We designed and offered a new nanocatalyst through three-step synthetic routes depicted in Fig. 2. For the performance of mesoporous MCM-41, morphology is a unique feature; it largely depends on how it is prepared. MCM-41 nanoparticles were ready through the reaction of NaOH, cetyltrimethylammonium bromide (CTAB), and tetraethyl orthosilicate (TEOS). Afterward, the CPTEO linker was fixed on the surface of MCM-41 nanoparticles, and the binding of the 2-aminothiophenol-Cu complex was easier. After the MCM-41-CPTEO-2-aminothiophenol-Cu synthesis, EDS, EMA, ICP, BET, SEM, TGA, TEM, XRD, AFM, CV, and FT-IR were employed to identify its nanostructure and nature accurately.Figure 2Showing the preparation steps of the catalyst.Catalyst characterizationUnderstanding a catalyst involves analyzing its physical, chemical, and structural properties65,66,67,68,69,70,71,72. This is essential for understanding its behavior and performance in various chemical reactions. In a study on nanocatalysts, the synthesized catalysts’ structural features and properties were discussed using diverse analytical techniques.FT-IRFor accuracy, the FT-IR spectrum is used to identify highly applicable functional groups in different samples, and it can help so much to know the properties of prepared samples. The FT-IR spectrum of nanocatalyst was recorded separately for each preparation stage (Fig. 3). In graph (a), for the pure MCM-41 sample, absorption bands at 1075, 818, and 454 cm−1 were observed, which can be attributed to asymmetric and symmetric stretching vibrations in the mesoporous (Si–O–Si) structure. The band at 3460 cm−1 corresponds to the stretching vibration of the O–H groups. Also, in graph (b), the observed peaks in 2954, 2860, and 618 cm−1 are related to C–H and C–Cl stretching vibrations, indicating the linker’s successful connection (CPTMO). Curve (c) shows stretching vibrations at 3395, and 3400 cm−1 corresponding to N–H and 2560 cm−1 corresponding to S–H; also 1624 cm−1 corresponding to C=C, which confirms the binding of 2-aminothiophenol ligand. Curve (d) shows Cu–N at 500 cm−1 and Cu–S at 600 cm−1 stretching vibrations. All functional groups are listed in Table 1.Figure 3Infra-red spectrum of MCM-41 (a), MCM-41-CPTEO (b), MCM-41-CPTEO-2-aminothiophenol (c), and MCM-41-CPTEO-2-aminothiophenol-Cu (d).Table 1 A summary of all functional groups related to the MCM-41-CPTEO-2-aminothiophenol-Cu synthesis process.XRDIn nanocatalyst fabrication, XRD analysis determines the catalyst material’s crystal structure, phase composition, and crystallite size. Additionally, the intensity of the diffraction peaks can be used to calculate the average crystallite size of the catalyst material. This is important because the size of the crystallites can significantly impact the catalytic activity of the material.Each peak in the XRD pattern corresponds to a specific set of lattice planes in the material’s crystal structure. MCM-41 (black): This mesoporous material is from the M41S family of silicate materials. It is characterized by a high degree of order in its pore structure and is commonly used as a catalyst or adsorbent. Its XRD pattern shows a very sharp peak at around 2 degrees 2 Theta, which is typical for the well-ordered hexagonal pore structure of MCM-41, MCM-41-CPTEO (orange): This sample appears to be MCM-41 that has been modified with some compound. The modification causes changes to the XRD pattern, as evidenced by the slight shift and change in the intensity of the primary peak. MCM-41-CPTEO-2-aminothiophenol (brown): Here, the MCM-41-CPTEO has been further modified with 2-aminothiophenol, which appears to affect the XRD pattern again, indicating changes in the material’s structure or the addition of new phases. There might be a slight broadening and decrease in peak intensity. MCM-41-CPTEO-2-aminothiophenol-Cu (purple): In this sample, copper (Cu) has been added to the previously modified MCM-41. The presence of copper seems to cause further changes to the material’s structure, as the XRD pattern shows additional modifications to the peak shapes and intensities56. What’s