Citation: Bao Yufei, Feng Ligang. Formic Acid Electro-Oxidation Catalyzed by PdNi/Graphene Aerogel[J]. Acta Physico-Chimica Sinica, ;2021, 37(9): 200803. doi: 10.3866/PKU.WHXB202008031 shu

Formic Acid Electro-Oxidation Catalyzed by PdNi/Graphene Aerogel

Bao Yufei ,
Feng Ligang ^,

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu Province, China

Corresponding author: Feng Ligang, ligang.feng@yzu.edu.cn
Received Date: 13 August 2020
Revised Date: 8 September 2020
Accepted Date: 8 September 2020
Available Online: 14 September 2020
Fund Project: the National Natural Science Foundation of China 21972124the National Natural Science Foundation of China 21603041The project was supported by the National Natural Science Foundation of China (21972124, 21603041)

Direct formic acid fuel cells involve two significant half-reactions, namely formic acid electro-oxidation and oxygen reduction reaction, and the more sluggish and complex process for anode formic acid oxide also determine the whole fuel cells energy conversion efficiency. The most efficient catalysts rely on the noble metal of Pt and Pd based catalysts and compared with Pt catalysts, Pd catalyst is more appealing because of the low CO poisoning effect during the electro-oxidation of formic acid that mainly follows the direct pathway. The Pd alloy effect and support effect should be considered for the catalyst fabrication since the resulted structure and electronic modification could largely increase the catalytic performance. Graphene emerges out as novel support while the easy agglomeration and destruction of pure graphene do not guarantee promising merits. In this work, we demonstrated the formic acid oxidation ability boosting by facile coupling PdNi alloy and 3D graphene aerogel (PdNi/GA) via a freezing-drying/thermal annealing reduction approach. The PdNi alloy crystal structure was well confirmed by the X-ray diffractions technique and the alloy nanoparticles were successfully anchored on the 3D graphene aerogel surface. The electrochemical performance was evaluated for formic acid oxidation in the acid electrolyte. The PdNi/GA catalyst displayed a larger peak current density of 136 mA·cm^-2, which was 2 and 3.45 times greater than Pd/GA (68 mA·cm^-2) and Pd/C (39.4 mA·cm^-2), respectively. The anti-CO poisoning ability was measured by CO stripping technique, and a low onset potential of 0.49 V was found on PdNi/GA catalyst, about 120 mV less than that of Pd/GA catalyst, indicating the oxophilic property of Ni to assist formic acid oxidation via the bi-functional mechanism. The oxidation peak potential of 0.67 V was observed on PdNi/GA, about 40 mV less than that of Pd/C catalyst, indicating the merits of 3D structure of graphene. Moreover, PdNi/GA catalyst had the highest mass activity of 1699 mA·mg^-1 compared to Pd/GA (851 mA·mg^-1) and Pd/C (537 mA·mg^-1) catalysts. The specific activity of PdNi/GA was 2.6 mA·cm^-2, which was 1.94 and 2.7 times of Pd/GA (1.34 mA·cm^-2) and Pd/C (0.96 mA·cm^-2) catalysts. The highly improved catalytic performance could be due to the combined alloy and support effect. The PdNi/GA was a promising catalyst for application in the direct formic acid fuel cells.
