A 3D/0D cobalt-embedded nitrogen-doped porous carbon/supramolecular porphyrin magnetic-separation photocatalyst with highly efficient pollutant degradation and water oxidation performance

doi:10.1016/j.jmst.2022.02.023

Abstract

Abstract:

A 3D/0D cobalt-embedded nitrogen-doped porous carbon nanocubes (Co-N-C)/supramolecular tetra (4-carboxylphenyl) porphyrin nanocrystals (SA-TCPP) photocatalyst was successfully self-assembled via π-π interaction, hydrogen bonding, and chemical bonding. Co-N-C/SA-TCPP heterostructure exhibited satisfactory visible photocatalytic oxidation performance on pollutant degradation and water evolution. The degradation rates of Co-N-C/ST (30%) composite towards 2,4-dichlorophenol, ofloxacin, and ethylene were 10.9, 7.2, and 2.1 times faster than SA-TCPP, respectively. The oxygen evolution efficiency was 1.9 times higher than SA-TCPP. The remarkably improved oxidation activities of Co-N-C/SA-TCPP were mainly ascribed to the following reasons: (1) Co-N-C could enhance the light absorption ability of SA-TCPP to produce more photoinduced carriers. (2) The well-developed porosity of Co-N-C could optimize the dispersibility of SA-TCPP to provide more reactive sites and charge separation channels. (3) The π-π interaction between SA-TCPP and Co-N-C was beneficial to interlayer charge mobility, while the embedded cobalt nanoparticles (Co NPs) and N-doped carbon matrix could serve as electron traps to accelerate interfacial electron transfer. Additionally, the ferromagnetic Co NPs endowed Co-N-C/SA-TCPP with magnetic-separation function to promote recyclability in practical application.

Key words: Visible-light photocatalysis, Supramolecular porphyrin, ZIF-67 derived co-catalyst, 3D/0D heterostructure, Magnetic-separation

Lufang Ning, Jing Xu, Yang Lou, Chengsi Pan, Zhouping Wang, Yongfa Zhu. A 3D/0D cobalt-embedded nitrogen-doped porous carbon/supramolecular porphyrin magnetic-separation photocatalyst with highly efficient pollutant degradation and water oxidation performance[J]. J. Mater. Sci. Technol., 2022, 124: 53-64.

Figures/Tables 13

Scheme 1. Synthesis process of Co-N-C, SA-TCPP, and Co-N-C/SA-TCPP.

Fig. 1. (a) SEM image of Co-N-C. TEM images of (b) Co-N-C, (c) SA-TCPP, and (d) Co-N-C/ST (30%). (e, f) HRTEM images of Co-N-C/ST (30%).

Fig. 2. (a) STEM image and (b-f) EDS mappings of Co-N-C/ST (30%).

Fig. 3. (a) XRD patterns, (b) Raman spectra, (c) FT-IR spectra, and (d) DRS of Co-N-C, SA-TCPP, and Co-N-C/SA-TCPP.

Table 1. Elemental analysis of SA-TCPP, Co-N-C/ST (30%), and Co-N-C (wt.%).

Sample	C	N	H	O	Co
SA-TCPP	65.83	6.41	3.95	23.81	-
Co-N-C/ST (30%)	43.83	9.12	2.25	24.66	20.14
Co-N-C	39.43	9.58	1.97	25.28	23.74

Fig. 4. XPS spectra of SA-TCPP, Co-N-C/ST(30%), and Co-N-C: (a) N 1s, (b) O 1s, and (c) Co 2p.

Scheme 2. Model illustration of the interaction in Co-N-C/SA-TCPP.

Fig. 5. (a) Apparent rate constants (k) for 2,4-DCP photodegradation of Co-N-C, SA-TCPP, Co-N-C/SA-TCPP, and g-C3N4 under visible light calculated via the pseudo-first-order kinetic fitting. (b) HPLC chromatograms of the 2,4-DCP solutions after different photodegradation times by Co-N-C/ST (30%). (c) Photocatalytic activities of Co-N-C/ST (30%) at different wavelengths for degradation of 20 ppm 2,4-DCP.

Fig. 6. (a) Apparent rate constant (k) for different pollutants degradation of Co-N-C, SA-TCPP, and Co-N-C/ST(30%) under visible light. (b) Stability of Co-N-C/ST(30%) for ethylene degradation under visible light. (c) Oxygen evolution rates of SA-TCPP and Co-N-C/ST (30%) under visible light. (d) Magnetic hysteresis loops of Co-N-C, SA-TCPP, and Co-N-C/ST (30%) at 300 K. The insert shows the magnetic separation function of Co-N-C/ST (30%) by using a magnet.

Fig. 7. (a) PL emission spectra of Co-N-C, SA-TCPP, and Co-N-C/ST (30%) under photoexcitation at 408 nm. (b) Time-resolved fluorescence decay spectroscopy of SA-TCPP and Co-N-C/ST(30%). (c) Photocurrent responses under chopped illumination and (d) EIS Nyquist plots under visible light of SA-TCPP, Co-N-C, and Co-N-C/ST(30%). The insert equivalent circuit is used to simulate the impedance.

Table 2. Fluorescence lifetimes of charge carriers for SA-TCPP and Co-N-C/ST (30%).

Sample	τ₁ (ns)	B₁	τ₂ (ns)	B₂	τ_ave (ns)
SA-TCPP	1.60	6130.48	7.40	2640.51	5.46
Co-N-C/ST (30%)	6.29	2689.10	8.70	7704.01	8.21

Fig. 8. (a) 2,4-DCP degradation activities of Co-N-C/ST (30%) with the addition of different scavengers under visible light. ESR spectra of SA-TCPP and Co-N-C/ST (30%) under dark and visible light for the detection of (b) 1O2 and (c) e-.

Scheme 3. Schematic diagram of the proposed mechanism of carriers separation and photocatalytic process under visible light in Co-N-C/SA-TCPP composite system.

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