Highly Efficient and Stable Potassium-Doped g-C3N4/Zn0.5Cd0.5S Quantum Dot Heterojunction Photocatalyst for Hydrogen Evolution

Chenxi Ye , Peiyuan Guo , Xiya Chen , Zining Zhang , Yudong Guo , Zhenjun Chen , Huakang Yang , Dongxiang Luo , Xiao Liu

Battery Energy ›› 2025, Vol. 4 ›› Issue (1) : 20240033

PDF
Battery Energy ›› 2025, Vol. 4 ›› Issue (1) : 20240033 DOI: 10.1002/bte2.20240033
RESEARCH ARTICLE

Highly Efficient and Stable Potassium-Doped g-C3N4/Zn0.5Cd0.5S Quantum Dot Heterojunction Photocatalyst for Hydrogen Evolution

Author information +
History +
PDF

Abstract

The advancement of efficient and robust photocatalysts for water splitting is pivotal for the sustainable production of clean hydrogen energy. This study introduces a novel photocatalyst, synthesized by integrating 0D Zn0.5Cd0.5S quantum dots (ZCS QDs) onto 2D K+-doped graphitic carbon nitride (K-CN) microribbons, via an in-situ hydrothermal growth method. A comprehensive characterization was performed to assess the optical characteristics, structural attributes, and charge transfer efficacy of the prepared photocatalysts. Our findings reveal that the incorporation of K+ ions effectively modulates the bandgap and valence band positions of g-C3N4, facilitating an optimal energy level alignment with ZCS QDs. Moreover, the integration of ZCS QDs improves the photon capture ability and concurrently diminishes the recombination rate of photogenerated charge carriers. The optimized ZCS 51%/K-CN photocatalyst demonstrates a promising simulated sunlight-driven hydrogen production rate of 9.606 mmol·h-1·g-1, surpassing that of pristine ZCS QDs by nearly three times, without the need for noble metal co-catalysts. Most notably, the photocatalyst maintains its hydrogen evolution performance consistently over five photocatalytic cycles, underscoring its stability. The remarkable photocatalytic activity is primarily ascribed to the formation of a type-II heterojunction between K-CN and ZCS QDs, which enhances charge separation and transfer. This research represents a significant step forward in the design of heterojunction photocatalysts by merging QDs with g-C3N4, offering a highly effective and durable solution for photocatalytic hydrogen production.

Keywords

K +-doped g-C 3N 4 / photocatalytic hydrogen evolution / type-Ⅱ heterojunction / Zn 0.5Cd 0.5S quantum dots

Cite this article

Download citation ▾
Chenxi Ye, Peiyuan Guo, Xiya Chen, Zining Zhang, Yudong Guo, Zhenjun Chen, Huakang Yang, Dongxiang Luo, Xiao Liu. Highly Efficient and Stable Potassium-Doped g-C3N4/Zn0.5Cd0.5S Quantum Dot Heterojunction Photocatalyst for Hydrogen Evolution. Battery Energy, 2025, 4(1): 20240033 DOI:10.1002/bte2.20240033

登录浏览全文

4963

注册一个新账户 忘记密码

References

[1]

S. Koohi-Fayegh and M. A. Rosen, “A Review of Energy Storage Types, Applications and Recent Developments,” Journal of Energy Storage 27 (2020):101047.

[2]

B. E. Lebrouhi, J. J. Djoupo, B. Lamrani, K. Benabdelaziz, and T. Kousksou, “Global Hydrogen Development-A Technological and Geopolitical Overview,” International Journal of Hydrogen Energy 47, no. 11 (2022):7016–7048.

[3]

T. J. Whittemore, C. Xue, J. Huang, J. C. Gallucci, and C. Turro, “Single-Chromophore Single-Molecule Photocatalyst for the Production of Dihydrogen Using Low-Energy Light,” Nature Chemistry 12, no. 2 (2020):180–185.

[4]

T.-F. Yeh, S.-J. Chen, and H. Teng, “Synergistic Effect of Oxygen and Nitrogen Functionalities for Graphene-Based Quantum Dots Used in Photocatalytic H2 Production From Water Decomposition,” Nano Energy 12 (2015):476–485.

