Citation: Liu Yuan, Li Weidong, Wu Han, Lu Siyu. Carbon Dots Enhance Ruthenium Nanoparticles for Efficient Hydrogen Production in Alkaline[J]. Acta Physico-Chimica Sinica, ;2021, 37(7): 200908. doi: 10.3866/PKU.WHXB202009082 shu

Carbon Dots Enhance Ruthenium Nanoparticles for Efficient Hydrogen Production in Alkaline

Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450000, China

Corresponding author: Lu Siyu, sylu2013@zzu.edu.cn
Received Date: 26 September 2020
Revised Date: 21 October 2020
Accepted Date: 22 October 2020
Available Online: 27 October 2020
Fund Project: This work was supported by the National Natural Science Foundation of China (51973200, 21905253) and the China Postdoctoral Science Foundation (2018M640681, 2019T120632)the National Natural Science Foundation of China 21905253the China Postdoctoral Science Foundation 2018M640681the China Postdoctoral Science Foundation 2019T120632the National Natural Science Foundation of China 51973200

In the 21st century, hydrogen energy is a novel energy source. Its use is expected to mitigate the problems of environmental pollution and global warming caused by the excessive use of conventional fossil fuels. The hydrogen evolution reaction (HER) for water splitting has attracted considerable attention because of its environmental friendliness. To improve electrocatalyst performance and reduce operation cost, carbon-based metal hybrid materials exhibiting high efficiency and catalytic activity have been developed. Among them, carbon dots (CDs) have garnered significant research attention and have been widely applied in biosensing, bioimaging, and energy conversion/storage because of their facile synthesis, biocompatibility, tunable photoluminescence, excellent stability, and good electronic properties. CDs are widely used as carriers in the construction of electrocatalysts prepared from carbon-based metal hybrid materials. At present, it is believed that CDs exhibit excellent confinement effects, which can effectively inhibit the growth and agglomeration of metal nanoparticles, thereby preparing well-distributed carbon-based metal hybrid materials with a uniform and controllable size. However, the formation process of the small-molecule raw materials of CDs has not been elucidated. In this study, CDs and small-molecule raw materials from synthetic CDs were used as precursors to prepare nitrogen-doped CD-supported ruthenium nanoparticle (Ru@CDs) and small-molecule-supported ruthenium nanoparticle (Ru@Molecule) hybrid materials, respectively. The interaction between the small molecules and Ru in the process of CD formation and the effect on HER performance were explored. Moreover, we prepared different carriers such as metal organic frameworks(MOF), carbon nanotubes (CNTs), and graphene (GO)-supported ruthenium nanoparticle hybrid materials. Among them, Ru@CDs exhibited controllable size and excellent dispersibility and exhibited outstanding HER activity and good stability. Ru@CDs were found to require a low overpotential of 22 mV to reach a current density of 10 mA·cm⁻². Moreover, we observed the presence of an intermediate state between the molecules and CDs and demonstrated that the intermediate state exhibits no confinement effect. Furthermore, we found that with increasing calcination temperature, the intermediate state gradually changes to CDs. The unique spatial confinement between CDs and metal ions is key to the formation of monodisperse Ru nanoparticles. Our results confirmed that Ru@CDs serve as excellent HER catalyst supports. This work not only reveals the effect of the unique spatial confinement of CDs on the supported metals and their promoting effect on electrocatalytic activity but also provides guides the future development of CD-based metal hybrid electrocatalysts.
