Functionalized Graphene via a One-Pot Reaction Enabling Exact Pore Sizes, Modifiable Pore Functionalization, and Precision Doping

Coe-Sessions, Kira; Davies, Alathea E.; Dhokale, Bhausaheb; Wenzel, Michael J.; Gahrouei, Masoumeh Mahmoudi; Vlastos, Nikiphoros; Klaassen, Jordan; Parkinson, Bruce A.; Oliveira, Laura de Sousa; Hoberg, John O.

doi:10.1021/jacs.4c10529

Title: Functionalized Graphene via a One-Pot Reaction Enabling Exact Pore Sizes, Modifiable Pore Functionalization, and Precision Doping

Journal Article · 20 November 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c10529 · OSTI ID:2480265

Coe-Sessions, Kira ^[1]; Davies, Alathea E. ^[1];

^[1]; Wenzel, Michael J. ^[1]; Gahrouei, Masoumeh Mahmoudi ^[1]; Vlastos, Nikiphoros ^[1]; Klaassen, Jordan ^[1];

^[1]; Oliveira, Laura de Sousa ^[1];

^[1]

University of Wyoming, Laramie, WY (United States)

Functionalizing graphene with exact pore size, specific functional groups, and precision doping poses many significant challenges. Current methods lack precision and produce random pore sizes, sites of attachment, and amounts of dopant, leading to compromised structural integrity and affecting graphene’s applications. In this work, we report a strategy for the synthesis of functionalized graphitic materials with modifiable nanometer-sized pores via a Pictet–Spengler polymerization reaction. This one-pot, four-step synthesis uses concepts based on covalent organic frameworks (COFs) synthesis to produce crystalline two-dimensional materials that were confirmed by PXRD, TEM measurements, and DFT studies. These new materials are structurally analogous to doped graphene and graphene oxide (GO) but, unlike GO, maintain their semiconductive properties when fully functionalized.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of Wyoming, Laramie, WY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0024156

