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Synthesis, characterization, thermal stability, and application of microporous hyper cross-linked polyphosphazenes with naphthylamine group for CO2 uptake

  • Amin Abid , Shahid Nazeer , Laraib Kiran , Saqlain Raza , Ikram Ahmad , Hafiz Tariq Masood , Ammar M. Tighezza , Sana Shahzadi , Muhammad Ramzan Khawar , Moonwoo La EMAIL logo and Dongwhi Choi EMAIL logo
Published/Copyright: June 21, 2024
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Nanotechnology Reviews
From the journal Nanotechnology Reviews Volume 13 Issue 1

Abstract

There are numerous problems in the world, but environmental pollution is the biggest threat to life. Air pollution is the most critical form of environmental pollution because air is the most essential need of life. However, industrialization, population growth, and fossil fuel use increase hazardous and greenhouse gas concentrations daily. Greenhouse gases like carbon dioxide (CO2) contribute to global warming; hence, efficient, inexpensive, sustainable, and ecologically friendly air purification solutions are required. This study proposed a new method for synthesizing N- and P-rich polyphosphazene-based hyper cross-linked polymer (HCP) for CO2 adsorption. Due to their persistent porosity, low density, and high surface area, hyper cross-linked porous organic–inorganic hybrid phosphorus and nitrogen-rich polymers are cost-effective and promising gas adsorption materials. We synthesized hybrid organic and inorganic polyphosphazenes with nitrogen and phosphorus backbones and aromatic side groups cross-linked by the Friedel–Crafts alkylation process. HCP-A and HCP-B were cross-linked phosphazene-based microporous hybrid organic–inorganic polymers. HCP-A and HCP-B were produced in two stages. Hexachlorocyclotriphosphazene reacts with 1-napthylamine to form naphthyl amino phosphazene, which is cross-linked under optimum conditions to make cyclic HCP-A. Phosphorous dichlorophosphazene reacts with 1-naphthylamine to form poly[bis(1-naphthylamino) phosphazene] and is cross-linked to form linear HCP-B. HCP-A and HCP-B porous networks were studied with Brunauer–Emmett–Teller surface areas of 170.89 and 492.03 m2 g−1 and narrow pore sizes of 0.8–1.18 nm. These polymers are promising CO2 adsorbents due to their easy and cost-effective production, thermal stability, surface area, and CO2 absorption capacity.

Keywords: polyphosphazenes; characterization; thermal stability; hyper cross linked; CO2 adsorption

1 Introduction

Developing methods to clean the air is becoming the most difficult challenge for scientists to overcome. In spite of the fact that there is no life without clean air, the concentration of poisonous chemicals and greenhouse gases is increasing every day as a result of industrialization, population growth, and the usage of fossil fuels. As time goes on, the situation in emerging countries such as Pakistan, India, and Bangladesh, among others, continues to deteriorate. It is of the utmost importance to develop ways that are efficient, inexpensive, sustainable, and environmental friendly in order to purify air to develop methods that remove greenhouse gases from the environment [1–3]. Greenhouse gases, such as carbon dioxide (CO2), are a key contributor to the phenomenon of global warming. As a result of the tremendous increase in the concentration of CO2 in the atmosphere that has occurred since the beginning of the industrial revolution, the current level of CO2 in the atmosphere has surpassed 400 parts per million. One of the most significant greenhouse gases is CO2, which is responsible for the establishment of the greenhouse effect and gradually heats the earth by absorbing and emitting radiation in the infrared range. Therefore, the accumulation of CO2 in the atmosphere has irreversible implications, such as climate change, global warming, the melting of glaciers, ocean acidification, sea level rise, and so on, which have led to alarm on a global scale. Several different techniques for capturing CO2 are utilized, such as liquid solvent-based absorption, solid sorbent-based adsorption, membrane process, and cryogenic separation process, but the adsorption technique shows great potential for CO2 uptake. Therefore, we synthesized a hyper cross-linked polymer (HCP) based on polyphosphazenes, rich in both nitrogen and phosphorus, which was developed for the purpose of adsorbing CO2. Hyper cross-linked porous organic–inorganic hybrid phosphorus and nitrogen-rich polymers (HCPMPs) are gas adsorption materials that are cost-effective and promising due to their persistent porosity, low density, and high surface area [4,5].

Porosity is a property of a polymer that is characterized by the presence of pores within its structure and the ability to efficiently adsorb substances through these pores. Over the past few years, porous polymers have become increasingly significant, and they have a wide variety of uses among them. The reason for this is that they possess a high surface area, great porosity, a small pore size, and a strong packing [6,7]. Micro-porous materials, meso-porous materials, and macro-porous materials are classified according to their pore size. To be more specific, micro-porous materials have a pore diameter of less than 2 nm (d ≤ 2 nm), meso-porous materials have a pore diameter of 2–50 nm (d ≤ 50 nm), and macro-porous materials have a pore diameter of larger than 50 nm (d > 50 nm) [6]. It is possible for pores to be open, closed, cylindrical, slit-shaped, characterized by planar walls, organized, or disordered. Pores can also be open or closed. Crystalline materials, such as metal–organic frameworks (MOFs), have holes that are regular and organized in shape, whereas amorphous materials have pores that are interconnected and irregular in shape [8,9].

In addition, porous polymers can be found in several morphological forms, including zero-dimensional (0D) nanoparticles [10], two-dimensional (2D) membranes and hollow capsules [11], as well as three-dimensional (3D) monolithic blocks [11,12]. Porous materials can be categorized into different classifications, including hybrid porous materials, inorganic porous materials, and pure organic materials [13–15]. MOFs are hybrid porous materials composed of both inorganic and organic constituents [1,13,14,16–18]. Inorganic porous materials are entirely composed of inorganic substances [16]. Pure organic polymers (POPs) consist primarily of benzene rings. There exist six distinct categories of POPs [19]. HCPs are of utmost significance among them. HCPs refer to highly cross-linked porous polymers, as indicated in the literature [1,14,18,20]. The hydrophobic chromatography process was initially introduced by Davankov et al. in the early 1970s [21]. The researchers created them by employing a thorough process of post-crosslinking linear polystyrene (PS) chains [22]. Their achievement is accomplished through Friedel–Craft reactions, which entail the formation of structural connections between adjacent aromatic rings and the remaining chains, resulting in a much-expanded state [12,23].

