Green Synthesis of Primary Nitroalkanes via Oxidation of Small-Molecule Aldoximes Catalyzed by Alkali-Modified TS-1

Green Synthesis of Primary Nitroalkanes via Oxidation of Small-Molecule Aldoximes Catalyzed by Alkali-Modified TS-1 | 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 Green Synthesis of Primary Nitroalkanes via Oxidation of Small-Molecule Aldoximes Catalyzed by Alkali-Modified TS-1 Yu-Qing Gu, Cong-Xuan Fan, Shi-Feng Xing, Hong-Jun Zhu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9397977/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 15 You are reading this latest preprint version Abstract Modified TS-1 catalysts were prepared by treating TS-1 with different alkalis for the nitration of aldoxime, and the effect of alkali treatment on catalytic performance was investigated. TS-1 was modified using organic amines such as ethylamine (EA), triethylamine (TEA), and tetrapropylammonium hydroxide (TPAOH), as well as inorganic bases such as NaOH, KOH. The catalysts were characterized by XRD, FT-IR, UV-vis, N adsorption etc., which showed that the volume of mesopores increased and the skeleton structure remained basically unchanged by the ethylamine-modified TS-1 and the TPAOH-modified TS-1. The highest yield of 1-nitropropane increased 78% when propionaldehyde oxime was catalyzed by the 0.1 mol/L ethylamine treated sample TS-1-EA-0.1. The enhanced catalytic performance of TS-1 after ethylamine treatment may be attributed to the matching between the pore size of modified TS‑1 and the molecular size of propionaldehyde oxime. Subsequently, TS-1-EA-0.1 was used to catalyze acetaldoxime and butyraldehyde oxime. The results revealed that this catalyst was suitable for acetaldehyde oxime as expected, but less effective for the oxidation of butyraldehyde oxime with a larger molecular diameter than propionaldehyde oxime to 1-nitrobutane. TS-1 Alkaline modification Primary nitroalkanes Green catalysis Figures Figure 1 Figure 2 Figure 3 Introduction As valuable basic raw materials for the production of a large number of chemicals such as solvents, fuels, pharmaceuticals, and explosives, the synthesis of nitroalkanes has been the subject of extensive research. (Patil et al. 2015; Ballini et al. 2018). Traditionally, nitroalkanes are synthesized via the nitration of alkanes with HNO 3 or NO 2 at high temperatures, involving the homolytic cleavage of alkane C–H bonds (Albright et al. 1996 ). However the reaction produced a large number of by-products, which complicated product purification and caused environmental pollution. Additionally, nitroalkanes were synthesized by oxidation of primary amines with ozone as oxidant, which had the disadvantages of poor selectivity and low yield (Bailey et al. 1968 ; Keinan et al. 1977). Moreover, the substitution reaction of halogenated alkanes with nitrites can produce nitroalkanes, but the reaction generated a large number of waste salt (Palmieri et al. 2013 ). Thus, it was urgent to develop a simple, effective and environmentally friendly nitroalkane production process. Notably, the synthesis of nitroalkanes through aldoxime oxidation is a very promising approach. A pioneering procedure reported that the conversion of oximes into nitroalkanes can be realized using a strong oxidant like anhydrous peroxytrifluoroacetic acid. (Emmons et al. 1955; Ballini et al. 1992 ). A method for the conversion of ketoximes to nitroalkanes using an inorganic oxide NaBO 3 in glacial acetic acid, which is ineffective for aldoximes (Olah et al. 1992 ). Furthermore, an Mo(VI) oxodiperoxo complex [BzOMoO(O 2 ) 2 ] − (t-Bu) 4 N + (Benz-Mo) 7 used as the oxidant to convert aldoximes and ketoximes into nitroalkanes in acetonitrile (Ballistreri et al. 1996 ). Nevertheless, these reactions suffer from critical drawbacks associated with environmental pollution. Accordingly, a green one-pot route to nitroalkanes via ketone ammoximation-oxidation has been reported recently, using TS-1 as a catalyst and H 2 O 2 as an oxidant (Chu et al. 2018 ). In recent years, TS-1 has been widely used because of its outstanding catalytic properties, such as the epoxidation of olefins, the hydroxylation of phenol and the ammonia oxidation of ketones (Wang et al. 2023 ; Luo et al. 2018 ; Lewis et al. 2022 ). However, the micropores of TS-1 restrict the diffusion of molecules in the pores, which limits its catalytic activity (Zhang et al. 2021 ; Yang et al. 2004 ). It is well known that the molecular diameter of the aldehyde oximes is larger than that of the ketone oximes with the same carbon number. For example, the 3D structures of acetoxime and propanal oxime were optimized by Chem3D (MM2 energy minimization), the molecular sizes of acetoxime and propionaldehyde oxime were computed to be 7.23 Å × 4.21 Å × 6.28 Å and 8.64 Å × 4.91 Å × 4.68 Å, respectively (Yoo et al. 2023 ; Lu et al. 2024) (Fig. 6S). Hence, we proposed that TS-1 with an enlarged pore size would exhibit enhanced catalytic activity for the synthesis of 1-nitropropane from propionaldehyde oxime. It was found that alkali treatment of titanium silicalite zeolite represents the most convenient approach to increase its mesopore volume, thereby enhancing its catalytic performance (Pérez-Ramírez et al. 2008 ). The selectivity and conversion of phenol hydroxylation were improved by inorganic alkali modification of TS-1 (Chao et al. 2009 ). Moreover, TS-1 was modified by tetramethylammonium hydroxide ( TPAOH ) and applied to the epoxidation of allyl chloride which improved the conversion and selectivity of the reaction (Wu et al. 2017 ). In recent years, a relatively abundant mesoporous TS-1 was obtained by post-treatment of TS-1 with organic amines and salts, which improved the catalytic performance of pentene epoxidation (Chang et al 2022 ). In addition, post-treatment of TS-1 with a mixed alkaline solution of TPAOH and isopropanolamine (IPA) enhanced its catalytic activity for acetone nitration (Zhang et al. 2022 ). Based on previous literature and our hypothesis proposed above, here we prepared TS-1 modified with different alkalis and applied them to the catalytic oxidation of aldoximes to primary nitroalkanes. The catalysts were characterized by XRD, FT-IR, UV-vis and N 2 adsorption which showed that the mesoporous pore volume of TS-1 modified by ethylamine increased and the skeleton structure remained basically unchanged. The results showed that TS-1 modified with ethylamine displayed the best catalytic performance, and the yield of 1-nitropropane was increased to 78%. Experimental Chemicals and materials The TS-1 and acetaldoxime were purchased from Shanghai Aladdin Biochemical Technology Ltd. Co. Propionaldehyde, ethylamine (EA) and ammonia (NH 3 ·H 2 O) were purchased from Beijing InnoChem Technology Ltd. Co. Methanol, hydroxylamine hydrochloride, TPAOH, diethylamine (DEA), triethylamine (TEA), tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), butyraldehyde oxime and sodium bicarbonate were purchased from Shanghai Macklin Biochemical Ltd. Co. Propylamine (PA) and butylamine (BA) were purchased from Shanghai Titan Scientific Ltd. Co. Alkaline modified TS-1 A certain concentration of alkaline solution was mixed with TS-1 and stirred at 323 K for 4 h. Subsequently, the mixture was sealed and kept at 443 K for 24 h in a 50 mL Teflon-lined autoclave. Following natural cooling to room temperature, the modified sample was rinsed with demineralised water until neutral, dried at 373 K for 12 h, and finally calcined at 823 K for 5 h. The catalyst was named TS-1-x-n (x is the abbreviation for the name of the alkali used, n is the concentration of alkali used (mol/L)) (Table. 1S). Nitration of propionaldehyde oxime Propionaldehyde oxime (1a) (0.73 g, 10 mmol), ammonia solution (1.5 mmol, 26 wt%), catalyst (0.4 g) and methanol (3.8 ml) were added to 20 mL reaction flask and the mixture was heated to 65°C. H 2 O 2 (20 mmol, 30 wt%) was slowly injected into the mixture by peristaltic pump within 0.5 h. Subsequently, continuous reflux of the reaction solution was maintained for 0.5 h at atmospheric pressure. The reaction mixtures were quantitatively analyzed using an internal standard method by gas chromatography (GC9790plus) (Fig. 5S). Results and discussion Characterization of catalyst The X-ray patterns were collected for all the studied samples (Fig. 1 and Fig. 1 S). Except for the sample modified with 0.1 mol/L KOH (TS-1-K-0.1), all the samples displayed characteristic diffraction peaks assignable to the typical MFI structure (Hwang et al. 2005 ). The MFI structure of TS-1 modified by KOH was destroyed (Fig. 1 ). With the exception of TS-1-K-0.1, all samples displayed diffraction peaks at 7.8 o , 8.8 o , 23.0 o , 23.9 o and 24.2 o , which are consistent with previous literature reports (Su et al. 2022 ). To further study the morphology and structure of the catalysts (TS-1, TS-1-EA-0.1, TS-1-TPAOH-0.1, TS-1-Na-0.1), SEM and TEM characterization were performed (Fig. 2 S and 3 S). The TS-1 possessed a relatively smooth particle surface, while the particle surface of TS-1-EA-0.1 was rough