interesting here is that the peak intensity significantly decreases, which could indicate that the copper addition disrupts the ordered structure or is highly dispersed within the material. More precisely, in Fig. 4, the black curve shows the reflections of the planes (100), (110), (200), and (210) in the regular hexagonal arrangement of the peaks in the areas it is related to the pure MCM-41 sample. MCM-41-CPTEO, MCM-41-CPTEO-2-aminothiophenol, and MCM-41-CPTEO-2-aminothiophenol-Cu had only one sharp peak associated with (100) were observed. This peak’s intensity was lower than pure MCM-41, which may be attributed to the pore-filling effect of one of the samples. After fixing the functional groups, a significant reduction in the XRD peaks was observed, which can be attributed to the thickness of the organic layers, so it can be concluded that the catalyst was formed on the Si-MCM-41 surface. It can be seen that the XRD patterns of MCM-41-CPTEO-2-aminothiophenol-Cu before and after recovery are almost overlapped, indicating the peak positions and intensities are quite similar. This means that the recovery process does not affect the structure of the sample. The material remains mesoporous and highly crystalline, which makes it suitable for adsorption and other functional applications such as catalysts.Figure 4XRD analysis images of MCM-41 (black), MCM-41-CPTEO (orange), MCM-41-CPTEO-2-aminothiophenol (brown), MCM-41-CPTEO-2-aminothiophenol-Cu (purple), and MCM-41-CPTEO-2-aminothiophenol-Cu after recovery (red).FE-SEMScanning Electron Microscopy (SEM) is a powerful technique used in nanocatalyst fabrication to analyze the surface morphology and structure of catalyst materials at the nanoscale. SEM images of the MCM-41 substrate and MCM-41-CPTEO-2-aminothiophenol-Cu are revealed in Fig. 5. Each micrograph shows spherical particles at 20 thousand times magnification (SEM MAG: 20.0 kx) with similar scale bars indicating 200 nm. This suggests all the particles are in the sub-micron to nanoscale size range.Figure 5SEM analysis images of MCM-41 (a) and MCM-41-CPTEO-2-aminothiophenol-Cu (b,c).The first image showcases MCM-41, a widely used mesoporous material with a well-designed spherical structure. At a magnification of 20,000 × and with a scale bar of 200 nm, the image perfectly captures the uniform and ordered composition of MCM-41, exemplifying its characteristic features with a smooth surface, adding to the image’s visual appeal. The following two images 5b and 5c display a modified form of MCM-41 that has undergone functionalization with CPTEO (chloropropyltriethoxysilane) and 2-aminothiophenol, followed by complexation with copper (Cu). Upon modification and functionalization, the material’s surface texture appears slightly rougher and less uniform than the initial MCM-41 image. This transformation in surface texture serves as evidence of the successful attachment of these elements, providing insight into the modification that can be inferred from Fig. 5b,c, which shows, that the morphology of the size distribution of nanoparticles is approximately 30 nm.MappingMapping analysis in nanocatalyst fabrication involves using various techniques to spatially visualize and analyze the distribution of elements or chemical species within the catalyst material. The result demonstrates how the elements are dispersed and acknowledges the attendance of the mentioned elements in the ultimate catalyst. Each hexagon is a map that shows how these elements are distributed within the sample at a microscopic level. The image provides visual data for the distribution of elements: O (oxygen) is shown in green, N (nitrogen) is shown in red, Cu (copper) is shown in light blue, C (carbon) is shown in yellow, and S (sulfur) is shown in dark blue. For instance, the areas with brighter intensity in each color represent regions with higher concentrations of the respective element (Fig. 6).Figure 6Mapping analysis of MCM-41-CPTEO-2-aminothiophenol-Cu.EDSEnergy-dispersive X-ray spectroscopy (EDS) analysis is an analytical technique used to characterize the elemental