Highly porous materials (HCPs) are the most effective method for purifying air because of their exceptional porosity and large surface area. Highly porous materials, such as HCPs, have been extensively utilized in recent years for various environmental applications. They not only store but also sequester hazardous gases such as CO2 [4]. HCPs are typically synthesized using three primary methods: After cross-linking the polymer precursors, the functional monomers undergo a direct single-step poly-condensation reaction. Additionally, cross-linking is achieved with the use of external cross-linkers. Hyper cross-linking is a method that creates numerous minuscule pores in polymers [24]. The presence of these pores leads to a significant increase in the surface area of the polymer, hence enhancing its reactivity. HCPs possess exceptional characteristics such as large surface areas, favorable porosity, low density, effective adsorption qualities, straightforward synthesis, cost-effectiveness, environmental friendliness, remarkable thermal and chemical stability, lightweight nature, and reusability [9]. The exceptional characteristics of HCPs, in comparison to conventional polymers, make them highly promising contenders for addressing both environmental pollution and energy issues. They possess numerous intriguing uses, including water treatment, gas storage, super-capacitors, sensing, catalysis, drug delivery, and chromatographic separations [12,13,20,25]. In recent decades, polyphosphazenes have garnered significant interest and have drawn researchers to investigate several uses, including thermal stability, gas adsorption capacity, energy storage, and medicinal applications [26–29]. Currently, there is extensive research being conducted on the use of HCPs as adsorbents to decrease the concentration of CO2 in the environment. For instance, the capacity to capture CO2 was evaluated in several types of MOP networks. Yao et al. synthesized this HCP by cross-linking tetraphenylethylene utilizing FDA as a cross-linking agent and FeCl3 as a catalyst. The purpose of this HCP was to enhance the uptake of CO2 [29–31].

HCPs possess a high surface area and include diverse functional groups, enabling them to effectively eliminate pollutants, particularly those of a biological, organic, and inorganic nature. This is due to their large surface area and the presence of functional group sites. HCP adsorbents with a hydrophobic surface exhibit high sorption capability for many compounds, including volatile organic components and organic contaminants. Nanoparticles of Davankov-type hyper cross-linked adsorbents with selective adsorption qualities were synthesized. The solid-phase microextraction method can utilize nanoparticles that are coated on the surface to effectively adsorb various organic contaminants, including alkanes and benzene molecules. The HCP-coated fibers were utilized for their adsorption capabilities and tested for their ability to adsorb polycyclic aromatic hydrocarbons from the air. The results obtained were quite satisfactory [32].

Yang et al. fabricated a porous polyphosphazene polymer by forming imine linkages using Schiff base condensation [33]. They synthesized cyclophosphazenes with aromatic side groups and cross-linked them using the well-established Friedel–Crafts procedure. The researcher then analyzed and described the heat stability of these compounds [34]. Wang et al. synthesized unique microspheres of N-doped porous carbon polyphosphazenes that incorporate oxygen and phosphorus, specifically designed for the purpose of adsorbing CO2 [35]. Abid et al. synthesized a cost-effective hybrid material by combining inorganic and organic components through a Friedel−Crafts reaction, resulting in the formation of hybrid coordination polymers with Lewis base sites. The researchers synthesized heteroatom-enriched precursors by performing nucleophilic substitution of hexachlorocyclotriphosphazene (HCCP) with 2-naphthol. Subsequently, the precursors were polymerized using Friedel−Crafts alkylation to obtain heteroatom-enriched cyclic phosphazene polymers (HCPs) with an increased content of phosphorus and nitrogen. These highly crystalline porous materials demonstrate a moderate ability to adsorb CO2 and iodine (I2) [16]. In recent years, there has been a growing interest in the development of porous materials, both organic and inorganic, that incorporate nitrogen and phosphorus. These materials, known as nitrogen- and phosphorus-rich microporous polymers, have attracted attention due to their unique characteristics such as large surface areas, nitrogen- and phosphorus-based molecular structures, low densities, and high chemical and thermal stability. These properties make them suitable for various applications in different fields [3,13,14,16,27,36].

2 Experimental section

2.1 Materials

1-Naphthylamine (monomer), formaldehyde dimethyl acetal (FDA) (cross-linker), dichloroethane (solvent), and ferric chloride (FeCl3) (catalyst) were obtained from Sigma Organics and used as received in their pure form. HCCP was purchased from Aldrich and used as received. Tetrahydrofuran (THF) (solvent) and n-hexane were also purchased from Sigma Organics, treated with molecular sieves, refluxed, and distilled under a nitrogen atmosphere, and then used in the experiment.

2.2 Synthesis of hyper cross-linked polyphosphazenes

2.2.1 Synthesis of HCP-A (cyclic)

Step 1. HCCP reaction with 1-naphthylamine (synthesis of naphthyl amino phosphazene [NAP])

About 5.31 g of 1-naphthylamine was dissolved in 20 ml THF and then added dropwise into a separate solution containing HCCP (0.2 g) in 20 ml THF. The reaction mixture was stirred and refluxed at 70°C for 48 h. The resultant solution was filtered, excess THF was removed by a rotatory evaporator, and the final product was precipitated in n-hexane and dried in the oven [26–28]. Through the reaction of HCCP with 1-naphthylamine, the synthesis of polyphosphazenes that are rich in nitrogen and phosphorus is accomplished. This reaction involves the substitution of chlorine atoms in HCCP with amino groups derived from 1-naphthylamine. As a result, this procedure results in the formation of NAP molecules that contain a significant amount of nitrogen and phosphorus. The reaction scheme is shown in Figure 1.

Figure 1 Synthesis of NAP.
Figure 1

Synthesis of NAP.