OSTI ID:: 2480265

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

A 6π Azaelectrocyclization Strategy towards the 1,5,9‐Triazacoronenes Sun, Yi‐Xun; Wang, Xiao‐Gang; Shen, Guo‐Dong Advanced Synthesis & Catalysis, Vol. 362, Issue 8 https://doi.org/10.1002/adsc.201901433	journal	January 2020
1,5,9-Triazacoronenes: A Family of Polycyclic Heteroarenes Synthesized by a Threefold Pictet-Spengler Reaction Wei, Junfa; Han, Bo; Guo, Qiang Angewandte Chemie International Edition, Vol. 49, Issue 44 https://doi.org/10.1002/anie.201002369	journal	September 2010
Chemical Conversion and Locking of the Imine Linkage: Enhancing the Functionality of Covalent Organic Frameworks Cusin, Luca; Peng, Haijun; Ciesielski, Artur Angewandte Chemie International Edition, Vol. 60, Issue 26 https://doi.org/10.1002/anie.202016667	journal	February 2021
Sequential Oxidation/Cyclization of Readily Available Imine Linkages to Access Benzoxazole‐Linked Covalent Organic Frameworks Zhu, Yanqiu; Huang, Dekang; Wang, Wanqin Angewandte Chemie International Edition, Vol. 63, Issue 11 https://doi.org/10.1002/anie.202319909	journal	February 2024
Triazacoronene Derivatives with Three peri -Benzopyrano Extensions: Synthesis, Structure, and Properties : Triazacoronene Derivatives with Three Liu, Bo; Shi, Donghui; Yang, Yihui European Journal of Organic Chemistry, Vol. 2018, Issue 7 https://doi.org/10.1002/ejoc.201701386	journal	November 2017
Boron trichloride as a selective demethylating agent Dean, F. M.; Goodchild, J.; Houghton, L. E. Tetrahedron Letters, Vol. 7, Issue 35 https://doi.org/10.1016/S0040-4039(00)76028-X	journal	January 1966
Covalent Organic Frameworks Linked by Amine Bonding for Concerted Electrochemical Reduction of CO2 Liu, Haoyu; Chu, Jun; Yin, Zhenglei Chem, Vol. 4, Issue 7 https://doi.org/10.1016/j.chempr.2018.05.003	journal	July 2018
BoltzTraP2, a program for interpolating band structures and calculating semi-classical transport coefficients Madsen, Georg K. H.; Carrete, Jesús; Verstraete, Matthieu J. Computer Physics Communications, Vol. 231 https://doi.org/10.1016/j.cpc.2018.05.010	journal	October 2018
Study of Optical and Electrical Properties of Graphene Oxide Sharma, Neeraj; Tomar, Stuti; Shkir, Mohd. Materials Today: Proceedings, Vol. 36 https://doi.org/10.1016/j.matpr.2020.04.861	journal	January 2021
Carboxyl-functionalized covalent organic framework as a two-dimensional nanofiller for mixed-matrix ultrafiltration membranes Duong, Phuoc H. H.; Kuehl, Valerie A.; Mastorovich, Bruce Journal of Membrane Science, Vol. 574 https://doi.org/10.1016/j.memsci.2018.12.042	journal	March 2019
Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials Willems, Thomas F.; Rycroft, Chris H.; Kazi, Michaeel Microporous and Mesoporous Materials, Vol. 149, Issue 1 https://doi.org/10.1016/j.micromeso.2011.08.020	journal	February 2012
Mechanistic study of pH effect on organic solvent nanofiltration using carboxylated covalent organic framework as a modeling and experimental platform Duong, Phuoc H. H.; Shin, Yun Kyung; Kuehl, Valerie A. Separation and Purification Technology, Vol. 282 https://doi.org/10.1016/j.seppur.2021.120028	journal	February 2022
pyCOFBuilder: A Python Package for Automated Creation of Covalent Organic Framework Models Based on the Reticular Approach Oliveira, Felipe L.; Esteves, Pierre M. Journal of Chemical Information and Modeling, Vol. 64, Issue 8 https://doi.org/10.1021/acs.jcim.3c01918	journal	March 2024
Electronic Properties of Oxidized Graphene: Effects of Strain and an Electric Field on Flat Bands and the Energy Gap Alihosseini, M.; Ghasemi, S.; Ahmadkhani, S. The Journal of Physical Chemistry Letters, Vol. 13, Issue 1 https://doi.org/10.1021/acs.jpclett.1c03286	journal	December 2021
Synthesis, Postsynthetic Modifications, and Applications of the First Quinoxaline-Based Covalent Organic Framework Kuehl, Valerie A.; Duong, Phuoc H. H.; Sadrieva, Deana ACS Applied Materials & Interfaces, Vol. 13, Issue 31 https://doi.org/10.1021/acsami.1c08854	journal	July 2021
Molecular Interactions and Layer Stacking Dictate Covalent Organic Framework Effective Pore Size Duong, Phuoc H. H.; Shin, Yun Kyung; Kuehl, Valerie A. ACS Applied Materials & Interfaces, Vol. 13, Issue 35 https://doi.org/10.1021/acsami.1c10866	journal	August 2021
Construction of Covalent Organic Frameworks via Three-Component One-Pot Strecker and Povarov Reactions Li, Xue-Tian; Zou, Jie; Wang, Tong-Hai Journal of the American Chemical Society, Vol. 142, Issue 14 https://doi.org/10.1021/jacs.0c00969	journal	March 2020
