Citation: Jianing Mao, Bingbao Mei, Ji Li, Shuai Yang, Fanfei Sun, Siyu Lu, Wei Chen, Fei Song, Zheng Jiang. Unraveling the Dynamic Structural Evolution of Phthalocyanine Catalysts during CO₂ Electroreduction[J]. Chinese Journal of Structural Chemistry, ;2022, 41(10): 2210082-2210088. doi: 10.14102/j.cnki.0254-5861.2022-0133 shu

Unraveling the Dynamic Structural Evolution of Phthalocyanine Catalysts during CO₂ Electroreduction

Jianing Mao ^{1, 2, 3} ,
Bingbao Mei ^{2, 3,,} ,
Ji Li ^{1, 2, 3} ,
Shuai Yang ^{1, 2, 3} ,
Fanfei Sun ^{2, 3} ,
Siyu Lu ⁴ ,
Wei Chen ^{2, 5} ,
Fei Song ^{1, 2, 3,,} ,
Zheng Jiang ^{1, 2, 3, 6,,}

1.
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201204, China
4.
College of Chemistry, College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450000, China
5.
Low-Carbon Conversion Science and Engineering Center, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201210, China
6.
Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Bingbao Mei, meibb@sari.ac.cn Fei Song, songfei@sinap.ac.cn Zheng Jiang, jiangzheng@sinap.ac.cn
Received Date: 21 May 2022
Accepted Date: 2 June 2022
Available Online: 8 June 2022

Figures(4)