composition of materials, including nanocatalysts. It is precious in the field of nanocatalyst preparation and characterization. EDS analysis is often performed with scanning electron microscopy (SEM) or transmission electron microscopy (TEM) to provide elemental information about the sample. The outcomes showed the attendance of C (35.21), N (6.65), O (25.57), Cu (0.33), S (11.00), and Si (21.24). Thus, it confirmed the successful binding of organic substances predicted in the material’s structure (Fig. 7).Figure 7EDS analysis diagram of MCM-41-CPTEO-2-aminothiophenol-Cu.As can be inferred from the crops, the percentage of copper saturation was two percent (ICP = 2.08).TGAIn the context of catalyst characterization, TGA is employed to investigate the thermal stability, decomposition, and other thermal properties of catalyst materials, including nanocatalysts. In Fig. 8, graph a is related to mesoporous materials MCM-41-CPTEO-2, graph b is related to MCM-41-CPTEO-2-aminothiophenol and graph c is associated with MCM-41-CPTEO-2-aminothiophenol-Cu is that in all three of these samples, they show the first weight loss below 200 °C, which is related to the release of water and solvents absorbed in the catalyst synthesis steps. Also, the other weight change, from 300 to 320 °C, indicates the thermal decomposition of the active organic groups fixed on the substrate. From 450 to 600 °C, the destruction of the nanocatalyst is visible. Graph a represents “MCM-41-CPTEO” and shows the least weight loss over the entire temperature range, indicating that this material is the most thermally stable among the three. Graph b represents “MCM-41-CPTEO-2-aminotriphenol” and shows moderate weight loss, with significant weight loss occurring as the temperature rises above 200 °C. This line indicates that the material’s stability is less than that of “MCM-41-CPTEO” but better than that of the third material. Graph c, represents “MCM-41-CPTEO-2-aminotriphenol-Cu” and it exhibits the greatest weight loss as temperature increases, starting to lose weight at the lowest temperature and continuing to do so throughout the entire range. This suggests that adding Cu to the “MCM-41-CPTEO-2-aminotriphenol” decreases thermal stability. For diagram d, which shows the thermal stability of the synthesized catalyst after recovery, we can see that the thermal stability of the considered catalyst is reduced after six to seven times recovery.Figure 8TGA plot of the MCM-41-CPTEO (a), MCM-41-CPTEO-2-aminothiophenol (b), MCM-41-CPTEO-2-aminothiophenol-Cu (c), and MCM-41-CPTEO-2-aminothiophenol-Cu after recovery (d).BETBrunauer–Emmett–Teller (BET) analysis is a widely used technique in nanocatalyst preparation for determining the surface area and porosity of catalyst materials. This information is crucial for understanding the physical properties of the catalyst and optimizing its performance in catalytic reactions. The BET analysis is based on the measurement of gas adsorption onto the surface of the catalyst material. Typically, nitrogen gas is used for this purpose. The principle behind BET analysis is that as a gas is adsorbed onto the material’s surface, a monolayer of gas molecules forms, and further adsorption occurs in multilayers. The BET equation is then used to analyze the relationship between the amount of gas adsorbed and the relative pressure to determine the specific surface area of the material.The specific surface area obtained from BET analysis provides valuable information about the available surface area for catalytic reactions. Figure 9 shows N2 adsorption/desorption isotherms of the MCM-41-CPTEO-2-aminothiophenol-Cu sample.Figure 9BJH analysis of MCM-41-CPTEO-2-aminothiophenol-Cu.The BJH analysis gives a remarkable insight into the surface area, which is appropriate to know the features of the sample for the specific application like catalysis, adsorption, or as a matrix for controlled release of active agents where the pore size and distribution form the significant part of the material. The BJH plot in Fig. 9 has a sharp peak in the pore radius range of about 30–40 nm, which