Citation: Ran Chen, Juan Chen, Huinan Che, Gang Zhou, Yanhui Ao, Bin Liu. Atomically Dispersed Main Group Magnesium on Cadmium Sulfide as the Active Site for Promoting Photocatalytic Hydrogen Evolution Catalysis[J]. Chinese Journal of Structural Chemistry, ;2022, 41(1): 220101. doi: 10.14102/j.cnki.0254-5861.2021-0027 shu

Atomically Dispersed Main Group Magnesium on Cadmium Sulfide as the Active Site for Promoting Photocatalytic Hydrogen Evolution Catalysis

Ran Chen ^{1, †} ,
Juan Chen ^{1, †} ,
Huinan Che ¹ ,
Gang Zhou ¹ ,
Yanhui Ao ^1,, ,
Bin Liu ^{2, 3,,}

1.
Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, College of Environment, Hohai University, Nanjing 210098, China
2.
School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637459, Singapore
3.
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore

Corresponding author: Yanhui Ao, andyao@hhu.edu.cn Bin Liu, liubin@ntu.edu.sg

^†

Received Date: 5 November 2021
Accepted Date: 1 December 2021

Figures(4)

Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis. Band structure engineering has been extensively applied to improve the light absorption of photocatalysts, however, most of the developed photocatalysts still suffer from low photocatalytic performance due to the limited active site(s) and fast recombination of photogenerated charge carriers. In this work, atomically dispersed main group magnesium (Mg) is introduced onto CdS monodispersed nanospheres, which greatly enhances the photocatalytic hydrogen evolution reaction. The photocatalytic hydrogen evolution reaction rate reaches 30.6 mmol·g_catalyst^-1·h^-1, which is about 11.8 and 2.5 times that of pure CdS and Pt (2 wt.%)-CdS. The atomically dispersed Mg on CdS acts as an electron sink to trap photogenerated electrons, and at the same time, greatly reduces the Gibbs free energy of hydrogen evolution reaction (HER) and accelerates HER.
- CdS,
- hydrogen,
- photocatalysis,
- atomically dispersed,
- main group metal
1. [1]
  Wang, J. F.; Chen, J.; Wang, P. F.; Hou, J.; Wang, C.; Ao, Y. H. Robust photocatalytic hydrogen evolution over amorphous ruthenium phosphide quantum dots modified g-C₃N₄ nanosheet. Appl. Catal. B-Environ. 2018, 239, 578–585. doi: 10.1016/j.apcatb.2018.08.048
2. [2]
  Lin, H. X.; Chen, C. P.; Zhou, T. H.; Zhang, J. Two-dimensional covalent-organic frameworks for photocatalysis: the critical roles of building block and linkage. Solar RRL 2020, 5, 2000458.
3. [3]
  Ouyang, T.; Wang, X. T.; Mai, X. Q.; Chen, A. N.; Tang, Z. Y.; Liu, Z. Q. Coupling magnetic single-crystal Co₂Mo₃O₈ with ultrathin nitrogen-rich carbon layer for oxygen evolution reaction. Angew. Chem. Int. Ed. 2020, 9, 11948–11957.
4. [4]
  Mu, R. H.; Ao, Y. H.; Wu, T. F.; Wang, C.; Wang, P. F. Synergistic effect of molybdenum nitride nanoparticles and nitrogen-doped carbon on enhanced photocatalytic hydrogen evolution performance of CdS nanorods. J. Alloy. Compd. 2020, 812, 151990. doi: 10.1016/j.jallcom.2019.151990
5. [5]
  Jiang, X. H.; Zhang, L. S.; Liu, H. Y.; Wu, D. S.; Wu, F. Y.; Tian, L.; Liu, L. L; Zou, J. P.; Luo, S. L.; Chen, B. B. Silver single atom in carbon nitride catalyst for highly efficient photocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 2020, 59, 23112–23116. doi: 10.1002/anie.202011495
6. [6]
