The morphologies of the prepared Zr-MOF, SiNPs and Zr-MOF/SiNPs were characterized through TEM images. As depicted in Fig. S1A (Supporting information), it can be clearly observed that the Zr-MOF possessed the typical cube shape with an average particle size of ~28 nm. Fig. S1B (Supporting information) showed that the SiNPs had a spherical shape and uniform dispersion with an average diameter of ~60 nm. The average diameter of Zr-MOF/SiNPs increased from 60 nm to 72 nm after the modification of SiNPs, indicating the formation of a more ordered structure Zr-MOF/SiNPs and adopted a more ordered structure (
Fig. 1A). The hydrodynamic size of Zr-MOF/SiNPs was 145.6 nm in HEPES buffer based on dynamic light scattering (DLS) measurement, which remain stable among 15 days (Fig. S2 in Supporting information). The loading of SiNPs was determined by inductively coupled plasma (ICP) technique. 4.98 mg Si and 5.99 mg Zr per liter (L) were obtained. Then, the element composition of Zr-MOF/SiNPs were characterized by X-ray photoelectron spectroscopy (XPS). As shown in
Fig. 1B, the Zr-MOF/SiNPs is mainly composed of Zr 3d (183.2 eV), Si 2p (101.48 eV), Si 2s (152.48 eV), C 1s (305.48 eV), N 1s (398.48 eV), and O 1s (531.48 eV). In the high-resolution XPS spectrum of Si 2p (
Fig. 1C), three fitting peaks at 101.48 eV, 102.18 eV, and 100.98 eV revealed the presence of Si–N, Si–O, and Si–C, respectively. The XPS spectrum of Zr 3d (
Fig. 1D) included two fitting peaks, which fitted to Zr 3d
5/2 (182.6 eV), Zr 3d
3/2 (184.8 eV). After coupling SiNPs, the binding energies for Zr 3d show a lower binding energy shift, which indicates a more electron deficiency and higher valence state of Zr
4+ ions and an intensely denoting electron from O to Zr. Moreover, relatively high peak intensity of Si 2P was observed, which might be assigned to surface oxidation of Si. As presented in infrared spectrum of Zr-MOF (
Fig. 1E), the characteristic peaks at 1720, 1601, 1550, and 1415 cm
−1 correspond to the big ring skeleton absorptions. The signals in the range of 500–700 cm
−1 can be allocated to asymmetric vibrations of the C=N, N–H, C=C and C–H of the pyrrole ring in TCPP [
50]. The absorption peaks of SiNPs at 2929 and 2856 cm
−1 represented the stretching and bending vibrations of C−H on the saturated carbon, respectively. The characteristic signal at 1090 cm
−1 was assigned to the extensional vibration of Si−O−Si, while the peak at 910 cm
−1 belonged to the Si−N stretching vibration. The characteristic peak position of Zr-MOF/SiNPs was accordance with that of the parent MOFs and SiNPs, revealing the SiNPs was attached successfully. The structure of the Zr-MOF/SiNPs was further confirmed by the powder X-ray diffraction (PXRD) patterns [
51,
52]. In
Fig. 1F, concisely matched peaks in small angle sections validated that the crystal structure of Zr-MOF was maintained. The peak emerging at 15°–35° was attributed to the scattering effect of the nanoparticles. Furthermore, the PXRD result of Zr-MOF/SiNPs is still consistent with that of Zr-MOF and the new peaks emerging at 20°–70° shows presence of silica, suggesting the Zr-MOF were attached on the surface of SiNPs.