resulting from the corrosion of TS-1 by alkali (Fig. 2Sb). In addition, the surface of sample TS-1-Na-0.1 was most severely corroded, which might be due to the higher alkalinity of NaOH (Fig. 2Sd). When comparing the TEM images of different catalysts, irregular hollows were observed in the TEM image of TS-1-EA-0.1, indicating the formation of a new mesoporous structure in the modified TS-1 (Fig. 3Sb). The structure characteristics of the samples (TS-1, TS-1-EA-0.05, TS-1-EA-0.1, TS-1-EA-0.3, TS-1-EA-0.5, TS-1-TPAOH-0.1, TS-1-Na-0.1) were studied using nitrogen adsorption–desorption isotherm (Fig. 2 a). The TS-1 exhibited a narrow hysteresis loop in the high relative pressure region (P/P 0 > 0.9), which was ascribed to the pore stacking of zeolite particles (Guo et al. 2024 ; Zhang et al. 2022 ). In comparison with the TS-1, the TS-1-EA-0.1 sample showed an obvious hysteresis loop in the range of 0.4 < P/P 0 < 1.0, which further confirmed the formation of mesopores. While TS-1 was modified with a higher concentration of ethylamine or more alkaline NaOH, the hysteresis loops of these samples disappeared completely at 0.4 < P/P₀ < 0.9. It could be reasonably inferred that the excessive corrosion of TS-1 caused by excessively high alkalinity led to the local collapse of its internal framework structure. Moreover, the pore size distribution was centered at 0.37 nm for these catalysts (Fig. 2 b). Next, the main physical characteristics of the studied samples were investigated (Table 1 ). The TS-1 sample possessed total surface areas of 470 cm 2 /g, external surface areas of 49 cm 2 /g and mesoporous volume of 0.05 cm 3 /g, whereas the TS-1-EA-0.1 sample exhibited higher values, with total surface areas of 485 cm 2 /g, external surface areas of 53 cm 2 /g and mesoporous volume of 0.15 cm 3 /g. Evidently, ethylamine post-treatment effectively increases the mesopore volume of TS-1. Hence, the higher surface areas and mesoporous volume of ethylamine-modified TS-1 might lead to superior catalytic performance. However, when TS-1 was modified with a higher concentration of ethylamine and more strongly alkaline NaOH, the mesoporous volume of these samples not only failed to increase but actually decreased, which also further confirmed that the excessive corrosion of TS-1 led to the local collapse of its internal structure. In addition, the Si/Ti ratio determined was 12.00 for the parent TS-1 and 10.58–11.97 for the alkali-treated TS-1 samples with ICP-OES (Table 1 ). The higher titanium content of the alkali-treated TS-1 samples indicates that silica is selectively removed during alkaline treatment. TS-1-EA-0.1, TS-1-TPAOH-0.1, and TS-1-Na-0.1 were prepared by modifying TS-1 with 0.1 mol/L EA, 0.1 mol/L TPAOH, and 0.1 mol/L NaOH, respectively. Among them, the Si/Ti ratio of TS-1-Na-0.1 decreased more significantly (Table 1 , entry 3, entry 6 to 7). Moreover, their Si/Ti ratios gradually decreased when TS-1 was modified with higher concentrations of ethylamine (Table 1 , entry 4 to 5), which indicated that the Si-O-Si bonds were severely corroded with increasing alkali concentration, and this might lead to the collapse of its framework structure. Then, the states of titanium in catalysts were studied by FT-IR (Fig. 2 c). These catalysts exhibited prominent characteristic absorption bands at 550 cm -1 , 800 cm -1 , 960 cm -1 , 1100 cm -1 , and 1230 cm -1 , consistent with the typical FT-IR fingerprint of TS-1 (Wang et al. 2010 ). In particular, a distinct characteristic band at 960 cm -1 was observed for these samples, which was generally accepted as proof that titanium had been successfully introduced into the zeolite framework (Ricchiardi et al. 2001 ). Finally, the coordination state of Ti atoms in catalysts was investigated by UV-vis (Fig. 2 d). The position of the absorption band of these samples at 210 nm, which is attributed to the tetrahedral titanium(IV) in the zeolite framework. (Ratnasamy et al. 2004 Table 1 Physicochemical properties of samples Entry Sample Si/Ti a S BET (m 2 ·g − 1 ) S exter (m 2 ·g − 1 ) V micro (cm 3 ·g − 1 ) V meso (cm 3 ·g − 1 ) 1 TS-1 12.00 470 49 0.16 0.05 2 TS-1-EA-0.05 11.97 419 47 0.15 0.04 3 TS-1-EA-0.1 11.62 485 53 0.16 0.15 4 TS-1-EA-0.3 11.16 404 50 0.14 0.04 5 TS-1-EA-0.5 10.58 347 39 0.12 0.03 6 TS-1-TPAOH-0.1 11.35 482 54 0.17 0.08 7 TS-1-Na-0.1 11.19 241 41 0.09 0.03 a The Si/Ti ratio of the TS-1 catalysts were determined by ICP-OES analysis S BET BET surface area, S exter external surface area, V micro micropore volume, V meso mesopore volume Alkali-modified TS-1 catalyzed nitration of propionaldehyde oxime After producing and characterizing the catalysts, the first step of our work was to investigate their catalytic activity in the nitration of propionaldehyde oxime (Table 2 ). In this context, TS-1 modified with 11 different types (EA, PA, BA, DEA, TEA, TMAOH, TEAOH, TPAOH, NH 3 ·H 2 O, NaOH, KOH) of alkali was used as the catalyst, and H 2 O 2 was used as the oxidizing agent to catalyze the oxidation of propionaldehyde oxime for the synthesis of 1-nitropropane. Among all the tested catalysts, TS-1-EA-0.1 exhibited the optimal catalytic performance, and the yield of 1-nitropropane increased to 40% (Table 2 , entry 3), which was attributed to the larger pore size of TS-1-EA-0.1 than that of TS-1 (Table 1 ). Subsequently, the catalytic activity of TS-1 modified with varying concentrations of ethylamine was also investigated for the synthesis of 1-nitropropane from propionaldehyde oxime (Table 2 , entry 2 to 5). The catalytic properties of TS-1-EA-0.05 was basically consistent with that of the TS-1, which indicated that the corrosion effect of ethylamine on TS-1 might be weak when its concentration was too low. In addition, the catalytic properties of TS-1-EA-0.3 and TS-1-EA-0.5 in catalyzing the synthesis of 1-nitropropane from propionaldehyde oxime gradually declined compared with TS-1-EA-0.1. Specifically, the catalytic properties of TS-1-EA-0.5 was even lower than that of the TS-1, which might be related to the excessive corrosion of TS-1 caused by the high-concentration ethylamine. In conclusion, the TS-1 modified with 0.1 mol/L ethylamine exhibited superior catalytic activity, which was in good agreement with the pore volume characterization of the catalysts. Table 2 Comparison of catalytic activity of different alkali modified TS-1 Entry Catalyst Yield of 1b ( 1c ) (%) Selectivity of 1b (%) 1 TS-1 24(0.8) 96 2 TS-1-EA-0.05 23(1.3) 95 3 TS-1-EA-0.1 40(0.9) 97 4 TS-1-EA-0.3 27(0.6) 97 5 TS-1-EA-0.5 19(0.8) 95 6 TS-1-PA-0.1 3.6(0) 99 7 TS-1-BA-0.1 11(0) 99 8 TS-1-DEA-0.1 13(0) 99 9 TS-1-TEA-0.1 3.1(0) 99 10 TS-1-TMAOH-0.1 3.2(0) 99 11 TS-1-TEAOH-0.1 2.7(0) 99 12 TS-1-TPAOH-0.1 30(0.5) 99 13 TS-1-NH 3 ·H 2 O-0.1 8(0) 99 14 TS-1-Na-0.1 21(1.4) 93 15 TS-1-K-0.1 0.9(0) 99 Reaction conditions: propionaldehyde oxime (10 mmol), catalyst (0.1 g), H 2 O 2 (2 equiv), NH 3 ·H 2 O (0.15 equiv), MeOH (3.8 mL), 65°C, 0.5 h, detected by GC Based on the previous study, the reaction conditions were further screened for the synthesis of 1-nitropropane via propionaldehyde oxime oxidation over TS-1-EA-0.1 (Table 3 ). Frist of all, the effect of the catalyst amount was investigated on oxidation activity of propionaldehyde oxime. First, the yield of 1-nitropropane gradually increased when the amount of catalyst was increased from 0.1 g to 0.4 g (Table 3 , entry 1 to 4). When the amount of catalyst was 0.4 g, the highest yield of 1-nitropropane reached 78% (Table 3 , entry 4). Upon further increasing the amount of catalyst to 0.5 g, the yield and selectivity of 1-nitropropane began to decrease (Table 3 , entry 5). Subsequently, the effect of the quantity of aqueous ammonia on oxidation activity of propionaldehyde oxime was investigated over TS-1-EA-0.1. Without aqueous ammonia, the yield and selectivity of 1-nitropropane were 31% and 90%, respectively (Table 3 , entry 6). The yield of 1-nitropropane gradually increased when the quantity of aqueous ammonia was increased from 1.0 mmol to 1.5 mmol. (Table 3 , entry 4, entry 7). Clearly, when the quantity of aqueous ammonia was 1.5 mmol, the yield of 1-nitropropane reached the highest point (Table 3 , entry 4). This may be attributed to the fact that aqueous ammonia can regulate the reaction pH and reduce the formation of by-product. In addition, there is an interaction between ammonia and titanium active sites according to the previous study (Alvear et al. 2025 ). Table 3 Optimization of reaction conditions for the synthesis of 1-nitropropane from propionaldehyde oxime Entry TS-1-EA-0.1(g) NH 3 ·H 2 O (mmol) Solvent Yield of 1b(1c) (%) Selectivity of 1b (%) 1 0.1 1.5 MeOH 40(0.9) 97 2 0.2 1.5 MeOH 42(0.1) 95 3 0.3 1.5 MeOH 50(0.3) 97 4 0.4 1.5 MeOH 78(0.2) 99 5 0.5 1.5 MeOH 60(2.8) 95 6 0.4 / MeOH 31(3.4) 90 7 0.4 1.0 MeOH 45(2.9) 93 8 0.4 2.0 MeOH 25(2.5) 90 9 a 0.4 1.5 MeOH / / 10 b 0.4 1.5 MeOH 50(0.1) 99 11 c 0.4 1.5 MeOH 34(3.2) 91 12 0.4 1.5 MeCN 37(0.1) 99 13 0.4 1.5 t-BuOH 1.9(0) 99 14 0.4 1.5 i-PrOH 8.8(0) 99 Reaction conditions: propionaldehyde oxime (10 mmol), TS-1-EA-0.1, H 2 O 2 , NH 