Citation: WU Qing-An, CHEN Hao, HUANG Dao-Chen, XIA Liang-Min, WANG Xiao-Jing, LOU Wen-Ya, WU Xiao-Feng, LUO Shu-Ping. Alkoxy Phenanthrolines: Design, Synthesis and Heteroleptic Copper Complexes as Photosensitizers in Water Reduction for Hydrogen Production[J]. Chinese Journal of Inorganic Chemistry, ;2018, 34(2): 270-276. doi: 10.11862/CJIC.2018.057 shu

Alkoxy Phenanthrolines: Design, Synthesis and Heteroleptic Copper Complexes as Photosensitizers in Water Reduction for Hydrogen Production

1.
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China
2.
Yiwu Science and Technology Research Institute, Zhejiang University of Technology, Yiwu, Zhejiang 322001, China

Corresponding author: LUO Shu-Ping, Luoshuping@zjut.edu
Received Date: 11 September 2017
Revised Date: 8 November 2017

Figures(6)

Aimed in the development of functionalized nitrogen ligands, a series of novel 2, 9-dialkoxyl-4, 7-diphenyl-1, 10-phenanthroline ligands 5a~5e were designed and synthesized from 4, 7-diphenyl-1, 10-phenanthroline under quaternization, oxidation, halogenation and etherification. Then using Xantphos as phosphorus ligands, a series of heteroleptic copper photosensitizers (CuPS A~H) were obtained by the in-situ method. In homogeneous photocatalytic water reduction system, their photosensitive activity for hydrogen production was studied. Research results show that 2, 9-diethoxy is the preferred substituent and the turnover number for hydrogen production (TON) of CuPS D is up to 270. In the analysis of photoelectric physical properties, it is found that this kind of heteroleptic copper complexes have a pair of similar redox potentials (E^oxd=-0.8 V, E^red=-1.2 V). Compared with other substituents in Cu-based complexes, CuPS D shows the weakest fluorescence, which indicates the ethoxy substituent could improve the photochemical conversion ability of CuPS by increasing the fluorescence quenching efficiency.
- phenanthroline-modification,
- copper photosensitizer,
- hydrogen evolution from water splitting,
- structure-activation relationship
1. [1]
  Fang B, Bonakdarpour A, Reilly K, et al. ACS Appl. Mater. Interfaces, 2014, 6(17):15488-15498 doi: 10.1021/am504128t
2. [2]
  Teoh W Y, Scott J A, Amal R. J. Phys. Chem. Lett., 2012, 3(5):629-639 doi: 10.1021/jz3000646
3. [3]
  Kamat P V. J. Phys. Chem. Lett., 2012, 3(5):663-672 doi: 10.1021/jz201629p
4. [4]
  Fukuzumi S, Yamada Y, Suenobu T, et al. Energy Environ. Sci., 2011, 4(8):2754-2766 doi: 10.1039/c1ee01551f
5. [5]
  Xing Y, Fang B, Bonakdarpour A, et al. Int. J. Hydrogen Energy, 2014, 39(15):7859-7867 doi: 10.1016/j.ijhydene.2014.03.106
6. [6]
  Yuan Y J, Yu Z T, Chen D Q, et al. Chem. Soc. Rev., 2017, 46(3):603-631 doi: 10.1039/C6CS00436A
7. [7]
  Hiraishi T, Kamachi T, Okura I. J. Mol. Catal. A:Chem., 2000, 151(1):7-15
8. [8]
  Kitamoto K, Ogawa M, Ajayakumar G, et al. Inorg. Chem. Front., 2016, 3(5):671-680 doi: 10.1039/C5QI00150A
9. [9]
  Kitamoto K, Sakai K. Chem. Eur. J., 2016, 22(35):12381-12390 doi: 10.1002/chem.v22.35
10. [10]
  Probst B, Guttentag M, Rodenberg A, et al. Inorg. Chem., 2011, 50(8):3404-3412 doi: 10.1021/ic102317u
11. [11]