Step 2. Cross-linking of NAP

HCP-A was synthesized by the Friedel–Crafts alkylation reaction. NAP (0.1 g) was dissolved in 1,2-dichloroethane (5–7 ml) and dispersed well, then iron chloride (FeCl3) (0.2–0.3 g) was added, and FDA or dimethoxymethane (0.5 ml) was also added to the reaction flask and stirred with an initial temp of 45–50°C for 5 h and then temperature was raised at 80°C for 14 h. Finally, the product was filtered and washed repeatedly with methanol and THF until the color of the catalyst disappeared to obtain pure HCPs and then dried in an oven [28,37,38]. The reaction scheme is shown in Figure 2.

Figure 2 Synthesis of HCP-A (HCCP+1-naphthylamine).
Figure 2

Synthesis of HCP-A (HCCP+1-naphthylamine).

2.2.2 Synthesis of HCP-B (linear)

Step 1. Reaction of phosphorous dichlorophosphazene (PDCP) with 1-naphthylamine (synthesis of poly[bis(1-naphthylamino)phosphazene] [PBNAP])

About 5.31 g of 1-naphthylamine was dissolved in 20 ml of THF and then added dropwise into a solution of PDCP (0.25 g) and THF (20 ml). The reaction mixture was stirred continuously and refluxed at 70°C for 48 h. The resultant solution was filtered, excess THF was removed by the rotatory evaporator, and the final product was precipitated in n-hexane and dried in the oven [26–28]. The reaction scheme is shown in Figure 3.

Figure 3 Synthesis of poly[bis(1-naphthylamino)]phosphazene.
Figure 3

Synthesis of poly[bis(1-naphthylamino)]phosphazene.

Step 2. Cross-linking procedure

HCP-B was synthesized by the Friedel–Crafts alkylation reaction of PBNAP. PBNAP (0.1 g) was dissolved in 1,2-dichloroethane (5–7 ml) and dispersed well, then iron chlorine (FeCl3) (0.2–0.3 g) was added, and FDA or dimethoxymethane (0.5 ml) was also added in a reaction flask and stirred continuously with an initial temperature of 45–50°C for 5 h and then the temperature was raised to 80°C for 14 h. Finally, the product was filtered, washed well with methanol, and dried in the oven. The obtained products were washed repeatedly with methanol and THF until the color of the catalyst disappeared to obtain pure HCPs [28,37,38]. The reaction scheme is shown in Figure 4.

The microporous hyper-crosslinked polyphosphazenes with naphthylamine groups for CO2 uptake appear to be an innovative approach to carbon capture. The incorporation of naphthylamine groups into microporous hyper-crosslinked polyphosphazenes represents a distinctive chemical design. The naphthylamine groups likely introduce specific interactions and binding sites for CO2 molecules, potentially enhancing the material’s selectivity and affinity for capturing CO2. Hyper-crosslinking often leads to increased porosity and surface area in materials. If this material achieves high porosity along with the naphthylamine groups, it could offer improved CO2 adsorption capacity compared to materials lacking this specific chemical composition. The combination of the unique chemical structure and enhanced porosity might result in a material that can efficiently adsorb CO2, potentially surpassing the performance of materials investigated in recent studies. Polyphosphazene-based materials are often tunable by modifying their chemical structure.

3 Characterization of synthesized HCP-A and HCP-B

3.1 Equipment

Fourier transform infrared spectroscopy (FTIR) graphs were recorded using a Thermo Nicolet Nexus 670 spectrophotometer. Elemental analysis of HCPs was determined using an energy dispersive X-ray spectroscopy (EDX). Thermogravimetry (TGA) was carried out using a Netzsch Jupiter thermal analyzer at a temperature range of 400–800°C at a heating rate of 10°C min−1. Scanning electron microscope (SEM) analysis was performed with Zeiss Ultra-55. The XRD powder (X-ray diffraction) analysis of the synthesized polymer was done with Smart Lab TM 3 kW. UV–VIS graphs were obtained from a UV–VIS spectrophotometer. For measurement of pore size, Brunauer–Emmett–Teller (BET) surface area, and pore size, CO2 adsorption/desorption isotherms on the polymers were recorded using Micromeritics ASAP 2020 M and porosity analyzer Micromeritics.

4 Results and discussion

The synthetic route for phosphazenes with a side group of 1-naphthylamine and their hyper cross-linking via Friedel crafts alkylation is shown in Figures 1 and 2. The precursor cyclic phosphazenes were obtained by reacting HCCP and 1-naphthylamine in THF at 70°C in the presence of triethylamine as a catalyst, as described in the experimental section. In another reaction, PDCP was reacted with 1-naphthylamine to produce PBNAP. Linear phosphazenes with side groups of 1-naphthylamine are displayed in Figure 3, and their hyper cross-linked reaction scheme is given in Figure 4. Linear polyphosphazenes were synthesized by replacing chloro groups of PDCP with 1-naphthylamine in THF, as reported in Section 2.

Figure 4 Synthesis of HCP-B (PDCP+1-naphthylamine).
Figure 4

Synthesis of HCP-B (PDCP+1-naphthylamine).

The synthesized HCP-A and HCP-B were characterized by 1H NMR and FT-IR, as discussed in the following.

The proposed structure of both HCPs is confirmed by 1H NMR, as shown in Figures 5 and 6. The peak shifting from 1H NMR of 1-naphthylamine indicates the effective grafting of 1-naphthylamine on HCCP (Figure 7).

Figure 5 1H NMR spectra of HCCP + 1-naphthylamine (HCP-A).
Figure 5

1H NMR spectra of HCCP + 1-naphthylamine (HCP-A).

Figure 6 1H NMR spectra of PDCP + 1-naphthylamine (HCP-B).
Figure 6

1H NMR spectra of PDCP + 1-naphthylamine (HCP-B).

Figure 7 IR spectrum of HCCP + 1-naphthylamine (HCP-A).
Figure 7

IR spectrum of HCCP + 1-naphthylamine (HCP-A).

4.1 IR results

Naphthylamine grafted cyclic phosphazenes showed FT-IR peaks at 1,276, 1,184(P═N), and 1,629 cm−1. Moreover, the absence of P–Cl peaks means that chlorine groups are grafted with naphthol effectively as shown in the FTIR spectra figure.

