Nitrogen-based Functional Groups Research Articles

Adsorption of Nitrogen Dioxide on Nitrogen-Enriched Activated Carbons.

The aim of this study was to obtain nitrogen-enriched activated carbons from orthocoking coal. The initial material was subjected to a demineralisation process. The demineralised precursor was pyrolysed at 500 °C and then activated with sodium hydroxide at 800 °C. Activated carbon adsorbents were subjected to the process of ammoxidation using a mixture of ammonia and air at two different temperature variants (300 and 350 °C). Nitrogen introduction was carried out on stages of demineralised precursor, pyrolysis product, and oxidising activator. The elemental composition, acid-base properties, and textural parameters of the obtained carbon adsorbents were determined. The activated carbons were investigated for their ability to remove nitrogen dioxide. The results demonstrated that the ammoxidation process incorporates new nitrogen-based functional groups into the activated carbon structure. Simultaneously, the ammoxidation process modified the acid-base characteristics of the surface and negatively affected the textural parameters of the resulting adsorbents. Furthermore, the study showed that all of the obtained carbon adsorbents exhibited a distinct microporous texture. Adsorption tests were carried out against NO2 and showed that the carbon adsorbents obtained were highly effective in removing this gaseous pollutant. The best sorption capacity towards NO2 was 23.5 mg/g under dry conditions and 75.0 mg/g under wet conditions.

One-step amination of MWCNTs in RF-dielectric barrier discharge Ar–N2-H2 plasmas

Plasmas technology is a simple way to functionalize the surface of multi-wall carbon nanotube MWCNT. Homogenous plasma of Ar–N2-H2 gas mixture was generated in radio frequency RF dielectric barrier Discharge DBD at discharge power of 60 W and total pressure of 500 Pa. The active plasma species was monitored by optical emission spectroscopy OES. While the untreated and treated MWCNTs were investigated with various techniques. The result from OES shows complex spectrum with spectral line/bands related various species such as OH, N2, CN, C2, Hα and Are I, confirming the rich plasma environment, as well as possible active interaction between the MWCNTs and the plasma species. The TEM images of the treated samples revealed the roughness of the CNT outer surface. The X-ray photo electron emission XPS results confirm the presence of nitrogen-based functional groups (C–NC, C–NHO and (CO)–N-(CO)) on the plasma treated MWCNTs. Raman spectrum analysis confirms the functionalization of the treated MWCNTs as the ID/IG ratio increased for the treated sample. The Ar–N2-H2 plasma treatment of MWCNTs undamaged the MWCNTs structure and preserved integrity as observed by XRD result and SEM image.

Nitrogen-rich carbon composite fabricated from waste shrimp shells for highly efficient oxo-vanadate adsorption-coupled reduction

Protein, calcium carbonate, and chitin are abundant in shrimp shells. In this study, chemical treatment followed by hydrothermal carbonization was used to synthesize the nitrogen-rich hydrochar (HSHC) from shrimp shells. The untreated hydrochar exhibited a higher amount of calcium (25.37%) and less amount of nitrogen (2.68%) with alkaline pH (9.1). Interestingly chemical pre-treatment on shrimp shells boosted the nitrogen content to 6.81% and eliminated the calcium while controlling the pH to 6.4, which was beneficial for oxo-vanadate removal. The HSHC achieved vanadium(V) adsorption capacity of 21.20 mg/g at an optimal solution pH of 3.0, whereas the pristine hydrochar performed poorly (0.66 mg/g). The abundance of oxygen and nitrogen-based functional groups that developed through the chemical treatment resulted in improved adsorption coupled reduction performance of HSHC. This study proposed an inexpensive and environmentally friendly method for converting waste shrimp shells into value-added adsorbent.

Cover Feature: Reactivity of Hypervalent Iodine(III) Reagents Bearing Transferable N‐Based Groups (Eur. J. Org. Chem. 25/2023)

The Cover Feature illustrates the potential and versatility of hypervalent iodine(III) compounds as the root of several methodologies that enable the introduction of nitrogen-based functional groups. The use of hypervalent iodine(III) compounds translates into a robust alternative to established synthetic methodologies. This review focuses on the latest results in the electrophilic transfer of nitrogen-containing functional groups. More information can be found in the Review by M. M. B. Marques et al.