  Yamauchi K, Masaoka S, Sakai K. Dalton Trans., 2011, 40(46):12447-12449 doi: 10.1039/c1dt11217a
12. [12]
  Kitamoto K, Sakai K. Angew. Chem. Int. Ed., 2014, 53(18):4618-4622 doi: 10.1002/anie.201311209
13. [13]
  Yamamoto K, Kitamoto K, Yamauchi K, et al. Chem. Commun., 2015, 51(77):14516-14519 doi: 10.1039/C5CC03558A
14. [14]
  Kagalwala H N, Gottlieb E, Li G, et al. Inorg. Chem., 2013, 52(15):9094-9101 doi: 10.1021/ic4013069
15. [15]
  Guo W, Lv H, Bacsa J, et al. Inorg. Chem., 2016, 47(14):461-466
16. [16]
  Yuan Y J, Yu Z T, Liu X J, et al. Sci. Rep., 2014, 4(2):4045(9 pages)
17. [17]
  Mejía E, Luo S P, Karnahl M, et al. Chem. Eur. J., 2013, 19(47):15972-15978 doi: 10.1002/chem.201302091
18. [18]
  Karnahl M, Mejía E, Rockstroh N, et al. ChemCatChem, 2014, 6(1):82-86 doi: 10.1002/cctc.v6.1
19. [19]
  Fischer S, Hollmann D, Tschierlei S, et al. ACS Catal., 2014, 4(6):1845-1849 doi: 10.1021/cs500387e
20. [20]
  Khnayzer R S, McCusker C E, Olaiya B S, et al. J. Am. Chem. Soc., 2013, 135(38):14068-14070 doi: 10.1021/ja407816f
21. [21]
  Kim J, Whang D R, Park S Y. Chemsuschem, 2017, 10(9):1-5
22. [22]
  ZHANG Hong-Mei, CAO Hu-Jun, ZHANG Zhi-Yong, et al. Chin. J. Org. Chem., 2012, 32(3):621-623
23. [23]
  Guo H C, Zheng R H, Jiang H J. Org. Prep. Proced. Int., 2012, 44(4):392-396 doi: 10.1080/00304948.2012.697745
24. [24]
  Frey J, Kraus T, Heitz V, et al. Chem. Eur. J., 2007, 13(27):7584-7594 doi: 10.1002/(ISSN)1521-3765
25. [25]
  Luo S P, Mejía E, Friedrich A, et al. Angew. Chem. Int. Ed., 2013, 52(1):419-423 doi: 10.1002/anie.201205915
26. [26]
  Lennox A, Fischer S, Beller M, et al. Chem. Eur. J., 2016, 22(4):1233-1238 doi: 10.1002/chem.201503812
27. [27]
  Dooley D M, Scott R A, Knowles P F, et al. J. Am. Chem. Soc., 1998, 120(11):2599-2605 doi: 10.1021/ja970312a
28. [28]
  Chen N Y, Xia L M, Sun Y Y, et al. Chem. Eur. J., 2017, 23(15):3631-3636 doi: 10.1002/chem.v23.15
29. [29]
  Knorn M, Rawner T, Czerwieniec R, et al. ACS Catal., 2015, 5(9):5186-5193 doi: 10.1021/acscatal.5b01071
30. [30]
  Zhu B Y, Han L, Li Y J, et al. Tetrahedron, 2017, 73(12):1602-1610 doi: 10.1016/j.tet.2017.02.003
31. [31]
  XIA Liang-Min, CHEN Hao, WU Qing-An, et al. Chinese J. Inorg. Chem., 2017, 33(4):560-568 doi: 10.11862/CJIC.2017.075
1. [1]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . Research Progress on Carbon-based Catalysts for Catalytic Dehydrogenation of Liquid Organic Hydrogen Carriers. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-0. doi: 10.1016/j.actphy.2024.100044
2. [2]
  Junqing WEN , Ruoqi WANG , Jianmin ZHANG . Regulation of photocatalytic hydrogen production performance in GaN/ZnO heterojunction through doping with Li and Au. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 923-938. doi: 10.11862/CJIC.20240243
3. [3]
  Ruizhi Duan , Xiaomei Wang , Panwang Zhou , Yang Liu , Can Li . The role of hydroxyl species in the alkaline hydrogen evolution reaction over transition metal surfaces. Acta Physico-Chimica Sinica, 2025, 41(9): 100111-0. doi: 10.1016/j.actphy.2025.100111
4. [4]
  Lei Feng , Ze-Min Zhu , Ying Yang , Zongbin He , Jiafeng Zou , Man-Bo Li , Yan Zhao , Zhikun Wu . Long-Pursued Structure of Au₂₃(S-Adm)₁₆ and the Unexpected Doping Effects. Acta Physico-Chimica Sinica, 2024, 40(5): 2305029-0. doi: 10.3866/PKU.WHXB202305029