It also showed peaks at 2,880 cm−1 (–CH2– stretching vibration) and 3,267 cm−1 (–CH2– deformation vibration). The peak at 1,600 cm describes the presence of an aromatic ring. The presence of the –CH2 peak proves the effective cross-linking between polymer chains.

FT-IR spectra analysis represented polyphosphazene backbones at 1,325 and 1,020 cm−1 (–N═P– stretching band), 921 cm−1 (–N–P– stretching vibration), and 1,108 cm−1, as shown in Figure 8. In the HCP-A and HCP-B, the disappearance of chlorine showed the successful replacement of 1-naphthylamine aromatic groups and showed peaks at 2,796 cm−1 (–CH2– stretching vibration) and 3,377 cm−1 (–CH2– deformation vibration). The peak at 3,377 cm denotes the presence of the N–H group. The peak at 770 indicates the presence of C–H bending. The presence of the –CH2 peak proves the successful cross-linking between polymer chains.

Figure 8 IR spectrum of PDCP+ 1-naphthylamine (HCP-B).
Figure 8

IR spectrum of PDCP+ 1-naphthylamine (HCP-B).

4.2 SEM analysis

The morphology of the HCP-A and HCP-B was investigated using an SEM, and it was found that they had abundant pores and is uniform. Because of their porous structure, these materials are very suitable for the adsorption of gases, as shown in Figures 9–14.

Figure 9 SEM image of HCP-A at mag. 20,000.
Figure 9

SEM image of HCP-A at mag. 20,000.

Figure 10 SEM image of HCP-A at mag. 40,000.
Figure 10

SEM image of HCP-A at mag. 40,000.

Figure 11 SEM image of HCP-A at mag. 80,000.
Figure 11

SEM image of HCP-A at mag. 80,000.

Figure 12 SEM image of HCP-B at mag. 20,000.
Figure 12

SEM image of HCP-B at mag. 20,000.

Figure 13 SEM image of HCP-B at mag. 40,000.
Figure 13

SEM image of HCP-B at mag. 40,000.

Figure 14 SEM image of HCP-B at mag. 50,000.
Figure 14

SEM image of HCP-B at mag. 50,000.

XRD graphs of HCP-A and HCP-B are shown in Figures 15 and 16, respectively. It can be observed from the figures that there is no sharp peak at 2θ, and it has some noisy pattern, which suggests that both polymers are amorphous in nature.

Figure 15 XRD graph of HCP-A.
Figure 15

XRD graph of HCP-A.

Figure 16 XRD graph of HCP-B.
Figure 16

XRD graph of HCP-B.

4.3 Percentage composition

The percentage composition of HCP-A and HCP-B shows that nitrogen and phosphorous content are present in abundance in HCP-A compared to HCP-B, which has a low concentration of nitrogen and phosphorous. This is due to the cyclic nature of HCP-A (Table 1).

Table 1

Elemental percentage composition of HCP-A and HCP-B

Sr. No Elements % Compositions
HCP-A HCP-B
1. Weight 2.1740 1.979
2. Nitrogen 10.73 1.01
3. Carbon 76.99 62.00
4. Hydrogen 7.498 5.19
5. Phosphorus 0.5 0.03

4.4 UV results

HCP-A shows lambda max at 352 nm with an absorbance of 1.394, and HCP-B shows lambda max at 291 nm with an absorbance of 1.49 (Figures 17 and 18).

Figure 17 UV–Vis graph of HCP-A.
Figure 17

UV–Vis graph of HCP-A.

Figure 18 UV–Vis graph of HCP-B.
Figure 18

UV–Vis graph of HCP-B.

4.5 Thermogravimetric analysis

TGA studies in the CO2 atmosphere showed that HCP-A and HCP-B are thermally stable under 420°C (HCP-A) and stable even higher than 800°C (HCP-B). It was observed that the first 5% weight loss was due to the volatilization of solvent adsorbed in the HCP surface, as shown in Figure 19. HCP-B degraded rapidly from 200 to 600°C, later becoming constant, and weight loss was not more than 60% even at 800°C while HCP-A degraded after 200°C very fast, and at 600°C it became constant and weight loss was 40. It was found that HCP-B is thermally more stable than HCP-A due to long-chain nitrogen and phosphorus backbone, so we conclude that HCP-B was not easily degraded.

Figure 19 TGA of HCP-A and HCP-B.
Figure 19

TGA of HCP-A and HCP-B.

4.6 Porosity

The porosity of the HCP-A and HCP-B was investigated by adsorption analysis using CO2 gas as the adsorbate molecule, and HCPs act as the adsorbent. Before adsorption, the materials were de-gassed at 120°C for 8 h under a nitrogen atmosphere. The porosity and surface area of HCP-A and HCP-B were studied by CO2 adsorption–desorption measurements at 77 K. The results are shown in Figures 20 and 21. HCP-A and HCP-B porous networks were investigated with a BET surface area of 170.89 m2 g−1 and 492.03 m2 g−1 respectively.

Figure 20 Brunauer–Emmett–Teller plot and pore size distribution of HCP-A.
Figure 20

Brunauer–Emmett–Teller plot and pore size distribution of HCP-A.

Figure 21 Brunauer–Emmett–Teller plot and pore size distribution of HCP-B.
Figure 21

Brunauer–Emmett–Teller plot and pore size distribution of HCP-B.

4.7 CO2 uptake capacity

Due to the increase in the level of CO2, scientists are finding ways to CO2 capturing. HCPs are very useful in capturing CO2 due to their characteristics, including low density, large surface area, thermal stability, smaller pore size, and easy functionalization [39]. Now, HCPs are widely studied as adsorbents to reduce CO2 concentration in the environment. For example, CO2 capturing capacity was tested in different types of MOP networks. This HCP was prepared by cross-linking of tetraphenylmethane by using FDA and catalyst FeCl3. It was found and reported that CO2 adsorption was 2.95 mmol/g at 273 K temperature and 1 bar pressure. Researchers have evaluated CO2 adsorption and its conversion into organic compounds. For example, the synthesis of imidazolium salt-modified porous HCPs shows CO2 adsorption up to 14.5 wt% at 273 K and 1 bar pressure. Such functionalized materials showed high activity to change it into cyclic carbonates. This is because of the synergistic effect of the salt used and the micro-porosity of the polymers [40].