- Carbon dots,
- Carbon-base carriers,
- Hybrid materials,
- Hydrogen evolution reaction
1. [1]
  Cheng, X.; Li, Y.; Zheng, L.; Yan, Y.; Zhang, Y.; Chen, G.; Sun, S.; Zhang, J. Energy Environ. Sci. 2017, 10, 2450. doi: 10.1039/C7EE02537H doi: 10.1039/C7EE02537H
2. [2]
  Mahmood, J.; Li, F.; Jung, S. M.; Okyay, M. S.; Ahmad, I.; Kim, S. J.; Park, N.; Jeong, H. Y.; Baek, J. B. Nat. Nanotechnol. 2017, 12, 441. doi: 10.1038/nnano.2016.304 doi: 10.1038/nnano.2016.304
3. [3]
  Jiao, Y.; Zheng, Y.; Davey, K.; Qiao, S. Z. Nat. Energy 2016, 1, 16130. doi: 10.1038/nenergy.2016.130 doi: 10.1038/nenergy.2016.130
4. [4]
  Xia, Z. Nat. Energy 2016, 1, 16155. doi: 10.1038/nenergy.2016.155 doi: 10.1038/nenergy.2016.155
5. [5]
  Popczun, E. J.; Mckone, J. R.; Read, C. G.; Biacchi, A. J.; Wiltrout, A. M.; Lewis, N. S.; Schaak, R. S. J. Am. Chem. Soc. 2013, 135, 9267. doi: 10.1021/ja403440e doi: 10.1021/ja403440e
6. [6]
  Xing, Z.; Han, C.; Wang, D.; Li, Q.; Yang, X. ACS Catal. 2017, 7, 7131. doi: 10.1021/acscatal.7b01994 doi: 10.1021/acscatal.7b01994
7. [7]
  Cao, Z.; Chen, Q.; Zhang, J.; Li, H.; Jiang, Y.; Shen, S.; Fu, G.; Lu, B. A.; Xie, Z.; Zheng, L. Nat. Commun. 2017, 8, 15131. doi: 10.1038/ncomms15131 doi: 10.1038/ncomms15131
8. [8]
  Liu, Y.; Yong, X.; Liu, Z.; Chen, Z. M.; Kang, Z. H.; Lu, S. Y. Adv. Sustainable Syst. 2019, 3, 1800161. doi: 10.1002/adsu.201800161 doi: 10.1002/adsu.201800161
9. [9]
  Huang, L.; Zhang, X.; Wang, Q.; Han, Y.; Fang, Y.; Dong, S. J. Am. Chem. Soc. 2018, 140, 1142. doi: 10.1021/jacs.7b12353 doi: 10.1021/jacs.7b12353
10. [10]
  Geng, Z.; Liu, Y.; Kong, X.; Li, P.; Li, K.; Liu, Z.; Du, J.; Shu, M.; Si, R.; Zeng, J. Adv. Mater. 2018, 30, 1803498. doi: 10.1002/adma.201870301 doi: 10.1002/adma.201870301
11. [11]
  Xu, F.; Li, Y. J.; Huang, C.; Xu, H. C. ACS Catal. 2018, 8, 3820. doi: 10.1021/acscatal.8b00373 doi: 10.1021/acscatal.8b00373
12. [12]
  Song, Q.; Li, J.; Wang, S.; Liu, J.; Liu, X.; Pang, L.; Li, H.; Liu, H. Small 2019, 15, 1903395. doi: 10.1002/smll.201903395 doi: 10.1002/smll.201903395
13. [13]
  Yang, X.; Sun, J. K.; Kitta, M.; Pang, H.; Xu, Q. Nat. Catal. 2018, 1, 214. doi: 10.1038/s41929-018-0030-8 doi: 10.1038/s41929-018-0030-8
14. [14]
  Cui, X.; Li, W.; Ryabchuk, P.; Junge, K.; Belletr, M. Nat. Catal. 2018, 1, 385. doi: 10.1038/s41929-018-0090-9 doi: 10.1038/s41929-018-0090-9
15. [15]
  Cheng, Q.; Han, S.; Mao, K.; Chen, C.; Yang, L.; Zou, Z.; Gu, M.; Hu, Z.; Yang, H. Nano Energy 2018, 52, 485. doi: 10.1016/j.nanoen.2018.08.005 doi: 10.1016/j.nanoen.2018.08.005
16. [16]
  Ning, X.; Li, Y.; Dong, B.; Wang, H.; Yu, H.; Peng, F.; Yang, Y. J. Catal. 2017, 348, 100. doi: 10.1016/j.jcat.2017.02.011 doi: 10.1016/j.jcat.2017.02.011
17. [17]
  Li, J.; Zhou, P.; Li, F.; Ren, R.; Liu, Y.; Niu, J.; Ma, J.; Zhang, X.; Tian, M.; Jin, J.; et al. J. Mater. Chem. A 2015, 3, 11261. doi: 10.1039/C5TA01805F doi: 10.1039/C5TA01805F
