1. Metal Nanoparticles@ Metal-Organic Frameworks (MOFs)
Metal Metal-Organic Frameworks (MOFs). Synthesis and evidences of Molecule Diffusion beyond the Aperture Size Limit
Guangchao Zheng1*, Vanesa López-Puente1, Sergio Rodal- Cedeira1, Lakshminarayana Polavarapu1, Luis M. Liz- Marzán1,2, Isabel Pastoriza-Santos1, Jorge Pérez-Juste1*
1 Departamento de Química Física, Universidade de Vigo, Vigo, Spain
2 BNP Laboratory, CIC biomaGUNE, Paseo de Miramón 182, Donostia, Spain

2. Outline Introduction & Objectives
Synthesis Plasmonic nanoparticles Zeolitic imidazolate frameworks (ZIF-8)
Molecule Diffusion through the ZIF-8 shell
Conclusions

3. 1.1 MOFs ZIF-8 1) Synthesis at the grame scale
2) Crystalline, High surface area, Porosity can be adjusted and chemical stablility.
Phys. Chem. Chem. Phys., 2014,16,
ZIF-8
Size-selective catalysis and sensing; gas sensing and storage

4. CTAB functionalize Zif-8
(D)
(E)
CTAB
0.025% CTAB
No CTAB
0.25% CTAB
CrystEngComm, 2011, 13, 6937–6940

5. 1.2 Integration of NPs with MOFs
1.2.1 Synthesis approaches:
Approach 2
(B)
Approach 1
(A)
J. Am. Chem. Soc. 2011, 133, 1304–1306
Nat Chem 2012, 4 (4),

6. Size-selective catalysis
1.2.2 Applications
(A)
(B)
Size-selective catalysis
Adv. Mater. 2014, 26, 4056–4060

7. Size-selective sensing
(A)
Size-selective sensing
Quantum dots
MOFs
How does the molecule selective diffuse through the MOFs ? How does it rely on the pore size and aperture size?
(B)
What!
Nature communications, DOI: /ncomms1234

8. 2.1 AIM: Integration NPs with MOFs & SERS
Great!
Step 2
Step 1

9. 2.2 SERs
Au NRs
Au nanostars
NRs

10. 2.3 Preparation of the Plasmonic NPs@Zif-8
200nm A B D

12. 2.3 Mapping of A B C D E F G H

13. 2.4 Monitor the growth of MOFs on the surface of Au@Ag core-shell NPsB D C A

14. 2.5 CTAB sufactant tune the size growth of Zif-8
Thickness (nm)
Count A B C D
(A) 0.84mM, (B) mM and (C) 0.084mM of CTAB.

15. 2.6 Molecules Size-selective diffusion
Table Structure Characteristics of Zif-8 calculated from single crystal x-ray analysis
PNAS , 2006, 103, 10186–
MGI
NAT
NBT

16. 2.6 Molecules Size-selective diffusionA B
(A) SERs spectra of the molecular probes used to test the diffusion through the Zif-8 shell. The shadow regions indicate the bands followed during the diffusion studies. (B) Kinetic trace of the diffusion of each probe through the Zif-8 shell based on their SERs intensity.

17. 3 Conclusions
We have developed a general strategy for the Zif-8 encapsulation of individual metal nanoparticles.
The SERs properties of the metal nanoparticles cores allowed us to study the transport of different guest molecules through the Zif-8 shell. The analysis of the results showed that it was mainly a diffusion process with size dependent rates (the larger the molecule the slower the rate of diffusion).

18. Thanks for their lots of help.
Acknowledgement
Isabel Pastoriza-Santos
Jorge Pérez-Juste
Luis M. Liz-Marzán
Vanesa López-Puente
Sergio Rodal-Cedeira
Thanks for their lots of help.

19. Thanks for your attention.

20. Au (simulated)
Zif-8 (simulated)