  Wang, J. F.; Wang, P. F.; Wang, C.; Ao, Y. H. In-situ synthesis of well dispersed CoP nanoparticles modified CdS nanorods composite with boosted performance for photocatalytic hydrogen evolution. Int. J. Hydrogen Energ. 2018, 43, 14934–14943. doi: 10.1016/j.ijhydene.2018.06.101
7. [7]
  Che, H. N.; Gao, X.; Chen, J.; Hou, J.; Ao, Y. H.; Wang, P. F. Iodide-induced fragmentation of polymerized hydrophilic carbon nitride for high-performance quasi-homogeneous photocatalytic H₂O₂ production. Angew. Chem. Int. Ed. 2020, 60, 25546–25550.
8. [8]
  Liu, X.; Zhao, Y. X.; Yang, X. F.; Liu, Q. Q.; Yu, X. H.; Li, Y. Y.; Tang, H.; Zhang, T. R. Porous Ni₅P₄ as a promising cocatalyst for boosting the photocatalytic hydrogen evolution reaction performance. Appl. Catal. B: Environ. 2020, 275, 119144. doi: 10.1016/j.apcatb.2020.119144
9. [9]
  Liu, M. R.; Hong, Q. L.; Li, Q. H.; Du, Y. H.; Zhang, H. X.; Chen, S. M.; Zhou, T. H.; Zhang, J. Cobalt boron imidazolate framework derived cobalt nanoparticles encapsulated in B/N codoped nanocarbon as efficient bifunctional electrocatalysts for overall water splitting. Adv. Funct. Mater. 2018, 28, 1801136. doi: 10.1002/adfm.201801136
10. [10]
  Zhou, S. Q.; Wang, Y.; Zhou, K.; Ba, D. Y.; Ao, Y. H.; Wang, P. F. In-situ construction of Z-scheme g-C₃N₄/WO₃ composite with enhanced visible-light responsive performance for nitenpyram degradation. Chin. Chem. Lett. 2021, 32, 2179–2182. doi: 10.1016/j.cclet.2020.12.002
11. [11]
  Yang, M. Q.; Han, C.; Xu, Y. J. Insight into the effect of highly dispersed MoS₂ versus layer-structured MoS₂ on the photocorrosion and photoactivity of CdS in graphene-CdS-MoS₂ composites. J. Phys. Chem. C 2015, 119, 27234–27246. doi: 10.1021/acs.jpcc.5b08016
12. [12]
  Shi, R.; Ye, H. F.; Liang, F.; Wang, Z.; Li, K.; Weng, Y. X.; Lin, Z. S.; Fu, W. F.; Che, C. M.; Chen, Y. Interstitial P-doped CdS with long-lived photogenerated electrons for photocatalytic water splitting without sacrificial agents. Adv. Mater. 2018, 1705941.
13. [13]
  Li, W.; Lee, J. R.; Jackel, F. Simultaneous optimization of colloidal stability and interfacial charge transfer efficiency in photocatalytic Pt/CdS nanocrystals. ACS Appl. Mater. Interfaces 2016, 8, 29434–29441. doi: 10.1021/acsami.6b09364
14. [14]
  Wang, J. F.; Wang, P. F.; Hou, J.; Qian, J.; Wang, C.; Ao, Y. H. In situ surface engineering of ultrafine Ni₂P nanoparticles on cadmium sulfide for robust hydrogen evolution. Catal. Sci. Technol. 2018, 8, 5406–5415. doi: 10.1039/C8CY00519B
15. [15]
  Yin, X. L.; He, G. Y.; Sun, B.; Jiang, W. J.; Xue, D. J.; Xia, A. D.; Wan, L. J.; Hu, J. S. Rational design and electron transfer kinetics of MoS₂/CdS nanodots-on-nanorods for efficient visible-light-driven hydrogen generation. Nano Energy 2016, 28, 319–329. doi: 10.1016/j.nanoen.2016.08.037
16. [16]
  Ma, X. W.; Lin, H. F.; Li, Y. Y.; Wang, L.; Pu, X. P.; Yi, X. J. Dramatically enhanced visible-light-responsive H₂ evolution of Cd_1-xZn_xS via the synergistic effect of Ni₂P and 1T/2H MoS₂ cocatalysts. Chin. J. Struct. Chem. 2021, 40, 7–22.
17. [17]
  Li, M. X.; Guan, R. Q.; Li, J. X.; Zhao, Z.; Zhang, J. K.; Dong, C. C.; Qi, Y. F.; Zhai, H. J. Performance and mechanism research of Au-HSTiO₂ on photocatalytic hydrogen production. Chin. J. Struct. Chem. 2020, 39, 1437–1443.
18. [18]
  Ran, J. R.; Gao, G. P.; Li, F. T.; Ma, T. Y.; Du, A. J.; Qiao, S. Z. Ti₃C₂ MXene co-catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production. Nat. Commun. 2017, 8, 1–10. doi: 10.1038/s41467-016-0009-6
