Pd On Thermo-Responsive Composite of Silica-Coated Carbon Nanotube And 1-Vinyl-3-Butylimidazolium-Based Ionic Liquid Copolymers As An Efficient Catalyst For Hydrogenation of Nitro Compounds

Pd On Thermo-Responsive Composite of Silica-Coated Carbon Nanotube And 1-Vinyl-3-Butylimidazolium-Based Ionic Liquid Copolymers As An Efficient Catalyst For Hydrogenation of Nitro Compounds | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Pd On Thermo-Responsive Composite of Silica-Coated Carbon Nanotube And 1-Vinyl-3-Butylimidazolium-Based Ionic Liquid Copolymers As An Efficient Catalyst For Hydrogenation of Nitro Compounds Samahe Sadjadi, Neda Abedian-Dehaghani, Majid M. Heravi This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1148099/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 10 Mar, 2022 Read the published version in Scientific Reports → Version 1 posted 8 You are reading this latest preprint version Abstract In this work, an ionic liquid-containing thermo-responsive heterogeneous catalyst with utility for promoting hydrogenation of nitro-compounds in aqueous media is developed. To prepare the catalyst, silica-coated carbon nanotubes were synthesized and vinyl-functionalized. The resulted compound was then polymerized with 1-viny-3-butylimidazolium bromide and N -isopropylacrylamide. The obtained ionic liquid-containing thermo-responsive composite was palladated via wet-impregnation method to give the final catalyst. Study of the performance of the catalyst confirmed high catalytic activity of the catalyst at temperature above the lower critical solution temperature. Furthermore, the catalyst was highly recyclable and showed negligible Pd leaching upon recycling. Broad substrate scope and selectivity of the catalyst towards reduction of nitro functionality were also confirmed. Furthermore, hot filtration test implied the heterogeneous nature of the catalysis. The comparison of the activity of Pd/CNT-P with some control catalysts approved the importance of hybridization of P and CNT and the presence of ionic liquid for the catalytic activity. Organic Chemistry Catalysis Carbon nanotube Ionic liquid Heterogeneous catalyst Thermo-responsive polymer N-isopropylacrylamide. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Introduction Smart polymers are polymeric compounds 1-3 that respond to the external stimuli, such as mechanical force, light 4 , temperature 5 , 6 , pH 7 etc. This class of polymers has gained considerable attention and has been successfully applied in diverse range of applications, including catalysis, thermochromic and electrochromic materials, biomedical fields, matrix chemistry, etc. 8 , 9 . Poly ( N -isopropylacrylamide), PNIPAM, is a well-known thermo-responsive polymer that in response to temperature can generate a phase-separation in the aqueous solution at the lower critical solution temperature (LCST) 10 . In fact, the hydrogen bonds between this polymer and water can result in dehydration and phase separation 10 , 11 . Among various carbon nanomaterials, carbon nanotubes 12-14 , CNTs, have received significant attention. These compounds benefit from some excellent properties, such as inertness, high surface area, thermal and chemical stability, electric conductivity and tune-ability. These features attracted many scientists to utilize CNTs in various research fields, such as catalysis. One of the drawbacks of CNTs for the catalysis is their low wet-ability. This characteristic restricted the use of CNTs for the reactions in the aqueous media 15-18 . To furnish a solution to this issue, CNT can be functionalized or hybridized with hydrophilic moieties 19 . Reduction of nitro functionality to amino group is a key chemical transformation that can be extensively utilized for the synthesis of complex chemicals and drugs 20-22 . Moreover, this reduction reaction can be exploited for de-colorization of dyes and waste water treatment 23 . This catalytic process proceeds in the presence of conventional hydrogenation catalysts, such as Pd nanoparticles. To reduce the required content of the precious metals and achieving fine nanoparticle size and high dispersion, supporting materials, such as clays 24 and carbohydrates 25 are employed. Mostly, supporting materials are modified by introduction of functional groups on their surface. This can be conducted through covalent or non-covalent approaches 26 . In this regard, one of the most investigated functional groups is ionic liquid, IL 27-29 that is an organic salt with low toxicity 27 , 30 , 31 . As ILs are electrically charged species, they can be a promising compounds to provide electrostatic interactions with metallic nanoparticles and stabilizing them on the support. On the other hand, these compounds can also exhibit catalytic activity 32 , 33 . In the pursuit of our research on the heterogeneous catalysts 24 , 34-39 , in this project we wish to report a novel heterogeneous catalyst, Pd/CNT-P, with utility for hydrogenation of nitro compounds under mild reaction condition. To prepare the catalyst, silica-coated CNT has been synthesized and then vinyl functionalized. The resulted compound was then polymerized with the as-prepared 1-viny-3-butylimidazolium bromide (VBIB) and N -isopropylacrylamide (NIPAM) to furnish a thermo-responsive composite, which was subsequently palladated to give the hydrogenation catalyst, Figure 1. Result And Discussion Structure of the catalyst To study the morphology of Pd/CNT-P, it was analyzed via TEM. In TEM image of Pd/CNT-P (Figure 2), polymeric moiety on the CNT tubes can be discerned. On the other hand, fine Pd nanoparticles (average diameter of 4.0 ± 0.1 nm) can be seen on the CNT-P. Pd/CNT-P was also characterized via EDS and elemental mapping analyses. As depicted in Figure 3, the as-prepared catalyst contains C, N, O, Si, Pd and Br atoms. C, O and Si atoms can represent CNT-SiO 2 , while C, N, O and Br can be assigned to the P component. The presence of Pd also can indicate stabilization of Pd nanoparticles on CNT-P. Elemental mapping analysis of Pd/CNT-P, Figure 4, showed uniform dispersion of Pd, N and Br atoms. This observation implies that both polymeric component (P) and Pd nanoparticles have been distributed of CNT-SiO 2 homogeneously. To confirm successful formation of CNT-SiO 2 , CNT-V and Pd/CNT-P, their FTIR spectrum has been recorded. As shown in Figure 5, CNT-SiO 2 showed the absorbance bands at 1085 cm -1 (Si-O-Si), 3410 cm -1 (–OH), 1463 cm -1 (-C-O), 2920 and 2850 cm -1 (–CH 2 stretching). Moreover, the band at 1631 cm -1 can be related to the –COOH functionality of the used CNT. CNT-V FTIR spectrum also exhibited the characteristic bands of CNT-SiO 2 , affirming the stability of CNT-SiO 2 upon functionalization. Moreover, the appearance of a small band at 1703 cm -1 (-C=O) can confirm conjugation of TMSPMA. In the FTIR spectrum of Pd/CNT-P, all of the characteristic absorbance bands of CNT-SiO 2 can be detected. Moreover, the appearance of sharp bands at 1645 cm -1 (amidic –C=O) and 1546 cm -1 (-C=N) can confirm conjugation of thermo-responsive co-polymer. Thermogravimetic analysis of CNT-SiO 2 and Pd/CNT-P samples has been conducted to compare their thermal stability and confirm conjugation of P. As depicted in Figure 6, CNT-SiO 2 showed high thermal stability. In fact, TG curve of CNT-SiO 2 showed two weight loss stages related to the loss of water (150 ºC) and degradation of CNT (above 550 ºC). TG curve of Pd/CNT-P is distinguished from TG curve of CNT-SiO 2 . In this curve an additional weigh loss stage (44.3 wt.%) at 290 ºC can be detected. This weigh loss is assigned to the degradation of P component. Using XRD analysis, the structure of Pd/CNT-P was investigated. In this regard, the XRD pattern of Pd/CNT-P was recorded and compared with that of CNT-SiO 2 (Figure 7). The broad peak in the XRD pattern of CNT-SiO 2 can be assigned to the amorphous silica coat and approve successful coverage of CNT with SiO 2 . Other small peaks can be attributed to CNT. In the XRD pattern of Pd/CNT-P, the CNT-SiO 2 characteristic peaks can be detected. Noteworthy, the characteristic peak of the polymeric moiety (2θ = 15-25°) overlapped with the characteristic peaks of CNT-SiO 2 19 . It is worth mentioning that the characteristic peaks of Pd nanoparticles were not discerned in the XRD pattern of Pd/CNT-P. This is assigned to the low content and high dispersion of Pd nanoparticles 40 . Activity of the catalyst Hydrogenation of nitro compounds is an important chemical reaction. This reaction not only is used for the synthesis of anilines, but also is applied for the synthesis of key chemical intermediates that can potentially be utilized for the synthesis of complicated organic compounds and drugs. Considering the importance of this reaction, we examined the catalytic activity of Pd/CNT-P for the hydrogenation of nitro compounds. To initiate the experiments, hydrogenation