- Formic acid oxidation reaction,
- Direct formic acid fuel cell,
- Electrocatalyst,
- Pd-base catalyst,
- Graphene aerogel
1. [1]
  Feng, L.; Chang, J.; Jiang, K.; Xue, H.; Liu, C.; Cai, W. B.; Xing, W.; Zhang, J. Nano Energy 2016, 30, 355. doi: 10.1016/j.nanoen.2016.10.023 doi: 10.1016/j.nanoen.2016.10.023
2. [2]
  Ong, B. C.; Kamarudin, S. K.; Basri, S. Int. J. Hydrogen Energy 2017, 42, 10142. doi: 10.1016/j.ijhydene.2017.01.117 doi: 10.1016/j.ijhydene.2017.01.117
3. [3]
  Yang, J. L. Acta Phys. -Chim. Sin. 2020, 36, 2003010. doi: 10.3866/PKU.WHXB202003010
4. [4]
  Lü, Y.; Song, Y. J.; Liu, H. Y.; Li, H. Q. Acta Phys. -Chim. Sin. 2017, 33, 283. doi: 10.3866/PKU.WHXB201611071
5. [5]
  Li, Q. W.; Wei, Z. D.; Chen, S. G.; Qi, X. Q.; Liu, X.; Ding, W.; Ma, Y. Acta Phys. -Chim. Sin. 2011, 27, 2857. doi: 10.3866/PKU.WHXB20112857
6. [6]
  Hu, S.; Che, F.; Khorasani, B.; Jeon, M.; Yoon, C. W.; McEwen, J. S.; Scudiero, L.; Ha, S. Appl. Catal. B: Environ. 2019, 254, 685. doi: 10.1016/j.apcatb.2019.03.072 doi: 10.1016/j.apcatb.2019.03.072
7. [7]
  Romero Hernández, A.; Arce Estrada, E. M.; Ezeta, A.; Manríquez, M. E. Electrochim. Acta 2019, 327, 134977. doi: 10.1016/j.electacta.2019.134977 doi: 10.1016/j.electacta.2019.134977
8. [8]
  Fang, B.; Feng, L. G. Acta Phys. -Chim. Sin. 2020, 36, 1905023. doi: 10.3866/PKU.WHXB201905023
9. [9]
  Wang, F.; Xue, H.; Tian, Z.; Xing, W.; Feng, L. J. Power Sources 2018, 375, 37. doi: 10.1016/j.jpowsour.2017.11.055 doi: 10.1016/j.jpowsour.2017.11.055
10. [10]
  Jiang, K.; Zhang, H. X.; Zou, S.; Cai, W. B. Phys. Chem. Chem. Phys. 2014, 16, 20360. doi: 10.1039/C4CP03151B doi: 10.1039/C4CP03151B
11. [11]
  Liu, H.; Yang, D.; Bao, Y.; Yu, X.; Feng, L. J. Power Sources 2019, 434, 226754. doi: 10.1016/j.jpowsour.2019.226754 doi: 10.1016/j.jpowsour.2019.226754
12. [12]
  Bao, Y.; Wang, F.; Gu, X.; Feng, L. Nanoscale 2019, 11, 18866. doi: 10.1039/C9NR07158J doi: 10.1039/C9NR07158J
13. [13]
  Bin, D.; Yang, B.; Ren, F.; Zhang, K.; Yang, P.; Du, Y. J. Mater. Chem. A 2015, 3, 14001. doi: 10.1039/C5TA02829A doi: 10.1039/C5TA02829A
14. [14]
  Chen, W.; Xue, J.; Bao, Y.; Feng, L. Chem. Eng. J. 2020, 381, 122752. doi: 10.1016/j.cej.2019.122752 doi: 10.1016/j.cej.2019.122752
15. [15]
  Zhang, X.; Zhu, J.; Tiwary, C. S.; Ma, Z.; Huang, H.; Zhang, J.; Lu, Z.; Huang, W.; Wu, Y. ACS Appl. Mater. Interfaces 2016, 8, 10858. doi: 10.1021/acsami.6b01580 doi: 10.1021/acsami.6b01580
16. [16]
  Siller-Ceniceros, A. A.; Sánchez-Castro, M. E.; Morales-Acosta, D.; Torres-Lubian, J. R.; Martínez G, E.; Rodríguez-Varela, F. J. Appl. Catal. B: Environ. 2017, 209, 455. doi: 10.1016/j.apcatb.2017.03.023 doi: 10.1016/j.apcatb.2017.03.023
17. [17]
  Tzorbatzoglou, F.; Brouzgou, A.; Jing, S.; Wang, Y.; Song, S.; Tsiakaras, P. Int. J. Hydrogen Energy 2018, 43, 11766. doi: 10.1016/j.ijhydene.2018.02.071 doi: 10.1016/j.ijhydene.2018.02.071
18. [18]
  Perivoliotis, D. K.; Tagmatarchis, N. Carbon 2017, 118, 493. doi: 10.1016/j.carbon.2017.03.073 doi: 10.1016/j.carbon.2017.03.073