Post-synthetic modification of Zr-MOFs using guanidine for cyclic carbonate formation catalysis

A post-synthetic modification of Zr-MOF using ionic nitrogen-based functional groups is proposed for the catalytic cycloaddition reaction of CO2 with epoxides. Herein, guanidinium salt derivatives are used as ionic liquid (IL) catalysts while MOFs are used as a superior absorbent for CO2, allowing the generation of heterogeneous catalysts for CO2 fixation reactions under mild conditions. The UiO66-NH2 and UiO67-NH2 were functionalized with carbodiimides N,N′-dicyclohexylcarbodiimide (DCC) and N,N′-diisopropylcarbodiimide (DIC) to produce cationic guanidinium-containing Zr-MOFs with free bromide ions UiO66-DCCBr, UiO66-DICBr, and UiO67-DICBr. The materials were characterized comprehensively by multiple techniques such as PXRD, FTIR, TGA, SEM, EDS, 1H NMR, 13C NMR, elemental analysis, as well as N2 and CO2 adsorption equilibrium measurements. UiO66-DCCBr showed a high TOF for the formation of cyclic carbonates using several small epoxides under mild conditions (0.5 MPa CO2, 90 °C, without co-catalyst and solvent). In addition, UiO67- DICBr owing to the larger aperture size of MOF displayed better catalytic performance for the conversion of larger epoxides than UiO66-DICBr and UiO66-DCCBr with high yield and selectivity. This result underlines the important role of MOF’s aperture size for the diffusion of substrates in CO2 fixation reactions.

A synthesized pyrimidine derivative with highly efficient long-term corrosion protection for API X60 steel in CO2-saturated NACE brine ID196 under hydrodynamic condition

This research investigates the CO2 corrosion inhibition characteristics of a synthesized pyrimidine derivative whose molecular structure is embellished with nitrogen-based functional groups with the intention of achieving highly effective and stable film formation, at low doses, after prolonged corrosion period under turbulent hydrodynamics. For this purpose, 5-(4-(dimethylamino)phenyl)-2,7-dithioxo-2,3,5,6,7,8-hexahydropyrimido[4,5-d]pyrimidin-4(1H)-one (DPP) was synthesized using the one-pot method, and investigated as inhibitor against the corrosion of API X60 steel after instantaneous and prolonged (72 h) immersion in CO2-saturated NACE ID196 brine under 1000 rpm rotation speed. Results from potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) measurements show that DPP is a mixed-type inhibitor which lowers the double layer capacitance and rate of charge transfer across the steel-solution interface with 97% efficiency. Its instantaneous adsorption blocks the steel surface from any noticeable microstructural damage, based on scanning electron microscopy (SEM) characterization. After prolonged exposure (72 h), the uninhibited steel experiences enhanced resistance, which inversely depreciated the DPP efficiency to > 73%. With DPP, however, the steel is significantly protected against surface microstructural degradation, based on SEM assessment. Computational modeling with density functional theory (DFT) and molecular dynamics simulation (MDS) provided molecular-level confirmation of the experimental results.

Mechanistic duality of indolyl 1,3-heteroatom transposition.

A novel mechanistic duality has been revealed from the indolyl 1,3-heteroatom transposition (IHT) of N-hydroxyindole derivatives. A series of in-depth mechanistic investigations suggests that two separate mechanisms are operating simultaneously. Moreover, the relative contribution of each mechanistic pathway, the energy barrier for each pathway, and the identity of the primary pathway were shown to be the functions of the electronic properties of the substrate system. Based on the mechanistic understanding obtained, a mechanism-driven strategy for the general and efficient introduction of a heteroatom at the 3-position of indole has been developed. The reaction developed exhibits a broad substrate scope to provide the products in various forms of the functionalised indole. Moreover, the method is applicable to the introduction of both oxygen- and nitrogen-based functional groups.