shows that the sample has a most probable pore size in the range. Thus, the pore volume reduces as the pore radius increases, showing that the sample has a narrow pore size distribution. Essentially, the curve conforms with the general trend of a mesoporous material like the MCM-41 structure, considering it has a highly ordered and uniform pore structure. Thus, the incorporation of 2-aminothiophenol and Cu functionalization to MCM-41 material may have affected the pore size and distribution as indicated by the BJH plot. This 30–40 nm enhancement suggests that the pore sizes have been altered from the parent MCM-41 material. All the obtained data are reported in Table 2. The reduction in surface area, pore size, and increment in wall diameter are the results and strong evidence that the copper metal complex is stabilized on the MCM-41 substrate. The thickness of the wall is calculated with the following relation (Eq. 1):Table 2 Comparison of tissue characteristics of MCM‐41 and MCM-41-CPTEO-2-aminothiophenol-Cu.$$\text{Wall tickness}=\frac{2\text{d}{ }_{100}}{\surd 3}$$
(1)
AFMBy analyzing the AFM images, researchers can quantitatively measure parameters such as particle height, size distribution, and surface roughness, which are essential for optimizing the performance of the nanocatalyst. In Fig. 10, the first scan on the left is a 3D representation of the roughness and texture of the surface. It is labeled with axes measuring 5 µm (µm) in the X and Y directions. The middle scan is a side view of the same 3D topography, emphasizing the height variations along a cross-section. The measured height range is around 1.1 µm, as indicated in the image. The scan in the bottom right is a 2D topography, presented as a heat map where the color scale, shown on the right, indicates the height variation. The height range of the color bar goes up to approximately 70.25 nm, with darker areas representing lower points and brighter areas representing higher points on the sample surface. The images show clustered structures that could represent materials like nanoparticles, thin films, or the surface of some material that has undergone texturing or patterning. These structures might affect materials science, nanotechnology, and surface engineering. The materials’ exact nature and properties would require additional contextual information not provided by the image.Figure 10AFM analysis of MCM-41-CPTEO-2-aminothiophenol-Cu.TEMTransmission Electron Microscopy (TEM) analysis is a powerful imaging and characterization technique used in nanocatalyst research to visualize and analyze the structure and morphology of catalyst materials at the nanoscale. This level of detail is crucial for understanding the physical properties of the catalyst and optimizing its performance in catalytic reactions. Figure 11 shows the TEM of the MCM-41-CPTEO-2-aminothiophenol-Cu catalyst.Figure 11TEM images of MCM-41-CPTEO-2-aminothiophenol-Cu.The image showcases the distinctive, highly ordered, hexagonal arrangement of pores, a defining characteristic of the MCM-41 material. This meticulous mesoporous structure is a product of the template-directed synthesis method employed in creating the MCM-41-CPTEO-2-aminothiophenol-Cu sample. The scale bar in the image underscores the pore size, indicating it to be approximately 150 nm. This is consistent with the commonplace pore size range of MCM-41 materials, which typically fall within the mesoporous range of 2–50 nm. The TEM image reveals a consistent distribution of the pores across the sample, signifying an exceptional degree of structural order and uniformity. The meticulously ordered mesoporous structure and even pore distribution noted in the TEM image are pivotal features contributing to the material’s remarkable surface area, as well as its adsorption and catalytic properties. These attributes are pivotal for applications such as catalysis, adsorption, and separation processes. The comprehensive understanding of the material’s porous structure and morphology derived from the combined analysis of the BJH plot and the TEM image is invaluable for