Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling

Walz Mitra, Kendahl L.; Chang, Christine H.; Hanrahan, Michael P.; Yang, Jiaying; Tofan, Daniel; Holden, William M.; Govind, Niranjan; Seidler, Gerald T.; Rossini, Aaron J.; Velian, Alexandra

doi:10.1002/anie.202016033

Title: Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling

Journal Article · Fri Dec 18 00:00:00 EST 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202016033· OSTI ID:1774051

^[1];

^[1]; Hanrahan, Michael P. ^[2];

^[1];

^[3];

^[1];

^[2];

^[1]

Univ. of Washington, Seattle, WA (United States)
Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Abstract Surface functionalization of two‐dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced herein is a mild, surface‐specific protocol for the surface functionalization of few‐layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational, X‐ray photoelectron, solid state ³¹ P NMR, and UV‐vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, ¹⁵ N‐labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-07CH11358; AC05-76RL01830

OSTI ID:: 1774051

Alternate ID(s):: OSTI ID: 1804569

Report Number(s):: IS-J-10,451

Journal Information:: Angewandte Chemie (International Edition), Vol. 60, Issue 16; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Dual-Gate Black Phosphorus Field-Effect Transistors with Hexagonal Boron Nitride as Dielectric and Passivation Layers Ra, Hyun-Soo; Lee, A-Young; Kwak, Do-Hyun ACS Applied Materials & Interfaces, Vol. 10, Issue 1 https://doi.org/10.1021/acsami.7b16809	journal	December 2017
Basal-Plane Functionalization of Chemically Exfoliated Molybdenum Disulfide by Diazonium Salts Knirsch, Kathrin C.; Berner, Nina C.; Nerl, Hannah C. ACS Nano, Vol. 9, Issue 6 https://doi.org/10.1021/acsnano.5b00965	journal	May 2015
Untersuchungen an der PN-Doppelbindung, VI. Darstellung und PN-Valenzschwingungsfrequenzen substituierter Phosphinimine Wiegräbe, Winfried; Bock, Hans Chemische Berichte, Vol. 101, Issue 4 https://doi.org/10.1002/cber.19681010433	journal	April 1968
Transient Protection of Organic Azides from Click Reactions with Alkynes by Phosphazide Formation Meguro, Tomohiro; Yoshida, Suguru; Igawa, Kazunobu Organic Letters, Vol. 20, Issue 13 https://doi.org/10.1021/acs.orglett.8b01692	journal	June 2018
Mechanism of the hydrolysis of N-aryliminotriphenylphosphoranes Pyun, S. -Y.; Lee, Y. -H.; Kim, T. -R. Kinetics and Catalysis, Vol. 46, Issue 1 https://doi.org/10.1007/s10975-005-0031-x	journal	January 2005
Control of Surface and Edge Oxidation on Phosphorene Kuntz, Kaci L.; Wells, Rebekah A.; Hu, Jun ACS Applied Materials & Interfaces, Vol. 9, Issue 10 https://doi.org/10.1021/acsami.6b16111	journal	March 2017
Selective attachment of benzonitrile on Si(111)-7×7: Configuration, selectivity, and mechanism Tao, Feng; Wang, Zhong Hai; Chen, Xian Feng Physical Review B, Vol. 65, Issue 11 https://doi.org/10.1103/PhysRevB.65.115311	journal	February 2002
Polarization-sensitive broadband photodetector using a black phosphorus vertical p–n junction Yuan, Hongtao; Liu, Xiaoge; Afshinmanesh, Farzaneh Nature Nanotechnology, Vol. 10, Issue 8 https://doi.org/10.1038/nnano.2015.112	journal	June 2015
Azide Passivation of Black Phosphorus Nanosheets: Covalent Functionalization Affords Ambient Stability Enhancement Liu, Yajuan; Gao, Pengfei; Zhang, Taiming Angewandte Chemie International Edition, Vol. 58, Issue 5 https://doi.org/10.1002/anie.201813218	journal	January 2019
