The Role of Adventitious Carbon in Photo-catalytic Nitrogen Fixation by Titania

Comer, Benjamin M.; Liu, Yu-Hsuan; Dixit, Marm B.; Hatzell, Kelsey B.; Ye, Yifan; Crumlin, Ethan J.; Hatzell, Marta C.; Medford, Andrew J.

doi:10.1021/jacs.8b08464

Title: The Role of Adventitious Carbon in Photo-catalytic Nitrogen Fixation by Titania

Journal Article · Mon Oct 29 00:00:00 UTC 2018 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.8b08464 · OSTI ID:1656473

Comer, Benjamin M. ^[1]; Liu, Yu-Hsuan ^[1]; Dixit, Marm B. ^[2];

^[2]; Ye, Yifan ^[3];

^[3];

^[1];

^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)
Vanderbilt Univ., Nashville, TN (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Photo-catalytic fixation of nitrogen by titania catalysts at ambient conditions has been reported for decades, yet the active site capable of adsorbing an inert N₂ molecule at ambient pressure and the mechanism of dissociating the strong dinitrogen triple bond at room temperature remain unknown. In this work in situ near-ambient-pressure X-ray photo-electron spectroscopy and density functional theory calculations are used to probe the active state of the rutile (110) surface. Furthermore, the experimental results indicate that photon-driven interaction of N₂ and TiO₂ is observed only if adventitious surface carbon is present, and computational results show a remarkably strong interaction between N2 and carbon substitution (C*) sites that act as surface-bound carbon radicals. Additionally, a carbon-assisted nitrogen reduction mechanism is proposed and shown to be thermodynamically feasible. The findings provide a molecular-scale explanation for the long-standing mystery of photo-catalytic nitrogen fixation on titania. The results suggest that controlling and characterizing carbon-based active sites may provide a route to engineering more efficient photo(electro)-catalysts and improving experimental reproducibility.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES), Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1656473

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 45 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (30)

