Graphene oxide bifunctionalized with NH2/NH3+ and their outstanding-performance against corrosion

Ramírez-Soria, Edgar H.; León-Silva, U.; Lara-Ceniceros, Tania E.; Bazán-Díaz, Lourdes; Advíncula, Rigoberto C.; Bonilla‐Cruz, José

doi:10.1016/j.apsusc.2021.150048

Cited by 30 publications

(17 citation statements)

References 65 publications

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“…Among the few studies on this topic, some report the nucleophilic epoxide opening combined with Michael addition of the hydroxyl groups, the concomitant nucleophilic epoxide opening with the Williamson reaction of the hydroxyl groups (esterification/etherification), and the combination of epoxide opening, carboxylation, and amidation reactions . Other studies report the nucleophilic substitution at both the epoxy and hydroxyl centers by a microwave-assisted method, the radical covalent functionalization on the carbonaceous surface with two different groups, and the photoinduced cycloaddition, followed by the nucleophilic substitution on a fluorographene derivative . Finally, there are some reports based on the successive reduction (leading to graphenides) and covalent reactions using diazonium salts and alkyl iodides …”

Section: Introductionmentioning

confidence: 99%

Neighboring Effects on the Selective Bifunctionalization of Graphene Oxide for Nanocatalytic Organophosphate Neutralization

Santos

Martinez

Veiga

et al. 2022

ACS Appl. Nano Mater.

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The bifunctionalization of graphene oxide (GO) has attracted attention as a promising tool for broadening applications, despite its many challenges, especially regarding site-specific reactions. Herein, we obtained mono-and bifunctionalized GO containing thiol and imidazole groups that were anchored on the carboxylic acid sites of GO via amidation reactions. We varied the bifunctionalization methodology and showed that consecutive addition of the reagents (containing imidazole and thiol groups) led to materials with higher degrees of functionalization, in contrast to their simultaneous addition. The functionalized materials were evaluated as nanocatalysts in the neutralization reaction of a toxic organophosphate. Also, it was evidenced that the effect of the mono-and bifunctionalized materials on the catalytic outcomes gives insight toward neighboring effects. All catalysts were effective in the reaction studied with the monofunctionalized materials (containing thiol or imidazole groups) showing similar activity. Among the bifunctionalized materials (with both thiol and imidazole moieties), the one with the lower degree of functionalization showed the best performance. This was attributed to a combination of mechanisms, strongly dependent on the neighboring groups: attraction on the GO surface, nucleophilic catalysis by thiol/imidazole groups, and bifunctional intramolecular catalysis, for example, by thiol and imidazole groups, assisting potential nucleophilic hydroxyl groups. Oddly, the bifunctionalized materials with the higher degree of functionalization did not show the most prominent activity; they were actually similar to the monofunctionalized ones. This can be attributed to the inhibition or hindering of some of the proposed mechanisms due to steric effects or a nonideal positioning of the groups. A lot remains to be clarified in this field, but one thing is clear: a higher degree of functionalization should not always be pursued because the application of the material is what should guide what characteristics should be determined. Several other applications should be impacted by neighboring effects, which are directly influenced by the functionalization procedure.

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Section: Introductionmentioning

confidence: 99%

Neighboring Effects on the Selective Bifunctionalization of Graphene Oxide for Nanocatalytic Organophosphate Neutralization

Santos

Martinez

Veiga

et al. 2022

ACS Appl. Nano Mater.

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“…There are also some other peaks appearing during the adsorption process, for example, the peaks at 1582 and 3027 cm –1 . The two peaks are normally ascribed to–NH 3 + in deformative and stretching vibration modes, respectively, in the literature . Herein, they should originate from the positively charged NH 3 , which is formed by the charge transfer from NH 3 to Lewis acidic sites on BN-MW-15.…”

Section: Resultsmentioning

confidence: 87%

Few-Layered Hexagonal Boron Nitrides as Highly Effective and Stable Solid Adsorbents for Ammonia Separation

Zhang

Cao

Ding

et al. 2023

Ind. Eng. Chem. Res.

