Sulfur and carbon co-doped g-C₃N₄ microtubes with enhanced photocatalytic H₂ production activity

Abstract

Metal-free graphitic carbon nitride (g-C₃N₄) has captured significant attention as a low-cost and efficient hydrogen production photocatalyst through. Effectively regulating the microstructure and accelerating the separation of photogenerated carriers remain crucial strategies for promoting the photocatalytic performance of this material. Herein, a novel sulfur–carbon co-doped g-C₃N₄ (SCCN) hierarchical microtubules filled with abundant nanosheets inside by thermal polymerization is reported. Numerous nanosheets create abundant pores and cavities inside the SCCN microtubes, thereby increasing the specific surface area of g-C₃N₄ and providing sufficient reactant attachment sites. Besides, the hierarchical structure of SCCN microtubules strengthens the reflection and scattering of light, and the utilization of visible light is favorably affected. More importantly, co-doping S and C has greatly improved the photocatalytic performance of graphitic carbon nitride, optimized the band gap structure and enhanced the photogenerated carrier splitting. Consequently, the SCCN exhibits a remarkable photocatalytic H₂ evolution rate of 4868 μmol/(g·h). This work demonstrates the potential of multi-nonmetal doped g-C₃N₄ as the ideal photocatalyst for H₂ evolution.

Graphical abstract

Keywords

carbon nitride / photocatalysis / hydrogen production

References

[1] Sun L J, Dong H L, Xu J. . Unravelling the synergy between phase engineering and interface regulation in TiO₂/1T-rich MoSe₂ heterostructures for efficient photocatalytic hydrogen evolution. ACS Sustainable Chemistry & Engineering, 2023, 11(21): 8009–8019

[2] Jourshabani M, Asrami M, Lee B. Advanced functional carbon nitride by implanting semi-isolated VO₂ active sites for photocatalytic H₂ production and organic pollutant degradation. Small, 2023, 19(28): 2300147

[3] Du S W, Lin S Q, Ren K K. . Revealing the effects of transition metal doping on CoSe cocatalyst for enhancing photocatalytic H₂ production. Applied Catalysis B: Environmental, 2023, 328: 122503

[4] Wang X, Maeda K, Chen X. . Polymer semiconductors for artificial photosynthesis: Hydrogen evolution by mesoporous graphitic carbon nitride with visible light. Journal of the American Chemical Society, 2009, 131(5): 1680–1681

[5] Xiao S T, Yin R, Wu L. . Hierarchically porous few-layer carbon nitride and its high H⁺ selectivity for efficient photocatalytic seawater splitting. Nano Letters, 2023, 23(10): 4390–4398

[6] Lin F, Zhou S, Wang G H. . Electrostatic self-assembly combined with microwave hydrothermal strategy: Construction of 1D/1D carbon nanofibers/crystalline g-C₃N₄ heterojunction for boosting photocatalytic hydrogen production. Nano Energy, 2022, 99: 107432–107441

[7] Zheng Y, Lin L H, Wang B. . Graphitic carbon nitride polymers toward sustainable photoredox catalysis. Angewandte Chemie International Edition, 2015, 54(44): 12868–12884

[8] Wang X C, Chen X F, Thomas A. . Metal-containing carbon nitride compounds: A new functional organic-metal hybrid material. Advanced Materials, 2009, 21(16): 1609–1612

[9] Liu Z X, Liu Y D, Sun X B. . Construction of Z-scheme Ag/AgVO₃/carbon-rich g-C₃N₄ heterojunction for enhanced photocatalytic degradation of sulfamethiadiazole: DFT calculation and mechanism study. Chemical Engineering Journal, 2022, 433: 133604–133616

[10] Liu Y J, Tayyab M, Pei W K. . The precision defect engineering with nonmetallic element refilling strategy in g-C₃N₄ for enhanced photocatalytic hydrogen production. Small, 2023, 19(21): 2208117

[11] Shen R C, Hao L, Chen Q. . P-doped g-C₃N₄ nanosheets with highly dispersed Co_0.2Ni_1.6Fe_0.2P cocatalyst for efficient photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2022, 38(7): 2110014

[12] Zhang J J, Wang L X, Mitra M. . Molecular-level engineering of S-scheme heterojunction: The sitespecific role for directional charge transfer. Chinese Journal of Structural Chemistry, 2022, 41(6): 2206003–2206005

[13] Jun Y S, Lee E Z, Wang X C. . From melamine-cyanuric acid supramolecular aggregates to carbon nitride hollow spheres. Advanced Functional Materials, 2013, 23(29): 3661–3667

[14] Sun J H, Zhang J S, Zhang M W. . Bioinspired hollow semiconductor nanospheres as photosynthetic nanoparticles. Nature Communications, 2012, 3(1): 1139

