One-pot synthesis of mesosilica/nano covalent organic polymer composites and their synergistic effect in photocatalysis

doi:10.1016/S1872-2067(21)63812-3

Abstract

Abstract:

Organic-inorganic hybrid materials provide a desirable platform for the development of novel functional materials. Here, we report the one-pot synthesis of mesoporous hybrid nanospheres by the in-situ sol-gel condensation of tetraethoxysilane around surfactant micelle-confined nano covalent organic polymer (nanoCOP) colloids. The hybrid nanospheres containing nanoCOPs uniformly distributed in the mesosilica network, inherited the visible light responsive properties of the nanoCOPs. The turnover frequency of the hybrid nanospheres is almost 12 times that of its corresponding bulk COP counterpart for the photocatalytic reductive dehalogenation of α-bromoacetophenone, which is attributed to activation of the Hantzsch ester reductant by the hydroxyl group. The existence of a volcano relationship between the activity and nanoCOP/mesosilica ratio confirmed the synergistic effect between nanoCOP and mesosilica. Our preliminary results suggest that hybridization of semiconductors and reactant-activating materials is an efficient strategy for enhancing the activity of a catalyst for photocatalysis.

Key words: Covalent organic polymers, Mesoporous silica, Hybrid materials, Synergy effect, Photocatalysis, Reductive dehylogenation reaction

Chengbin Li, He Li, Chunzhi Li, Xiaomin Ren, Qihua Yang. One-pot synthesis of mesosilica/nano covalent organic polymer composites and their synergistic effect in photocatalysis[J]. Chinese Journal of Catalysis, 2021, 42(10): 1821-1830.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63812-3

https://www.cjcatal.com/EN/Y2021/V42/I10/1821

Figures/Tables 12

Fig. 1. (a) Schematic illustration of the mesoporous silica-nanoCOP hybrid material preparation procedure; (b) A photograph of the Tyndall effect with laser penetration through the TP-TAPB nanoCOP solution; (c) The size distribution of the TP-TAPB nanoCOP solution obtained from DLS; (d) A photograph of the representative C/S-0.65 catalyst.

Fig. 2. (a) FTIR spectra of the C/S-x samples; (b) Solid state 13C CP-MAS NMR spectrum of C/S-0.65.

Table 1 The physicochemical parameters of C/S-x, mesoSiO2, and TP-TAPB COF/COP.

Sample	BET SSA (m²/g)	V total (cm³/g)	Pore size (nm)	COF/COPContent^a(wt%)	N content^b(mmol/g)	Water contact angle (°)
TP-TAPB COF	628	0.5	1-2	100	6.09	43.5
TP-TAPB COP	664	1.2	1-2	100	6.22	33.0
C/S-0.3	641	0.6	1-2, 3.4	34.2	2.33	26.8
C/S-0.65	660	2.1	1.6, 3.2	22.6	1.82	27.2
C/S-1.3	656	2.0	1.6, 3.2	18.1	1.64	25.3
C/S-2.6	662	0.9	1-2, 3.4	14.4	1.48	21.6
MesoSiO₂	608	0.9	1.6, 3.4	0	0	23.8

Fig. 3. (a-d) High-resolution scanning electron microscopy (HRSEM) images of the C/S-x samples; HRSEM image (e), and the corresponding high-angle annular dark ?eld scanning transmission electron microscopy (HAADF-STEM) image (f) of C/S-1.3 after in-situ photodeposition of 3 wt% Pt (inset is the particle size distribution of the Pt NPs).

Fig. 4. (a-d) HRTEM images of C/S-x; (e) STEM image and EDS elemental mapping images of C/S-0.65.

Fig. 5. (a) N2 sorption isotherms (the N2 sorption isotherms were vertically shifted) and (b) non-local density functional theory (NLDFT) pore size distribution curves of the C/S-x samples and mesoSiO2.

Fig. 6. (a) UV-vis diffuse reflectance spectra (UV-vis DRS) of the C/S-x samples; (b) Band gap energy of C/S-0.65; (c) Schematic energy band structure of the C/S-x samples; EPR spectra of DMPO ?O2￣ (d) and TEMPO h+ (e) for the C/S-x and TP-TAPB COF materials under blue LED light irradiation and (f) transient absorption spectra of TP-TAPB COF and C/S-0.65 (inset).

Fig. 7. (a) Reaction profiles for C/S-x, TP-TAPB COF, and TP-TAPB COP; (b) The relationship between activity and the nanoTP-TAPB/SiO2 ratio.

Table 2 Photoreductive dehalogenation of α-bromoacetophenone with different catalysts under blue LED light irradiation.a.

Photocatalyst	Yield^b(%)	TOF^c(h^-1)	Photocatalyst	Yield^b(%)
TP-TAPB COF	88	15	mesoSiO₂	7
NanoTP-TAPB COP	83	6	C/S-0.65^d	1
C/S-0.3	65	22	C/S-0.65^e	15
C/S-0.65	87	68	C/S-0.65^f	81
C/S-1.3	88	58	C/S-0.65^g	1
C/S-2.6	86	54	C/S-0.65^h	33
C/SMe-0.65	37	18	C/S-0.65ⁱ	36

Scheme 1. Proposed mechanism for the photocatalytic dehalogenation reaction over the C/S-x catalysts.

Fig. 8. Reaction profiles of C/S-0.65 (a) and TP-TAPB COF (b) in the photoreductive dehalogenation of α-bromoacetophenone using different amounts of HE.

Table 3 Photoreductive dehalogenation of phenacyl bromide derivatives using C/S-0.65 as photocatalyst.a

Substrate	Product	Substrate	Product
1a	2a 85%	1e	2e 37%
1b	2b 35%	1f	2f 91%
1c	2c 78%	1g	2g 67%
1d	2d 39%	1h	2h 71%

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