3 ·H 2 O, Solvent (3.8 mL), 65°C, 0.5 h, detected by GC a Without H 2 O 2 . b H 2 O 2 (10 mmol). c H 2 O 2 (30 mmol) Next, the effect of the amount of H 2 O 2 on oxidation activity of propionaldehyde oxime over TS-1-EA-0.1 was investigated. In a blank experiment, propionaldehyde oxime could not be oxidized to 1-nitropropane without H 2 O 2 (Table 3 , entry 9). The yield of 1-nitropropane increased first and then decreased as the molar amount of H 2 O 2 varied from 10 mmol to 30 mmol (Table 3 , entry 4, entry 10 to 11), reaching the highest value of 78% at 20 mmol (Table 3 , entry 4). As the amount of H 2 O 2 continued to increase, the yield of by-product began to increase and the selectivity of the product began to decrease (Table 3 , entry 11). Moreover, the effect of solvent species on oxidation activity of propionaldehyde oxime was studied (Table 3 , entry 4, entry 12 to 14). When methanol was used as the solvent, the yield of 1-nitropropane was the highest (Table 3 , entry 4). These experimental results are consistent with the finding that the methanol is the optimal proton transfer carrier when the active site of TS-1 is Ti(OSi) 4 (Yu et al. 2023 ; Zhang et al. 2022 ) Furthermore, the influence of reaction temperature on oxidation activity was studied (Fig. 3 a). Clearly, the yield of 1-nitropropane showed a trend of increasing first and then decreasing at 55–70 o C, reaching the highest point of 78% at 65 o C. When the reaction temperature continued to rise, the yield of 1-nitropropane began to decrease, which might be due to the ineffective decomposition of H 2 O 2 at elevated temperatures. In addition, while the reaction temperature was 65 o C, the yield of 1-nitropropane increased with prolonged reaction time from 10 min to 0.5 h (Fig. 3 b). In the case of 0.5 h, the highest yield of 1-nitropropane reached 78%. Subsequently, the yield of 1-nitropropane began to decrease with increasing the reaction time to 35 minutes. Furthermore, TS-1-EA-0.1 exhibited superior catalytic activity relative to the TS-1 (Fig. 3 a and 3 b). In addition, to evaluate the reusability of regenerated TS-1-EA-0.1 zeolite, the recycling experiments were carried out five times (Fig. 3 c). Over five consecutive cycles, the yield of 1-nitropropane decreased from 78% to 62%. Oxidation of aldoximes with different chain lengths to primary nitroalkanes over TS-1-EA-0.1 Finally, the catalytic activity of TS-1-EA-0.1 for acetaldehyde oxime and butyraldehyde oxime was investigated and contrasted with that of the TS-1 (Table 4 ). Both TS-1-EA-0.1 and TS-1 afforded a 99% yield of nitroethane in the oxidation of acetaldoxime (Table 4 , entry 3–4). However, the yields of 1-nitrobutane from butyraldehyde oxime oxidation catalyzed by TS-1 and TS-1-EA-0.1 were 33% and 34%, respectively, which indicated that the modified TS-1 zeolite was not suitable for butyraldehyde oxime with larger molecular diameter than propionaldehyde oxime (Table 4 , entry 5 to 6). Table 4 Synthesis of nitroalkanes by oxidation of aldehyde oximes Entry R Catalyst GC yield of 2 (3) (%) Selectivity of 2 (%) 1 n-C 2 H 5 TS-1 56(0.1) 99 2 n-C 2 H 5 TS-1-EA-0.1 78(0.2) 99 3 Me TS-1 99 99 4 Me TS-1-EA-0.1 99 99 5 n-C 3 H 7 TS-1 33(0.9) 97 6 n-C 3 H 7 TS-1-EA-0.1 34(1.2) 96 Reaction conditions: reaction substrate (10 mmol), TS-1-EA-0.1(0.4 g), NH 3 ·H 2 O (0.15 equiv.), H 2 O 2 (2 equiv), MeOH (3.8 mL), 65°C, 0.5h, detected by GC Possible mechanism analysis The used TS-1-EA-0.1 was recovered and calcined at 623 K for 2 h, and then characterized by UV-vis spectroscopy. Compared with fresh TS-1-EA-0.1, the used TS-1-EA-0.1 exhibited a new absorption peak at 427 nm, which was attributed to the adsorption of H 2 O 2 on Ti site to produce peroxyhexa-coordinated titanium (Ti-OOH) (Lin et al. 2025 ) (Fig. 7S). Based on literature reports (Chu et al. 2018 ; Zecchina et al. 1996 ; Zhang et al. 2022 ) and our experimental results, a possible mechanism for the TS-1 catalyzed oxidation of aldoximes had been proposed (Scheme 1 ). Initially, the tetrahedral Ti 4+ active center ( A ) in TS-1 interacts with ammonia to generate six-fold coordinated Ti (IV) complex ( B ), which is subsequently oxidized by H 2 O 2 to form Ti-OOH ( C ). Then, the aldoxime is oxidized to the nitroalkane under the combined action of the Ti-OOH and H 2 O 2 . In addition, TS-1-EA-0.1 possessed more mesopores compared with the parent TS-1, allowing more small-molecule aldoximes to enter the channels and reducing the diffusion limitation of the reaction. Therefore, TS-1-EA-0.1 displayed excellent catalytic activity in the nitration reaction of propionaldehyde oxime. Conclusions In this work, the influence of alkaline treatment of TS-1 was studied on catalytic performance for aldoxime nitration. The results showed that the alkaline treatment can selectively remove silicon, and the framework of MFI zeolites remains intact. Compared with the untreated TS-1 catalyst, TS-1-EA-0.1 exhibits abundant mesopores and larger pore sizes, thereby enhancing its catalytic performance in the nitration of propionaldehyde oxime. In contrast, the yield of 1-nitrobutane from butyraldehyde oxime over TS-1-EA-0.1 was not improved, which is attributed to the larger molecular diameter of butyraldehyde oxime compared to propionaldehyde oxime. In conclusion, the exceptional catalytic activity of the alkali-modified TS-1 stems from the generation of mesopores. 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J Chem Phys 161:082503. https://doi.org/10.1063/5.0216272 Luo Y, Xiong J, Pang C, Li G, Hu C (2018) Direct hydroxylation of benzene to phenol over TS-1 catalysts. Catalysts 8:49. https://doi.org/10.3390/catal8020049 Olah GA, Ramaiah P, Lee C-S, Prakash GKS (1992) Convenient oxidation of oximes to nitro compounds with sodium perborate in glacial acetic acid. Synlett 4:337–339. https://doi.org/10.1055/s-1992-22006 Palmieri A, Gabrielli S, Ballini R (2013) Easy and direct onversion of tosylates and mesylates into nitroalkanes. Beilstein J Org Chem 9:533–536. https://doi.org/10.3762/bjoc.9.58 Patil VV, Shankarling GS (2015) Steric-hindrance-induced regio- and chemoselective oxidation of aromatic amines. J Org Chem 80:7876–7883. https://doi.org/10.1021/acs.joc.5b00582 Pérez-Ramírez J, Christensen CH, Egeblad K, Christensen CH, Groen JC (2008) Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design. 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Catal Lett 153:2693–2705. https://doi.org/10.1007/s10562-022-04146-5 Wang XB, Zhang XF, Liu HO, Yeung KL, Wang JQ (2010) Preparation of titanium silicalite-1 catalytic films and application as catalytic membrane reactors. Chem Eng J 156:562–570. https://doi.org/10.1016/j.cej.2009.04.018 Wang Y, Lin M, Tuel A (2007) Hollow TS-1 crystals formed via a dissolution–recrystallization process. Micro Meso Mat 102:80–85. https://doi.org/10.1016/j.micromeso.2006.12.019 Wu G, Lin Z, Li L, Zhang L, Hong Y, Wang W, Chen C, Jiang Y, Yan X (2017) Experiments and kinetics of the epoxidation of allyl chloride with H 2 O 2 over organic base treated TS-1 catalysts. Chem Eng J 320:1–10. https://doi.org/10.1016/j.cej.2017.03.030 Yang X, Han Y, Lin K, Tian G, Feng Y, Meng X, Di Y, Du Y, Zhang Y, Xiao F (2004) Ordered mesoporous titanosilicates with catalytically stable and active four-coordinated titanium sites. Chem Commun 2612–2613. https://doi.org/10.1039/B410305J Yoo SH, Lee SC, Jang HY, Kim SB (2023) Characterization of ibuprofen removal by calcined spherical hydrochar through adsorption experiments, molecular modeling, and artificial neural network predictions. Chemosphere 311:137074. https://doi.org/10.1016/j.chemosphere.2022.137074 Yu Y, Wang J, Fang N, Chen Z, Liu D, Liu Y, He M (2023) Evidence of solvent-mediated proton transfer during H 2 O 2 activation in titanosilicate-catalyzed oxidation systems. Phys Chem Chem Phys 25:12220–12230. https://doi.org/10.1039/D2CP05483C Zecchina A, Bordiga S, Lamberti C, Ricchiardi G, Lamberti C, Ricchiardi G, Scarano D, Petrini G, Leofanti G, Mantegazza M (1996) Structural characterization of Ti centres in Ti-silicalite and reaction mechanisms in cyclohexanone ammoximation. Catal Today 32:97–106. https://doi.org/10.1016/S0920-5861(96)00075-2 Zhang M, Ren S, Guo Q, Shen B (2021) Synthesis of hierarchically porous zeolite TS-1 with small crystal size and its performance of 1-hexene epoxidation reaction. Micropor mesopor mat 326:111395. https://doi.org/10.1016/j.micromeso.2021.111395 Zhang Z, Chu Q, SUN Y, Wang H, Lu D, Liu Y, Xiao H, Wang P, Cui H, Wang M (2022) Green synthesis of 2-nitropropane via ammoximation-oxidation over organic base modified TS-1 catalysts. Chem Select 7:e202202475. https://doi.org/10.1002/slct.202202475 Scheme 1 Scheme 1 is available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files SupportingInformation.docx SC1.png Scheme 1 The possible reaction mechanism for the synthesis of primary nitroalkanes from aldoximes catalyzed by TS-1 GA.png Cite Share Download PDF Status: Under Review Version 1 posted Reviews received at journal 16 May, 2026 Reviews received at journal 15 May, 2026 Reviews