Graphite and Graphene Fairy Circles: A Bottom-Up Approach for the Formation of Nanocorrals
- Thanh Hai Phan*Thanh Hai Phan*E-mail: [email protected]Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumDepartment of Physics, Quy Nhon University, 170 An Duong Vuong, Quy Nhon, VietnamMore by Thanh Hai Phan
- ,
- Hans Van GorpHans Van GorpDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Hans Van Gorp
- ,
- Zhi LiZhi LiDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Zhi Li
- ,
- Thi Mien Trung HuynhThi Mien Trung HuynhDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumDepartment of Chemistry, Quy Nhon University, 170 An Duong Vuong, Quy Nhon, VietnamMore by Thi Mien Trung Huynh
- ,
- Yasuhiko FujitaYasuhiko FujitaDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Yasuhiko Fujita
- ,
- Lander VerstraeteLander VerstraeteDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Lander Verstraete
- ,
- Samuel EyleySamuel EyleyDepartment of Chemical Engineering, Renewable Materials and Nanotechnology Group, Campus Kortrijk, KU Leuven, Etienne Sabbelaan 53, 8500 Kortrijk, BelgiumMore by Samuel Eyley
- ,
- Wim ThielemansWim ThielemansDepartment of Chemical Engineering, Renewable Materials and Nanotechnology Group, Campus Kortrijk, KU Leuven, Etienne Sabbelaan 53, 8500 Kortrijk, BelgiumMore by Wim Thielemans
- ,
- Hiroshi Uji-iHiroshi Uji-iDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Hiroshi Uji-i
- ,
- Brandon E. HirschBrandon E. HirschDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Brandon E. Hirsch
- ,
- Stijn F. L. MertensStijn F. L. MertensDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumDepartment of Chemistry, Lancaster University, Lancaster LA1 4YB, United KingdomMore by Stijn F. L. Mertens
- ,
- John GreenwoodJohn GreenwoodDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by John Greenwood
- ,
- Oleksandr Ivasenko*Oleksandr Ivasenko*E-mail: [email protected]Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Oleksandr Ivasenko
- , and
- Steven De Feyter*Steven De Feyter*E-mail: [email protected]Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, BelgiumMore by Steven De Feyter
Abstract
A convenient covalent functionalization approach and nanopatterning method of graphite and graphene is developed. In contrast to expectations, electrochemically activated dediazotization of a mixture of two aryl diazonium compounds in aqueous media leads to a spatially inhomogeneous functionalization of graphitic surfaces, creating covalently modified surfaces with quasi-uniform spaced islands of pristine graphite or graphene, coined nanocorrals. Cyclic voltammetry and chronoamperometry approaches are compared. The average diameter (45–130 nm) and surface density (20–125 corrals/μm2) of these nanocorrals are tunable. These chemically modified nanostructured graphitic (CMNG) surfaces are characterized by atomic force microscopy, scanning tunneling microscopy, Raman spectroscopy and microscopy, and X-ray photoelectron spectroscopy. Mechanisms leading to the formation of these CMNG surfaces are discussed. The potential of these surfaces to investigate supramolecular self-assembly and on-surface reactions under nanoconfinement conditions is demonstrated.
Cited By
This article is cited by 29 publications.
