Journal Home > Volume 16 , Issue 5
Nano Research 2023, 16(5): 6679-6686 https://doi.org/10.1007/s12274-023-5462-z
Research Article | Issue | Published: 16 February 2023

N2 photofixation promoted by in situ photoinduced dynamic iodine vacancies at step edge in Bi5O7I nanotubes

Show Author's Information Xing’an Dong1,  Kaiwen Wang2,  Zhihao Cui3,  Xian Shi1,  Zhiming Wang1,  Fan Dong1( )
Research Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, China
Beijing Key Lab of Microstructure and Properties of Advanced Materials, Beijing University of Technology, Beijing 100124, China
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, USA
Keywords:
nitrogen fixation, photoreduction, halogen vacancy, surface tensile strain, rapid scan in situ Fourier transform infrared (FT-IR)
Topics:
Catalytic
Cite this article:
Dong X, Wang K, Cui Z, et al. N2 photofixation promoted by in situ photoinduced dynamic iodine vacancies at step edge in Bi5O7I nanotubes. Nano Research, 2023, 16(5): 6679-6686. https://doi.org/10.1007/s12274-023-5462-z
Download citation
EndNote(RIS)
BibTeX

674

Views

37

Downloads

Citations

6

Crossref

5

WoS

6

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Heterogeneous photosynthesis is a promising route for sustainable ammonia production, which can utilize renewable energy and water as the hydrogen source under ambient condition. In this study, a series of Bi5O7I (BOI) nanosheets and nanotubes are synthesized, and the surface tensile strain is formed by curling the nanosheets into nanotubes to tune the concentration and location of dynamic vacancies. Scanning transmission electron microscopy (STEM) with spherical aberration correction confirms the presence of intrinsic areal defects on the surface of the BOI nanotube resulted from surface tensile strain. The presence of areal defects lowers the formation energy of I vacancies (IV) at step edge site, thus the IV with higher concentration would be favorably generated under visible light. Rapid scan in situ Fourier transform infrared (FT-IR) analysis in the aqueous media reveals that the IV promotes photocatalytic N2 activation and reduction, and proceeds through an associative alternating mechanism. Specially, after turning off the light, the surface vacancy sites can be reoccupied by I− ions, which enables the protection and regeneration of photocatalyst surface in an aerobic and dark environment. This work provides an innovative strategy to tune concentration and location of dynamic surface vacancies on photocatalysts by building surface tensile strain for advancing sustainable ammonia production.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

N2 photofixation promoted by in situ photoinduced dynamic iodine vacancies at step edge in Bi5O7I nanotubes

Show Author's information Xing’an Dong1, Kaiwen Wang2, Zhihao Cui3, Xian Shi1, Zhiming Wang1, Fan Dong1( )
Research Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, China
Beijing Key Lab of Microstructure and Properties of Advanced Materials, Beijing University of Technology, Beijing 100124, China
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, USA

Abstract

Heterogeneous photosynthesis is a promising route for sustainable ammonia production, which can utilize renewable energy and water as the hydrogen source under ambient condition. In this study, a series of Bi5O7I (BOI) nanosheets and nanotubes are synthesized, and the surface tensile strain is formed by curling the nanosheets into nanotubes to tune the concentration and location of dynamic vacancies. Scanning transmission electron microscopy (STEM) with spherical aberration correction confirms the presence of intrinsic areal defects on the surface of the BOI nanotube resulted from surface tensile strain. The presence of areal defects lowers the formation energy of I vacancies (IV) at step edge site, thus the IV with higher concentration would be favorably generated under visible light. Rapid scan in situ Fourier transform infrared (FT-IR) analysis in the aqueous media reveals that the IV promotes photocatalytic N2 activation and reduction, and proceeds through an associative alternating mechanism. Specially, after turning off the light, the surface vacancy sites can be reoccupied by I− ions, which enables the protection and regeneration of photocatalyst surface in an aerobic and dark environment. This work provides an innovative strategy to tune concentration and location of dynamic surface vacancies on photocatalysts by building surface tensile strain for advancing sustainable ammonia production.