19. [19]
  Ran, J. R.; Zhang, J.; Yu, J. G.; Jaroniec, M.; Qiao, S. Z. Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. Chem. Soc. Rev. 2014, 43, 7787–7812. doi: 10.1039/C3CS60425J
20. [20]
  Yao, X. X.; Hu, X. L.; Cui, Y. Y.; Huang, J. L.; Zhang, W. J.; Wang, X. H.; Wang, D. W. Effect of Mie resonance on photocatalytic hydrogen evolution over dye-sensitized hollow C-TiO₂ nanoshells under visible light irradiation. Chin. Chem. Lett. 2021, 32, 1135–1138. doi: 10.1016/j.cclet.2020.08.043
21. [21]
  Bi, W. T.; Li, X. G.; Zhang, L.; Jin, T.; Zhang, L. D.; Zhang, Q.; Luo, Y.; Wu, C. Z.; Xie, Y. Molecular co-catalyst accelerating hole transfer for enhanced photocatalytic H₂ evolution. Nat. Commun. 2015, 6, 8647. doi: 10.1038/ncomms9647
22. [22]
  Yu, F.; Wang, L. C.; Xing, Q. J.; Wang, D. K.; Jiang, X. H.; Li, G. C.; Zheng, A. M.; Ai, F. R.; Zoua, J. P. Functional groups to modify g-C₃N₄ for improved photocatalytic activity of hydrogen evolution from water splitting. Chin. Chem. Lett. 2020, 31, 1648–1653. doi: 10.1016/j.cclet.2019.08.020
23. [23]
  Zhang, H. B.; Wang, Y.; Zuo, S. W.; Zhou, W.; Zhang, J.; Lou, X. W. D. Isolated cobalt centers on W₁₈O₄₉ nanowires perform as a reaction switch for efficient CO₂ photoreduction. J. Am. Chem. Soc. 2021, 143, 2173–2177. doi: 10.1021/jacs.0c08409
24. [24]
  Cheng, N. C.; Stambula, S.; Wang, D.; Banis, M. N.; Liu, J.; Riese, A.; Xiao, B. W.; Li, R. Y.; Sham, T. K.; Liu, L. M. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nat. Commun. 2016, 7, 13638. doi: 10.1038/ncomms13638
25. [25]
  Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981–5079. doi: 10.1021/acs.chemrev.7b00776
26. [26]
  Lai, W. H.; Miao, Z. C.; Wang, Y. X.; Wang, J. Z.; Chou, S. L. Atomic-local environments of single-atom catalysts: synthesis, electronic structure, and activity. Adv. Energy Mater. 2019, 9, 1900722. doi: 10.1002/aenm.201900722
27. [27]
  Ding, S. P.; Hulsey, M. J.; Perez-Ramirez, J.; Yang, N. Transforming energy with single-atom catalysts. Joule 2019, 3, 2897–2929. doi: 10.1016/j.joule.2019.09.015
28. [28]
  Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981–5079. doi: 10.1021/acs.chemrev.7b00776
29. [29]
  Zhu, B. J.; Qiu, K. P.; Shang, C. X.; Guo, Z. X. Naturally derived porous carbon with selective metal-and/or nitrogen-doping for efficient CO₂ capture and oxygen reduction. J. Mater. Chem. A 2015, 3, 5212–5222. doi: 10.1039/C4TA06072E
30. [30]
  Mahajan, R.; Prakash, R.; Kumar, S.; Kumar, V.; Choudhary, R. J.; Phase, D. M. Surface and luminescent properties of Mg₃(PO₄)₂: Dy³⁺ phosphors. Optik 2021, 225, 165717. doi: 10.1016/j.ijleo.2020.165717
31. [31]
  Du, C. L.; Zhu, Y. Q.; Wang, Z. T.; Wang, L. Q.; Younas, W.; Ma, X. L.; Cao, C. B. Cuprous self-doping regulated mesoporous CuS nanotube cathode materials for rechargeable magnesium batteries. ACS Appl. Mater. Interfaces 2020, 12, 35035–35042. doi: 10.1021/acsami.0c09466
32. [32]
  Yuan, Y. J.; Chen, D. Q.; Yang, S. H.; Yang, L. X.; Wang, J. J.; Cao, D. P.; Tu, W. G.; Yu, Z. T.; Zou, Z. G. Constructing noble-metal-free Z-scheme photocatalytic overall water splitting systems using MoS₂ nanosheets modified CdS as a H₂ evolution photocatalyst. J. Mater. Chem. A 2013, 5, 21205–21213.
33. [33]