Graphitic N-doped graphene via solution plasma with a single dielectric barrier

Graphitic nitrogen-doped graphene (g-NG) with significantly high nitrogen content, i.e., 18.79 at.%, could be produced by the electrical discharge in liquid, so-called “solution plasma”, with a single dielectric barrier. The proposed system could reduce the excessive current, resulting in stabilizing the glow plasma and maintaining the overall temperature. It could promote the preservation of nitrogen atoms from evaporation during the synthesis process and the formation of a graphitic carbon framework. Moreover, the influence of the precursors, i.e., six-membered ring organic molecules with and without the substitution of nitrogen atoms and the nitrogen-based functional groups, was also investigated to provide the guideline for the synthesis of g-NG via this proposed method. The substitution of nitrogen atoms in the benzene ring could be used to synthesize g-NG with higher nitrogen dopants, compared to the benzene ring with only nitrogen-based functional groups. • Graphitic nitrogen-doped graphene (g-NG) was successfully synthesized. • The nitrogen doping concentration was incredibly high (18.79 at.%). • The synthesis was conducted by solution plasma with single dielectric barrier. • Lower discharge current in the solution plasma was a key for formation of g-NG.

Site- and Enantioselective Manganese-Catalyzed Benzylic C-H Azidation of Indolines.

A manganese-catalyzed highly site- and enantioselective benzylic C-H azidation of indolines has been described. The practical method is applicable for azidation of a tertiary benzylic C-H bond with good functional group tolerance, allowing facile access to structurally diverse tertiary azide-containing indolines in high efficiency with excellent site-, chemo-, and enantioselectivity. The generality of the method was further demonstrated by site- and enantioselective azidation of the secondary benzylic C-H bond for a range of secondary azide-containing indolines. The benzylic C-H azidation method allows to straightforwardly and enantioselectively install a variety of nitrogen-based functional groups and diverse bioactive molecules at the C3 position of indoline frameworks through post-azidation manipulations. Gram-scale synthesis was also demonstrated, further highlighting the synthetic potential of the method. Mechanistic studies by combined experiments and computations elucidated the reaction mechanism and origins of stereoselectivity.

A Comprehensive Study of Pristine and Calcined f-MWCNTs Functionalized by Nitrogen-Containing Functional Groups.

We present the study of pristine and calcined f-MWCNTs functionalized by nitrogen-containing functional groups. We focus on the structural and microstructural modification tuned by the previous annealing. However, our primary goal was to analyze the electronic structure and magnetic properties in relation to the structural properties using a multi-technique approach. The studies carried out by X-ray diffraction, XPS, and 57Fe Mössbauer spectrometry revealed the presence of γ-Fe nanoparticles, Fe3C, and α-FeOOH as catalyst residues. XPS analysis based on the deconvolution of core level lines confirmed the presence of various nitrogen-based functional groups due to the purification and functionalization process of the nanotubes. The annealing procedure leads to a structural modification mainly associated with removing surface impurities as purification residues. Magnetic studies confirmed a significant contribution of Fe3C as evidenced by a Curie temperature estimated at TC = 452 ± 15 K. A slight change in magnetic properties upon annealing was revealed. The detailed studies performed on nanotubes are extremely important for the further synthesis of composite materials based on f-MWCNTs.

Hybrid Plasma-Liquid Treatment of Carbon Nanotubes for Application in Direct Absorption Solar Thermal Collectors

