English

Cu-Based Catalyst Derived from Nitrogen-Containing Metal Organic Frameworks for Electroreduction of CO₂

• Jin Huidong ^1,2,†, ,
• Xiong Likun ^1,2,†, ,
• Zhang Xiang ^1,2, ,
• Lian Yuebin ^1,2, ,
• Chen Si ^1,2, ,
• Lu Yongtao ^{1,2, ,} ,
• Deng Zhao ^1,2, ,
• Peng Yang ^{1,2, ,}

• 1.

  Soochow Institute of Energy and Material Innovations, College of Energy, Soochow University, Suzhou 215006, Jiangsu Province, China

• 2.

  Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies, Soochow University, Suzhou 215006, Jiangsu Province, China

Corresponding author: Email: sudalyt@suda.edu, cn (Y. L.); Email: ypeng@suda.edu.cn (Y. P.)

• Received Date: 09 June 2020
  Accepted Date: 04 July 2020
  Revised Date: 04 July 2020
  Available Online: 15 November 2021
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (21701118), Major Project of Natural Science Research in Universities of Jiangsu Province, China (18KJA480004), Six Talent Peak Programs in Jiangsu Province, China (XCL-057, XCL-062, TD-XCL-006)

• ^† These authors contributed equally.

Abstract: With the development of human society and economy, the demand for energy resources has also increased rapidly. However, the use of traditional fossil energy leads to high amounts of carbon dioxide emissions, causing severe greenhouse effects. This, in turn, triggers a series of environmental problems. Harnessing renewable energy such as solar energy, wind energy, and hydropower to replace the traditional energy sources is very urgent. Conversion CO₂ into value-added fuels and chemicals could be a useful strategy to mitigate the current energy and environmental crisis. It is well known that Cu-based materials are good electrocatalysts for the electrochemical reduction of CO₂ (ECR-CO₂). However, they suffer from some disadvantages such as high overpotential and poor selectivity and durability. Therefore, the development of copper based electrocatalysts with high activity and selectivity is essential.Metal-organic frameworks (MOFs) materials that have the advantages of large specific surface area, tunable pore size and porosity, and highly dispersed unsaturated metal centers can be used as electrocatalysts for CO₂ reduction or as precursors for further preparation of catalysts with excellent performance. Through thermal decomposition in an inert atmosphere, metal ions in MOF can be transformed into metal clusters, metal oxides, or even metal mono-atoms. Meanwhile, organic ligands are carbonized into porous carbon materials. The addition of some heteroatoms such as B, N, P, and S to carbon materials has also been shown to be effective in changing the electron state and coordination structure of the catalysts. These heteroatoms combine with carbon atoms to form a new active site, denoted as M-X-C (M is the central metal ion and X is the mixed heteroatom) to enhance the catalytic activity of the ECR-CO₂.Herein, pre-synthesized Cu-NBDC MOF (a Cu-based MOF synthesized by using 2-aminoterephthalic acid (NBDC) as ligand) is used as a precursor to anchor Cu₂O/Cu on nitrogen doped porous carbon (Cu₂O/Cu@NC) by annealing at different temperatures. XPS analysis shows that the Cu-N content in Cu₂O/Cu@NC decreases with increasing annealing temperature. Investigation of the ECR-CO₂ reveals that Cu₂O/Cu@NC can inhibit the HER more effectively compared to Cu₂O/Cu@C, thereby improving the overall catalytic activity and multi-electron product selectivity of the ECR-CO₂. While the Faradic efficiency of formate (FE_formate) increases with increasing temperature, those of ethylene and methane (FE_C2H4 and FE_CH4, respectively) decreases with increasing temperature. Specifically, upon annealing at 400 ℃, the CO₂ Faradic efficiency of Cu₂O/Cu@NC-400 is higher than 86% (−1.4 to −1.6 V vs. RHE), including 20.4% of FE_C2H4 (−1.4 V vs. RHE) and 23.9% of FE_CH4 (−1.6 V vs. RHE). By contrast, FE_CH4 (−1.6 V vs. RHE) in the presence of Cu₂O/Cu@C-400 without nitrogen doping is only 2.33%, and no C₂H₄ is detected. These significant differences in the catalytic behavior can be attributed to the fact that Cu-N is conducive for the stable adsorption of the *CH₂ intermediate during the ECR-CO₂, thus inhibiting the evolution of H₂. These results indicate that the pathway of the ECR-CO₂ and its performance can be effectivel regulated by complexing nitrogen with Cu motifs.

