Tuning nitrogen defects and doping sulfur in carbon nitride for enhanced visible light photocatalytic activity

Abstract

Defect construction and heteroatom doping are effective strategies for improving photocatalytic activity of carbon nitride (g-C₃N₄). In this work, N defects were successfully prepared via cold plasma. High-energy electrons generated by plasma can produce N defects and embed sulfur atoms into g-C₃N₄. The N defects obviously promoted photocatalytic degradation performance that was 7.5 times higher than that of pure g-C₃N₄. The concentration of N defects can be tuned by different power and time of plasma. With the increase in N defects, the photocatalytic activity showed a volcanic trend. The g-C₃N₄ with moderate concentration of N defects exhibited the highest photocatalytic activity. S-doped g-C₃N₄ exhibited 11.25 times higher photocatalytic activity than pure g-C₃N₄. It provided extra active sites for photocatalytic reaction and improved stability of N defects. The N vacancy-enriched and S-doped g-C₃N₄ are beneficial for widening absorption edge and improving the separation efficiency of electron and holes.

Key words： g-C₃N₄; nitrogen defect; sulfur doping; photodegradation; plasma

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 21878214 and 21938009). The authors thank Dr. Yifu Chen (Tianjin University) for his help in analysis of atomic force microscope of this study.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2175-x and is accessible for authorized users.

References

1 WangX C, MaedaK, ThomasA, TakanabeK, XinG, CarlssonJ M, DomenK, AntoniettiM. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nature Materials, 2009, 8( 1): 76– 80

2 MengA Y, TengZ Y, ZhangQ, SuC L. Intrinsic defects in polymeric carbon nitride for photocatalysis applications. Chemistry, an Asian Journal, 2020, 15( 21): 3405– 3415

3 Ong W J, Tan L L, Ng Y H, Yong S T, Chai S P. Graphitic carbon nitride (g-C₃N₄)-based photocatalysts for artificial photosynthesis and environmental remediation: are we a step closer to achieving sustainability? Chemical Reviews, 2016, 116(12): 7159–7329

4 ZhangS, GuP C, MaR, LuoC, WenT, ZhaoG, ChengW C, WangX. Recent developments in fabrication and structure regulation of visible-light-driven g-C₃N₄-based photocatalysts towards water purification: a critical review. Catalysis Today, 2019, 335 : 65– 77

5 DengQ H, LiH P, BaG M, HuoT T, HouW G. The pivotal role of defects in fabrication of polymeric carbon nitride homojunctions with enhanced photocatalytic hydrogen evolution. Journal of Colloid and Interface Science, 2021, 586 : 748– 757

6 DuanY Y, WangY, GanL Y, MengJ Z, FengY J, WangK W, ZhouK, WangC, HanX D, ZhouX Y. Amorphous carbon nitride with three coordinate nitrogen (N_3C) vacancies for exceptional NO_x abatement in visible light. Advanced Energy Materials, 2021, 11( 19): 2004001

7 HuangL L, ChenR, XieC, ChenC, WangY Y, ZengY F, ChenD W, WangS Y. Rapid cationic defect and anion dual-regulated layered double hydroxides for efficient water oxidation. Nanoscale, 2018, 10( 28): 13638– 13644

8 ChaW S, KimI Y Y, LeeJ M, KimS H, RamadassK, GopalakrishnanK, PremkumarS, UmapathyS, VinuA. Sulfur-doped mesoporous carbon nitride with an ordered porous structure for sodium-ion batteries. ACS Applied Materials & Interfaces, 2019, 11( 30): 27192– 27199

9 ChuK, LiQ Q, LiuY P, WangJ, ChengY H. Filling the nitrogen vacancies with sulphur dopants in graphitic C₃N₄ for efficient and robust electrocatalytic nitrogen reduction. Applied Catalysis B: Environmental, 2020, 267 : 118693

10 WangH, BianY R, HuaJ T, DaiL M. Highly crystalline sulfur-doped carbon nitride as photocatalyst for efficient visible-light hydrogen generation. Applied Catalysis B: Environmental, 2018, 238 : 592– 598

11 FuJ W, XuQ L, LowJ X, JiangC J, YuJ G. Ultrathin 2D/2D WO₃/g-C₃N₄ step-scheme H₂-production photocatalyst. Applied Catalysis B: Environmental, 2019, 243 : 556– 565

12 MoradiM, HasanvandianF, IsariA A, HayatiF Z, KakavandiB, SetayeshS R. CuO and ZnO co-anchored on g-C₃N₄ nanosheets as an affordable double Z-scheme nanocomposite for photocatalytic decontamination of amoxicillin. Applied Catalysis B: Environmental, 2021, 285 : 119838

13 XuM, ZhuY, YangJ K, LiW, SunC Y, CuiY, LiuL, ZhaoH L, LiangB. Enhanced interfacial electronic transfer of BiVO₄ coupled with 2D g-C₃N₄ for visible-light photocatalytic performance. Journal of the American Ceramic Society, 2021, 104( 7): 3004– 3018

14 PatnaikS, MarthaS, ParidaK M. An overview of the structural, textural and morphological modulations of g-C₃N₄ towards photocatalytic hydrogen production. RSC Advances, 2016, 6( 52): 46929– 46951

15 NiuP, LiuG, ChengH M. Nitrogen vacancy-promoted photocatalytic activity of graphitic carbon nitride. Journal of Physical Chemistry C, 2012, 116( 20): 11013– 11018