Photofixierung von Stickstoff an nanostrukturierten Eisentitanatfilmen Rusina, Olga; Eremenko, Anna; Frank, Gerhard Angewandte Chemie, Vol. 113, Issue 21 https://doi.org/10.1002/1521-3757(20011105)113:21<4115::AID-ANGE4115>3.0.CO;2-Z	journal	November 2001
Photocatalytic Conversion of CO ₂ into Renewable Hydrocarbon Fuels: State-of-the-Art Accomplishment, Challenges, and Prospects Tu, Wenguang; Zhou, Yong; Zou, Zhigang Advanced Materials, Vol. 26, Issue 27 https://doi.org/10.1002/adma.201400087	journal	May 2014
Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon-Enhanced TiO ₂ Photoelectrodes Li, Chengcheng; Wang, Tuo; Zhao, Zhi-Jian Angewandte Chemie, Vol. 130, Issue 19 https://doi.org/10.1002/ange.201713229	journal	March 2018
Photoreduction of Nitrogen on TiO₂ and TiO₂-Containing Minerals Schrauzer, Gerhard N. Energy Efficiency and Renewable Energy Through Nanotechnology https://doi.org/10.1007/978-0-85729-638-2_18	book	January 2011
X-ray photoelectron spectroscopy (XPS) studies of hydrogen reduced rutile (TiO2-x) surfaces Lazarus, M. S.; Sham, T. K. Chemical Physics Letters, Vol. 92, Issue 6 https://doi.org/10.1016/0009-2614(82)83672-5	journal	November 1982
Photocatalytic reduction of CO₂ with H₂O on various titanium oxide catalysts Anpo, Masakazu; Yamashita, Hiromi; Ichihashi, Yuichi Journal of Electroanalytical Chemistry, Vol. 396, Issue 1-2, p. 21-26 https://doi.org/10.1016/0022-0728(95)04141-A	journal	October 1995
Surface defects of TiO2(110): A combined XPS, XAES AND ELS study Göpel, W.; Anderson, J. A.; Frankel, D. Surface Science, Vol. 139, Issue 2-3 https://doi.org/10.1016/0039-6028(84)90054-2	journal	April 1984
The Auger spectrum of solid ammonia Larkins, F. P.; Lubenfeld, A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 15, Issue 1 https://doi.org/10.1016/0368-2048(79)87024-3	journal	January 1979
Photo-oxidation of short-chain hydrocarbons over titania Brigden, Clive T.; Poulston, Stephen; Twigg, Martyn V. Applied Catalysis B: Environmental, Vol. 32, Issue 1-2 https://doi.org/10.1016/S0926-3373(00)00292-7	journal	July 2001
Carbon-doped TiO2 photocatalyst synthesized without using an external carbon precursor and the visible light activity Park, Yiseul; Kim, Wooyul; Park, Hyunwoong Applied Catalysis B: Environmental, Vol. 91, Issue 1-2 https://doi.org/10.1016/j.apcatb.2009.06.001	journal	September 2009
Recent progress towards the electrosynthesis of ammonia from sustainable resources Shipman, Michael A.; Symes, Mark D. Catalysis Today, Vol. 286 https://doi.org/10.1016/j.cattod.2016.05.008	journal	May 2017
Photon-Driven Nitrogen Fixation: Current Progress, Thermodynamic Considerations, and Future Outlook Medford, Andrew J.; Hatzell, Marta C. ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.7b00439	journal	March 2017
Computational Screening of Rutile Oxides for Electrochemical Ammonia Formation Höskuldsson, Árni B.; Abghoui, Younes; Gunnarsdóttir, Anna B. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 11 https://doi.org/10.1021/acssuschemeng.7b02379	journal	September 2017
Analysis of Photocatalytic Nitrogen Fixation on Rutile TiO ₂ (110) Comer, Benjamin M.; Medford, Andrew J. ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 4 https://doi.org/10.1021/acssuschemeng.7b03652	journal	February 2018
Photolysis of Water and Photoreduction of Nitrogen on Titanium Dioxide Schrauzer, G. N.; Guth, T. D. Journal of the American Chemical Society, Vol. 99, Issue 22 https://doi.org/10.1021/ja00464a015	journal	October 1977
Role of Water and Carbonates in Photocatalytic Transformation of CO ₂ to CH ₄ on Titania Dimitrijevic, Nada M.; Vijayan, Baiju K.; Poluektov, Oleg G. Journal of the American Chemical Society, Vol. 133, Issue 11 https://doi.org/10.1021/ja108791u	journal	March 2011
Conversion of Dinitrogen to Ammonia by FeN ₃ -Embedded Graphene Li, Xiao-Fei; Li, Qin-Kun; Cheng, Jin Journal of the American Chemical Society, Vol. 138, Issue 28 https://doi.org/10.1021/jacs.6b04778	journal	July 2016
Photocatalytic Conversion of Nitrogen to Ammonia with Water on Surface Oxygen Vacancies of Titanium Dioxide Hirakawa, Hiroaki; Hashimoto, Masaki; Shiraishi, Yasuhiro Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.7b06634	journal	July 2017
High-Efficiency “Working-in-Tandem” Nitrogen Photofixation Achieved by Assembling Plasmonic Gold Nanocrystals on Ultrathin Titania Nanosheets Yang, Jianhua; Guo, Yanzhen; Jiang, Ruibin Journal of the American Chemical Society, Vol. 140, Issue 27 https://doi.org/10.1021/jacs.8b03537	journal	June 2018
Photoelectron Spectroscopic Investigation of Nitrogen-Doped Titania Nanoparticles Chen, Xiaobo; Burda, Clemens The Journal of Physical Chemistry B, Vol. 108, Issue 40 https://doi.org/10.1021/jp0469160	journal	October 2004
The Nature of Water Nucleation Sites on TiO ₂ (110) Surfaces Revealed by Ambient Pressure X-ray Photoelectron Spectroscopy Ketteler, Guido; Yamamoto, Susumu; Bluhm, Hendrik The Journal of Physical Chemistry C, Vol. 111, Issue 23 https://doi.org/10.1021/jp068606i	journal	June 2007
Properties of O ₂ ^• ^- and OH ^• Formed in TiO ₂ Aqueous Suspensions by Photocatalytic Reaction and the Influence of H ₂ O ₂ and Some Ions Hirakawa, Tsutomu; Nosaka, Yoshio Langmuir, Vol. 18, Issue 8 https://doi.org/10.1021/la015685a	journal	April 2002
Nitrate formation from atmospheric nitrogen and oxygen photocatalysed by nano-sized titanium dioxide Yuan, Shi-Jie; Chen, Jie-Jie; Lin, Zhi-Qi Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3249	journal	July 2013
Fullerene Embedded Shape Memory Nanolens Array Jeon, Sohee; Jang, Jun Young; Youn, Jae Ryoun Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03269	journal	November 2013
Challenges in reduction of dinitrogen by proton and electron transfer van der Ham, Cornelis J. M.; Koper, Marc T. M.; Hetterscheid, Dennis G. H. Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00085D	journal	January 2014
Photocatalytic methane conversion coupled with hydrogen evolution from water over Pd/TiO ₂ Yu, Linhui; Li, Danzhen Catalysis Science & Technology, Vol. 7, Issue 3 https://doi.org/10.1039/C6CY02435A	journal	January 2017
On the mechanism of nitrogen photofixation at nanostructured iron titanate films Linnik, Oksana; Kisch, Horst Photochemical & Photobiological Sciences, Vol. 5, Issue 10 https://doi.org/10.1039/b608396j	journal	January 2006
Isolated catalyst sites on amorphous supports: A systematic algorithm for understanding heterogeneities in structure and reactivity Goldsmith, Bryan R.; Sanderson, Evan D.; Bean, Daniel The Journal of Chemical Physics, Vol. 138, Issue 20 https://doi.org/10.1063/1.4807384	journal	May 2013
Nature of the use of adventitious carbon as a binding energy standard Barr, Tery L.; Seal, Sudipta Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 13, Issue 3 https://doi.org/10.1116/1.579868	journal	May 1995
First-Principles View on Photoelectrochemistry: Water-Splitting as Case Study Hellman, Anders; Wang, Baochang Inorganics, Vol. 5, Issue 2 https://doi.org/10.3390/inorganics5020037	journal	June 2017

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Photo(electro)catalytic Nitrogen Fixation: Problems and Possibilities Vu, Manh‐Hiep; Sakar, Mohan; Hassanzadeh‐Tabrizi, Sayed Ali Advanced Materials Interfaces, Vol. 6, Issue 12 https://doi.org/10.1002/admi.201900091	journal	April 2019
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Potassium‐Ion‐Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons: Visible‐Light‐Driven Photocatalytic Nitrogen Reduction Wang, Weikang; Zhang, Haimin; Zhang, Shengbo Angewandte Chemie International Edition, Vol. 58, Issue 46 https://doi.org/10.1002/anie.201908640	journal	November 2019
Photocatalytic CO ₂ reduction by H ₂ O: insights from modeling electronically relaxed mechanisms Poudyal, Samiksha; Laursen, Siris Catalysis Science & Technology, Vol. 9, Issue 4 https://doi.org/10.1039/c8cy02046a	journal	January 2019
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