of nitrobenzene was selected as a model hydrogenation reaction. In the first step, the optimum reaction condition was found by studying the effects of reaction solvent, temperature and Pd/CNT-P loading on the yield of aniline. First, the effect of the reaction solvent was appraised. In this regard, hydrogenation of nitrobenzene at room temperature and 5 mg Pd/CNT-P was performed in H 2 O, EtOH, H 2 O: EtOH (1:1), CH 3 CN and THF. As tabulated in Table 1, the reaction in water led to slightly lower yield of aniline. In the other four solvents, similar yields of aniline were furnished, indicating that the nature of solvent did not have a significant effect on the yield of the reaction. Considering these results and environmental concerns, H 2 O: EtOH (1:1) was selected as the reaction solvent. In the next step, the effect of Pd/CNT-P loading was examined by repeating the model reaction in the presence of 5, 10 and 15 mg of Pd/CNT-P loading. As summarized in Table 1, by increasing the loading of the catalyst to 10 mg, the reaction yield increased from 70 to 80%. However, more increment of Pd/CNT-P loading did not improve the reaction yield. Therefore, 10 mg Pd/CNT-P was selected as the best loading. Table 1. Optimization of the reaction condition for the model reaction. Entry Pd/CNT-P (mg) Solvent Temp. (°C) Yield (%) 1 5 H 2 O 25 60 2 5 EtOH 25 70 3 5 CH 3 CN 25 70 4 5 THF 25 70 5 5 H 2 O: EtOH (1:1) 25 70 6 10 H 2 O: EtOH (1:1) 25 80 7 15 H 2 O: EtOH (1:1) 25 80 8 10 H 2 O: EtOH (1:1) 30 85 9 10 H 2 O: EtOH (1:1) 40 98 Finally, the effect of the reaction temperature was investigated. To this purpose, the model reaction was conducted at 25, 30 and 40 °C. According to the results, elevating the reaction temperature was beneficiary for the reaction yield and the increase of the reaction temperature above LCST resulted in higher yield of aniline. This observation is in good accordance to the previous reports 10 , 41 . In fact, at temperature above the LCST (~37 °C), P component in the backbone of Pd/CNT-P collapses to furnish a hydrophobic periphery that is favorable for the mass-transfer of hydrophobic reactants, Figure 8. Having the optimum reaction condition in hand, other nitro compounds have been examined as substrates to confirm the generality of this protocol. As listed in Table 2, various nitro compounds can tolerate hydrogenation reaction under Pd/CNT-P catalysis to give the corresponding products in high yields. According to the results, the electronic feature of the substrates did not significantly affect the yield of the expected products and the substrates with both electron-donating and electron-withdrawing groups can furnish the products in high yields. However, steric effects can influence the reaction yield and huge and hydrophobic substrates led to lower yields. It is worth mentioning that Pd/CNT-P could catalyze the reaction of nitro compounds with carbonyl groups (4-nitroacetophenone and 4-nitrobenzaldehyde) selectively to give 4-aminoacetophenone and 4-aminobenzaldehyde as sole products. This observation approved high selectivity of Pd/CNT-P towards reduction of nitro functionality. Table 2. Hydrogenation of nitro compounds under Pd/CNT-P catalysis a . Control catalysts In this project, we aimed to design a thermos-responsive catalyst, which could promote hydrogenation of nitro-compounds in aqueous media efficiently. To this purpose, we conjugated P that is an IL-containing thermoresponsive polymer with CNT covalently to benefit from the characteristics of the two components and the possible synergism between them. To elucidate whether the activity of the as-prepared composite is superior to each components, several control catalysts, including, Pd/PNIPAM Pd/P, Pd/CNT-V-PNIPAM, Pd/CNT-V, were prepared and their activity for the model reaction was compared with that of Pd/CNT-P, Table 3. First, Pd/CNT-V was synthesized through the exact procedure used for the palladation of CNT-P, except, CNT-V was applied as a support and its activity was evaluated for the model reaction under the optimum reaction condition. As shown in Table 3, Pd/CNT-V showed moderate activity and led to the formation of aniline in 45 % yield. Moreover, this sample was not thermos-responsive and its recovery from the reaction media was tedious. This observation confirmed the necessity of the presence of P for achieving high catalytic performance. Next, Pd/CNT-V-PNIPAM was prepared through polymerization of CNT-V and NIPAM, followed by palladation. The study of the catalytic activity of this sample that did not contain IL in its structure approved that its catalytic activity was lower than that of the catalyst. This result confirmed the importance of IL in the structure of the catalyst for achieving high activity. Two other catalysts, Pd/PNIPAM and Pd/P were also prepared through palladation of PNIPAM and P. The catalytic studies showed that these two control samples that did not contain CNT exhibited moderate activity and led to the formation of aniline in 30 and 40% respectively. This observation affirmed the role of CNT in the catalysis. In conclusion, the higher activity of Pd/CNT-P compared to the studied control catalysts indicated the positive role of hybridization of P and CNT and the presence of IL in the catalytic activity. Table 3. Comparison of the catalytic activity of Pd/CNT-P and control catalysts for the nitrobenzene hydrogenation. Entry Catalyst Yield (%) a 1 Pd/PNIPAM 30 2 Pd/P 40 3 Pd/CNT-V-PNIPAM b 80 4 Pd/CNT-V 45 5 Pd/CNT-P 98 a Reaction condition: nitrobenzene (1 mmol), catalyst (10 mg), H 2 O: EtOH (1:1) 6 ml, H 2 (1 bar) at 40 °C in 2 h. b Pd was loaded on the CNT-V, which was polymerized with NIPAM. Recyclability As facile recovery and efficient recyclability are important factors for heterogeneous catalysts, recyclability of Pd/CNT-P for the model reaction was appraised. The recycling test was simply conducted by separation of Pd/CNT-P from the first run of the model reaction and its recovery through washing with toluene and drying at 50 °C in oven. The recovered Pd/CNT-P was then used as a catalyst for catalyzing the second run of the model reaction under similar condition. Upon completion of the reaction, the recovery-reuse cycle was repeated for seven consecutive runs. As shown in Figure 9, Pd/CNT-P can be efficiently recycled and only slight loss of the activity was detected after each recycling. To study the stability of Pd/CNT-P structure upon recycling, the reused catalyst (obtained after seventh run) was characterized via FTIR spectroscopy. As shown in Figure 10, the FTIR spectrum of the reused Pd/CNT-P exhibited all of the absorbance bands of fresh Pd/CNT-P. This observation affirms the stability of Pd/CNT-P upon recycling. The measurement of leaching of Pd was performed via ICP analysis. To this purpose, the recovered catalyst after seventh run of the reaction was analyzed by ICP. It was found that Pd leaching was insignificant (1.6 wt.% of initial loading). Hot filtration test There are two possibilities in heterogeneous catalysis. In true heterogeneous catalysis, it is expected that the catalytic species remains stabilized on the support, while in the second possibility, the catalytic species can leach to the reaction media and then stabilized on the support. The well-known test for determining the nature of the catalysis is hot filtration, in which the catalyst is removed from the reaction after a short period and then the reaction is pursued in the absence of the catalyst. In the case of true heterogeneous catalysis, in which no leaching of the catalytic species occurs, the reaction does not proceed after removal of the catalyst, while in the other pass way, the reaction proceeds in the absence of the catalyst due to the leached catalytic species. Hot filtration test approved that Pd/CNT-P was a true heterogeneous catalyst. In more detail, hydrogenation of nitrobenzene did not proceed after removing of Pd/CNT-P from the reaction vessel. Experimental Section Materials and instruments COOH-functionalized multi-wall carbon nanotubes (MWCNTs) (purity > 95%, content of COOH = 3.86 wt. %, inner diameter: 2-5 nm and outer diameter> 7 nm) were obtained from US Research Nanomaterials. Other reagents and solvents applied for the synthesis of the catalyst and conducting hydrogenation reaction of nitro-compounds are as follow: (3-trimethoxysilyl) propyl methacrylate (TMSPMA), cetyltrimethyl ammonium bromide (CTAB), tetraethyl orthosilicate (TEOS), 1-vinylimidazole, NIPAM, azobisisobutyronitrile (AIBN), triethylamine (Et 3 N), palladium(П) acetate Pd(OAc) 2 , sodium borohydride (NaBH 4 ), N,N -dimethylformamide (DMF), nitro-compounds, 1-bromo butane, sodium hydroxide, toluene, ethanol (EtOH) and methanol (MeOH), all was purchased from Sigma-Aldrich ( Germany, Taufkitchen) and used without further purification. The formation of Pd/CNT-P was confirmed by various