Highly efficient visible photocatalytic disinfection and degradation performances of microtubular nanoporous g-C3N4 via hierarchical construction and defects engineering

doi:10.1016/j.jmst.2020.02.024

Abstract

Abstract:

Herein, microtubular nanoporous g-C₃N₄ (TPCN) with hierarchical structure and nitrogen defects was prepared via a facile self-templating approach. On one hand, the hexagonal tubular structure can facilitate the light reflection/scattering, provide internal/external active sites, and endow the electron with oriented transfer channels. The well-developed nanoporosity can result in large specific surface area and abundant accessible channels for charge migration. On the other hand, the existence of nitrogen vacancies can improve the light harvesting (λ > 450 nm) and prompt charge separation by acting as the shallow charge traps. More NH_x groups in g-C₃N₄ framework can promote the interlayer charge transport by generating hydrogen-bonding interaction between C₃N₄ layers. Therefore, TPCN possessed highly efficient visible photocatalytic performances to effectively inactivate Escherichia coli (E. coli) cells and thoroughly mineralize organic pollutants. TPCN with the optimum bactericidal efficiency can completely inactivated 5 × 10⁶ cfu mL^-1 of E. coli cells after 4 h of irradiation treatment, while about 74.4 % of E. coli cells were killed by bulk g-C₃N₄ (BCN). Meanwhile, the photodegradation rate of TPCN towards methylene blue, amaranth, and bisphenol A were almost 3.1, 2.5 and 1.6 times as fast as those of BCN. Furthermore, h⁺ and ?O₂^- were the reactive species in the photocatalytic process of TPCN system.

Key words: g-C₃N₄photocatalyst, Hierarchical structure, Nitrogen defects, Disinfection, Degradation

Jing Xu, Zhouping Wang, Yongfa Zhu. Highly efficient visible photocatalytic disinfection and degradation performances of microtubular nanoporous g-C₃N₄ via hierarchical construction and defects engineering[J]. J. Mater. Sci. Technol., 2020, 49: 133-143.

Figures/Tables 17

Scheme 1. Synthetic process of TPCN photocatalyst.

Fig. 1. SEM images of supramolecular precursor (a, b) and TPCN-5 (c-e), TEM images of TPCN-5 (f-h).

Fig. 2. (a) N2 adsorption-desorption isotherms and (b) pore size distributions of BCN and TPCN.

Table 1 BET specific surface area and pore volume of BCN and TPCN.

Sample	BET specific surface area (m² g^-1)	Pore volume (cm³ g^-1)
BCN	3.4	0.021
TPCN-2	32.8	0.14
TPCN-5	72.3	0.30
TPCN-8	54.7	0.23

Fig. 3. (a) XRD patterns and (b) FTIR spectra of BCN and TPCN.

Fig. 4. (a) UV-vis diffuse reflectance spectra of BCN and TPCN, (b) the schematic band structures of BCN and TPCN-5.

Fig. 5. (a) C/N atomic ratio of BCN and TPCN from element analysis; ESR spectra (b) and XPS N 1s spectra (c) of BCN and TPCN-5; (d) schematic of TPCN-5 with VN.

Table 2 Distribution of N atoms based on XPS N 1s spectra for BCN and TPCN-5.

Sample	N_2C	N_3C	NH_x	N_3C/N_2C	NH_x/N_3C
BCN	74.02 %	16.93 %	9.05 %	0.229	0.535
TPCN-5	76.48%	13.48 %	10.04 %	0.176	0.745

Fig. 6. Photocatalytic inactivation efficiency against E. coli under visible light irradiation over BCN and TPCN.

Fig. 7. Fluorescent images of live and dead E. coli cells exposed to different treatments (light control, dark control, BCN and TPCN under visible light irradiation). Green fluorescence shows both live and dead E. coli cells, and red fluorescence shows only dead E. coli cells.

Fig. 8. SEM images of E. coli cells (a) alone, (b) mixing with TPCN-5 before irradiation, (c, d) after disinfection for 4 h using TPCN-5.

Fig. 9. (a) Apparent rate constants for photocatalytic degradation of MB, amaranth and BPA under visible light irradiation over BCN and TPCN-5; (b) cycling runs for photodegradation of MB in presence of TPCN-5 under visible light irradiation.

Fig. 10. (a) PL spectra of BCN and TPCN under photoexcitation at 365 nm, (b) ns-level time-resolved fluorescence decay spectra of BCN and TPCN monitored under a 375 nm laser excitation.

Table 3 Radiative fluorescence lifetimes of charge carriers for BCN and TPCN samples.

Sample	τ₁ (ns)-Rel %	τ₂ (ns)-Rel %	τ_av (ns)
BCN	1.39-47.33	5.42-52.67	3.51
TPCN-2	1.50-42.07	7.66-57.93	5.07
TPCN-5	1.55-27.33	8.94-72.67	6.92
TPCN-8	2.28-36.66	8.08-63.34	5.95

Fig. 11. (a) Photocurrent responses of BCN and TPCN and (b) EIS Nyquist plots of BCN and TPCN-5 under dark and visible-light conditions.

Fig. 12. (a) ESR spectra of TPCN-5 in DMSO and H2O under dark and visible-light conditions, (b) photodegradation of amaranth over TPCN-5 in presence of different reactive species scavengers under visible light irradiation.

Scheme 2. Proposed mechanism for charge transfer and photocatalytic process in TPCN system under visible light irradiation.

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Highly efficient visible photocatalytic disinfection and degradation performances of microtubular nanoporous g-C₃N₄ via hierarchical construction and defects engineering

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