Key words:
• Copper-based MOFs material
•  /  Nitrogen doping
•  /  Cu₂O/Cu
•  /  CO₂ reduction

• 1. [1]

     白晓芳, 陈为, 冯光辉, 魏伟, 焦正, 孙予罕.物理化学学报, 2017, 33, 2388. doi: 10.3866/PKU.WHXB201706131Bai, X. F.; Chen, W.; Wang, B. Y.; Feng, G. H.; Wei, W.; Jiao, Z.; Sun, Y. H. Acta Phys. -Chim. Sin. 2017, 33, 2388. doi: 10.3866/PKU.WHXB201706131

  2. [2]

     Costentin, C.; Robert, M.; Saveant, J. M. Chem. Soc. Rev. 2013, 42, 2423. doi: 10.1039/TF9050100085

  3. [3]

     Hori, Y.; Murata, A.; Takahashi, R. J. Chem. Soc. Faraday. Trans. 1 1989, 85, 2309. doi: 10.1039/F19898502309

  4. [4]

     Hori, Y.; Kikuchi, K.; Murata, A.; Suzuki, S. Chem. Lett. 1986, 15, 897. doi: 10.1246/cl.1986.897

  5. [5]

     Hori, Y.; Takahashi, R.; Yoshinami, Y.; Murata, A. J. Phys. Chem. B 1997, 101, 7075. doi: 10.1021/jp970284i

  6. [6]

     Bagger, A.; Ju, W.; Varela, A. S.; Strasser, P.; Rossmeisl, J. ChemPhysShem 2017, 18, 3266. doi: 10.1002/cphc.201700736

  7. [7]

     Peterson, A. A.; Nørskov, J. K. J. Phys. Chem. Lett. 2012, 3, 251. doi: 10.1021/jz201461p

  8. [8]

     Hansen, H. A.; Varley, J. B.; Peterson, A. A.; Norskov, J. K. J. Phys. Chem. Lett. 2013, 4, 388. doi: 10.1021/jz3021155

  9. [9]

     朱庆宫, 孙晓甫, 康欣晨, 马珺, 钱庆利, 韩布兴.物理化学学报, 2016, 32, 261. doi: 10.3866/PKU.WHXB201512101Zhu, Q. G.; Sun, X. F.; Kang, X. C.; Ma, J.; Qian, Q. L.; Han, B. X. Acta Phys. -Chim. Sin. 2016, 32, 261. doi: 10.3866/PKU.WHXB201512101

  10. [10]

      Kuhl, K. P.; Cave, E. R.; Abram, D. N.; Jaramillo, T. F. Energy Environ. Sci. 2012, 5. doi: 10.1039/C2EE21234J

  11. [11]

      Kim, D.; Kley, C. S.; Li, Y.; Yang, P. Proc. Natl. Acad. Sci. U. S. A. 2017, 114, 10560. doi: 10.1073/pnas.1711493114

  12. [12]

      孟怡辰, 况思宇, 刘海, 范群, 马新宾, 张生.物理化学学报, 2021, 37, 2006034. doi: 10.3866/PKU.WHXB202006034Meng, Y. C.; Kuang, S. Y.; Liu, H.; Fan, Q.; Ma, X. B.; Zhang, S. Acta Phys. -Chim. Sin. 2021, 37, 2006034. doi: 10.3866/PKU.WHXB202006034

  13. [13]

      Gattrell, M.; Gupta, N.; Co, A. J. Electroanal. Chem. 2006, 594, 1. doi: 10.1016/j.jelechem.2006.05.013

  14. [14]

      Peterson, A. A.; Abild-Pedersen, F.; Studt, F.; Rossmeisl, J.; Norskov, J. K. Energy Environ. Sci. 2010, 3, 1311. doi: 10.1039/C0EE00071J

  15. [15]

      Baturina, O. A.; Lu, Q.; Padilla, M. A.; Xin, L.; Li, W.; Serov, A. ACS Catal. 2014, 4, 3682. doi: 10.1021/cs500537y

  16. [16]

      Li, Y.; Cui, F.; Ross, M. B.; Kim, D.; Sun, Y.; Yang, P. Nano Lett. 2017, 17, 1312. doi: 10.1021/acs.nanolett.6b05287

  17. [17]

      Li, Q.; Zhu, W.; Fu, J.; Zhang, H.; Wu, G.; Sun, S. Nano Energy 2016, 24, 1. doi: 10.1016/j.nanoen.2016.03.024

  18. [18]

      宁汇, 王文行, 毛勤虎, 郑诗瑞, 杨中学, 赵青山, 吴明铂.物理化学学报, 2018, 34, 938. doi: 10.3866/PKU.WHXB201801263Ning, H.; Wang, W.; Mao, Q.; Zheng, S.; Yang, Z.; Zhao, Q.; Wu, M. Acta Phys. -Chim. Sin. 2018, 34, 938. doi: 10.3866/PKU.WHXB201801263

  19. [19]

