0D/2D P-doped ZnxCd1-xS/g-C3N4 Heterojunctions towards Highly Efficient Photocatalytic Hydrogen Evolution

  • Hongfei Yin Nanjing University of Science and Technology
  • Xiaoheng Liu Key Laboratory of Education Ministry for Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Nanjing, China
Keywords: P-doped ZnxCd1-xS/g-C3N4, heterojuctions, photocatalysis, hydrogen evolution


Solar-driven water splitting over semiconductor photocatalysts is a promising approach for converting solar energy into renewable and storable chemical energy. CdS, an efficient photocatalyst for hydrogen evolution, suffers from high recombination of photogenerated electron-hole pairs and high photocorrosion in aqueous media, which limit its practical applications. Doping and the formation of heterojunctions are two efficient methods to improve the photocatalytic activities of photocatalysts. Herein, we rationally designed and fabricated P-doped 0D/2D ZnxCd1-xS/g-C3N4 nanocomposites by in-situ immobilizing ZnxCd1-xS onto the surface of g-C3N4 nanosheets in a hydrothermal environment, followed by a phosphorization process. The as-prepared P-doped ZnxCd1-xS/g-C3N4 nanocomposites were systematically characterized by analyzing the phase structure, chemical components, electronic and optical properties and separation of charge carriers. More importantly, these P-doped ZnxCd1-xS/g-C3N4 heterostructures have been proven to be highly efficient visible light responsive photocatalysts for hydrogen evolution, and meanwhile exhibit excellent photo-stability during recycling runs. The sufficient evidence exhibit that the significantly improved photocatalytic performance is mainly attributed to the prolonged lifetime of charge carriers and the improved separation efficiency of photogenerated electron-hole pairs.


A. Fujishima and K. Honda, “Electrochemical photolysis of water at a semiconductor electrode,” Nature, vol. 238, pp. 37-38, July 1972.

D. Q. Zeng, P. Y. Wu, W. J. Ong, B. S. Tang, M. D. Wu, H. F. Zheng, Y. Z. Chen, and D. L. Peng, “Construction of network-like and flower-like 2H-MoSe2 nanostructures coupled with porous g-C3N4 for noble-metal-free photocatalytic H2 evolution under visible light,” Applied Catalysis B: Environment, vol. 233, pp. 26-34, October 2018.

J. R. Ran, M. Jaroniec, and S. Z. Qiao, “Cocatalysts in semiconductor-based photocatalytic CO2 reduction: achievements, challenges, and opportunities,” Advanced Materials, vol. 30, pp. 1704649, February 2018.

W. Chen, Z. C. He, G. B. Huang, C. L. Wu, W. F. Chen, and X. H. Liu, “Direct z-scheme 2D/2D MnIn2S4/g-C3N4 architectures with highly efficient photocatalytic activities towards treatment of pharmaceutical wastewater and hydrogen evolution,” Chemical Engineering Journal, vol. 359, pp. 244-253, March 2019.

X. Z. Chen, N. Li, Z. Z. Kong, W. J. Ong, and X. J. Zhao, “Photocatalytic fixation of nitrogen to ammonia: state-of-the-art advancements and future prospects,” Materials Horizons, vol. 5, pp. 9-27, January 2018.

R. B. We, Z. L. Huang, G. H. Gu, Z. Wang, L. X. Zeng, Y. B. Chen, and Z. Q. Liu, “Dual-cocatalysts decorated rimous CdS spheres advancing highly-efficient visible-light photocatalytic hydrogen production,” Applied Catalysis B: Environment, vol. 231, pp. 101-107, September 2018.

S. Guo, Z. Deng, M. Li, B. Jiang, C. Tian, Q. Pan, and H. Fu, “Phosphorus-doped carbon nitride tubes with a layered micro-nanostructure for enhanced visible-light photocatalytic hydrogen evolution,” Angewandte Chemie International Edition, vol. 55 pp. 1830-1834, December 2015.

L. Zhao, L. Zhang, H. Lin, Q. Nong, M. Cui, Y. Wu, and Y. He, “Fabrication and characterization of hollow CdMoO4 coupled g-C3N4 heterojunction with enhanced photocatalytic activity,” Journal of Hazardous Material, vol. 299, pp. 333-342, December 2015.