characterization techniques, including: Fourier transform Infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), inductively coupled plasma mass spectroscopy (ICP-MS), energy-dispersive X-ray spectroscopy (EDS) and elemental mapping analysis. Recording of FTIR spectra was carried out by using BRUKER TENSOR 35 spectrophotometer 65 with scan time of 1 s and spectral resolution of 2 cm -1 by using KBr pellets. The XRD pattern of Pd/CNT-P was recorded using a Rigaku Ultima IV with Cu Kα radiation from a sealed tube. Thermal stability of Pd/CNT-P was investigated by applying METTLER TOLEDO thermogravimetric analysis apparatus. To record the catalyst thermogram, inert atmosphere and heating rate of 10 °C min -1 were applied. TEM images of Pd/CNT-P were recorded on a Phillips EM 208S microscope at 100 kV. Pd loading of Pd/CNT-P was estimated using ICP analyzer Varian, Vista-pro instrument. EDX and elemental mapping analyses were carried out by Tescan Mira II. Preparation of Pd/CNT-P Surface modification of carbon nanotubes: synthesis of CNT-SiO 2 Surface modification of CNT with silica was performed according to the previous report 42 . Typically, to a solution of CTAB (1.7 g) in distilled water (40 ml), CNT (0.2 g) was added and the resulting suspension was homogenized under ultrasonic irradiation (160 W for 30 min). Afterwards, NaOH (0.08 g) was added and the resulting mixture was stirred for 30 min at 60 °C. In the next step, a solution of TEOS (10 mL) in EtOH was introduced to the aforementioned suspension under stirring condition at 60 °C. After 24 h, the product, CNT-SiO 2 , was separated via centrifugation, washed repeatedly with warm EtOH and dried in oven overnight. Vinyl-functionalization of CNT-SiO 2 : synthesis of CNT-V In order to vinyl-functionalize CNT-SiO 2 , the as-prepared CNT-SiO 2 (0.5 g) was dispersed in dry toluene (20 mL) by using ultrasonic irradiation (160 W) for 20 min. Then TMSPMA (0.5 g) was added to CNT-SiO 2 suspension and the resulting mixture was refluxed at 110 °C for 24 h under Ar atmosphere. Upon completion of the reaction, the precipitate, CNT-V, was collected via centrifuge, washed with toluene and dried in oven at 80 °C overnight. Synthesis of VBIB VBIB was prepared according to the previous report 43 . Briefly, the mixture of 1-bromobutane (4 g) and 1-vinylimidazole (2 g) was stirred at 70 °C under solvent-free condition for 16 h under inert atmosphere. Then, the reaction mixture was allowed to cool to room temperature and the product was collected, washed several times with ethyl acetate and dried in a vacuum oven overnight. Polymerization of NIPAM, VBIB and CNT-V: synthesis of CNT-P CNT-V (0.5 g) was added to a solution of NIPAM (0.5 g) in DMF (20 mL) under stirring condition under Ar atmosphere at 70 °C. After 20 min, a solution of AIBN (0.15 g) in DMF (10 mL) was added to the aforesaid mixture in a dropwise manner and stirring was maintained for 40 min. Subsequently, a solution of VBIB (0.5 g) in DMF (10 mL) was added and the resulting mixture was stirred for 24 h at 70 °C under Ar atmosphere. After completion of the reaction, the solvent was evaporated and the solid was collected, rinsed with DMF and dried in oven at 70 °C overnight. Immobilization of Pd nanoparticles on CNT-P: Synthesis of Pd/CNT-P In order to prepare Pd/CNT-P, CNT-P (1.5 g) was stirred in toluene (20 mL) in a 2-neck round flask under Ar atmosphere at room temperature for 30 min. Subsequently, a solution of Pd(OAc) 2 (0.02 g) in toluene (15 mL) was gently introduced to the aforementioned suspension. After 1 h, a solution of NaBH 4 (0.2 N) in MeOH (20 mL) was slowly added and the obtained mixture was stirred for 2 h. Finally, the as-prepared Pd/CNT-P was collected via centrifugation, washed with toluene and dried in oven at 50 °C overnight, Figure 1. According to the ICP analysis, Pd loading in Pd/CNT-P was 1 wt %. Typical procedure for the hydrogenation of nitro-compounds Hydrogenation of nitro-compounds was conducted under mild reaction condition. Typically, a mixture of nitro aromatic compound (1 mmol) and Pd/CNT-P (0.01 g) in H 2 O/EtOH (1/1) was heated to 40 °C under H 2 gas (1 bar). The progress of the hydrogenation reaction was traced by TLC. Upon completion of the process, Pd/CNT-P was separated and recovered by washing with toluene (30 mL) and drying at 50 °C in an oven overnight. The recovered catalyst was reused for the next run of the reaction. The hydrogenized product was obtained after evaporation of the solvent. The reaction yield was measured via GC analysis. Conclusion A novel thermo-responsive catalyst, Pd/CNT-P, was designed and synthesized through vinyl functionalization of CNT-SiO 2 , followed by polymerization with NIPAM and VBIB and palladation. The catalytic performance of the resulting catalyst was examined for the hydrogenation of nitro-compounds in aqueous media under mild reaction condition. The results affirmed high catalytic activity of the catalyst, broad substrate scope and high selectivity of the catalyst towards nitro group. Moreover, the catalyst was recyclable up to seven reaction runs with slight Pd leaching. Hot filtration test also indicated the true heterogeneous nature of the catalysis. The comparison of the catalytic activity of Pd/CNT-P with several control catalysts confirmed the importance of conjugation of P and CNT for achieving high catalytic activity. Declaration Acknowledgment The authors appreciate the partial supports of Iran Polymer and Petrochemical Institute and Alzahra University. 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Inorg. Chem. Commun. 132 , 108818, doi:https://doi.org/10.1016/j.inoche.2021.108818 (2021). 33 Afzali, E., Mirjafary, Z., Akbarzadeh, A. & Saeidian, H. vvComplexation of copper ion-containing immobilized ionic liquid in designed hierarchical-functionalized layered double hydroxide nanoreactor for azide–alkyne cycloaddition reaction. Inorg. Chem. Commun. 132 , 108858, doi:https://doi.org/10.1016/j.inoche.2021.108858 (2021). 34 Tabrizi, M. et al. Efficient hydro-finishing of polyalfaolefin based lubricants under mild reaction condition using Pd on ligands decorated halloysite. J. Colloid Interface Sci. 581 , 939-953, doi:https://doi.org/10.1016/j.jcis.2020.08.112 (2021). 35 Sadjadi, S., Lazzara, G., Malmir, M. & Heravi, M. M. Pd nanoparticles immobilized on the poly-dopamine decorated halloysite nanotubes hybridized with N-doped porous carbon monolayer: A versatile catalyst for promoting Pd catalyzed reactions. J. Catal. 366 , 245-257, doi:https://doi.org/10.1016/j.jcat.2018.08.013 (2018). 36 Sadjadi, S., Akbari, M., Léger, B., Monflier, E. & Heravi, M. M. Eggplant-Derived Biochar-Halloysite Nanocomposite as Supports of Pd Nanoparticles for the Catalytic Hydrogenation of Nitroarenes in the Presence of Cyclodextrin. ACS Sustain. Chem. Eng. 7 , 6720-6731, doi:10.1021/acssuschemeng.8b05992 (2019). 37 Karimi, S. et al. Pd on nitrogen rich polymer–halloysite nanocomposite as an environmentally benign and sustainable catalyst for hydrogenation of polyalfaolefin based lubricants. J. Ind. Eng. Chem. 97 , 441-451, doi:https://doi.org/10.1016/j.jiec.2021.02.031 (2021). 38 Sadjadi, S., Koohestani, F. & Heravi, M. M. Fabrication of a metal free catalyst for chemical reactions through decoration of chitosan with ionic liquid terminated dendritic moiety. Sci. Rep. 10 , 19666, doi:10.1038/s41598-020-76795-8 (2020). 39 Sadjadi, S., Malmir, M., Lazzara, G., Cavallaro, G. & Heravi, M. M. Preparation of palladated porous nitrogen-doped carbon using halloysite as porogen: disclosing its utility as a hydrogenation catalyst. Sci. Rep. 10 , 2039, doi:10.1038/s41598-020-59003-5 (2020). 40 Mallik, S., Dash, S. S., Parida, K. M. & Mohapatra, B. K. Synthesis, characterization, and catalytic activity of phosphomolybdic acid supported on hydrous zirconia. J. Colloid Interface Sci. 300 , 237–243. (2006). 41 Gao, C., Möhwald, H. & Shen, J. Thermosensitive poly (allylamine)-g-poly (N-isopropylacrylamide): synthesis, phase separation and particle formation. Polymer 46 , 4088-4097 (2005). 42 Sadjadi, S. & Koohestani, F. Pd immobilized on polymeric network containing imidazolium salt, cyclodextrin and carbon nanotubes: Efficient and recyclable catalyst for the hydrogenation of nitroarenes in aqueous media. J. Mol. Liq. 301 , 112414, doi:https://doi.org/10.1016/j.molliq.2019.112414 (2020). 43 Sadjadi, S., Koohestani, F. & Heravi, M. Biochar-Based Graphitic Carbon Nitride Adorned with Ionic Liquid Containing Acidic Polymer: A Versatile, Non-Metallic Catalyst for Acid Catalyzed Reaction. Molecules 25 , 5958 (2020). Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 10 Mar, 2022 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Major revision 31 Dec, 2021 Reviews received at journal 23 Dec, 2021 Reviewers agreed at journal 19 Dec, 2021 Reviewers invited by journal 19 Dec, 2021 Editor assigned by journal 10 Dec, 2021 Editor invited by journal 10 Dec, 2021 Submission checks completed at journal 10 Dec, 2021 First submitted to journal 07 Dec, 2021 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-1148099","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":69214298,"identity":"4febc291-06c2-4094-8cd8-0e446c42af6f","order_by":0,"name":"Samahe Sadjadi","email":"","orcid":"","institution":"Iran polymer and Petrochemical Institute","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Samahe","middleName":"","lastName":"Sadjadi","suffix":""},{"id":69214299,"identity":"3c30a0ef-7907-4a99-af21-c6f3772a2c8e","order_by":1,"name":"Neda Abedian-Dehaghani","email":"","orcid":"","institution":"Alzahra University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Neda","middleName":"","lastName":"Abedian-Dehaghani","suffix":""},{"id":69214300,"identity":"8e082fee-3142-47e1-87ff-07f048986922","order_by":2,"name":"Majid M. Heravi","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA4klEQVRIiWNgGAWjYFACHgjJz8DcwMDYABVMIEaLZAMjiVoYDA4ga8EHdKedPfi4ouawjPHxg80ffu64J8/AfvgBw8M9uLWY3c5LNjxz7DCP2ZnEBsPeM8WGDTxpBgwJz/BpyTGTbGBL4zE7kNiQwNuWAHRbDtAvB/BqMf/Z8C+Nx7j/YcPBv20J9g38bwhqMWNsbLPhMZBIbGwG2pLYIEHYFmPJxj4bHokbD5uZZdsSktsknhkcIKDF8GPDNwl7/v7kwx/ftiXY9vMnP3z4A48WTMAGxCRpGAWjYBSMglGACQBnx1P4FpcwNQAAAABJRU5ErkJggg==","orcid":"","institution":"Alzahra University","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Majid","middleName":"M.","lastName":"Heravi","suffix":""}],"badges":[],"createdAt":"2021-12-07 08:29:12","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-1148099/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-1148099/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-022-07708-0","type":"published","date":"2022-03-10T11:55:26+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":16414944,"identity":"4d2ecf5f-59c9-4c97-ae74-d2f4fc6661f2","added_by":"auto","created_at":"2021-12-13 23:02:25","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":95227,"visible":true,"origin":"","legend":"Schematic procedure for the preparation of Pd/CNT-P.","description":"","filename":"Figure1.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/428bb9060216a3f83285abee.png"},{"id":16415268,"identity":"b7d644f8-f188-4473-9dbc-85cb2ef11d68","added_by":"auto","created_at":"2021-12-13 23:05:26","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":174304,"visible":true,"origin":"","legend":"TEM image of Pd/CNT-P.","description":"","filename":"Figure2.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/121c993709bce244bf723750.png"},{"id":16414945,"identity":"cb4f20e3-44ec-402b-b75a-792ac878993a","added_by":"auto","created_at":"2021-12-13 23:02:25","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":67119,"visible":true,"origin":"","legend":"EDS analysis of Pd/CNT-P","description":"","filename":"Figure3.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/9ff2768bfeb3df32f67dabc0.png"},{"id":16415699,"identity":"92ea2808-df85-4eed-beee-09174b36877c","added_by":"auto","created_at":"2021-12-13 23:08:26","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":387209,"visible":true,"origin":"","legend":"Elemental mapping of Pd/CNT-P.","description":"","filename":"Figure4.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/3724756b871afa2fd0564aad.png"},{"id":16415697,"identity":"ba2f4738-9152-4cff-a174-6e45a9356371","added_by":"auto","created_at":"2021-12-13 23:08:26","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":24291,"visible":true,"origin":"","legend":"FTIR spectra of CNT-SiO2, CNT-V and Pd/CNT-P. ","description":"","filename":"Figure5.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/3c48b41e54b0949a83ce6b46.png"},{"id":16414947,"identity":"1551aaca-36c9-498f-8aee-188f855c0512","added_by":"auto","created_at":"2021-12-13 23:02:26","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":12790,"visible":true,"origin":"","legend":"TG curves of CNT-SiO2 and Pd/CNT-P.","description":"","filename":"Figure6.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/6ba910eed269d3716a9a09c2.png"},{"id":16415698,"identity":"ef810e1e-6e06-404f-9486-bf54b0a4c521","added_by":"auto","created_at":"2021-12-13 23:08:26","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":20144,"visible":true,"origin":"","legend":"XRD patterns of Pd/CNT-P and CNT-SiO2","description":"","filename":"Figure7.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/5bbdab7e56af3b86388c2a81.png"},{"id":16414953,"identity":"5a516436-4726-468f-a1dc-2d7c65ba45c1","added_by":"auto","created_at":"2021-12-13 23:02:26","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":77050,"visible":true,"origin":"","legend":"Schematic presentation of structural change of the thermo-responsive catalyst at temperature above LCST for the hydrogenation of nitro compounds","description":"","filename":"Figure8.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/4ac0080db41ca4a7f7ff9c5e.png"},{"id":16414952,"identity":"7eba84f5-c205-4d46-aaa7-e4d81010bdf7","added_by":"auto","created_at":"2021-12-13 23:02:26","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":11617,"visible":true,"origin":"","legend":"Recyclability of the catalyst for the model reaction under the optimum reaction condition.","description":"","filename":"Figure9.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/86e101d1a3ea2b16aab60bf3.png"},{"id":16414946,"identity":"36fafa7f-7879-40b0-a383-a889083bcb50","added_by":"auto","created_at":"2021-12-13 23:02:26","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":23773,"visible":true,"origin":"","legend":"Comparison of the FTIR spectra of fresh and recycled catalyst after seven runs.","description":"","filename":"Figure10.png","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/4a128a508c941f86b4d128dc.png"},{"id":19072408,"identity":"041f92ef-acaf-4390-9a47-c3fa320e23cb","added_by":"auto","created_at":"2022-03-10 11:55:29","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1250817,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-1148099/v1/17d4fe92-a238-4b71-aff5-3f2ef3c736fe.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003ePd On Thermo-Responsive Composite of Silica-Coated Carbon Nanotube And 1-Vinyl-3-Butylimidazolium-Based Ionic Liquid Copolymers As An Efficient Catalyst For Hydrogenation of Nitro Compounds\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eSmart polymers are polymeric compounds \u003ca href=\"#_ENREF_1\" title=\"Ahn, 2013 #54\"\u003e\u003csup\u003e1-3\u003c/sup\u003e\u003c/a\u003e that respond to the external stimuli, such as mechanical force, light\u0026nbsp;\u003ca href=\"#_ENREF_4\" title=\"Jiang, 2006 #52\"\u003e\u003csup\u003e4\u003c/sup\u003e\u003c/a\u003e, temperature\u0026nbsp;\u003ca href=\"#_ENREF_5\" title=\"Li, 2015 #48\"\u003e\u003csup\u003e5\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_6\" title=\"Roy, 2013 #50\"\u003e\u003csup\u003e6\u003c/sup\u003e\u003c/a\u003e, pH\u0026nbsp;\u003ca href=\"#_ENREF_7\" title=\"Xiao, 2016 #46\"\u003e\u003csup\u003e7\u003c/sup\u003e\u003c/a\u003e etc. This class of polymers has gained considerable attention and has been successfully applied in diverse range of applications, including catalysis, thermochromic and electrochromic materials, biomedical fields, matrix chemistry, etc.\u0026nbsp;\u003ca href=\"#_ENREF_8\" title=\"Moon, 2015 #58\"\u003e\u003csup\u003e8\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_9\" title=\"Beaujuge, 2010 #60\"\u003e\u003csup\u003e9\u003c/sup\u003e\u003c/a\u003e. Poly (\u003cem\u003eN\u003c/em\u003e-isopropylacrylamide),\u0026nbsp;PNIPAM,\u0026nbsp;is a well-known thermo-responsive polymer that in response to temperature can generate a phase-separation in the aqueous solution at the lower critical solution temperature (LCST)\u0026nbsp;\u003ca href=\"#_ENREF_10\" title=\"Massaro, 2016 #62\"\u003e\u003csup\u003e10\u003c/sup\u003e\u003c/a\u003e. In fact, the hydrogen bonds between this polymer and water can result in dehydration and phase separation\u0026nbsp;\u003ca href=\"#_ENREF_10\" title=\"Massaro, 2016 #62\"\u003e\u003csup\u003e10\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_11\" title=\"Shibayama, 1996 #64\"\u003e\u003csup\u003e11\u003c/sup\u003e\u003c/a\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAmong various carbon nanomaterials, carbon nanotubes \u003ca href=\"#_ENREF_12\" title=\"Stodolak-Zych, 2016 #3\"\u003e\u003csup\u003e12-14\u003c/sup\u003e\u003c/a\u003e, CNTs, have received significant attention. These compounds benefit from some excellent properties, such as inertness, high surface area, thermal and chemical stability, electric conductivity and tune-ability. These features attracted many scientists to utilize CNTs in various research fields, such as catalysis. \u0026nbsp;One of the drawbacks of CNTs for the catalysis is their low wet-ability. This characteristic restricted the use of CNTs for the reactions in the aqueous media \u003ca href=\"#_ENREF_15\" title=\"Fan, 2017 #415\"\u003e\u003csup\u003e15-18\u003c/sup\u003e\u003c/a\u003e. To furnish a solution to this issue, CNT can be functionalized or hybridized with hydrophilic moieties\u0026nbsp;\u003ca href=\"#_ENREF_19\" title=\"Sadjadi, 2018 #107\"\u003e\u003csup\u003e19\u003c/sup\u003e\u003c/a\u003e.