Electronic Supplementary Material

Rapid room-temperature synthesis of a porphyrinic MOF forencapsulating metal nanoparticles Huihui He1, Luyan Li3, Yang Liu1, Meruyert Kassymova3, Dandan Li2 (), Liangliang Zhang1 (), and Hai-Long Jiang3

1 Frontiers Science Center for Flexible Electronics (FSCFE), Shaanxi Institute of Flexible Electronics (SIFE) & Shaanxi Institute of Biomedical

Materials and Engineering (SIBME), Northwestern Polytechnical University (NPU), Xi'an 710072, China 2 Institutes of Physics Science and Information Technology, Anhui University, Hefei 230601, China 3 Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China,

Hefei 230026, China Supporting information to https://doi.org/10.1007/s12274-020-3077-1

1 Synthesis of PCN-224-RT and PCN-224-T

1.1 Synthesis of PCN-224-RT (the other proportion)

100 mg prepared Zr6 cluster was dissolved in a mixed solution of acetic acid (HOAc, n mL, n = 1-5) and N, N’-dimethylformamide (DMF, 5-n mL) (solution A), tetrakis(4-carboxyphenyl)porphyrin (TCPP) linker was dissolved in 5 mL DMF with ultrasonication (solution B). The other preparation process is basically the same as the proportion of 6:4.

1.2 Synthesis of PCN-224-T (at different temperature)

The preparation method of PCN-224-T is consistent with the PCN-224-RT, except for the reaction temperature (40, 80, 120 ºC, provided by oil bath).

2 Preparation of metal nanoparticles

2.1 Preparation of Pt nanoparticles ( 3 nm)

The Pt nanoparticles (NPs) with average sizes of ~3 nm were prepared according to a reported procedure [1]. The as-synthesized Pt NPs were dispersed in DMF to form 1 mg/mL suspension.

2.2 Preparation of Pd nanocubes ( 10 nm)

The preparation of Pd nanocubes was carried out by the following route with minor modifications [2]. Typically, an aqueous solution (8 mL) containing 105 mg of PVP, 60 mg of L-ascorbic acid, and 5 mg of KBr and 185 mg of KCl were charged into a 20 mL vial. The solution was pre-heated under magnetic stirring at 80 °C for 10 min. Next, 3 mL of another aqueous solution of dissolved 57 mg of K2PdCl4 was added by using a pipette. The reaction proceeded at 80 °C for 3 hours. The products were collected by centrifugation and washed for 3 times with water to remove excess PVP, L-ascorbic acid and KBr and KCl.

2.3 Preparation of Pd nanocubes ( 20 nm)

The synthesis of Pd nanocubes ( 20 nm) was similar to that of Pd nanocubes ( 10 nm). Typically, an aqueous solution (8 mL) containing 105 mg of PVP, 60 mg of L-ascorbic acid, and 600 mg of KBr were charged into a 20 mL vial. The solution was pre-heated under magnetic stirring at 80 °C for 15 min. Next, 3 mL of another aqueous solution dissolving 57 mg of K2PdCl4 was added by using a pipette. The reaction proceeded at 80 °C for 3 hours. The products were collected by centrifugation and washed for 3 times with water to remove excess PVP, L-ascorbic acid and KBr.

3 Light-driven reactive oxygen species (ROS) generation detection 2,7-dichlorofluorescin diacetate (DCFH-DA) was used as the ROS-monitoring agent by lighting-on signal (green-emitting centered at 525 nm) when reacting with ROS. Briefly, Pt-3@PCN-224 (100 μg/mL) and DCFH-DA (5 μM) was mixed and then exposed to visible light (LED light, λ = 400-700 nm, 40 mW/cm2). The emission spectra of DCFH-DA were recorded at various irradiation times.

1,3-diphenylisobenzofuran (DPBF), a specific singlet oxygen (1O2) trap, was employed as the 1O2 indicator. Briefly, Pt-3@PCN-224 (100 μg/mL) and DPBF (0.1 mM) was mixed and then exposed to visible light (LED light, λ = 400-700 nm, 40 mW/cm2). The absorption spectra of DPBF were recorded at various irradiation times. The decrease of DPBF absorption intensity around 425 nm could be observed due to the reaction between DPBF and 1O2.

Address correspondence to Dandan Li, chemlidd@163.com; Liangliang Zhang, iamllzhang@nwpu.edu.cn

Nano Res.

| www.editorialmanager.com/nare/default.asp

2

4 General Characterizations.

 Figure S1 PXRD pattern of Zr6 cluster

 Figure S2 The TGA of the PCN-224-RT

 Figure S3 PXRD patterns of PCN-224-RT prepared by different reaction time.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

3

 Figure S4 N2 adsorption/desorption isotherms at 77 K of PCN-224-RT prepared by different reaction time.

 Figure S5 BET surface area plot of PCN-224-RT-0.5 h.

 Figure S6 The detailed pore volume and pore width for PCN-224-RT-0.5 h.

 Figure S7 BET surface area plot of PCN-224-RT-3 h.

Nano Res.

| www.editorialmanager.com/nare/default.asp

4

 Figure S8 The detailed pore volume and pore width for PCN-224-RT-3 h.

 Figure S9 BET surface area plot of PCN-224-RT-9 h.

 Figure S10 The detailed pore volume and pore width for PCN-224-RT-9 h.

 Figure S11 BET surface area plot of PCN-224-single crystal.

 Figure S12 The detailed pore volume and pore width for PCN-224-single crystal.

Nano Res.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

5

Figure S13 DFT calculated pore size distribution of PCN-224-RT prepared by different reaction time.

 Figure S14 PXRD of Pt-1@PCN-224-RT, Pt-3@PCN-224-RT and Pt-5@PCN-224-RT.

 Figure S15 TEM images of (a) Pt-1@PCN-224-RT, (b) Pt-3@PCN-224-RT and (c) Pt-5@PCN-224-RT.

 Figure S16 TEM images of (a) 10 nm Pd nanocubes, (b) 20 nm Pd nanocubes, (c) Pd (10 nm)@PCN-224-RT and (d) Pd (20 nm)@PCN-224-RT

Nano Res.

| www.editorialmanager.com/nare/default.asp

6

 Figure S17 PXRD patterns of Pt-3@PCN-224-RT before and after photocatalytic reaction.

Reference [1] Xiao, J.-D.; Shang, Q.; Xiong, Y.; Zhang, Q.; Luo, Y.; Yu, S.-H.; Jiang, H.-L. Boosting Photocatalytic Hydrogen Production of a Metal-Organic

Framework Decorated with Platinum Nanoparticles: The Platinum Location Matters. Angew. Chem. Int. Ed. 2016, 128, 9535-9539. [2] Long, R.; Mao, K.; Ye, X.; Yan, W.; Huang, Y.; Wang, J.; Fu, Y.; Wang, X.; Wu, X.; Xie, Y.; Xiong, Y. Surface facet of palladium nanocrystals: a key

parameter to the activation of molecular oxygen for organic catalysis and cancer treatment. J. Am. Chem. Soc. 2013, 135, 3200-3207.