characterizing and optimizing its performance across diverse applications.CVElectrochemical consideration was performed to prove the existence of Cu2+ in nanocatalyst further. For this purpose, cyclic voltammetry (CV) as an electrochemical technique was used. CV test was performed in three electrodes configuration in 0.5 M H2SO4 electrolyte solution, which modified glassy carbon electrode (MGC), Ag/AgCl, and platinum sheet electrodes were used as working, reference, and counter electrodes, respectively. MGC electrode was prepared by drop coating mixture of AC:PVDF:Nanocatalyst with a ratio of 10:10:80 dissolved in ethanol. Figure 12 shows the CV plot of the GC and MGC electrodes. According to the black diagram، no redox peaks for the GC electrode are visible، but as shown in the CV curve of the MGC electrode، the peak of copper oxidation has been fully manifested in the region of about 0.3 V, and its Reducing peak is also about − 0.2 to 0.4 V. The appearance of these peaks indicates the presence of Cu2+ in the nanocatalyst structure. The redox reaction of Cu in H2SO4 electrolyte solution occurs according to the following reaction, which confirms the presence of this metal in the nanocatalyst structure according to the previous literature73.$$\begin{gathered} {\text{Cu}} \rightleftharpoons {\text{C}}{{\text{u}}^{2 + }} + 2{{\text{e}}^- }\quad {\text{Oxidation}}\,{\text{reaction}} \hfill \\ {\text{C}}{{\text{u}}^{2 + }} + 2{{\text{e}}^- } \rightleftharpoons {\text{Cu}}\quad {\text{Reduce reaction}} \hfill \\ \end{gathered}$$Figure 12CV curve of the GC and MGC electrode in H2SO4 (0.5 M) electrolyte solution.Factor optimization for C–C coupling reaction catalyzed using MCM 41-CPTEO-2-aminothiophenol-CuIn organic reaction, its activity was executed using the Suzuki coupling reaction to evaluate the catalytic prowess of the obtaining catalyst. To create a more effective catalytic method, the parameters like base type (K2CO3, Et3N, and Na2CO3), solvent (H2O, EtOH, acetone, PEG, n-hexane, and DMF), temperature, and the catalyst loading (30, 40 and 50 mg) were surveyed.Initially, to find the optimum reaction status for the efficient and excellent yield synthesis of biphenyl (3a), iodobenzene (1a), and benzeneboronic acid (2), (1:1.5, molar ratio) was chosen as a sample reaction. The reaction was investigated without applying a catalyst. As expected, the corresponding product was not acquired (Table 3, entry 1), and it was shown that the presence of a catalyst is necessary for the reaction to occur. The product outcome in H2O as a green solvent was significantly higher than that of other solvents under similar reaction conditions.Table 3 The effect of various factors on the biaryl ‘s synthesis.Synthesis of compound 3a with varying amounts of MCM 41-CPTEO-2-aminothiophenol-Cu was exanimated. Accordingly, it was achieved that using 40 mg of the respective catalyst, K2CO3, and water afforded excellent yield in a shorter period (Table 3, entry 3). Further increase in catalyst concentration did not significantly improve the performance (Table 3, entry 4). The use of different solvents in the reaction was investigated, but no relevant results were obtained (Table 3, entries 5–10). Other bases were also examined, and the reaction yield was included (Table 3, entries 6–14).To establish the efficiency and general scope of the mechanochemical reaction, aryl iodides, bromides, and benzeneboronic acid were reacted using nanocatalyst at reflux status to generate the desired products at excellent yields (Table 4, yield; 81–98%).Table 4 Coupling of phenylboronic acid with aryl halides catalyzed by MCM 41-CPTEO-2-aminothiophenol-Cu.Mechanistic study of C–C bonding reaction using nanocatalyst MCM-41-CPTEO-2-aminothiophenol-CuFigure 13 depicts the reaction pathway for synthesizing 3a–g using MCM-41-CPTEO-2-aminothiophenol-Cu. Accordingly, the oxidative addition of aryl halides 1a–l to MCM-41-CPTEO-2-aminothiophenol-Cu is the first stage to afford complex Cu as an intermediate I. An organoborane reagent reacts with intermediate I in transmetalation, leading to intermediate