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J. Mater. Sci. Technol.  2020, Vol. 49 Issue (0): 133-143    DOI: 10.1016/j.jmst.2020.02.024
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Highly efficient visible photocatalytic disinfection and degradation performances of microtubular nanoporous g-C3N4 via hierarchical construction and defects engineering
Jing Xua,b,c,d, Zhouping Wanga,b,c,d,*(), Yongfa Zhue,**()
a State Key Laboratory of Food Science and Technology, Jiangnan University, Wuxi 214122, China
b School of Food Science and Technology, Jiangnan University, Wuxi 214122, China
c International Joint Laboratory on Food Safety, Jiangnan University, Wuxi 214122, China
d Collaborative Innovation Center of Food Safety and Quality Control in Jiangsu Province, Jiangnan University, Wuxi 214122, China
e Department of Chemistry, Tsinghua University, Beijing 100084, China
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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 NHx 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     
Received:  16 December 2019     
Corresponding Authors:  Zhouping Wang,Yongfa Zhu     E-mail:;

Cite this article: 

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. Mater. Sci. Technol., 2020, 49(0): 133-143.

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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.
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
Table 1  BET specific surface area and pore volume of BCN and TPCN.
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.
Sample N2C N3C NHx N3C/N2C NHx/N3C
BCN 74.02 % 16.93 % 9.05 % 0.229 0.535
TPCN-5 76.48% 13.48 % 10.04 % 0.176 0.745
Table 2  Distribution of N atoms based on XPS N 1s spectra for BCN and TPCN-5.
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.
Sample τ1 (ns)-Rel % τ2 (ns)-Rel % τav (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
Table 3  Radiative fluorescence lifetimes of charge carriers for BCN and TPCN samples.
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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