang, J. Yang, Y.Y. Liu, S.Y. Song, J.F. Ma, A porphyrin-based porous rtl metal-organic
framework as an efficient catalyst for the cycloaddition of CO 2 to epoxides, Chem. Eur. J. 22
(2016) 16991-16997.
[8] S.N. Ansari, P. Kumar, A.K. Gupta, P. Mathur, S.M. Mobin, Catalytic CO 2 fixation over a
robust lactam-functionalized Cu(II) metal organic framework, Inorg. Chem. 58 (2019) 9723-9732.
[9] J. Liu, Y.Z. Fan, X. Li, Y.W. Xu, L. Zhang, C.Y. Su, Catalytic space engineering of porphyrin
metal-organic frameworks for combined CO2 capture and conversion at a low concentration,
ChemSusChem 11 (2018) 2340-2347.
[10] A.K. Gupta, N. Guha, S. Krishnan, P. Mathur, D.K. Rai, A three-dimensional Cu(II)-MOF
with Lewis acid−base dual functional sites for chemical fixation of CO 2 via cyclic carbonate
synthesis, J. CO2 Util. 39 (2020) 101173.
[11] T.T. Liu, J. Liang, R. Xu, Y.B. Huang, R. Cao, Salen-Co(iii) insertion in multivariate cationic
metal-organic frameworks for the enhanced cycloaddition reaction of carbon dioxide, Chem.
Commun. (Camb) 55 (2019) 4063-4066.
[12] Y. Sun, X. Jia, H. Huang, X. Guo, Z. Qiao, C. Zhong, Solvent-free mechanochemical route
for the construction of ionic liquid and mixed-metal MOF composites for synergistic CO 2 fixation,
J. Mater. Chem. A 8 (2020) 3180-3185.
[13] J. Gu, X. Sun, X. Liu, Y. Yuan, H. Shan, Y. Liu, Highly efficient synergistic CO 2 conversion
with epoxide using copper polyhedron-based MOFs with Lewis acid and base sites, Inorg. Chem.
Front. 7 (2020) 4517-4526.
[14] X. Guo, Z. Zhou, C. Chen, J. Bai, C. He, C. Duan, New rht-type metal-organic frameworks
decorated with acylamide groups for efficient carbon dioxide capture and chemical fixation from
raw power plant flue gas, ACS Appl. Mater. Interfaces 8 (2016) 31746-31756.
References