Keywords: nitrogen fixation, photoreduction, halogen vacancy, surface tensile strain, rapid scan in situ Fourier transform infrared (FT-IR)

References(43)

[1]

Spatzal, T.; Perez, K. A.; Einsle, O.; Howard, J. B.; Rees, D. C. Ligand binding to the FeMo-cofactor: Structures of CO-bound and reactivated nitrogenase. Science 2014, 345, 1620–1623.
DOI Google Scholar
[2]

Lan, R.; Irvine, J. T. S.; Tao, S. W. Ammonia and related chemicals as potential indirect hydrogen storage materials. Int. J. Hydrogen Energy 2012, 37, 1482–1494.
DOI Google Scholar
[3]

Brown, K. A.; Harris, D. F.; Wilker, M. B.; Rasmussen, A.; Khadka, N.; Hamby, H.; Keable, S.; Dukovic, G.; Peters, J. W.; Seefeldt, L. C. et al. Light-driven dinitrogen reduction catalyzed by a CdS: nitrogenase MoFe protein biohybrid. Science 2016, 352, 448–450.
DOI Google Scholar
[4]

Hoffman, B. M.; Lukoyanov, D.; Yang, Z. Y.; Dean, D. R.; Seefeldt, L. C. Mechanism of nitrogen fixation by nitrogenase: The next stage. Chem. Rev. 2014, 114, 4041–4062.
DOI Google Scholar
[5]

Rosca, V.; Duca, M.; De Groot, M. T.; Koper, M. T. M. Nitrogen cycle electrocatalysis. Chem. Rev. 2009, 109, 2209–2244.
DOI Google Scholar
[6]

Kitano, M.; Inoue, Y.; Yamazaki, Y.; Hayashi, F.; Kanbara, S.; Matsuishi, S.; Yokoyama, T.; Kim, S. W.; Hara, M.; Hosono, H. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. Nat. Chem. 2012, 4, 934–940.
DOI Google Scholar
[7]

Kuriyama, S.; Arashiba, K.; Nakajima, K.; Matsuo, Y.; Tanaka, H.; Ishii, K.; Yoshizawa, K.; Nishibayashi, Y. Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand. Nat. Commun. 2016, 7, 12181.
DOI Google Scholar
[8]

Ali, M.; Zhou, F. L.; Chen, K.; Kotzur, C.; Xiao, C. L.; Bourgeois, L.; Zhang, X. Y.; MacFarlane, D. R. Nanostructured photoelectrochemical solar cell for nitrogen reduction using plasmon-enhanced black silicon. Nat. Commun. 2016, 7, 11335.
DOI Google Scholar
[9]

Lu, Y. H.; Yang, Y.; Zhang, T. F.; Ge, Z.; Chang, H. C.; Xiao, P. S.; Xie, Y. Y.; Hua, L.; Li, Q. Y.; Li, H. Y. et al. Photoprompted hot electrons from bulk cross-linked graphene materials and their efficient catalysis for atmospheric ammonia synthesis. ACS Nano 2016, 10, 10507–10515.
DOI Google Scholar
[10]

Guo, C. X.; Ran, J. R.; Vasileff, A.; Qiao, S. Z. Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions. Energy Environ. Sci. 2018, 11, 45–56.
DOI Google Scholar
[11]

Chen, G. F.; Cao, X. R.; Wu, S. Q.; Zeng, X. Y.; Ding, L. X.; Zhu, M.; Wang, H. H. Ammonia electrosynthesis with high selectivity under ambient conditions via a Li+ incorporation strategy. J. Am. Chem. Soc. 2017, 139, 9771–9774.
DOI Google Scholar
[12]

Nishibayashi, Y. Recent progress in transition-metal-catalyzed reduction of molecular dinitrogen under ambient reaction conditions. Inorg. Chem. 2015, 54, 9234–9247.
DOI Google Scholar
[13]

Lai, F. L.; Feng, J. R.; Ye, X. B.; Zong, W.; He, G. J.; Yang, C.; Wang, W.; Miao, Y. E.; Pan, B. C.; Yan, W. S. et al. Oxygen vacancy engineering in spinel-structured nanosheet wrapped hollow polyhedra for electrochemical nitrogen fixation under ambient conditions. J. Mater. Chem. A 2020, 8, 1652–1659.
DOI Google Scholar
[14]

Shi, M. M.; Bao, D.; Wulan, B. R.; Li, Y. H.; Zhang, Y. F.; Yan, J. M.; Jiang, Q. Au sub-nanoclusters on TiO2 toward highly efficient and selective electrocatalyst for N2 conversion to NH3 at ambient conditions. Adv. Mater. 2017, 29, 1606550.
DOI Google Scholar
[15]

Licht, S.; Cui, B. C.; Wang, B. H.; Li, F. F.; Lau, J.; Liu, S. Z. Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3. Science 2014, 345, 637–640.
DOI Google Scholar
[16]

Jacobsen, C. J. H.; Dahl, S.; Clausen, B. S.; Bahn, S.; Logadottir, A.; Nørskov, J. K. Catalyst design by interpolation in the periodic table: Bimetallic ammonia synthesis catalysts. J. Am. Chem. Soc. 2001, 123, 8404–8405.
DOI Google Scholar
[17]