received at journal 14 May, 2026 Reviewers agreed at journal 13 May, 2026 Reviews received at journal 13 May, 2026 Reviews received at journal 11 May, 2026 Reviewers agreed at journal 07 May, 2026 Reviewers agreed at journal 07 May, 2026 Reviewers agreed at journal 06 May, 2026 Reviewers agreed at journal 06 May, 2026 Reviewers agreed at journal 03 May, 2026 Reviewers invited by journal 03 May, 2026 Editor assigned by journal 13 Apr, 2026 Submission checks completed at journal 13 Apr, 2026 First submitted to journal 12 Apr, 2026 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-9397977","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":637037486,"identity":"35361eb0-3530-4c8e-b108-74cef8b0e9ff","order_by":0,"name":"Yu-Qing Gu","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Yu-Qing","middleName":"","lastName":"Gu","suffix":""},{"id":637037487,"identity":"c16baa92-c7f2-45ef-9697-03ad5fb38230","order_by":1,"name":"Cong-Xuan Fan","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Cong-Xuan","middleName":"","lastName":"Fan","suffix":""},{"id":637037488,"identity":"b9ba9383-4013-47be-88ca-5b51514edccb","order_by":2,"name":"Shi-Feng Xing","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Shi-Feng","middleName":"","lastName":"Xing","suffix":""},{"id":637037489,"identity":"74716626-8830-4d6d-8675-2b3172ba8589","order_by":3,"name":"Hong-Jun Zhu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2klEQVRIie3RsQrCMBCA4SuBZLkHuCLSVygILSLoq7QUdCmO4tAhINRFcBUUH6OzUOgU38DBqZODTyDGuse4CeaHwA35uOEAXK5fjIADLYHpkevHbIkCht8RrwSwJ8F+E12Hx4uYiFV7heUoleJ8MhLvoOLQr1qG2MQhqFkqcZ4YCaM8Ir+qGVLOySvrVBKGRsI7ctAkuGnysCDYEfnagppIC0I0XRA1mqhpREkzG5SYm0mwy6oeFXUm1nVL92LU3wplJq8YAWTdlMD7Oh/z7gBjm48ul8v1pz0BUgc30NEm3TEAAAAASUVORK5CYII=","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":true,"prefix":"","firstName":"Hong-Jun","middleName":"","lastName":"Zhu","suffix":""}],"badges":[],"createdAt":"2026-04-13 03:08:14","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9397977/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9397977/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":108977828,"identity":"94f6e63c-1860-4561-9472-aae1b08b2b9b","added_by":"auto","created_at":"2026-05-11 11:33:06","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":31520,"visible":true,"origin":"","legend":"\u003cp\u003eX-ray diffraction patterns of the parent TS-1 and different alkali-modified TS-1 (TS-1-EA-0.05, TS-1-EA-0.1, TS-1-EA-0.3, TS-1-EA-0.5, TS-1-TPAOH-0.1, TS-1-Na-0.1, TS-1-K-0.1)\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-9397977/v1/d18e6c3711297e2165da0bcc.png"},{"id":108974007,"identity":"45e15c0f-bfef-4e4d-8c37-616fb42d86da","added_by":"auto","created_at":"2026-05-11 10:47:01","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":71574,"visible":true,"origin":"","legend":"\u003cp\u003eThe characterizations of the TS-1, ethylamine modified TS-1, TPAOH modified TS-1 and NaOH modified TS-1: (\u003cstrong\u003eA\u003c/strong\u003e) N\u003csub\u003e2\u003c/sub\u003e sorption isotherms, (\u003cstrong\u003eB\u003c/strong\u003e) the corresponding pore size distributions, (\u003cstrong\u003eC\u003c/strong\u003e) FT-IR spectra, (\u003cstrong\u003eD\u003c/strong\u003e) UV-vis spectra\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-9397977/v1/a940bc2b4d02ee184335e8f8.png"},{"id":108974008,"identity":"0cc43189-1883-479f-8409-7e974eddc855","added_by":"auto","created_at":"2026-05-11 10:47:01","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":22330,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003eA\u003c/strong\u003e) The yield of 1-nitropropane was compared between parent TS-1 and TS-1-EA-0.1 at different reaction temperatures, (\u003cstrong\u003eB\u003c/strong\u003e) the yield of 1-nitropropane was compared between parent TS-1 and TS-1-EA-0.1 at different reaction time, (\u003cstrong\u003eC\u003c/strong\u003e) the reaction-regeneration cycles on TS-1-EA-0.1, reaction conditions: propionaldehyde oxime (10 mmol), H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (2 equiv, 30 wt %), NH\u003csub\u003e3\u003c/sub\u003e·H\u003csub\u003e2\u003c/sub\u003eO (0.15 equiv, 26.5 wt %), catalyst ( 0.4 g), MeOH (3.8 ml), 65 \u003csup\u003eo\u003c/sup\u003eC, 0.5 h, detected by GC\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-9397977/v1/a87f943b7a48c48863e0b3d5.png"},{"id":109252348,"identity":"a8411531-e335-43e2-8cd9-c5662c1e6dff","added_by":"auto","created_at":"2026-05-14 09:25:05","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":434118,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9397977/v1/c97ac367-56f2-4f13-bb03-4d23d171f369.pdf"},{"id":108974004,"identity":"82c85769-a0da-4f7b-b5e4-76a873778e49","added_by":"auto","created_at":"2026-05-11 10:47:00","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":26345594,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-9397977/v1/c74e96f36090d4161c55f032.docx"},{"id":108974005,"identity":"a26dbaac-5594-4625-9b9e-ef1029183bd6","added_by":"auto","created_at":"2026-05-11 10:47:00","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":40664,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1\u003c/strong\u003e The possible reaction mechanism for the synthesis of primary nitroalkanes from aldoximes catalyzed by TS-1\u003c/p\u003e","description":"","filename":"SC1.png","url":"https://assets-eu.researchsquare.com/files/rs-9397977/v1/eaa446917047ef82d00aeb10.png"},{"id":109037010,"identity":"e29e9c87-6f70-4b17-bb63-f72d75bcc228","added_by":"auto","created_at":"2026-05-12 02:49:55","extension":"png","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":230742,"visible":true,"origin":"","legend":"","description":"","filename":"GA.png","url":"https://assets-eu.researchsquare.com/files/rs-9397977/v1/8c8508c0ea08bf32b8a08b82.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Green Synthesis of Primary Nitroalkanes via Oxidation of Small-Molecule Aldoximes Catalyzed by Alkali-Modified TS-1","fulltext":[{"header":"Introduction","content":"\u003cp\u003eAs valuable basic raw materials for the production of a large number of chemicals such as solvents, fuels, pharmaceuticals, and explosives, the synthesis of nitroalkanes has been the subject of extensive research. (Patil et al. 2015; Ballini et al. 2018). Traditionally, nitroalkanes are synthesized via the nitration of alkanes with HNO\u003csub\u003e3\u003c/sub\u003e or NO\u003csub\u003e2\u003c/sub\u003e at high temperatures, involving the homolytic cleavage of alkane C\u0026ndash;H bonds (Albright et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1996\u003c/span\u003e). However the reaction produced a large number of by-products, which complicated product purification and caused environmental pollution. Additionally, nitroalkanes were synthesized by oxidation of primary amines with ozone as oxidant, which had the disadvantages of poor selectivity and low yield (Bailey et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e1968\u003c/span\u003e; Keinan et al. 1977). Moreover, the substitution reaction of halogenated alkanes with nitrites can produce nitroalkanes, but the reaction generated a large number of waste salt (Palmieri et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Thus, it was urgent to develop a simple, effective and environmentally friendly nitroalkane production process.\u003c/p\u003e \u003cp\u003eNotably, the synthesis of nitroalkanes through aldoxime oxidation is a very promising approach. A pioneering procedure reported that the conversion of oximes into nitroalkanes can be realized using a strong oxidant like anhydrous peroxytrifluoroacetic acid. (Emmons et al. 1955; Ballini et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e1992\u003c/span\u003e). A method for the conversion of ketoximes to nitroalkanes using an inorganic oxide NaBO\u003csub\u003e3\u003c/sub\u003e in glacial acetic acid, which is ineffective for aldoximes (Olah et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e1992\u003c/span\u003e). Furthermore, an Mo(VI) oxodiperoxo complex [BzOMoO(O\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e\u0026minus;\u003c/sup\u003e(t-Bu)\u003csub\u003e4\u003c/sub\u003eN\u003csup\u003e+\u003c/sup\u003e (Benz-Mo)\u003csup\u003e7\u003c/sup\u003e used as the oxidant to convert aldoximes and ketoximes into nitroalkanes in acetonitrile (Ballistreri et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e1996\u003c/span\u003e). Nevertheless, these reactions suffer from critical drawbacks associated with environmental pollution. Accordingly, a green one-pot route to nitroalkanes via ketone ammoximation-oxidation has been reported recently, using TS-1 as a catalyst and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e as an oxidant (Chu et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). In recent years, TS-1 has been widely used because of its outstanding catalytic properties, such as the epoxidation of olefins, the hydroxylation of phenol and the ammonia oxidation of ketones (Wang et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Luo et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Lewis et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). However, the micropores of TS-1 restrict the diffusion of molecules in the pores, which limits its catalytic activity (Zhang et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Yang et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2004\u003c/span\u003e). It is well known that the molecular diameter of the aldehyde oximes is larger than that of the ketone oximes with the same carbon number. For example, the 3D structures of acetoxime and propanal oxime were optimized by Chem3D (MM2 energy minimization), the molecular sizes of acetoxime and propionaldehyde oxime were computed to be 7.23 \u0026Aring; \u0026times; 4.21 \u0026Aring; \u0026times; 6.28 \u0026Aring; and 8.64 \u0026Aring; \u0026times; 4.91 \u0026Aring; \u0026times; 4.68 \u0026Aring;, respectively (Yoo et al. \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Lu et al. 2024) (Fig.