Complexity in the Photofunctionalization of Single-Wall Carbon Nanotubes with Hypochlorite

Espinoza, Vanessa B.; Bachilo, Sergei M.; Zheng, Yu; Htoon, Han; Weisman, R. Bruce

doi:10.1021/acsnano.4c13605

Title: Complexity in the Photofunctionalization of Single-Wall Carbon Nanotubes with Hypochlorite

Journal Article · 08 January 2025 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.4c13605 · OSTI ID:2500879

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^[1]; Zheng, Yu ^[2];

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Rice Univ., Houston, TX (United States)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

The reaction of aqueous suspensions of single-wall carbon nanotubes (SWCNTs) with UV-excited sodium hypochlorite has previously been reported to be an efficient route for doping nanotubes with oxygen atoms. Here, we have investigated how this reaction system is affected by pH level, dissolved O₂ content, and radical scavengers and traps. Products were characterized with near-IR fluorescence, Raman, and XPS spectroscopy. The reaction is greatly accelerated by removal of dissolved O₂ and strongly suppressed by TEMPO, a radical trap. Alcohols added as radical scavengers alter the reaction efficiency and the product peak emission wavelengths. Photofunctionalization with 300 nm irradiation is substantially less efficient at pH levels low enough to protonate the OCl^– ion to HOCl. We deduce that in mildly treated high pH samples, the main product is sp² hybridized O-doped adducts formed by reaction of SWCNTs with atomic oxygen in its ³P (ground) level. By contrast, treatment under low pH conditions leads to sp³ hybridized SWCNT adducts formed by the addition of secondary radicals from reactions of ^•OH and ^•Cl. There is also evidence for additional photoreactions of product species under stronger irradiation. Researchers using photoexcited hypochlorite for SWCNT functionalization should be alert to the range of products and the sensitivity to reaction conditions in this system.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2500879

