Supplementary Information

Synthesis of Catalytically Active Bimetallic Nanoparticles within

Solution-Processable Metal-Organic-Framework Scaffolds

Wendi Zhang,‡ac Shuping Wang,‡ac Fei Yang,a Zhijie Yang,ab Huiying Wei,*a

Yanzhao Yang,*ac Jingjing Wei*a

aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100,

P. R. China

bKey Laboratory of Colloid and Interface Chemistry, Ministry of Education, Shandong

University, Jinan 250100, P.R. China

cKey Laboratory for Special Functional Aggregate Materials of Education Ministry,

Shandong University, Jinan 250100, P. R. China

*Corresponding Authors.

Email: weihuiying@sdu.edu.cn; yzhyang@sdu.edu.cn; weijingjing@sdu.edu.cn.

‡ These authors contributed equally.

Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2019

1. TOF calculations

1.1 CO oxidation catalysis measurement

During the catalytic reaction, the surface of the catalyst generally undergoes

remodeling, and the active center is varied, which is a dynamic process. The frequency

of transformation (TOF), the number of conversions of a single active site per unit time,

is the intrinsic activity of the catalyst and can be used to judge the trend of catalytic

activity.

Total flow of gas is 60 ml/min, the beginning volume fraction of CO is 1%, the loading

of Cu3Au nanoparticles (the molarity of Cu=1.88*10-2 mmol/L, Au=6.11*10-3 mmol/L)

is 0.90% (mole fraction), 100% conversion time is 70 mins. The loading of Au0.61Pd0.39

nanoparticles (the molarity of Au=4.13*10-3 mmol/L, Pd=2.63*10-3 mmol/L) is 0.26%

(mole fraction), 100% conversion time is 61mins. The loading of Au0.77Pt0.23

nanoparticles (the molarity of Pt=1.34*10-3 mmol/L, Au=4.53*10-3 mmol/L) is 0.28%

(mole fraction), 100% conversion time is 92 mins.

TOF =

𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑂𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑖𝑠 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

The TOF of Cu3Au/CeO2 = = 22320 h-1

𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑂𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝐶𝑢𝐴𝑢 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

The TOF of Au0.61Pd0.39/CeO2 = = 58201.2 h-1 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑂 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑃𝑑𝐴𝑢 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

The TOF of Au0.77Pt0.23/CeO2 = = 36284.31 h-1 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑂𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑃𝑡𝐴𝑢 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

1.2 4-nitrophenol reduction catalysis measurement

The reduction of 4-nitrophenol by NaBH4; the original amount of 4-nitrophenol is

6 mM. The loading capacity of Cu3Au nanoparticles (the amount of Cu=1.203 mg/L,

Au=1.195 mg/L) is 0.0125 (quality fraction), the final conversion time is 270s. The

loading capacity of Au0.61Pd0.39 nanoparticles (the amount of Au=0.813 mg/L, Pd=0.28

mg/L) is 0.002 (quality fraction), the final conversion time is 180s. The loading capacity

of Au0.77Pt0.23 nanoparticles (the amount of Pt=0.262 mg/L, Au=0.892 mg/L) is 0.0039

(quality fraction), the final conversion time is 630s.

TOF =

𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 4 ‒ 𝑛𝑖𝑡𝑟𝑜𝑝ℎ𝑒𝑛𝑜𝑙 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑖𝑠 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

The TOF of Au0.61Pd0.39/CeO2 = = 2480 h-1

𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 4 ‒ 𝑛𝑖𝑡𝑟𝑜𝑝ℎ𝑒𝑛𝑜𝑙 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑃𝑑𝐴𝑢 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

The TOF of Cu3Au/CeO2 = = 9700.2 h-1

𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 4 ‒ 𝑛𝑖𝑡𝑟𝑜𝑝ℎ𝑒𝑛𝑜𝑙 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝐶𝑢𝐴𝑢 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

The TOF of Au0.77Pt0.23/CeO2 = = 1727.82 h-1

𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 4 ‒ 𝑛𝑖𝑡𝑟𝑜𝑝ℎ𝑒𝑛𝑜𝑙 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑃𝑡𝐴𝑢 ∗ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒

Figure S1. XRD pattern of (a) Cs-CD-MOF. (b) CD-MOF-Pd0.61Au0.39. (c) CD-MOF-

Cu3Au. (d) CD-MOF-Pt0.77Au0.23.