\u0026nbsp;6S). Hence, we proposed that TS-1 with an enlarged pore size would exhibit enhanced catalytic activity for the synthesis of 1-nitropropane from propionaldehyde oxime.\u003c/p\u003e \u003cp\u003eIt was found that alkali treatment of titanium silicalite zeolite represents the most convenient approach to increase its mesopore volume, thereby enhancing its catalytic performance (P\u0026eacute;rez-Ram\u0026iacute;rez et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). The selectivity and conversion of phenol hydroxylation were improved by inorganic alkali modification of TS-1 (Chao et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). Moreover, TS-1 was modified by tetramethylammonium hydroxide ( TPAOH ) and applied to the epoxidation of allyl chloride which improved the conversion and selectivity of the reaction (Wu et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). In recent years, a relatively abundant mesoporous TS-1 was obtained by post-treatment of TS-1 with organic amines and salts, which improved the catalytic performance of pentene epoxidation (Chang et al \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). In addition, post-treatment of TS-1 with a mixed alkaline solution of TPAOH and isopropanolamine (IPA) enhanced its catalytic activity for acetone nitration (Zhang et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Based on previous literature and our hypothesis proposed above, here we prepared TS-1 modified with different alkalis and applied them to the catalytic oxidation of aldoximes to primary nitroalkanes. The catalysts were characterized by XRD, FT-IR, UV-vis and N\u003csub\u003e2\u003c/sub\u003e adsorption which showed that the mesoporous pore volume of TS-1 modified by ethylamine increased and the skeleton structure remained basically unchanged. The results showed that TS-1 modified with ethylamine displayed the best catalytic performance, and the yield of 1-nitropropane was increased to 78%.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eChemicals and materials\u003c/h2\u003e \u003cp\u003eThe TS-1 and acetaldoxime were purchased from Shanghai Aladdin Biochemical Technology Ltd. Co. Propionaldehyde, ethylamine (EA) and ammonia (NH\u003csub\u003e3\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO) were purchased from Beijing InnoChem Technology Ltd. Co. Methanol, hydroxylamine hydrochloride, TPAOH, diethylamine (DEA), triethylamine (TEA), tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), butyraldehyde oxime and sodium bicarbonate were purchased from Shanghai Macklin Biochemical Ltd. Co. Propylamine (PA) and butylamine (BA) were purchased from Shanghai Titan Scientific Ltd. Co.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eAlkaline modified TS-1\u003c/h3\u003e\n\u003cp\u003eA certain concentration of alkaline solution was mixed with TS-1 and stirred at 323 K for 4 h. Subsequently, the mixture was sealed and kept at 443 K for 24 h in a 50 mL Teflon-lined autoclave. Following natural cooling to room temperature, the modified sample was rinsed with demineralised water until neutral, dried at 373 K for 12 h, and finally calcined at 823 K for 5 h. The catalyst was named TS-1-x-n (x is the abbreviation for the name of the alkali used, n is the concentration of alkali used (mol/L)) (Table. 1S).\u003c/p\u003e\n\u003ch3\u003eNitration of propionaldehyde oxime\u003c/h3\u003e\n\u003cp\u003ePropionaldehyde oxime \u003cb\u003e(1a)\u003c/b\u003e (0.73 g, 10 mmol), ammonia solution (1.5 mmol, 26 wt%), catalyst (0.4 g) and methanol (3.8 ml) were added to 20 mL reaction flask and the mixture was heated to 65\u0026deg;C. H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (20 mmol, 30 wt%) was slowly injected into the mixture by peristaltic pump within 0.5 h. Subsequently, continuous reflux of the reaction solution was maintained for 0.5 h at atmospheric pressure. The reaction mixtures were quantitatively analyzed using an internal standard method by gas chromatography (GC9790plus) (Fig.\u0026nbsp;5S).\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\n \u003ch2\u003eCharacterization of catalyst\u003c/h2\u003e\n \u003cp\u003eThe X-ray patterns were collected for all the studied samples (Fig. \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Fig. \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eS). Except for the sample modified with 0.1 mol/L KOH (TS-1-K-0.1), all the samples displayed characteristic diffraction peaks assignable to the typical MFI structure (Hwang et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2005\u003c/span\u003e). The MFI structure of TS-1 modified by KOH was destroyed (Fig. \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). With the exception of TS-1-K-0.1, all samples displayed diffraction peaks at 7.8\u003csup\u003eo\u003c/sup\u003e, 8.8\u003csup\u003eo\u003c/sup\u003e, 23.0\u003csup\u003eo\u003c/sup\u003e, 23.9\u003csup\u003eo\u003c/sup\u003e and 24.2\u003csup\u003eo\u003c/sup\u003e, which are consistent with previous literature reports (Su et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eTo further study the morphology and structure of the catalysts (TS-1, TS-1-EA-0.1, TS-1-TPAOH-0.1, TS-1-Na-0.1), SEM and TEM characterization were performed (Fig. \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eS and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eS). The TS-1 possessed a relatively smooth particle surface, while the particle surface of TS-1-EA-0.1 was rough resulting from the corrosion of TS-1 by alkali (Fig.\u0026nbsp;2Sb). In addition, the surface of sample TS-1-Na-0.1 was most severely corroded, which might be due to the higher alkalinity of NaOH (Fig.\u0026nbsp;2Sd). When comparing the TEM images of different catalysts, irregular hollows were observed in the TEM image of TS-1-EA-0.1, indicating the formation of a new mesoporous structure in the modified TS-1 (Fig.\u0026nbsp;3Sb).\u003c/p\u003e\n \u003cp\u003eThe structure characteristics of the samples (TS-1, TS-1-EA-0.05, TS-1-EA-0.1, TS-1-EA-0.3, TS-1-EA-0.5, TS-1-TPAOH-0.1, TS-1-Na-0.1) were studied using nitrogen adsorption\u0026ndash;desorption isotherm (Fig. \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea). The TS-1 exhibited a narrow hysteresis loop in the high relative pressure region (P/P\u003csub\u003e0\u003c/sub\u003e\u0026thinsp;\u0026gt;\u0026thinsp;0.9), which was ascribed to the pore stacking of zeolite particles (Guo et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). In comparison with the TS-1, the TS-1-EA-0.1 sample showed an obvious hysteresis loop in the range of 0.4\u0026thinsp;\u0026lt;\u0026thinsp;P/P\u003csub\u003e0\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;1.0, which further confirmed the formation of mesopores. While TS-1 was modified with a higher concentration of ethylamine or more alkaline NaOH, the hysteresis loops of these samples disappeared completely at 0.4\u0026thinsp;\u0026lt;\u0026thinsp;P/P₀ \u0026lt; 0.9. It could be reasonably inferred that the excessive corrosion of TS-1 caused by excessively high alkalinity led to the local collapse of its internal framework structure. Moreover, the pore size distribution was centered at 0.37 nm for these catalysts (Fig. \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb). Next, the main physical characteristics of the studied samples were investigated (Table \u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The TS-1 sample possessed total surface areas of 470 cm\u003csup\u003e2\u003c/sup\u003e/g, external surface areas of 49 cm\u003csup\u003e2\u003c/sup\u003e/g and mesoporous volume of 0.05 cm\u003csup\u003e3\u003c/sup\u003e/g, whereas the TS-1-EA-0.1 sample exhibited higher values, with total surface areas of 485 cm\u003csup\u003e2\u003c/sup\u003e/g, external surface areas of 53 cm\u003csup\u003e2\u003c/sup\u003e/g and mesoporous volume of 0.15 cm\u003csup\u003e3\u003c/sup\u003e/g. Evidently, ethylamine post-treatment effectively increases the mesopore volume of TS-1. Hence, the higher surface areas and mesoporous volume of ethylamine-modified TS-1 might lead to superior catalytic performance. However, when TS-1 was modified with a higher concentration of ethylamine and more strongly alkaline NaOH, the mesoporous volume of these samples not only failed to increase but actually decreased, which also further confirmed that the excessive corrosion of TS-1 led to the local collapse of its internal structure.