[5]

X. Zou and Y. Zhang, “Noble Metal-Free Hydrogen Evolution Catalysts for Water Splitting,” Chemical Society Reviews 44, no. 15 (2015):5148–5180.

[6]

L. Cheng, H. Yin, C. Cai, J. Fan, and Q. Xiang, “Single Ni Atoms Anchored on Porous Few-Layer g-C3N4 for Photocatalytic CO2 Reduction: The Role of Edge Confinement,” Small 16, no. 28 (2020): e2002411.

[7]

R.-H. Gao, Q. Ge, N. Jiang, H. Cong, M. Liu, and Y.-Q. Zhang, “Graphitic Carbon Nitride (g-C3N4)-Based Photocatalytic Materials for Hydrogen Evolution,” Frontiers in Chemistry 10 (2022):1048504.

[8]

L. Yao, D. Wei, Y. Ni, D. Yan, and C. Hu, “Surface Localization of CdZnS Quantum Dots Onto 2D g-C3N4 Ultrathin Microribbons: Highly Efficient Visible Light-Induced H2-Generation,” Nano Energy 26 (2016):248–256.

[9]

Y. Li, F. Gong, Q. Zhou, X. Feng, J. Fan, and Q. Xiang, “Crystalline Isotype Heptazine-/Triazine-Based Carbon Nitride Heterojunctions for an Improved Hydrogen Evolution,” Applied Catalysis, B: Environmental 268 (2020):118381.

[10]

C. Li, H. Wu, D. Zhu, et al., “High-Efficient Charge Separation Driven Directionally by Pyridine Rings Grafted on Carbon Nitride Edge for Boosting Photocatalytic Hydrogen Evolution,” Applied Catalysis, B: Environmental 297 (2021):120433.

[11]

S. Hu, F. Li, Z. Fan, F. Wang, Y. Zhao, and Z. Lv, “Band Gap-Tunable Potassium Doped Graphitic Carbon Nitride With Enhanced Mineralization Ability,” Dalton Transactions 44, no. 3 (2015):1084–1092.

[12]

Q. Zhang, P. Chen, L. Chen, et al., “Facile Fabrication of Novel Ag2S/K-g-C3N4 Composite and Its Enhanced Performance in Photocatalytic H2 Evolution,” Journal of Colloid and Interface Science 568 (2020):117–129.

[13]

M. Zhu, C. Zhai, M. Sun, Y. Hu, B. Yan, and Y. Du, “Ultrathin Graphitic C3N4 Nanosheet as a Promising Visible-Light-Activated Support for Boosting Photoelectrocatalytic Methanol Oxidation,” Applied Catalysis, B: Environmental 203 (2017):108–115.

[14]

J. Yi, T. Fei, L. Li, et al., “Large-Scale Production of Ultrathin Carbon Nitride-Based Photocatalysts for High-Yield Hydrogen Evolution,” Applied Catalysis, B: Environmental 281 (2021):119475.

[15]

L. Hong, H. Xu, Y. Zhu, Z. Li, B. Bai, and G. Ding, “Surface Plasmon Resonance Enhanced Hydrogen Evolution From Water With Graphitic Carbon Nitride Photocatalyst,” Catalysis Letters 153, no. 8 (2023):2296–2307.

[16]

T. Ren, Y. Dang, Y. Xiao, et al., “Depositing Ag Nanoparticles on g-C3N4 by Facile Silver Mirror Reaction for Enhanced Photocatalytic Hydrogen Production,” Inorganic Chemistry Communications 123 (2021):108367.

[17]

S. Feng, T. Chen, Z. Liu, J. Shi, X. Yue, and Y. Li, “Z-Scheme CdS/CQDs/g-C3N4 Composites With Visible-Near-Infrared Light Response for Efficient Photocatalytic Organic Pollutant Degradation,” Science of the Total Environment 704 (2020):135404.

[18]

Z. Chen, F. Guo, H. Sun, Y. Shi, and W. Shi, “Well-Designed Three-Dimensional Hierarchical Hollow Tubular g-C3N4/Znln2S4 Nanosheets Heterostructure for Achieving Efficient Visible-Light Photocatalytic Hydrogen Evolution,” Journal of Colloid and Interface Science 607 (2022):1391–1401.