19. [19]
  Zhang, H.; Zhai, C.; Gao, H.; Fu, N.; Zhu, M. J. Colloid Interface Sci. 2019, 547, 102. doi: 10.1016/j.jcis.2019.03.090 doi: 10.1016/j.jcis.2019.03.090
20. [20]
  Zhang, Z.; Gong, Y.; Wu, D.; Li, Z.; Li, Q.; Zheng, L.; Chen, W.; Yuan, W.; Zhang, L. Y. Int. J. Hydrogen Energy 2019, 44, 2731. doi: 10.1016/j.ijhydene.2018.12.004 doi: 10.1016/j.ijhydene.2018.12.004
21. [21]
  Kotal, M.; Kim, J.; Oh, J.; Oh, I. K. Front. Mater. 2016, 3. doi: 10.3389/fmats.2016.00029 doi: 10.3389/fmats.2016.00029
22. [22]
  Zhang, X.; Han, Y.; Huang, L.; Dong, S. ChemSusChem 2016, 9, 3049. doi: 10.1002/cssc.201600904 doi: 10.1002/cssc.201600904
23. [23]
  Zhao, L.; Wang, Z. B.; Li, J. L.; Zhang, J. J.; Sui, X. L.; Zhang, L. M. Electrochim. Acta 2016, 189, 175. doi: 10.1016/j.electacta.2015.12.072 doi: 10.1016/j.electacta.2015.12.072
24. [24]
  Zhang, X.; Hao, N.; Dong, X.; Chen, S.; Zhou, Z.; Zhang, Y.; Wang, K. RSC Adv. 2016, 6, 69973. doi: 10.1039/C6RA12562J doi: 10.1039/C6RA12562J
25. [25]
  Xia, W.; Qu, C.; Liang, Z.; Zhao, B.; Dai, S.; Qiu, B.; Jiao, Y.; Zhang, Q.; Huang, X.; Guo, W.; et al. Nano Lett. 2017, 17, 2788. doi: 10.1021/acs.nanolett.6b05004 doi: 10.1021/acs.nanolett.6b05004
26. [26]
  Fu, G.; Yan, X.; Chen, Y.; Xu, L.; Sun, D.; Lee, J. M.; Tang, Y. Adv. Mater. 2018, 30, 1704609. doi: 10.1002/adma.201704609 doi: 10.1002/adma.201704609
27. [27]
  Çögenli, M. S.; Ayşe, B. Y. Mater. Res. Express 2018, 5, 075513. doi: 10.1088/2053-1591/aad0e8 doi: 10.1088/2053-1591/aad0e8
28. [28]
  Çögenli, M. S.; Bayrakçeken Yurtcan, A. Int. J. Hydrogen Energy 2020, 45, 650. doi: 10.1016/j.ijhydene.2019.10.226 doi: 10.1016/j.ijhydene.2019.10.226
29. [29]
  Zhao, S.; Yin, H.; Du, L.; Yin, G.; Tang, Z.; Liu, S. J. Mater. Chem. A 2014, 2, 3719. doi: 10.1039/C3TA14809B doi: 10.1039/C3TA14809B
30. [30]
  Wang, F.; Yu, H.; Tian, Z.; Xue, H.; Feng, L. J. Energy Chem. 2018, 27, 395. doi: 10.1016/j.jechem.2017.12.011 doi: 10.1016/j.jechem.2017.12.011
31. [31]
  Bao, Y.; Liu, H.; Liu, Z.; Wang, F.; Feng, L. Appl. Catal. B: Environ. 2020, 274, 119106. doi: 10.1016/j.apcatb.2020.119106 doi: 10.1016/j.apcatb.2020.119106
32. [32]
  Sun, L.; Liao, B.; Ren, X.; Li, Y.; Zhang, P.; Deng, L.; Gao, Y. Electrochim. Acta 2017, 235, 543. doi: 10.1016/j.electacta.2017.03.159 doi: 10.1016/j.electacta.2017.03.159
33. [33]
  Lohrasbi, E.; Javanbakht, M.; Mozaffari, S. A. Ind. Eng. Chem. Res. 2016, 55, 9154. doi: 10.1021/acs.iecr.6b00980 doi: 10.1021/acs.iecr.6b00980
34. [34]
  Pei, C.; Ding, R.; Yu, X.; Feng, L. ChemCatChem 2019, 11, 4617. doi: 10.1002/cctc.201900886 doi: 10.1002/cctc.201900886
35. [35]
  Lim, E. J.; Kim, H. J.; Kim, W. B. Catal. Commun. 2012, 25, 74. doi: 10.1016/j.catcom.2012.04.011 doi: 10.1016/j.catcom.2012.04.011
36. [36]
  Xu, C.; Liu, Y.; Hao, Q.; Duan, H. J. Mater. Chem. A 2013, 1, 13542. doi: 10.1039/C3TA12765F doi: 10.1039/C3TA12765F
37. [37]
  Wang, Y.; He, Q.; Wei, H.; Guo, J.; Ding, K.; Wang, Q.; Wang, Z.; Wei, S.; Guo, Z. Electrochim. Acta 2015, 184, 452. doi: 10.1016/j.electacta.2015.10.046 doi: 10.1016/j.electacta.2015.10.046
38. [38]