- Sota Aoi, Shingo Hirose, Wakana Soeda, Hiromasa Kaneko, Kunal S. Mali, Steven De Feyter, Kazukuni Tahara. Spatially Controlled Aryl Radical Grafting of Graphite Surfaces Guided by Self-Assembled Molecular Networks of Linear Alkane Derivatives: The Importance of Conformational Dynamics. Langmuir 2023, 39 (17) , 5986-5994. https://doi.org/10.1021/acs.langmuir.2c03434
- Thi Mien Trung Huynh, Thanh Hai Phan, Steven De Feyter. Surface Engineering of Graphite and Graphene by Viologen Self-Assembling: From Global to Local Architectures. The Journal of Physical Chemistry C 2022, 126 (14) , 6413-6419. https://doi.org/10.1021/acs.jpcc.1c10940
- Roelof Steeno, Hans Van Gorp, Peter Walke, Kunal S. Mali, Steven De Feyter. AFM Nanoshaving of Covalently Modified Graphite for Studying Molecular Self-Assembly under Lateral Nanoconfinement. The Journal of Physical Chemistry C 2021, 125 (39) , 21624-21634. https://doi.org/10.1021/acs.jpcc.1c05700
- Yi Hu, Shern-Long Lee, Wenli Deng. Structural Diversity and Phase Transition Control via Kinetics and Thermodynamics in Mixed Solvents: Two-Dimensional Self-Assembly at the Liquid/Solid Interface. The Journal of Physical Chemistry C 2020, 124 (49) , 27148-27157. https://doi.org/10.1021/acs.jpcc.0c08110
- Roelof Steeno, Miriam C. Rodríguez González, Samuel Eyley, Wim Thielemans, Kunal S. Mali, Steven De Feyter. Covalent Functionalization of Carbon Surfaces: Diaryliodonium versus Aryldiazonium Chemistry. Chemistry of Materials 2020, 32 (12) , 5246-5255. https://doi.org/10.1021/acs.chemmater.0c01393
- Kazukuni Tahara, Yuki Kubo, Shingo Hashimoto, Toru Ishikawa, Hiromasa Kaneko, Anton Brown, Brandon E. Hirsch, Steven De Feyter, Yoshito Tobe. Porous Self-Assembled Molecular Networks as Templates for Chiral-Position-Controlled Chemical Functionalization of Graphitic Surfaces. Journal of the American Chemical Society 2020, 142 (16) , 7699-7708. https://doi.org/10.1021/jacs.0c02979
- Chunmei Zhang, Xin Zhou, Chunlei Zhu, Yufen Zong, Hai Cao. STM studies on porphyrins and phthalocyanines at the liquid/solid interface for molecular-scale electronics. Dalton Transactions 2023, 52 (32) , 11017-11024. https://doi.org/10.1039/D3DT01518A
- Thi Mien Trung Huynh, Kazukuni Tahara, Steven De Feyter, Thanh Hai Phan. On the role of functional groups in the formation of diazonium based covalent attachments: dendritic vs. layer-by-layer growth. RSC Advances 2023, 13 (35) , 24576-24582. https://doi.org/10.1039/D3RA02661B
- Sasikumar Rahul, Miriam C. Rodríguez González, Shingo Hirose, Hiromasa Kaneko, Kazukuni Tahara, Kunal S. Mali, Steven De Feyter. Nanoscale chemical patterning of graphite at different length scales. Nanoscale 2023, 15 (24) , 10295-10305. https://doi.org/10.1039/D3NR00632H
- Thi Mien Trung Huynh, Duy Dien Nguyen, Nhat Hieu Hoang, Thanh Hai Phan. Reversible Tuning of Surface Properties of Graphene-like Material via Covalently Functionalized Hydrophobic Layer. Crystals 2023, 13 (4) , 635. https://doi.org/10.3390/cryst13040635
- Zhi Li, Yiming Guo, Kai Li, Shuang Wang, Enrico De Bonis, Hai Cao, Stijn F.L. Mertens, Chao Teng. Shape control of bimetallic MOF/Graphene composites for efficient oxygen evolution reaction. Journal of Electroanalytical Chemistry 2023, 930 , 117144. https://doi.org/10.1016/j.jelechem.2023.117144
- Cecilia Wetzl, Alessandro Silvestri, Marina Garrido, Hui‐Lei Hou, Alejandro Criado, Maurizio Prato. The Covalent Functionalization of Surface‐Supported Graphene: An Update. Angewandte Chemie International Edition 2023, 62 (6) https://doi.org/10.1002/anie.202212857
- Cecilia Wetzl, Alessandro Silvestri, Marina Garrido, Hui‐Lei Hou, Alejandro Criado, Maurizio Prato. The Covalent Functionalization of Surface‐Supported Graphene: An Update. Angewandte Chemie 2023, 135 (6) https://doi.org/10.1002/ange.202212857
- Yuanzhi Xia, Semih Sevim, João Pedro Vale, Johannes Seibel, David Rodríguez-San-Miguel, Donghoon Kim, Salvador Pané, Tiago Sotto Mayor, Steven De Feyter, Josep Puigmartí-Luis. Covalent transfer of chemical gradients onto a graphenic surface with 2D and 3D control. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-34684-w