Synthesis of Stable Thiazole-Linked Covalent Organic Frameworks via a Multicomponent Reaction Wang, Kewei; Jia, Zhifang; Bai, Yang Journal of the American Chemical Society, Vol. 142, Issue 25 https://doi.org/10.1021/jacs.0c03418	journal	May 2020
Pyrimidazole-Based Covalent Organic Frameworks: Integrating Functionality and Ultrastability via Isocyanide Chemistry Liu, Jiao; Yang, Tong; Wang, Zhi-Peng Journal of the American Chemical Society, Vol. 142, Issue 50 https://doi.org/10.1021/jacs.0c10919	journal	December 2020
Amine-Linked Covalent Organic Frameworks as a Platform for Postsynthetic Structure Interconversion and Pore-Wall Modification Grunenberg, Lars; Savasci, Gökcen; Terban, Maxwell W. Journal of the American Chemical Society, Vol. 143, Issue 9 https://doi.org/10.1021/jacs.0c12249	journal	February 2021
Integrating Bifunctionality and Chemical Stability in Covalent Organic Frameworks via One-Pot Multicomponent Reactions for Solar-Driven H₂O₂ Production Das, Prasenjit; Chakraborty, Gouri; Roeser, Jérôme Journal of the American Chemical Society, Vol. 145, Issue 5 https://doi.org/10.1021/jacs.2c11454	journal	January 2023
Chemical Conversion of Linkages in Covalent Organic Frameworks Waller, Peter J.; Lyle, Steven J.; Osborn Popp, Thomas M. Journal of the American Chemical Society, Vol. 138, Issue 48 https://doi.org/10.1021/jacs.6b08377	journal	November 2016
Conversion of Imine to Oxazole and Thiazole Linkages in Covalent Organic Frameworks Waller, Peter J.; AlFaraj, Yasmeen S.; Diercks, Christian S. Journal of the American Chemical Society, Vol. 140, Issue 29 https://doi.org/10.1021/jacs.8b05830	journal	June 2018
Energy Band-Gap Engineering of Conjugated Microporous Polymers via Acidity-Dependent in Situ Cyclization Lee, Jiyoung; Buyukcakir, Onur; Kwon, Tae-woo Journal of the American Chemical Society, Vol. 140, Issue 35 https://doi.org/10.1021/jacs.8b05978	journal	August 2018
A Highly Ordered Nanoporous, Two-Dimensional Covalent Organic Framework with Modifiable Pores, and Its Application in Water Purification and Ion Sieving Kuehl, Valerie A.; Yin, Jiashi; Duong, Phuoc H. H. Journal of the American Chemical Society, Vol. 140, Issue 51 https://doi.org/10.1021/jacs.8b11482	journal	December 2018
Phenazine-Based Covalent Organic Framework Cathode Materials with High Energy and Power Densities Vitaku, Edon; Gannett, Cara N.; Carpenter, Keith L. Journal of the American Chemical Society, Vol. 142, Issue 1 https://doi.org/10.1021/jacs.9b08147	journal	December 2019
Constructing Robust Covalent Organic Frameworks via Multicomponent Reactions Wang, Peng-Lai; Ding, San-Yuan; Zhang, Zhi-Cong Journal of the American Chemical Society, Vol. 141, Issue 45 https://doi.org/10.1021/jacs.9b10625	journal	October 2019
Insulator to Semimetal Transition in Graphene Oxide Eda, Goki; Mattevi, Cecilia; Yamaguchi, Hisato The Journal of Physical Chemistry C, Vol. 113, Issue 35 https://doi.org/10.1021/jp9051402	journal	August 2009
Ion selectivity of graphene nanopores Rollings, Ryan C.; Kuan, Aaron T.; Golovchenko, Jene A. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11408	journal	April 2016
Conjugated organic framework with three-dimensionally ordered stable structure and delocalized π clouds Guo, Jia; Xu, Yanhong; Jin, Shangbin Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3736	journal	November 2013
Selective molecular sieving through porous graphene Koenig, Steven P.; Wang, Luda; Pellegrino, John Nature Nanotechnology, Vol. 7, Issue 11 https://doi.org/10.1038/nnano.2012.162	journal	October 2012
Water desalination using nanoporous single-layer graphene Surwade, Sumedh P.; Smirnov, Sergei N.; Vlassiouk, Ivan V. Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.37	journal	March 2015
Topochemical conversion of an imine- into a thiazole-linked covalent organic framework enabling real structure analysis Haase, Frederik; Troschke, Erik; Savasci, Gökcen Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04979-y	journal	July 2018
Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks Li, Xinle; Zhang, Changlin; Cai, Songliang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05462-4	journal	July 2018
Constructing chemical stable 4-carboxyl-quinoline linked covalent organic frameworks via Doebner reaction for nanofiltration Yang, Yongliang; Yu, Ling; Chu, Tiancheng Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30319-2	journal	May 2022
Graphene oxide for photonics, electronics and optoelectronics Wu, Jiayang; Lin, Han; Moss, David J. Nature Reviews Chemistry, Vol. 7, Issue 3 https://doi.org/10.1038/s41570-022-00458-7	journal	January 2023