[19]

T. Feng, J. Jin, Y. Cao, H. Li, B. Dong, and L. Cao, “A Novel CoSeO3 Photocatalyst Assisting g-C3N4 in Enhancing Hydrogen Evolution through Z Scheme Mode,” International Journal of Hydrogen Energy 47, no. 9 (2022):5999–6010.

[20]

Y. Li, S. Zhu, Y. Liang, et al., “One-Step Synthesis of Mo and S Co-Doped Porous g-C3N4 Nanosheets for Efficient Visible-Light Photocatalytic Hydrogen Evolution,” Applied Surface Science 536 (2021):147743.

[21]

Y. Wu, W. Xu, N. W, et al., “Bridging and Bonding: Zinc and Potassium Co-Assisted Crystalline g-C3N4 for Significant Highly Efficient Upon Photocatalytic Hydrogen Evolution,” Applied Surface Science 542 (2021):148620.

[22]

H. Zhang, Y. Tang, Z. Liu, Z. Zhu, X. Tang, and Y. Wang, “Study on Optical Properties of Alkali Metal Doped g-C3N4 and Their Photocatalytic Activity for Reduction of CO2,” Chemical Physics Letters 751 (2020):137467.

[23]

J. Jiang, S. Cao, C. Hu, and C. Chen, “A Comparison Study of Alkali Metal-Doped g-C3N4 for Visible-Light Photocatalytic Hydrogen Evolution,” Chinese Journal of Catalysis 38, no. 12 (2017):1981–1989.

[24]

A. Mehtab and T. Ahmad, “Unveiling the Bifunctional Photo/Electrocatalytic Activity of In Situ Grown CdSe QDs on g-C3N4 Nanosheet Z-Scheme Heterostructures for Efficient Hydrogen Generation,” ACS Catalysis 14, no. 2 (2024):691–702.

[25]

C. Cui, G. Zhang, Y. Yang, T. Wu, and L. Wang, “Ultra-Thin Carbon Bridged MoC Quantum Dots/g-C3N4 With Charge-Transfer-Reaction Highways for Boosting Photocatalytic Hydrogen Production,” Journal of Alloys and Compounds 910 (2022):164864.

[26]

H. Hua, F. Feng, M. Du, et al., “0D-2D Z-Scheme Photocatalyst Cd0.5Zn0.5S@Bi2Fe4O9 for Effective Hydrogen Evolution From Water,” Applied Surface Science 541 (2021):148428.

[27]

J. Li, L. Liu, Q. Liang, et al., “Novel Triptycene-Based Microporous Polymers Decorated With Cd0.5Zn0.5S Quantum Dots to Form 0D/3D Heterojunction for Efficient Photocatalytic Hydrogen Evolution,” International Journal of Hydrogen Energy 45, no. 38 (2020):18985–18994.

[28]

X. Chen, R. Guo, W. Pan, et al., “A Novel Double S-Scheme Photocatalyst Bi7O9I3/Cd0.5Zn0.5S QDs/WO3-X With Efficient Full-Spectrum-Induced Phenol Photodegradation,” Applied Catalysis, B: Environmental 318 (2022):121839.

[29]

F. Mei, Z. Li, K. Dai, J. Zhang, and C. Liang, “Step-Scheme Porous g-C3N4/Zn0.2Cd0.8S-Deta Composites for Efficient and Stable Photocatalytic H2 Production,” Chinese Journal of Catalysis 41, no. 1 (2020):41–49.

[30]

D. Qin, Y. Xia, Q. Li, C. Yang, Y. Qin, and K. Lv, “One-Pot Calcination Synthesis of Cd0.5Zn0.5S/g-C3N4 Photocatalyst With a Step-Scheme Heterojunction Structure,” Journal of Materials Science &Technology 56 (2020):206–215.

[31]

L. Yu, X. Zhao, J. He, et al., “High Efficient and Stable Z-Scheme g-C3N4/Zn0.5Cd0.5S Photocatalyst Driven by Visible Light for Hydrogen Evolution,” Materials Science and Engineering: B 286 (2022):116062.