The synthesized HCP has a high surface area, which enables it to be used for CO2 adsorption. HCP-A showed a lower level of CO2 adsorption ability of 5.2 mmol g−1 at 273 K and 4.21 mmol g−1 at 298 K as compared to HCP-B, exhibited a higher CO2 adsorption ability of 7.20 mmol g−1 at 273 K and 4.30 mmol g−1 at 298 K, as shown in Figure 22 which is due to less surface area of HCP-A as compared to HCP-B.

Figure 22 CO2 adsorption–desorption isotherm of HCP-A and HCP-B.
Figure 22

CO2 adsorption–desorption isotherm of HCP-A and HCP-B.

4.8 Isosteric heat of adsorption of CO2

For further understanding of the relationship between HCP-A and HCP-B toward CO2 adsorption, the isosteric heat of adsorption (Q st) was determined with the help of CO2 isotherms measured at 273 and 298 K. Two isotherms were obtained at two different temperatures with CO2 sorption on HCP-A and HCP-B. Q st was determined by the following formula. It shows the advantage of capturing the effect of surface coverage upon enthalpy of adsorption

Q st = R [ ( T 2 × T 1 ) / ( T 2 − T 1 ) ] / In ( P 2 / P 1 ) .

From the graph, it was found that at a lower temperature, the kinetic energy of CO2 molecules seized and indicated higher adsorption ability of HCP-A and HCP-B, while upon increasing the temperature, the CO2 gas molecule released at a higher rate and showed less adsorption (Table 2).

Table 2

Summary of CO2 uptake and Q st by HCP-A and HCP-B

Polymer CO2 uptake at 273 K (%) CO2 uptake at 298 K (%) Q st for CO2 uptake (kJ/mol)
HCP-A 5.2 7.20 30.2–26.5
HCP-B 4.21 4.30 28.3–27.3

Figure 23 shows that the heat of adsorption of HCP-B is greater than HCP-A, and it decreases as the quantity of CO2 adsorbed increases. HCP-A shows less heat of adsorption as compared to HCP-B due to its structure.

Figure 23 CO2 adsorption isotherm at STP of HCP-A and HCP-B.
Figure 23

CO2 adsorption isotherm at STP of HCP-A and HCP-B.

5 Conclusion

The presence of clean air is essential for sustaining life. However, as a result of industrialization, population growth, and the usage of fossil fuels, the levels of hazardous chemicals and greenhouse gases are steadily rising. Developing cost-effective and environmentally friendly methods to purify air has become a significant challenge for scientists. We have synthesized two porous hybrid polymers using phosphazenes as a starting material. These polymers are rich in phosphorus and nitrogen. The synthesis involved replacing the chlorine atoms of HCCP with 1-naphthylamine, followed by cross-linking through the Friedel–Crafts alkylation. PDCP, a different polymer, was synthesized and then underwent chlorination replacement with 1-naphthylamine. It was then cross-linked, as described earlier. The polymers HCP-A and HCP-B exhibited a significant presence of micro-pores, a favorable surface area, and exceptional thermal stability. The BET surface area of the HCP-A porous network is 170.89 m2 g−1, while the HCP-B porous network has a BET surface area of 492.03 m2 g−1. Additionally, it was discovered that the phosphorus and nitrogen levels in HCP-A and HCP-B promoted the absorption of CO2. This study presents a new approach for the systematic production of highly effective nitrogen- and phosphorus-based HCPs with the ability to adsorb gases in their micropores.

6 Future perspective

Hyper cross-linked polyphosphazenes with naphthylamine group materials have great selectivity and capacity for CO2 capture, along with good stability and regeneration capabilities, and they have the potential for promising future possibilities. If they demonstrate efficacy and cost-effectiveness, they could be applied in various practical contexts.

It has the potential to be utilized in businesses such as power plants, where there is a significant amount of CO2 emissions, to capture CO2 prior to its release into the environment, thereby mitigating greenhouse gas emissions. This technology could be utilized in gas purification operations to effectively eliminate CO2 from natural gas or biogas streams. Possible applications could encompass environmental remediation endeavors, such as the removal of CO2 from enclosed areas or the capture of emissions from vehicles. This area of study shows potential in aiding worldwide efforts to address climate change by absorbing and neutralizing CO2 emissions. However, additional testing, optimization, and economic evaluations are required to ensure its successful integration in everyday situations.

Acknowledgments

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (RS-2024-00357072) and Researchers Supporting Project number (RSPD2024R765), King Saud University, Riyadh, Saudi Arabia.

  1. Funding information: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (RS-2024-00357072) and Researchers Supporting Project number (RSPD2024R765), King Saud University, Riyadh, Saudi Arabia. M. La was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2022R1C1C1003091).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2023-11-09
Revised: 2023-12-29
Accepted: 2024-01-02
Published Online: 2024-06-21