X-ray photoelectron study of amorphous phosphorus preparedbyplasmachemical transport. Comparison with crystalline polymorphs Brunner, J.; Thüler, M.; Veprek, S. Journal of Physics and Chemistry of Solids, Vol. 40, Issue 12 https://doi.org/10.1016/0022-3697(79)90126-4	journal	January 1979
Gate-Tuned Thermoelectric Power in Black Phosphorus Saito, Yu; Iizuka, Takahiko; Koretsune, Takashi Nano Letters, Vol. 16, Issue 8 https://doi.org/10.1021/acs.nanolett.6b00999	journal	August 2016
Covalent bulk functionalization of graphene Englert, Jan M.; Dotzer, Christoph; Yang, Guang Nature Chemistry, Vol. 3, Issue 4 https://doi.org/10.1038/nchem.1010	journal	March 2011
Gitteröffnung durch reduktive kovalente Volumen‐Funktionalisierung von schwarzem Phosphor Wild, Stefan; Fickert, Michael; Mitrovic, Aleksandra Angewandte Chemie, Vol. 131, Issue 17 https://doi.org/10.1002/ange.201811181	journal	March 2019
Vibrational spectroscopy of Methyl benzoate Maiti, Kiran Sankar Physical Chemistry Chemical Physics, Vol. 17, Issue 30 https://doi.org/10.1039/C5CP02281A	journal	January 2015
Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A. Nature Chemistry, Vol. 8, Issue 6 https://doi.org/10.1038/nchem.2505	journal	May 2016
Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering Voiry, Damien; Goswami, Anandarup; Kappera, Rajesh Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2108	journal	November 2014
Efficiency and Quality Issues in the Production of Black Phosphorus by Mechanochemical Synthesis: A Multi-Technique Approach Ferrara, Chiara; Vigo, Emanuele; Albini, Benedetta ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.9b00132	journal	March 2019
Structural absorption by barbule microstructures of super black bird of paradise feathers McCoy, Dakota E.; Feo, Teresa; Harvey, Todd Alan Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-017-02088-w	journal	January 2018
Decomposition and addition reactions of organic azides L'abbe, G. Chemical Reviews, Vol. 69, Issue 3 https://doi.org/10.1021/cr60259a004	journal	June 1969
Recent advances in the staudinger reaction Gololobov, Yuri G.; Kasukhin, Leonid F. Tetrahedron, Vol. 48, Issue 8, p. 1353-1406 https://doi.org/10.1016/S0040-4020(01)92229-X	journal	February 1992
Covalently Functionalized Hexagonal Boron Nitride Nanosheets by Nitrene Addition Sainsbury, Toby; Satti, Amro; May, Peter Chemistry - A European Journal, Vol. 18, Issue 35 https://doi.org/10.1002/chem.201201734	journal	July 2012
Novel λ ³ -Iodane-Based Functionalization of Synthetic Carbon Allotropes (SCAs)-Common Concepts and Quantification of the Degree of Addition Hof, Ferdinand; Schäfer, Ricarda A.; Weiss, Cornelius Chemistry - A European Journal, Vol. 20, Issue 50 https://doi.org/10.1002/chem.201404662	journal	October 2014
Über neue organische Phosphorverbindungen III. Phosphinmethylenderivate und Phosphinimine Staudinger, H.; Meyer, Jules Helvetica Chimica Acta, Vol. 2, Issue 1, p. 635-646 https://doi.org/10.1002/hlca.19190020164	journal	January 1919
Mechanisms of Tetrazole Formation by Addition of Azide to Nitriles Himo, Fahmi; Demko, Zachary P.; Noodleman, Louis Journal of the American Chemical Society, Vol. 124, Issue 41 https://doi.org/10.1021/ja0206644	journal	October 2002
Phosphorene: An Unexplored 2D Semiconductor with a High Hole Mobility Liu, Han; Neal, Adam T.; Zhu, Zhen ACS Nano, Vol. 8, Issue 4 https://doi.org/10.1021/nn501226z	journal	March 2014