[32]

M. Zhang, X. Bai, D. Liu, J. Wang, and Y. Zhu, “Enhanced Catalytic Activity of Potassium-Doped Graphitic Carbon Nitride Induced by Lower Valence Position,” Applied Catalysis, B: Environmental 164 (2015):77–81.

[33]

X. Liu, D. Wen, Z. Liu, J. Wei, D. Bu, and S. Huang, “Thiocyanate-Capped CdSe@Zn1-XCdXS Gradient Alloyed Quantum Dots for Efficient Photocatalytic Hydrogen Evolution,” Chemical Engineering Journal 402 (2020):126178.

[34]

Y. Li, D. Zhang, X. Feng, and Q. Xiang, “Enhanced Photocatalytic Hydrogen Production Activity of Highly Crystalline Carbon Nitride Synthesized by Hydrochloric Acid Treatment,” Chinese Journal of Catalysis 41, no. 1 (2020):21–30.

[35]

Y. Sun, D. Jin, Y. Sun, et al., “g-C3N4/Ti3C2TX(MXenes) Composite With Oxidized Surface Groups for Efficient Photocatalytic Hydrogen Evolution,” Journal of Materials Chemistry A 6, no. 19 (2018):9124–9131.

[36]

D. Zheng, C. Pang, Y. Liu, and X. Wang, “Shell-Engineering of Hollow g-C3N4 Nanospheres via Copolymerization for Photocatalytic Hydrogen Evolution,” Chemical Communications 51, no. 47 (2015):9706–9709.

[37]

T. Bai, X. Shi, M. Liu, H. Huang, J. Zhang, and X.-H. Bu, “g-C3N4/ZnCDs Heterojunction for Efficient Visible Light-Driven Photocatalytic Hydrogen Production,” RSC Advances 11, no. 60 (2021):38120–38125.

[38]

S. Zhao, J. Huang, Q. Huo, X. Zhou, and W. Tu, “A Non-Noble Metal MoS2-Cd0.5Zn0.5S Photocatalyst With Efficient Activity for High H2 Evolution Under Visible Light Irradiation,” Journal of Materials Chemistry A 4, no. 1 (2016):193–199.

[39]

S. Wang, J. Liu, Y. Huang, and N. Yang, “Selective Sensing of Mn2+ Based on ZnCdS/ZnS QD/Carboxymethyl Chitosan/g-C3N4 Nanosheet Nanocomposite Film by the Conformational Regulation of Polymer Chain,” Applied Surface Science 530 (2020):147255.

[40]

J. Zhang, Y. Wang, J. Jin, et al., “Efficient Visible-Light Photocatalytic Hydrogen Evolution and Enhanced Photostability of Core/Shell CdS/g-C3N4 Nanowires,” ACS Applied Materials &Interfaces 5, no. 20 (2013):10317–10324.

[41]

H. J. Kong, D. H. Won, J. Kim, and S. I. Woo, “Sulfur-Doped g-C3N4/BiVO4 Composite Photocatalyst for Water Oxidation Under Visible Light,” Chemistry of Materials 28, no. 5 (2016):1318–1324.

[42]

S. Li, W. Si, L. Cui, and L. Shi, “Improved Photocatalytic H2 Evolution Performance of Mesoporous Graphitic Carbon Nitride With Cyano-Group,” Diamond and Related Materials 110 (2020):108149.

[43]

J. Fu, Q. Xu, J. Low, C. Jiang, and J. Yu, “Ultrathin 2D/2D WO3/g-C3N4 Step-Scheme H2-Production Photocatalyst,” Applied Catalysis, B: Environmental 243 (2019):556–565.

[44]

L. Ma, C. Lin, W. Jiang, et al., “Achieving Highly Efficient Photocatalytic Hydrogen Evolution through the Construction of g-C3N4@PdS@Pt Nanocomposites,” Molecules 29, no. 2 (2024):493.

[45]

J. Zhang, X. Fu, Y. Guo, et al., “CAZ Composite Photocatalysts for H2 Production and Degradation under Visible Light,” Langmuir 40, no. 24 (2024):12512–12525.