18. [18]
  Chen, J.; Wang, J.; Chen, J.; Wang, L. J. Mater. Sci. 2017, 52, 13064. doi: 10.1007/s10853-017-1410-1 doi: 10.1007/s10853-017-1410-1
19. [19]
  Luo, F.; Zhang, Q.; Yu, X.; Xiao, S.; Ling, Y.; Hu, H.; Guo, L.; Yang, Z.; Huang, L.; Cai, W.; et al. Angew. Chem. Int. Ed. 2018, 57, 14862. doi: 10.1002/anie.201810102 doi: 10.1002/anie.201810102
20. [20]
  Jing, S.; Zhang, L.; Luo, L.; Lu, J.; Yin, S.; Shen, P. K.; Tsiakaras, P. Appl. Catal. B: Environ. 2018, 224, 533. doi: 10.1016/j.apcatb.2017.10.025 doi: 10.1016/j.apcatb.2017.10.025
21. [21]
  Bai, S.; Wang, C.; Deng, M.; Gong, M.; Bai, Y.; Jiang, J.; Xiong, Y. Angew. Chem. Int. Ed. 2014, 53, 12120. doi: 10.1002/anie.201406468 doi: 10.1002/anie.201406468
22. [22]
  Tavakkoli, M.; Holmberg, N.; Kronberg, R.; Jiang, H.; Sainio, J.; Kauppinen, E. I.; Kallio, T.; Laasonen, K. ACS Catal. 2017, 7, 3121. doi: 10.1021/acscatal.7b00199 doi: 10.1021/acscatal.7b00199
23. [23]
  Lu, S.; Sui, L.; Liu, J.; Zhu, S.; Chen, A.; Jin, M.; Yang, B. Adv. Mater. 2017, 29, 1603443. doi: 10.1002/adma.201603443 doi: 10.1002/adma.201603443
24. [24]
  Lu, S.; Xiao, G.; Sui, L.; Feng, T.; Yong, X.; Zhu, S.; Li, B.; Liu, Z.; Zou, B.; Jin, M. Angew. Chem. Int. Ed. 2017, 56, 6187. doi: 10.1002/anie.201700757 doi: 10.1002/anie.201700757
25. [25]
  Kong, B.; Tang, J.; Zhang, Y.; Jiang, T.; Gong, X.; Peng, C.; Wei, J.; Yang, J.; Wang, Y.; Wang, X.; et al. Nat. Chem. 2016, 8, 171. doi: 10.1038/nchem.2405 doi: 10.1038/nchem.2405
26. [26]
  Tang, J.; Kong, B.; Wu, H.; Xu, M.; Wang, Y.; Wang, Y.; Zhao, D.; Zheng, G. Adv. Mater. 2013, 25, 6569. doi: 10.1002/adma.201303124 doi: 10.1002/adma.201303124
27. [27]
  Lu, S.; Cong, R.; Zhu, S.; Zhao, X.; Liu, J.; Tse, J. S.; Meng, S.; Yang, B. ACS Appl. Mater. Interfaces 2016, 8, 4062. doi: 10.1021/acsami.5b11579 doi: 10.1021/acsami.5b11579
28. [28]
  Li, W.; Liu, Y.; Wu, M.; Feng, X.; Redfern, S. A. T.; Shang, Y.; Yong, X.; Feng, T.; Wu, K.; Liu, Z.; et al. Adv. Mater. 2018, 30, 1800676. doi: 10.1002/adma.201800676 doi: 10.1002/adma.201800676
29. [29]
  Liu, Y.; Li, X.; Zhang, Q.; Li, W.; Xie, Y.; Liu, H.; Shang, L.; Liu, Z.; Chen, Z.; Gu, L.; et al. Angew. Chem. Int. Ed. 2020, 59, 1718. doi: 10.1002/anie.201913910 doi: 10.1002/anie.201913910
30. [30]
  Song, H.; Li, Y.; Shang, L.; Tang, Z.; Zhang, T.; Lu, S. Nano Energy 2020, 72, 104730. doi: 10.1016/j.nanoen.2020.104730 doi: 10.1016/j.nanoen.2020.104730
31. [31]
  Liu, Y.; Yang, Y.; Peng, Z.; Liu, Z.; Chen, Z.; Shang, L.; Lu, S.; Zhang, T. Nano Energy 2019, 65, 104023. doi: 10.1016/j.nanoen.2019.104023 doi: 10.1016/j.nanoen.2019.104023
32. [32]
  Wang, B.; Li, J.; Tang, Z.; Yang, B.; Lu, S. Sci. Bull. 2019, 64, 1285. doi: 10.1016/j.scib.2019.07.021 doi: 10.1016/j.scib.2019.07.021
33. [33]
  Lu, S.; Zhao, X.; Zhu, S.; Song, Y.; Yang, B. Nanoscale 2014, 6, 13939. doi: 10.1039/C4NR03965C doi: 10.1039/C4NR03965C
34. [34]
  Li, W.; Wei, Z.; Wang, B.; Liu, Y.; Song, H.; Tang, Z.; Yang, B.; Lu, S. Mater. Chem. Front. 2020, 4, 277. doi: 10.1039/C9QM00618D doi: 10.1039/C9QM00618D
35. [35]
  Wang, P.; Zhang, X.; Zhang, J.; Wan, S.; Guo, S.; Lu, G.; Yao, J.; Huang, X. Nat. Commun. 2017, 8, 14580. doi: 10.1038/ncomms14580 doi: 10.1038/ncomms14580
36. [36]
  Wang, J.; Xu, F.; Jin, H.; Chen, Y.; Wang, Y. Adv. Mater. 2017, 29, 1605838. doi: 10.1002/adma.201605838 doi: 10.1002/adma.201605838