16 TayQ L, KanhereP, NgC F, ChenS, ChakrabortyS, HuanA C H, SumT C, AhujaR, ChenZ. Defect engineered g-C₃N₄ for efficient visible light photocatalytic hydrogen production. Chemistry of Materials, 2015, 27( 14): 4930– 4933

17 WangX, ZhaoY, GaoM M, CaoN W, LiuK N, LiC, ZhaoX Y, RenY M, FengJ, WeiT. Nitrogen-defective g-C₃N₄ with enhanced photocatalytic performance fabrication by destructing C–N–C bond via H₂O₂. Separation and Purification Technology, 2021, 264 : 118424

18 RanJ R, MaT Y, GaoJ P, DuX W, QiaoS Z. Porous P-doped graphitic carbon nitride nanosheets for synergistically enhanced visible-light photocatalytic H₂ production. Energy & Environmental Science, 2015, 8( 12): 3708– 3717

19 ZhouY, LvW H, ZhuB L, TongF, PanJ L, BaiJ R, ZhouQ F, QinH F. Template-free one-step synthesis of g-C₃N₄ nanosheets with simultaneous porous network and S-doping for remarkable visible-light-driven hydrogen evolution. ACS Sustainable Chemistry & Engineering, 2019, 7( 6): 5801– 5807

20 Wang Z, Zhang Y, Neyts E C, Cao X X, Zhang X S, Jang B W L, Liu C J. Catalyst preparation with plasmas: how does it work? ACS Catalysis, 2018, 8(3): 2093–2110

21 ZhengJ X, PengX F, WangZ. Plasma-assisted defect engineering of N-doped NiCo₂O₄ for efficient oxygen reduction. Physical Chemistry Chemical Physics, 2021, 23( 11): 6591– 6599

22 OvcharovM, ShcherbanN, FilonenkoS, MishuraA, SkorykM, ShvalaginV, GranchakV. Hard template synthesis of porous carbon nitride materials with improved efficiency for photocatalytic CO₂ utilization. Materials Science and Engineering B, 2015, 202 : 1– 7

23 ZhangB, PengX J, WangZ. Noble metal-free TiO₂-coated carbon nitride layers for enhanced visible light-driven photocatalysis. Nanomaterials (Basel, Switzerland), 2020, 10( 4): 805

24 WangB X, ZhangX, BaiH Y, LvY J, HuS H. Hydrogen production from methanol through dielectric barrier discharge. Frontiers of Chemical Science and Engineering, 2011, 5( 2): 209– 214

25 LauV W H, LotschB V. A tour-guide through carbon nitride-land: structure and dimensionality dependent properties for photo (electro) chemical energy conversion and storage. Advanced Energy Materials, 2021, 12( 4): 2101078

26 KesslerF K, ZhengY, SchwarzD, MerschjannC, SchnickW, WangX C, BojdysM J. Functional carbon nitride materials design strategies for electrochemical devices. Nature Reviews. Materials, 2017, 2( 6): 17030

27 ZhangB, WangZ H, PengX F, WangZ, ZhouL, YinQ X. A novel route to manufacture 2D layer MoS₂ and g-C₃N₄ by atmospheric plasma with enhanced visible-light-driven photocatalysis. Nanomaterials (Basel, Switzerland), 2019, 9( 8): 1139

28 LiangZ W, ZhuangX J, TangZ C, DengQ H, LiH N, KangW B. High-crystalline polymeric carbon nitride flake composed porous nanotubes with significantly improved photocatalytic water splitting activity: the optimal balance between crystallinity and surface area. Chemical Engineering Journal, 2022, 432 : 134388

29 ZhuB C, ZhangL Y, ChengB, YuJ G. First-principle calculation study of tri-s-triazine-based g-C₃N₄: a review. Applied Catalysis B: Environmental, 2018, 224 : 983– 999

30 BaiX J, JiaT Q, WangX Y, HouS, HaoD, BingJ N. High carrier separation efficiency for a defective g-C₃N₄ with polarization effect and defect engineering: mechanism, properties and prospects. Catalysis Science & Technology, 2021, 11( 16): 5432– 5447

31 LiuG, NiuP, SunC H, SmithS C, ChenZ G, LuG Q, ChengH M. Unique electronic structure induced high photoreactivity of sulfur-doped graphitic C₃N₄. Journal of the American Chemical Society, 2010, 132( 33): 11642– 11648

32 TanH Q, ZhaoZ, ZhuW B, CokerE N, LiB S, ZhengM, YuW X, FanH Y, SunZ C. Oxygen vacancy enhanced photocatalytic activity of pervoskite SrTiO₃. ACS Applied Materials & Interfaces, 2014, 6( 21): 19184– 19190

33 GuoQ Y, ZhangY H, QiuJ, DongG P. Engineering the electronic structure and optical properties of g-C₃N₄ by non-metal ion doping. Journal of Materials Chemistry. C, Materials for Optical and Electronic Devices, 2016, 4( 28): 6839– 6847

34 YangX, ZhangL, WangD, ZhangQ, ZengJ, ZhangR. Facile synthesis of nitrogen-defective g-C₃N₄ for superior photocatalytic degradation of rhodamine B. RSC Advances, 2021, 11( 49): 30503– 30509

35 QuanH Y, QianK J, XuanY, LouL, YuK, LiuS X. Superior performance in visible-light-driven hydrogen evolution reaction of three-dimensionally ordered macroporous SrTiO₃ decorated with Zn_xCd_1−xS. Frontiers of Chemical Science and Engineering, 2021, 15( 6): 1561– 1571