[15] Cui L F, Song J L, McGuire A. . Constructing highly uniform onion-ring-like graphitic carbon nitride for efficient visible-light-driven photocatalytic hydrogen evolution. ACS Nano, 2018, 12(6): 5551–5558

[16] Shen R C, He K L, Zhang A P. . In-situ construction of metallic Ni₃C@Ni core–shell cocatalysts over g-C₃N₄ nanosheets for shell-thickness-dependent photocatalytic H₂ production. Applied Catalysis B: Environmental, 2021, 291: 120104

[17] Huang H W, Xiao K, Tian N. . Template-free precursor-surface-etching route to porous, thin g-C₃N₄ nanosheets for enhancing photocatalytic reduction and oxidation activity. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(33): 17452–17463

[18] Zhao Z W, Dai K, Zhang J F. . In situ preparation of Mn_0·2Cd_0·8S-diethylenetriamine/porous g-C₃N₄ S-scheme heterojunction with enhanced photocatalytic hydrogen production. Advanced Sustainable Systems, 2023, 7(1): 2100498

[19] Ou H H, Lin L H, Zheng Y. . Tri-s-triazine-based crystalline carbon nitride nanosheets for an improved hydrogen evolution. Advanced Materials, 2017, 29(22): 1700008

[20] Zhang J S, Zhang M W, Yang C. . Nanospherical carbon nitride frameworks with sharp edges accelerating charge collection and separation at a soft photocatalytic interface. Advanced Materials, 2014, 26(24): 4121–4126

[21] Sun Z Z, Dong H Z, Yuan Q. . Self-supported hierarchical crystalline carbon nitride arrays with triazine-heptazine heterojunctions for highly efficient photoredox catalysis. Chemical Engineering Journal, 2022, 435: 134865

[22] Fu J W, Zhu B C, Jiang C J. . Hierarchical porous O-doped g-C₃N₄ with enhanced photocatalytic CO₂ reduction activity. Small, 2017, 13(15): 1603938

[23] Zhang Y, Mori T, Ye J. . Phosphorus-doped carbon nitride solid: enhanced electrical conductivity and photocurrent generation. Journal of the American Chemical Society, 2010, 132(18): 6294–6295

[24] Dong G H, Zhao K, Zhang L Z. Carbon self-doping induced high electronic conductivity and photoreactivity of g-C₃N₄. Chemical Communications, 2012, 48(49): 6178–6180

[25] Wang H, Bian Y R, Hu J T. . Highly crystalline sulfur-doped carbon nitride as photocatalyst for efficient visible-light hydrogen generation. Applied Catalysis B: Environmental, 2018, 238: 592–598

[26] Chu Y C, Lin T J, Lin Y R. . Influence of P,S,O-doping on g-C₃N₄ for hydrogel formation and photocatalysis: An experimental and theoretical study. Carbon, 2020, 169: 338–348

[27] Samanta S, Yadav R, Kumar A. . Surface modified C, O co-doped polymeric g-C₃N₄ as an efficient photocatalyst for visible light assisted CO₂ reduction and H₂O₂ production. Applied Catalysis B: Environmental, 2019, 259: 118054

[28] Huang J X, Li D G, Li R B. . An efficient metal-free phosphorus and oxygen co-doped g-C₃N₄ photocatalyst with enhanced visible light photocatalytic activity for the degradation of fluoroquinolone antibiotics. Chemical Engineering Journal, 2019, 374: 242–253

[29] Zheng X S, Zhang Q X, Chen T S. . A novel synthetic carbon and oxygen doped stalactite-like g-C₃N₄ for broad-spectrum-driven indometacin degradation. Journal of Hazardous Materials, 2020, 386: 121961

[30] Hu C C, Hung W Z, Wang M S. . Phosphorus and sulfur codoped g-C₃N₄ as an efficient metal-free photocatalyst. Carbon, 2018, 127: 374–383

[31] Ye M Y, Zhao Z H, Hu Z F. . 0D/2D heterojunctions of vanadate quantum dots/graphitic carbon nitride nanosheets for enhanced visible-light-driven photocatalysis. Angewandte Chemie International Edition, 2017, 56(29): 8407–8411

[32] Wang Y G, Xia Q N, Bai X. . Carbothermal activation synthesis of 3D porous g-C₃N₄/carbon nanosheets composite with superior performance for CO₂ photoreduction. Applied Catalysis B: Environmental, 2018, 239: 196–203

[33] Liang Z Z, Bai J X, Hao L. . Photodeposition of NiS cocatalysts on g-C₃N₄ with edge grafting of 4-(1H-imidazol-2-yl) benzoic acid for highly elevated photocatalytic H₂ evolution. Advanced Sustainable Systems, 2023, 7(1): 2200143

[34] Da Silva E, Moura N, Coutinho A. . β-cyclodextrin as a precursor to holey C-doped g-C₃N₄ nanosheets for photocatalytic hydrogen generation. ChemSusChem, 2018, 11(16): 2681–2694