Covalent functionalization of carbon nanotubes (CNTs) with oxygen-based or nitrogen-based functional groups is one of the most popular techniques to modify the surface energy and inherent properties of the CNTs.1 This functionalization generates interest for a broad range of applications including mechanically superior advanced composites,2 more sensitive gas sensors,3 enhanced energy storage materials4 or ultra-conductive fibers.5 As an alternative to the harsh chemicals used by traditional chemical functionalization, plasma-based surface treatments can be used with great efficacy and reduced reaction times, providing an array of application-specific benefits.Awareness of the environmental pollution caused by fossil fuels and the ever-increasing demand for energy has driven research focussed on zero-carbon renewable energy sources. Conscious of this, direct absorption solar thermal collectors are gaining prominence, both for domestic heating and steam generation. CNTs have been investigated as an additive to take advantage of the near blackbody absorption and high thermal conductivity to improve system efficiency. Critical to the success of the additive nanoparticles is the stability in the fluid, however, due to their high surface energy CNTs tend to agglomerate which can limit the efficacy of their integration into real-world products.In this work, macroscopic ribbon-like assemblies of carbon nanotubes are functionalized by plasma-induced non-equilibrium electrochemistry (PiNE) implemented through a simple direct current-based plasma-liquid system. This system utilizes the plasma-generated species in an electrolyte of 10 %vol ethanol in water, with or without a nitrogen precursor, for the oxygen and/or nitrogen functionalization of the carbon nanotube assembly. For this treatment, a ribbon-like piece of CNT was used as the anode and a helium plasma discharge triggered by applying 10 mA and 1 - 1.6 kV to act as the cathode. The plasma-generated species are then expected to migrate towards the CNTs and functionalize the sidewalls.The oxygen content is shown to be increased by between 70 % and 300 % when the treatment solution of 10 %vol ethanol is used in the ribbon electrode configuration. When ethylenediamine is added as a nitrogen precursor, the atomic concentration of nitrogen reaches 23 %, with amine groups, pyrrolic groups and graphitic nitrogen observed in the x-ray photoelectron spectra. This nitrogen content is unmatched in quantity when compared to either a simple soaking procedure or an electrolysis process with a platinum foil replacing the plasma as the counter-electrode. This demonstrates that the plasma either directly or indirectly, through plasma-generated species, facilitates and enhances the availability of nitrogen from the ethylenediamine precursor. The potential plasma-induced chemical pathways which lead to the functionalization of the CNTs are also investigated and discussed.In the application of a direct absorption solar collector system, it is found that the covalent functionalization provided by the plasma-liquid system enhances the stability of the CNT-ethylene glycol nanofluid, with the oxygen-functionalized samples producing the most stable nanofluids. This is explained through the lower value for contact angle measurements, suggesting greater hydrophobicity of the CNTs.References(1) Mallakpour, S.; Soltanian, S. Surface Functionalization of Carbon Nanotubes: Fabrication and Applications. RSC Adv. 2016, 6 (111), 109916–109935. https://doi.org/10.1039/c6ra24522f.(2) Williams, J.; Broughton, W.; Koukoulas, T.; Rahatekar, S. S. Plasma Treatment as a Method for Functionalising and Improving Dispersion of Carbon Nanotubes in Epoxy Resins. J. Mater. Sci. 2013, 48 (3), 1005–1013. https://doi.org/10.1007/s10853-012-6830-3.(3) Ham, S. W.; Hong, H. P.; Kim, J. H.; Min, S. J.; Min, N. K. Effect of Oxygen Plasma Treatment on Carbon Nanotube-Based Sensors. J. Nanosci. Nanotechnol. 2014, 14 (11), 8476–8481. https://doi.org/10.1166/jnn.2014.10007.(4) Hulicova-Jurcakova, D.; Seredych, M.; Lu, G. Q.; Bandosz, T. J. Combined Effect of Nitrogen- and Oxygen-Containing Functional Groups of Microporous Activated Carbon on Its Electrochemical Performance in Supercapacitors. Adv. Funct. Mater. 2009, 19 (3), 438–447. https://doi.org/10.1002/adfm.200801236.(5) Li, L.; Liu, E.; Shen, H.; Yang, Y.; Huang, Z.; Xiang, X.; Tian, Y. Charge Storage Performance of Doped Carbons Prepared from Polyaniline for Supercapacitors. J. Solid State Electrochem. 2011, 15 (1), 175–182. https://doi.org/10.1007/s10008-010-1087-8. Figure 1

Hybrid Plasma-Liquid Treatment of Carbon Nanotubes for Application in Direct Absorption Solar Thermal Collectors