\u003c/p\u003e\n \u003cp\u003eIn addition, the Si/Ti ratio determined was 12.00 for the parent TS-1 and 10.58\u0026ndash;11.97 for the alkali-treated TS-1 samples with ICP-OES (Table \u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The higher titanium content of the alkali-treated TS-1 samples indicates that silica is selectively removed during alkaline treatment. TS-1-EA-0.1, TS-1-TPAOH-0.1, and TS-1-Na-0.1 were prepared by modifying TS-1 with 0.1 mol/L EA, 0.1 mol/L TPAOH, and 0.1 mol/L NaOH, respectively. Among them, the Si/Ti ratio of TS-1-Na-0.1 decreased more significantly (Table \u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entry 3, entry 6 to 7). Moreover, their Si/Ti ratios gradually decreased when TS-1 was modified with higher concentrations of ethylamine (Table \u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entry 4 to 5), which indicated that the Si-O-Si bonds were severely corroded with increasing alkali concentration, and this might lead to the collapse of its framework structure.\u003c/p\u003e\n \u003cp\u003eThen, the states of titanium in catalysts were studied by FT-IR (Fig. \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec). These catalysts exhibited prominent characteristic absorption bands at 550 cm\u003csup\u003e-1\u003c/sup\u003e, 800 cm\u003csup\u003e-1\u003c/sup\u003e, 960 cm\u003csup\u003e-1\u003c/sup\u003e, 1100 cm\u003csup\u003e-1\u003c/sup\u003e, and 1230 cm\u003csup\u003e-1\u003c/sup\u003e, consistent with the typical FT-IR fingerprint of TS-1 (Wang et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). In particular, a distinct characteristic band at 960 cm\u003csup\u003e-1\u003c/sup\u003e was observed for these samples, which was generally accepted as proof that titanium had been successfully introduced into the zeolite framework (Ricchiardi et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2001\u003c/span\u003e). Finally, the coordination state of Ti atoms in catalysts was investigated by UV-vis (Fig. \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed). The position of the absorption band of these samples at 210 nm, which is attributed to the tetrahedral titanium(IV) in the zeolite framework. (Ratnasamy et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2004\u003c/span\u003e\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\n \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003cbr\u003e\u003c/div\u003e\u0026nbsp;\u0026nbsp;\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003ePhysicochemical properties of samples\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eSample\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eSi/Ti\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003eS\u003csub\u003eBET\u003c/sub\u003e(m\u003csup\u003e2\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eS\u003csub\u003eexter\u003c/sub\u003e(m\u003csup\u003e2\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003eV\u003csub\u003emicro\u003c/sub\u003e(cm\u003csup\u003e3\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003eV\u003csub\u003emeso\u003c/sub\u003e(cm\u003csup\u003e3\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e12.00\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e470\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e49\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.05\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.05\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e11.97\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e419\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e47\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e11.62\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e485\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e53\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.15\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e11.16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e404\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e10.58\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e347\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e39\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.03\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-TPAOH-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e11.35\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e482\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e54\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.17\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.08\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-Na-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e11.19\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e241\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e41\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.09\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.03\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colspan=\"7\" nameend=\"c7\" namest=\"c1\"\u003e\n \u003cp\u003e\u003csup\u003ea\u003c/sup\u003e The Si/Ti ratio of the TS-1 catalysts were determined by ICP-OES analysis\u003c/p\u003e\n \u003cp\u003eS\u003csub\u003eBET\u003c/sub\u003e BET surface area, S\u003csub\u003eexter\u003c/sub\u003e external surface area, V\u003csub\u003emicro\u003c/sub\u003e micropore volume, V\u003csub\u003emeso\u003c/sub\u003e mesopore volume\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\u003e\u003cbr\u003e\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n \u003ch2\u003eAlkali-modified TS-1 catalyzed nitration of propionaldehyde oxime\u003c/h2\u003e\n \u003cp\u003eAfter producing and characterizing the catalysts, the first step of our work was to investigate their catalytic activity in the nitration of propionaldehyde oxime (Table \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). In this context, TS-1 modified with 11 different types (EA, PA, BA, DEA, TEA, TMAOH, TEAOH, TPAOH, NH\u003csub\u003e3\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO, NaOH, KOH) of alkali was used as the catalyst, and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e was used as the oxidizing agent to catalyze the oxidation of propionaldehyde oxime for the synthesis of 1-nitropropane. Among all the tested catalysts, TS-1-EA-0.1 exhibited the optimal catalytic performance, and the yield of 1-nitropropane increased to 40% (Table \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, entry 3), which was attributed to the larger pore size of TS-1-EA-0.1 than that of TS-1 (Table \u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Subsequently, the catalytic activity of TS-1 modified with varying concentrations of ethylamine was also investigated for the synthesis of 1-nitropropane from propionaldehyde oxime (Table \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, entry 2 to 5). The catalytic properties of TS-1-EA-0.05 was basically consistent with that of the TS-1, which indicated that the corrosion effect of ethylamine on TS-1 might be weak when its concentration was too low. In addition, the catalytic properties of TS-1-EA-0.3 and TS-1-EA-0.5 in catalyzing the synthesis of 1-nitropropane from propionaldehyde oxime gradually declined compared with TS-1-EA-0.1. Specifically, the catalytic properties of TS-1-EA-0.5 was even lower than that of the TS-1, which might be related to the excessive corrosion of TS-1 caused by the high-concentration ethylamine. In conclusion, the TS-1 modified with 0.1 mol/L ethylamine exhibited superior catalytic activity, which was in good agreement with the pore volume characterization of the catalysts.