[35] Ho W K, Zhang Z Z, Lin W. . Copolymerization with 2,4,6-triaminopyrimidine for the rolling-up the layer structure, tunable electronic properties, and photocatalysis of g-C₃N₄. ACS Applied Materials & Interfaces, 2015, 7(9): 5497–5505

[36] Liu C, Wu K L, Meng G H. . Explore the properties and photocatalytic performance of iron-doped g-C₃N₄ nanosheets decorated with Ni₂P. Molecular Catalysis, 2017, 437: 80–88

[37] Zhu Y P, Ren T Z, Yuan Z Y. Mesoporous phosphorus-doped g-C₃N₄ nanostructured flowers with superior photocatalytic hydrogen evolution performance. ACS Applied Materials & Interfaces, 2015, 7(30): 16850–16856

[38] Shi L, Chang K, Zhang H B. . Drastic enhancement of photocatalytic activities over phosphoric acid protonated porous g-C₃N₄ nanosheets under visible light. Small, 2016, 12(32): 4431–4439

[39] Li S, Dong G, Hailili R. . Effective photocatalytic H₂O₂ production under visible light irradiation at g-C₃N₄ modulated by carbon vacancies. Applied Catalysis B: Environmental, 2016, 190: 26–35

[40] WangKLi QLiuB S, . Sulfur-doped g-C₃N₄ with enhanced photocatalytic CO₂-reduction performance. Applied Catalysis B: Environmental, 2015, 176–177: 44–52

[41] Liu T, Li Y F, Sun H J. . Asymmetric structure awakened n-π* electron transition in sulfur and selenium co-doped g-C₃N₄ with efficient photocatalytic performance. Chinese Journal of Structural Chemistry, 2022, 41(6): 2206055–2206061

[42] Ge F Y, Huang S Q, Yan J. . Sulfur promoted n-π* electron transitions in thiophene-doped g-C₃N₄ for enhanced photocatalytic activity. Chinese Journal of Catalysis, 2021, 42(3): 450–459

[43] Liu Y, Wang H, Yuan X Z. . Roles of sulfur-edge sites, metal-edge sites, terrace sites, and defects in metal sulfides for photocatalysis. Chem Catalysis, 2021, 1(1): 44–68

[44] Lu X Y, Xie J, Chen X B. . Engineering MP_X (M = Fe, Co or Ni) interface electron transfer channels for boosting photocatalytic H₂ evolution over g-C₃N₄/MoS₂ layered heterojunctions. Applied Catalysis B: Environmental, 2019, 252: 250–259

[45] Wang Y B, Zhao X, Cao D. . Peroxymonosulfate enhanced visible light photocatalytic degradation bisphenol A by single-atom dispersed Ag mesoporous g-C₃N₄ hybrid. Applied Catalysis B: Environmental, 2017, 211: 79–88

[46] Xu H T, Xiao R, Huang J R. . In situ construction of protonated g-C₃N₄/Ti₃C₂ MXene Schottky heterojunctions for efficient photocatalytic hydrogen production. Chinese Journal of Catalysis, 2021, 42(1): 107–114

[47] Zong X P, Miao X, Hua S X. . Structure defects assisted photocatalytic H₂ production for polythiophene nanofibers. Applied Catalysis B: Environmental, 2017, 211: 98–105

[48] Tian N, Huang H W, Wang S B. . Facet-charge-induced coupling dependent interfacial photocharge separation: A case of BiOI/g-C₃N₄ p-n junction. Applied Catalysis B: Environmental, 2020, 267: 118697

[49] Guo Q Y, Zhang Y H, Zhang H S. . 3D foam strutted graphene carbon nitride with highly stable optoelectronic properties. Advanced Functional Materials, 2017, 27(42): 1703711

[50] Sahoo R C, Lu H J, Garg D. . Bandgap engineered g-C₃N₄ and its graphene composites for stable photoreduction of CO₂ to methanol. Carbon, 2022, 192: 101–108

[51] Zhang J G, Zhu Q H, Ma Y F. . Photo-generated charges escape from P⁺ center through the chemical bridges between P-doped g-C₃N₄ and Ru_xP nanoparticles to enhance the photocatalytic hydrogen evolution. Catalysis Today, 2021, 380: 223–229

[52] Wang H, Wu Y, Feng M B. . Visible-light-driven removal of tetracycline antibiotics and reclamation of hydrogen energy from natural water matrices and wastewater by polymeric carbon nitride foam. Water Research, 2018, 144: 215–225

[53] Chen J Y, Qin C C, Mou Y. . Linker regulation of iron-based MOFs for highly effective Fenton-like degradation of refractory organic contaminants. Chemical Engineering Journal, 2023, 459: 141588

RIGHTS & PERMISSIONS

Higher Education Press 2023