  Lebedeva, N. P.; Koper, M. T. M.; Feliu, J. M.; van Santen, R. A. J. Electroanal. Chem. 2002, 524–525, 242. doi: 10.1016/S0022-0728(02)00669-1 doi: 10.1016/S0022-0728(02)00669-1
39. [39]
  Seland, F.; Tunold, R.; Harrington, D. A. Electrochim. Acta 2008, 53, 6851. doi: 10.1016/j.electacta.2007.12.021 doi: 10.1016/j.electacta.2007.12.021
40. [40]
  Li, S.; Dong, Z.; Yang, H.; Guo, S.; Gou, G.; Ren, R.; Zhu, Z.; Jin, J.; Ma, J. Chem. Euro. J. 2013, 19, 2384. doi: 10.1002/chem.201203686 doi: 10.1002/chem.201203686
1. [1]
  Pingfan Zhang , Shihuan Hong , Ning Song , Zhonghui Han , Fei Ge , Gang Dai , Hongjun Dong , Chunmei Li . Alloy as advanced catalysts for electrocatalysis: From materials design to applications. Chinese Chemical Letters, 2024, 35(6): 109073-. doi: 10.1016/j.cclet.2023.109073
2. [2]
  Hanqing Zhang , Xiaoxia Wang , Chen Chen , Xianfeng Yang , Chungli Dong , Yucheng Huang , Xiaoliang Zhao , Dongjiang Yang . Selective CO2-to-formic acid electrochemical conversion by modulating electronic environment of copper phthalocyanine with defective graphene. Chinese Journal of Structural Chemistry, 2023, 42(10): 100089-100089. doi: 10.1016/j.cjsc.2023.100089
3. [3]
  Jing Cao , Dezheng Zhang , Bianqing Ren , Ping Song , Weilin Xu . Mn incorporated RuO₂ nanocrystals as an efficient and stable bifunctional electrocatalyst for oxygen evolution reaction and hydrogen evolution reaction in acid and alkaline. Chinese Chemical Letters, 2024, 35(10): 109863-. doi: 10.1016/j.cclet.2024.109863
4. [4]
  Min Song , Qian Zhang , Tao Shen , Guanyu Luo , Deli Wang . Surface reconstruction enabled o-PdTe@Pd core-shell electrocatalyst for efficient oxygen reduction reaction. Chinese Chemical Letters, 2024, 35(8): 109083-. doi: 10.1016/j.cclet.2023.109083
5. [5]
  Yi Zhang , Biao Wang , Chao Hu , Muhammad Humayun , Yaping Huang , Yulin Cao , Mosaad Negem , Yigang Ding , Chundong Wang . Fe–Ni–F electrocatalyst for enhancing reaction kinetics of water oxidation. Chinese Journal of Structural Chemistry, 2024, 43(2): 100243-100243. doi: 10.1016/j.cjsc.2024.100243
6. [6]
  Huipeng Zhao , Xiaoqiang Du . Polyoxometalates as the redox anolyte for efficient conversion of biomass to formic acid. Chinese Journal of Structural Chemistry, 2024, 43(2): 100246-100246. doi: 10.1016/j.cjsc.2024.100246
7. [7]
  Xiaoxiao Huang , Zhi-Long He , Yangpeng Chen , Lei Li , Zhenyu Yang , Chunyang Zhai , Mingshan Zhu . Novel P-doping-tuned Pd nanoflowers/S,N-GQDs photo-electrocatalyst for high-efficient ethylene glycol oxidation. Chinese Chemical Letters, 2024, 35(6): 109271-. doi: 10.1016/j.cclet.2023.109271
8. [8]
  Di Wang , Qing-Song Chen , Yi-Ran Lin , Yun-Xin Hou , Wei Han , Juan Yang , Xin Li , Zhen-Hai Wen . Tuning strategies and electrolyzer design for Bi-based nanomaterials towards efficient CO2 reduction to formic acid. Chinese Journal of Structural Chemistry, 2024, 43(8): 100346-100346. doi: 10.1016/j.cjsc.2024.100346
9. [9]
  Yiyue Ding , Qiuxiang Zhang , Lei Zhang , Qilu Yao , Gang Feng , Zhang-Hui Lu . Exceptional activity of amino-modified rGO-immobilized PdAu nanoclusters for visible light-promoted dehydrogenation of formic acid. Chinese Chemical Letters, 2024, 35(7): 109593-. doi: 10.1016/j.cclet.2024.109593