Awareness of the environmental pollution caused by fossil fuels and the ever-increasing demand for energy has driven research focussed on zero-carbon renewable energy sources. Conscious of this, direct absorption solar thermal collectors are gaining prominence, both for domestic heating and steam generation. Carbon nanotubes (CNTs) have been investigated as an additive to take advantage of the near blackbody absorption and high thermal conductivity to improve system efficiency. Critical to the success of the additive nanoparticles is the stability in the fluid, however, due to their high surface energy CNTs tend to agglomerate which can limit the efficacy of their integration into real-world products. Covalent functionalization of the CNT sidewalls with oxygen-based or nitrogen-based functional groups is one of the most popular techniques to modify the surface energy of the CNTs.1 As an alternative to the harsh chemicals used by traditional chemical functionalisation, plasma-based surface treatments can be used with great efficacy and reduced reaction times.In this work, macroscopic ribbon-like assemblies of carbon nanotubes are functionalized using a simple direct current-based plasma-liquid system. This system utilizes the plasma-generated species in a fluid of 10 %vol ethanol in water, with or without a nitrogen precursor, for the oxygen and/or nitrogen functionalisation of the carbon nanotube assembly. For this treatment, a ribbon-like piece of CNT was used as the anode and a helium plasma discharge triggered by applying 10 mA and 1 - 1.6 kV to act as the cathode. The plasma-generated species are then expected to migrate towards the CNTs and functionalisation the sidewalls.The oxygen content is shown to be increased by between 50 % and 200 % when the treatment solution of 10 %vol ethanol is used in the ribbon electrode configuration. When ethylenediamine is added as a nitrogen precursor, the atomic concentration of nitrogen reaches 23 % in the ribbon electrode configuration, with amine groups, pyrrolic groups and graphitic nitrogen observed in the x-ray photoelectron spectra. This nitrogen content is unmatched in quantity when compared to either a simple soaking procedure or an electrolysis process with a platinum foil replacing the plasma as the counter-electrode. This demonstrates that the plasma either directly or indirectly, by means of plasma-generated species, facilitates and enhances the availability of nitrogen from the ethylenediamine precursor. The potential plasma-induced chemical pathways which lead to the functionalization of the CNTs are also investigated and discussed.In the application of a DASC system, it is found that the covalent functionalisation provided by the plasma-liquid system enhances the stability of the CNT-EG nanofluid, with the oxygen-functionalized samples producing the most stable nanofluids. This functionalization method generates interest for a broader range of applications including mechanically superior advanced composites,2 more sensitive gas sensors,3 enhanced energy storage materials4 or ultra-conductive fibres.5 References (1) Mallakpour, S.; Soltanian, S. Surface Functionalization of Carbon Nanotubes: Fabrication and Applications. RSC Adv. 2016, 6 (111), 109916–109935.(2) Williams, J.; Broughton, W.; Koukoulas, T.; Rahatekar, S. S. Plasma Treatment as a Method for Functionalising and Improving Dispersion of Carbon Nanotubes in Epoxy Resins. J. Mater. Sci. 2013, 48 (3), 1005–1013.(3) Ham, S. W.; Hong, H. P.; Kim, J. H.; Min, S. J.; Min, N. K. Effect of Oxygen Plasma Treatment on Carbon Nanotube-Based Sensors. J. Nanosci. Nanotechnol. 2014, 14 (11), 8476–8481.(4) Hulicova-Jurcakova, D.; Seredych, M.; Lu, G. Q.; Bandosz, T. J. Combined Effect of Nitrogen- and Oxygen-Containing Functional Groups of Microporous Activated Carbon on Its Electrochemical Performance in Supercapacitors. Adv. Funct. Mater. 2009, 19 (3), 438–447.(5) Li, L.; Liu, E.; Shen, H.; Yang, Y.; Huang, Z.; Xiang, X.; Tian, Y. Charge Storage Performance of Doped Carbons Prepared from Polyaniline for Supercapacitors. J. Solid State Electrochem. 2011, 15 (1), 175–182. Figure 1

Simple synthesis of N-doped catalysts with controllable Pt–Ni nanoparticles for high-efficiency ethanol oxidation

Herein, the catalysts contained metal- and nitrogen-doped carriers were synthesized by a novel and simple method. The synthesized catalysts with different particle size and distribution were controlled by adjusting the ratio of urea and metal salt solution. The morphology, microstructure, and particle distribution of the catalysts were confirmed by transmission electron microscopy and X-ray powder diffraction. The catalytic performance of the catalysts was tested by cyclic voltammetry (CV) and amperometric i-t curves. It was found that the urea content had an influence on the distribution of metal particles and the size of the nanoparticles. More catalyst active sites were formed on the surface of the catalyst due to that many nitrogen-based functional groups were formed on the surface of the carrier. Compared with other samples, catalyst with urea amount of 100 mg (Pt2Ni3/C–N3 samples) possessed small particle size and uniform distribution, which exhibited higher electrocatalytic activity and stability, and the maximum of forward anodic peak reached 1454 mA mg−1.

Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation.

Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.