The chemistry of graphene oxide Dreyer, Daniel R.; Park, Sungjin; Bielawski, Christopher W. Chem. Soc. Rev., Vol. 39, Issue 1 https://doi.org/10.1039/B917103G	journal	January 2010
Parent and trisubstituted triazacoronenes: synthesis, crystal structure and physicochemical properties Tan, Qitao; Chen, Huanhuan; Xia, Huaida Chemical Communications, Vol. 52, Issue 3 https://doi.org/10.1039/C5CC08853D	journal	January 2016
Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications Segura, José L.; Mancheño, María J.; Zamora, Félix Chemical Society Reviews, Vol. 45, Issue 20 https://doi.org/10.1039/C5CS00878F	journal	January 2016
Progress in the functional modification of graphene/graphene oxide: a review Yu, Wang; Sisi, Li; Haiyan, Yang RSC Advances, Vol. 10, Issue 26 https://doi.org/10.1039/D0RA01068E	journal	January 2020
A self-assembling, biporous, metal-binding covalent organic framework and its application for gas separation Spaulding, Veronica; Zosel, Katarina; Duong, Phuoc H. H. Materials Advances, Vol. 2, Issue 10 https://doi.org/10.1039/D1MA00056J	journal	January 2021
Pitfalls in the synthesis of polyimide-linked two-dimensional covalent organic frameworks Kuehl, Valerie A.; Wenzel, Michael J.; Parkinson, Bruce A. Journal of Materials Chemistry A, Vol. 9, Issue 27 https://doi.org/10.1039/D1TA01954F	journal	January 2021
Electronic properties of graphene oxide: nanoroads towards novel applications Khabibrakhmanov, Almaz I.; Sorokin, Pavel B. Nanoscale, Vol. 14, Issue 11 https://doi.org/10.1039/D2NR00251E	journal	January 2022
A High Yield Easy Method for the Preparation of Alkoxy-Substituted Triphenylenes Naarmann, Herbert; Hanack, Michael; Mattmer, Robert Synthesis, Vol. 1994, Issue 05 https://doi.org/10.1055/s-1994-25505	journal	January 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Geometrically induced transitions between semimetal and semiconductor in graphene Dvorak, Marc; Wu, Zhigang Physical Review B, Vol. 90, Issue 11 https://doi.org/10.1103/PhysRevB.90.115415	journal	September 2014
Bottom-up synthesis of multifunctional nanoporous graphene Moreno, César; Vilas-Varela, Manuel; Kretz, Bernhard Science, Vol. 360, Issue 6385 https://doi.org/10.1126/science.aar2009	journal	April 2018
Products of complex formation in CoCl2-1-amino-8-hydroxynaphthalene-2,4-disulfonic acid-α-hydroxy-α-phenylacetophenone (benzaldehyde and its hydroxy derivatives) systems Skorokhod, L. S.; Seifullina, I. I.; Vlasenko, V. G. Russian Journal of General Chemistry, Vol. 79, Issue 1 https://doi.org/10.1134/S107036320901006X	journal	January 2009
Higher Electrical Conductivity of Functionalized Graphene Oxide Doped with Silver and Copper (II) Ions Pereira, Nelson Gustavo Alves; Gonzaléz, Maria Elena Leyva; Queiroz, Alvaro Antonio Alencar de Energies, Vol. 16, Issue 20 https://doi.org/10.3390/en16207019	journal	October 2023
The Influence of Disorder in the Synthesis, Characterization and Applications of a Modifiable Two-Dimensional Covalent Organic Framework Brophy, Jordan; Summerfield, Kyle; Yin, Jiashi Materials, Vol. 14, Issue 1 https://doi.org/10.3390/ma14010071	journal	December 2020
Effect of Nitrogen Doping on the Optical Bandgap and Electrical Conductivity of Nitrogen-Doped Reduced Graphene Oxide Witjaksono, Gunawan; Junaid, Muhammad; Khir, Mohd Haris Molecules, Vol. 26, Issue 21 https://doi.org/10.3390/molecules26216424	journal	October 2021
Study on Morphological, Optical and Electrical Properties of Graphene Oxide (GO) and Reduced Graphene Oxide (rGO) Jaafar, E.; Kashif, Muhammad; Sahari, S. K. Materials Science Forum, Vol. 917 https://doi.org/10.4028/www.scientific.net/MSF.917.112	journal	March 2018

Similar Records

A facile one-pot method to Au–SnO{sub 2}-graphene ternary hybrid

Journal Article · 2014 · Materials Research Bulletin · OSTI ID:22420607

Xu, Diou; Li, Xiaotian; Zhang, Dawei

Bottom-up Assembly of Nanoporous Graphene with Emergent Electronic States

Journal Article · 2020 · Journal of the American Chemical Society · OSTI ID:1783114

Jacobse, Peter H.; McCurdy, Ryan D.; Jiang, Jingwei; +7 more

Water Desalination Using Nanoporous Single-Layer Graphene with Tunable Pore Size

Journal Article · 2015 · Nature Nanotechnology · OSTI ID:1185491

Surwade, Sumedh P.; Smirnov, Sergei N.; Vlassiouk, Ivan V.; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Covalent organic frameworks
Diffraction
Electrical conductivity
Materials
Two dimensional materials

Title: Functionalized Graphene via a One-Pot Reaction Enabling Exact Pore Sizes, Modifiable Pore Functionalization, and Precision Doping

Citation Formats

References (52)

Similar Records

Related Subjects