J. Zhang, J. G. Yu, M. Jaroniec, and J. R. Gong, “Noble metal-Free reduced graphene oxide-ZnxCd1–xS nanocomposite with enhanced solar photocatalytic H2-production performance, ” Nano Letter, vol. 12, pp. 4584-4589, August 2012.

Q. J. Xiang, B. Cheng, and J. G. Yu, “Hierarchical porous CdS nanosheet-assembled flowers with enhanced visible-light photocatalytic H2-production performance,” Applied Catalysis B: Environment, vol. 138-139, pp. 299-303, July 2013.

A. Kudo and Y. Miseki, “Heterogeneous photocatalyst materials for water splitting,” Chemical Society Reviews, vol. 38, pp. 253-278, November 2008.

W. Chen, G. R. Duan, T. Y. Liu, Z. M. Jia, X. H. Liu, S. M. Chen, and X. J. Yang, “Synthesis of homogeneous one-dimensional NixCd1-xS nanorods with enhanced visible-light response by ethanediamine-assisted decomposition of complex precursors,” Journal of Material Science, vol. 50, pp. 3920-3928, June 2015.

M. Liu, L. Zhang, X. He, B. Zhang, H. Song, S. Li, and W. You, “L-Cystine-assisted hydrothermal synthesis of Mn1-xCdxS solid solutions with hexagonal wurtzite structure for efficient photocatalytic hydrogen evolution under visible light irradiation,” Journal of Material Chemistry A, vol. 2, pp. 4619-4626, January 2014.

S. Xie, X. Lu, T. Zhai, J. Gan, W. Li, M. Xu, M. Yu, Y. M. Zhang, and Y. Tong, “Controllable synthesis of ZnxCd1-xS@ZnO core@shell nanorods with enhanced photocatalytic activity,” Langmuir, vol. 28, pp. 10558-10564, June 2012.

R. Shi, H. F. Ye, F. Liang, Z. Wang, K. Li, Y. X. Weng, Z. S. Lin, W. F. Fu, C. M. Che, and Y. Chen, “Interstitial p-doped CdS with long-lived photogenerated electrons for photocatalytic water splitting without sacrificial agents,” Advanced Materials, vol. 30, 1705941, December 2017.

Z. Wu, G. Zhao, Y. Zhang, H. Tian, and D. Li, “Enhanced photocurrent responses and antiphotocorrosion performance of CdS hybrid derived from triple heterojunction,” The Journal of Physical Chemistry C, vol. 116, pp. 12829-12835, May 2012.

N. N. Hewa-Kasakarage, P. Z. El-Khoury, A. N. Tarnovsky, M. Kirsanova, I. Nemitz, A. Nemchinov, and M. Zamkov, “Ultrafast carrier dynamics in type II ZnSe/CdS/ZnSe Nanobarbells,” ACS Nano, vol. 4, pp. 1837-1844, March 2010.

Y. Tak, H. Kim, D. Lee, and K. Yong, “Type-II CdS nanoparticle-ZnO nanowire heterostructure arrays fabricated by a solution process: enhanced photocatalytic activity,” Chemical Communication, pp. 4585-4587, August 2008.

S. Liu, N. Zhang, Z. R. Tang, and Y. J. Xu, “Synthesis of one-dimensional CdS@TiO2 core-shell nanocomposites photocatalyst for selective redox: the dual role of TiO2 shell,” ACS Applied Materials & Interfaces, vol. 4, pp. 6378-6385, November 2012.

H. Wang, L. Zhang, Z. Chen, J. Hu, S. Li, Z. Wang, J. Liu, and X. Wang, “Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances,” Chemical Society Reviews, vol. 43, pp. 5234-5244, May 2014.

S. J. Moniz, S. A. Shevlin, D. J. Martin, Z. X. Guo, and J. Tang, “Visible-light driven heterojunction photocatalysts for water splitting: a critical review,” Energy & Environmental Science, vol. 8, pp. 731-759, January 2015.

M. C. Liu, D. W. Jing, Z. H. Zhou, and L. J. Guo, “Twin-induced one-dimensional homojunctions yield high quantum efficiency for solar hydrogen generation,” Nature Communications, September 2013.