[46]

H. Li, Y. Wang, S. Wang, and X. Xiao, “The Preparation of g-C3N4/Znln2S4 Nano-Heterojunctions and Their Enhanced Efficient Photocatalytic Hydrogen Production,” Molecules 29, no. 11 (2024):2571.

[47]

F. Dong, Y. Li, Z. Wang, and W.-K. Ho, “Enhanced Visible Light Photocatalytic Activity and Oxidation Ability of Porous Graphene-Like g-C3N4 Nanosheets via Thermal Exfoliation,” Applied Surface Science 358 (2015):393–403.

[48]

G. Di, Z. Zhu, H. Zhang, et al., “Visible-Light Degradation of Sulfonamides by Z-Scheme ZnO/g-C3N4 Heterojunctions With Amorphous Fe2O3 as Electron Mediator,” Journal of Colloid and Interface Science 538 (2019):256–266.

[49]

Z. You, X. Yue, D. Zhang, J. Fan, and Q. Xiang, “Construction 0D/2D Heterojunction by Highly Dispersed Ag2S Quantum Dots (QDs) Loaded on the g-C3N4 Nanosheets for Photocatalytic Hydrogen Evolution,” Journal of Colloid and Interface Science 607 (2022):662–675.

[50]

W. Fan, H. Chang, J. Zhong, et al., “Facile Synthesis of ZnCds Quantum Dots via a Novel Photoetching MOF Strategy for Boosting Photocatalytic Hydrogen Evolution,” Separation and Purification Technology 330 (2024):125258.

[51]

Y. Li, P. Zhu, N. Tsubaki, and Z. Jin, “Fabrication of Hierarchical CoP/ZnCdS/Co3O4 Quantum Dots (800≫40≫4.5 nm) Bi-Heterostructure Cages for Efficient Photocatalytic Hydrogen Evolution,” Renewable Energy 198 (2022):626–636.

[52]

J. Chen, S. Lv, Z. Shen, P. Tian, J. Chen, and Y. Li, “Novel ZnCds Quantum Dots Engineering for Enhanced Visible-Light-Driven Hydrogen Evolution,” ACS Sustainable Chemistry &Engineering 7, no. 16 (2019):13805–13814.

[53]

L. Ding, Y. Tang, S. Wang, Y. Zhang, X. Chen, and H. Zhou, “Construction of Interfacial Electric Field via Bimetallic Mo2Ti2C3 QDs/g-C3N4 Heterojunction Achieves Efficient Photocatalytic Hydrogen Evolution,” Journal of Colloid and Interface Science 653 (2024):1671–1682.

[54]

L. Shao, D. Jiang, P. Xiao, L. Zhu, S. Meng, and M. Chen, “Enhancement of g-C3N4 Nanosheets Photocatalysis by Synergistic Interaction of ZnS Microsphere and RGO Inducing Multistep Charge Transfer,” Applied Catalysis, B: Environmental 198 (2016):200–210.

[55]

X. Zhou, X. Wang, X. Feng, et al., “Loading Cd0.5Zn0.5S Quantum Dots Onto Onion-Like Carbon Nanoparticles to Boost Photocatalytic Hydrogen Generation,” ACS Applied Materials &Interfaces 9, no. 27 (2017):22560–22567.

[56]

X.-Q. Tan, P. Zhang, B. Chen, A. R. Mohamed, and W.-J. Ong, “Synergistic Effect of Dual Phase Cocatalysts: MoC-MO2C Quantum Dots Anchored on g-C3N4 for High-Stability Photocatalytic Hydrogen Evolution,” Journal of Colloid and Interface Science 662 (2024):870–882.

[57]

J. Zhang, Y. Zhao, K. Qi, and S. Liu, “CuInS2 Quantum-Dot-Modified g-C3N4 S-Scheme Heterojunction Photocatalyst for Hydrogen Production and Tetracycline Degradation,” Journal of Materials Science &Technology 172 (2024):145–155.

[58]

X. Li, Z. Wang, J. Zhang, K. Dai, K. Fan, and G. Dawson, “Branch-Like CdxZn1-xSe/Cu2O@Cu Step-Scheme Heterojunction for CO2 Photoreduction,” Materials Today Physics 26 (2022):100729.