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u0026nbsp;\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eComparison of catalytic activity of different alkali modified TS-1\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colspan=\"4\" nameend=\"c4\" namest=\"c1\"\u003e\n \u003cp\u003e\u003cimg 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\"\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eCatalyst\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eYield of \u003cstrong\u003e1b\u003c/strong\u003e(\u003cstrong\u003e1c\u003c/strong\u003e) (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003eSelectivity of \u003cstrong\u003e1b\u003c/strong\u003e (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e24(0.8)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e96\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.05\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e23(1.3)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e40(0.9)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e27(0.6)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e19(0.8)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-PA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e3.6(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-BA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e11(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-DEA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e13(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-TEA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e3.1(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-TMAOH-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e3.2(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-TEAOH-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e2.7(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-TPAOH-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e30(0.5)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e13\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-NH\u003csub\u003e3\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e8(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-Na-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e21(1.4)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e93\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-K-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003e0.9(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"4\"\u003eReaction conditions: propionaldehyde oxime (10 mmol), catalyst (0.1 g), H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (2 equiv), NH\u003csub\u003e3\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO (0.15 equiv), MeOH (3.8 mL), 65\u0026deg;C, 0.5 h, detected by GC\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003eBased on the previous study, the reaction conditions were further screened for the synthesis of 1-nitropropane via propionaldehyde oxime oxidation over TS-1-EA-0.1 (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). Frist of all, the effect of the catalyst amount was investigated on oxidation activity of propionaldehyde oxime. First, the yield of 1-nitropropane gradually increased when the amount of catalyst was increased from 0.1 g to 0.4 g (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 1 to 4). When the amount of catalyst was 0.4 g, the highest yield of 1-nitropropane reached 78% (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 4). Upon further increasing the amount of catalyst to 0.5 g, the yield and selectivity of 1-nitropropane began to decrease (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 5). Subsequently, the effect of the quantity of aqueous ammonia on oxidation activity of propionaldehyde oxime was investigated over TS-1-EA-0.1. Without aqueous ammonia, the yield and selectivity of 1-nitropropane were 31% and 90%, respectively (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 6). The yield of 1-nitropropane gradually increased when the quantity of aqueous ammonia was increased from 1.0 mmol to 1.5 mmol. (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 4, entry 7). Clearly, when the quantity of aqueous ammonia was 1.5 mmol, the yield of 1-nitropropane reached the highest point (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 4). This may be attributed to the fact that aqueous ammonia can regulate the reaction pH and reduce the formation of by-product. In addition, there is an interaction between ammonia and titanium active sites according to the previous study (Alvear et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2025\u003c/span\u003e).\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\n \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003cbr\u003e\u003c/div\u003e\n \u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eOptimization of reaction conditions for the synthesis of 1-nitropropane from propionaldehyde oxime\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eTS-1-EA-0.1(g)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\n \u003cp\u003eNH\u003csub\u003e3\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO (mmol)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eSolvent\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003eYield of 1b(1c) (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003eSelectivity of 1b (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003e0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e40(0.9)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003e0.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e42(0.1)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003e0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e50(0.3)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e78(0.2)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003e0.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e60(2.8)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e/\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e31(3.4)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e45(2.9)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e93\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e2.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e25(2.5)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e9\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e/\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e/\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e10\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e50(0.1)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e11\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e34(3.2)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eMeCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e37(0.1)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e13\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003et-BuOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e1.9(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003ei-PrOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e8.8(0)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"7\"\u003eReaction conditions: propionaldehyde oxime (10 mmol), TS-1-EA-0.1, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, NH\u003csub\u003e3\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO, Solvent (3.8 mL), 65\u0026deg;C, 0.5 h, detected by GC\u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"7\"\u003e\u003csup\u003ea\u003c/sup\u003e Without H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. \u003csup\u003eb\u003c/sup\u003e H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (10 mmol). \u003csup\u003ec\u003c/sup\u003e H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (30 mmol)\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003eNext, the effect of the amount of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e on oxidation activity of propionaldehyde oxime over TS-1-EA-0.1 was investigated. In a blank experiment, propionaldehyde oxime could not be oxidized to 1-nitropropane without H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 9). The yield of 1-nitropropane increased first and then decreased as the molar amount of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e varied from 10 mmol to 30 mmol (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 4, entry 10 to 11), reaching the highest value of 78% at 20 mmol (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 4). As the amount of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e continued to increase, the yield of by-product began to increase and the selectivity of the product began to decrease (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 11). Moreover, the effect of solvent species on oxidation activity of propionaldehyde oxime was studied (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 4, entry 12 to 14). When methanol was used as the solvent, the yield of 1-nitropropane was the highest (Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 4). These experimental results are consistent with the finding that the methanol is the optimal proton transfer carrier when the active site of TS-1 is Ti(OSi)\u003csub\u003e4\u003c/sub\u003e (Yu et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2022\u003c/span\u003e)\u003c/p\u003e\n \u003cp\u003eFurthermore, the influence of reaction temperature on oxidation activity was studied (Fig. \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). Clearly, the yield of 1-nitropropane showed a trend of increasing first and then decreasing at 55\u0026ndash;70\u003csup\u003eo\u003c/sup\u003eC, reaching the highest point of 78% at 65\u003csup\u003eo\u003c/sup\u003eC. When the reaction temperature continued to rise, the yield of 1-nitropropane began to decrease, which might be due to the ineffective decomposition of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e at elevated temperatures. In addition, while the reaction temperature was 65\u003csup\u003eo\u003c/sup\u003eC, the yield of 1-nitropropane increased with prolonged reaction time from 10 min to 0.5 h (Fig. \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). In the case of 0.5 h, the highest yield of 1-nitropropane reached 78%. Subsequently, the yield of 1-nitropropane began to decrease with increasing the reaction time to 35 minutes. Furthermore, TS-1-EA-0.1 exhibited superior catalytic activity relative to the TS-1 (Fig. \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). In addition, to evaluate the reusability of regenerated TS-1-EA-0.1 zeolite, the recycling experiments were carried out five times (Fig. \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). Over five consecutive cycles, the yield of 1-nitropropane decreased from 78% to 62%.