Figure S2. XRD pattern of (a) Cs-CD-MOF. (b) CD-MOF-Pd0.61Au0.39. (c) CD-MOF-

Cu3Au. (d) CD-MOF-Pt0.77Au0.23.

Figure S3. (a) N2 adsorption isotherms and (b) DFT method pore size distribution of

Cs-CD-MOF.

Figure S4. TEM images of (a) Pt0.77Au0.23. (b) Pd0.61Au0.39. (c) Cu3Au nanoparticles.

Figure S5 XPS spectra of CD-MOF-Cu3Au. (a) Cs 3d. (b) Cu 2p. (c)Au 4f. (d) O 1s.

Figure S6. XPS spectra of CD-MOF-Pd0.61Au0.39. (a) Cs 3d. (b) Pd 3d. (c)Au 4f. (d) O

1s.

Figure S7. XPS spectra of CD-MOF-Pt0.77Au0.23. (a) Cs 3d. (b) Pt 4f. (c)Au 4f. (d) O

1s.

Figure S8. TEM image of (a) Cu3Au /CeO2, (b) Pd0.61Au0.39/CeO2, (c) Pt0.77Au0.23/CeO2

after pre-activation treatment: the samples were heated to 250 ℃ under pure oxygen

flow for 3 hours.

Figure S9. Stability tests (three cycles of CO oxidation catalysis) of (a) Cu3Au/CeO2,

(b) Pd0.61Au0.39/CeO2, (c) Pt0.77Au0.23/CeO2 and the corresponding TEM images of (d)

Cu3Au/CeO2, (e) Pd0.61Au0.39/CeO2 and (f) Pt0.77Au0.23/CeO2 after three cycles of CO

oxidation catalysis.

Figure S10. TEM image of Pd0.61Au0.39/CeO2 after 10 cycles of CO oxidation catalysis.

Figure S11. UV-vis absorption spectra of the reduction of 4-nitrophenol by NaBH4 in

the presence of pure CeO2.

Figure S12. (a) Successive UV-vis absorption spectra of the reduction of 4-nitrophenol

by NaBH4 in the presence of Cu3Au/CeO2. (b) The dependency of the ln(A0/At) over

reaction time. Life test of the catalytic performance in 4-NP reduction of Cu3Au/CeO2.

(c) The dependency of the ln(A0/At) over reaction time under different cycles. (d) The

relation of reaction rate constant and cycle.

Figure S13. Life test of the catalytic performance in 4-NP reduction of

Pd0.61Au0.39/CeO2. (a) The diagram of ln(A0/At) and absorbance in different cycles. (b)

The relation of reaction rate constant and cycle.

Figure S14. (a) Successive UV-vis absorption spectra of the reduction of 4-nitrophenol

by NaBH4 in the presence of Pt0.77Au0.23/CeO2. (b) The dependency of the ln(A0/At)

over reaction time.

Figure S15. TEM images of (a) Pt0.77Au0.23/CeO2, (b) Pd0.61Au0.39/CeO2 and (c)

Cu3Au/CeO2 after the reduction of 4-nitrophenol by NaBH4.

Table S1: the ICP data of Cu3Au/CeO2, Au0.61Pd0.39/CeO2, Au0.77Pt0.23/CeO2

sample Ce

(mg/L)

Pd

(mg/L)

Pt

(mg/L)

Au

(mg/L)

Cu

(mg/L)

Quality

fraction (%)

Mole

Fraction (%)

CuAu/CeO2 95.381 1.195 1.203 1.25 0.90

PdAu/CeO2 136.668 0.280 0.813 0.20 0.26

PtAu/CeO2 67.710 0.262 0.892 0.39 0.28

Table S2. Reducing capacity of the hydroxyl group in CD-MOF

sample Pd Pt Cu Au Cu3Au Au0.61Pd0.39 Au0.77Pt0.23

Reducing

possibility

× × × √ √ √ √

Note: single component Cu, Pt or Pd nanoparticles could not be synthesized when only one type of

metal salt is present alone in the system. The addition of Au precursor assists the formation of

bimetallic nanoparticles.

Table S3. Catalysis data of CO oxidation over Cu3Au/CeO2, Au0.69Pd0.31/CeO2 and

Pt0.77Au0.23/CeO2.

Samples Starting temperature (℃) T50 (℃) T90 (℃)

Cu3Au/ CeO2 60 100 120

Au0.61Pd0.39/CeO2 50 104 120

Au0.77Pt0.23/CeO2 80 130 160