Understanding the atomic and electronic changes of active sites promotes the whole new sight into electrochemical carbon dioxide reduction reaction (CO₂RR), which provides a feasible strategy to achieve carbon neutrality. Here we employ operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) to track the structural evolution of Ni(II) phthalocyanine (NiPc), considered as the model catalysts with uniform Ni-N₄-C₈ moiety, during the CO₂RR. The HERFD-XAS method is in favor of elucidating the interaction of the reactant/catalyst interface from the atomic electronic structure dimension, facilitating the establishment of the catalytic mechanism and the dynamic structure changes. Based on operando measurement, surface sensitive difference spectra (∆µ) and spectroscopy simulation, the interfacial interactions between the active sites of NiPc and reactants are monitored and the Ni species gradually reduced by increasing the applied potential is discovered. HERFD-XAS method offers an advanced and powerful tool for elucidating the complex catalytic mechanism in further various systems.
- CO₂ electrochemical reduction,
- HERFD-XAS,
- model catalysts,
- difference spectra,
- structural evolution
1. [1]
  Li, J.; Gong, J. Operando characterization techniques for electrocatalysis. Energy Environ. Sci. 2020, 13, 3748-3779. doi: 10.1039/D0EE01706J
2. [2]
  Liu, M.; Pang, Y.; Zhang, B.; De Luna, P.; Voznyy, O.; Xu, J.; Zheng, X.; Dinh, C. T.; Fan, F.; Cao, C.; De Arquer, F. P.; Safaei, T. S.; Mepham, A.; Klinkova, A.; Kumacheva, E.; Filleter, T.; Sinton, D.; Kelley, S. O.; Sargent, E. H. Enhanced electrocatalytic CO₂ reduction via field-induced reagent concentration. Nature 2016, 537, 382-386. doi: 10.1038/nature19060
3. [3]
  Qiao, J.; Liu, Y.; Hong, F.; Zhang, J. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 2014, 43, 631-675.
4. [4]
  Zhang, Y. -J.; Sethuraman, V.; Michalsky, R.; Peterson, A. A. Competition between CO₂ reduction and H₂ evolution on transition-metal electrocatalysts. ACS Catal. 2014, 4, 3742-3748.
5. [5]
  Kim, D.; Resasco, J.; Yu, Y.; Asiri, A. M.; Yang, P. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles. Nat. Commun. 2014, 5, 4948. doi: 10.1038/ncomms5948
6. [6]
  Francke, R.; Schille, B.; Roemelt, M. Homogeneously catalyzed electroreduction of carbon dioxide-methods, mechanisms, and catalysts. Chem. Rev. 2018, 118, 4631-4701. doi: 10.1021/acs.chemrev.7b00459
7. [7]
  Wang, M.; Torbensen, K.; Salvatore, D.; Ren, S.; Joulie, D.; Dumoulin, F.; Mendoza, D.; Lassalle-Kaiser, B.; Isci, U.; Berlinguette, C. P.; Robert, M. CO₂ electrochemical catalytic reduction with a highly active cobalt phthalocyanine. Nat. Commun. 2019, 10, 3602. doi: 10.1038/s41467-019-11542-w
8. [8]
  Weng, Z.; Wu, Y. S.; Wang, M. Y.; Jiang, J. B.; Yang, K.; Huo, S. J.; Wang, X. F.; Ma, Q.; Brudvig, G. W.; Batista, V. S.; Liang, Y. Y.; Feng, Z. X.; Wang, H. L. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 2018, 9, 415. doi: 10.1038/s41467-018-02819-7
9. [9]
  Wu, Y.; Jiang, Z.; Lu, X.; Liang, Y.; Wang, H. Domino electroreduction of CO₂ to methanol on a molecular catalyst. Nature 2019, 575, 639-642. doi: 10.1038/s41586-019-1760-8
10. [10]
  Liu, J. Catalysis by supported single metal atoms. ACS Catal. 2016, 7, 34-59.
11. [11]
  Yang, M.; Li, S.; Wang, Y.; Herron, J. A.; Xu, Y.; Allard, L. F.; Lee, S.; Huang, J.; Mavrikakis, M.; Flytzani-Stephanopoulos, M. Catalytically active Au-O(OH)_x- species stabilized by alkali ions on zeolites and mesoporous oxides. Science 2014, 346, 1498-1501. doi: 10.1126/science.1260526
12. [12]