J. G. Song, H. T. Zhao, R. R. Sun, X. Y. Li, and D. J. Sun, “An efficient hydrogen evolution catalyst composed of palladium phosphorous sulfide (PdP~0.33S∼1.67) and twin nanocrystal Zn0.5Cd0.5S solid solution with both homo and hetero-junctions,” Energy & Environmental Science, vol. 10, pp. 225-235, November 2016.

Q. Tay, P. Kanhere, C. F. Ng, S. Chen, S. Chakraborty, A. C. H. Huan, T. C. Sum, R. Ahuja, and Z. Chen, “Defect engineered g-C3N4 for efficient visible light photocatalytic hydrogen production,” Chemistry of Materials, vol. 27, pp. 4930-4933, July 2015.

Q. Lin, L. Li, S. Liang, M. Liu, J. Bi, and L. Wu, “Efficient synthesis of monolayer carbon nitride 2D nanosheets with tunable concentration and enhanced visible-light photocatalytic activities,” Applied Catalysis B: Environment, vol. 163, pp. 135-142, February 2015.

X. X. Wang, J. Chen, X. J. Guan, and L. J. Guo, “Enhanced efficiency and stability for visible light driven water splitting hydrogen production over Cd0.5Zn0.5S/g-C3N4 composite photocatalyst,” International Journal of Hydrogen Energy, vol. 40, pp. 7546-7552, June 2015.

H. Liu, Z. T. Jin, and Z. Z. Xu, “Hybridization of Cd0.2Zn0.8S with g-C3N4 nanosheets: a visible-light-driven photocatalyst for H2 evolution from water and degradation of organic pollutants,” Dalton Transaction, vol.44, pp. 14368-14375, July 2015.

J. Luo, X. Zhou, L. Ma, and X. Xu, “Enhancing visible-light photocatalytic activity of g-C3N4 by doping phosphorus and coupling with CeO2 for the degradation of methyl orange under visible light irradiation,” RSC Advances, vol. 5, pp. 68728-68735, August 2015.

B. C. Zhu, P. F. Xia, W. K. Ho, and J. G. Yu, “Isoelectric point and adsorption activity of porous g-C3N4,” Applied Surface Science, vol. 344, pp. 188-195, July 2015.

J. Zhang, Y. Hu, X. Jiang, S. Chen, S. Meng, and X. Fu, “Design of a direct z-scheme photocatalyst: preparation and characterization of Bi2O3/g-C3N4 with high visible light activity,” Journal of Hazardous Materials, vol. 280, pp. 713-722, September 2014.

X. J. Bai, L. Wang, and Y. F. Zhu, “Visible photocatalytic activity enhancement of ZnWO4 by graphene hybridization,” ACS Catalysis, vol. 2, pp. 2769-2778, November 2012.

N. Zhang, S. Q. Liu, X. Z. Fu, and Y. J. Xu, “Synthesis of M@TiO2(M = Au, Pd, Pt) core-shell nanocomposites with tunable photoreactivity,” The Journal of Physical Chemistry C, vol. 115, pp. 9136-9145, April 2011.

H. X. Xong, T. Zhao, G. D. Zhou, R. F. Qian, T. Feng, and J. H. Pan, “Revisiting structural and photocatalytic properties of g-C3N4/TiO2: is surface modification of TiO2 by calcination with urea an effective route to solar photocatalyst ?” Catalysis Today, December 2018.

R. F. Qian, H. X. Zong, J. Schneider, G. D. Zhou, T. Zhao, Y. L. Li, J. Yang, B. W. Bahnemann, and J. H. Pan, “Charge carrier trapping, recombination and transfer during TiO2 photocatalysis: an overview,” Catalysis Today, October 2018.

X. Z. Jiang, M. Manawan, T. Feng, R. F. Qian, T. Zhao, G. D. Zhou, F. T. Kong, Q. Wang, S. Y. Dai, and J. H. Pan, “Anatase and rutile in evonik aeroxide P25: heterojunctioned or individual nanoparticles?” vol. 300, pp. 12-17, February 2018.

How to Cite
H. Yin and X. Liu, “0D/2D P-doped ZnxCd1-xS/g-C3N4 Heterojunctions towards Highly Efficient Photocatalytic Hydrogen Evolution”, Proc. eng. technol. innov., vol. 13, pp. 32-40, Sep. 2019.