Report Number(s):: LA-UR--24-30534

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 2 Vol. 19; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Solid-State Approach for Fabrication of Photostable, Oxygen-Doped Carbon Nanotubes Ma, Xuedan; Baldwin, Jon K. S.; Hartmann, Nicolai F. Advanced Functional Materials, Vol. 25, Issue 39 https://doi.org/10.1002/adfm.201502580	journal	September 2015
Luminescent Defects in Single‐Walled Carbon Nanotubes for Applications Zaumseil, Jana Advanced Optical Materials, Vol. 10, Issue 2 https://doi.org/10.1002/adom.202101576	journal	November 2021
Absolute and relative rate constants for the reactions of hydroxyl radicals and chlorine atoms with a series of aliphatic alcohols and ethers at 298 K Nelson, Linda; Rattigan, Oliver; Neavyn, Ruaidhri International Journal of Chemical Kinetics, Vol. 22, Issue 11 https://doi.org/10.1002/kin.550221102	journal	November 1990
Rate constants for the gas-phase reactions of alkanes with Cl atoms at 296 ± 2 K: GAS-PHASE REACTIONS OF ALKANES Aschmann, Sara M.; Atkinson, Roger International Journal of Chemical Kinetics, Vol. 27, Issue 6 https://doi.org/10.1002/kin.550270611	journal	June 1995
Fluorimetric characterization of single-walled carbon nanotubes Weisman, R. Bruce Analytical and Bioanalytical Chemistry, Vol. 396, Issue 3 https://doi.org/10.1007/s00216-009-3062-8	journal	September 2009
Photolysis of aqueous chlorine at sunlight and ultraviolet wavelengths—II. Hydroxyl radical production Nowell, Lisa H.; Hoigné, Jürg Water Research, Vol. 26, Issue 5 https://doi.org/10.1016/0043-1354(92)90233-T	journal	May 1992
Optical properties of single-wall carbon nanotubes Kataura, H.; Kumazawa, Y.; Maniwa, Y. Synthetic Metals, Vol. 103, Issue 1-3 https://doi.org/10.1016/S0379-6779(98)00278-1	journal	June 1999
Atomic oxygen functionalization of double walled C nanotubes Larciprete, R.; Gardonio, S.; Petaccia, L. Carbon, Vol. 47, Issue 11 https://doi.org/10.1016/j.carbon.2009.05.008	journal	September 2009
Rate constants of the O(1D) reactions with N2, O2, N2O, and H2O at 295 K Takahashi, Kenshi; Takeuchi, Yukari; Matsumi, Yutaka Chemical Physics Letters, Vol. 410, Issue 4-6 https://doi.org/10.1016/j.cplett.2005.05.062	journal	July 2005
Wavelength-dependent chlorine photolysis and subsequent radical production using UV-LEDs as light sources Yin, Ran; Ling, Li; Shang, Chii Water Research, Vol. 142 https://doi.org/10.1016/j.watres.2018.06.018	journal	October 2018
Carbon Nanotube Photoluminescence Modulation by Local Chemical and Supramolecular Chemical Functionalization Shiraki, Tomohiro; Miyauchi, Yuhei; Matsuda, Kazunari Accounts of Chemical Research, Vol. 53, Issue 9 https://doi.org/10.1021/acs.accounts.0c00294	journal	August 2020
The Impact of pH and Irradiation Wavelength on the Production of Reactive Oxidants during Chlorine Photolysis Bulman, Devon Manley; Mezyk, Stephen P.; Remucal, Christina K. Environmental Science & Technology, Vol. 53, Issue 8 https://doi.org/10.1021/acs.est.8b07225	journal	March 2019
Surface Coating- and Light-Controlled Oxygen Doping of Carbon Nanotubes Xhyliu, Fjorela; Ao, Geyou The Journal of Physical Chemistry C, Vol. 125, Issue 17 https://doi.org/10.1021/acs.jpcc.1c00257	journal	April 2021
Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes Gifford, Brendan J.; Kilina, Svetlana; Htoon, Han The Journal of Physical Chemistry C, Vol. 122, Issue 3 https://doi.org/10.1021/acs.jpcc.7b09558	journal	November 2017
Enantiomers of Single-Wall Carbon Nanotubes Show Distinct Coating Displacement Kinetics Zheng, Yu; Bachilo, Sergei M.; Weisman, R. Bruce The Journal of Physical Chemistry Letters, Vol. 9, Issue 13 https://doi.org/10.1021/acs.jpclett.8b01683	journal	June 2018
Controlled Patterning of Carbon Nanotube Energy Levels by Covalent DNA Functionalization Zheng, Yu; Bachilo, Sergei M.; Weisman, R. Bruce ACS Nano, Vol. 13, Issue 7 https://doi.org/10.1021/acsnano.9b03488	journal	June 2019
Ultrafast Exciton Trapping at sp ³ Quantum Defects in Carbon Nanotubes Sykes, Matthew E.; Kim, Mijin; Wu, Xiaojian ACS Nano, Vol. 13, Issue 11 https://doi.org/10.1021/acsnano.9b06279	journal	October 2019
Photoexcited Aromatic Reactants Give Multicolor Carbon Nanotube Fluorescence from Quantum Defects Zheng, Yu; Bachilo, Sergei M.; Weisman, R. Bruce ACS Nano, Vol. 14, Issue 1 https://doi.org/10.1021/acsnano.9b07606	journal	December 2019
A Dynamic, Mathematical Model for Quantitative Glycoprofiling Using Label-Free Lectin Microarrays Salem, Daniel P.; Nelson, Justin T.; Kim, Sojin ACS Sensors, Vol. 1, Issue 8 https://doi.org/10.1021/acssensors.6b00121	journal	July 2016
Fundamental Electronic Properties and Applications of Single-Walled Carbon Nanotubes Ouyang, Min; Huang, Jin-Lin; Lieber, Charles M. Accounts of Chemical Research, Vol. 35, Issue 12 https://doi.org/10.1021/ar0101685	journal	December 2002
Attachment of Nitrogen and Oxygen Centered Radicals to Single-Walled Carbon Nanotube Salts Mukherjee, Arnab; Combs, Rachel; Chattopadhyay, Jayanta Chemistry of Materials, Vol. 20, Issue 23 https://doi.org/10.1021/cm8014226	journal	November 2008
Photochemical production of chlorinated organics in aqueous solutions containing chlorine Oliver, Barry G.; Carey, John H. Environmental Science & Technology, Vol. 11, Issue 9 https://doi.org/10.1021/es60132a003	journal	September 1977
Hypochlorous acid decomposition in the pH 5-8 region Adam, Luke C.; Fabian, Istvan; Suzuki, Kazunori Inorganic Chemistry, Vol. 31, Issue 17 https://doi.org/10.1021/ic00043a011	journal	August 1992