  Kumar, D. P.; Hong, S.; Reddy, D. A.; Kim, T. K. Ultrathin MoS₂ layers anchored exfoliated reduced graphene oxide nanosheet hybrid as a highly efficient cocatalyst for CdS nanorods towards enhanced photocatalytic hydrogen production. Appl. Catal. B-Environ. 2017, 212, 7–14. doi: 10.1016/j.apcatb.2017.04.065
34. [34]
  Ildefonse, P.; Calas, G.; Flank, A. M.; Lagarde, P. Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems. Nucl. Instrum. Methods Phys. Res. Sect. B: Beam Interact. Mater. At. 1995, 97, 172–175. doi: 10.1016/0168-583X(94)00710-1
35. [35]
  Yoshimura, T.; Tamenori, Y.; Iwasaki, N.; Hasegawa, H.; Suzuki, A.; Kawahata, H. Magnesium K-edge XANES spectroscopy of geological standards. J. Synchrotron Radiat. 2013, 20, 734–740. doi: 10.1107/S0909049513016099
36. [36]
  Li, S.; Zhang, L. J.; Jiang, T. F.; Chen, L. P.; Lin, Y. H.; Wang, D. J.; Xie, T. F. Construction of shallow surface states through light Ni doping for high-efficiency photocatalytic hydrogen production of CdS nanocrystals. Chem. Eur. J. 2014, 20, 311–316. doi: 10.1002/chem.201302679
37. [37]
  Huang, Q. Z.; Tao, Z. J.; Ye, L. Q.; Yao, H. C.; Li, Z. J. Mn_0.2Cd_0.8S nanowires modified by CoP₃ nanoparticles for highly efficient photocatalytic H₂ evolution under visible light irradiation. Appl. Catal. B-Environ. 2018, 237, 689–698. doi: 10.1016/j.apcatb.2018.06.040
38. [38]
  Zhou, G.; Hu, Y. Y.; Long, L. Y.; Wang, P. F.; Shan, Y.; Wang, L. L.; Guo, J. H.; Zhang, C. G.; Zhang, Y. M.; Liu, L. Z. Charged excited state induced by ultrathin nanotip drives highly efficient hydrogen evolution. Appl. Catal. B-Environ. 2020, 262, 118305. doi: 10.1016/j.apcatb.2019.118305
1. [1]
  Kaihui Huang , Boning Feng , Xinghua Wen , Lei Hao , Difa Xu , Guijie Liang , Rongchen Shen , Xin Li . Effective photocatalytic hydrogen evolution by Ti3C2-modified CdS synergized with N-doped C-coated Cu2O in S-scheme heterojunctions. Chinese Journal of Structural Chemistry, 2023, 42(12): 100204-100204. doi: 10.1016/j.cjsc.2023.100204
2. [2]
  Jun LI , Huipeng LI , Hua ZHAO , Qinlong LIU . Preparation and photocatalytic performance of AgNi bimetallic modified polyhedral bismuth vanadate. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 601-612. doi: 10.11862/CJIC.20230401
3. [3]
  Wenda WANG , Jinku MA , Yuzhu WEI , Shuaishuai MA . Waste biomass-derived carbon modified porous graphite carbon nitride heterojunction for efficient photodegradation of oxytetracycline in seawater. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 809-822. doi: 10.11862/CJIC.20230353
4. [4]
  Huirong LIU , Hao XU , Dunru ZHU , Junyong ZHANG , Chunhua GONG , Jingli XIE . Syntheses, structures, photochromic and photocatalytic properties of two viologen-polyoxometalate hybrid materials. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1368-1376. doi: 10.11862/CJIC.20240066
5. [5]
  Fei ZHOU , Xiaolin JIA . Co₃O₄/TiO₂ composite photocatalyst: Preparation and synergistic degradation performance of toluene. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2232-2240. doi: 10.11862/CJIC.20240236
6. [6]
  Wenbiao Zhang , Bolong Yang , Zhonghua Xiang . Atomically dispersed Cu-based metal-organic framework directly for alkaline polymer electrolyte fuel cells. Chinese Chemical Letters, 2025, 36(2): 109630-. doi: 10.1016/j.cclet.2024.109630
7. [7]