- Yuanzhi Xia, Johannes Seibel, Steven De Feyter. Self‐templated covalent functionalization of graphitic surfaces with a quasi‐periodic pattern. Aggregate 2022, 3 (4) https://doi.org/10.1002/agt2.205
- Antonio Dominguez-Alfaro, Ngoc Do Quyen Chau, Stephen Yan, Donato Mancino, Sushma Pamulapati, Steven Williams, Lauren W. Taylor, Oliver S. Dewey, Matteo Pasquali, Maurizio Prato, Alberto Bianco, Alejandro Criado. Electrochemical modification of carbon nanotube fibres. Nanoscale 2022, 14 (26) , 9313-9322. https://doi.org/10.1039/D1NR07495D
- Zhi Li, Kai Li, Shuang Wang, Chao Teng. Covalent Patterning of Graphene for Controllable Functionalization from Microscale to Nanoscale: A Mini-Review. Frontiers in Chemistry 2022, 10 https://doi.org/10.3389/fchem.2022.829614
- Thi Mien Trung Huynh, Thanh Hai Phan, Roald Phillipson, Alexander Volodine, Steven De Feyter. Doping of graphene via adlayer formation of electrochemically reduced dibenzyl viologen. Journal of Materials Chemistry C 2022, 10 (7) , 2696-2702. https://doi.org/10.1039/D1TC03142B
- Cristina Gutiérrez-Sánchez, Encarnación Lorenzo. Review—Advances on Oxidase Enzymes Modified Nanoporous Carbon and Gold Surfaces for Bioelectrochemical Applications. Journal of The Electrochemical Society 2022, 169 (2) , 027513. https://doi.org/10.1149/1945-7111/ac527b
- Miriam C. Rodríguez González, Kunal S. Mali, Steven De Feyter. Covalent Modification of Graphite and Graphene Using Diazonium Chemistry. 2022, 157-181. https://doi.org/10.1007/978-3-031-04398-7_8
- Shingo Hashimoto, Hiromasa Kaneko, Steven De Feyter, Yoshito Tobe, Kazukuni Tahara. Symmetry and spacing controls in periodic covalent functionalization of graphite surfaces templated by self-assembled molecular networks. Nanoscale 2022, 23 https://doi.org/10.1039/D2NR02858A
- Stephan Getzin, Hezi Yizhaq, Walter R. Tschinkel, . Definition of “fairy circles” and how they differ from other common vegetation gaps and plant rings. Journal of Vegetation Science 2021, 32 (6) https://doi.org/10.1111/jvs.13092
- Lander Verstraete, Steven De Feyter. 2D Self-assembled molecular networks and on-surface reactivity under nanoscale lateral confinement. Chemical Society Reviews 2021, 50 (10) , 5884-5897. https://doi.org/10.1039/D0CS01338B
- Martin K. L. Silva, Alcides L. Leão, Mohini Sain, Ivana Cesarino. A functionalized renewable carbon-based surface for sensor development. Journal of Solid State Electrochemistry 2021, 25 (3) , 1093-1099. https://doi.org/10.1007/s10008-020-04882-x
- Cristina Gutiérrez-Sánchez, Emiliano Martínez-Periñán, Carlos Busó-Rogero, Mónica Revenga-Parra, Félix Pariente, Encarnación Lorenzo. Carbon nanodots: a new precursor to achieve reactive nanoporous HOPG surfaces. Nano Research 2020, 13 (12) , 3425-3432. https://doi.org/10.1007/s12274-020-3030-3
- Byeonggwan Kim, Cheolhyun Cho, Imad Arfaoui, Céline Paris, Christophe Petit, Tangui Le Bahers, Eunkyoung Kim, André-Jean Attias. 2D host–guest supramolecular chemistry for an on-monolayer graphene emitting platform. Materials Horizons 2020, 7 (10) , 2741-2748. https://doi.org/10.1039/D0MH00950D
- Adam J. Clancy, Heather Au, Noelia Rubio, Gabriel O. Coulter, Milo S. P. Shaffer. Understanding and controlling the covalent functionalisation of graphene. Dalton Transactions 2020, 49 (30) , 10308-10318. https://doi.org/10.1039/D0DT01589J
- Yuanzhi Xia, Cristina Martin, Johannes Seibel, Samuel Eyley, Wim Thielemans, Mark van der Auweraer, Kunal S. Mali, Steven De Feyter. Iodide mediated reductive decomposition of diazonium salts: towards mild and efficient covalent functionalization of surface-supported graphene. Nanoscale 2020, 12 (22) , 11916-11926. https://doi.org/10.1039/D0NR03309J
- Zhi Li, Joachim F. R. Van Guyse, Victor R. de la Rosa, Hans Van Gorp, Peter Walke, Miriam C. Rodríguez González, Hiroshi Uji‐i, Richard Hoogenboom, Steven De Feyter, Stijn F. L. Mertens. One‐Step Covalent Immobilization of β‐Cyclodextrin on sp 2 Carbon Surfaces for Selective Trace Amount Probing of Guests. Advanced Functional Materials 2019, 29 (36) https://doi.org/10.1002/adfm.201901488