Laser Flash Photolysis of Pyridine N-Oxide: Kinetic Studies of Atomic Oxygen [O(3P)] in Solution Bucher, Gotz; Scaiano, J. C. The Journal of Physical Chemistry, Vol. 98, Issue 48 https://doi.org/10.1021/j100099a004	journal	December 1994
Production of hydroxyl from photolysis of hypochlorous acid at 307-309 nm Molina, Mario J.; Ishiwata, Takashi; Molina, Luisa T. The Journal of Physical Chemistry, Vol. 84, Issue 8 https://doi.org/10.1021/j100445a004	journal	April 1980
The Acid Ionization Constant of HOCl from 5 to 35° Morris, J. Carrell The Journal of Physical Chemistry, Vol. 70, Issue 12 https://doi.org/10.1021/j100884a007	journal	December 1966
Helicity-Selective Photoreaction of Single-Walled Carbon Nanotubes with Organosulfur Compounds in the Presence of Oxygen Maeda, Yutaka; Higo, Junki; Amagai, Yuri Journal of the American Chemical Society, Vol. 135, Issue 16 https://doi.org/10.1021/ja402199n	journal	April 2013
Molecularly Tunable Fluorescent Quantum Defects Kwon, Hyejin; Furmanchuk, Al’ona; Kim, Mijin Journal of the American Chemical Society, Vol. 138, Issue 21 https://doi.org/10.1021/jacs.6b03618	journal	May 2016
Defect-Induced Near-Infrared Photoluminescence of Single-Walled Carbon Nanotubes Treated with Polyunsaturated Fatty Acids Chiu, Cheuk Fai; Saidi, Wissam A.; Kagan, Valerian E. Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.7b00390	journal	March 2017
Functionalization of Carbon Nanotubes by Free Radicals Ying, Yunming; Saini, Rajesh K.; Liang, Feng Organic Letters, Vol. 5, Issue 9 https://doi.org/10.1021/ol0342453	journal	May 2003
Ultraviolet absorption spectrum of HOCl Burkholder, James B. Journal of Geophysical Research: Atmospheres, Vol. 98, Issue D2 https://doi.org/10.1029/92JD02522	journal	February 1993
Atomic structure and electronic properties of single-walled carbon nanotubes Odom, Teri Wang; Huang, Jin-Lin; Kim, Philip Nature, Vol. 391, Issue 6662 https://doi.org/10.1038/34145	journal	January 1998
Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects Piao, Yanmei; Meany, Brendan; Powell, Lyndsey R. Nature Chemistry, Vol. 5, Issue 10 https://doi.org/10.1038/nchem.1711	journal	July 2013
Room-temperature single-photon generation from solitary dopants of carbon nanotubes Ma, Xuedan; Hartmann, Nicolai F.; Baldwin, Jon K. S. Nature Nanotechnology, Vol. 10, Issue 8 https://doi.org/10.1038/nnano.2015.136	journal	July 2015
Creating fluorescent quantum defects in carbon nanotubes using hypochlorite and light Lin, Ching-Wei; Bachilo, Sergei M.; Zheng, Yu Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10917-3	journal	June 2019
Detection of ovarian cancer via the spectral fingerprinting of quantum-defect-modified carbon nanotubes in serum by machine learning Kim, Mijin; Chen, Chen; Wang, Peng Nature Biomedical Engineering, Vol. 6, Issue 3 https://doi.org/10.1038/s41551-022-00860-y	journal	March 2022
Controlling the optical properties of carbon nanotubes with organic colour-centre quantum defects Brozena, Alexandra H.; Kim, Mijin; Powell, Lyndsey R. Nature Reviews Chemistry, Vol. 3, Issue 6 https://doi.org/10.1038/s41570-019-0103-5	journal	June 2019
Oxygen-doped carbon nanotubes for near-infrared fluorescent labels and imaging probes Iizumi, Yoko; Yudasaka, Masako; Kim, Jaeho Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-24399-8	journal	April 2018
Fluorescent sp3 Defect-Tailored Carbon Nanotubes Enable NIR-II Single Particle Imaging in Live Brain Slices at Ultra-Low Excitation Doses Mandal, Amit Kumar; Wu, Xiaojian; Ferreira, Joana S. Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-62201-w	journal	March 2020
Emergence of new red-shifted carbon nanotube photoluminescence based on proximal doped-site design Shiraki, Tomohiro; Shiraishi, Tomonari; Juhász, Gergely Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep28393	journal	June 2016
Measurement of the rate coefficient for the reaction of O(1D) with H2O and re-evaluation of the atmospheric OH production rate Dunlea, Edward J.; Ravishankara, A. R. Physical Chemistry Chemical Physics, Vol. 6, Issue 13 https://doi.org/10.1039/b402483d	journal	January 2004
Radiation chemistry and photochemistry of oxychlorine ions. Part 2.—Photodecomposition of aqueous solutions of hypochlorite ions Buxton, G. V.; Subhani, M. S. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 68, Issue 0 https://doi.org/10.1039/f19726800958	journal	January 1972
Ozone formation in laser flash photolysis of oxoacids and oxoanions of chlorine and bromine Kläning, Ulrik K.; Sehested, Knud; Wolff, Thomas Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 80, Issue 11 https://doi.org/10.1039/f19848002969	journal	January 1984
Femtosecond photolysis of aqueous HOCl Thomsen, C. L.; Madsen, D.; Poulsen, J. Aa. The Journal of Chemical Physics, Vol. 115, Issue 20 https://doi.org/10.1063/1.1413964	journal	November 2001
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555805	journal	April 1988
Oxygen Doping Modifies Near-Infrared Band Gaps in Fluorescent Single-Walled Carbon Nanotubes Ghosh, S.; Bachilo, S. M.; Simonette, R. A. Science, Vol. 330, Issue 6011 https://doi.org/10.1126/science.1196382	journal	November 2010
Photolysis of aqueous free chlorine species (HOCl and OCl) with 254 nm ultraviolet light Feng, Yangang; Smith, Daniel W.; Bolton, James R. Journal of Environmental Engineering and Science, Vol. 6, Issue 3 https://doi.org/10.1139/s06-052	journal	May 2007

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Title: Complexity in the Photofunctionalization of Single-Wall Carbon Nanotubes with Hypochlorite

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