  Yue Pan , Wenping Si , Yahao Li , Haotian Tan , Ji Liang , Feng Hou . Promoting exciton dissociation by metal ion modification in polymeric carbon nitride for photocatalysis. Chinese Chemical Letters, 2024, 35(12): 109877-. doi: 10.1016/j.cclet.2024.109877
8. [8]
  Zongyi Huang , Cheng Guo , Quanxing Zheng , Hongliang Lu , Pengfei Ma , Zhengzhong Fang , Pengfei Sun , Xiaodong Yi , Zhou Chen . Efficient photocatalytic biomass-alcohol conversion with simultaneous hydrogen evolution over ultrathin 2D NiS/Ni-CdS photocatalyst. Chinese Chemical Letters, 2024, 35(7): 109580-. doi: 10.1016/j.cclet.2024.109580
9. [9]
  Minying Wu , Xueliang Fan , Wenbiao Zhang , Bin Chen , Tong Ye , Qian Zhang , Yuanyuan Fang , Yajun Wang , Yi Tang . Highly dispersed Ru nanospecies on N-doped carbon/MXene composite for highly efficient alkaline hydrogen evolution. Chinese Chemical Letters, 2024, 35(4): 109258-. doi: 10.1016/j.cclet.2023.109258
10. [10]
  Xinyu Hou , Xuelian Yu , Meng Liu , Hengxing Peng , Lijuan Wu , Libing Liao , Guocheng Lv . Ultrafast synthesis of Mo₂N with highly dispersed Ru for efficient alkaline hydrogen evolution. Chinese Chemical Letters, 2025, 36(4): 109845-. doi: 10.1016/j.cclet.2024.109845
11. [11]
  Yaxuan Jin , Chao Zhang , Guigang Zhang . Atomically dispersed low-valent Au on poly(heptazine imide) boosts photocatalytic hydroxyl radical production. Chinese Journal of Structural Chemistry, 2024, 43(12): 100414-100414. doi: 10.1016/j.cjsc.2024.100414
12. [12]
  Lu Qi , Zhaoyang Chen , Xiaoyu Luan , Zhiqiang Zheng , Yurui Xue , Yuliang Li . Atomically dispersed Mn enhanced catalytic performance for overall water splitting on graphdiyne-coated copper hydroxide nanowire. Chinese Journal of Structural Chemistry, 2024, 43(1): 100197-100197. doi: 10.1016/j.cjsc.2023.100197
13. [13]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
14. [14]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
15. [15]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
16. [16]
  Yingqi BAI , Hua ZHAO , Huipeng LI , Xinran REN , Jun LI . Perovskite LaCoO₃/g-C₃N₄ heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 480-490. doi: 10.11862/CJIC.20240259
17. [17]
  Huizhong Wu , Ruiheng Liang , Ge Song , Zhongzheng Hu , Xuyang Zhang , Minghua Zhou . Enhanced interfacial charge transfer on Bi metal@defective Bi₂Sn₂O₇ quantum dots towards improved full-spectrum photocatalysis: A combined experimental and theoretical investigation. Chinese Chemical Letters, 2024, 35(6): 109131-. doi: 10.1016/j.cclet.2023.109131
18. [18]
  Guoliang Gao , Guangzhen Zhao , Guang Zhu , Bowen Sun , Zixu Sun , Shunli Li , Ya-Qian Lan . Recent advancements in noble-metal electrocatalysts for alkaline hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(1): 109557-. doi: 10.1016/j.cclet.2024.109557
19. [19]
  Jia-Cheng Hou , Wei Cai , Hong-Tao Ji , Li-Juan Ou , Wei-Min He . Recent advances in semi-heterogenous photocatalysis in organic synthesis. Chinese Chemical Letters, 2025, 36(2): 110469-. doi: 10.1016/j.cclet.2024.110469
20. [20]
  Jiangping Chen , Hongju Ren , Kai Wu , Huihuang Fang , Chongqi Chen , Li Lin , Yu Luo , Lilong Jiang . Boosting hydrogen production of ammonia decomposition via the construction of metal-oxide interfaces. Chinese Journal of Structural Chemistry, 2024, 43(2): 100236-100236. doi: 10.1016/j.cjsc.2024.100236

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(498)
HTML views(12)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142