  Qiao, B.; Wang, A.; Yang, X.; Allard, L. F.; Jiang, Z.; Cui, Y.; Liu, J.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt₁/FeO_x. Nat. Chem. 2011, 3, 634-641.
13. [13]
  Zhong, M.; Tran, K.; Min, Y.; Wang, C.; Wang, Z.; Dinh, C. T.; De Luna, P.; Yu, Z.; Rasouli, A. S.; Brodersen, P.; Sun, S.; Voznyy, O.; Tan, C. S.; Askerka, M.; Che, F.; Liu, M.; Seifitokaldani, A.; Pang, Y.; Lo, S. C.; Ip, A.; Ulissi, Z.; Sargent, E. H. Accelerated discovery of CO₂ electrocatalysts using active machine learning. Nature 2020, 581, 178-183. doi: 10.1038/s41586-020-2242-8
14. [14]
  Li, Y.; Cheng, W.; Su, H.; Zhao, X.; He, J.; Liu, Q. Operando infrared spectroscopic insights into the dynamic evolution of liquid-solid (photo)electrochemical interfaces. Nano Energy 2020, 77, 105121. doi: 10.1016/j.nanoen.2020.105121
15. [15]
  Dong, J. C.; Zhang, X. G.; Briega-Martos, V.; Jin, X.; Yang, J.; Chen, S.; Yang, Z. L.; Wu, D. -Y.; Feliu, J. M.; Williams, C. T.; Tian, Z. -Q.; Li, J. F. In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces. Nat. Energy 2018, 4, 60-67.
16. [16]
  Bergmann, A.; Martinez-Moreno, E.; Teschner, D.; Chernev, P.; Gliech, M.; De Araujo, J. F.; Reier, T.; Dau, H.; Strasser, P. Reversible amorphization and the catalytically active state of crystalline Co₃O₄ during oxygen evolution. Nat. Commun. 2015, 6, 8625.
17. [17]
  Hutchings, G. S.; Zhang, Y.; Li, J.; Yonemoto, B. T.; Zhou, X.; Zhu, K.; Jiao, F. In situ formation of cobalt oxide nanocubanes as efficient oxygen evolution catalysts. J. Am. Chem. Soc. 2015, 137, 4223-4229.
18. [18]
  Hu, C.; Ma, Q.; Hung, S. -F.; Chen, Z. -N.; Ou, D.; Ren, B.; Chen, H. M.; Fu, G.; Zheng, N. In Situ electrochemical production of ultrathin nickel nanosheets for hydrogen evolution electrocatalysis. Chem. 2017, 3, 122-133.
19. [19]
  Mei, B.; Liu, C.; Li, J.; Gu, S.; Du, X.; Lu, S.; Song, F.; Xu, W.; Jiang, Z. Operando HERFD-XANES and surface sensitive Δμ analyses identify the structural evolution of copper(II) phthalocyanine for electroreduction of CO₂. J. Energy Chem. 2022, 64, 1-7.
20. [20]
  Hung, S. F.; Chan, Y. T.; Chang, C. C.; Tsai, M. K.; Liao, Y. F.; Hiraoka, N.; Hsu, C. S.; Chen, H. M. Identification of stabilizing high valent active sites by operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy for high-efficiency water oxidation. J. Am. Chem. Soc. 2018, 140, 17263-17270.
21. [21]
  Kanan, M. W.; Yano, J.; Surendranath, Y.; Dinca, M.; Yachandra, V. K.; Nocera, D. G. Structure and valency of a cobalt-phosphate water oxidation catalyst determined by in situ X-ray spectroscopy. J. Am. Chem. Soc. 2010, 132, 13692-13701.
22. [22]
  Eisenberger, P.; Platzman, P. M.; Winick, H. X-ray resonant Raman scattering: observation of characteristic radiation narrower than the lifetime width. Phys. Rev. Lett. 1976, 36, 623-626.
23. [23]
  Bauer, M. HERFD-XAS and valence-to-core-XES: new tools to push the limits in research with hard X-rays? Phys. Chem. Chem. Phys. 2014, 16, 13827-13837.
24. [24]
  Srivastava, U. C.; Nigam, H. L. X-ray absorption edge spectrometry (XAES) as applied to coordination chemistry. Coord. Chem. Rev. 1973, 9, 275-310.
25. [25]
  Mei, B.; Gu, S.; Du, X.; Li, Z.; Cao, H.; Song, F.; Huang, Y.; Jiang, Z. A wavelength-dispersive X-ray spectrometer for in/ex situ resonant inelastic X-ray scattering studies. X-ray Spectrom. 2019, 49, 251-259.
26. [26]
  Bergmann, U.; Glatzel, P. X-ray emission spectroscopy. Photosynth. Res. 2009, 102, 255-266.
27. [27]
  Al Samarai, M.; Delgado-Jaime, M. U.; Ishii, H.; Hiraoka, N.; Tsuei, K. -D.; Rueff, J. P.; Lassale-Kaiser, B.; Weckhuysen, B. M.; De Groot, F. M. F. 1s3p Resonant inelastic X-ray scattering of cobalt oxides and sulfides. J. Phys. Chem. C 2016, 120, 24063-24069.