\u003c/p\u003e\n\u003cp\u003eReduction of nitro functionality to amino group is a key chemical transformation that can be extensively utilized for the synthesis of complex chemicals and drugs \u003ca href=\"#_ENREF_20\" title=\"Metin, 2017 #15\"\u003e\u003csup\u003e20-22\u003c/sup\u003e\u003c/a\u003e. Moreover, this reduction reaction can be exploited for de-colorization of dyes and waste water treatment\u0026nbsp;\u003ca href=\"#_ENREF_23\" title=\"Vahedi-Notash, 2020 #300\"\u003e\u003csup\u003e23\u003c/sup\u003e\u003c/a\u003e. This catalytic process proceeds in the presence of conventional hydrogenation catalysts, such as Pd nanoparticles. To reduce the required content of the precious metals and achieving fine nanoparticle size and high dispersion, supporting materials, such as clays\u0026nbsp;\u003ca href=\"#_ENREF_24\" title=\"Sadjadi, 2020 #20\"\u003e\u003csup\u003e24\u003c/sup\u003e\u003c/a\u003e and carbohydrates\u0026nbsp;\u003ca href=\"#_ENREF_25\" title=\"Leonhardt, 2010 #234\"\u003e\u003csup\u003e25\u003c/sup\u003e\u003c/a\u003e are employed.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eMostly, supporting materials are modified by introduction of functional groups on their surface. This can be conducted through covalent or non-covalent approaches \u003ca href=\"#_ENREF_26\" title=\"Sadjadi, 2021 #122\"\u003e\u003csup\u003e26\u003c/sup\u003e\u003c/a\u003e. In this regard, one of the most investigated functional groups is ionic liquid, IL \u003ca href=\"#_ENREF_27\" title=\"Karimi, 2019 #116\"\u003e\u003csup\u003e27-29\u003c/sup\u003e\u003c/a\u003e that is an organic salt with low toxicity \u003ca href=\"#_ENREF_27\" title=\"Karimi, 2019 #116\"\u003e\u003csup\u003e27\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_30\" title=\"Teimuri-Mofrad, 2018 #117\"\u003e\u003csup\u003e30\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_31\" title=\"Rafiee, 2016 #160\"\u003e\u003csup\u003e31\u003c/sup\u003e\u003c/a\u003e. As ILs are electrically charged species, they can be a promising compounds to provide electrostatic interactions with metallic nanoparticles and stabilizing them on the support. On the other hand, these compounds can also exhibit catalytic activity \u003ca href=\"#_ENREF_32\" title=\"Feng, 2021 #2364\"\u003e\u003csup\u003e32\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_33\" title=\"Afzali, 2021 #2365\"\u003e\u003csup\u003e33\u003c/sup\u003e\u003c/a\u003e.\u003c/p\u003e\n\u003cp\u003eIn the pursuit of our research on the heterogeneous catalysts \u003ca href=\"#_ENREF_24\" title=\"Sadjadi, 2020 #20\"\u003e\u003csup\u003e24\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_34\" title=\"Tabrizi, 2021 #179\"\u003e\u003csup\u003e34-39\u003c/sup\u003e\u003c/a\u003e, in this project we wish to report a novel heterogeneous catalyst, Pd/CNT-P, with utility for hydrogenation of nitro compounds under mild reaction condition. To prepare the catalyst, silica-coated CNT has been synthesized and then vinyl functionalized. The resulted compound was then polymerized with the as-prepared 1-viny-3-butylimidazolium bromide (VBIB) and \u003cem\u003eN\u003c/em\u003e-isopropylacrylamide (NIPAM) to furnish a thermo-responsive composite, which was subsequently palladated to give the hydrogenation catalyst, Figure 1. \u0026nbsp;\u003c/p\u003e"},{"header":"Result And Discussion","content":"\u003cp\u003e\u003cstrong\u003eStructure of the catalyst\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo study the morphology of Pd/CNT-P, it was analyzed via TEM. In TEM image of Pd/CNT-P (Figure 2), polymeric moiety on the CNT tubes can be discerned. On the other hand, fine Pd nanoparticles (average diameter of 4.0 \u0026plusmn; 0.1 nm) can be seen on the CNT-P.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ePd/CNT-P was also characterized via EDS and elemental mapping analyses. As depicted in Figure 3, the as-prepared catalyst contains C, N, O, Si, Pd and Br atoms. C, O and Si atoms can represent CNT-SiO\u003csub\u003e2\u003c/sub\u003e, while C, N, O and Br can be assigned to the P component. The presence of Pd also can indicate stabilization of Pd nanoparticles on CNT-P.\u003c/p\u003e\n\u003cp\u003eElemental mapping analysis of Pd/CNT-P, Figure 4, showed uniform dispersion of Pd, N and Br atoms. This observation implies that both polymeric component (P) and Pd nanoparticles have been distributed of CNT-SiO\u003csub\u003e2\u003c/sub\u003e homogeneously.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo confirm successful formation of CNT-SiO\u003csub\u003e2\u003c/sub\u003e, CNT-V and Pd/CNT-P, their FTIR spectrum has been recorded. As shown in Figure 5, CNT-SiO\u003csub\u003e2\u003c/sub\u003e showed the absorbance bands at 1085 cm\u003csup\u003e-1\u003c/sup\u003e (Si-O-Si), 3410 cm\u003csup\u003e-1\u003c/sup\u003e (\u0026ndash;OH), 1463 cm\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003e(-C-O), 2920 and 2850 cm\u003csup\u003e-1\u003c/sup\u003e(\u0026ndash;CH\u003csub\u003e2\u0026nbsp;\u003c/sub\u003estretching). Moreover, the band at 1631 cm\u003csup\u003e-1\u003c/sup\u003e can be related to the \u0026ndash;COOH functionality of the used CNT. CNT-V FTIR spectrum also exhibited the characteristic bands of CNT-SiO\u003csub\u003e2\u003c/sub\u003e, affirming the stability of CNT-SiO\u003csub\u003e2\u003c/sub\u003e upon functionalization. Moreover, the appearance of a small band at 1703 cm\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003e(-C=O) can confirm conjugation of TMSPMA. In the FTIR spectrum of\u0026nbsp;Pd/CNT-P, all of the characteristic absorbance bands of CNT-SiO\u003csub\u003e2\u003c/sub\u003e can be detected. Moreover, the appearance of sharp bands at 1645 cm\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003e(amidic \u0026ndash;C=O) and 1546 cm\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003e(-C=N) can confirm conjugation of thermo-responsive co-polymer.\u003c/p\u003e\n\u003cp\u003eThermogravimetic analysis of CNT-SiO\u003csub\u003e2\u003c/sub\u003e and Pd/CNT-P samples has been conducted to compare their thermal stability and confirm conjugation of P. As depicted in Figure 6, CNT-SiO\u003csub\u003e2\u003c/sub\u003e showed high thermal stability. In fact, TG curve of CNT-SiO\u003csub\u003e2\u003c/sub\u003e showed two weight loss stages related to the loss of water (150 \u0026ordm;C) and degradation of CNT (above 550 \u0026ordm;C). TG curve of Pd/CNT-P is distinguished from TG curve of CNT-SiO\u003csub\u003e2\u003c/sub\u003e. In this curve an additional weigh loss stage (44.3 wt.%) at 290 \u0026ordm;C can be detected. This weigh loss is assigned to the degradation of P component.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eUsing XRD analysis, the structure of\u0026nbsp;Pd/CNT-P was investigated. In this regard, the XRD pattern of Pd/CNT-P was recorded and compared with that of CNT-SiO\u003csub\u003e2\u003c/sub\u003e (Figure 7). The broad peak in the XRD pattern of CNT-SiO\u003csub\u003e2\u003c/sub\u003e can be assigned to the amorphous silica coat and approve successful coverage of CNT with SiO\u003csub\u003e2\u003c/sub\u003e. Other small peaks can be attributed to CNT. In the XRD pattern of Pd/CNT-P, the CNT-SiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003echaracteristic peaks can be detected. Noteworthy, the characteristic peak of the polymeric moiety (2\u0026theta; = 15-25\u0026deg;) overlapped with the characteristic peaks of CNT-SiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e\u003ca href=\"#_ENREF_19\" title=\"Sadjadi, 2018 #107\"\u003e\u003csup\u003e19\u003c/sup\u003e\u003c/a\u003e. It is worth mentioning that the characteristic peaks of Pd nanoparticles were not discerned in the XRD pattern of Pd/CNT-P. This is assigned to the low content and high dispersion of Pd nanoparticles \u003ca href=\"#_ENREF_40\" title=\"Mallik, 2006 #26\"\u003e\u003csup\u003e40\u003c/sup\u003e\u003c/a\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eActivity of the catalyst\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eHydrogenation of nitro compounds is an important chemical reaction. This reaction not only is used for the synthesis of anilines, but also is applied for the synthesis of key chemical intermediates that can potentially be utilized for the synthesis of complicated organic compounds and drugs. Considering the importance of this reaction, we examined the catalytic activity of Pd/CNT-P for the hydrogenation of nitro compounds. To initiate the experiments, hydrogenation of nitrobenzene was selected as a model hydrogenation reaction. In the first step, the optimum reaction condition was found by studying the effects of reaction solvent, temperature and Pd/CNT-P loading on the yield of aniline.