[59]

X. Li, Y. Hu, F. Dong, et al., “Non-Noble-Metallic Ni2P Nanoparticles Modified OV-BiOBr With Boosting Photoelectrochemical Hydrogen Evolution Without Sacrificial Agent,” Applied Catalysis, B: Environmental 325 (2023):122341.

[60]

J. H. Lee, S. Y. Jeong, Y. D. Son, and S. W. Lee, “Facile Fabrication of TiO2 Quantum Dots-Anchored g-C3N4 Nanosheets as 0D/2D Heterojunction Nanocomposite for Accelerating Solar-Driven Photocatalysis,” Nanomaterials 13, no. 9 (2023):1565.

[61]

H. Wang, Z. Liu, L. Wang, et al., “Fabrication of g-C3N4/Sns2 Type-II Heterojunction for Efficient Photocatalytic Conversion of CO2,” Journal of Materials Science: Materials in Electronics 34, no. 5 (2023):350.

[62]

A. B. Yousaf, M. Imran, M. Farooq, S. Kausar, S. Yasmeen, and P. Kasak, “Graphitic Carbon Nitride Nanosheets Decorated With Zinc-Cadmium Sulfide for Type-II Heterojunctions for Photocatalytic Hydrogen Production,” Nanomaterials 13, no. 18 (2023):2609.

[63]

B. Tatykayev, B. Chouchene, L. Balan, et al., “Heterostructured g-CN/TiO2 Photocatalysts Prepared by Thermolysis of g-CN/MIL-125(Ti) Composites for Efficient Pollutant Degradation and Hydrogen Production,” Nanomaterials 10, no. 7 (2020):1387.

[64]

L. Wang, R. Lian, Y. Zhang, et al., “Rational Preparation of Cocoon-Like g-C3N4/COF Hybrids: Accelerated Intramolecular Charge Delivery for Photocatalytic Hydrogen Evolution,” Applied Catalysis, B: Environmental 315 (2022):121568.

[65]

Y. Che, Q. Liu, B. Lu, J. Zhai, K. Wang, and Z. Liu, “Plasmonic Ternary Hybrid Photocatalyst Based on Polymeric g-C3N4 Towards Visible Light Hydrogen Generation,” Scientific Reports 10, no. 1 (2020):721.

[66]

L. Ge, F. Zuo, J. Liu, et al., “Synthesis and Efficient Visible Light Photocatalytic Hydrogen Evolution of Polymeric g-C3N4 Coupled With CdS Quantum Dots,” The Journal of Physical Chemistry C 116, no. 25 (2012):13708–13714.

[67]

X. Qin, R. Cao, W. Gong, et al., “Hydrothermal Growth of ZnCds/TiO2 Nanoparticles on the Surface of the Ti3C2 Mxene Sheet to Enhance Photocatalytic Performance Under Visible Light,” Journal of Solid State Chemistry 306 (2022):122750.

[68]

C. Zheng, G. Jiang, and Z. Jin, “ZnCdS/NiAl Hydrotalcite S-Scheme Heterojunction for Efficient Photocatalytic Hydrogen Evolution,” International Journal of Hydrogen Energy 47, no. 1 (2022):292–304.

[69]

Y. Wang, H. Jin, Y. Li, J. Fang, and C. Chen, “Ce-Based Organic Framework Enhanced the Hydrogen Evolution Ability of ZnCdS Photocatalyst,” International Journal of Hydrogen Energy 47, no. 2 (2022):962–970.

[70]

J. Jia, W. Sun, Q. Zhang, et al., “Inter-Plane Heterojunctions Within 2D/2D FeSe2/g-C3N4 Nanosheet Semiconductors for Photocatalytic Hydrogen Generation,” Applied Catalysis, B: Environmental 261 (2020):118249.

[71]

B. Wang, L. Huang, T. Peng, et al., “Attapulgite-Intercalated g-C3N4/ZnIn2S4 3D Hierarchical Z-Scheme Heterojunction for Boosting Photocatalytic Hydrogen Production,” Journal of Colloid and Interface Science 675 (2024):52–63.

RIGHTS & PERMISSIONS

2024 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.

AI Summary AI Mindmap
PDF

279

Accesses

0

Citation

Detail

Sections
Recommended

AI思维导图

/