37. [37]
  Zheng, Y.; Jiao, Y.; Vasileff, A.; Qiao, S. -Z. Angew. Chem. Int. Ed. 2018, 57, 7568. doi: 10.1002/anie.201710556 doi: 10.1002/anie.201710556
38. [38]
  Morales-Guio, C. G.; Stern, L. -A.; Hu, X. Chem. Soc. Rev. 2014, 43, 6555. doi: 10.1039/C3CS60468C doi: 10.1039/C3CS60468C
39. [39]
  Zhang, C.; Liu, Y.; Chang, Y.; Lu, Y.; Zhao, S.; Xu, D.; Dai, Z.; Han, M.; Bao, J. ACS Appl. Mater. Interfaces 2017, 9, 17326. doi: 10.1021/acsami.7b01114 doi: 10.1021/acsami.7b01114
40. [40]
  Döner, A.; Tezcan, F.; Kardaş, G. Int. J. Hydrog. Energy 2013, 38, 3881. doi: 10.1016/j.ijhydene.2013.01.141 doi: 10.1016/j.ijhydene.2013.01.141
1. [1]
  Xiao Li , Wanqiang Yu , Yujie Wang , Ruiying Liu , Qingquan Yu , Riming Hu , Xuchuan Jiang , Qingsheng Gao , Hong Liu , Jiayuan Yu , Weijia Zhou . Metal-encapsulated nitrogen-doped carbon nanotube arrays electrode for enhancing sulfion oxidation reaction and hydrogen evolution reaction by regulating of intermediate adsorption. Chinese Chemical Letters, 2024, 35(8): 109166-. doi: 10.1016/j.cclet.2023.109166
2. [2]
  Quanxing Mao , Zhengliang Wang , Zhinan Hu , Ziqi Yang , Hui Li , Yali Yao , Zijun Yong , Tianyi Ma . Facial detection of formaldehyde by using acidichromic carbon dots and the reaction between formaldehyde and ammonium chloride. Chinese Chemical Letters, 2025, 36(7): 110499-. doi: 10.1016/j.cclet.2024.110499
3. [3]
  Sili Qing , Xuanzhao Lu , Yujing Jiang , Charitha Thambiliyagodage , Bing Song , Ao Xia , Jian-Rong Zhang , Wenlei Zhu , Li-Ping Jiang , Xiaoge Wu , Jun-Jie Zhu . ZIF-8 confined carbon dots/bilirubin oxidase on microalgal cells to boost oxygen reduction reaction in photo-biocatalytic fuel cells for pollutants removal. Chinese Chemical Letters, 2026, 37(1): 110576-. doi: 10.1016/j.cclet.2024.110576
4. [4]
  Yanan Zhou , Li Sheng , Lanlan Chen , Wenhua Zhang , Jinlong Yang . Axial coordinated iron-nitrogen-carbon as efficient electrocatalysts for hydrogen evolution and oxygen redox reactions. Chinese Chemical Letters, 2025, 36(1): 109588-. doi: 10.1016/j.cclet.2024.109588
5. [5]
  Yuting Fu , Haoran Wang , Nan Li , Lujiao Mao , Xusheng Wang , Qipeng Li , Jinjie Qian . Pt inclusion effect on Ni-ABDC-derived PtNi-carbon nanomaterials for hydrogen evolution. Chinese Chemical Letters, 2025, 36(10): 110890-. doi: 10.1016/j.cclet.2025.110890
6. [6]
  Ping Wang , Chunmao Chen , Hongwei Ren , Erhong Duan . A review of carbon dots in synthesis strategies, photoluminescence mechanisms, and applications in wastewater treatment. Chinese Chemical Letters, 2025, 36(9): 110725-. doi: 10.1016/j.cclet.2024.110725
7. [7]
  Yupeng Liu , Hui Wang , Songnan Qu . Review on near-infrared absorbing/emissive carbon dots: From preparation to multi-functional application. Chinese Chemical Letters, 2025, 36(5): 110618-. doi: 10.1016/j.cclet.2024.110618
8. [8]
  Zhuo Li , Peng Yu , Di Shen , Xinxin Zhang , Zhijian Liang , Baoluo Wang , Lei Wang . Low-loading Pt anchored on molybdenum carbide-based polyhedral carbon skeleton for enhancing pH-universal hydrogen production. Chinese Chemical Letters, 2025, 36(4): 109713-. doi: 10.1016/j.cclet.2024.109713
9. [9]
  Qiang Fu , Shouhong Sun , Kangzhi Lu , Ning Li , Zhanhua Dong . Boron-doped carbon dots: Doping strategies, performance effects, and applications. Chinese Chemical Letters, 2024, 35(7): 109136-. doi: 10.1016/j.cclet.2023.109136