Jin, H. Y.; Guo, C. X.; Liu, X.; Liu, J. L.; Vasileff, A.; Jiao, Y.; Zheng, Y.; Qiao, S. Z. Emerging two-dimensional nanomaterials for electrocatalysis. Chem. Rev 2018, 118, 6337–6408.
DOI Google Scholar
[18]

Xiong, L. J.; Hu, Y. J.; Yang, Y.; Deng, Q. H.; Tang, Z.; Li, P. J.; Shen, J. Y.; Zhang, X. Y.; Wang, T. Y.; Xu, X. Y. et al. Electron pump strengthened facet engineering: Organic half-metallic C(CN)3 enclosed (100) facet exposed WO3 for efficient and selective photocatalytic nitrogen fixation. Appl. Catal. B: Environ. 2022, 317, 121660.
DOI Google Scholar
[19]

Tang, Z.; Xiong, L. J.; Zhang, X. Y.; Shen, J. Y.; Sun, A. W.; Lin, X. Y.; Yang, Y. Biomass-induced diphasic carbon decoration for carbon nitride: Band and electronic engineering targeting efficient N2 photofixation. Small 2022, 18, 2105217.
DOI Google Scholar
[20]

Gao, X.; An, L.; Qu, D.; Jiang, W. S.; Chai, Y. X.; Sun, S. R.; Liu, X. Y.; Sun, Z. C. Enhanced photocatalytic N2 fixation by promoting N2 adsorption with a co-catalyst. Sci. Bull. 2019, 64, 918–925.
DOI Google Scholar
[21]

Wang, L.; Zhao, X.; Lv, D. D.; Liu, C. W.; Lai, W. H.; Sun, C. Y.; Su, Z. M.; Xu, X.; Hao, W. C.; Dou, S. X. et al. Promoted photocharge separation in 2D lateral epitaxial heterostructure for visible-light-driven CO2 photoreduction. Adv. Mater. 2020, 32, 2004311.
DOI Google Scholar
[22]

Qiu, P. Y.; Wang, J. W.; Liang, Z. Q.; Xue, Y. J.; Zhou, Y. L.; Zhang, X. L.; Cui, H. Z.; Cheng, G. Q.; Tian, J. The metallic 1T-WS2 as cocatalysts for promoting photocatalytic N2 fixation performance of Bi5O7Br nanosheets. Chin. Chem. Lett. 2021, 32, 3501–3504.
DOI Google Scholar
[23]

Wu, X. L.; Ng, Y. H.; Wang, L.; Du, Y.; Dou, S. X.; Amal, R.; Scott, J. Improving the photo-oxidative capability of BiOBr via crystal facet engineering. J. Mater. Chem. A 2017, 5, 8117–8124.
DOI Google Scholar
[24]

Dong, X. A.; Cui, Z. H.; Shi, X.; Yan, P.; Wang, Z. M.; Co, A. C.; Dong, F. Insights into dynamic surface bromide sites in Bi4O5Br2 for sustainable N2 photofixation. Angew. Chem., Int. Ed. 2022, 61, e202200937.
DOI Google Scholar
[25]

Shi, X.; Dong, X. A.; He, Y.; Yan, P.; Zhang, S. H.; Dong, F. Photoswitchable chlorine vacancies in ultrathin Bi4O5Cl2 for selective CO2 photoreduction. ACS Catal. 2022, 12, 3965–3973.
DOI Google Scholar
[26]

Shi, X.; Dong, X. A.; He, Y.; Yan, P.; Dong, F. Light-induced halogen defects as dynamic active sites for CO2 photoreduction to CO with 100% selectivity. Sci. Bull. 2022, 67, 1137–1144.
DOI Google Scholar
[27]

Mao, C. L.; Cheng, H. G.; Tian, H.; Li, H.; Xiao, W. J.; Xu, H.; Zhao, J. C.; Zhang, L. Z. Visible light driven selective oxidation of amines to imines with BiOCl: Does oxygen vacancy concentration matter? Appl. Catal. B: Environ. 2018, 228, 87–96.
DOI Google Scholar
[28]

Pacchioni, G. Oxygen vacancy: The invisible agent on oxide surfaces. ChemPhysChem 2003, 4, 1041–1047.
DOI Google Scholar
[29]

Ganduglia-Pirovano, M. V.; Hofmann, A.; Sauer, J. Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges. Surf. Sci. Rep. 2007, 62, 219–270.
DOI Google Scholar
[30]

Luo, M. C.; Zhao, Z. L.; Zhang, Y. L.; Sun, Y. J.; Xing, Y.; Lv, F.; Yang, Y.; Zhang, X.; Hwang, S.; Qin, Y. N. et al. PdMo bimetallene for oxygen reduction catalysis. Nature 2019, 574, 81–85.
DOI Google Scholar
[31]