5. [5]
  Haiying Jiang , Liuhong Song , Yangyang Cheng , Kefen Yue , Mingli Peng , Huilin Guo . Ph―C≡C―Cu_2.5的力致变色现象探究——推荐一个物理化学实验. University Chemistry, 2025, 40(8): 249-254. doi: 10.12461/PKU.DXHX202410003
6. [6]
  Xue-Peng Zhang , Yuchi Long , Yushu Pan , Jiding Wang , Baoyu Bai , Rui Ding . 定量构效关系方法学习探索：以钴卟啉活化氧气为例. University Chemistry, 2025, 40(8): 345-359. doi: 10.12461/PKU.DXHX202410107
7. [7]
  Xi YANG , Chunxiang CHANG , Yingpeng XIE , Yang LI , Yuhui CHEN , Borao WANG , Ludong YI , Zhonghao HAN . Co-catalyst Ni₃N supported Al-doped SrTiO₃: Synthesis and application to hydrogen evolution from photocatalytic water splitting. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 440-452. doi: 10.11862/CJIC.20240371
8. [8]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
9. [9]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts. Acta Physico-Chimica Sinica, 2025, 41(3): 100024-0. doi: 10.3866/PKU.WHXB202404012
10. [10]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
11. [11]
  Chenyang WANG , Yiyan BAI , Wei ZHANG , Zhaorong LIU , Yuchun WANG . Performance of photo-assisted copper oxide catalyzed hydrolysis of ammonia borane to produce hydrogen. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 97-110. doi: 10.11862/CJIC.20250116
12. [12]
  Wei Sun , Yongjing Wang , Kun Xiang , Saishuai Bai , Haitao Wang , Jing Zou , Arramel , Jizhou Jiang . CoP Decorated on Ti₃C₂T_x MXene Nanocomposites as Robust Electrocatalyst for Hydrogen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015-0. doi: 10.3866/PKU.WHXB202308015
13. [13]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
14. [14]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Research on Cu-Based and Pt-Based Catalysts for Hydrogen Production through Methanol Steam Reforming. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-0. doi: 10.1016/j.actphy.2025.100049
15. [15]
  Asif Hassan Raza , Shumail Farhan , Zhixian Yu , Yan Wu . Double S-Scheme ZnS/ZnO/CdS Heterostructure Photocatalyst for Efficient Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(11): 2406020-0. doi: 10.3866/PKU.WHXB202406020
16. [16]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . Construction of 4-Amino-1H-imidazole-5-carbonitrile Modified Carbon Nitride-Based Donor-Acceptor Photocatalyst for Efficient Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-0. doi: 10.3866/PKU.WHXB202406026
17. [17]
  Shi-Yu Lu , Wenzhao Dou , Jun Zhang , Ling Wang , Chunjie Wu , Huan Yi , Rong Wang , Meng Jin . Amorphous-Crystalline Interfaces Coupling of CrS/CoS₂ Few-Layer Heterojunction with Optimized Crystallinity Boosted for Water-Splitting and Methanol-Assisted Energy-Saving Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(8): 2308024-0. doi: 10.3866/PKU.WHXB202308024
18. [18]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-0. doi: 10.3866/PKU.WHXB202312014
19. [19]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
20. [20]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1309)
HTML views(176)

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