Surface Coordination of Black Phosphorus for Robust Air and Water Stability Zhao, Yuetao; Wang, Huaiyu; Huang, Hao Angewandte Chemie International Edition, Vol. 55, Issue 16 https://doi.org/10.1002/anie.201512038	journal	March 2016
Valence band and core-level photoemission spectra of black phosphorus single crystals Taniguchi, M.; Suga, S.; Seki, M. Solid State Communications, Vol. 45, Issue 2 https://doi.org/10.1016/0038-1098(83)90340-X	journal	January 1983
Surface Coordination of Black Phosphorus for Robust Air and Water Stability Zhao, Yuetao; Wang, Huaiyu; Huang, Hao Angewandte Chemie, Vol. 128, Issue 16 https://doi.org/10.1002/ange.201512038	journal	March 2016
Covalent Functionalization of Few-Layer Black Phosphorus Using Iodonium Salts and Comparison to Diazonium Modified Black Phosphorus van Druenen, Maart; Davitt, Fionán; Collins, Timothy Chemistry of Materials, Vol. 30, Issue 14 https://doi.org/10.1021/acs.chemmater.8b01306	journal	June 2018
Covalent functionalization of black phosphorus nanoflakes by carbon free radicals for durable air and water stability Hu, Haiguo; Gao, Hong; Gao, Lili Nanoscale, Vol. 10, Issue 13 https://doi.org/10.1039/C7NR06085H	journal	January 2018
NMR study of InP quantum dots: Surface structure and size effects Tomaselli, M.; Yarger, J. L.; Bruchez, M. The Journal of Chemical Physics, Vol. 110, Issue 18 https://doi.org/10.1063/1.478858	journal	May 1999
Black phosphorus field-effect transistors Li, Likai; Yu, Yijun; Ye, Guo Jun Nature Nanotechnology, Vol. 9, Issue 5 https://doi.org/10.1038/nnano.2014.35	journal	March 2014
Black Phosphorus Mid-Infrared Photodetectors with High Gain Guo, Qiushi; Pospischil, Andreas; Bhuiyan, Maruf Nano Letters, Vol. 16, Issue 7 https://doi.org/10.1021/acs.nanolett.6b01977	journal	June 2016
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazoleElectronic supplementary information (ESI) available: Calculated molecular geometries, rotational constants, energies and dipole moments. Definition of internal symmetry coordinates used in the normal mode analysis. Experimental spectrum of polycrystalline 5-chlorotetrazole and calculated spectrum for the 1H-tautomer. See http://www.rsc.org/suppdata/cp/b1/b111329c/ C. S. Bugalho, Susana; Serra, A. C.; Lapinski, Leszek Physical Chemistry Chemical Physics, Vol. 4, Issue 10 https://doi.org/10.1039/b111329c	journal	April 2002
Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus Wild, Stefan; Fickert, Michael; Mitrovic, Aleksandra Angewandte Chemie International Edition, Vol. 58, Issue 17 https://doi.org/10.1002/anie.201811181	journal	March 2019

Similar Records

Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling

Journal Article · Tue Mar 09 00:00:00 EST 2021 · Angewandte Chemie · OSTI ID:1774051

Walz Mitra, Kendahl L.; Chang, Christine H.; Hanrahan, Michael P.; +7 more

Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds Using Isotopic Labeling

Journal Article · Mon Apr 12 00:00:00 EDT 2021 · Angewandte Chemie International Edition · OSTI ID:1774051

Walz, Kendall; Chang, Christine H.; Hanrahan, Michael P.; +7 more

Metabolic Incorporation of N ‐Acetyl Muramic Acid Probes into Bacterial Peptidoglycan

Journal Article · Thu Oct 10 00:00:00 EDT 2019 · Current Protocols in Chemical Biology · OSTI ID:1774051

DeMeester, Kristen E.; Liang, Hai; Zhou, Junhui; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ambient stability
black phosphorus
isotopic labeling
nitrene functionalization
surface modification

Title: Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling

Citation Formats

References (35)

Similar Records

Related Subjects