\u003c/p\u003e\n\u003c/div\u003e\n\u003ch3\u003eOxidation of aldoximes with different chain lengths to primary nitroalkanes over TS-1-EA-0.1\u003c/h3\u003e\n\u003cp\u003eFinally, the catalytic activity of TS-1-EA-0.1 for acetaldehyde oxime and butyraldehyde oxime was investigated and contrasted with that of the TS-1 (Table \u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). Both TS-1-EA-0.1 and TS-1 afforded a 99% yield of nitroethane in the oxidation of acetaldoxime (Table \u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, entry 3\u0026ndash;4). However, the yields of 1-nitrobutane from butyraldehyde oxime oxidation catalyzed by TS-1 and TS-1-EA-0.1 were 33% and 34%, respectively, which indicated that the modified TS-1 zeolite was not suitable for butyraldehyde oxime with larger molecular diameter than propionaldehyde oxime (Table \u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, entry 5 to 6).\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\" class=\"fr-table-selection-hover\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eSynthesis of nitroalkanes by oxidation of aldehyde oximes\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colspan=\"5\" nameend=\"c5\" namest=\"c1\"\u003e\n \u003cp\u003e\u003cimg 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style=\"width: 1221px;\"\u003e\u003cbr\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eR\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eCatalyst\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003eGC yield of \u003cstrong\u003e2 (3)\u003c/strong\u003e (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eSelectivity of \u003cstrong\u003e2\u003c/strong\u003e (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003en-C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eTS-1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e56(0.1)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003en-C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eTS-1-EA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e78(0.2)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eMe\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eTS-1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eMe\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eTS-1-EA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e99\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003en-C\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eTS-1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e33(0.9)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003en-C\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eTS-1-EA-0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e34(1.2)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e96\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"5\"\u003eReaction conditions: reaction substrate (10 mmol), TS-1-EA-0.1(0.4 g), NH\u003csub\u003e3\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO (0.15 equiv.), H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (2 equiv), MeOH (3.8 mL), 65\u0026deg;C, 0.5h, detected by GC\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003ch3\u003ePossible mechanism analysis\u003c/h3\u003e\n\u003cp\u003eThe used TS-1-EA-0.1 was recovered and calcined at 623 K for 2 h, and then characterized by UV-vis spectroscopy. Compared with fresh TS-1-EA-0.1, the used TS-1-EA-0.1 exhibited a new absorption peak at 427 nm, which was attributed to the adsorption of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e on Ti site to produce peroxyhexa-coordinated titanium (Ti-OOH) (Lin et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2025\u003c/span\u003e) (Fig.\u0026nbsp;7S).\u003c/p\u003e\n\u003cp\u003eBased on literature reports (Chu et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Zecchina et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e1996\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2022\u003c/span\u003e) and our experimental results, a possible mechanism for the TS-1 catalyzed oxidation of aldoximes had been proposed (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Initially, the tetrahedral Ti\u003csup\u003e4+\u003c/sup\u003e active center (\u003cstrong\u003eA\u003c/strong\u003e) in TS-1 interacts with ammonia to generate six-fold coordinated Ti (IV) complex (\u003cstrong\u003eB\u003c/strong\u003e), which is subsequently oxidized by H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e to form Ti-OOH (\u003cstrong\u003eC\u003c/strong\u003e). Then, the aldoxime is oxidized to the nitroalkane under the combined action of the Ti-OOH and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. In addition, TS-1-EA-0.1 possessed more mesopores compared with the parent TS-1, allowing more small-molecule aldoximes to enter the channels and reducing the diffusion limitation of the reaction. Therefore, TS-1-EA-0.1 displayed excellent catalytic activity in the nitration reaction of propionaldehyde oxime.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eIn this work, the influence of alkaline treatment of TS-1 was studied on catalytic performance for aldoxime nitration. The results showed that the alkaline treatment can selectively remove silicon, and the framework of MFI zeolites remains intact. Compared with the untreated TS-1 catalyst, TS-1-EA-0.1 exhibits abundant mesopores and larger pore sizes, thereby enhancing its catalytic performance in the nitration of propionaldehyde oxime. In contrast, the yield of 1-nitrobutane from butyraldehyde oxime over TS-1-EA-0.1 was not improved, which is attributed to the larger molecular diameter of butyraldehyde oxime compared to propionaldehyde oxime. In conclusion, the exceptional catalytic activity of the alkali-modified TS-1 stems from the generation of mesopores.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eCRediT authorship contribution statementYu-Qing Gu: Writing - original draft. Cong-Xuan Fan: Formal analysis. Shi-Feng Xing: Investigation. Hong-Jun Zhu: Writing - review \u0026amp; editing, Project administration.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThis research was supported by the National Key Research and Development Program of China (2016YFB0301703).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAlbright L, Carr R, Schmitt R (1996) Nitration: recent laboratory and industrial developments. 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Chem Select 7:e202202475. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/slct.202202475\u003c/span\u003e\u003cspan address=\"10.1002/slct.202202475\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Scheme 1","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"chemical-papers","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"chpa","sideBox":"Learn more about [Chemical Papers](http://link.springer.com/journal/11696)","snPcode":"11696","submissionUrl":"https://www.editorialmanager.com/CHPA/default.aspx","title":"Chemical Papers","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"TS-1, Alkaline modification, Primary nitroalkanes, Green catalysis","lastPublishedDoi":"10.21203/rs.3.rs-9397977/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9397977/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Modified TS-1 catalysts were prepared by treating TS-1 with different alkalis for the nitration of aldoxime, and the effect of alkali treatment on catalytic performance was investigated. TS-1 was modified using organic amines such as ethylamine (EA), triethylamine (TEA), and tetrapropylammonium hydroxide (TPAOH), as well as inorganic bases such as NaOH, KOH. The catalysts were characterized by XRD, FT-IR, UV-vis, N adsorption etc., which showed that the volume of mesopores increased and the skeleton structure remained basically unchanged by the ethylamine-modified TS-1 and the TPAOH-modified TS-1. The highest yield of 1-nitropropane increased 78% when propionaldehyde oxime was catalyzed by the 0.1 mol/L ethylamine treated sample TS-1-EA-0.1. The enhanced catalytic performance of TS-1 after ethylamine treatment may be attributed to the matching between the pore size of modified TS‑1 and the molecular size of propionaldehyde oxime. Subsequently, TS-1-EA-0.1 was used to catalyze acetaldoxime and butyraldehyde oxime. The results revealed that this catalyst was suitable for acetaldehyde oxime as expected, but less effective for the oxidation of butyraldehyde oxime with a larger molecular diameter than propionaldehyde oxime to 1-nitrobutane.","manuscriptTitle":"Green Synthesis of Primary Nitroalkanes via Oxidation of Small-Molecule Aldoximes Catalyzed by Alkali-Modified TS-1","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-05-11 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