28. [28]
  Yamamoto, T. Assignment of pre-edge peaks in K-edge X-ray absorption spectra of 3d transition metal compounds: electric dipole or quadrupole? X-ray Spectrom. 2008, 37, 572-584.
29. [29]
  Rossi, G.; D'Acapito, F.; Amidani, L.; Boscherini, F.; Pedio, M. Local environment of metal ions in phthalocyanines: K-edge X-ray absorption spectra. Phys. Chem. Chem. Phys. 2016, 18, 23686-23694.
30. [30]
  Jia, Q.; Ramaswamy, N.; Hafiz, H.; Tylus, U.; Strickland, K.; Wu, G.; Barbiellini, B.; Bansil, A.; Holby, E. F.; Zelenay, P.; Mukerjee, S. Experimental observation of redox-induced Fe-N switching behavior as a determinant role for oxygen reduction activity. ACS Nano. 2015, 9, 12496-12505.
31. [31]
  Yang, H. B.; Hung, S. -F.; Liu, S.; Yuan, K.; Miao, S.; Zhang, L.; Huang, X.; Wang, H. -Y.; Cai, W.; Chen, R.; Gao, J.; Yang, X.; Chen, W.; Huang, Y.; Chen, H. M.; Li, C. M.; Zhang, T.; Liu, B. Atomically dispersed Ni(I) as the active site for electrochemical CO₂ reduction. Nat. Energy 2018, 3, 140-147.
32. [32]
  Hammer, B.; Norskov, J. Why gold is the noblest of all the metals. Nature 1995, 376, 238-240.
33. [33]
  Norskov, J. K.; Abild-Pedersen, F.; Studt, F.; Bligaard, T. Density functional theory in surface chemistry and catalysis. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 937-943.
34. [34]
  Bunau, O.; Joly, Y. Self-consistent aspects of X-ray absorption calculations. J. Phys. : Condens. Matter. 2009, 21, 345501.
35. [35]
  Kresse, G.; Hafner, J. Ab initio molecular dynamics for open-shell transition metals. Phys. Rev. B 1993, 48, 13115-13118.
36. [36]
  Kresse, G.; Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169-11186.
37. [37]
  Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15-50.
38. [38]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865-3868.
1. [1]
  WANG Huan , KONG Jiao , WANG Mei-jun , CHANG Li-ping . Structural evolution of a bituminous coal char related to its synchronized gasification behavior with H₂O and/or CO₂. Journal of Fuel Chemistry and Technology, 2019, 47(4): 393-401.
2. [2]
  Hao Zhang , Caihong He , Sumei Han , Zeyang Du , Ling Wang , Qinbai Yun , Wenbin Cao , Bowei Zhang , Ya-Hui Tian , Qipeng Lu . Crystal facet-dependent electrocatalytic performance of metallic Cu in CO₂ reduction reactions. Chinese Chemical Letters, 2022, 33(8): 3641-3649. doi: 10.1016/j.cclet.2021.12.018
3. [3]
  Yongxia Shi , Man Hou , Junjun Li , Li Li , Zhicheng Zhang . Cu-Based Tandem Catalysts for Electrochemical CO₂ Reduction. Acta Physico-Chimica Sinica, 2022, 38(11): 2206020-0. doi: 10.3866/PKU.WHXB202206020
4. [4]
  WANG Yan , LI Xiong , HU Shanwei , XU Qian , JU Huanxin , ZHU Junfa . Morphologies and Electronic Structures of Calcium-Doped Ceria Model Catalysts and Their Interaction with CO₂. Acta Physico-Chimica Sinica, 2018, 34(12): 1381-1389. doi: 10.3866/PKU.WHXB201804092
5. [5]
  Baoling Tian , Shujuan Li , Shulai Lei , Liangxu Lin , Wenyue Guo , Hao Ren . Structural insights of catalytic intermediates in dialumene based CO₂ capture: Evidences from theoretical resonance Raman spectra. Chinese Chemical Letters, 2021, 32(8): 2469-2473. doi: 10.1016/j.cclet.2021.02.011
6. [6]
  Hao Leiduan , Sun Zhenyu . Metal Oxide-Based Materials for Electrochemical CO₂ Reduction. Acta Physico-Chimica Sinica, 2021, 37(7): 2009033-0. doi: 10.3866/PKU.WHXB202009033
7. [7]
  Xiu-Hui ZHAO , De-Huang ZHUO , Qing-Song CHEN , Guo-Cong GUO . Enhancing Electrochemical Reduction of CO₂ to Formate by Regulating the Support Morphology. Chinese Journal of Structural Chemistry, 2021, 40(3): 376-382. doi: 10.14102/j.cnki.0254–5861.2011–2903