Xia, Z. H.; Guo, S. J. Strain engineering of metal-based nanomaterials for energy electrocatalysis. Chem. Soc. Rev. 2019, 48, 3265–3278.
DOI Google Scholar
[32]

Di, J.; Song, P.; Zhu, C.; Chen, C.; Xiong, J.; Duan, M. L.; Long, R.; Zhou, W. Q.; Xu, M. Z.; Kang, L. X. et al. Strain-engineering of Bi12O17Br2 nanotubes for boosting photocatalytic CO2 reduction. ACS Mater. Lett. 2020, 2, 1025–1032.
DOI Google Scholar
[33]

Zhu, H.; Gao, G. H.; Du, M. L.; Zhou, J. H.; Wang, K.; Wu, W. B.; Chen, X.; Li, Y.; Ma, P. M.; Dong, W. F. et al. Atomic-scale core/shell structure engineering induces precise tensile strain to boost hydrogen evolution catalysis. Adv. Mater. 2018, 30, 1707301.
DOI Google Scholar
[34]

Qin, H. S.; Sorkin, V.; Pei, Q. X.; Liu, Y. L.; Zhang, Y. W. Failure in two-dimensional materials: Defect sensitivity and failure criteria. J. Appl. Mech. 2020, 87, 030802.
DOI Google Scholar
[35]

Huang, H. W.; Liu, K.; Chen, K.; Zhang, Y. L.; Zhang, Y. H.; Wang, S. C. Ce and F comodification on the crystal structure and enhanced photocatalytic activity of Bi2WO6 photocatalyst under visible light irradiation. J. Phys. Chem. C 2014, 118, 14379–14387.
DOI Google Scholar
[36]

Zhou, Y. G.; Zhang, Y. F.; Lin, M. S.; Long, J. L.; Zhang, Z. Z.; Lin, H. X.; Wu, J. C. S.; Wang, X. X. Monolayered Bi2WO6 nanosheets mimicking heterojunction interface with open surfaces for photocatalysis. Nat. Commun. 2015, 6, 8340.
DOI Google Scholar
[37]

Qiao, J. S.; Kong, X. H.; Hu, Z. X.; Yang, F.; Ji, W. High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus. Nat. Commun. 2014, 5, 4475.
DOI Google Scholar
[38]

Sheng, H.; Zhang, H. N.; Song, W. J.; Ji, H. W.; Ma, W. H.; Chen, C. C.; Zhao, J. C. Activation of water in titanium dioxide photocatalysis by formation of surface hydrogen bonds: An in situ IR spectroscopy study. Angew. Chem., Int. Ed. 2015, 54, 5905–5909.
DOI Google Scholar
[39]

Tsai, M. C.; Ship, U.; Bassignana, I. C.; Küppers, J.; Ertl, G. A vibrational spectroscopy study on the interaction of N2 with clean and K-promoted Fe (111) surfaces: π-bonded dinitrogen as precursor for dissociation. Surf. Sci. 1985, 155, 387–399.
DOI Google Scholar
[40]

Ding, K. Y.; Pierpont, A. W.; Brennessel, W. W.; Lukat-Rodgers, G.; Rodgers, K. R.; Cundari, T. R.; Bill, E.; Holland, P. L. Cobalt-dinitrogen complexes with weakened N–N bonds. J. Am. Chem. Soc. 2009, 131, 9471–9472.
DOI Google Scholar
[41]

Edwards, J. G.; Davies, J. A.; Boucher, D. L.; Mennad, A. An opinion on the heterogeneous photoreactions of N2 with H2O. Angew. Chem., Int. Ed. 1992, 31, 480–482.
DOI Google Scholar
[42]

Liu, S. S.; Qian, T.; Wang, M. F.; Ji, H. Q.; Shen, X. W.; Wang, C.; Yan, C. L. Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis. Nat. Catal. 2021, 4, 322–331.
DOI Google Scholar
[43]

Zhao, Y. X.; Zhao, Y. F.; Shi, R.; Wang, B.; Waterhouse, G. I. N.; Wu, L. Z.; Tung, C. H.; Zhang, T. R. Tuning oxygen vacancies in ultrathin TiO2 nanosheets to boost photocatalytic nitrogen fixation up to 700 nm. Adv. Mater. 2019, 31, 1806482.
DOI Google Scholar
File
12274_2022_5462_MOESM1_ESM.pdf (2.2 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 13 October 2022
Revised: 04 January 2023
Accepted: 05 January 2023
Published: 16 February 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the National key Research and Development project of China (No. 2020YFA0710000), the National Natural Science Foundation of China (Nos. 22225606, 22176029, and 21822601), the Sichuan Natural Science Foundation for Distinguished Scholars (No. 2021JDJQ0006), and the Fundamental Research Funds for the Central Universities (No. ZYGX2019Z021).

Return