II. Eventually, an elimination-reduction stage produces the biphenyls and the initial catalyst.Figure 13The admissible mechanism for synthesizing 3a–l under MCM-41-CPTEO-2-aminothiophenol-Cu74.Catalyst recoverabilityThe catalyst’s sustainability and recoverability are essential factors in reducing waste and improving the overall efficiency of the reaction process. The ability to reuse the catalyst multiple times without significant loss of activity can contribute to a more environmentally friendly and cost-effective approach. The possibility of catalyst reusability is an essential privilege for pharmaceutical and other applications, etc. For this matter, the recyclability of MCM-41-CPTEO-2-aminothiophenol-Cu nanocatalyst for the reaction in the C–C coupling was investigated. When the reaction was over, the catalyst was quickly separated by centrifugation. It has been observed that the catalyst can be reused at least six cycles without notable diminution in catalytic activity with 98, 96, 91, 86, 83, and 81% of product yields, respectively (Fig. 14). There is a recyclability bar chart for a catalyst named MCM-41-CPTEO-2-aminothiophenol-Cu. The chart tracks six consecutive runs and illustrates the yield percentage for each run. The time of each run was about 4–20 min.Figure 14Recycle chart of the catalyst MCM-41-CPTEO-2-aminothiophenol-Cu.The chart shows a gradual decrease in yield percentage with each run, indicating that the catalyst’s efficiency slightly diminishes with use but still maintains a high yield percentage even after six runs. Based on the trend shown in the graph, the catalyst MCM-41-CPTEO 2 aminothiophenol Cu carries a level of activity over at least six uses with only a minor decline in yield. This suggests that it possesses reusability and stability for its role. Such consistent high yields across runs are traits for a catalyst implying potential cost-effectiveness and environmental friendliness if employed in chemical processes. SEM, TEM, and IR analyzes of the recovered catalyst of step six are also in the supplementary file. With this result, it can be inferred that the synthesized catalyst has phenomenal advantages.Hot filtrationDuring the hot filtration test, the reaction synthesis involved refluxing the MCM-41-CPTEO-2-aminothiophenol-Cu in the presence of its heterogeneous nature. The catalyst was easily filtered from the reaction medium after 1 min, half of the reaction time. However, no reaction progress was observed. Subsequently, upon adding the nanocatalyst, the reaction proceeded with high efficiency, achieving 98% efficiency within just 1 min. The test result is detailed in Fig. 15.Figure 15Hot filtration images of MCM-41-CPTEO-2-aminothiophenol-Cu.To perform a laboratory process in an industrial scale, it is required to make the scale-up investigation. The scale-up study used 10 times higher volume, keeping all the other reaction conditions the same. The process was made by stirring with iodobenzene (10 mmol), PhB(OH)2 (15 mmol), and K2CO3 (20 mmol) in solvent (10 mL) at the same temperature. The high yield of the reaction (89%) in 30 min is a sign of the high efficiency of the catalyst in high-scale conditions.Table 5 data reveals that the catalyst MCM-41-CPTEO-2-aminothiophenol-Cu (Entry 1) reigns superior in both yield and reaction time, boasting a remarkable 98% yield in just 30 min when using water as the solvent. The other catalysts listed pale compared to lower results and longer reaction times. Entry 2 employs Ni(II)-β-CD in water, which reacts for 6 h to yield 96%. Entry 3, CuO, managed an 86% yield in 20 h using DMSO as the solvent, while entry 4, Cu(OAc)2, achieved 85% yield in 30 h with Et3N as the solvent. The Cu–N,N‐bis(salicylidene) arylmethanediamine complex (Entry 5) displayed a yield of 91% in 15 h when water was used as the solvent. Entry 6, Pd(0)-MCM-41, achieved a yield of 96% in 24 h.Table 5 Comparison of the efficiency of diverse catalysts described in the literature in C–C, coupling reaction.
MCM-41 supported 2-aminothiophenol/Cu complex as a sustainable nanocatalyst for Suzuki coupling reaction