10. [10]
  Chenghao Liu , Xiaofeng Lin , Jing Liao , Min Yang , Min Jiang , Yue Huang , Zhizhi Du , Lina Chen , Sanjun Fan , Qitong Huang . Carbon dots-based dopamine sensors: Recent advances and challenges. Chinese Chemical Letters, 2024, 35(12): 109598-. doi: 10.1016/j.cclet.2024.109598
11. [11]
  Quan Zhang , Shunjie Xing , Jingqian Han , Li Feng , Jianchun Li , Zhaosheng Qian , Jin Zhou . Organic pollutant sensing for human health based on carbon dots. Chinese Chemical Letters, 2025, 36(1): 110117-. doi: 10.1016/j.cclet.2024.110117
12. [12]
  Yuan Liu , Boyang Wang , Yaxin Li , Weidong Li , Siyu Lu . Understanding excitonic behavior and electroluminescence light emitting diode application of carbon dots. Chinese Chemical Letters, 2025, 36(2): 110426-. doi: 10.1016/j.cclet.2024.110426
13. [13]
  Xiangyuan Zhao , Jinjin Wang , Jinzhao Kang , Xiaomei Wang , Hong Yu , Cheng-Feng Du . Ni nanoparticles anchoring on vacuum treated Mo2TiC2Tx MXene for enhanced hydrogen evolution activity. Chinese Journal of Structural Chemistry, 2023, 42(10): 100159-100159. doi: 10.1016/j.cjsc.2023.100159
14. [14]
  Haibin Yang , Duowen Ma , Yang Li , Qinghe Zhao , Feng Pan , Shisheng Zheng , Zirui Lou . Mo doped Ru-based cluster to promote alkaline hydrogen evolution with ultra-low Ru loading. Chinese Journal of Structural Chemistry, 2023, 42(11): 100031-100031. doi: 10.1016/j.cjsc.2023.100031
15. [15]
  Jianye Kang , Xinyu Yang , Xuhao Yang , Jiahui Sun , Yuhang Liu , Shutao Wang , Wenlong Song . Carbon dots-enhanced pH-responsive lubricating hydrogel based on reversible dynamic covalent bondings. Chinese Chemical Letters, 2024, 35(5): 109297-. doi: 10.1016/j.cclet.2023.109297
16. [16]
  Rui Cheng , Tingting Zhang , Xin Huang , Jian Yu . Facile synthesis of high-brightness green-emitting carbon dots with narrow bandwidth towards backlight display. Chinese Chemical Letters, 2024, 35(5): 108763-. doi: 10.1016/j.cclet.2023.108763
17. [17]
  Wu-Jian Long , Yang Yu , Chuang He . A novel and promising engineering application of carbon dots: Enhancing the chloride binding performance of cement. Chinese Chemical Letters, 2024, 35(6): 108943-. doi: 10.1016/j.cclet.2023.108943
18. [18]
  Qiang Li , Jiangbo Fan , Hongkai Mu , Lin Chen , Yongzhen Yang , Shiping Yu . Nucleus-targeting orange-emissive carbon dots delivery adriamycin for enhanced anti-liver cancer therapy. Chinese Chemical Letters, 2024, 35(6): 108947-. doi: 10.1016/j.cclet.2023.108947
19. [19]
  Boran Cheng , Lei Cao , Chen Li , Fang-Yi Huo , Qian-Fang Meng , Ganglin Tong , Xuan Wu , Lin-Lin Bu , Lang Rao , Shubin Wang . Fluorine-doped carbon quantum dots with deep-red emission for hypochlorite determination and cancer cell imaging. Chinese Chemical Letters, 2024, 35(6): 108969-. doi: 10.1016/j.cclet.2023.108969
20. [20]
  Xiaoning Li , Quanyu Shi , Meng Li , Ningxin Song , Yumeng Xiao , Huining Xiao , Tony D. James , Lei Feng . Functionalization of cellulose carbon dots with different elements (N, B and S) for mercury ion detection and anti-counterfeit applications. Chinese Chemical Letters, 2024, 35(7): 109021-. doi: 10.1016/j.cclet.2023.109021

Get Citation

PDF

XML

Metrics

PDF Downloads(32)
Abstract views(1888)
HTML views(343)

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