Highly enhanced electrochemical activity of Ni foam electrodes decorated with nitrogen-doped carbon nanotubes for non-aqueous redox flow batteries

Nitrogen-doped carbon nanotubes (NCNTs) are directly grown on the surface of a three-dimensional (3D) Ni foam substrate by floating catalytic chemical vapor deposition (FCCVD). The electrochemical properties of the 3D NCNT-Ni foam are thoroughly examined as a potential electrode for non-aqueous redox flow batteries (RFBs). During synthesis, nitrogen atoms can be successfully doped onto the carbon nanotube (CNT) lattices by forming an abundance of nitrogen-based functional groups. The 3D NCNT-Ni foam electrode exhibits excellent electrochemical activities toward the redox reactions of [Fe (bpy)3]2+/3+ (in anolyte) and [Co(bpy)3]+/2+ (in catholyte), which are mainly attributed to the hierarchical 3D structure of the NCNT-Ni foam electrode and the catalytic effect of nitrogen atoms doped onto the CNTs; this leads to faster mass transfer and charge transfer during operation. As a result, the RFB cell assembled with 3D NCNT-Ni foam electrodes exhibits a high energy efficiency of 80.4% in the first cycle; this performance is maintained up to the 50th cycle without efficiency loss.

Metal-catalysed azidation of tertiary C-H bonds suitable for late-stage functionalization.

Some enzymes are able to selectively oxidize unactivated aliphatic C-H bonds to form alcohols; however biological systems do not possess enzymes that are able to catalyze the analogous amination of a C-H bond.1,2 The absence of such chemistry is limiting because nitrogen-containing groups are found in therapeutic agents and clinically useful natural products. In one prominent example, the conversion of the ketone of erythromycin to the –N(Me)CH2– group in azithromycin leads to a compound that can be dosed once daily with a shorter length of treatment.3,4 For such reasons, synthetic chemists are very interested in identifying catalysts that can directly convert C-H bonds to C-N bonds. Most currently used catalysts for C-H bond amination are ill suited for the functionalization of complex molecules, because they require excess substrate or directing groups, harsh reaction conditions, weak or acidic C-H bonds, or reagents containing specialized groups on the nitrogen atom.5-14 Among C-H bond amination reactions, those forming a carbon-nitrogen bond at a tertiary alkyl group would be particularly valuable, because this linkage is difficult to generate enzymatically from ketone or alcohol precursors.15 In this manuscript, we report a mild, selective, iron-catalyzed azidation of tertiary C-H bonds with substrate as limiting reagent. The reaction tolerates aqueous environments and is suitable for “late-stage” functionalization of complex structures. Moreover, this azidation creates the ability to install a range of nitrogen functional groups, including those from bio-orthogonal Huisgen “click” cycloadditions and the Staudinger ligation.16-19 For these reasons, we anticipate this methodology will create opportunities to easily modify natural products, their precursors, and their derivatives to analogs that contain distinct polarity and charge from nitrogen-containing groups. It could also be used to help identify targets of biologically active molecules by creating a point of attachment, for example to fluorescent tags or ‘handles’ for affinity chromatography, directly onto complex molecular structures.

2‐Aminobenzaldehydes as Versatile Substrates for Rhodium‐Catalyzed Alkyne Hydroacylation: Application to Dihydroquinolone Synthesis

2‐Aminobenzaldehydes as Versatile Substrates for Rhodium‐Catalyzed Alkyne Hydroacylation: Application to Dihydroquinolone Synthesis

Ageing of surface treated thermoplastic polyolefins

Thermoplastic polyolefin panels were treated with a flame, flame & water, and accelerated thermo molecular adhesion process (ATmaP) treatment. XPS, contact angle and adhesion test (pull off) results were acquired over a one year period to determine the changes in the elemental composition, surface energy and adhesion strength respectively over time. All surface-treated thermoplastic polyolefin samples showed a sharp decline in adhesion strength up to an ageing period totalling 6 months. The decline in adhesion strength was correlated with a decline in the nitrogen-containing constituents and C–O functional groups at the surface and a decline in surface energy for the flame & water-treated sample. There was no significant change in adhesion strength for all samples for ageing periods greater than 6 months. ATmaP-treated thermoplastic polyolefin outperformed the other two surface treatments in adhesion strength tests due to ATmaP retaining nitrogen-based functional groups (mainly nitrogen oxides) over the year long study. This retention of functionality allowed for a slower ageing process for ATmaP-treated surfaces in comparison to the other surface treatments.