      Wang, J.; Li, Z.; Dong, C.; Feng, Y.; Yang, J.; Liu, H.; Du, X. ACS Appl. Mater. Interfaces 2019, 11, 2763. doi: 1021/acsami.8b20545

  20. [20]

      Ting, L. R. L.; Piqué, O.; Lim, S. Y.; Tanhaei, M.; Calle-Vallejo, F.; Yeo, B. S. ACS Catal. 2020, 10, 4059. doi: 10.1021/acscatal.9b05319

  21. [21]

      Li, Y. C.; Wang, Z.; Yuan, T.; Nam, D. H.; Luo, M.; Wicks, J.; Chen, B.; Li, J.; Li, F. W.; de Arguer, F. P. G.; et al. J. Am. Chem. Soc. 2019, 141, 8584. doi: 10.1021/jacs.9b02945

  22. [22]

      Kottakkat, T.; Klingan, K.; Jiang, S.; Jovanov, Z. P.; Davies, V. H.; El-Nagar, G. A. M.; Dau, H.; Roth, C. ACS Appl. Mater. Interfaces 2019, 11, 14734. doi: 10.1021/acsami.8b22071

  23. [23]

      张楚风, 陈哲伟, 连跃斌, 陈宇杰, 李沁, 顾银冬, 陆永涛, 邓昭, 彭扬.物理化学学报, 2019, 35, 1404. doi: 10.3866/PKU.WHXB201905030Zhang, C.; Chen, Z.; Lian, Y.; Chen, Y.; Li, Q.; Gu, Y.; Lu, Y.; Deng, Z.; Peng, Y. Acta Phys. -Chim. Sin. 2019, 35, 1404. doi: 10.3866/PKU.WHXB201905030

  24. [24]

      Machan, C. W.; Chabolla, S. A.; Yin, J.; Gilson, M. K.; Tezcan, F. A.; Kubiak, C. P. J. Am. Chem. Soc. 2014, 136, 14598. doi: 10.1021/ja5085282

  25. [25]

      Hinogami, R.; Yotsuhashi, S.; Deguchi, M.; Zenitani, Y.; Hashiba, H.; Yamada, Y. ECS Electrochem. Lett. 2012, 1, H17. doi: 10.1149/2.001204eel

  26. [26]

      Kumar, R. S.; Kumar, S. S.; Kulandainathan, M. A. Electrochem. Commun. 2012, 25, 70. doi: 10.1016/j.elecom.2012.09.018

  27. [27]

      Albo, J.; Vallejo, D.; Beobide, G.; Castillo, O.; Castano, P.; Irabien, A. ChemSusChem 2017, 10, 1100. doi: 10.1002/cssc.201600693

  28. [28]

      Kang, X.; Zhu, Q.; Sun, X.; Hu, J.; Zhang, J.; Liu, Z.; Han, B. Chem. Sci. 2016, 7, 266. doi: 10.1039/c5sc03291a

  29. [29]

      刘志敏.物理化学学报, 2019, 35, 1307. doi: 10.3866/PKU.WHXB201908014Liu, Z. M. Acta Phys. -Chim. Sin. 2019, 35, 1307. doi: 10.3866/PKU.WHXB201908014

  30. [30]

      Hod, I.; Sampson, M. D.; Deria, P.; Kubiak, C. P.; Farha, O. K.; Hupp, J. T. ACS Catal. 2015, 5, 6302. doi: 10.1021/acscatal.5b01767

  31. [31]

      Kornienko, N.; Zhao, Y.; Kley, C. S.; Zhu, C.; Kim, D.; Lin, S.; Chang, C. J.; Yaghi, O. M.; Yang, P. J. Am. Chem. Soc. 2015, 137, 14129. doi: 10.1021/jacs.5b08212

  32. [32]

      Chen, L.; Li, Y.; Xu, N.; Zhang, G. Carbon 2018, 132, 172. doi: 10.1016/j.carbon.2018.02.051

  33. [33]

      Ye, J.; Johnson, J. K. Catal. Sci. Tech. 2016, 6, 8392. doi: 10.1039/c6cy01245k

  34. [34]

      Rungtaweevoranit, B.; Baek, J.; Araujo, J. R.; Archanjo, B. S.; Choi, K. M.; Yaghi, O. M.; Somorjai, G. A. Nano Lett. 2016, 16, 7645. doi: 10.1021/acs.nanolett.6b03637

  35. [35]

      Diercks, C. S.; Liu, Y.; Cordova, K. E.; Yaghi, O. M. Nat. Mater. 2018, 17, 301. doi: 10.1038/s41563-018-0033-5

  36. [36]