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFirst, the effect of the reaction solvent was appraised. In this regard, hydrogenation of nitrobenzene at room temperature and 5 mg Pd/CNT-P was performed in\u0026nbsp;H\u003csub\u003e2\u003c/sub\u003eO, EtOH, H\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1), CH\u003csub\u003e3\u003c/sub\u003eCN and THF. As tabulated in Table 1, the reaction in water led to slightly lower yield of aniline. In the other four solvents, similar yields of aniline were furnished, indicating that the nature of solvent did not have a significant effect on the yield of the reaction. Considering these results and environmental concerns, H\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1) was selected as the reaction solvent.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn the next step, the effect of Pd/CNT-P loading was examined by repeating the model reaction in the presence of 5, 10 and 15 mg of Pd/CNT-P loading. As summarized in Table 1, by increasing the loading of the catalyst to 10 mg, the reaction yield increased from 70 to 80%. However, more increment of Pd/CNT-P loading did not improve the reaction yield. Therefore, 10 mg Pd/CNT-P was selected as the best loading.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 1.\u003c/strong\u003e Optimization of the reaction condition for the model reaction.\u003c/p\u003e\n\u003ctable border=\"1\" cellpadding=\"0\" cellspacing=\"0\" width=\"100%\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003ePd/CNT-P\u0026nbsp;(mg)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.611898016997166%\"\u003e\n \u003cp\u003eSolvent\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003eTemp. \u0026nbsp; \u0026nbsp; (\u0026deg;C)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003eYield \u0026nbsp; \u0026nbsp; (%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.611898016997166%\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e60\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.611898016997166%\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e70\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.611898016997166%\"\u003e\n \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e70\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.611898016997166%\"\u003e\n \u003cp\u003eTHF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e70\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.611898016997166%\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e70\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.611898016997166%\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e80\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.611898016997166%\"\u003e\n \u003cp dir=\"LTR\"\u003e\u003cspan dir=\"LTR\"\u003eH\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e80\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.611898016997166%\"\u003e\n \u003cp dir=\"LTR\"\u003e\u003cspan dir=\"LTR\"\u003eH\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e30\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e85\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"12.464589235127479%\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"21.813031161473088%\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.611898016997166%\"\u003e\n \u003cp dir=\"LTR\"\u003e\u003cspan dir=\"LTR\"\u003eH\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.546742209631727%\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.56373937677054%\"\u003e\n \u003cp\u003e98\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003eFinally, the effect of the reaction temperature was investigated. To this purpose, the model reaction was conducted at 25, 30 and 40 \u0026deg;C. According to the results, elevating the reaction temperature was beneficiary for the reaction yield and the increase of the reaction temperature above LCST resulted in higher yield of aniline. This observation is in good accordance to the previous reports \u003ca href=\"#_ENREF_10\" title=\"Massaro, 2016 #62\"\u003e\u003csup\u003e10\u003c/sup\u003e\u003c/a\u003e\u003csup\u003e,\u003c/sup\u003e\u003ca href=\"#_ENREF_41\" title=\"Gao, 2005 #28\"\u003e\u003csup\u003e41\u003c/sup\u003e\u003c/a\u003e. In fact, at temperature above the LCST (~37 \u0026deg;C), P component in the backbone of Pd/CNT-P collapses to furnish a hydrophobic periphery that is favorable for the mass-transfer of hydrophobic reactants, Figure 8.\u003c/p\u003e\n\u003cp\u003eHaving the optimum reaction condition in hand, other nitro compounds have been examined as substrates to confirm the generality of this protocol. As listed in Table 2, various nitro compounds can tolerate hydrogenation reaction under Pd/CNT-P catalysis to give the corresponding products in high yields. According to the results, the electronic feature of the substrates did not significantly affect the yield of the expected products and the substrates with both electron-donating and electron-withdrawing groups can furnish the products in high yields. However, steric effects can influence the reaction yield and huge and hydrophobic substrates led to lower yields. It is worth mentioning that Pd/CNT-P could catalyze the reaction of nitro compounds with carbonyl groups (4-nitroacetophenone and 4-nitrobenzaldehyde) selectively to give 4-aminoacetophenone and 4-aminobenzaldehyde as sole products. This observation approved high selectivity of Pd/CNT-P towards reduction of nitro functionality.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong id=\"isPasted\"\u003eTable 2.\u003c/strong\u003e Hydrogenation of nitro compounds under Pd/CNT-P catalysis \u003csup\u003ea\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\"\u003e\u003c/p\u003e\n\u003cp id=\"isPasted\"\u003e\u003cstrong\u003eControl catalysts\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn this project, we aimed to design a thermos-responsive catalyst, which could promote hydrogenation of nitro-compounds in aqueous media efficiently. To this purpose, we conjugated P that is an IL-containing thermoresponsive polymer with CNT covalently to benefit from the characteristics of the two components and the possible synergism between them. To elucidate whether the activity of the as-prepared composite is superior to each components, several control catalysts, including, Pd/PNIPAM Pd/P, Pd/CNT-V-PNIPAM, Pd/CNT-V, were prepared and their activity for the model reaction was compared with that of Pd/CNT-P, Table 3. First, Pd/CNT-V was synthesized through the exact procedure used for the palladation of CNT-P, except, CNT-V was applied as a support and its activity was evaluated for the model reaction under the optimum reaction condition. As shown in Table 3, Pd/CNT-V showed moderate activity and led to the formation of aniline in 45 % yield. Moreover, this sample was not thermos-responsive and its recovery from the reaction media was tedious. This observation confirmed the necessity of the presence of P for achieving high catalytic performance.\u003c/p\u003e\n\u003cp id=\"isPasted\"\u003eNext, Pd/CNT-V-PNIPAM was prepared through polymerization of CNT-V and NIPAM, followed by palladation. The study of the catalytic activity of this sample that did not contain IL in its structure approved that its catalytic activity was lower than that of the catalyst. This result confirmed the importance of IL in the structure of the catalyst for achieving high activity.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTwo other catalysts, Pd/PNIPAM and Pd/P were also prepared through palladation of PNIPAM and P. The catalytic studies showed that these two control samples that did not contain CNT exhibited moderate activity and led to the formation of aniline in 30 and 40% respectively. This observation affirmed the role of CNT in the catalysis. In conclusion, the higher activity of Pd/CNT-P compared to the studied control catalysts indicated the positive role of hybridization of P and CNT and the presence of IL in the catalytic activity.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong id=\"isPasted\"\u003eTable 3.\u0026nbsp;\u003c/strong\u003eComparison of the catalytic activity of Pd/CNT-P and control catalysts for the nitrobenzene hydrogenation.