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/ntrev-2023-0197
Keywords for this article
polyphosphazenes; characterization; thermal stability; hyper cross linked; CO2 adsorption
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. Tension buckling and postbuckling of nanocomposite laminated plates with in-plane negative Poisson’s ratio
  3. Polyvinylpyrrolidone-stabilised gold nanoparticle coatings inhibit blood protein adsorption
  4. Energy and mass transmission through hybrid nanofluid flow passing over a spinning sphere with magnetic effect and heat source/sink
  5. Surface treatment with nano-silica and magnesium potassium phosphate cement co-action for enhancing recycled aggregate concrete
  6. Numerical investigation of thermal radiation with entropy generation effects in hybrid nanofluid flow over a shrinking/stretching sheet
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  14. Antibacterial, mechanical, and dielectric properties of hydroxyapatite cordierite/zirconia porous nanocomposites for use in bone tissue engineering applications
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  16. Durability prediction of geopolymer mortar reinforced with nanoparticles and PVA fiber using particle swarm optimized BP neural network
  17. Utilization of zein nano-based system for promoting antibiofilm and anti-virulence activities of curcumin against Pseudomonas aeruginosa
  18. Antibacterial effect of novel dental resin composites containing rod-like zinc oxide
  19. An extended model to assess Jeffery–Hamel blood flow through arteries with iron-oxide (Fe2O3) nanoparticles and melting effects: Entropy optimization analysis
  20. Comparative study of copper nanoparticles over radially stretching sheet with water and silicone oil
  21. Cementitious composites modified by nanocarbon fillers with cooperation effect possessing excellent self-sensing properties
  22. Confinement size effect on dielectric properties, antimicrobial activity, and recycling of TiO2 quantum dots via photodegradation processes of Congo red dye and real industrial textile wastewater
  23. Biogenic silver nanoparticles of Moringa oleifera leaf extract: Characterization and photocatalytic application
  24. Novel integrated structure and function of Mg–Gd neutron shielding materials
  25. Impact of multiple slips on thermally radiative peristaltic transport of Sisko nanofluid with double diffusion convection, viscous dissipation, and induced magnetic field
  26. Magnetized water-based hybrid nanofluid flow over an exponentially stretching sheet with thermal convective and mass flux conditions: HAM solution
  27. A numerical investigation of the two-dimensional magnetohydrodynamic water-based hybrid nanofluid flow composed of Fe3O4 and Au nanoparticles over a heated surface
  28. Development and modeling of an ultra-robust TPU-MWCNT foam with high flexibility and compressibility
  29. Effects of nanofillers on the physical, mechanical, and tribological behavior of carbon/kenaf fiber–reinforced phenolic composites
  30. Polymer nanocomposite for protecting photovoltaic cells from solar ultraviolet in space
  31. Study on the mechanical properties and microstructure of recycled concrete reinforced with basalt fibers and nano-silica in early low-temperature environments
  32. Synergistic effect of carbon nanotubes and polyvinyl alcohol on the mechanical performance and microstructure of cement mortar
  33. CFD analysis of paraffin-based hybrid (Co–Au) and trihybrid (Co–Au–ZrO2) nanofluid flow through a porous medium
  34. Forced convective tangent hyperbolic nanofluid flow subject to heat source/sink and Lorentz force over a permeable wedge: Numerical exploration
  35. Physiochemical and electrical activities of nano copper oxides synthesised via hydrothermal method utilising natural reduction agents for solar cell application
  36. A homotopic analysis of the blood-based bioconvection Carreau–Yasuda hybrid nanofluid flow over a stretching sheet with convective conditions
  37. In situ synthesis of reduced graphene oxide/SnIn4S8 nanocomposites with enhanced photocatalytic performance for pollutant degradation
  38. A coarse-grained Poisson–Nernst–Planck model for polyelectrolyte-modified nanofluidic diodes
  39. A numerical investigation of the magnetized water-based hybrid nanofluid flow over an extending sheet with a convective condition: Active and passive controls of nanoparticles
  40. The LyP-1 cyclic peptide modified mesoporous polydopamine nanospheres for targeted delivery of triptolide regulate the macrophage repolarization in atherosclerosis
  41. Synergistic effect of hydroxyapatite-magnetite nanocomposites in magnetic hyperthermia for bone cancer treatment
  42. The significance of quadratic thermal radiative scrutinization of a nanofluid flow across a microchannel with thermophoretic particle deposition effects
  43. Ferromagnetic effect on Casson nanofluid flow and transport phenomena across a bi-directional Riga sensor device: Darcy–Forchheimer model
  44. Performance of carbon nanomaterials incorporated with concrete exposed to high temperature
  45. Multicriteria-based optimization of roller compacted concrete pavement containing crumb rubber and nano-silica
  46. Revisiting hydrotalcite synthesis: Efficient combined mechanochemical/coprecipitation synthesis to design advanced tunable basic catalysts
  47. Exploration of irreversibility process and thermal energy of a tetra hybrid radiative binary nanofluid focusing on solar implementations
  48. Effect of graphene oxide on the properties of ternary limestone clay cement paste
  49. Improved mechanical properties of graphene-modified basalt fibre–epoxy composites
  50. Sodium titanate nanostructured modified by green synthesis of iron oxide for highly efficient photodegradation of dye contaminants
  51. Green synthesis of Vitis vinifera extract-appended magnesium oxide NPs for biomedical applications
  52. Differential study on the thermal–physical properties of metal and its oxide nanoparticle-formed nanofluids: Molecular dynamics simulation investigation of argon-based nanofluids
  53. Heat convection and irreversibility of magneto-micropolar hybrid nanofluids within a porous hexagonal-shaped enclosure having heated obstacle
  54. Numerical simulation and optimization of biological nanocomposite system for enhanced oil recovery
  55. Laser ablation and chemical vapor deposition to prepare a nanostructured PPy layer on the Ti surface
  56. Cilostazol niosomes-loaded transdermal gels: An in vitro and in vivo anti-aggregant and skin permeation activity investigations towards preparing an efficient nanoscale formulation
  57. Linear and nonlinear optical studies on successfully mixed vanadium oxide and zinc oxide nanoparticles synthesized by sol–gel technique
  58. Analytical investigation of convective phenomena with nonlinearity characteristics in nanostratified liquid film above an inclined extended sheet