      Nam, D. H.; Bushuyev, O. S.; Li, J.; De Luna, P.; Seifitokaldani, A.; Dinh, C. T. de Arquer, F. P. G.; Wang, Y.; Liang, Z.; Proppe, A. H.; et al. J. Am. Chem. Soc. 2018, 140, 11378. doi: 10.1021/jacs.8b06407

  37. [37]

      Qiu, Y. L.; Zhong, H. X.; Zhang, T. T.; Xu, W. B.; Su, P. P.; Li, X. F.; Zhang, H. M. ACS Appl. Mater. Interfaces 2018, 10, 2480. doi: 10.1021/acsami.7b15255

  38. [38]

      Wang, R. M.; Sun, X. H.; Ould-Chikh, S.; Osadchii, D.; Bai, F.; Kapteijn, F.; Gascon, J. ACS Appl. Mater. Interfaces 2018, 10, 14751. doi: 10.1021/acsami.8b02226

  39. [39]

      Zhou, W.; Jia, J.; Lu, J.; Yang, L.; Hou, D.; Li, G.; Chen, S. Nano Energy 2016, 28, 29. doi: 10.1016/j.nanoen.2016.08.027

  40. [40]

      Huan, T. N.; Ranjbar, N.; Rousse, G.; Sougrati, M.; Zitolo, A.; Mougel, V.; Jaouen, F.; Fontecave, M. ACS Catal. 2017, 7, 1520. doi: 10.1021/acscatal.6b03353

  41. [41]

      Ju, W.; Bagger, A.; Hao, G. P.; Varela, A. S.; Sinev, I.; Bon, V.; Roldan Cuenya, B.; Kaskel, S.; Rossmeisl, J.; Strasser, P. Nat. Commun. 2017, 8, 944. doi: 10.1038/s41467-017-01035-z

  42. [42]

      Cheng, Y. S.; Chu, X. P.; Ling, M.; Li, N.; Wu, K. L.; Wu, F. H.; Li, H.; Yuan, G.; Wei, X. W. Catal. Sci. Tech. 2019, 9, 5668. doi: 10.1039/C9CY01131E

  43. [43]

      Rostamnia, S.; Alamgholiloo, H.; Liu, X. J. Colloid Interface Sci. 2016, 469, 310. doi: 10.1016/j.jcis.2016.02.021

  44. [44]

      Wang, R.; Wang, K.; Wang, Z.; Song, H.; Wang, H.; Ji, S. J. Power Sources 2015, 297, 295. doi: 10.1016/j.jpowsour.2015.07.107

  45. [45]

      Zhao, K.; Liu, Y.; Quan, X.; Chen, S.; Yu, H. ACS Appl. Mater. Interfaces 2017, 9, 5302. doi: 10.1021/acsami.6b15402

  46. [46]

      Han, X.; He, X.; Sun, L.; Han, X.; Zhan, W.; Xu, J.; Wang, X.; Chen, J. ACS Catal. 2018, 8, 4, 3348-3356. doi: 10.1021/acscatal.7b04219

  47. [47]

      Han, X.; He, X.; Wang, F.; Chen, J.; Xu, J.; Wang, X.; Han, X. J. Mater. Chem. A 2017, 5, 10220. doi: 10.1039/c7ta01909b

  48. [48]

      Ishizuka, S.; Kato, S.; Maruyama, T.; Akimoto, K. Jpn. J. Appl. Phys. 2001, 40, 2765. doi: 10.1143/JJAP.40.2765

  49. [49]

      Zheng, Y.; Cheng, P.; Xu, J.; Han, J.; Wang, D.; Hao, C.; Alanagh, H. R.; Long, C.; Shi, X.; Tang, Z. Nanoscale 2019, 11, 4911. doi: 10.1039/c8nr10236h

  50. [50]

      Zhang, L. S.; Liang, X. Q.; Song, W. G.; Wu, Z. Y. Phys. Chem. Chem. Phys. 2010, 12, 12055. doi: 10.1039/c0cp00789g

  51. [51]

      Zhong, H. X.; Wang, J.; Zhang, Y. W.; Xu, W. L.; Xing, W.; Xu, D.; Zhang, Y. F.; Zhang, X. B. Angew. Chem. Int. Ed. 2014, 53, 14235. doi: 10.1002/anie.201408990

  52. [52]

      Nie, X.; Luo, W.; Janik, M. J.; Asthagiri, A. J. Catal. 2014, 312, 108. doi: 10.1016/j.jcat.2014.01.013

  53. [53]

      Sharma, P. P.; Wu, J.; Yadav, R. M.; Liu, M.; Wright, C. J.; Tiwary, C. S.; Yakobson, B. I.; Lou, J.; Ajayan, P. M.; Zhou, X. D. Angew. Chem. Int. Ed. 2015, 54, 13701. doi: 10.1002/anie.201506062

•