\u003c/p\u003e\n\u003cdiv align=\"center\" id=\"isPasted\"\u003e\n \u003ctable border=\"1\" cellpadding=\"0\" cellspacing=\"0\" width=\"100%\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" width=\"17.821782178217823%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003eEntry\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"53.88967468175389%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003eCatalyst\u0026nbsp;\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.28854314002829%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003eYield (%)\u003csup\u003ea\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" width=\"17.821782178217823%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"53.88967468175389%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003ePd/PNIPAM\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.28854314002829%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e30\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" width=\"17.821782178217823%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e2\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"53.88967468175389%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003ePd/P\u0026nbsp;\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.28854314002829%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e40\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" width=\"17.821782178217823%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e3\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"53.88967468175389%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003ePd/CNT-V-PNIPAM \u003csup\u003eb\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.28854314002829%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e80\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" width=\"17.821782178217823%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e4\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"53.88967468175389%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003ePd/CNT-V\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.28854314002829%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e45\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" width=\"17.821782178217823%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e5\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"53.88967468175389%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003ePd/CNT-P\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" width=\"28.28854314002829%\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e98\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp dir=\"LTR\" id=\"isPasted\"\u003e\u003csup\u003e\u003cspan dir=\"LTR\"\u003ea\u003c/span\u003e\u003c/sup\u003e\u003cspan dir=\"LTR\"\u003eReaction condition: nitrobenzene (1 mmol), catalyst (10 mg), H\u003csub\u003e2\u003c/sub\u003eO: EtOH (1:1) 6 ml, H\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e(1 bar) at 40 \u0026deg;C in 2 h.\u003c/span\u003e\u003c/p\u003e\n\u003cp\u003e\u003csup\u003eb\u0026nbsp;\u003c/sup\u003ePd was loaded on the CNT-V, which was polymerized with NIPAM.\u003c/p\u003e\n\u003cp id=\"isPasted\"\u003e\u003cstrong\u003eRecyclability\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAs facile recovery and efficient recyclability are important factors for heterogeneous catalysts, recyclability of Pd/CNT-P for the model reaction was appraised. The recycling test was simply conducted by separation of Pd/CNT-P from the first run of the model reaction and its recovery through washing with toluene and drying at 50 \u0026deg;C in oven. The recovered Pd/CNT-P was then used as a catalyst for catalyzing the second run of the model reaction under similar condition. Upon completion of the reaction, the recovery-reuse cycle was repeated for seven consecutive runs. As shown in Figure 9, Pd/CNT-P can be efficiently recycled and only slight loss of the activity was detected after each recycling.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo study the stability of Pd/CNT-P structure upon recycling, the reused catalyst (obtained after seventh run) was characterized via FTIR spectroscopy. As shown in Figure 10, the FTIR spectrum of the reused Pd/CNT-P exhibited all of the absorbance bands of fresh Pd/CNT-P. This observation affirms the stability of Pd/CNT-P upon recycling.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe measurement of leaching of Pd was performed via ICP analysis. To this purpose, the recovered catalyst after seventh run of the reaction was analyzed by ICP. It was found that Pd leaching was insignificant (1.6 wt.% of initial loading).\u003c/p\u003e\n\u003cp id=\"isPasted\"\u003e\u003cstrong\u003eHot filtration test\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThere are two possibilities in heterogeneous catalysis. In true heterogeneous catalysis, it is expected that the catalytic species remains stabilized on the support, while in the second possibility, the catalytic species can leach to the reaction media and then stabilized on the support. The well-known test for determining the nature of the catalysis is hot filtration, in which the catalyst is removed from the reaction after a short period and then the reaction is pursued in the absence of the catalyst. In the case of true heterogeneous catalysis, in which no leaching of the catalytic species occurs, the reaction does not proceed after removal of the catalyst, while in the other pass way, the reaction proceeds in the absence of the catalyst due to the leached catalytic species. Hot filtration test approved that Pd/CNT-P was a true heterogeneous catalyst. In more detail, hydrogenation of nitrobenzene did not proceed after removing of Pd/CNT-P from the reaction vessel.\u003c/p\u003e"},{"header":"Experimental Section","content":"\u003cp\u003e\u003cstrong\u003e\u0026nbsp;Materials and instruments\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCOOH-functionalized multi-wall carbon nanotubes (MWCNTs) (purity \u0026gt; 95%, content of COOH = 3.86 wt. %, inner diameter: 2-5 nm and outer diameter\u0026gt; 7 nm) were obtained from US Research Nanomaterials. Other\u0026nbsp;reagents and solvents applied for the synthesis of the catalyst and conducting hydrogenation reaction of nitro-compounds are as follow: (3-trimethoxysilyl) propyl methacrylate (TMSPMA), cetyltrimethyl ammonium bromide (CTAB), tetraethyl orthosilicate (TEOS), 1-vinylimidazole, NIPAM, azobisisobutyronitrile (AIBN), triethylamine (Et\u003csub\u003e3\u003c/sub\u003eN), palladium(П) acetate Pd(OAc)\u003csub\u003e2\u003c/sub\u003e, sodium borohydride (NaBH\u003csub\u003e4\u003c/sub\u003e), \u003cem\u003eN,N\u003c/em\u003e-dimethylformamide (DMF), nitro-compounds, 1-bromo butane, sodium hydroxide, toluene, ethanol (EtOH) and methanol (MeOH), all was purchased from Sigma-Aldrich ( Germany, Taufkitchen) and used without further purification.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe formation of Pd/CNT-P was confirmed by various characterization techniques, including: Fourier transform Infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), inductively coupled plasma mass spectroscopy (ICP-MS), energy-dispersive X-ray spectroscopy (EDS) and elemental mapping analysis.\u003c/p\u003e\n\u003cp\u003eRecording of FTIR spectra was carried out by using BRUKER TENSOR 35 spectrophotometer 65 with scan time of 1 s and spectral resolution of 2 cm\u003csup\u003e-1\u003c/sup\u003e by using KBr pellets. The XRD pattern of Pd/CNT-P was recorded using a Rigaku Ultima IV with Cu K\u0026alpha; radiation from a sealed tube. Thermal stability of Pd/CNT-P was investigated by applying METTLER TOLEDO thermogravimetric analysis apparatus. To record the catalyst thermogram, inert atmosphere and heating rate of 10 \u0026deg;C min\u003csup\u003e-1\u003c/sup\u003e were applied. TEM images of Pd/CNT-P were recorded on a Phillips EM 208S microscope at 100 kV. Pd loading of Pd/CNT-P was estimated using ICP analyzer Varian, Vista-pro instrument. EDX and elemental mapping analyses were carried out by Tescan Mira II.\u003c/p\u003e\n\u003cp id=\"isPasted\"\u003e\u003cstrong\u003ePreparation of\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ePd/CNT-P\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSurface modification of carbon nanotubes: synthesis of CNT-SiO\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSurface modification of CNT with silica was performed according to the previous report\u0026nbsp;\u003ca href=\"#_ENREF_42\" title=\"Sadjadi, 2020 #81\"\u003e\u003csup\u003e42\u003c/sup\u003e\u003c/a\u003e. Typically, to a solution of CTAB (1.7 g) in distilled water (40 ml), CNT (0.2 g) was added and the resulting suspension was homogenized under ultrasonic irradiation\u0026nbsp;(160 W for 30 min). Afterwards,\u0026nbsp;NaOH (0.08 g) was added and the resulting mixture was stirred for 30 min at 60 \u0026deg;C. In the next step, a solution of TEOS (10 mL) in EtOH was introduced to the aforementioned suspension under stirring condition at 60 \u0026deg;C. After 24 h, the product, CNT-SiO\u003csub\u003e2\u003c/sub\u003e, was separated via centrifugation, washed repeatedly with warm EtOH and dried in oven overnight.