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Solid adsorbents with high NH3 separation performance and good stability are particularly important for industrial applications. In our work, few-layered hexagonal boron nitrides (h-BNs) were synthesized and proposed as a kind of solid adsorbent by utilizing the abundant Lewis acidic B atoms on h-BNs. The synthesized h-BNs were investigated for NH3 separation both experimentally and theoretically. It is found that the NH3 isotherms of h-BNs slightly deviate from the ideal profiles, suggesting that the h-BNs enable moderate interactions with NH3. At the pressure of 0.1 and 1 bar, the h-BNs can adsorb as much as 2.33 and 8.67 mmol/g of NH3, respectively. The h-BNs also demonstrate highly selective adsorption of NH3 from other gases such as N2, H2, and CO2, regardless of calculated ideal selectivities or breakthrough adsorption of mixed gases. The NH3 adsorption of h-BNs can be completely reversed, and the h-BNs also exhibit high oxidative resistance, which is of vital importance for the long-term application in industry. Density functional theory calculations and molecular dynamics simulations were further conducted to rationalize the effective separation of NH3 by h-BNs and disclose the underlying mechanism at the molecular level.

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“…23 For this reason, only half of its atomic composition was available to be functionalized. Furthermore, the peaks observed at 285.7 and 102.5 eV in C 1s and Si 2p (Figure 2e), respectively, suggest that functionalization with TMPS molecules was achieved, 24 reaching up to 7.5 atom % of Si 2p, as shown in Table S1.…”

Section: ■ Introductionmentioning

confidence: 78%

“…It is well-known that the donor electron ability of OH and C–O–C functionalities is higher than that of CO and O–C–OH, and the electronegativity of silicon (1.8) is smaller than that of carbon (2.5) . Thus, the OH and C–O–C functionalities act as nucleophiles, and the silicon atoms work like electrophiles . As a result, a nucleophilic substitution type 2 (S N 2) was conducted.…”

Section: Resultsmentioning

confidence: 99%

“…38 Thus, the OH and C−O−C functionalities act as nucleophiles, and the silicon atoms work like electrophiles. 24 As a result, a nucleophilic substitution type 2 (S N 2) was conducted. Two different routes of the synthesis Because the epoxy functionality possesses simultaneous neighboring carbon atoms, these can provide a proton that induces the OEt elimination as HOEt.…”

Section: ■ Introductionmentioning

confidence: 99%

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Reduced Graphene Oxide Nanoplatelets Functionalized with Nonpolar Aliphatic Groups for High-Performance Coatings against Corrosion

Ramírez-Soria

León-Silva

Lara-Ceniceros

et al. 2022

ACS Appl. Nano Mater.

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A fast and straightforward chemical method to attain reduced graphene oxide (rGO) nanoplatelets that highly functionalized with nonpolar aliphatic groups and their high performance against corrosion is disclosed for the first time. Graphene oxide (GO) was functionalized with trimethoxy(propyl)silane (TMPS) to obtain Propyl-GO through a microwave-assisted method in just 10 min. Scanning electron microscopy–energy-dispersive X-ray revealed a homogeneous distribution of TMPS on the GO surface. Propyl-GO was reduced to obtin highly exfoliated and functionalized nanosheets (Propyl-rGO). Moreover, Propyl-rGO and Propyl-GO were used as additives (0.5 wt %) within an epoxy resin (ER) to obtain ER/Propyl-rGO and ER/Propyl-GO nanocomposite coatings, respectively. ER/Propyl-rGO deposited on A36 structural steel (ER/Propyl-rGO/A36SS) exhibited a hydrophobic behavior, strong adhesion, and significant corrosion protection in a saline medium (1 M NaCl; 58.4 g/L). Interestingly, this functional nanocomposite coating, diminished the corrosion current density by 6 orders of magnitude (i corr = 3.6 × 10–12 A/cm2) compared with A36SS coated with ER (i corr = 1.6 × 10–6 A/cm2). Also, the corrosion potential (E corr) was noticeably decremented from −530 mV (neat ER) to −190 mV (ER/Propyl-rGO). Electrochemical impedance spectroscopy assessments suggested a corrosion mechanism controlled by a charge-transfer adsorption process promoted by basal-plane restructuration from rGO. The strategy proposed herein offers an original pathway to achieve nanocomposites with outstanding hydrophobicity, hardness, adhesion, and exceptional protection against corrosion.

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Graphene oxide bifunctionalized with NH2/NH3+ and their outstanding-performance against corrosion

Cited by 30 publications

References 65 publications

Neighboring Effects on the Selective Bifunctionalization of Graphene Oxide for Nanocatalytic Organophosphate Neutralization

Neighboring Effects on the Selective Bifunctionalization of Graphene Oxide for Nanocatalytic Organophosphate Neutralization

Few-Layered Hexagonal Boron Nitrides as Highly Effective and Stable Solid Adsorbents for Ammonia Separation

Reduced Graphene Oxide Nanoplatelets Functionalized with Nonpolar Aliphatic Groups for High-Performance Coatings against Corrosion

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