  59. Optimization method for low-velocity impact identification in nanocomposite using genetic algorithm
  60. Analyzing the 3D-MHD flow of a sodium alginate-based nanofluid flow containing alumina nanoparticles over a bi-directional extending sheet using variable porous medium and slip conditions
  61. A comprehensive study of laser irradiated hydrothermally synthesized 2D layered heterostructure V2O5(1−x)MoS2(x) (X = 1–5%) nanocomposites for photocatalytic application
  62. Computational analysis of water-based silver, copper, and alumina hybrid nanoparticles over a stretchable sheet embedded in a porous medium with thermophoretic particle deposition effects
  63. A deep dive into AI integration and advanced nanobiosensor technologies for enhanced bacterial infection monitoring
  64. Effects of normal strain on pyramidal I and II 〈c + a〉 screw dislocation mobility and structure in single-crystal magnesium
  65. Computational study of cross-flow in entropy-optimized nanofluids
  66. Significance of nanoparticle aggregation for thermal transport over magnetized sensor surface
  67. A green and facile synthesis route of nanosize cupric oxide at room temperature
  68. Effect of annealing time on bending performance and microstructure of C19400 alloy strip
  69. Chitosan-based Mupirocin and Alkanna tinctoria extract nanoparticles for the management of burn wound: In vitro and in vivo characterization
  70. Electrospinning of MNZ/PLGA/SF nanofibers for periodontitis
  71. Photocatalytic degradation of methylene blue by Nd-doped titanium dioxide thin films
  72. Shell-core-structured electrospinning film with sequential anti-inflammatory and pro-neurogenic effects for peripheral nerve repairment
  73. Flow and heat transfer insights into a chemically reactive micropolar Williamson ternary hybrid nanofluid with cross-diffusion theory
  74. One-pot fabrication of open-spherical shapes based on the decoration of copper sulfide/poly-O-amino benzenethiol on copper oxide as a promising photocathode for hydrogen generation from the natural source of Red Sea water
  75. A penta-hybrid approach for modeling the nanofluid flow in a spatially dependent magnetic field
  76. Advancing sustainable agriculture: Metal-doped urea–hydroxyapatite hybrid nanofertilizer for agro-industry
  77. Utilizing Ziziphus spina-christi for eco-friendly synthesis of silver nanoparticles: Antimicrobial activity and promising application in wound healing
  78. Plant-mediated synthesis, characterization, and evaluation of a copper oxide/silicon dioxide nanocomposite by an antimicrobial study
  79. Effects of PVA fibers and nano-SiO2 on rheological properties of geopolymer mortar
  80. Investigating silver and alumina nanoparticles’ impact on fluid behavior over porous stretching surface
  81. Potential pharmaceutical applications and molecular docking study for green fabricated ZnO nanoparticles mediated Raphanus sativus: In vitro and in vivo study
  82. Effect of temperature and nanoparticle size on the interfacial layer thickness of TiO2–water nanofluids using molecular dynamics
  83. Characteristics of induced magnetic field on the time-dependent MHD nanofluid flow through parallel plates
  84. Flexural and vibration behaviours of novel covered CFRP composite joints with an MWCNT-modified adhesive
  85. Experimental research on mechanically and thermally activation of nano-kaolin to improve the properties of ultra-high-performance fiber-reinforced concrete
  86. Analysis of variable fluid properties for three-dimensional flow of ternary hybrid nanofluid on a stretching sheet with MHD effects
  87. Biodegradability of corn starch films containing nanocellulose fiber and thymol
  88. Toxicity assessment of copper oxide nanoparticles: In vivo study
  89. Some measures to enhance the energy output performances of triboelectric nanogenerators
  90. Reinforcement of graphene nanoplatelets on water uptake and thermomechanical behaviour of epoxy adhesive subjected to water ageing conditions
  91. Optimization of preparation parameters and testing verification of carbon nanotube suspensions used in concrete
  92. Max-phase Ti3SiC2 and diverse nanoparticle reinforcements for enhancement of the mechanical, dynamic, and microstructural properties of AA5083 aluminum alloy via FSP
  93. Advancing drug delivery: Neural network perspectives on nanoparticle-mediated treatments for cancerous tissues
  94. PEG-PLGA core–shell nanoparticles for the controlled delivery of picoplatin–hydroxypropyl β-cyclodextrin inclusion complex in triple-negative breast cancer: In vitro and in vivo study
  95. Conduction transportation from graphene to an insulative polymer medium: A novel approach for the conductivity of nanocomposites
  96. Review Articles
  97. Developments of terahertz metasurface biosensors: A literature review
  98. Overview of amorphous carbon memristor device, modeling, and applications for neuromorphic computing
  99. Advances in the synthesis of gold nanoclusters (AuNCs) of proteins extracted from nature
  100. A review of ternary polymer nanocomposites containing clay and calcium carbonate and their biomedical applications
  101. Recent advancements in polyoxometalate-functionalized fiber materials: A review
  102. Special contribution of atomic force microscopy in cell death research
  103. A comprehensive review of oral chitosan drug delivery systems: Applications for oral insulin delivery
  104. Cellular senescence and nanoparticle-based therapies: Current developments and perspectives
  105. Cyclodextrins-block copolymer drug delivery systems: From design and development to preclinical studies
  106. Micelle-based nanoparticles with stimuli-responsive properties for drug delivery
  107. Critical assessment of the thermal stability and degradation of chemically functionalized nanocellulose-based polymer nanocomposites
  108. Research progress in preparation technology of micro and nano titanium alloy powder
  109. Nanoformulations for lysozyme-based additives in animal feed: An alternative to fight antibiotic resistance spread
  110. Incorporation of organic photochromic molecules in mesoporous silica materials: Synthesis and applications
  111. A review on modeling of graphene and associated nanostructures reinforced concrete
  112. A review on strengthening mechanisms of carbon quantum dots-reinforced Cu-matrix nanocomposites
  113. Review on nanocellulose composites and CNFs assembled microfiber toward automotive applications
  114. Nanomaterial coating for layered lithium rich transition metal oxide cathode for lithium-ion battery
  115. Application of AgNPs in biomedicine: An overview and current trends
  116. Nanobiotechnology and microbial influence on cold adaptation in plants
  117. Hepatotoxicity of nanomaterials: From mechanism to therapeutic strategy
  118. Applications of micro-nanobubble and its influence on concrete properties: An in-depth review
  119. A comprehensive systematic literature review of ML in nanotechnology for sustainable development