10. [10]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939
11. [11]
  Shiyu Pan , Bo Cao , Deling Yuan , Tifeng Jiao , Qingrui Zhang , Shoufeng Tang . Complexes of cupric ion and tartaric acid enhanced calcium peroxide Fenton-like reaction for metronidazole degradation. Chinese Chemical Letters, 2024, 35(7): 109185-. doi: 10.1016/j.cclet.2023.109185
12. [12]
  Xinghui Yao , Zhouyu Wang , Da-Gang Yu . Sustainable electrosynthesis: Enantioselective electrochemical Rh(III)/chiral carboxylic acid-catalyzed oxidative CH cyclization coupled with hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(9): 109916-. doi: 10.1016/j.cclet.2024.109916
13. [13]
  Miaomiao Li , Mengwei Yuan , Xingzi Zheng , Kunyu Han , Genban Sun , Fujun Li , Huifeng Li . Highly polar CoP/Co₂P heterojunction composite as efficient cathode electrocatalyst for Li-air battery. Chinese Chemical Letters, 2024, 35(9): 109265-. doi: 10.1016/j.cclet.2023.109265
14. [14]
  Tao Yu , Vadim A. Soloshonok , Zhekai Xiao , Hong Liu , Jiang Wang . Probing the dynamic thermodynamic resolution and biological activity of Cu(Ⅱ) and Pd(Ⅱ) complexes with Schiff base ligand derived from proline. Chinese Chemical Letters, 2024, 35(4): 108901-. doi: 10.1016/j.cclet.2023.108901
15. [15]
  Yanling Yang , Zhenfa Ding , Huimin Wang , Jianhui Li , Yanping Zheng , Hongquan Guo , Li Zhang , Bing Yang , Qingqing Gu , Haifeng Xiong , Yifei Sun . Dynamic tracking of exsolved PdPt alloy/perovskite catalyst for efficient lean methane oxidation. Chinese Chemical Letters, 2024, 35(4): 108585-. doi: 10.1016/j.cclet.2023.108585
16. [16]
  Linhui Liu , Wuwan Xiong , Mingli Fu , Junliang Wu , Zhenguo Li , Daiqi Ye , Peirong Chen . Efficient NO_x abatement by passive adsorption over a Pd-SAPO-34 catalyst prepared by solid-state ion exchange. Chinese Chemical Letters, 2024, 35(4): 108870-. doi: 10.1016/j.cclet.2023.108870
17. [17]
  Guan-Nan Xing , Di-Ye Wei , Hua Zhang , Zhong-Qun Tian , Jian-Feng Li . Pd-based nanocatalysts for oxygen reduction reaction: Preparation, performance, and in-situ characterization. Chinese Journal of Structural Chemistry, 2023, 42(11): 100021-100021. doi: 10.1016/j.cjsc.2023.100021
18. [18]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
19. [19]
  Mengli Xu , Zhenmin Xu , Zhenfeng Bian . Achieving Ullmann coupling reaction via photothermal synergy with ultrafine Pd nanoclusters supported on mesoporous TiO2. Chinese Journal of Structural Chemistry, 2024, 43(7): 100305-100305. doi: 10.1016/j.cjsc.2024.100305
20. [20]
  Wenyi Mei , Lijuan Xie , Xiaodong Zhang , Cunjian Shi , Fengzhi Wang , Qiqi Fu , Zhenjiang Zhao , Honglin Li , Yufang Xu , Zhuo Chen . Design, synthesis and biological evaluation of fluorescent derivatives of ursolic acid in living cells. Chinese Chemical Letters, 2024, 35(5): 108825-. doi: 10.1016/j.cclet.2023.108825

Get Citation

PDF

XML

Metrics

PDF Downloads(22)
Abstract views(966)
HTML views(171)

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