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eVinyl-functionalization of CNT-SiO\u003csub\u003e2\u003c/sub\u003e: synthesis of CNT-V\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn order to vinyl-functionalize CNT-SiO\u003csub\u003e2\u003c/sub\u003e, the as-prepared CNT-SiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e(0.5 g) was dispersed in dry toluene (20 mL) by using ultrasonic irradiation (160 W) for 20 min. Then TMSPMA (0.5 g) was added to CNT-SiO\u003csub\u003e2\u003c/sub\u003e suspension and the resulting mixture was refluxed at 110 \u0026deg;C for 24 h under Ar atmosphere. Upon completion of the reaction, the precipitate, CNT-V, was collected via centrifuge, washed with toluene and dried in oven at 80 \u0026deg;C overnight.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of VBIB\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eVBIB was prepared according to the previous report\u0026nbsp;\u003ca href=\"#_ENREF_43\" title=\"Sadjadi, 2020 #375\"\u003e\u003csup\u003e43\u003c/sup\u003e\u003c/a\u003e. Briefly, the mixture of 1-bromobutane (4 g) and 1-vinylimidazole (2 g) was stirred at 70 \u0026deg;C under solvent-free condition for 16 h under inert atmosphere. Then, the reaction mixture was allowed to cool to room temperature and the product was collected, washed several times with ethyl acetate and dried in a vacuum oven overnight.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePolymerization of NIPAM, VBIB and CNT-V: synthesis of CNT-P\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCNT-V (0.5 g) was added to a solution of NIPAM (0.5 g) in DMF (20 mL) under stirring condition under Ar atmosphere at 70\u0026nbsp;\u0026deg;C. After 20 min,\u0026nbsp;a solution of AIBN (0.15 g) in DMF (10 mL) was added to the aforesaid mixture in a dropwise manner and stirring was maintained for 40 min. Subsequently, a solution of VBIB (0.5 g) in DMF (10 mL) was added and the resulting mixture was stirred for 24 h at 70 \u0026deg;C under Ar atmosphere. After completion of the reaction, the solvent was evaporated and\u0026nbsp;the solid was collected, rinsed with DMF and dried in oven at 70 \u0026deg;C overnight.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eImmobilization of Pd nanoparticles on CNT-P: Synthesis of Pd/CNT-P\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn order to prepare Pd/CNT-P, CNT-P (1.5 g) was stirred in toluene (20 mL) in a 2-neck round flask under Ar atmosphere at room temperature for 30 min. Subsequently, a solution of Pd(OAc)\u003csub\u003e2\u003c/sub\u003e (0.02 g) in toluene (15 mL) was gently introduced to the aforementioned suspension. After 1 h, a solution of NaBH\u003csub\u003e4\u0026nbsp;\u003c/sub\u003e(0.2 N) in MeOH (20 mL) was slowly added and the obtained mixture was stirred for 2 h. Finally, the as-prepared Pd/CNT-P was collected via centrifugation, washed with toluene and dried in oven at 50 \u0026deg;C overnight, Figure 1. According to the ICP analysis, Pd loading in Pd/CNT-P was 1 wt %.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTypical procedure for the hydrogenation of nitro-compounds\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eHydrogenation of nitro-compounds was conducted under mild reaction condition. Typically, a mixture of nitro aromatic compound (1 mmol) and\u0026nbsp;Pd/CNT-P\u0026nbsp;(0.01 g) in H\u003csub\u003e2\u003c/sub\u003eO/EtOH (1/1) was heated to 40 \u0026deg;C under H\u003csub\u003e2\u003c/sub\u003e gas (1 bar). The progress of the hydrogenation reaction was traced by TLC. Upon completion of the process, Pd/CNT-P was separated and recovered by washing with toluene (30 mL) and drying at 50 \u0026deg;C in an oven overnight. The recovered catalyst was reused for the next run of the reaction. The hydrogenized product was obtained after evaporation of the solvent. The reaction yield was measured via GC analysis.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eA novel thermo-responsive catalyst, Pd/CNT-P, was designed and synthesized through vinyl functionalization of CNT-SiO\u003csub\u003e2\u003c/sub\u003e, followed by polymerization with NIPAM and VBIB and palladation. The catalytic performance of the resulting catalyst was examined for the hydrogenation of nitro-compounds in aqueous media under mild reaction condition. The results affirmed high catalytic activity of the catalyst, broad substrate scope and high selectivity of the catalyst towards nitro group. Moreover, the catalyst was recyclable up to seven reaction runs with slight Pd leaching. Hot filtration test also indicated the true heterogeneous nature of the catalysis. \u0026nbsp;The comparison of the catalytic activity of Pd/CNT-P with several control catalysts confirmed the importance of conjugation of P and CNT for achieving high catalytic activity.\u0026nbsp;\u003c/p\u003e"},{"header":"Declaration","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgment\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors appreciate the partial supports of Iran Polymer and Petrochemical Institute and Alzahra University.\u0026nbsp;\u003c/p\u003e"},{"header":"Reference ","content":"\u003cp dir=\"LTR\"\u003e1 \u0026nbsp;Ahn, Y., Jang, Y., Selvapalam, N., Yun, G. \u0026amp; Kim, K. Supramolecular velcro for reversible underwater adhesion. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e \u003cstrong\u003e52\u003c/strong\u003e, 3140-3144 (2013).\u003c/p\u003e\n\u003cp dir=\"LTR\"\u003e2 \u0026nbsp;Guo, J., Yuan, C., Guo, M., Wang, L. \u0026amp; Yan, F. 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Biochar-Based Graphitic Carbon Nitride Adorned with Ionic Liquid Containing Acidic Polymer: A Versatile, Non-Metallic Catalyst for Acid Catalyzed Reaction. \u003cem\u003eMolecules\u003c/em\u003e \u003cstrong\u003e25\u003c/strong\u003e, 5958 (2020).\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Carbon nanotube, Ionic liquid, Heterogeneous catalyst, Thermo-responsive polymer, N-isopropylacrylamide. ","lastPublishedDoi":"10.21203/rs.3.rs-1148099/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-1148099/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn this work, an ionic liquid-containing thermo-responsive heterogeneous catalyst with utility for promoting hydrogenation of nitro-compounds in aqueous media is developed. To prepare the catalyst, silica-coated carbon nanotubes were synthesized and vinyl-functionalized. The resulted compound was then polymerized with 1-viny-3-butylimidazolium bromide and \u003cem\u003eN\u003c/em\u003e-isopropylacrylamide. The obtained ionic liquid-containing thermo-responsive composite was palladated via wet-impregnation method to give the final catalyst. Study of the performance of the catalyst confirmed high catalytic activity of the catalyst at temperature above the lower critical solution temperature. Furthermore, the catalyst was highly recyclable and showed negligible Pd leaching upon recycling. Broad substrate scope and selectivity of the catalyst towards reduction of nitro functionality were also confirmed. Furthermore, hot filtration test implied the heterogeneous nature of the catalysis. The comparison of the activity of Pd/CNT-P with some control catalysts approved the importance of hybridization of P and CNT and the presence of ionic liquid for the catalytic activity.\u003c/p\u003e","manuscriptTitle":"Pd On Thermo-Responsive Composite of Silica-Coated Carbon Nanotube And 1-Vinyl-3-Butylimidazolium-Based Ionic Liquid Copolymers As An Efficient Catalyst For Hydrogenation of Nitro Compounds","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2021-12-13 23:02:24","doi":"10.21203/rs.3.rs-1148099/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Major revision","date":"2021-12-31T07:40:53+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2021-12-23T05:52:02+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"54390fbb-efe9-4b67-8faf-4ba6dbed4567","date":"2021-12-20T01:43:55+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2021-12-20T01:40:41+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2021-12-10T08:11:52+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2021-12-10T07:27:06+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2021-12-10T07:24:37+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2021-12-07T08:23:06+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"981afec6-aaca-4447-9b2b-096da8907bd0","owner":[],"postedDate":"December 13th, 2021","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":9108493,"name":"Organic Chemistry"},{"id":9108494,"name":"Catalysis"}],"tags":[],"updatedAt":"2022-03-10T11:55:26+00:00","versionOfRecord":{"articleIdentity":"rs-1148099","link":"https://doi.org/10.1038/s41598-022-07708-0","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2022-03-10 11:55:26","publishedOnDateReadable":"March 10th, 2022"},"versionCreatedAt":"2021-12-13 23:02:24","video":"","vorDoi":"10.1038/s41598-022-07708-0","vorDoiUrl":"https://doi.org/10.1038/s41598-022-07708-0","workflowStages":[]},"version":"v1","identity":"rs-1148099","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-1148099","identity":"rs-1148099","version":["v1"]},"buildId":"WrCJVZZCHTDjtuVLN7oU0","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}