  120. Exploiting the nanotechnological approaches for traditional Chinese medicine in childhood rhinitis: A review of future perspectives
  121. Twisto-photonics in two-dimensional materials: A comprehensive review
  122. Current advances of anticancer drugs based on solubilization technology
  123. Recent process of using nanoparticles in the T cell-based immunometabolic therapy
  124. Future prospects of gold nanoclusters in hydrogen storage systems and sustainable environmental treatment applications
  125. Preparation, types, and applications of one- and two-dimensional nanochannels and their transport properties for water and ions
  126. Microstructural, mechanical, and corrosion characteristics of Mg–Gd–x systems: A review of recent advancements
  127. Functionalized nanostructures and targeted delivery systems with a focus on plant-derived natural agents for COVID-19 therapy: A review and outlook
  128. Mapping evolution and trends of cell membrane-coated nanoparticles: A bibliometric analysis and scoping review
  129. Nanoparticles and their application in the diagnosis of hepatocellular carcinoma
  130. In situ growth of carbon nanotubes on fly ash substrates
  131. Structural performance of boards through nanoparticle reinforcement: An advance review
  132. Reinforcing mechanisms review of the graphene oxide on cement composites
  133. Seed regeneration aided by nanomaterials in a climate change scenario: A comprehensive review
  134. Surface-engineered quantum dot nanocomposites for neurodegenerative disorder remediation and avenue for neuroimaging
  135. Graphitic carbon nitride hybrid thin films for energy conversion: A mini-review on defect activation with different materials
  136. Nanoparticles and the treatment of hepatocellular carcinoma
  137. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part II
  138. Highly safe lithium vanadium oxide anode for fast-charging dendrite-free lithium-ion batteries
  139. Recent progress in nanomaterials of battery energy storage: A patent landscape analysis, technology updates, and future prospects
  140. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part II
  141. Calcium-, magnesium-, and yttrium-doped lithium nickel phosphate nanomaterials as high-performance catalysts for electrochemical water oxidation reaction
  142. Low alkaline vegetation concrete with silica fume and nano-fly ash composites to improve the planting properties and soil ecology
  143. Mesoporous silica-grafted deep eutectic solvent-based mixed matrix membranes for wastewater treatment: Synthesis and emerging pollutant removal performance
  144. Electrochemically prepared ultrathin two-dimensional graphitic nanosheets as cathodes for advanced Zn-based energy storage devices
  145. Enhanced catalytic degradation of amoxicillin by phyto-mediated synthesised ZnO NPs and ZnO-rGO hybrid nanocomposite: Assessment of antioxidant activity, adsorption, and thermodynamic analysis
  146. Incorporating GO in PI matrix to advance nanocomposite coating: An enhancing strategy to prevent corrosion
  147. Synthesis, characterization, thermal stability, and application of microporous hyper cross-linked polyphosphazenes with naphthylamine group for CO2 uptake
  148. Engineering in ceramic albite morphology by the addition of additives: Carbon nanotubes and graphene oxide for energy applications
  149. Nanoscale synergy: Optimizing energy storage with SnO2 quantum dots on ZnO hexagonal prisms for advanced supercapacitors
  150. Aging assessment of silicone rubber materials under corona discharge accompanied by humidity and UV radiation
  151. Tuning structural and electrical properties of Co-precipitated and Cu-incorporated nickel ferrite for energy applications
  152. Sodium alginate-supported AgSr nanoparticles for catalytic degradation of malachite green and methyl orange in aqueous medium
  153. An environmentally greener and reusability approach for bioenergy production using Mallotus philippensis (Kamala) seed oil feedstock via phytonanotechnology
  154. Micro-/nano-alumina trihydrate and -magnesium hydroxide fillers in RTV-SR composites under electrical and environmental stresses
  155. Mechanism exploration of ion-implanted epoxy on surface trap distribution: An approach to augment the vacuum flashover voltages
  156. Nanoscale engineering of semiconductor photocatalysts boosting charge separation for solar-driven H2 production: Recent advances and future perspective
  157. Excellent catalytic performance over reduced graphene-boosted novel nanoparticles for oxidative desulfurization of fuel oil
  158. Special Issue on Advances in Nanotechnology for Agriculture
  159. Deciphering the synergistic potential of mycogenic zinc oxide nanoparticles and bio-slurry formulation on phenology and physiology of Vigna radiata
  160. Nanomaterials: Cross-disciplinary applications in ornamental plants
  161. Special Issue on Catechol Based Nano and Microstructures
  162. Polydopamine films: Versatile but interface-dependent coatings
  163. In vitro anticancer activity of melanin-like nanoparticles for multimodal therapy of glioblastoma
  164. Poly-3,4-dihydroxybenzylidenhydrazine, a different analogue of polydopamine
  165. Chirality and self-assembly of structures derived from optically active 1,2-diaminocyclohexane and catecholamines
  166. Advancing resource sustainability with green photothermal materials: Insights from organic waste-derived and bioderived sources
  167. Bioinspired neuromelanin-like Pt(iv) polymeric nanoparticles for cancer treatment
  168. Special Issue on Implementing Nanotechnology for Smart Healthcare System
  169. Intelligent explainable optical sensing on Internet of nanorobots for disease detection
  170. Special Issue on Green Mono, Bi and Tri Metallic Nanoparticles for Biological and Environmental Applications
  171. Tracking success of interaction of green-synthesized Carbopol nanoemulgel (neomycin-decorated Ag/ZnO nanocomposite) with wound-based MDR bacteria
  172. Green synthesis of copper oxide nanoparticles using genus Inula and evaluation of biological therapeutics and environmental applications
  173. Biogenic fabrication and multifunctional therapeutic applications of silver nanoparticles synthesized from rose petal extract
  174. Metal oxides on the frontlines: Antimicrobial activity in plant-derived biometallic nanoparticles
  175. Controlling pore size during the synthesis of hydroxyapatite nanoparticles using CTAB by the sol–gel hydrothermal method and their biological activities
  176. Special Issue on State-of-Art Advanced Nanotechnology for Healthcare
  177. Applications of nanomedicine-integrated phototherapeutic agents in cancer theranostics: A comprehensive review of the current state of research
  178. Smart bionanomaterials for treatment and diagnosis of inflammatory bowel disease
  179. Beyond conventional therapy: Synthesis of multifunctional nanoparticles for rheumatoid arthritis therapy
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