8. [8]
  Wen LI , Yuan Qi YIN , Rui Ling HOU , Pei Ju NHENG . The Evolution of IR Spectra of H₂ Adsorbed on ZrO₂ with Changing Temperature(298-723K). Chinese Chemical Letters, 1996, 7(11): 1051-1053.
9. [9]
  Yuting Sun , Shuang Wang , Dongxu Jiao , Fengyu Li , Siyao Qiu , Zhongxu Wang , Qinghai Cai , Jingxiang Zhao , Chenghua Sun . Two-dimensional Pt₂P₃ monolayer: A promising bifunctional electrocatalyst with different active sites for hydrogen evolution and CO₂ reduction. Chinese Chemical Letters, 2022, 33(8): 3987-3992. doi: 10.1016/j.cclet.2021.11.034
10. [10]
  Zheng Ping HAO , Li Dun AN , Hong Li WANG . THE SUPPORTED GOLD CATALYSTS FOR CLOSED CYCLE CO₂ LASER. Chinese Chemical Letters, 1995, 6(5): 447-448.
11. [11]
  Cui Xinjiang , Shi Feng . Selective Conversion of CO₂ by Single-Site Catalysts. Acta Physico-Chimica Sinica, 2021, 37(5): 2006080-0. doi: 10.3866/PKU.WHXB202006080
12. [12]
  Hongyu Ma , Yong Liu , Rui Xiong , Jianhong Wei . Hetero-structured ZnIn₂S₄-NiO@MOF photo-catalysts for efficient hydrogen evolution. Chinese Chemical Letters, 2022, 33(2): 1042-1046. doi: 10.1016/j.cclet.2021.08.048
13. [13]
  Qin Tian , Qian Yao , Zhang Fan , Lin Bo-Lin . Cloride-derived copper electrode for efficient electrochemical reduction of CO₂ to ethylene. Chinese Chemical Letters, 2019, 30(2): 314-318. doi: 10.1016/j.cclet.2018.07.003
14. [14]
  Luo Daibing , Liu Shanhu , Nakata Kazuya , Fujishima Akira . Electrochemical reduction of CO₂ and degradation of KHP on boron-doped diamond electrodes in a simultaneous and enhanced process. Chinese Chemical Letters, 2019, 30(2): 509-512. doi: 10.1016/j.cclet.2018.06.010
15. [15]
  Xiaoxiong Huang , Yingjie Ma , Linjie Zhi . Ultrathin Nitrogenated Carbon Nanosheets with Single-Atom Nickel as an Efficient Catalyst for Electrochemical CO₂ Reduction. Acta Physico-Chimica Sinica, 2022, 38(2): 2011050-0. doi: 10.3866/PKU.WHXB202011050
16. [16]
  Zengqiang Gao , Junjun Li , Zhicheng Zhang , Wenping Hu . Recent advances in carbon-based materials for electrochemical CO₂ reduction reaction. Chinese Chemical Letters, 2022, 33(5): 2270-2280. doi: 10.1016/j.cclet.2021.09.037
17. [17]
  Ming Hong ZHONG , Bu Xing HAN , Jie KE , Zhi Min LIU , Hai Ke YAN , Ding Yu PENG . A New Model for Correlating the Solubility of Solids in Supercritical CO₂ and Study on Some Systems (Ⅱ):Correlation and Prediction. Chinese Chemical Letters, 1998, 9(3): 295-298.
18. [18]
  Sun Jie , Kong Wenhan , Jin Zhaoyong , Han Yaqian , Ma Liangyu , Ding Xiaoteng , Niu Yusheng , Xu Yuanhong . Recent advances of MXene as promising catalysts for electrochemical nitrogen reduction reaction. Chinese Chemical Letters, 2020, 31(4): 953-960. doi: 10.1016/j.cclet.2020.01.035
19. [19]
  Yanming Liu , Haolei Yang , Xinfei Fan , Bing Shan , Thomas J. Meyer . Promoting electrochemical reduction of CO₂ to ethanol by B/N-doped sp³/sp² nanocarbon electrode. Chinese Chemical Letters, 2022, 33(10): 4691-4694. doi: 10.1016/j.cclet.2021.12.063
20. [20]
  HIGAKI Tatsuya , JIN Rongchao . Structural Evolution Patterns of FCC-Type Gold Nanoclusters. Acta Physico-Chimica Sinica, 2018, 34(7): 755-761. doi: 10.3866/PKU.WHXB201801191

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(37)
HTML views(1)

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

Unraveling the Dynamic Structural Evolution of Phthalocyanine Catalysts during CO2 Electroreduction

Metrics

通讯作者: 陈斌, bchen63@163.com

Unraveling the Dynamic Structural Evolution of Phthalocyanine Catalysts during CO₂ Electroreduction